CN103987797B - Solvent-based varnishes coating composition, Its Preparation Method And Use - Google Patents
Solvent-based varnishes coating composition, Its Preparation Method And Use Download PDFInfo
- Publication number
- CN103987797B CN103987797B CN201280057344.5A CN201280057344A CN103987797B CN 103987797 B CN103987797 B CN 103987797B CN 201280057344 A CN201280057344 A CN 201280057344A CN 103987797 B CN103987797 B CN 103987797B
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- China
- Prior art keywords
- methyl
- solvent
- paint compositions
- varnish paint
- acrylate
- Prior art date
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- 239000002966 varnish Substances 0.000 title claims abstract description 139
- 239000008199 coating composition Substances 0.000 title claims abstract description 21
- 239000002904 solvent Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title description 20
- 239000000203 mixture Substances 0.000 claims abstract description 149
- 239000003973 paint Substances 0.000 claims abstract description 126
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229920001577 copolymer Polymers 0.000 claims abstract description 84
- 239000004952 Polyamide Substances 0.000 claims abstract description 50
- 229920002647 polyamide Polymers 0.000 claims abstract description 48
- -1 carbamide compound Chemical class 0.000 claims abstract description 47
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 47
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 47
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 37
- 239000004202 carbamide Substances 0.000 claims abstract description 31
- 235000013877 carbamide Nutrition 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 230000009477 glass transition Effects 0.000 claims abstract description 19
- 239000004971 Cross linker Substances 0.000 claims abstract description 17
- 125000000524 functional group Chemical group 0.000 claims abstract description 14
- KNYKHCLCBHSFCK-UHFFFAOYSA-N 1-methoxypropan-1-amine Chemical compound CCC(N)OC KNYKHCLCBHSFCK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 48
- 229920000728 polyester Polymers 0.000 claims description 46
- 229920000058 polyacrylate Polymers 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 21
- 238000004132 cross linking Methods 0.000 claims description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 14
- 239000000194 fatty acid Substances 0.000 claims description 14
- 229930195729 fatty acid Natural products 0.000 claims description 14
- 239000004922 lacquer Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 229920000768 polyamine Polymers 0.000 claims description 10
- 238000013007 heat curing Methods 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 229920003180 amino resin Polymers 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 8
- AKABKVXLWWIVIW-UHFFFAOYSA-N 1,1-diisocyanatohexane Chemical compound CCCCCC(N=C=O)N=C=O AKABKVXLWWIVIW-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000005829 trimerization reaction Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 42
- 150000001875 compounds Chemical class 0.000 description 35
- 238000000576 coating method Methods 0.000 description 34
- 239000011248 coating agent Substances 0.000 description 32
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 18
- 239000001993 wax Substances 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 239000000178 monomer Substances 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 11
- 239000004033 plastic Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000003999 initiator Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- 238000007665 sagging Methods 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 150000005846 sugar alcohols Polymers 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000035882 stress Effects 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
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- 230000037452 priming Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 150000002596 lactones Chemical class 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229910052615 phyllosilicate Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- JISVIRFOSOKJIU-UHFFFAOYSA-N hexylidene Chemical group [CH2+]CCCC[CH-] JISVIRFOSOKJIU-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 2
- GHPVDCPCKSNJDR-UHFFFAOYSA-N 2-hydroxydecanoic acid Chemical compound CCCCCCCCC(O)C(O)=O GHPVDCPCKSNJDR-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- CCXLOQVMDTWRSP-UHFFFAOYSA-N 2-cyclohexylpropan-2-ylcyclohexane Chemical compound C1CCCCC1C(C)(C)C1CCCCC1 CCXLOQVMDTWRSP-UHFFFAOYSA-N 0.000 description 1
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- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- CSNFMBGHUOSBFU-UHFFFAOYSA-N pyrimidine-2,4,5-triamine Chemical compound NC1=NC=C(N)C(N)=N1 CSNFMBGHUOSBFU-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical group OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
The present invention relates to solvent-based varnishes coating composition, described varnish paint compositions comprises following component: (A) OH official composed of the following components can (methyl) acrylate (co) polymer: (A1) can at least one OH number that quality is 30 99 weight % of nonvolatile part of (methyl) acrylate (co) polymer component (A) be 60 200mg KOH/g and glass transition temperature (T based on OH officialg) be 15 100 DEG C OH official can (methyl) acrylate (co) polymer, (A2) can at least one OH number that quality is 1 70 weight % of nonvolatile part of (methyl) acrylate (co) polymer component (A) be 60 200mg KOH/g and glass transition temperature T based on OH officialgIt it is OH official's energy (methyl) acrylate (co) polymer of 100 DEG C to 120 DEG C, (B) crosslinker component comprising following component: at least one has the cross-linking agent of functional group reactive to OH group, and at least one polyamide that quality is 0.02 1.2 weight % of (C) nonvolatile part based on OH official's energy (methyl) acrylate (co) polymer component (A), (D) carbamide compound of the adduct that at least one is polyisocyanates and methoxy propanamine that quality is 0.04 2.9 weight % of nonvolatile part based on OH official's energy (methyl) acrylate (co) polymer component (A).The invention still further relates to prepare the method for solvent-based varnishes coating composition, the purposes of solvent-based varnishes coating composition and the varnish system using varnish paint compositions to prepare.
Description
The present invention relates to wrap solvent-laden varnish paint compositions, described varnish paint compositions comprises work
For base material at least two OH official can (methyl) acrylate (co) polymer, at least one synthesize polyamides
Amine Wax particles, at least one is as polyisocyanates and the carbamide compound of the adduct of monoamine and has
The cross-linking agent of functional group reactive to OH group.The invention still further relates to varnish paint compositions
Preparation and its purposes in coating different substrate materials.
In Hyundai Motor is covered with paint, lacquer, colour wash, etc., to different base material japannings, the such as car being made up of metal or plastics
Body and body part.Generally in this type of is applied, build multiple tracks paint system.On metal base many
Road paint system is generally made up of electrodeposited coating, priming paint surfacer coating, priming coat and varnish.?
In the case of plastic basis material, build single coating final lacquer or again pull up multiple tracks paint system.Rear one
In the case of Zhong, use can be used for the conventional primer surfacer coating to painting of plastics, single coating finish paint,
Priming coat and varnish paint compositions, wherein selection and the use of these compositionss is people in the art
Member is known.
High-tech requirement to the final lacquer in modern automobile industry field, and described each independent coating
Function and technical performance known to those skilled in the art.In this type of system, particularly varnish is bright
Really the gloss of this type of necessary technology performance, such as painted surface and brightness or reflection definition (DOI),
Ageing stability and to condensation and the toleration that turns white.It is critical only that of these performances builds varnish institute
The varnish paint compositions needed has the application properties of excellence.This meaning coating composition especially must have
There is good levelability.This shows that varnish paint compositions must have mobile performance, thus by it
After being applied to base material, make such as owing to spraying the uneven smooth of mist generation, and gained final lacquer
Therefore surface is smooth.Additionally, it is also important that coating composition has good to hang characteristic from above.
As it is known by the man skilled in the art, after coating composition is applied to base material, as long as coating composition
It is still liquid condition, exists for the risk that sagging is formed.This means that use is still the coating of liquid
Compositions carries out part and hangs from above.Result is to have obviously to cover with paint, lacquer, colour wash, etc. in the final lacquer being subsequently cured to lack
Fall into.The trend of formation sagging disproportionately increases along with selected wet-film thickness, it is therefore necessary to suitably
Select wet-film thickness.But, it is impossible to select the least wet-film thickness, so that it is guaranteed that base material is completely covered
Surface so that meet surface quality requirements.In the covering with paint of complicated shape goods, such as, it is coated with at automobile
Through being commonly encountered in the case of decorations (such as car body, car door or bumper), more often occur to form sagging
Problem, because now can not be at horizontal level to whole finish coatings.
The loop wire accounting for significant portion of other problem particularly coating composition in automobile covering with paint field is steady
Qualitative (circuit line stability).Due to its lasting rotation in application device, coating composition
Being exposed under lasting load or shear stress, this frequently results in the significant change of rheological property such as viscosity,
And therefore may negatively affect above-mentioned application properties.
Existing bag solvent-laden varnish paint compositions often cannot ensure effective levelling, and simultaneously
Prevent from being formed sagging in varnish prepared therefrom.In order to solve this problem, automaker often drops
The film thickness of low varnish, but this compromises the retentivity of this required performance, such as finish paint, stream significantly
Levelling, gloss, reflection definition and aging and UV stability, and may result in the delustring of varnish.
For part varnish manufacturer, attempt keeping away by adding a large amount of auxiliary rheological agents or rheology control additive
Exempt from this problem, such as by application WO94/22968A1, EP0 276 501A1,
EP0 249 201A1 or WO97/12945A1 is known and based on the most specific urea adduct to hang down
Hang controlling agent (SCA).The polymer particles of crosslinking is similarly used, such as such as EP0 008 127A1
Disclosed, inorganic phyllosilicate (phyllosilicate), the Magnesiumaluminumsilicate of such as smectite type, sodium magnesium
With sodium magnesium fluorine lithium phyllosilicate (sodium magnesium and sodium magnesium fluorine
Lithium phyllosilicate), silicon dioxide, such as Aerosils, or there is ion and/or association base
The synthetic polymer of group, such as polyvinyl alcohol, poly-(methyl) acrylamide, poly-(methyl) acrylic acid, poly-
Vinylpyrrolidone, styrene-maleic anhydride copolymer or ethylene maleic acid anhydride copolymer and derivative
Thing or the ethoxylated urethane of hydrophobically modified or polyacrylate.But, this use can
Can cause damaging finish paint retentivity, because such as adversely affecting the levelling of varnish.
Polyamide is used for wrapping solvent-laden coating by textbook " Lackadditive " as thickening agent,
Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, page 62 with
And application WO04/11139 is known.
The most such as by from C.H., DISPARLON6900-20X, in October, 1986
Technical data sheet 11.20.3 it is known that the swellable particles of synthesizing polyamides wax can be used as anti-current in following
Extension/anti-settling reagent: resin system based on solvent (such as varnish), solvent, the high film of epoxy resin
Thick coating, tar/epoxy resin composition, tar/polyurethane mixture, chlorinated rubber, automobile are used
Aluminum pigment in paint, the heavy pigment in antirusting paint, carpet backing coating (carpet-backing
And gel coating (plastics of glass fiber reinforcement) coating).Patent application WO2004/111139A1
Use the combination of carbamide compound based on hexylamine and polyamide wax granule as auxiliary rheological agents.But, i.e.
Just use the swellable particles of these synthesizing polyamides waxes or itself and the combination of described carbamide compound, also can not
It is provided that the gratifying solution asked a question above, and realizes application properties such as levelling and shape
Become sagging and the condensation-resistant the best to the high stability of shear stress and coating performance.
Therefore, present invention aim at providing a kind of varnish paint compositions, described varnish paint combines
Thing no longer has a shortcoming of prior art, but show on the contrary levelling and formed sagging application properties it
Between excellent balance, thus on base material solidification after obtain varnish there is high optical quality such as high glaze.
Additionally, solidification developing coatings goes out the height endurability condensed and turn white.Additionally, to being used in particular for automobile
Other important technology requirement of the coating in covering with paint field have also been obtained satisfied.Varnish paint has good especially
Good loop wire stability or stability under shear stress, it means that its rheological property curve, more
Even if specially its viscosity is exposed under shear stress and spends change only.The most above-mentioned use
Property retention is constant, even if such as rotating for a long time in ring system.
For the present invention, find that these purposes can realize by wrapping solvent-laden varnish paint compositions,
Described varnish paint compositions comprises:
-(A) comprises the OH official of following components can (methyl) acrylate (co) polymer:
-(A1) nonvolatile part based on OH official's energy (methyl) acrylate (co) polymer component (A)
At least one OH number that quality is 30-99 weight % be 60-200mg KOH/g and vitrification
Transition temperature TgFor 15-100 DEG C OH official can (methyl) acrylate (co) polymer,
-(A2) nonvolatile part based on OH official's energy (methyl) acrylate (co) polymer component (A)
At least one OH number that quality is 1-70 weight % be 60-200mg KOH/g and vitrification
Transition temperature TgFor-100 DEG C to-20 DEG C OH officials can (methyl) acrylate (co) polymer,
-(B) comprises the crosslinker component of following component:
At least one has the cross-linking agent of functional group reactive to OH group,
And
The matter of-(C) nonvolatile part based on OH official's energy (methyl) acrylate (co) polymer component (A)
Amount is at least one polyamide of 0.02-1.2 weight %, and
The matter of-(D) nonvolatile part based on OH official's energy (methyl) acrylate (co) polymer component (A)
Amount is the urea of the adduct that at least one is polyisocyanates and methoxy propanamine of 0.04-2.9 weight %
Compound.
Hereinafter, solvent-laden varnish paint compositions will be wrapped and be referred to as varnish paint compositions of the present invention.
Varnish paint compositions of the present invention has the good stability relative to shear stress, has excellence in addition
Application properties.After being applied to base material, it is achieved suitably levelling and the slightest sagging trend
Extraordinary balance, therefore cured varnish has such as good gloss.Additionally, achieve good cold
Solidifying.Notable suitably base material include from automobile cover with paint, lacquer, colour wash, etc. field the vehicle body being made up of metal or plastics and
Body part, it often has complicated shape.Varnish paint compositions can be used for structure itself or conduct
A part for multiple tracks paint system covers metal or the varnish of plastic basis material.
For the present invention, unless otherwise, select controlled condition non-to measure in each case
Volatile part (NVF, solid).In order to measure nonvolatile part, by the described composition that amount is 2g
As polymer or the resin dispersion in suitable solvent heats 2 hours at 125 DEG C, it is cooled to
20 DEG C, then residue is weighed (referring also to ISO3251).Measure and be such as present in varnish of the present invention
Polymer in coating composition and/or the nonvolatile part of the corresponding dispersion of resin, thus allow
Determine the such as special component weight fraction relative to the amount of another composition.
For the present invention, hydroxyl value or OH number represent the amount (milligram) of potassium hydroxide, and it is equal to second
The mole of the acetic acid of bonding during acylated 1 gram of corresponding composition.For the present invention, unless otherwise,
Hydroxyl value is by real according to DIN53240-2 (mensuration hydroxyl value-part 2: the method using catalyst) titration
Test is fixed.
For the present invention, glass transition temperature TgSo that based on DIN51005, " heat analyzes (TA)
Term " and the methods experiment mensuration of DIN53765 " heat analyzes Dynamic Scanning Calometry (DSC) ".
Utilize the method, 10mg samples weighing is added sample boat and introduces in DSC instrument.It is cooled to
To initial temperature, then utilize the inert gas flow (N of 50ml/ minute2) and the heating of 10K/ minute
Speed carries out the 1st time and the 2nd measurement process, is wherein again cooled to initiate between measurement process
Temperature.Measure generally lower than the glass transition temperature of prediction about 50 DEG C to than glass transition temperature
Carry out within the temperature range of high about 50 DEG C.For the present invention, based on DIN53765, Section 8.1,
Glass transition temperature be the 2nd time measure during at specific heat capacity (0.5 δ cpHalf change is realized under)
Time temperature.Its by DSC figure (hot-fluid is relative to the curve chart of temperature) determine, and be glass transition it
Before and the temperature of center line between extrapolated baseline and the intersection location of experiment curv afterwards.
(A) OH official can (methyl) acrylate (co) polymer component
Varnish paint compositions comprises OH official can (methyl) acrylate (co) polymer component (A).Group
Dividing (A) to comprise the OH official being described below after at least one can (methyl) acrylate (co) polymer
(A1) the OH official, and being described below after at least one can (methyl) acrylate (co) polymer
(A2)。
As known, (methyl) acrylate (co) polymer is by different acrylate and/or metering system
The polymerizable organic compound of acid ester monomer composition.For the present invention, term (methyl) acrylate generation
Table acrylate and/or methacrylate, or comprise acrylate and/or methacrylate or
By its those constituted compound.The example of this type of acrylate and methacrylate monomer includes respectively
Plant (methyl) alkyl acrylate and (methyl) acrylate base ester, such as, the following is art technology
Compound known to personnel: ethyl acrylate, ethyl methacrylate, propyl acrylate, methyl-prop
Olefin(e) acid propyl ester, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, methacrylic acid
Butyl ester, Isobutyl 2-propenoate, isobutyl methacrylate, tert-butyl acrylate, methacrylic acid uncle
Butyl ester, amyl acrylate, pentylmethacrylate, Hexyl 2-propenoate, N-Hexyl methacrylate, third
Olefin(e) acid Octyl Nitrite, ethylhexyl methacrylate, the own ester of acrylic acid 3,3,5-trimethyl, methyl-prop
The own ester of olefin(e) acid 3,3,5-trimethyl, octadecyl acrylate, octadecyl methacrylate, third
Olefin(e) acid dodecyl ester or lauryl methacrylate, acrylate base ester and acrylic acid ring
Pentyl ester, methacrylic acid ring pentyl ester, isobornyl acrylate, isobornyl methacrylate, propylene
Acid cyclohexyl and cyclohexyl methacrylate.
(methyl) acrylate (co) polymer (A1) and (A2) are OH official's energy, and OH number is
60-200mg KOH/g, preferably 70-180mg KOH/g, highly preferred 80-160mg KOH/g.
Correspondingly, there is this type of acrylate of OH group and some part knot of methacrylate monomer
It is combined in polymer architecture, and therefore constitutes the OH official of (methyl) acrylate (co) polymer base material
Energy.
For preparing the hydroxyl monomeric unit bag of (methyl) acrylate (co) polymer (A1) and (A2)
Include (methyl) acrylic acid hydroxy alkyl ester, such as HEA, methacrylic acid 2-ethoxy
Ester, acrylic acid 2-hydroxypropyl ester, methacrylic acid 2-hydroxypropyl ester, acrylic acid 3-hydroxypropyl ester, first
Base acrylic acid 3-hydroxypropyl ester, acrylic acid 3-hydroxyl butyl ester, methacrylic acid 3-hydroxyl butyl ester, and
Particularly acrylic acid 4-hydroxyl butyl ester and/or methacrylic acid 4-hydroxyl butyl ester.
Other monomeric unit for (methyl) acrylate (co) polymer (A1) and (A2) can be ethylene
Base aromatic hydrocarbons, such as vinyltoluene, α-methyl styrene or particularly styrene, acrylic acid or methyl
Acrylic acid amide or nitrile, vinyl esters or vinyl ethers, and a small amount of particularly acrylic acid and/or first
Base acrylic acid.
The glass transition temperature T of at least one (methyl) acrylate (co) polymer (A1)gFor
15-100 DEG C, preferably 20-70 DEG C, highly preferred 25-50 DEG C.At least one (methyl) acrylate (being total to)
The glass transition temperature T of polymer (A2)gFor-100 DEG C to-20 DEG C, preferably-90 DEG C to-35 DEG C, non-
Chang Youxuan-80 DEG C to-45 DEG C.As it is known by the man skilled in the art, (methyl) acrylate (co) polymer
Glass transition temperature such as by there is the character of monomer and being limited by its ratio in the polymer
Fixed.Technical staff can select accordingly, without substantive effort.
According to the present invention, the mark of (methyl) acrylate (co) polymer (A1) can (first based on OH official
Base) quality of nonvolatile part of acrylate (co) polymer component (A) is 30-99 weight %, excellent
Select 55-90 weight %, more specifically 70-85 weight %.
According to the present invention, the mark of (methyl) acrylate (co) polymer base material (A2) is based on OH official's energy
The quality of the nonvolatile part of (methyl) acrylate (co) polymer component (A) is 1-70 weight %,
Preferably 10-45 weight %, more specifically 15-30 weight %.
The quality of nonvolatile part based on whole coating composition, (methyl) acrylate (co) polymerization
The mark of thing (A1) is preferably greater than (methyl) acrylate (co) polymer that glass transition temperature is lower
(A2) mark.The mark of (methyl) acrylate (co) polymer (A1) is preferably than (methyl) acrylate
The big twice of mark of (co) polymer (A2).
OH official as a whole coating composition part can (methyl) acrylate (co) polymer group
The mark dividing (A) is preferably 30-80 weight %, more preferably 40-70 weight %, more specifically 45-55
Weight %, in each case nonvolatile part based on whole varnish paint compositions.
The model that the molecular weight of (methyl) acrylate (co) polymer (A1) and (A2) is familiar with technical staff
In enclosing, and finally it is not carried out any restriction.Preferred number average molecular weight Mn is
1000-20000g/mol, more specifically 1000-10000g/mol.
Number-average molecular weight Mn by gel permeation chromatography utilize at 40 DEG C high pressure liquid chromatography pump and
RI-detector measures.Eluent used is oxolane, and elution rate is 1ml/ minute.Correction
Carried out by polystyrene standard.
For (methyl) acrylate (co) polymer (A1) and (A2), not only can use the commercially available of routine
(methyl) acrylate (co) polymer, and independently prepared (methyl) acrylate (being total to) can be used to gather
Compound.The example of commercially available (methyl) acrylate (co) polymer includes from " Macrynal " product system
Row (Cytec Surface Specialities) or the polyacrylate of Setalux product line, such as
Setalux1753SS-70(Nuplex Resins)。
The preparation of (methyl) acrylate (co) polymer (A1) and (A2) does not have technology for technique
Characteristic, but contrary the most such as draw by means of conventional in plastic applications and known continuously or in batches free radical
Send out copolymerization process realize, the method in body, solution, emulsion, miniemulsion or microemulsion in greatly
At stirred tank, autoclave, tubular reactor, loop reactor or Taylor under gas or superatmospheric pressure
In reactor preferably at a temperature of 50-200 DEG C.
Suitably the example of copolymerization process be described in patent application DE197 09 465A1,
DE197 09 476A1、DE28 48 906A1、DE195 24 182A1、
DE198 28 742A1、DE196 28 143A1、DE196 28 142A1、
EP0 554 783A1, WO95/27742A1, WO82/02387A1 or WO98/02466A1
In.Such as described in German patent application DE198 50 243A1, copolymerization or can be as reaction
The polyhydric alcohol (heat-setting reactive diluent) of medium is carried out.
The example of suitable free radical initiator is dialkyl peroxide, such as di-tert-butyl peroxide
Or two cumenyl peroxide, hydroperoxides, such as cumene hydroperoxide or tert-butyl group hydrogen peroxide
Compound, perester, such as TBPB tertiary butyl perbenzoate, t-butyl peroxypivalate, tert-butyl group mistake-3,5,5-
Tri-methyl hexanoic acid ester or tert-butyl group mistake-2-ethylhexanoate, peroxydicarbonate, potassium peroxydisulfate,
Sodium or ammonium, azo initiator, wherein example is azo dintrile such as azodiisobutyronitrile, and C-C fracture is drawn
Send out agent such as benzpinacol silyl ether, or the combination of non-oxide initiator and hydrogen peroxide.Also
The combination of above-mentioned initiator can be used.
Other example of initiator appropriate is described in German patent application DE196 28 142A1, and the 3rd
Page the 49th walks in page 4 the 6th row.Additionally, be used as thiono sulfur-based compound or mercaptan such as
Lauryl mercaptan is as chain-transferring agent or molecular weight regulator.
Be different from OH official can other of (methyl) acrylate (co) polymer component (A) compound organic
Monomer, oligomeric and polymerizable compound, predominantly polymerizable compound also can be additionally present in varnish paint group
As base material in compound.Base material refer to familiar to the person skilled in the art in the coating composition with exist afterwards
Cross-linking agent hereinafter described is mainly used in the compound of film forming together.These the most correspondingly include before
(methyl) acrylate (co) polymer (A1) mentioned above and (A2).As known, oligomeric compound is
Those compositions the most several, that the most for example, at least 2-10 monomeric unit is connected to each other.Correspondingly,
Polymerizable compound is wherein to be greater than 10 monomeric units connect and wherein depend on monomer used
Molal weight, number-average molecular weight is often greater than those of 1000g/mol.S known as technical staff,
This kind of polymerizable compound is the (co) polymer of such as at least one monomeric compound, described (co) polymer
For random, alternately and/or block structure and linear, branched and/or pectinate structure.Except before above
Described (methyl) acrylate (co) polymer (A1) and (A2) and the crosslinking being described below afterwards
Outside agent, final it is contemplated that this respect be known to the art all organic monomers, oligomeric and polymerization
Compound, predominantly polymerizable compound.
Can there is other (co) polymer of ethylenically unsaturated monomer especially, described (co) polymer is nothing
Advise, alternately construct and linear, branched and/or pectinate structure with block.Except described OH official energy (methyl)
Acrylate (co) polymer (A1) and (A2) outward, such as, are different from (methyl) acrylate (co) polymer
And other (methyl) acrylate (co) polymer of (A2) also is present in varnish paint compositions (A1)
In, it has previously in (methyl) acrylate (co) polymer (A1) mentioned above and the glass of (A2)
The glass transition temperature T that glass transition temperature is different with OH numbergAnd/or OH number.
Except (methyl) acrylate (co) polymerization beyond the region of objective existence of description comprehensively, other of ethylenically unsaturated monomer
The example of suitable (co) polymer includes the polyvinyl ester of partial hydrolysis.
Polyaddition resin and/or condensation resin also can exist as base material.Suitable addition polymerization resin and/or polycondensation
The example of resin is polyester, alkyd resin, polyurethane, polylactone, Merlon, polyethers, epoxy
Resin-amine adduct, polyureas, polyamide, polyimides, polyester-polyurethane, polyether-polyurethane or
Polyester-polyether-polyurethane.
In the varnish paint compositions of the present invention, preferably there is at least one polyester, the most just
Good a kind of polyester.As known, polyester is for comprising organic polyhydric alcohol and polybasic organic carboxylic acid or by this class group
The polymerizable organic compound being grouped into.These polyhydric alcohol and polycarboxylic acid are connected to each other by esterification, change and
Speech pass through condensation reaction.Correspondingly, polyester is attributed to condensation resin group.Depend on starting ingredient
Character, degree of functionality, mark used and ratio, such as, obtain linear or branched product.But, when making
During with two sense starting ingredients (glycol, dicarboxylic acids), mainly produce linear product, use senior many officials
Can such as produce branched by alcohol (OH degree of functionality, the OH radical amount of per molecule is more than 2 in other words).
In preparation process, the most also can proportionally use mono-functional component, such as monocarboxylic acid.As known,
Replacing corresponding organic carboxyl acid or in addition to it, polyester is used as the anhydride of carboxylic acid, more specifically dicarboxylic acids
Anhydride prepare.Equally can be by using hydroxy carboxylic acid or by intramolecular esterification derived from hydroxy carboxylic acid
Lactone prepare.
The most usually, in the preparation of polyester, polycarboxylic acid and polyhydric alcohol, such as aliphatic series can be used many
Carboxylic acid and aliphatic polyol.Aromatic multi-carboxy acid and aromatic polyol can be used equally, or except identifying it
Outside the functional group of classes of compounds possibly together with (linear, branched and/or ring-type) aliphatic series and aromatic group many
Carboxylic acid and polyhydric alcohol.Be used as linear, branched and/or cyclic aliphatic and/or aromatic hydroxycarboxylic acids with
And lactone, in other words except identify its classes of compounds functional group in addition to, have linear, branched and/
Or cyclic aliphatic and/or the hydroxy carboxylic acid of aromatic group and lactone.
Suitably glycol is such as aklylene glycol, such as ethylene glycol, propylene glycol, butanediol, butane
-Isosorbide-5-Nitrae-glycol, hexane-1,6-glycol, neopentyl glycol and other glycol, such as Isosorbide-5-Nitrae-dihydroxymethyl hexamethylene
Alkane or 2-butyl-2-ethyl-1,3-propanediol.Suitable senior polyfunctional alcohol (OH degree of functionality is more than 2)
For such as trimethylolpropane, glycerol and tetramethylolmethane.
The acid constituents of polyester generally comprises has 2-44 in molecule, the two of preferably 4-36 carbon atom
Carboxylic acid.The example of appropriate acid is phthalic acid, M-phthalic acid, p-phthalic acid, tetrahydrochysene neighbour's benzene
Dioctyl phthalate, hexahydrophthalic acid, cyclohexane cyclohexanedimethanodibasic, succinic acid, adipic acid, Azelaic Acid, the last of the ten Heavenly stems
Diacid, maleic acid, fumaric acid, 1,3-propanedicarboxylic acid, chlordene heptane dicarboxylic acid, tetrachlorophthalic acid and/
Or dimer (fatty acid) yl.Replace acid, it is possible to use its anhydride (if they exist, which) prepare polyester.But,
Preferably the anhydride of M-phthalic acid and/or hexahydrophthalic acid and hexahydrophthalic acid is used for
Prepare polyester.Particularly preferably use hexahydrophthalic acid and the anhydride of hexahydrophthalic acid.Polyester
Therefore described preferred dicarboxylic acids is preferably comprised as monomeric unit.It is used as having 3 or more
The senior polyfunctional carboxylic acids (and/or corresponding anhydride) of carboxyl, wherein example is trimellitic anhydride.Also warp
Often proportionally use monocarboxylic acid, such as unsaturated fatty acid.
The example of spendable hydroxy carboxylic acid is hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid and/or 12-
Hydroxy stearic acid.The example of spendable lactone is conventional β, γ, δ and ε-lactone, more specifically
6-caprolactone.
In addition to above-mentioned monomeric compound, it is possible to such as use the starting products for polymer, such as make
With by making the lactone normal polyester glycol with diol reaction acquisition as glycol.At least one polyester
It is more specifically OH official's energy.Varnish paint compositions of the present invention is a kind of,
A kind of OH number is 80-280mg KOH/g, preferably 100-260mg KOH/g, very
The polyester (E) of preferably 175-200mg KOH/g.Polyester (E) the most preferably has a large amount of OH group.
The glass transition temperature T of at least one polyester (E)gFor-80 DEG C to 20 DEG C, preferably-60 DEG C extremely
10 DEG C, very preferably-40 DEG C to-10 DEG C.
For polyester (E), not only can use commercially available normal polyester, and can use and oneself prepare
Polyester.The example of commercial polyesters includes the polyester of Setal product line, and wherein example is Setal166
SS-80(Nuplex Resins)。
The preparation of polyester does not have characteristic for technique, general by traditional and known polymerization
Carrying out, more specifically polycondensation method, described method is at body, solution, emulsion, miniemulsion or microemulsion
In liquid in stirred tank, autoclave, tubular reactor, loop reactor or Taylor reactor preferably
At a temperature of 50-300 DEG C, if appropriate, use and be usually used in this type of catalyst reacted, and/or often
Water separator for condensation reaction.
Be different from OH official can (methyl) acrylate (co) polymer component (A) compound as base material
Other organic monomer, oligomeric and polymerizable compound, mainly polymerizable compound, the most more
Body is that the mark of at least one polyester is preferably based on OH official's energy (methyl) acrylate (co) polymer group
The quality dividing the nonvolatile part of (A) is not more than 50 weight %.
Preferably at least one polyester (E) is with 10-50 weight %, more specifically 20-45 weight %, very
The amount of preferably 25-40 weight % exists, in each case can (methyl) acrylate (being total to) based on OH official
The quality of the nonvolatile part of polymers compositions (A).
As known, as described organic monomer, the oligomeric and polymerizable compound of base material, predominantly polymerization
Compound can such as heat cure and/or utilize actinic radiation to solidify.Additionally, they self-crosslinkables and/or
Outside crosslinking, it means that the Liang Zhong functional group needed for concrete cross-linking reaction is present in having as base material
In machine compound itself, and/or they contain only needed for two kinds of concrete cross-linking reaction one in functional group
Kind, and use the cross-linking agents containing complementary functional groups and being described below afterwards.
These curings being familiar with for comprehensive description technique personnel, reference Lexikon
Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York,
Page 1998,274 276 and page 542 544.
As noted, (methyl) acrylate (co) polymer (A1) and (A2) they are OH official's energy, and because of
This contains OH group.S known as technical staff, can be by the OH base as functional group in base material
Group produces cross-linking reaction.For the present invention, (methyl) acrylate (co) polymer (A1) and (A2) is used
OH group, to produce the three-dimensional of the complementary functional groups of varnish paint compositions of the present invention and cross-linking agent
Crosslinking, solidifies in other words.Correspondingly, for the OH group that it is existing, main by (methyl)
Acrylate (co) polymer (A1) and (A2) are interpreted as outside crosslinking, varnish paint compositions bag of the present invention
Containing linked (B), it comprises at least one crosslinking with functional group reactive to OH group
Agent.
(B) crosslinker component
Varnish paint compositions comprises crosslinker component (B).For the present invention, crosslinker component (B)
Referring to all summations that there is cross-linking agent, wherein cross-linking agent more specifically refers to participate in the official in above-mentioned base material
The cross-linking reaction that can roll into a ball, the most therefore has all organic of the functional group complementary with this type of group
Monomer, oligomeric and polymerizable compound.
For the purpose of the present invention, it is necessary that crosslinker component (B) comprises at least one to be had OH group
The cross-linking agent of reactive functional group.This kind of cross-linking agent used is particularly including not end-blocking, part
The polyisocyanates blocked and/or block and amino resins.Very particularly preferably use and there is no end-blocking
Polyisocyanates.For the present invention, the polyisocyanates as cross-linking agent is interpreted as that per molecule contains
There is the organic compound of at least two isocyanate groups.Per molecule can be used in principle to contain at least two
All organic compound of individual isocyanate groups.It is used as containing isocyanate groups with by such as
The product that polyhydric alcohol and polyamines are formed with polyisocyanates.
It is used as aliphatic series or cycloaliphatic polyisocyanate, preferably diisocyanate, very preferably aliphatic series
Diisocyanate, but the hexylidene two of more specifically hexylidene diisocyanate, dimerization and/or trimerization is different
Cyanate.
Other example of Suitable polyisocyanates is isophorone diisocyanate, 2-NCO third
Butylcyclohexyl isocyanates, dicyclohexyl methyl hydride 2,4'-diisocyanate or dicyclohexyl methyl hydride 4,4'-
The kind that diisocyanate, Henkel sell with trade name DDI1410 derived from dimer (fatty acid) yl
Diisocyanate, 1,8-diisocyanate base-4-isocyanatomethyl octane, 1,7-diisocyanate
Base-4-isocyanatomethyl heptane or 1-NCO-2-(3-NCO propyl group) hexamethylene,
Or the mixture of these polyisocyanates.
The most noteworthy have such as butylidene 1,4-diisocyanate, cyclohexyl 1,4-bis-Carbimide.
Ester, 1,5-dimethyl-2,4-two (isocyanatomethyl) benzene, 1,5-dimethyl-2,4-two (NCO
Ethyl) benzene, 1,3,5-trimethyl-2,4-two (isocyanatomethyl) benzene, 1,3,5-triethyl group-2,4-two be (different
Cyanate ylmethyl) benzene, dicyclohexyl dimethylmethane 4,4'-diisocyanate, 2,4-toluene diisocyanate
Acid esters, 2,6-toluene di-isocyanate(TDI) and diphenyl methane 4,4'-diisocyanate.
In especially preferred embodiment, by hexylidene 1, the trimer of 6-diisocyanate is used as to hand over
Connection agent；This compound such as commercially available prod with title Desmodur N3390 (Bayer
Or Basonat HI190 (BASF SE) obtains MaterialScience).
Other example of Suitable polyisocyanates is organic multiple isocyanate, more specifically have aliphatic series,
The so-called paint polyisocyanates of the free isocyanate groups group that cyclic aliphatic, araliphatic and/or aromatics connect.
Per molecule is preferably used and there is 2-5 isocyanate groups and viscosity is 100-10000mPa.s, preferably
The polyisocyanates of 100-5000mPa.s, more specifically 100-2000mPa.s (23 DEG C).Optionally,
Also can be mixed with a small amount of organic solvent by polyisocyanates, being preferably based on pure polyisocyanates is 1-25 weight
Therefore amount %, to improve the easy degree of the combination of isocyanates, and optionally by the viscosity of polyisocyanates
It is reduced to level within the above range.The example adding the suitable solvent of polyisocyanates includes third
Acid ethoxy ethyl ester, amyl methyl ketone or butyl acetate.Additionally, polyisocyanates can be carried out routine
Hydrophilic or hydrophobically modified.
The most such as polyurethane prepolymer, it contains isocyanate groups, can be polynary by making
Alcohol and excess of polyisocyanate react preparation, and preferably have low viscosity.Its of Suitable polyisocyanates
Its example is containing isocyanuric acid ester, biuret, allophanate, imino groupOxadiazinediones, urine
The polyisocyanates of alkane, urea and/or uretdion groups.Polyisocyanates containing urethane group is the most logical
Cross and make some isocyanate groups obtain with polyhydric alcohol such as trimethylolpropane and glycerine reaction.
Other example of Suitable isocyanate is described in " Methoden der organischen
Chemie ", Houben-Weyl, volume 14/2, the 4th edition, Georg Thieme Verlag,
Stuttgart1963, the 61-70 page, W.Siefken, Liebigs Ann.Chem.562,75-136,
European patent EP-A-101832 or US patent US-PS-3,290,350, UP-PS-4,130,577 and
In US-PS-4,439,616.
Above-mentioned polyisocyanates for exist with its free form, the cross-linking agent the most not blocked.
S known as technical staff, these free polyisocyanates are generally used for multi-component coating system, more
Body is two-component coating system.It means that with respect to the present invention that at two-component lacquer coating composition
In the case of, component (A) and the crosslinker component (B) of varnish paint compositions of the present invention are protected independent of one another
Deposit, and only next-door neighbour just merges before using varnish paint compositions.This is done to prevent base material,
The more specifically OH group of (methyl) acrylate (co) polymer (A1) and (A2) and free polyisocyanic acid
The too early crosslinking of ester cross-linking agent.
But, as it has been described above, be used as the polyisocyanates of end-blocking equally.It is coated with in single component varnish
In the case of feed composition, the polyisocyanates these blocked in the context of the present invention is used as crosslinking
Agent, it is, therefore, intended that OH official can (methyl) acrylate (co) polymer component (A) and cross-linking agent
Component (B) can preserve by mixture each other, and is not the most just to be mixed with each other.With trip
From isocyanates contrary, the polyisocyanate crosslinker of end-blocking the most at elevated temperatures could be with base
The functional group of material, more specifically the OH group of (methyl) acrylate (co) polymer (A1) and (A2) are anti-
Should, to build three-dimensional network and therefore to cause coating composition.It should be appreciated that this type of envelope
The polyisocyanate crosslinker of end can also be used for multicomponent system, more specifically bicomponent system.
The cross-linking agent of end-blocking only causes coating composition solid at the temperature (about > 80 DEG C to 100 DEG C) raised
The reason changed is known as end-capping reagent and the most just eliminates from isocyanate functional group, the most so
After could be with the complementation group of base material, more specifically (methyl) acrylate (co) polymer (A1) and (A2)
OH radical reaction.
The example of typical case's end-capping reagent be the acid compound of phenol, alcohol, oxime, pyrazoles, amine and CH-such as
Diethyl malonate.End capping reaction is typically by making dissociateive NCO group with described end-capping reagent such as
React in the presence of catalyst such as dibutyl tin dilaurate or two (2 ethyl hexanoic acid) stannum (II) and carry out.End-blocking
Agent and respective reaction are known to the art, and are fully described in such as US patent specification
In US-A-4,444,954.Be preferably used as end-capping reagent be caprolactam, diacetylmonoxime, acetone oxime, third
Diethyl adipate, dimethyl pyrazole or phenol.
For the present invention, it is also possible to advantageously use amino resins as cross-linking agent.The most suitable
Be conventional and known amino resins, such as carbamide, benzoguanamine-formaldehyde
And urea-formaldehyde resins.Melamine formaldehyde resin is preferably used.They are generally rudimentary wherein to utilize
The form that they are etherified by alcohol, generally methanol and/or butanol uses.A kind of suitably amino resins example
As for hexoxymethyl tripolycyanamide.But, the condensation product of other amine and amide can be used equally,
Wherein example is triazine, diazine, triazole, guanidine, guanidine imines (guanimine) and this compounds
Alkyl and the aldehyde condensate of the substituted derivant of aryl (including alkyl and the substituted tripolycyanamide of aryl).
Some examples of this compounds be N, N'-dimethyl urea, benzo urea, dicyandiamide, formyl guanamines,
Acetylguanamine, ammeline, 2-chloro-4,6-diaminostilbene, 3,5-triazine, 6-methyl-2,4-diamino
Base-1,3,5-triazine, 3,5-diaminourea triazole, Triaminopyrimidine, 2-sulfydryl-4,6-di-amino-pyrimidine, 3,4,6-
Three (ethylamino)-1,3,5-triazine and three (alkoxycarbonyl amino) triazine etc..It should be appreciated that remove
Outside with the condensation product of formaldehyde, it is possible to use with the condensation product of other aldehyde.
The most conventional and known amino resins, some of methylol and/or methoxy can
Functionalization is gone by carbamate groups or allophanate groups.This kind of cross-linking agent is described in patent
Description US-A-4 710 542 and EP-B-0 245 700 and B.Singh and the opinion of common author
Literary composition, " tripolycyanamide of carbamoyl methyl, for the novel crosslinker of coatings industry ", high
Organic coating science and technology book series, volume 1991,13, in the 193-207 page.
For the present invention suitable amino group resin such as can with trade mark Cymel, Luwipal,
Maprenal, Resimene and Beetle are commercially available.
In the case of preferred cross-linking agent contains isocyanate groups, preferably with a certain amount of use at least
A kind of cross-linking agent, so that previously in the compound as base material mentioned above, the most particularly (first
Base) acrylate (co) polymer (A1) compares with the total amount of hydroxyl in (A2), cross-linking agent used reacts
Property NCO group total amount excess.Particularly preferably be used as base material compound hydroxy compounds with extremely
The ratio of the NCO group of few a kind of cross-linking agent is 1:1-1:1.5, highly preferred 1:1.05-1:1.25, more
It is specially 1:1.05-1:1.15.
Linked, more specifically polyisocyanates and/or amino resins, the most do not block many
Isocyanates preferably with 30-80 weight %, more specifically 40-70 weight %, highly preferred 50-65
The amount of weight % exists, in each case can (methyl) acrylate (co) polymer group based on OH official
Divide the quality of the nonvolatile part of (A).
Now, the mark preferably as the crosslinker component (B) of a whole coating composition part is
10-50 weight %, more preferably 20-40 weight %, combines based on whole varnish paint in each case
The nonvolatile part of thing.
(C) polyamide
Varnish paint compositions of the present invention comprises at least one polyamide as auxiliary rheological agents.Polyamide is
Molecule contains the organic compound of at least two amide structure.This compounds can be such as many by making
Carboxylic acid reacts with polyamines and/or monoamine, or makes polyamines and monocarboxylic acid react preparation.
The polyamide wax that polyamide is preferably synthetic.Synthetic wax is generally interpreted as having institute by technical staff
The synthesis of organic products of definition physical property.These performances are particularly including following true: they are at most
Can mediate at 20 DEG C, be that solid is the most brittle, coarse-crystalline is to thin crystalloid, but is not glassy.Typically
For, they are only melted more than 40 DEG C, and do not decompose, and more than its fusing point, they are changed into low viscous
The liquid melt state of degree.Denseness is highly dependent on temperature.
Show described waxy performance and therefore can be described as the polyamide of polyamide wax for such as many by making
Amine and fatty acid, more specifically per molecule contain that of the fatty acid response acquisition of 16-20 C atom
A bit.The example being suitable to prepare the polyamines of this type of polyamide or polyamide wax includes having more than an amido
The monomeric organic compound (monomeric polyamines) of group, wherein example is 1,6-hexamethylene diamine.The most preferably by this kind of
Synthesizing polyamides wax is in varnish paint compositions of the present invention.Particularly preferred as auxiliary rheological agents
Polyamide or synthesizing polyamides wax are the fat that 1,6-hexamethylene diamine and per molecule have 16-20 C atom
Acid and/or hydroxy fatty acid, more specifically hydroxy fatty acid, the reaction of preferably 12-hydroxy stearic acid is produced
Thing.
Preferably polyamide wax uses the most in the form of granules.The typical case of this type of polyamide granules
Average-size can be such as less than 100 microns, more preferably less than 80 microns, highly preferred 60 microns
Hereinafter, more specifically less than 50 microns.The scope of 5-40 micron is especially advantageous especially.Should
The mensuration of particle mean size is carried out by known laser diffractometry, more specifically according to DIN ISO
(measuring particle mean size, it is d to 13320:200950Value) carry out.
Synthesizing polyamides used according to the invention, more specifically preferably polyamide wax granule can former state
Add according in the varnish paint compositions of the present invention.However, it is advantageous that with at typical organic solvents
(C), the form of the more specifically dispersion in alcohol and/or dimethylbenzene adds them.This dispersion non-
Volatile part alterable is the biggest.They are preferably with 5-40 weight %, preferably 10-30 weight %, more
The amount being specially 15-25 weight % comprises polyamide (C) used according to the invention, more specifically polyamides
Amine Wax particles, in each case total amount based on dispersion.This type of point of various polyamide wax granules
A prose style free from parallelism is such as with trade name Disparlon (King Industries, USA, Kusumoto, Japan
Or, Germany) and commercially available.
For the present invention, the most preferably as described above with the form of dispersion in organic solvent
Use polyamide wax granule based on hydroxy stearic acid and 1,6-hexamethylene diamine.Corresponding commercially available prod is permissible
Title Disparlon6900-20X () obtain.
Particularly preferably in varnish paint compositions of the present invention, use polyamide (C) with the form of pastel,
More specifically polyamide wax.In addition to polyamide, described pastel also comprises above-mentioned (methyl) acrylate (being total to)
Polymer, such as (methyl) acrylate (co) polymer (A1) and/or (A2), and at least one typical case
Organic solvent, wherein example is alcohol and/or arsol such as dimethylbenzene and/or solvent naphtha.Institute
State pastel and comprise preferred 20-60 weight %, more preferably 25-55 weight %, more specifically 30-50
Weight % above-mentioned (methyl) acrylate (co) polymer, 3-9 weight %, preferably 4-8 weight %, more
It is specially 5-7 weight % polyamide, and at least one typical organic solvent, in each case
Total amount based on described pastel.
This type of pastel can be prepared by mixing and homogenizing composition by means of conventional mixing techniques and device,
And there is no the complexity in terms of special charges or method.Especially, the dispersion of above-mentioned polyamide wax granule
Body (such as Disparlon6900-20X,) can with (methyl) acrylate (co) polymer by than
Example mixes to obtain the ratio of each composition in above-mentioned pastel.
According to the present invention, varnish paint compositions of the present invention comprises can (methyl) acrylic acid based on OH official
The quality of the nonvolatile part of ester (co) polymer component (A) is 0.02-1.2 weight %, preferably 0.1-1
At least one polyamide of weight %.
(D) as the carbamide compound of polyisocyanates Yu the adduct of monoamine
Varnish paint compositions of the present invention comprises at least one carbamide compound as other auxiliary rheological agents, institute
State the adduct that carbamide compound is polyisocyanates and methoxy propanamine.
The most spendable polyisocyanates is the institute that per molecule contains at least two isocyanate groups
Having inorganic compound, wherein example is above-mentioned polyisocyanates.It is used as containing isocyanate groups
And be the product of the product that such as polyhydric alcohol and polyamines react with polyisocyanates.It is preferably used two
Isocyanates, highly preferred aliphatic vulcabond, more specifically hexylidene diisocyanate.Mention
The following example as spendable polyisocyanates: butylidene 1,4-diisocyanate, hexylidene 1,6-
Diisocyanate, cyclohexyl 1,4-diisocyanate, dicyclohexyl methyl hydride 4,4-diisocyanate, 1,5-
Dimethyl-(2,4-ω-cyanato methyl) benzene, 1,5-dimethyl-(2,4-ω-diisocyanate base second
Base) benzene, 1,3,5-trimethyl-(2,4-ω-cyanato methyl) benzene, 1,3,5-triethyl group-(2,4-ω-two
Isocyanatomethyl) benzene, three polyhexamethylene 1,6-diisocyanate, isophorone diisocyanate,
2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI).
In varnish paint compositions of the present invention, carbamide compound is preferably with the form of pastel, and at least
The typical organic solvents that is described below and at least one polyester and/or (methyl) acrylic acid after a kind of
Ester (co) polymer, preferably polyester (E) are used in mixed way.Therefore carbamide compound can be such as direct at polyester,
Prepare in the presence of being more specifically the one in above-mentioned polyester (E) in other words.Now, program for example, will
Methoxy propanamine adds in polyester solution in organic solvent or ORGANIC SOLVENT MIXTURES, is subsequently adding
Polyisocyanates.Desired organic solvent is described below after a while, more specifically selects it
So that they are not involved in composition present in course of reaction, methoxy propanamine, extremely in other words
Few a kind of polyisocyanates and any destructive of at least one polyester interact.In this respect, example
As also there is polyisocyanates and/or carbamide compound, (wherein it contains and is still free NCO
Group) and the connection of polyester.Such as when polyester contains OH group, so situation is exactly.Described pasty state
Thing then comprises the polyester utilizing carbamide compound used according to the invention modified.It is therefore preferable that at least become
Ratio ground uses carbamide compound with the form of polyester with the adduct of carbamide compound.As varnish paint group
The ratio of the carbamide compound described further below of a compound part is the most also based only upon urea chemical combination
Thing, rather than carbamide compound and the product of polyester.
Then by gained pastel, the auxiliary rheological agents and the polyester that contain urea groups in other words are molten with organic
The mixture of agent or complex, in bag of the present invention solvent-laden varnish paint compositions.
In the urea as polyisocyanates Yu the adduct of methoxy propanamine with the form of mixtures of polyester
Compound also can such as obtain with trade name Setal, such as Setal82166SS-64 or Setal81462
SS-55 (Nuplex Resins), and can be readily used in varnish paint compositions of the present invention.
According to the present invention, varnish paint compositions of the present invention comprises can (methyl) acrylic acid based on OH official
The quality of the nonvolatile part of ester (co) polymer component (A) is 0.04-2.9 weight %, preferably
At least one of 0.3-1.5 weight % is as the urea chemical combination of polyisocyanates Yu the adduct of methoxy propanamine
Thing.
Varnish paint compositions of the present invention also comprises at least one organic solvent.Suitably organic solvent is more
Be specially in varnish paint compositions compound (A) and (B) in chemical inertness, and solidification by
Those do not reacted with (A) and (B) during varnish prepared by invention varnish paint compositions.
Use and do not suppress varnish paint compositions of the present invention crosslinking and/or be not involved in same varnish of the present invention to be coated with
The organic solvent of the chemical reaction of other composition of feed composition.Technical staff therefore can be known based on it
Solvability and reactivity be readily selected suitable solvent.
The example of this kind solvent be aliphatic series and/or aromatic hydrocarbon, such as toluene, dimethylbenzene, solvent naphtha,
Solvesso100 or(from ARAL), ketone, such as acetone, methyl ethyl ketone or first
Base amyl ketone, ester, such as ethyl acetate, butyl acetate, acetic acid butyl glycol ester, pentyl acetate
Or the mixture of ethyl-ethoxypropionate, ether, or aforementioned solvents.
Varnish paint compositions of the present invention preferably comprises 30-70 weight %, more preferably 40-60 weight %
Organic solvent.
Varnish paint compositions of the present invention is that bag is solvent-laden.In addition to the above-mentioned fact that there is organic solvent,
This especially means that varnish paint compositions total amount based on compositions does not comprises more than 1 weight %, bag
Containing preferably no greater than 0.5 weight %, especially preferably no more than 0.25 weight % water.To this end, it is favourable
It is present in the water content of the organic solvent in varnish paint compositions or solvent mixture based on solvent not
More than 1 weight %, the most no more than 0.5 weight %.
Additionally, varnish paint compositions of the present invention can be with effective dose, the most preferably up to maximum 30
Weight %, the most maximum 25 weight %, the amount of the most maximum 20 weight % comprises
At least one conventional coating additive, based on varnish paint compositions non-volatile in each case
Composition.
The example of suitable coating additive is as follows:
-especially UV absorbent；
-especially light stabilizer, such as HALS compound, benzotriazole or oxanilide；
-non-opacifying property transparent filler, such as SiO2Nano-particle, barium sulfate, zinc oxide and Aerosil
-free radical scavenger；
-lubricating additive；
-polymerization inhibitor；
-defoamer；
-it is known in the art the reactive diluent of general knowledge kind；
-wetting agent, such as siloxanes, fluorochemical, dicarboxylic acid monoester,
-phosphate ester, polyacrylic acid and copolymer thereof or polyurethane；
-viscosifier, such as Tricyclodecane Dimethanol；
-coalescents, such as cellulose derivative；
-and/or fire retardant.
In addition to varnish paint compositions of the present invention, present invention also offers varnish paint compositions of the present invention
Preparation.
For method, described preparation does not have characteristic, but on the contrary by utilizing routine mixing skill
Art and device mixing and homogenizing mentioned component and carry out, described device be such as agitator tank, Ball-stirring mill,
Extruder, blender, Ultraturraxx, online dissolvers, static mixer, gear disperser,
Decompression nozzle and/or microfluidization device, optionally get rid of actinic radiation.
In the case of preferred two-component lacquer coating system, the most particularly when at cross-linking agent
When component (B) using the polyisocyanates not having end-blocking as cross-linking agent, it is important that by component (A)
The hydroxyl-functional polyester preferably existed is retained separately with crosslinker component (B), until just using clearly
Just merge before paint coating composition and mix, to prevent base material, more specifically (methyl) acrylate (being total to)
The OH group of polymer (A1), (A2) and polyester cross-links with the too early of free polyisocyanates.Double
In the case of component varnish coating system, generally by the mentioned component of varnish paint compositions of the present invention,
More specifically any coating of auxiliary rheological agents (C) and (D), polyester (E) and organic solvent and existence adds
Agent mixes with component (A) and optionally preserves.Then will before next-door neighbour uses varnish paint compositions of the present invention
This mixture with typically mix with the crosslinker component (B) existed with the mixture of organic solvent.With regard to this
For bright, next-door neighbour uses mixing before and refers to before administration less than 30 minutes, preferably more than 15 points
Mixing in clock.
Present invention also offers the purposes of varnish paint compositions of the present invention.Varnish paint of the present invention combines
Thing is more specifically applicable to automobile and is coated with and is decorated with and prepares varnish on different substrate materials, and correspondingly uses.Accordingly
Ground, present invention also offers the varnish using varnish paint compositions of the present invention to prepare on base material.
Varnish paint compositions of the present invention is applied to base material to be realized by all conventional application method,
Such as spray, scratch, sprawl, pour into a mould, dip-coating, dipping, drip or roller coat.Used this kind of
Cheng Zhong, base material to be coated itself can transfixion, wherein move administration unit or device.Or,
Also may move base material to be coated, more specifically coiled material, wherein administration unit is static relative to base material not
Dynamic or the most mobile.
Spray application method it is preferably used, such as compressed air spraying (pneumatic administration system), without air
Spraying, high-speed rotation, electrostatic spraying are used (ESTA), such as optionally use such as hot-air with thermal spraying
Spraying combines.
The thickness of the dry state of solidification is preferably 20-70 micron.
After the using of varnish paint compositions of the present invention and before solidification, certain time of repose can be there is
Or evaporation time.Time of repose is such as levelling and the devolatilization of film, or is used for evaporating volatile
Composition such as solvent.Time of repose can the atmospheric humidity of temperature and/or reduction by using rising be tieed up
Holding and/or shorten, condition is that this will not cause any painting membrane damage or change, too the earlyest friendship completely
Connection.
If varnish paint compositions of the present invention being applied to base material and implementing, after evaporation time, carry out
It is cured to form varnish.
For method, the heat cure of varnish paint compositions of the present invention does not have characteristic, but leads on the contrary
Cross conventional method as heated in forced air draft oven or utilizing IR light irradiation to carry out.In this heat cure also
Can carry out stage by stage.Another kind of curing is for utilizing near-infrared (NIR irradiation) to solidify.Advantageous particularly
Be heat cure varnish paint of the present invention compositions.General at 30-200 DEG C, more preferably 40-190 DEG C,
At a temperature of particularly 50-180 DEG C, heat cure 1 minute is to 10h, more preferably 2 minutes to 5h, more
Body is the 3 minutes time to 3h.In the case of two-component lacquer coating system is preferably used, excellent
It is selected at a temperature of 80-160 DEG C and carries out heat cure 20-60 minute.In the case of metal is as base material,
At 100-160 DEG C, preferably carry out heat cure 20-40 minute.At plastics as the situation of preferred substrates
Under, at 60-100 DEG C, carry out heat cure 30-60 minute (" low temperature baking " method).
Directly coat base material (single coating final lacquer), or using and the showing of optionally drying and/or solidification
Having formation varnish film on film, result is then multiple tracks paint system.Preferred substrates is metal base or moulds
Material base material, such as preparing the variety of components of the device in vehicle or on vehicle in automobile construction
Those, such as PP/EPDM, polyamide and/or ABS.Particularly preferably plastic basis material.
In the case of metallic substrate, advantageously it is used as to include electropaining coating, priming paint surfacer by varnish
A part for the multiple tracks paint system of coating, priming coat and varnish of the present invention.Situation at plastic basis material
Under, build single coating final lacquer, or same structure multiple tracks paint system.In the case of the latter, make
With can be used for the conventional primer surfacer of painting of plastics, single coating finish paint, priming coat and varnish paint group
Compound, wherein selection and the use of these compositionss is known to the art.
Embodiment:
Preparation embodiment 1, the synthesis of (methyl) acrylate (co) polymer
Preparation is by the aromatic hydrocarbon fraction that 94.5g boiling range is 158-172 DEG C and 57.9g di-tert-butyl peroxide
The premix of the initiator solution composition of thing initiator.This mixture is transferred to Dropping funnel.
The premix being made up of 1869.9g EHA and 684.6g 2-(Acryloyloxy)ethanol
It is placed in the 2nd Dropping funnel.
The aromatic hydrocarbon fraction that 1022.4g boiling range is 158-172 DEG C is equipped with agitator, 2 dropping liquids
Funnel (respectively for initiator solution and monomer mixture), nitrogen inlet pipe, internal thermometer and return
The capacity of flow condenser is in the laboratory reactor of 4L.
The solvent being introduced into is heated to 150 DEG C.After reaching that temperature, by monomer mixture under stirring
With initiator mixture 4 during 4 hours3/4Initial throwing is added with uniform rate during hour
In material.The first time of initiator is added in addition monomer for the first time and carries out, the most then for first 15 minutes
It was carried out continuously during 4.5 hours.It is continuously added to monomer mixture during 4 hours.Poly-
During conjunction, there is exothermic reaction, wherein by cooling, temperature is continuously held in 150 DEG C.
After the end of the addition, hold the mixture in 150 DEG C other 1 hour, then cool down.
The aromatic hydrocarbon fraction is utilized by the regulation of gained methacrylate copolymer solution to solids content to be
67 weight % (forced air draft oven: 1h at 130 DEG C).
The OH number of (methyl) the acrylate (co) polymer thus prepared is 131mg KOH/g, glass
Glass transition temperature TgFor-70 DEG C, nonvolatile part is 67 weight %.
Preparation embodiment 2, comprises the preparation of the polyamide thickening agent pastel of polyamide wax granule (C)
In Laboratory mill mixing and homogenizing 30 weight portion fromDisparlon
9600-20X1With 70 weight portions from the Macrynal SM510 of Cytec Surface Specialities
N2。
1Polyamide wax granule dispersion in organic solvent (alcohol, dimethylbenzene).The non-volatile portion of dispersion
It is divided into 20 weight %.
2OH number is 150mg KOH/g and glass transition temperature TgIt it is (methyl) acrylate (being total to) of 36 DEG C
Polymer dispersion in organic solvent (butyl acetate, dimethylbenzene, solvent naphtha).Dispersion
Nonvolatile part be 60 weight %.
The preparation of varnish paint compositions
According to table 1, prepare Comparative composition 1 and 2 by mixing its composition and homogenizing gained mixture
And compositions 3.Compositions can store a few week and quality does not reduces.In each case by compositions
With cross-linking agent based on isocyanates based on three polyhexamethylene diisocyanate (this cross-linking agent solution
Composition: from Desmodur N3390 and the butyl acetate of equal portions of Bayer MaterialScience
With the aromatic hydrocarbon fraction that boiling point is 158 DEG C-172 DEG C, it is thus achieved that the nonvolatile part of 68 weight %) mixed
Close, and as being described below being applied to base material afterwards in 10 minutes.From table 1 mixture 1,
2 and 3 are 100 weight portion abrasives with the blending ratio of cross-linking agent solution: 30 parts by weight of crosslinking agent are molten
Liquid.Use butyl acetate by all varnish paint compositionss regulation to spray viscosity (38 seconds, at ISO4
In Bei, at 23 DEG C).
Table 1: without the compositions of crosslinker component (B)
The most all numerals are weight %
1Macrynal SM 510 N (nonvolatile part: 60 from Cytec Surface Specialities
Weight %, OH number (resin)=150mg KOH/g, Tg(resin)=36 DEG C).
2According to preparation embodiment 1 (methyl) acrylate (co) polymer (nonvolatile part: 67 weight %,
OH number (resin)=131mg KOH/g, Tg(resin)=-70 DEG C).
3Setal 166 SS-80 (80% concentration polyester (OH number (resin)=191mg from Nuplex Resins
KOH/g, Tg(resin)=-25 DEG C) diluent in dimethylbenzene/butyl acetate, nonvolatile part:
80 weight %).
4Setal82166SS-64 (the polyester that urea is modified from Nuplex Resins；Based on Setal166
The mixture of SS-80, wherein methoxy propanamine is as the amine component (nonvolatile part: 64 weights of urea
Amount %, content based on polyester non-volatile activity urea material: 4.1 weight %)).
5Polyamide thickening agent pastel according to preparation embodiment 2
6Commercially available flowing controls additive
7Commercially available UV absorbent
8Commercially available UV absorbent
The preparation of varnish 1-4 and performance and the performance of compositions 1-4
UseAutomatic coating device is pneumatic uses varnish paint compositions.The most in each case
The compositions 1,2 and 3 used is made to solidify at 90 DEG C 30 minutes.Additionally, preparation according to from
Other Comparative composition (varnish paint compositions 4) of the V5 of WO2004111139, uses
Automatic system is pneumatic to be used, and solidifies 30 according to the description of test in WO2004111139 at 140 DEG C
Minute prepare varnish 4.
In order to work out table, use varnish paint compositions with wedge shape.Now, varnish paint combination
Thing each covers the thickness of 10-60 micron in bakeing paint film.
It is that there is on 320 × 600mm, diagonal mensuration sagging on the coil coating test board of a round in size
Stability.In each case by measuring the dry varnish as the function of sagging length at this round
Thickness evaluates sag resistance.
In order to measure levelling and outward appearance, with constant dried film thickness, it is 20 and 35 micro-in each case
Rice varnish paint compositions is applied to size be 500 × 200mm, the coil coating test board that do not has hole, and
Solidification.It is evaluated in described film thickness range by Wavescan measurement method (long wave/shortwave).
The test of the shear stability of compositions 1-4 is by with mixing speed U=20 minute-1Stirring combination
Thing many skies (7 days) are carried out.Be then used by rotational rheometer (2D method) measure not have expose sample with
It is exposed to the time dependence viscosity of the stirring test sample of 7 days.Now, paint sample under study for action
First at 23 DEG C aging about 10 minutes, it is then exposed to 1000 seconds-1Shear rate 5 minutes (negative
Carry phase), then it is close to thereafter (unsupported phase) and is switched to 1 second–1Shear rate 8 minutes.According to viscous
The evaluation of the time dependence change of degree, is measured by formerly stirring by the rising after 10s and 60s
Expose the rheology infringement that material is caused.If with without exposure to stirring sample compared with, due to
First stirring exposes and finds the reduction of rising characteristic, then can be by the damage of the rising compared with different samples
Lose percent and determine the sample more stable with other sample phase comparison shearing.
The storage stability test of varnish sample is by room temperature (23 DEG C) and the storage temperature (40 DEG C) of rising
Lower storage varnish sample is carried out for several days.Then pass through outflow viscosity and/or rheometry uses to rotate and glues
Degree meter measuring samples, and be compared to each other.According to delivery time and the difference of rheological behavior and change, with
It is possible that fresh sample compares the change of each sample viscosity under different conditions of storage and rheological behavior
, the raising percent of such as delivery time.
Table 2: varnish 1-4 and the performance of compositions 1-4
Result shown in table 2 show the varnish prepared by varnish paint compositions of the present invention show levelling and
The excellent balance used between quality of sag resistance.Meanwhile, shearing according to the compositions of the present invention
There is under stress and long term storage good stability, i.e. its rheological property and viscograph thereof shearing
Stress and only slight variations under storing.
Claims (34)
1. wrap a solvent-laden varnish paint compositions, comprise following component:
-(A) nonvolatile part based on whole varnish paint compositions is that comprising of 30-80 weight % is as follows
OH official's energy (methyl) acrylate polymer component of component:
The matter of-(A1) nonvolatile part based on OH official's energy (methyl) acrylate polymer component (A)
Amount is 60-200mg KOH/g and glass transition at least one OH number of 30-99 weight %
Temperature TgFor 15-100 DEG C OH official can (methyl) acrylate polymer,
The matter of-(A2) nonvolatile part based on OH official's energy (methyl) acrylate polymer component (A)
Amount is 60-200mg KOH/g and glass transition at least one OH number of 1-70 weight %
Temperature TgFor-100 DEG C to-20 DEG C OH officials can (methyl) acrylate polymer,
-(B) comprises the crosslinker component of following component:
At least one has the cross-linking agent of functional group reactive to OH group,
And
The quality of-(C) nonvolatile part based on OH official's energy (methyl) acrylate polymer component (A) is
At least one polyamide of 0.02-1.2 weight %, and
The quality of-(D) nonvolatile part based on OH official's energy (methyl) acrylate polymer component (A) is
At least one of 0.04-2.9 weight % is the urea chemical combination of the adduct of polyisocyanates and methoxy propanamine
Thing,
The OH number that quality is 10-50 weight % of-(E) nonvolatile part based on component (A) is
80-280mg KOH/g and glass transition temperature TgFor the polyester of-80 DEG C to 20 DEG C.
Bag the most according to claim 1 solvent-laden varnish paint compositions, it is characterised in that (methyl)
The OH number of acrylate polymer (A1) and (A2) is 70-180mg KOH/g.
Bag the most according to claim 1 solvent-laden varnish paint compositions, it is characterised in that crosslinking group
(B) is divided to comprise at least one polyisocyanates and/or at least one amino resins as cross-linking agent.
Bag the most according to claim 2 solvent-laden varnish paint compositions, it is characterised in that crosslinking group
(B) is divided to comprise at least one polyisocyanates and/or at least one amino resins as cross-linking agent.
Bag the most according to claim 1 solvent-laden varnish paint compositions, it is characterised in that crosslinking group
Dividing the cross-linking agent in (B) is the polyisocyanates not blocked.
Bag the most according to claim 2 solvent-laden varnish paint compositions, it is characterised in that crosslinking group
Dividing the cross-linking agent in (B) is the polyisocyanates not blocked.
Bag the most according to claim 3 solvent-laden varnish paint compositions, it is characterised in that cross-linking agent
Hexylidene diisocyanate for trimerization.
Bag the most according to claim 4 solvent-laden varnish paint compositions, it is characterised in that cross-linking agent
Hexylidene diisocyanate for trimerization.
Bag the most according to claim 5 solvent-laden varnish paint compositions, it is characterised in that cross-linking agent
Hexylidene diisocyanate for trimerization.
Bag the most according to claim 6 solvent-laden varnish paint compositions, it is characterised in that crosslinking
Agent is the hexylidene diisocyanate of trimerization.
11. bag as claimed in one of claims 1-10 solvent-laden varnish paint compositions, it is special
Levy and be that it is two-component lacquer coating composition.
12. bag as claimed in one of claims 1-10 solvent-laden varnish paint compositions, it is special
Levy the polyamide wax being that polyamide (C) is synthesis.
13. bag according to claim 11 solvent-laden varnish paint compositions, it is characterised in that polyamides
Amine (C) is the polyamide wax of synthesis.
14. bag as claimed in one of claims 1-10 solvent-laden varnish paint compositions, it is special
Levy be polyamide (C) fatty acid that to be monomeric polyamines contain 16-20 C atom with per molecule and/or
The product of hydroxy fatty acid.
15. bag according to claim 11 solvent-laden varnish paint compositions, it is characterised in that polyamides
Amine (C) is fatty acid and/or the hydroxy fatty acid that monomeric polyamines contains 16-20 C atom with per molecule
Product.
16. bag according to claim 12 solvent-laden varnish paint compositions, it is characterised in that polyamides
Amine (C) is fatty acid and/or the hydroxy fatty acid that monomeric polyamines contains 16-20 C atom with per molecule
Product.
17. bag according to claim 13 solvent-laden varnish paint compositions, it is characterised in that polyamides
Amine (C) is fatty acid and/or the hydroxy fatty acid that monomeric polyamines contains 16-20 C atom with per molecule
Product.
18. bag as claimed in one of claims 1-10 solvent-laden varnish paint compositions, it is special
Levy and be that (methyl) acrylate polymer is (methyl) acrylate copolymer.
19. bag according to claim 11 solvent-laden varnish paint compositions, it is characterised in that (methyl)
Acrylate polymer is (methyl) acrylate copolymer.
20. bag according to claim 12 solvent-laden varnish paint compositions, it is characterised in that (methyl)
Acrylate polymer is (methyl) acrylate copolymer.
21. bag according to claim 13 solvent-laden varnish paint compositions, it is characterised in that (methyl)
Acrylate polymer is (methyl) acrylate copolymer.
22. bag according to claim 14 solvent-laden varnish paint compositions, it is characterised in that (methyl)
Acrylate polymer is (methyl) acrylate copolymer.
23. bag according to claim 15 solvent-laden varnish paint compositions, it is characterised in that (methyl)
Acrylate polymer is (methyl) acrylate copolymer.
24. bag according to claim 16 solvent-laden varnish paint compositions, it is characterised in that (methyl)
Acrylate polymer is (methyl) acrylate copolymer.
25. bag according to claim 17 solvent-laden varnish paint compositions, it is characterised in that (methyl)
Acrylate polymer is (methyl) acrylate copolymer.
Prepare according to comprising any one of claim 1-17 by mixing comprised composition for 26. 1 kinds
The method of the varnish paint compositions of solvent.
27. methods according to claim 26, it is characterised in that can (methyl) acrylate by OH official
Polymers compositions (A) mixes with other composition in addition to crosslinker component (B), and is only being applied to base material
To be mixed into containing the crosslinker component (B) of at least one organic solvent added in first 30 minutes.
28. methods according to claim 26, it is characterised in that add urea chemical combination with the form of pastel
Thing, described pastel comprises carbamide compound and polyester and/or (methyl) acrylate polymer and at least
Plant the mixture of organic solvent.
29. methods according to claim 27, it is characterised in that add urea chemical combination with the form of pastel
Thing, described pastel comprises carbamide compound and polyester and/or (methyl) acrylate polymer and at least
Plant the mixture of organic solvent.
30. according to the method any one of claim 26-29, it is characterised in that in the form of dispersion
Add polyamide, described dispersion comprise polyamide and (methyl) acrylate polymer and at least one
The mixture of organic solvent.
31. according to the method any one of claim 26-29, it is characterised in that (methyl) acrylate
Polymer is (methyl) acrylate copolymer.
32. methods according to claim 30, it is characterised in that (methyl) acrylate polymer is (first
Base) acrylate copolymer.
33. according to the solvent-laden varnish paint compositions of the bag any one of claim 1-25 at base material
On by the purposes used and during cured varnish is prepared in heat cure at a temperature of 40-190 DEG C subsequently.
34. use on base material and prepare according to the varnish paint compositions any one of claim 1-25
Varnish.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161563623P | 2011-11-25 | 2011-11-25 | |
| EP11190752 | 2011-11-25 | ||
| US61/563,623 | 2011-11-25 | ||
| EP11190752.3 | 2011-11-25 | ||
| PCT/EP2012/073392 WO2013076208A1 (en) | 2011-11-25 | 2012-11-22 | Solventborne clearcoat coating composition, process for producing it and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103987797A CN103987797A (en) | 2014-08-13 |
| CN103987797B true CN103987797B (en) | 2016-11-30 |
Family
ID=
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| WO2002044235A1 (en) * | 2000-11-30 | 2002-06-06 | Bollig & Kemper Gmbh & Co. Kg | Acrylate-based coating composition containing fluoromodified polymers |
| WO2003000807A2 (en) * | 2001-06-21 | 2003-01-03 | Basf Coatings Ag | Aqueous coating substance that can be cured physically, thermally or thermally and by using actinic radiation and use thereof |
| WO2004069884A1 (en) * | 2003-02-07 | 2004-08-19 | Basf Coatings Ag | Coating materials, method for the production thereof, and use thereof |
| WO2004111139A1 (en) * | 2003-06-12 | 2004-12-23 | Basf Coatings Ag | Coating substances that are free of covering pigments, contain solvents, and can be hardened thermally or by actinic radiation, method for the production thereof, and use of the same |
| WO2010121791A1 (en) * | 2009-04-21 | 2010-10-28 | Basf Coatings Gmbh | Water-free high-solids base paints, the production thereof and the use thereof for producing multilayer paint coatings, and multilayer paint coatings comprising a base coating made of a water-free high-solids base paint |
| EP2292675A1 (en) * | 2009-09-08 | 2011-03-09 | BYK-Chemie GmbH | Polyureas as a rheology controlling agents. |
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|---|---|---|---|---|
| US4444954A (en) * | 1982-09-30 | 1984-04-24 | The Sherwin-Williams Company | Water reducible quaternary ammonium salt containing polymers |
| WO2002044235A1 (en) * | 2000-11-30 | 2002-06-06 | Bollig & Kemper Gmbh & Co. Kg | Acrylate-based coating composition containing fluoromodified polymers |
| WO2003000807A2 (en) * | 2001-06-21 | 2003-01-03 | Basf Coatings Ag | Aqueous coating substance that can be cured physically, thermally or thermally and by using actinic radiation and use thereof |
| WO2004069884A1 (en) * | 2003-02-07 | 2004-08-19 | Basf Coatings Ag | Coating materials, method for the production thereof, and use thereof |
| WO2004111139A1 (en) * | 2003-06-12 | 2004-12-23 | Basf Coatings Ag | Coating substances that are free of covering pigments, contain solvents, and can be hardened thermally or by actinic radiation, method for the production thereof, and use of the same |
| WO2010121791A1 (en) * | 2009-04-21 | 2010-10-28 | Basf Coatings Gmbh | Water-free high-solids base paints, the production thereof and the use thereof for producing multilayer paint coatings, and multilayer paint coatings comprising a base coating made of a water-free high-solids base paint |
| EP2292675A1 (en) * | 2009-09-08 | 2011-03-09 | BYK-Chemie GmbH | Polyureas as a rheology controlling agents. |
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