CN1910245A - Method for production of thermally cured coatings - Google Patents
Method for production of thermally cured coatings Download PDFInfo
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- CN1910245A CN1910245A CN 200480034959 CN200480034959A CN1910245A CN 1910245 A CN1910245 A CN 1910245A CN 200480034959 CN200480034959 CN 200480034959 CN 200480034959 A CN200480034959 A CN 200480034959A CN 1910245 A CN1910245 A CN 1910245A
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- coating
- ester
- resin
- coating composition
- lipid acid
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- 238000000576 coating method Methods 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000011248 coating agent Substances 0.000 claims abstract description 82
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 48
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 32
- 229930195729 fatty acid Natural products 0.000 claims abstract description 32
- 239000000194 fatty acid Substances 0.000 claims abstract description 32
- 239000008199 coating composition Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 230000004913 activation Effects 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 125000002252 acyl group Chemical group 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 49
- 150000002632 lipids Chemical class 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 32
- 150000002148 esters Chemical class 0.000 claims description 30
- -1 phenolic aldehyde Chemical class 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 18
- 229920000728 polyester Polymers 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- 150000004702 methyl esters Chemical class 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims description 5
- 150000002118 epoxides Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 3
- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229920003180 amino resin Polymers 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- 230000003628 erosive effect Effects 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 238000002203 pretreatment Methods 0.000 claims 1
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- 239000000203 mixture Substances 0.000 description 59
- 238000006243 chemical reaction Methods 0.000 description 32
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- 239000002904 solvent Substances 0.000 description 15
- 238000009472 formulation Methods 0.000 description 13
- 238000001723 curing Methods 0.000 description 11
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 11
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- 238000009998 heat setting Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000284 extract Substances 0.000 description 6
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- 229920001187 thermosetting polymer Polymers 0.000 description 6
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
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- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- HIMXAERGQMNODV-UHFFFAOYSA-N 2-N,4-N,1,2,3,4-hexamethoxy-2-N-methyl-1,3,5-triazine-2,4,6-triamine Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(C)OC)OC)OC)OC HIMXAERGQMNODV-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000006115 industrial coating Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- LPTWEDZIPSKWDG-UHFFFAOYSA-N benzenesulfonic acid;dodecane Chemical compound OS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC LPTWEDZIPSKWDG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 230000002950 deficient Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
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- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 description 1
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 description 1
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 244000188595 Brassica sinapistrum Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical group CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
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- 238000007761 roller coating Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- RRBYUSWBLVXTQN-UHFFFAOYSA-N tricyclene Chemical group C12CC3CC2C1(C)C3(C)C RRBYUSWBLVXTQN-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Method for production of a coating on a solid substrate comprising the steps of applying a liquid coating composition comprising a polyfunctional resin, a fatty acid or derivative thereof acting as a reactive diluent and optionally a curing agent and/or one or more additives, wherein the resin comprises functional groups capable of reacting with carboxyl or acyl groups of the fatty acid or derivative thereof, onto the substrate, and curing the coating by heat activation. The invention further relates to the liquid coating composition as well as a substrate comprising a coating obtained by heat activation of such a coating composition.
Description
Invention field
The present invention relates to the purposes that lipid acid and derivative thereof are used to prepare heat-curable coating.In coating program according to the present invention, the amount of the volatile organic solvent in the coating composition can reduce significantly, thereby reduces cost and improve the coating environmental performance.The effect of this lipid acid or reacting property of derivative thinner; At first by reducing viscosity and making this coating be coated to the effect of playing solvent on the base material with liquid form.Subsequently, the chemical reaction between the group that is fit on the carboxyl by this thinner or acyl group and this resin is during this thinner is incorporated into and finally films.This derivative of fatty acid can also be used to regulating the mechanical property of coating, promptly is incorporated in this thermoset coating as toughner.The base material that the invention still further relates to the coating composition that comprises the lipid acid or derivatives thereof and have the coating that obtains by this type of coating composition of thermofixation.
Background of invention
Heat-curable coating is used more and morely in industry, especially in the precoat metal plate that increases rapidly (sheet metal) industry.The steel coiled material applies with one or more coatings and is sold to building, OEM and transportation industry as precoat metal plate.The thermofixation organic coating that one deck of this coating system normally applies with roller coating technology.Usually carry out coated with forming wet film, this wet film of thermofixation in the convection current baker then with liquid coating.One of main drawback of this technology is to need a large amount of organic solvents to reduce the viscosity of this coating, and it could apply on this coiled material like this.During drying evaporation and smog (fumes) burn to avoid the solvent discharge thing this solvent then.The use of solvent is environmental problem still not, and the cost of this coating is significantly increased, because it must be handled with a kind of method or another kind of method.Be incorporated in this final dry coating if this solvent changes into, then will be significantly improved.Above-mentioned identical reason is applicable to that also wherein solvent is other thermofixation organic coating that is used for regulating viscosity.
Can list following requirement to reactive diluent:
The goal tree resin system had good dissolving ability.
Low viscosity.
Low volatility.
This thinner should have the reactive group that it can be incorporated in the dry film.
This reactive diluent should be in target condition of cure (temperature, atmosphere, curing speed etc.) reaction down.
This reactive diluent should not be incorporated into the coating that is used for intended application with unsuitable physicals.
In organic coating, has long historical class monomer/molecule and is vegetables oil and derivative thereof people such as () Derksen.These monomers are generally used for air-dry type coating, and wherein the unsaturated part in this lipid acid is reacted the formation thermoset network via oxidizing reaction.The example of these air-dry type systems is Toenol 1140 coating and air-dry type Synolac.Other lipid acid system is based on other functional group hydroxyl in the Viscotrol C for example.
In order to reduce or fully to replace volatile organic solvent, fatty acid ester was before described in many patent applications as the purposes of reactive diluent in coating.
In EP 685543, DE 3803141, DE 3701410, the ester of unsaturated fatty acids and various alcohol is as reactive diluent.In DE 4129528 and EP 357128, reactive diluent is made of the fatty acid ester of various unsaturated alkyl ether alcohols.EP 305007 and EP 305006 use the ester that is made of unsaturated fatty acids and unsaturated alcohol structure division as reactive diluent.GB 2190672 uses the reactive diluent that combines unsaturated allyl polyol and unsaturated fatty acids in ester.Though these reports advocate to use reactive diluent in many binding agents and resin system, the introducing of this reactive diluent is that reaction via the unsaturated link(age) in this thinner and binding agent and diluent molecule realizes under all these situations.This reaction is usually by air-dry curing.
In DE 19533168 and US 4,877,838, this reactive diluent is made of the ester that contains reactive epoxy groups in lipid acid or pure structure division.In these cases, the reaction of this thinner and this coating system is the ring-opening reaction between this thinner and the reactive hydroxyl in resin and thinner.
At US 4,477, in 534, resin contains unsaturated fatty acid ester and reactive diluent is air-dry type Yi Xi oxazolin ester.This thinner in air with this resin in unsaturated link(age) reaction.
Derivative of fatty acid also has report in several patents relevant with the thermal curable coating.In JP09137078, the ester of unsaturated conjugated lipid acid and polyvalent alcohol is as the base-material of the paint that requires heat or photocuring.Curing is undertaken by the reaction of this unsaturated fatty acids.Similarly, unsaturated fatty acids is used in the binding agent in BE 805300.This curing is at high temperature undertaken by the reaction between the unsaturated fatty acids.
Several contrivers have reported the purposes in the Resins, epoxy of fatty acid ester in heat cured system.But JP08325509 uses the thermoset water central dispersion epoxy resins that contains lipid acid and P-bonded hydroxy to obtain to be suitable for the coating of metal.The Resins, epoxy that JP 63248869 uses by epoxy compounds and fatty acid response are obtained.This resin is suitable for printing on metal.In these two reports, this lipid acid is incorporated in this resin before applying on this surface.This curing is via unsaturated prepolymer in this resin and incompatible the carrying out of radical polymerization that contains the stiffening agent of amine.US 4,962, a kind of diverse ways of 179 reports, and this method is used the lipid acid of the epoxide modification of epoxidized vegetable oil form.This coating is solidified via the epoxide group of lipid acid and the reaction between the amine in the coating formulation under heating.
In DD 257442, by reduce the solvent of this coating with this Synolac binding agent of dicyclopentadiene aliphatic ester derivatives modification.At US 4,100, in 046, cycloalkenyl group is added in the lipid acid to obtain heat-setting binding agent.In these two reports, lipid acid was incorporated in the resin before applying and is not used as thinner in system.This curing reaction is undertaken by the reaction of unsaturated cyclene group.
In JP 2000212483, the polyglycerol ester of lipid acid is added in the water-miscible paint.This ester does not reduce viscosity (promptly playing the thinner effect) or does not participate in the curing of this coating.
Fatty acid ester also has been used for the thermal curable powder coating.In NL 1009254, unsaturated fatty acid ester is used for improving adhesivity and solidifies outward appearance afterwards.In JP 06345822, the fluorine powdex contains the ester of lipid acid and unsaturated ethylene enol.In these two examples, this fatty acid ester does not play the thinner effect, because this coating is solid and on-liquid.
These examples show that the needs searching reduces the approach that solvent uses in coating.It shows that also fatty acid ester has greater advantage as the composition in the paint formulation material.When lipid acid during as the reactive part of formulation, or it is as can be at solidified unsaturated compound under the air, perhaps as with this formulation in the epoxide that reacts of other composition.
Summary of the invention
Design of the present invention is to use lipid acid or derivative of fatty acid to be replaced to the amount that is reduced in the volatile solvent in the thermofixation liquid coating at least significantly as reactive diluent.
When derivative of fatty acid was used as reactive diluent, the present invention used and the significantly different reaction of previously described system.The invention describes the carboxyl that when the reaction of this thinner enters in the network, uses the fatty acid ester or derivatives thereof or acyl group as the reactive behavior site.This derivative of fatty acid is acid amides, acid anhydrides or ester, the especially alkyl ester of lipid acid preferably.This carboxyl or acyl group and coating resin react with form integration (integrated) part of dry film.The chemical reaction that relates to carboxylic acid or its ester is very suitable for hot activation and solidifies, and high reaction rate can at high temperature obtain.
Derivative of fatty acid has long history in coating, and introduces in the coating resin them on the books in a lot of documents via esterification/transesterify.Yet the use of these reactions is always carried out in chemical reactor between synthesis phase at resin.The present invention uses similar chemical process, but difference is: just carry out this reaction after as thin film coated on base material at coating formulation.This allows this derivative of fatty acid to be used as viscosity-depression agent in this coating formulation, thereby has reduced the needs to conventional solvent.
Previously described use derivative of fatty acid all uses functional group and the drying mechanism different with reaction described in the present invention as the invention of reactive diluent.
The most general means are to use unsaturated fatty acids, they under envrionment conditions with atmosphere in oxygen react and form dry film (for example, in EP 685543).This so-called " air-dry " type coating.This method is limited to unsaturated fatty acids, and wherein the thiazolinyl in this lipid acid makes the oxidation cross-linked possibility that becomes.Solidify for this, the existence of atmosphericoxygen also is necessary.The air-dry solidification process quite slowly that is commonly referred to be is not suitable for the industrial coating that wherein high processing speed has importance.
Also in the system of heat and radiation-curable, be described based on the reactive diluent of the lipid acid with other functional group is previous.These for example are to have hydroxyl, epoxy group(ing) or the acrylate-based lipid acid that is connected on the fatty acid carbon chain.Hydroxy-functional lipid acid for example is present in the Viscotrol C, and wherein hydroxyl is positioned on the 12nd carbon on the ricinolic acid.Epoxy group(ing) is introduced by the thiazolinyl in the oxidation unsaturated fatty acids usually, and acrylate is introduced by the hydroxyl on the chemical modification ricinolic acid.Reactive diluent based on these structures can be used for coating system, still compares with the present invention to have some defectives.
Lipid acid exists as mixture usually, and wherein a part of lipid acid has the functional group of possibility and target curing reaction react with.Unreacted derivative of fatty acid can be moved to this coatingsurface and be caused the change of aspect of performance along with the time.All are above-mentioned to be not always the case based on the reactive diluent with the derivative of fatty acid that is present in the reactive group on the carbochain, but the present invention is not like this, because with good grounds reactive diluent of the present invention contains carboxyl or acyl group functional group.In addition, chemical conversion, for example acidylate increases with molecular weight and polar usually, and the two increase all can increase viscosity.Because the viscosity that a purpose of reactive diluent is the minimizing system is to allow to paint as thin film coated on base material, so this is the side effect of the passiveness of these systems.The present invention is based on the reactive diluent that can not produce this defective.
Advantage of the present invention can be summarized as follows:
All fatty acid alkyl ester contain reactive group, can use the mixture of lipid acid when promptly keeping a functionality.Therefore, exist the risk of the non-reacted parts of lipid acid to reduce significantly in this coating.
This alkyl ester preferably monofunctional and only can react with multiple functionalized resin, therefore, all thinner promotes to produce thermoset network.Using triglyceride is not like this, and viscosity still is higher in this case.
This reactive diluent can react with any coating resin that has the functional group of carboxylic acid or its responding property of ester.
This reactivity is suitable for the coating system of thermofixation under high temperature and short period of time, because esterification/transesterify at high temperature is very fast.
Alkyl fatty acid has low viscosity and low volatility, makes them be suitable as the viscosity-depression agent of liquid coating.
In addition, this derivative of fatty acid can be used for regulating the snappiness of coating.
Atmosphericoxygen can not influence described curing reaction.
Detailed Description Of The Invention
The present invention is based on two kinds of can be mixed with the thermal curable liquid coating together or randomly three kinds of film-forming components A, B and C.Component A is multiple functionalized coating resin, and it can form thermoset thing (thermoset) independently or with solidifying agent B under hot activation.The example of this resinoid (component A) is Synolac, vibrin, polyacrylate resin or the polymethacrylate resin with hydroxyl, carboxylic acid or epoxy-functional of being suitable for crosslinking reaction.Resol and aminoresin are other examples.Solidifying agent (B component) is aminocompound normally, for example hexa methoxy methylol melamine or epoxy-functional solidifying agent, for example bisphenol-A-diglycidylether or triglycidyl group isocyanuric acid ester (TGIC).Other solidifying agent can be the phenol that can react with component A-, hydroxyl-, amine-, carboxylicesters or isocyanic ester-functionalized linking agent.Component C can react with the integration reactive diluent partly that forms dry film with A and/or B under hot activation.Component C is saturated or undersaturated lipid acid or derivative of fatty acid, especially ester, acid anhydrides or acid amides, and wherein carboxyl is the functional group that can react with component A and/or B.Except being used for the carboxyl or the acyl group of the reaction according to the present invention, component C also may contain other functional group of other component reaction in participation to a certain extent and the composition.At room temperature, component C is a liquid, has low viscosity and is not volatile.The effect of component C is the viscosity that reduces coating so that its can as liquid coating be coated on the base material and have a reduction amount can evaporable routine organic solvent when dry.To low viscous demand with the fatty acid carbon chain limitation of length to being 22 carbon to the maximum.This ester can be the monofunctional ester of lipid acid, for example alkyl ester such as methyl esters, isopropyl ester, ethyl ester; Perhaps multiple functionalized ester, for example glycerine ester.
Prepare this coating with suitable proportion by following component and be suitable for wet film and apply that for example the wet paint of the viscosity of roller coat: component A, B and C are together with other component to form to have, for example solubility promoter, pigment, catalyzer and other additive comprise solid particulate.Component A, B and C should select like this, make can not occur being separated in solidification process.In a preferred embodiment of the invention, have relative high functionality (OH＞3 moles/mole) but have low polar resin simultaneously as component A, and rapeseed methylester (RME) is as component C.Then this coating is coated on the base material and by hot activation and solidifies.The base material that this coating is fit to is anyly can bear hot activation solidified material.Typical base material is the metallic surface, and is randomly for example pretreated to introduce erosion resistance and required binding property with zinc or phosphoric acid salt.Such surface modification that example is the steel coiled material, this steel coiled material are used the roller coat device to be coated with coating composition and are solidified under the temperature more than 200 ℃.Preferred oven drying temperature is at least 100 ℃ among the present invention, greater than 200 ℃ and especially be higher than 250 ℃.Using the preferred method of the present invention is in air themperature is 300 ℃ baker, and the coiled material that carries out steel plate under 240 ℃ maximum base material temperature applies.Yet desired temperature will depend on that existing catalyzer in the said composition and described composition stand the time length degree of condition of cure in concrete the application.To under the stable condition, this can easily be determined by those skilled in the art.
This solidification value and time must be through selecting so that the volatility of component C under this temperature is not very remarkable.For example, when slow raising temperature (up to 300 ℃), estimate RME itself (pure) simultaneously and as the volatility of a coating formulation part.Under this typical base material temperature (240 ℃), 23% pure RME volatilizees.Under 300 ℃, all pure RME disappear, and only 50% RME disappearance in the product of this preparation.The amount of evaporable component C depends on the relative rate with resin (component A) and atmospheric reaction, and the phase stability of formulation and volatility.Stop volatilization with the rapid reaction meeting of this resin.Rapid reaction can realize by using better to contact between each component in functionality higher on catalyzer, the resin and the formulation.When identical measurement repeats, can obtain similar value in nitrogen atmosphere.This shows that this RME mainly introduces via oxidizing reaction under these conditions as described in EP 685543, DE 3803141, DE 3701410 etc.In addition, use saturated ester (methyl stearate) to replace RME.This ester can not carry out oxidizing reaction, but still shows to be incorporated in this final film with the similar degree of the mixture with RME.
The introducing of this derivative of fatty acid also shows the change of coating performance.The formulation that will have a RME of increasing amount is coated on the steel surface and solidifies down at conventional condition of cure (300 ℃ air themperature, 37 seconds, 240 ℃ final base material temperature).Along with the amount of the RME that is added is increased to 10% from 0, in this way the film of Huo Deing demonstrates Tg and drops to 35 ℃ from 45 ℃.Can not exist in order to ensure this RME, extract this film and weighing extract, analyze fatty acid methyl ester then with hexane as unreacted reactant.The never coating of RME and the Discrepancy Description that contains the amount that extracts in those coatings up to 15% RME only about 10% not reaction of thinner in this film.The unreacted ester of lower amount can be realized by selecting different catalyzer, resin or condition of cure.
Under this condition, obtained optimum with following coating composition, wherein this resin is that functionality is the hydroxy-functionalized polyesters of 3OH at least, this solidifying agent is that hexamethoxy methyl cyanuramide and this reactive diluent are the methyl esters of rapeseed oil.This coating composition is coated on the steel surface and at 300 ℃ to descend to solidify 37 seconds.
Therefore, in aspect first, the present invention relates on solid substrate, prepare the method for coating, may further comprise the steps:
Coating comprises that the liquid coating composition of following component is to this base material:
Multiple functionalized resin, lipid acid or derivatives thereof and optional solidifying agent and/or one or more additives,
Wherein this resin comprises the functional group that can react with the carboxyl or the acyl group of this lipid acid or derivatives thereof; With
By the hot activation solidified coating.
The invention still further relates to solid substrate, it has the coating according to the method preparation that may further comprise the steps:
Coating comprises that the liquid coating composition of following component is to this base material:
Multiple functionalized resin, lipid acid or derivatives thereof and optional solidifying agent and/or one or more additives,
Wherein this resin comprises the functional group that can react with the carboxyl or the acyl group of this lipid acid or derivatives thereof; With
By the hot activation solidified coating.
In one embodiment of the invention, form film thereby peel off the coating for preparing at this base material from base material.In this case, this substrate surface and this solidified coating have this surperficial surface energy difference of the adhesion of prevention, and the force of cohesion in this film breaks to being enough to when this base material is peeled off when it stop by force simultaneously.
According to another aspect of the present invention, provide liquid coating composition, it can solidify by hot activation.Said composition comprises:
Multiple functionalized resin, lipid acid or derivatives thereof and optional solidifying agent and/or one or more additives,
Wherein this resin comprises the functional group that can react with the carboxyl or the acyl group of this lipid acid or derivatives thereof.
Embodiment
Embodiment 1
Material
A. hydroxy-functionalized polyesters:
Acid number: 8mg KOH/g resin, 0.14mmol acid/g resin
Hydroxyl value: 121mg KOH/g resin, 2.15mmol OH/g resin
Tg：-6℃
Molecular weight, Mn:1530g/mol
70% solids content (w/w), solvent: Solvesso 100 (CAS-number: 64742-95-6, branching skeleton)
Functionality (moles/mole resin): 3.3OH, 0.2 acid
Supplier: Akzo Nobel Nippon Paint AB, Gamlebyn, Sweden
B. hexamethoxy methyl cyanuramide (HMMM):
C
15N
6O
6H
30
Molecular weight: 390g/mol
Functionality: 6
Supplier: Akzo Nobel Nippon Paint AB
C1. fatty acid ester methyl ester (FAME):
C
19O
2H
36, (rape-seed oil methyl ester, Witconol 2301, methyl stearate etc.)
Molecular weight: 296g/mol
Functionality: 1
By Svenska Lantm nnen supply, trade name: RME
C2. fatty acid ester methyl ester (FAME):
C
19O
2H
38, (methyl stearate)
Molecular weight: 298.5g/mol
Functionality: 1
Buy by Lancaster
Catalyzer: right-dodecylbenzyl sulfonic acid (DDBSA)
Mixture 1
A. polyester mixture (70% solids content) 121.4g 183.3mmol OH
B.HMMM 15g 230.8mmol methylol
C1.RME 0g 0mml
DDBSA 1.36g
Amount to 137.76g (73.6% solids content)
Mixture 2
With mixture 1, except adding 5g (16.9mmol ester) C1 (RME).
Mixture 3
With mixture 1, except adding 10g (33.8mmol ester) C1 (RME).
Mixture 4
With mixture 1, except adding 15g (50.7mmol ester) C1 (RME).
Mixture 5
With mixture 1, except adding 6g (20.1mmol ester) C2 (MSt).
Apply and curing
Wire-wound rod with 16 μ m is coated in steel base material (thickness is 0.6mm) upward to obtain the build of 10 μ m with this mixture.In 300 ℃ baker, solidified this coating 37 seconds then, and promptly in cold water, cool off then.With regard to this coating, obtain 241 ℃ peak metal temperature (PMT).This final coating has high glossiness, good adhesion and H pencil hardness.Opposite with film (they do not show yellowing) from mixture 1-3 and 5, from the coating flavescence a little of mixture 4.These performances are suitable with the performance of the coating of using volatile organic solvent rather than FAME preparation.
Measuring mechanical property
Mechanical property is measured with stretch mode on self-supporting (free-standing) film with TA-instrument DMA Q800.Self-supported membrane by cutting this coating tape and take off them with scalpel from this tinsel and obtain.Measure carry out tensile modulus and glass transition temp based on the cured film of mixture 1-3.With regard to regard to the film of mixture 1,2 and 3, the Tg that reduces starting point mensuration by modulus is respectively 45,35,30 ℃.This shows that the amount that increases RME can soften this film and Tg is moved towards low value more, and the amount of RME can be used as the means of the Tg of this solidified coating of adjusting.
The analysis of unreacted FAME in the coating
Band with this coating of n-hexane extraction.The evaporation extract also reclaims residue.The amount of extract is very low, approximately the 0.1mg/mg coating.Use this extract of gc analysis to differentiate unreacted FAME and lipid acid.The FAME of coating band and the amount of lipid acid (in % (w/w)) provide in table 1.
Table 1:
| Coating from formulation | FAME+ lipid acid |
| Mixture 1 | 0.2％ |
| Mixture 2 | 0.6％ |
| Mixture 3 | 1.3％ |
| Mixture 4 | 0.3％ |
| Mixture 5 | 0.6％ |
This scale is bright to have about 10% FAME not react in this formulation.
Embodiment 2
In order to determine that this FAME does not have during heating to use thermogravimetric analysis (TGA) to monitor weight loss via volatilization loss in solidification process.In this was not put, the temperature that can not duplicate exactly from this true coiled material coated conditions increased and convection of air.In this instrument, this temperature is increased to 300 ℃ with 20 ℃/minute speed from 30 ℃, and this sample kept 5 minutes down at 300 ℃ subsequently.Air or nitrogen gas stream are passed through above sample.It is 1.5mm that the aliquots containig of the formulation of about 30mg is put into surface-area
2The aluminum oxide cup in.
Mixture 1 to 4 is with embodiment 1.
Mixture 6: with mixture 1, except adding 10g (33.5mmol ester) C2 (MSt).
The weight loss that is write down is owing to several processes: (i) volatilization of solvent in the polyester, the (ii) thermolysis of polyester, the (iii) volatilization of FAME.
The loss weight loss (in %, the w of w/ total mixture) afterwards that deduction belongs to solvent provides in table 2.
Table 2:
| Formulation | 240 ℃ of weight loss | 300 ℃ of weight loss |
| Mixture 1 | 0.1％ | 6％ |
| Mixture 2 | 2.0％ | 10％ |
| Mixture 3 | 1.7％ | 10％ |
| Mixture 4 | 2.4％ | 12％ |
| Mixture 6 | 3.6％ | 10％ |
| Pure RME | 23％ | 99％ |
These measurements show at 300 ℃ of pure RME volatilizees fully from this metallic surface.In containing the formulation of polyester, under this temperature, approximately 50% of RME be retained in the coating.At 240 ℃, the typical PMT that coiled material applies approximately 75% of RME is retained in the formulation.
Deduction belongs to after the loss of solvent that solidified weight loss (in %, w/w) provides in nitrogen atmosphere in table 3.
Table 3
| Formulation | 240 ℃ of weight loss | 300 ℃ of weight loss |
| Mixture 1 | 1.3％ | 6％ |
| Mixture 2 | 1.0％ | 7.5％ |
| Mixture 3 | 3.5％ | 16％ |
| Mixture 4 | 4.5％ | 13％ |
| Mixture 6 | 3.1％ | 10％ |
| Pure RME | 23％ | 99％ |
| Pure MSt | 10％ | 34％ |
Difference between nitrogen and airborne observed value is very little, shows that oxidizing reaction is not that this FAME is introduced main path in this film.
Embodiment 3
Material
A. hydroxy-functionalized polyesters:
Acid number: 8-12mg KOH/g resin=＞0.14mmol acid/g resin
Hydroxyl value: 120mg KOH/g resin=＞the 2.14mmolOH/g resin
Tg：-6℃
Mn：2500g/mol
60% solids content (w/w), solvent: dimethylbenzene
The branching skeleton
Functionality: 5.3OH, 0.5 acid
Supplier: Beckers Industrial Coatings
B. hexamethoxy methyl cyanuramide (HMMM):
C
15N
6O
6H
30
Molecular weight: 390g/mol
Functionality: 6
Supplier: Beckers Industrial Coatings
C3. fatty acid ester methyl ester (FAME):
C
19O
2H
36, (methyl linoleate, Witconol 2301 etc.)
Molecular weight: 296g/mol
Functionality: 1
Supplier: Svenska Lantm nnen, trade name: Linutin
Catalyzer: sulfuric acid
Composition
Polyester mixture (60% solids content) 7.55g 9.7mmolOH
HMMM 1.25g 19.2mmol methylol
FAME 0.52g 1.76mmol ester
Catalyzer 0.024g
Amount to 9.34g (67.7% solids content)
Apply and curing
Wire-wound rod with 16 μ m is coated in chromating steel base material (thickness is 0.6mm) upward to obtain the build of 10 μ m with this mixture.In 300 ℃ baker, solidified this coating 37 seconds then, and promptly in cold water, cool off then.With regard to this coating, obtain 241 ℃ peak metal temperature (PMT).Final FAME content in this coating is about 8% (w/w).This final coating has high glossiness, good adhesion, does not have yellowing and H pencil hardness.These performances are suitable with the performance of the coating of using volatile organic solvent rather than FAME preparation.
Reference
Derksen，J.T.P.，F.P.Cuperus，and P.Kolster，Renewable resources incoatings technology：a review.Progress in Organic Coatings，1996.27(1-4)：p.45-53
Claims (12)
1. on solid substrate, prepare the method for coating, may further comprise the steps:
Coating comprises that the liquid coating composition of following component is to this base material:
Multiple functionalized resin, lipid acid or derivatives thereof and optional solidifying agent and/or one or more additives,
Wherein this resin comprises the functional group that can react with the carboxyl or the acyl group of this lipid acid or derivatives thereof;
With by the hot activation solidified coating.
2. the process of claim 1 wherein that multiple functionalized resin is alkyd, polyester, polyacrylic ester, polymethacrylate, phenolic aldehyde or aminoresin.
3. according to the method for claim 1 or 2, wherein solidifying agent is an aminocompound, for example the hexa methoxy methylol melamine; Epoxide functional compound, for example bisphenol-A-diglycidylether or triglycidyl group isocyanuric acid ester; Or phenol-, hydroxyl-, amine-, the linking agent of carboxylicesters or isocyanate-functional.
4. according to each method among the claim 1-3, wherein derivative of fatty acid is the monofunctional ester, and alkyl ester for example is as methyl esters; Or multiple functionalized ester, for example glycerine ester.
5. according to each method among the claim 1-4, wherein the lipid acid or derivatives thereof has the carbon chain lengths that is no more than 22 carbon atoms.
6. according to each method among the claim 1-5, wherein base material is the metallic surface, steel for example, randomly by pre-treatment make its be erosion resistance and the time this coating composition be have fusible.
7. has solid substrate according to the coating of each method preparation among the claim 1-6.
8. liquid coating composition; it can solidify by hot activation; it comprises: multiple functionalized resin, lipid acid or derivatives thereof and optional solidifying agent and/or one or more additives, wherein this resin comprises the functional group that can react with the carboxyl or the acyl group of this lipid acid or derivatives thereof.
9. the coating composition of claim 8, wherein multiple functionalized resin is alkyd, polyester, polyacrylic ester, polymethacrylate, phenolic aldehyde or aminoresin.
10. according to Claim 8 or 9 coating composition, wherein solidifying agent is an aminocompound, for example the hexa methoxy methylol melamine; Epoxide functional compound, for example bisphenol-A-diglycidylether or triglycidyl group isocyanuric acid ester; Or phenol-, hydroxyl-, amine-, the linking agent of carboxylicesters or isocyanate-functional.
11. each coating composition according to Claim 8-10, wherein derivative of fatty acid is the monofunctional ester, and alkyl ester for example is as methyl esters; Or multiple functionalized ester, for example glycerine ester.
12. each coating composition according to Claim 8-11, wherein the lipid acid or derivatives thereof has the carbon chain lengths that is no more than 22 carbon atoms.
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