EP2588051A1 - Single-component coating having alkoxysilane-terminated n-substituted urea resins - Google Patents
Single-component coating having alkoxysilane-terminated n-substituted urea resinsInfo
- Publication number
- EP2588051A1 EP2588051A1 EP10854202.8A EP10854202A EP2588051A1 EP 2588051 A1 EP2588051 A1 EP 2588051A1 EP 10854202 A EP10854202 A EP 10854202A EP 2588051 A1 EP2588051 A1 EP 2588051A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- resin
- polyisocyanate based
- aminopropyltrimethoxysilane
- butyl
- aliphatic polyisocyanate
- 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.)
- Withdrawn
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 76
- 239000011248 coating agent Substances 0.000 title claims abstract description 48
- 229920001807 Urea-formaldehyde Polymers 0.000 title claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 49
- -1 N-substituted urea Chemical class 0.000 claims abstract description 46
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000077 silane Inorganic materials 0.000 claims abstract description 19
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 17
- 239000003085 diluting agent Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000000049 pigment Substances 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 239000005056 polyisocyanate Substances 0.000 claims description 41
- 229920001228 polyisocyanate Polymers 0.000 claims description 41
- 125000001931 aliphatic group Chemical group 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 13
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 12
- 239000007983 Tris buffer Substances 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 8
- 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 description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000013638 trimer Substances 0.000 claims description 8
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 8
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 claims description 7
- XCOASYLMDUQBHW-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)butan-1-amine Chemical compound CCCCNCCC[Si](OC)(OC)OC XCOASYLMDUQBHW-UHFFFAOYSA-N 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- KFOZMMAXUUCIKU-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)butan-1-amine Chemical compound CCCCNCCC[Si](OCC)(OCC)OCC KFOZMMAXUUCIKU-UHFFFAOYSA-N 0.000 claims description 4
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 claims description 4
- KGNDVXPHQJMHLX-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)cyclohexanamine Chemical compound CO[Si](OC)(OC)CCCNC1CCCCC1 KGNDVXPHQJMHLX-UHFFFAOYSA-N 0.000 claims description 4
- SLTAOXPOORASCD-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]butan-1-amine Chemical compound CCCCNCCC[Si](C)(OC)OC SLTAOXPOORASCD-UHFFFAOYSA-N 0.000 claims description 4
- PSIDVLNBMQXBFV-UHFFFAOYSA-N n-ethyl-3-triethoxysilylpropan-1-amine Chemical compound CCNCCC[Si](OCC)(OCC)OCC PSIDVLNBMQXBFV-UHFFFAOYSA-N 0.000 claims description 4
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 claims description 4
- GOIPELYWYGMEFQ-UHFFFAOYSA-N dimethoxy-methyl-octylsilane Chemical compound CCCCCCCC[Si](C)(OC)OC GOIPELYWYGMEFQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- AYJGUKJXZWHFOL-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)hexan-1-amine Chemical compound CCCCCCNCCC[Si](OC)(OC)OC AYJGUKJXZWHFOL-UHFFFAOYSA-N 0.000 claims description 3
- LWDDGEHGRVTSHO-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)pentan-1-amine Chemical compound CCCCCNCCC[Si](OC)(OC)OC LWDDGEHGRVTSHO-UHFFFAOYSA-N 0.000 claims description 3
- BCBKPXFYSWZHJH-UHFFFAOYSA-N n-propan-2-yl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCNC(C)C BCBKPXFYSWZHJH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims description 3
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 3
- KACJBFAYIKNLCP-UHFFFAOYSA-N 2-methyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCC(C)C KACJBFAYIKNLCP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 abstract description 8
- 230000005855 radiation Effects 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- 229920004482 WACKER® Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CNWSQCLBDWYLAN-UHFFFAOYSA-N butylurea Chemical compound CCCCNC(N)=O CNWSQCLBDWYLAN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- OKKDHVXHNDLRQV-UHFFFAOYSA-N 6-[3-(6-isocyanatohexyl)-2,4-dioxo-1,3-diazetidin-1-yl]hexyl n-(6-isocyanatohexyl)carbamate Chemical compound O=C=NCCCCCCNC(=O)OCCCCCCN1C(=O)N(CCCCCCN=C=O)C1=O OKKDHVXHNDLRQV-UHFFFAOYSA-N 0.000 description 1
- 229920005706 BASONAT® HB 100 Polymers 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- VSHTWPWTCXQLQN-UHFFFAOYSA-N n-butylaniline Chemical compound CCCCNC1=CC=CC=C1 VSHTWPWTCXQLQN-UHFFFAOYSA-N 0.000 description 1
- VXXLEXCQCSPKFI-UHFFFAOYSA-N n-butylcyclohexanamine Chemical compound CCCCNC1CCCCC1 VXXLEXCQCSPKFI-UHFFFAOYSA-N 0.000 description 1
- AGVKXDPPPSLISR-UHFFFAOYSA-N n-ethylcyclohexanamine Chemical compound CCNC1CCCCC1 AGVKXDPPPSLISR-UHFFFAOYSA-N 0.000 description 1
- MTEWAFVECQBILW-UHFFFAOYSA-N n-tert-butylcyclohexanamine Chemical compound CC(C)(C)NC1CCCCC1 MTEWAFVECQBILW-UHFFFAOYSA-N 0.000 description 1
- 150000002829 nitrogen Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Definitions
- the present application relates generally to the synthesis of alkoxysilane- terminated N-substituted urea resins and their application in single-component coatings.
- This coating which is a silicone alkyd, has been used by the Navy for over 50 years, even though the technology continues to provide poor exterior durability (color and gloss retention upon exposure to an oxidative environment with UV and visible light), poor chemical resistance, low hardness, slow cure times and limited cleanability.
- the formulation of low volatile organic component (“VOC”) versions has also recently become difficult, as the utilization of lower viscosity raw materials are increased in effort to maintain sprayable and/or rollable formulations. Unfortunately, this continued decrease in viscosity is typically accompanied by a reduction in resin molecular weight and cross-linkable functionality, thereby reducing the cross-link density and hardness of the resulting cured coating.
- a reduction in the molecular weight of resin components can also lead to sagging of the coating when applied.
- the VOC of silicone alkyd formulations has also been lowered by using exempt solvents, such as Oxsol 100, which do not count against the VOC rule. Although these solvents do not contribute to ozone depletion, it remains beneficial for paint applicators to use coatings with the lowest solvent content possible.
- Silicone alkyd coatings can be formulated as single-component (also known as
- IK insky et al.
- 2K two-component (2K) systems because they cross-linking mechanism occurs as a result of atmospheric oxygen reacting with residual alkenes contained within the resins of the coating.
- the coating does not begin to cure until it is applied on a surface and the solvent evaporates, thereby giving it essentially a limitless pot-life, unlike two-component (2K) systems that begin to react once the components are mixed. Because it is a single-component system, no specialty mixing, equipment, or training is needed to apply the coating, as it can be easily spray-applied by individuals during depot level painting.
- Acrylic siloxanes are conventionally used as both additives and base resins in commercial coatings. These resins are easily manufactured via polymerization of alkoxysilane- functional acrylate monomers with ethyl, butyl, or hexyl acrylate and/or meth(acrylate) monomers. Depending on the molecular weight, acrylic siloxane resins may contain moderate- to-high VOC levels, yet because the alkoxysilane groups are the only reactive functionality, these resins can be used to generate single-component (IK) coatings. Nevertheless, while these moisture curable resins are found in commercial IK coatings, they are not without their drawbacks. The biggest problem with acrylic siloxanes is that they are slow to cure when not exposed to high humidity environments.
- the coating described herein attempts to provide this solution by synthesizing alkoxysilane-terminated N-substituted urea resins, then formulating them into moisture-curable single-component (IK) topside coatings. These coatings will provide greater external stability (color and gloss retention upon exposure to UV and visible light), cleanability, flexibility, cure times and lower VOC content than the currently qualified silicone alkyd topside coatings that are found on Navy ships.
- a single-component coating comprises an alkoxysilane- terminated N-substituted urea resin, a reactive diluent, a pigment, a filler, and a catalyst.
- a resin comprises an amino-functional silane substituted at the N-position and a non-aromatic isocyanate.
- a method for producing a single component coating comprises synthesizing a resin from an amino-functional silane substituted at the N- position and a non-aromatic isocyanate; and mixing the synthesized resin with a catalyst, a pigment, a filler, and a reactive diluent.
- a single-component coating is one that is pre-mixed and does not require any additional additives before being applied to a surface.
- the coating may need to be shaken before use, but the entire product is contained within a single can.
- By using a single-component coating less material is wasted and the product is easier to use.
- the term "single-component" or "IK" is not intended to mean that the coating is made from a single chemical or substance, but rather that the end product does not need to be mixed with another component before application as a coating.
- the single-component coating described herein can be applied to a primer or directly to a metal substrate.
- An exemplary single-component coating has various components, including, but not limited to, a resin formed from an amino-functional silane substituted at the N-position and a non-aromatic isocyanate.
- the resin should be alkoxysilane-terminated and be a urea resin.
- the resin is formed of a combination of an isocyanate and a N- substituted amino-functional alkoxysilane in a ratio of about 1 : 1. In other examples, the ratio can range from about 1.05: 1 to about 1 : 1.05.
- the amino-functional silane substituted at the N-position can be an alkoxysilane.
- Examples include N-butyl-3-aminopropyltrimethoxysilane, commercially available as SIB1932.2 from Gelest or Dynasylan 1189 from Evonik; N-butyl-3-aminopropylmethyldimethoxysilane, commercially available as 3B3-073658 from 3B Scientific Corp.; N-butyl-3- aminopropyltriethoxysilane; N-ethyl-3 -aminopropyltriethoxysilane; N-phenyl-3 - aminopropyltrimethoxysilane, commercially available as SIP6724.0 from Gelest; N-cyclohexyl- 3-aminopropyltrimethoxysilane, commercially available as 3B3-072498 from 3B Scientific Corp.; N-hexyl-3-aminopropyltrimethoxysilane; N-pentyl-3-aminopropyltrimethoxysilane; N- isopropyl-3
- the non-aromatic isocyanate can be an aliphatic or cycloaliphatic polyisocyanate, which is more durable to exterior elements than an aromatic isocyanate.
- examples include aliphatic polyisocyanate based on HDI trimer, commercially available as Desmodur N 3600 from Bayer; aliphatic polyisocyanate based on HDI uretdione, commercially available as Desmodur XP 2730 from Bayer; aliphatic polyisocyanate based on HDI biuret, commercially available as Desmodur N 3200 from Bayer; aliphatic polyisocyanate based on HDI allophanate trimer, commercially available as Desmodur XP 2731 from Bayer; aliphatic polyisocyanate based on asymmetric HDI trimer, commercially available as Desmodur XP 2410 from Bayer; cycloaliphatic polyisocyanate based on IPDI trimer, commercially available as Desmodur Z 4700 from
- the reaction was heated at 50 °C for 30 minutes. Drying agents, such as vinyltrimethoxysilane, can also be added to the reaction in amounts of about 1.5% by weight.
- the resin was 76 wt.% solids (as determined by 110 °C for 1 hour).
- the resin can be synthesized using aromatic solvents, ester-based solvents, or others known to one of ordinary skill in the art.
- the resin is a trimethoxysilane-terminated N-butyl urea resin, which has the chemical name urea, N,N",N""-[( remind5-trioxo-l procur5-triazine-l, 3,(2H,4H,6H)-triyl)tri-6,l- hexanediyl]tris[N-butyl-N'-[3-(trimethoxysilyl)propyl]- or 1,1 ', l"-(6,6',6"-(2,4,6-trioxo-l ,3,5- triazinane-l,3,5-triyl)tris(hexane-6,l-diyl))tris(3-butyl-3-(trimethoxysilyl)propyl)urea).
- the resin described herein allows terminal alkoxysilane groups to be moderate-to- fast reacting due to inclusion of a substituent on a nitrogen atom of the urea linkage.
- Commercial acrylic siloxane resins are slow to react because they do not have nitrogen's electron density to aid with moisture hydrolysis.
- the urea linkage would no longer remain planar as the substituted nitrogen fragment rotates to alleviate sterric interactions, and nitrogen's lone pair would now become available to aid with hydrolysis of the tethered alkoxysilane group.
- Greater rotation within the urea linkages will also lead to less intermolecular hydrogen bonding, thereby yielding coatings with greater flexibility and lower viscosity.
- Alternative versions of the resin can be synthesized using mixtures of N- substituted aminoalkoxysilanes and di-substituted amines, so that all portions of the resulting resin do not contain terminal alkoxysilane groups, yet the resin still remains an N-substituted urea.
- Examples of commercially available di-substituted amines include, but are not limited to, ⁇ , ⁇ -dibutylamine, N,N-diethylamine, ⁇ , ⁇ -dimethylamine, N,N-diisopropylamine,
- N,N-dicyclohexylamine, ⁇ , ⁇ -diphenylamine N-methylcyclohexylamine, N-tert- butylcyclohexylamine, N-ethylcyclohexylamine, N-butylcyclohexylamine, N-ethylaniline, N- butylaniline.
- the resin can be used to form a single component coating.
- About 105.26g of the resin from the figure of the first example above is mixed with 35g of various pigments (e.g., titanium dioxide or colorants), 5g of a matting agent (e.g., amorphous silica or micronized urea), 20g of an alkoxysilane-functional diluent (e.g., hexyltrimethoxysilane, oligomeric methyl silicates), and 0.5g of a catalyst (e.g., dibutyltin dilaurate).
- various pigments e.g., titanium dioxide or colorants
- a matting agent e.g., amorphous silica or micronized urea
- an alkoxysilane-functional diluent e.g., hexyltrimethoxysilane, oligomeric methyl silicates
- a catalyst e.g., dibut
- the formulas were coated on tinplate test panels and allowed to cure for 7 days at ambient conditions (75 °F, 50% R.H.) before being tested.
- the coatings were tack-free after several hours. Once cured, the coatings demonstrated good hardness, flexibility, and solvent resistance.
- the cured coatings also showed good color and gloss retention upon exposure to ultraviolet and visible radiation from QUV-B and weatherometer (WOM) instruments. For instance, the color change (delta E) of the coatings was ⁇ 0.4 after 1000 hours WOM exposure.
- coatings of various gloss levels and colors have been made using a variety of pigments, reactive diluents, fillers, and other additives.
- the coating can also include a silicone-based diluent, such as methoxy-functional silicone resin, commercially available as Silres SY 231 from Wacker; oligomeric methyl silicates, commercially available as Silres MSE 100 from Wacker; hexyltrimethoxysilane, commercially available as SIH6168.5 from Gelest; octylmethyldiethoxysilane, commercially available as SI06712.4 from Gelest; n-octyltrimethoxysilane, commercially available as SI06715.5 from Gelest; and methoxy functional silicone, commercially available as DC-3074 Intermediate from Dow Corning.
- methoxy-functional silicone resin commercially available as Silres SY 231 from Wacker
- oligomeric methyl silicates commercially available as Silres MSE 100 from Wacker
- the single-component coating can also include a catalyst, which can be used to accelerate the rate of cure.
- the catalyst can include dibutyltin dilaurate (“DBTDL").
- DBTDL dibutyltin dilaurate
- the single-component coating can also include one or more of various pigments, fillers, additives (e.g., adhesion promoters, wetting and dispersing agents, thickening agents), and solvents known to a person having ordinary skill in the art.
- Silicone-containing coatings are becoming increasing popular within the global coatings market due to their outstanding external durability, chemical resistance, ability to cure with atmospheric moisture, and reduced VOC requirements.
- Siloxane coatings have an inherent advantage over conventional organic coatings due to the presence of silicone-oxygen bonds. For instance, the Si-0 bond, which has an enthalpy of 110 kcal/mol, is much stronger than a carbon- hydrogen (99 kcal/mol) or carbon-carbon bond (83 kcal/mol), thereby leading to an increased ultraviolet (UV), oxidative and thermal stability.
- siloxane-based materials are designed to react in the presence of moisture.
- these siloxane materials contain hydrolyzable alcohol groups, such as methanol or ethanol, which are bound to the silicone atom.
- alcohol groups When moisture is present, the alcohol groups are released and silanol (Si-OH) groups are formed.
- Si-OH silanol
- the silanols then condense with one another, both intra- and intermolecularly, to yield a cured siloxane network.
- the number of alcohol groups on a silicone atom will determine the potential points of hydrolysis, and a greater number of condensed silanol groups will result in a higher cross-link density within the coating.
- Example 1 Semi-gloss, light gray
- N-substituted urea resin (as shown in the figure 63.50%
- Titanium dioxide 18.20%
- N-substituted urea resin (as shown in the figure 61.64% in the first example)
- Titanium dioxide 16.40%
- N-substituted urea resin (as shown in the figure 71.00% in the first example)
- N-substituted urea resin (as shown in the figure 64.35%) in the first example)
- Titanium dioxide 7.12%
- Example 5 High gloss, white
- Titanium dioxide 21.77%
- Titanium dioxide 21.77%
- the single-component, low VOC, moisture-curable silicone-containing coating described herein can solve many of the problems that are inherent with many commercial single component coatings, while also remaining applicable to both depot level and ship's force painters.
- the developed coating should greatly outperform the Navy's qualified silicone alkyd coatings in terms of exterior durability (color stability and gloss retention), cleanability, flexibility and cure times, while also overcoming a limit of acrylic siloxane coatings, which is the inability to properly cure when not exposed to a high humidity environment.
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Abstract
The coating described herein attempts to provide this solution by synthesizing alkoxysilane- terminated N-substituted urea resins, then formulating them into moisture-curable single- component (IK) topside coatings. These coatings will provide greater external stability (to UV and visible radiation), cleanability, flexibility, cure times and lower VOC content than the currently qualified silicone alkyd topside coatings that are found on Navy ships. The single- component coating can include at least an alkoxysilane-terminated N-substituted urea resin, a reactive diluent, a pigment, a filler, and a catalyst. The resin can include an amino-functional silane substituted at the N-position and a non-aromatic isocyanate.
Description
SINGLE-COMPONENT COATING HAVING ALKOXYSILANE-TERMINATED
N-SUBSTITUTED UREA RESINS
TECHNICAL FIELD
[0001] The present application relates generally to the synthesis of alkoxysilane- terminated N-substituted urea resins and their application in single-component coatings.
BACKGROUND
[0002] The Navy currently has only one topside coating that is qualified for use under
MIL-PRF-24635. This coating, which is a silicone alkyd, has been used by the Navy for over 50 years, even though the technology continues to provide poor exterior durability (color and gloss retention upon exposure to an oxidative environment with UV and visible light), poor chemical resistance, low hardness, slow cure times and limited cleanability. The formulation of low volatile organic component ("VOC") versions has also recently become difficult, as the utilization of lower viscosity raw materials are increased in effort to maintain sprayable and/or rollable formulations. Unfortunately, this continued decrease in viscosity is typically accompanied by a reduction in resin molecular weight and cross-linkable functionality, thereby reducing the cross-link density and hardness of the resulting cured coating. A reduction in the molecular weight of resin components can also lead to sagging of the coating when applied. The VOC of silicone alkyd formulations has also been lowered by using exempt solvents, such as Oxsol 100, which do not count against the VOC rule. Although these solvents do not contribute to ozone depletion, it remains beneficial for paint applicators to use coatings with the lowest solvent content possible.
[0003] Silicone alkyd coatings can be formulated as single-component (also known as
"IK") systems because their cross-linking mechanism occurs as a result of atmospheric oxygen reacting with residual alkenes contained within the resins of the coating. The coating does not begin to cure until it is applied on a surface and the solvent evaporates, thereby giving it essentially a limitless pot-life, unlike two-component (2K) systems that begin to react once the components are mixed. Because it is a single-component system, no specialty mixing, equipment, or training is needed to apply the coating, as it can be easily spray-applied by individuals during depot level painting. Navy sailors are routinely found applying (via roller or
brush) silicone alkyd coatings to a ship for the sake of touch-up and/or beauty coating, yet this mundane and non war-related task would not be required if the silicone alkyd coatings already on the ship did not fade, chalk, discolor or stain within only a few months after application.
[0004] Acrylic siloxanes are conventionally used as both additives and base resins in commercial coatings. These resins are easily manufactured via polymerization of alkoxysilane- functional acrylate monomers with ethyl, butyl, or hexyl acrylate and/or meth(acrylate) monomers. Depending on the molecular weight, acrylic siloxane resins may contain moderate- to-high VOC levels, yet because the alkoxysilane groups are the only reactive functionality, these resins can be used to generate single-component (IK) coatings. Nevertheless, while these moisture curable resins are found in commercial IK coatings, they are not without their drawbacks. The biggest problem with acrylic siloxanes is that they are slow to cure when not exposed to high humidity environments.
SUMMARY OF THE INVENTION
[0005] It is desirable have a single component topside coating. The coating described herein attempts to provide this solution by synthesizing alkoxysilane-terminated N-substituted urea resins, then formulating them into moisture-curable single-component (IK) topside coatings. These coatings will provide greater external stability (color and gloss retention upon exposure to UV and visible light), cleanability, flexibility, cure times and lower VOC content than the currently qualified silicone alkyd topside coatings that are found on Navy ships.
[0006] In one embodiment, a single-component coating comprises an alkoxysilane- terminated N-substituted urea resin, a reactive diluent, a pigment, a filler, and a catalyst.
[0007] In another embodiment, a resin comprises an amino-functional silane substituted at the N-position and a non-aromatic isocyanate.
[0008] In yet another embodiment, a method for producing a single component coating, the method comprises synthesizing a resin from an amino-functional silane substituted at the N- position and a non-aromatic isocyanate; and mixing the synthesized resin with a catalyst, a pigment, a filler, and a reactive diluent.
[0009] Additional features and advantages of an embodiment will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be
realized and attained by the structure particularly pointed out in the exemplary embodiments in the written description and claims hereof as well as the appended drawings.
[0010] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.
DETAILED DESCRIPTION
[0011] Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.
[0012] A single-component coating is one that is pre-mixed and does not require any additional additives before being applied to a surface. The coating may need to be shaken before use, but the entire product is contained within a single can. By using a single-component coating, less material is wasted and the product is easier to use. The term "single-component" or "IK" is not intended to mean that the coating is made from a single chemical or substance, but rather that the end product does not need to be mixed with another component before application as a coating. The single-component coating described herein can be applied to a primer or directly to a metal substrate.
[0013] An exemplary single-component coating has various components, including, but not limited to, a resin formed from an amino-functional silane substituted at the N-position and a non-aromatic isocyanate. The resin should be alkoxysilane-terminated and be a urea resin. In an exemplary embodiment, the resin is formed of a combination of an isocyanate and a N- substituted amino-functional alkoxysilane in a ratio of about 1 : 1. In other examples, the ratio can range from about 1.05: 1 to about 1 : 1.05.
[0014] The amino-functional silane substituted at the N-position can be an alkoxysilane.
Examples include N-butyl-3-aminopropyltrimethoxysilane, commercially available as SIB1932.2 from Gelest or Dynasylan 1189 from Evonik; N-butyl-3-aminopropylmethyldimethoxysilane, commercially available as 3B3-073658 from 3B Scientific Corp.; N-butyl-3- aminopropyltriethoxysilane; N-ethyl-3 -aminopropyltriethoxysilane; N-phenyl-3 - aminopropyltrimethoxysilane, commercially available as SIP6724.0 from Gelest; N-cyclohexyl- 3-aminopropyltrimethoxysilane, commercially available as 3B3-072498 from 3B Scientific
Corp.; N-hexyl-3-aminopropyltrimethoxysilane; N-pentyl-3-aminopropyltrimethoxysilane; N- isopropyl-3 -aminopropyltrimethoxysilane; or N-isobutyl-3 -aminopropyltrimethoxysilane .
[0015] The non-aromatic isocyanate can be an aliphatic or cycloaliphatic polyisocyanate, which is more durable to exterior elements than an aromatic isocyanate. Examples include aliphatic polyisocyanate based on HDI trimer, commercially available as Desmodur N 3600 from Bayer; aliphatic polyisocyanate based on HDI uretdione, commercially available as Desmodur XP 2730 from Bayer; aliphatic polyisocyanate based on HDI biuret, commercially available as Desmodur N 3200 from Bayer; aliphatic polyisocyanate based on HDI allophanate trimer, commercially available as Desmodur XP 2731 from Bayer; aliphatic polyisocyanate based on asymmetric HDI trimer, commercially available as Desmodur XP 2410 from Bayer; cycloaliphatic polyisocyanate based on IPDI trimer, commercially available as Desmodur Z 4700 from Bayer; cycloaliphatic polyisocyanate based on IPDI allophanate, commericallly available as Desmodur XP 2565 from Bayer; aliphatic polyisocyanate based on HMDI biuret, commercially available as Basonat HB 100 from BASF; and aliphatic polyisocyanate based on HDI trimer, commercially available as Basonat HI 100 from BASF.
[0016] An exemplary process for producing the single-component coating follows. To synthesize the resin depicted below, 81.6g (0.446 mol) of Desmodur N 3600 (an aliphatic polyisocyanate resin from Bayer Material Science) was dissolved in 60g butyl propionate (commercially available from Aldrich) in a 500 ml 3 -neck round bottom flask equipped with an Argon inlet and thermometer. The temperature of the solution was heated to 50 °C, then 104.9g (0.446 mol) of N-butyl-3 -aminopropyltrimethoxysilane (commercially available as Dynasylan 1189 from Evonik Corporation) was added dropwise to the solution while keeping the temperature between 50-60 °C. After the addition was complete, the reaction was heated at 50 °C for 30 minutes. Drying agents, such as vinyltrimethoxysilane, can also be added to the reaction in amounts of about 1.5% by weight. The resin was 76 wt.% solids (as determined by 110 °C for 1 hour). The resin can be synthesized using aromatic solvents, ester-based solvents, or others known to one of ordinary skill in the art.
[0017] Referring to the figure below, in a first example, the synthesis of trimethoxysilane-terminated N-butyl urea resin is shown. Infrared (IR) spectroscopy showed that no more free or reactive isocyanate (NCO) (2260 cm"1) remained in solution.
[0018] The resin is a trimethoxysilane-terminated N-butyl urea resin, which has the chemical name urea, N,N",N""-[(„5-trioxo-l„5-triazine-l, 3,(2H,4H,6H)-triyl)tri-6,l- hexanediyl]tris[N-butyl-N'-[3-(trimethoxysilyl)propyl]- or 1,1 ', l"-(6,6',6"-(2,4,6-trioxo-l ,3,5- triazinane-l,3,5-triyl)tris(hexane-6,l-diyl))tris(3-butyl-3-(trimethoxysilyl)propyl)urea).
[0019] The resin described herein allows terminal alkoxysilane groups to be moderate-to- fast reacting due to inclusion of a substituent on a nitrogen atom of the urea linkage. Commercial acrylic siloxane resins are slow to react because they do not have nitrogen's electron density to aid with moisture hydrolysis. However, if a urea linkage has a substituent on a nitrogen atom, as is the case with the herein described resins, then the urea linkage would no longer remain planar as the substituted nitrogen fragment rotates to alleviate sterric interactions, and nitrogen's lone pair would now become available to aid with hydrolysis of the tethered alkoxysilane group. Greater rotation within the urea linkages will also lead to less intermolecular hydrogen bonding, thereby yielding coatings with greater flexibility and lower viscosity.
[0020] Alternative versions of the resin can be synthesized using mixtures of N- substituted aminoalkoxysilanes and di-substituted amines, so that all portions of the resulting resin do not contain terminal alkoxysilane groups, yet the resin still remains an N-substituted urea.
[0021] As shown in the figure directly above, in a second example, two-thirds of the isocyanate groups were reacted with N-butyl-3-aminopropyltrimethoxysilane, whereas one-third of the isocyanate groups were reacted with a di-substituted amine. This di-substituted amine can contain aliphatic, cycloaliphatic, or aromatic groups, and Ri and R2 can be the same group or different.
[0022] As shown directly above, in a third example, one-third of the isocyanate groups were reacted with N-butyl-3-aminopropyltrimethoxysilane, whereas two-thirds of the isocyanate
groups were reacted with a di-substituted amine. This di-substituted amine can contain aliphatic, cycloaliphatic, or aromatic groups, and Ri and R2 can be the same group or different.
[0023] Examples of commercially available di-substituted amines include, but are not limited to, Ν,Ν-dibutylamine, N,N-diethylamine, Ν,Ν-dimethylamine, N,N-diisopropylamine,
N,N-dicyclohexylamine, Ν,Ν-diphenylamine, N-methylcyclohexylamine, N-tert- butylcyclohexylamine, N-ethylcyclohexylamine, N-butylcyclohexylamine, N-ethylaniline, N- butylaniline.
[0024] The resin can be used to form a single component coating. About 105.26g of the resin from the figure of the first example above is mixed with 35g of various pigments (e.g., titanium dioxide or colorants), 5g of a matting agent (e.g., amorphous silica or micronized urea), 20g of an alkoxysilane-functional diluent (e.g., hexyltrimethoxysilane, oligomeric methyl silicates), and 0.5g of a catalyst (e.g., dibutyltin dilaurate). In testing, the formulas were coated on tinplate test panels and allowed to cure for 7 days at ambient conditions (75 °F, 50% R.H.) before being tested. The coatings were tack-free after several hours. Once cured, the coatings demonstrated good hardness, flexibility, and solvent resistance. The cured coatings also showed good color and gloss retention upon exposure to ultraviolet and visible radiation from QUV-B and weatherometer (WOM) instruments. For instance, the color change (delta E) of the coatings was <0.4 after 1000 hours WOM exposure.
[0025] In other embodiments, coatings of various gloss levels and colors have been made using a variety of pigments, reactive diluents, fillers, and other additives. For example, the coating can also include a silicone-based diluent, such as methoxy-functional silicone resin, commercially available as Silres SY 231 from Wacker; oligomeric methyl silicates, commercially available as Silres MSE 100 from Wacker; hexyltrimethoxysilane, commercially available as SIH6168.5 from Gelest; octylmethyldiethoxysilane, commercially available as SI06712.4 from Gelest; n-octyltrimethoxysilane, commercially available as SI06715.5 from Gelest; and methoxy functional silicone, commercially available as DC-3074 Intermediate from Dow Corning.
[0026] The single-component coating can also include a catalyst, which can be used to accelerate the rate of cure. In one example, the catalyst can include dibutyltin dilaurate ("DBTDL"). The single-component coating can also include one or more of various pigments,
fillers, additives (e.g., adhesion promoters, wetting and dispersing agents, thickening agents), and solvents known to a person having ordinary skill in the art.
[0027] Silicone-containing coatings are becoming increasing popular within the global coatings market due to their outstanding external durability, chemical resistance, ability to cure with atmospheric moisture, and reduced VOC requirements. Siloxane coatings have an inherent advantage over conventional organic coatings due to the presence of silicone-oxygen bonds. For instance, the Si-0 bond, which has an enthalpy of 110 kcal/mol, is much stronger than a carbon- hydrogen (99 kcal/mol) or carbon-carbon bond (83 kcal/mol), thereby leading to an increased ultraviolet (UV), oxidative and thermal stability.
[0028] A large majority of commercially available siloxane-based materials are designed to react in the presence of moisture. Typically, these siloxane materials contain hydrolyzable alcohol groups, such as methanol or ethanol, which are bound to the silicone atom. When moisture is present, the alcohol groups are released and silanol (Si-OH) groups are formed. The silanols then condense with one another, both intra- and intermolecularly, to yield a cured siloxane network. The number of alcohol groups on a silicone atom will determine the potential points of hydrolysis, and a greater number of condensed silanol groups will result in a higher cross-link density within the coating.
[0029] Examples of the single component coating are provided below. The percentages of each material in the single-component coatings are merely exemplary and are not intended to be limited to those particular percentages or ratios.
[0030] Example 1 - Semi-gloss, light gray
Trade/Chemical Name Wt.% of Formula
DBTDL 0.30%
N-substituted urea resin (as shown in the figure 63.50%
in the first example)
Titanium dioxide 18.20%
Shepherd black 10C909A 3.00%
Amorphous silica 3.00%
Silres MSE 100 12.00%
[0031] Example 2 - Semi-gloss, light gray
Trade/Chemical Name Wt.% of Formula
DBTDL 0.30%
N-substituted urea resin (as shown in the figure 61.64% in the first example)
Titanium dioxide 16.40%
Shepherd black 10C909A 7.03%
Amorphous silica 2.93%
Hexyltrimethoxysilane 11.70%
[0032] Example 3 - Flat, haze gray
Trade/Chemical Name Wt.% of Formula
DBTDL 0.48%
N-substituted urea resin (as shown in the figure 71.00% in the first example)
Titanium dioxide 7.00%
Shepherd Black 30C940 1.74%
Shepherd Green 410 1.17%
Shepherd Yellow 30C119 0.60%
Amorphous silica 12.00%
Hexyltrimethoxysilane 6.00%
[0033] Example 4 - Flat, haze gray
Trade/Chemical Name Wt.% of Formula
DBTDL 0.49%
N-substituted urea resin (as shown in the figure 64.35%) in the first example)
Titanium dioxide 7.12%
Shephard Black 30C940 1.77%
Shephard Green 410 1.19%
Shephard Yellow 30C119 0.61%
Amorphous silica 12.22%
Silres SY 231 12.22%
[0034] Example 5 - High gloss, white
Trade/Chemical Name Wt.% of Formula
DBTDL 0.30%
N-substituted urea resin (as shown in the figure 65.47%)
in the first example)
Titanium dioxide 21.77%
Silres SY 231 12.44%
[0035] Example 6 - High gloss, white
Trade/Chemical Name Wt.% of Formula
DBTDL 0.30%
N-substituted urea resin (as shown in the figure 65.47%)
in the first example)
Titanium dioxide 21.77%
Hexyltrimethoxysilane 12.44%
[0036] The single-component, low VOC, moisture-curable silicone-containing coating described herein can solve many of the problems that are inherent with many commercial single component coatings, while also remaining applicable to both depot level and ship's force painters. The developed coating should greatly outperform the Navy's qualified silicone alkyd coatings in terms of exterior durability (color stability and gloss retention), cleanability, flexibility and cure times, while also overcoming a limit of acrylic siloxane coatings, which is the inability to properly cure when not exposed to a high humidity environment.
[0037] The embodiments described above are intended to be exemplary. One skilled in the art recognizes that numerous alternative components and embodiments that may be substituted for the particular examples described herein and still fall within the scope of the invention.
Claims
1. A single-component coating comprising: an alkoxysilane-terminated N-substituted urea resin; a reactive diluent; a pigment; a filler; and a catalyst.
2. The single-component coating according to claim 1, wherein the alkoxysilane-terminated N-substituted urea resin comprises an amino-functional silane substituted at the N-position and a non-aromatic isocyanate.
3. The single-component coating according to claim 2, wherein the alkoxysilane-terminated N-substituted urea resin comprises an amino-functional silane substituted at one isocyanate group.
4. The single-component coating according to claim 2, wherein the alkoxysilane-terminated N-substituted urea resin comprises an amino-functional silane substituted at two isocyanate groups.
5. The single-component coating according to claim 2, wherein the silane is an
alkoxysilane.
6. The single-component coating according to claim 1 , wherein the resin is a urea resin.
7. The single-component coating according to claim 1, wherein the resin comprises subtanstially equal parts of an amino-functional silane and an isocyanate.
8. The single-component coating according to claim 2, wherein the amino-functional silane is selected from the group of: N-butyl-3-aminopropyltrimethoxysilane, N-butyl-3- aminopropylmethyldimethoxysilane, N-butyl-3 -aminopropyltriethoxysilane, N-ethyl-3 - aminopropyltriethoxysilane, N-cyclohexyl-3 -aminopropyltrimethoxysilane, N-phenyl-3 - aminopropyltrimethoxysilane, N-hexyl-3 -aminopropyltrimethoxysilane, N-pentyl-3 - aminopropyltrimethoxysilane, N-isopropyl-3 -aminopropyltrimethoxysilane, and N-isobutyl-3 - aminopropyltrimethoxysilane .
9. The single-component coating according to claim 1, wherein the resin is N,N",N""-[(„5- trioxo-l„5-triazine-l, 3,(2H,4H,6H)-triyl)tri-6,l-hexanediyl]tris[N-butyl-N'-[3- (trimethoxysilyl)propyl]- or 1,1 ',l"-(6,6',6"-(2,4,6-trioxo-l,3,5-triazinane-l,3,5- triyl)tris(hexane-6,l-diyl))tris(3-butyl-3-(trimethoxysilyl)propyl)urea).
10. The single-component coating according to claim 2, wherein the non-aromatic isocyanate comprises an aliphatic or cycloaliphatic polyisocyanate.
11. The single-component coating according to claim 2, wherein the non-aromatic isocyanate is selected from the group of: aliphatic polyisocyanate based on HDI trimer, aliphatic polyisocyanate based on HDI uretdione, aliphatic polyisocyanate based on HDI biuret, aliphatic polyisocyanate based on HDI allophanate trimer, aliphatic polyisocyanate based on asymmetric HDI trimer, cycloaliphatic polyisocyanate based on IPDI trimer, cycloaliphatic polyisocyanate based on IPDI allophanate, aliphatic polyisocyanate based on HMDI biuret, and aliphatic polyisocyanate based on HDI trimer.
12. The single-component coating according to claim 1, wherein the diluent is a silicone- based diluent.
13. The single-component coating according to claim 12, wherein the reactive diluent is selected from the group of: methoxy-functional silicone resin, oligomeric methyl silicates, hexyltrimethoxysilane, octylmethyldiethoxysilane, n-octyltrimethoxysilane, and methoxy functional silicone.
14. The single-component coating according to claim 1, wherein the alkoxysilane-terminated N-substituted urea resin comprises about 50 to 100 percent of the formula by weight.
15. The single-component coating according to claim 14, wherein the alkoxysilane- terminated N-substituted urea resin comprises about 61 to 71 percent of the formula by weight.
16. A resin comprising: an amino-functional silane substituted at the N-position; and a non-aromatic isocyanate.
17. The resin according to claim 16, wherein the silane is an alkoxysilane.
18. The resin according to claim 16, wherein the resin is a urea resin.
19. The resin according to claim 16, wherein the resin comprises substantially equal parts of the amino-functional silane and the isocyanate.
20. The resin according to claim 16, wherein the amino-functional silane is selected from the group of: N-butyl-3-aminopropyltrimethoxysilane, N-butyl-3- aminopropylmethyldimethoxysilane, N-butyl-3-aminopropyltriethoxysilane, N-ethyl-3- aminopropyltriethoxy silane, N-cyclohexyl-3-aminopropyltrimethoxysilane, N-phenyl-3- aminopropyltrimethoxysilane, N-hexyl-3 -ammopropyltrimethoxysilane, N-pentyl-3 - ammopropyltrimethoxysilane, N-isopropyl-3 -ammopropyltrimethoxysilane, and N-isobutyl-3 - ammopropyltrimethoxysilane .
21. The resin according to claim 16, wherein the resin is N,N",N""-[(„5-trioxo-l„5-triazine- 1, 3,(2H,4H,6H)-triyl)tri-6,l-hexanediyl]tris[N-butyl-N'-[3-(trimethoxysilyl)propyl]- or Ι,Γ,Γ'- (6,6 6''-(2,4,6-trioxo-l,3,5-triazinane-l,3,5-triyl)tris(hexane-6,l-diyl))tris(3-butyl-3- (trimethoxy sily l)propy l)urea) .
22. The resin according to claim 16, wherein the non-aromatic isocyanate comprises an aliphatic or cycloaliphatic polyisocyanate.
23. The resin according to claim 16, wherein the non-aromatic isocyanate is selected from the group of: aliphatic polyisocyanate based on HDI trimer, aliphatic polyisocyanate based on HDI uretdione, aliphatic polyisocyanate based on HDI biuret, aliphatic polyisocyanate based on HDI allophanate trimer, aliphatic polyisocyanate based on asymmetric HDI trimer, cycloaliphatic polyisocyanate based on IPDI trimer, cycloaliphatic polyisocyanate based on IPDI allophanate, aliphatic polyisocyanate based on HMDI biuret, and aliphatic polyisocyanate based on HDI trimer.
24. A method for producing a single component coating, the method comprising: synthesizing a resin from an amino-functional silane substituted at the N-position and a non-aromatic isocyanate; and mixing the synthesized resin with a reactive diluent, a pigment, a filler, and a catalyst.
25. The method according to claim 24, wherein the synthesized resin is an alkoxysilane- terminated N-substituted urea resin.
26. The method according to claim 24, wherein the silane is an alkoxysilane.
27. The method according to claim 24, wherein the synthesized resin is a urea resin.
28. The method according to claim 24, wherein synthesizing the resin comprises mixing substantially equal parts of the amino-functional silane and the isocyanate.
29. The method according to claim 24, wherein the amino-functional silane is selected from the group of: N-butyl-3-aminopropyltrimethoxysilane, N-butyl-3- aminopropylmethyldimethoxysilane, N-butyl-3 -aminopropyltriethoxysilane, N-ethyl-3 - aminopropyltriethoxysilane, N-cyclohexyl-3 -aminopropyltrimethoxysilane, N-phenyl-3 - aminopropyltrimethoxysilane, N-hexyl-3 -aminopropyltrimethoxysilane, N-pentyl-3 - aminopropyltrimethoxysilane, N-isopropyl-3 -aminopropyltrimethoxysilane, and N-isobutyl-3- aminopropy ltrimethoxy silane .
30. The method according to claim 24, wherein the synthesized resin is N,N",N""-[(„5- trioxo-l„5-triazine-l, 3,(2H,4H,6H)-triyl)tri-6,l-hexanediyl]tris[N-butyl-N'-[3- (trimethoxysilyl)propyl]- or 1,1 ',l"-(6,6',6"-(2,4,6-trioxo-l,3,5-triazinane-l,3,5- triyl)tris(hexane-6,l-diyl))tris(3-butyl-3-(trimethoxysilyl)propyl)urea).
31. The method according to claim 24, wherein the non-aromatic isocyanate comprises an aliphatic or cycloaliphatic polyisocyanate.
32. The method according to claim 24, wherein the non-aromatic isocyanate is selected from the group of: aliphatic polyisocyanate based on HDI trimer, aliphatic polyisocyanate based on HDI uretdione, aliphatic polyisocyanate based on HDI biuret, aliphatic polyisocyanate based on HDI allophanate trimer, aliphatic polyisocyanate based on asymmetric HDI trimer,
cycloaliphatic polyisocyanate based on IPDI trimer, cycloaliphatic polyisocyanate based on IPDI allophanate, aliphatic polyisocyanate based on HMDI biuret, and aliphatic polyisocyanate based on HDI trimer.
33. The method according to claim 24, wherein the diluent is a silicone-based reactive diluent.
34. The method according to claim 24, wherein the diluent is selected from the group of: methoxy-functional silicone resin, oligomeric methyl silicates, hexyltrimethoxysilane, octylmethyldiethoxysilane, n-octyltrimethoxysilane, and methoxy functional silicone.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2010/040332 WO2012002932A1 (en) | 2010-06-29 | 2010-06-29 | Single-component coating having alkoxysilane-terminated n-substituted urea resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2588051A1 true EP2588051A1 (en) | 2013-05-08 |
Family
ID=45402384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP10854202.8A Withdrawn EP2588051A1 (en) | 2010-06-29 | 2010-06-29 | Single-component coating having alkoxysilane-terminated n-substituted urea resins |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP2588051A1 (en) |
| WO (1) | WO2012002932A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9303149B2 (en) * | 2012-06-21 | 2016-04-05 | Prc-Desoto International, Inc. | Adhesion promoting adducts containing metal ligands, compositions thereof, and uses thereof |
| AU2014342552B2 (en) * | 2013-10-29 | 2017-08-17 | Prc-Desoto International, Inc. | Adhesion promoting adducts containing metal ligands, compositions thereof, and uses thereof |
| US9328275B2 (en) | 2014-03-07 | 2016-05-03 | Prc Desoto International, Inc. | Phosphine-catalyzed, michael addition-curable sulfur-containing polymer compositions |
| EP3505548A1 (en) * | 2017-12-28 | 2019-07-03 | Covestro Deutschland AG | Alkoxysilane modified polyurea compounds based on a mixture of dialkoxy and trialkoxysilanes |
| EP3505549A1 (en) * | 2017-12-28 | 2019-07-03 | Covestro Deutschland AG | Silane-modified polyurea compounds based on polyisocyanates with isocyanurate and allophanate groups |
| JP2021066799A (en) * | 2019-10-23 | 2021-04-30 | 旭化成株式会社 | Coating composition and film |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4923755A (en) * | 1989-03-28 | 1990-05-08 | Dow Corning Corporation | Organosilicone resin coating compositions |
| US5423735A (en) * | 1993-04-16 | 1995-06-13 | Minnesota Mining And Manufacturing Company | Orthopedic cast composed of an alkoxysilane terminated resin |
| US5919860A (en) * | 1997-12-17 | 1999-07-06 | Bayer Corporation | Aqueous polyurethane/urea dispersions containing alkoxysilane groups |
| US6077902A (en) * | 1998-10-14 | 2000-06-20 | Bayer Corporation | Moisture-curable compounds containing isocyanate and alkoxysilane groups |
| US6764026B2 (en) * | 2001-12-18 | 2004-07-20 | Bayer Polymers Llc | Process for spraying one-component compositions with air-assisted, low pressure equipment having an improved spray nozzle |
| DE102004059378A1 (en) * | 2004-12-09 | 2006-06-22 | Consortium für elektrochemische Industrie GmbH | Alpha-aminomethyl-alkoxysilanes with high reactivity and improved stability |
| DE102004059379A1 (en) * | 2004-12-09 | 2006-06-22 | Consortium für elektrochemische Industrie GmbH | Alkoxysilane-terminated prepolymers |
| US20070129527A1 (en) * | 2005-12-06 | 2007-06-07 | Griswold Roy M | Silylated polyurethane-polyurea protective coating compositions |
-
2010
- 2010-06-29 WO PCT/US2010/040332 patent/WO2012002932A1/en active Application Filing
- 2010-06-29 EP EP10854202.8A patent/EP2588051A1/en not_active Withdrawn
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| Title |
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| See references of WO2012002932A1 * |
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| WO2012002932A1 (en) | 2012-01-05 |
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