CN118146709A - Double-component polyurethane varnish, preparation method thereof, paint layer and paint layer product - Google Patents
Double-component polyurethane varnish, preparation method thereof, paint layer and paint layer product Download PDFInfo
- Publication number
- CN118146709A CN118146709A CN202410334181.5A CN202410334181A CN118146709A CN 118146709 A CN118146709 A CN 118146709A CN 202410334181 A CN202410334181 A CN 202410334181A CN 118146709 A CN118146709 A CN 118146709A
- Authority
- CN
- China
- Prior art keywords
- parts
- component
- acrylic resin
- polyurethane varnish
- component polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000004972 Polyurethane varnish Substances 0.000 title claims abstract description 120
- 239000003973 paint Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 181
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 180
- 229920003180 amino resin Polymers 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 23
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 15
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 15
- 238000007665 sagging Methods 0.000 claims abstract description 11
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 26
- -1 hydroxyalkyl methacrylate Chemical compound 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 21
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical class C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 18
- 150000001735 carboxylic acids Chemical class 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- 125000005907 alkyl ester group Chemical group 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004611 light stabiliser Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 5
- 150000007974 melamines Chemical class 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 3
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 3
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 claims description 3
- VHNJXLWRTQNIPD-UHFFFAOYSA-N 3-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(O)CCOC(=O)C(C)=C VHNJXLWRTQNIPD-UHFFFAOYSA-N 0.000 claims description 3
- JRCGLALFKDKSAN-UHFFFAOYSA-N 3-hydroxybutyl prop-2-enoate Chemical compound CC(O)CCOC(=O)C=C JRCGLALFKDKSAN-UHFFFAOYSA-N 0.000 claims description 3
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 claims description 3
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 claims description 3
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 3
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 3
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 3
- 229940011051 isopropyl acetate Drugs 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 3
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims 1
- 230000003993 interaction Effects 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 130
- 230000000052 comparative effect Effects 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 13
- 238000010992 reflux Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000000010 aprotic solvent Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000012855 volatile organic compound Substances 0.000 description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 8
- 229920003270 Cymel® Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013530 defoamer Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000003678 scratch resistant effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229940124543 ultraviolet light absorber Drugs 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- 229920003275 CYMEL® 325 Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- ZKEUVTROUPQVTM-UHFFFAOYSA-N 1-pentylperoxypentane Chemical compound CCCCCOOCCCCC ZKEUVTROUPQVTM-UHFFFAOYSA-N 0.000 description 1
- IHYBDNMNEPKOEB-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 6-hydroxyhexanoate Chemical group CC(=C)C(=O)OCCOC(=O)CCCCCO IHYBDNMNEPKOEB-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- QIWOLHBPMWGIMU-UHFFFAOYSA-N 3-(2-hydroxyethyl)oxepan-2-one Chemical compound OCCC1CCCCOC1=O QIWOLHBPMWGIMU-UHFFFAOYSA-N 0.000 description 1
- LFIKCMRWRRZRAP-UHFFFAOYSA-N 3-(2-hydroxyethyl)oxepan-2-one prop-2-enoic acid Chemical compound OCCC1C(=O)OCCCC1.C(C=C)(=O)O LFIKCMRWRRZRAP-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- LBKOBSXMPMKAKL-UHFFFAOYSA-N [Li].[F].[Na].[Mg] Chemical compound [Li].[F].[Na].[Mg] LBKOBSXMPMKAKL-UHFFFAOYSA-N 0.000 description 1
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- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 1
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- 238000000937 dynamic scanning calorimetry Methods 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
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- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- NEMFQSKAPLGFIP-UHFFFAOYSA-N magnesiosodium Chemical compound [Na].[Mg] NEMFQSKAPLGFIP-UHFFFAOYSA-N 0.000 description 1
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- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical group OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 description 1
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- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
- C08G18/544—Polycondensates of aldehydes with nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application relates to a double-component polyurethane varnish, a preparation method thereof, a paint layer and a paint layer product. The two-component polyurethane varnish comprises a component A and a component B; the component A comprises the following components in parts by weight: 8-25 parts of a first acrylic resin, 36-55 parts of a second acrylic resin and 5-20 parts of an amino resin; the first acrylic resin and the second acrylic resin each contain hydroxyl groups; the weight average molecular weight Mw of the first acrylic resin is 10000-20000 daltons, and the weight average molecular weight Mw of the second acrylic resin is 2000-9000 daltons; the component B comprises the following components in parts by weight: 70-90 parts of polyisocyanate and 10-30 parts of first solvent. The two-component polyurethane varnish is further matched with amino resin through interaction of the first acrylic resin and the second acrylic resin with hydroxyl groups and different molecular weights, so that the wear resistance, sagging resistance, appearance performance and hardness of the two-component polyurethane varnish can be effectively improved, and the VOC content is low.
Description
Technical Field
The application relates to the field of paint, in particular to a double-component polyurethane varnish, a preparation method thereof, a paint layer and a paint layer product.
Background
The improvement of scratch resistance of the two-component polyurethane (2K-PUR) varnish mainly comprises the following technical routes: (1) The scratch resistance of the polyurethane coating is improved by using a polyisocyanate cross-linking agent modified by silane and other groups; (2) The scratch resistance of the polyurethane coating is improved by adopting inorganic nano silicon dioxide particles and the like in an additive mode, but the additive gradually wears out from the surface of the coating over time to cause the scratch resistance to be lost; or the scratch-resistant additive is grafted on the polymer skeleton to ensure that the scratch-resistant additive is uniformly distributed in the coating, so that the loss is minimized, but the cost of raw materials is greatly increased, and the application range of the scratch-resistant additive is limited; (3) The scratch resistance of the polyurethane coating is improved by using hyperbranched polyester resin, introducing functional monomer synthetic resin and the like. However, conventional two-component polyurethane varnishes do not combine high appearance, high hardness and high scratch resistance.
With the formal implementation of the limit of harmful substances of automobile paint GB 24409-2020, the VOC mandatory standard of the paint is further severe for the low-volatile organic compounds of the paint; according to the technical requirements of low-volatile organic compound content paint products GB/T38597-2020, VOC of double-component varnishes in automobile factories is less than or equal to 420g/L, and most of traditional double-component paints cannot be satisfied.
Therefore, there is a need for improvements over the conventional art.
Disclosure of Invention
Based on the two-component polyurethane varnish, a preparation method thereof, a paint layer and a paint layer product are provided, wherein the two-component polyurethane varnish is low in VOC content, good in appearance, high in hardness and good in scratch resistance.
The technical scheme for solving the technical problems is as follows.
The application provides a two-component polyurethane varnish, which is characterized by comprising a component A and a component B;
The component A comprises the following components in parts by weight:
8-25 parts of a first acrylic resin;
36-55 parts of a second acrylic resin; and
5-20 Parts of amino resin;
The first acrylic resin and the second acrylic resin each contain hydroxyl groups; the weight average molecular weight Mw of the first acrylic resin is 10000-20000 daltons, and the weight average molecular weight Mw of the second acrylic resin is 2000-9000 daltons;
The component B comprises the following components in parts by weight:
70-90 parts of polyisocyanate; and
10-30 Parts of a first solvent.
In some of these embodiments, the two-component polyurethane varnish satisfies at least one of the following characteristics:
The mass ratio of the first acrylic resin to the second acrylic resin is 1 (2-5);
the ratio of the mass of the amino resin to the total mass of the first acrylic resin and the second acrylic resin is 1 (6-13).
In some of these embodiments, the preparation monomers of the first acrylic resin and the second acrylic resin each independently comprise the structure of formula (I):
（Ⅰ）
wherein R 1 is H or CH 3,R2 is alkyl or cycloalkyl having 2-20 carbon atoms, and n is an integer of 1-10.
In some of these embodiments, the preparation monomers of the first acrylic resin and the second acrylic resin, in parts by mass, each independently include:
0-30 parts of hydroxyl alkyl acrylate;
10-90 parts of hydroxyalkyl methacrylate;
5-50 parts of caprolactone modified hydroxyethyl (meth) acrylate;
0-50 parts of vinyl aromatic hydrocarbon;
0-5 parts of other ethylenically unsaturated carboxylic acid; and
0-50 Parts of other alkyl esters of ethylenically unsaturated carboxylic acids.
In some of these embodiments, the two-component polyurethane varnish comprises, in parts by mass, monomers forming the first acrylic resin and the second acrylic resin, each independently comprising:
20-60 parts of hydroxyalkyl methacrylate;
5-20 parts of caprolactone modified hydroxyethyl (meth) acrylate;
10-30 parts of vinyl aromatic hydrocarbon;
0.5-2 parts of other ethylenically unsaturated carboxylic acid; and
20-30 Parts of an alkyl ester of another ethylenically unsaturated carboxylic acid.
In some of these embodiments, the two-component polyurethane varnishes each independently satisfy at least one of the following characteristics:
The hydroxyl alkyl acrylate comprises at least one of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxybutyl acrylate and 4-hydroxybutyl acrylate;
the hydroxyalkyl methacrylate comprises at least one of 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate and 4-hydroxybutyl methacrylate;
the caprolactone-modified hydroxyethyl (meth) acrylate comprises at least one of hydroxyethyl caprolactone acrylate and hydroxyethyl caprolactone methacrylate;
The vinylarenes include styrene;
The other ethylenically unsaturated carboxylic acids include acrylic monomers;
The other ethylenically unsaturated carboxylic acids include acrylic acid;
The alkyl esters of other ethylenically unsaturated carboxylic acids include alkyl acrylate monomers;
The alkyl esters of other ethylenically unsaturated carboxylic acids include at least one of n-butyl methacrylate and n-butyl acrylate.
In some embodiments, the hydroxyl value of the first acrylic resin and the second acrylic resin are respectively and independently 100 KOH/g-200 mg KOH/g, the acid value is respectively and independently 0 KOH/g-30 mg KOH/g, and the Tg value is respectively and independently-40 ℃ to 50 ℃.
In some of these embodiments, the two-component polyurethane varnish, the amino resin satisfies at least one of the following characteristics:
the amino resin comprises melamine compounds;
the amino resin includes at least one of hexamethoxymethyl melamine, tetramethoxymethyl benzoguanamine, tetramethoxymethyl urea, and butoxy/methoxy combination substituted melamine.
In some of these embodiments, the B component in the two-component polyurethane varnish satisfies at least one of the following characteristics:
the polyisocyanate includes a hexamethylene diisocyanate oligomer;
The first solvent includes at least one of acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, isobutyl acetate, 3-methoxybutyl acetate, butyl acetate, sec-butyl acetate, isopropyl acetate, ethyl 3-ethoxypropionate, methyl isobutyl ketone, methyl amyl ketone, trimethylbenzene, tetramethylbenzene, propylene glycol methyl ether acetate, toluene, xylene, ethylbenzene, diethyl carbonate, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 1, 3-dioxolane, and ethylene glycol diethyl ester.
In some embodiments, the two-component polyurethane varnish further comprises 10-50 parts of an additive in parts by weight, wherein the additive comprises at least one of anti-sagging resin, light stabilizer, defoamer, leveling agent, catalyst and second solvent.
In some embodiments, the molar ratio of hydroxyl groups in the A component to isocyanate groups in the B component in the two-component polyurethane varnish is (0.9-1.5): 1.
The second aspect of the application provides a method for preparing a two-component polyurethane varnish, which comprises the following steps:
Providing a raw material according to the components of the two-component polyurethane varnish provided in the first aspect;
mixing the raw materials corresponding to the component A to obtain the component A;
and mixing the raw materials corresponding to the component B to obtain the component B.
According to a third aspect of the present application, there is provided a paint layer, the paint layer being as a raw material of the two-component polyurethane varnish provided in the second aspect.
In a fourth aspect the present application provides a paint article comprising the paint layer provided in the third aspect.
Compared with the prior art, the two-component polyurethane varnish has the following beneficial effects:
The double-component polyurethane varnish comprises a component A and a component B, wherein the component A comprises a first acrylic resin, a second acrylic resin and an amino resin in a specific proportion, the component B comprises a polyisocyanate curing agent, and the first acrylic resin and the second acrylic resin with hydroxyl groups with different molecular weights are interacted and further matched with the amino resin, so that the wear resistance, sagging resistance, appearance performance and hardness of the double-component polyurethane varnish can be effectively improved, and the VOC content is low.
Detailed Description
Reference now will be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a further embodiment.
Accordingly, it is intended that the present invention cover such modifications and variations as fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention will be disclosed in or be apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise. The meaning of "a plurality of" means at least two, e.g., two, three, etc., unless explicitly defined otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present invention may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present invention are scaled up or down within the scope of the disclosure of the embodiments of the present invention. Specifically, the weight described in the specification of the embodiment of the invention can be mass units known in the chemical industry field such as mu g, mg, g, kg.
Except where shown or otherwise indicated in the operating examples, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, therefore, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be varied appropriately by those skilled in the art utilizing the teachings disclosed herein seeking to obtain the desired properties. The use of numerical ranges by endpoints includes all numbers subsumed within that range and any range within that range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like.
In the present application, the hydroxyl value represents the amount (milligrams, mg) of potassium hydroxide (KOH), which is equal to the molar amount of acetic acid bonded when 1g of the corresponding solid resin component is acetylated;
in the present application, the acid value means the amount (milligrams, mg) of KOH consumed for neutralizing 1g of the solid resin;
in the present application, tg values represent glass transition temperatures, determined on the basis of DIN5376 "thermal analysis-Dynamic Scanning Calorimetry (DSC)";
In the present application, the weight average molecular weight Mw is measured by gel chromatography (GPC) using polystyrene as a standard.
An embodiment of the application provides a two-component polyurethane varnish, which comprises a component A and a component B;
The component A comprises the following components in parts by weight:
8-25 parts of a first acrylic resin;
36-55 parts of a second acrylic resin; and
5-20 Parts of amino resin;
The first acrylic resin and the second acrylic resin each contain hydroxyl groups; the weight average molecular weight Mw of the first acrylic resin is 10000-20000 daltons, and the weight average molecular weight Mw of the second acrylic resin is 2000-9000 daltons;
The component B comprises the following components in parts by weight:
70-90 parts of polyisocyanate; and
10-30 Parts of a first solvent.
The double-component polyurethane varnish comprises a component A and a component B, wherein the component A comprises a first acrylic resin, a second acrylic resin and an amino resin in a specific proportion, the component B comprises a polyisocyanate curing agent, and the first acrylic resin and the second acrylic resin with hydroxyl groups with different molecular weights are interacted and further matched with the amino resin, so that the wear resistance, sagging resistance, appearance performance and hardness of the double-component polyurethane varnish can be effectively improved, and the VOC content is low.
It will be appreciated that in component a, the first acrylic resin includes, but is not limited to, 8 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 22 parts, 25 parts by weight; the second acrylic resin includes, but is not limited to, 36 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 52 parts, 55 parts; amino resins include, but are not limited to, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20; in the component B, the polyisocyanate comprises, but is not limited to, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts and 90 parts by mass; the first solvent includes, but is not limited to, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts. The following holds true for the range that any two of these point values may be made up as end values in some examples.
In some examples, the two-component polyurethane varnish comprises the following components in parts by mass:
10-20 parts of a first acrylic resin;
40-50 parts of a second acrylic resin; and
5-10 Parts of amino resin;
The component B comprises the following components in parts by weight:
75-85 parts of polyisocyanate; and
15-25 Parts of a first solvent.
In some examples, the ratio of the mass of the first acrylic resin to the mass of the second acrylic resin in the two-component polyurethane varnish is 1 (2-5).
It is understood that the mass ratio of the first acrylic resin to the second acrylic resin includes, but is not limited to, 1:2, 1:3, 1:4, 1:5.
In some examples, the ratio of the mass of the amino resin to the total mass of the first acrylic resin and the second acrylic resin in the two-component polyurethane varnish is 1 (6 to 13).
It is understood that the ratio of the mass of the amino resin to the total mass of the first acrylic resin and the second acrylic resin includes, but is not limited to, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13.
In some examples, the total mass of the first acrylic resin and the second acrylic resin in the two-component polyurethane varnish is 20% -70% of the total mass of the a-component.
It is understood that the total mass of the first acrylic resin and the second acrylic resin comprises, but is not limited to, 20%, 30%, 40%, 50%, 60%, 70% of the total mass of the a-component.
In some examples, the total mass of the first acrylic resin and the second acrylic resin in the two-component polyurethane varnish is 30% -60% of the total mass of the a-component.
It is understood that the weight average molecular weight Mw of the first acrylic resin includes, but is not limited to 10000 daltons, 11000 daltons, 12000 daltons, 13000 daltons, 14000 daltons, 15000 daltons, 16000 daltons, 17000 daltons, 18000 daltons, 19000 daltons, 20000 daltons; the weight average molecular weight Mw of the second acrylic resin includes, but is not limited to, 2000 daltons, 3000 daltons, 4000 daltons, 5000 daltons, 6000 daltons, 7000 daltons, 8000 daltons, 9000 daltons.
In some examples, the weight average molecular weight Mw of the first acrylic resin is 11000-18000 daltons and the weight average molecular weight Mw of the second acrylic resin is 3000-7000 daltons in the two-component polyurethane varnish.
In some examples, the weight average molecular weight Mw of the first acrylic resin is 12000-16000 daltons and the weight average molecular weight Mw of the second acrylic resin is 4000-7000 daltons.
In some examples, the two-component polyurethane varnish, the preparation monomers of the first acrylic resin and the second acrylic resin each independently include the following structure of formula (I):
（Ⅰ）
wherein R 1 is H or CH 3,R2 is alkyl or cycloalkyl having 2-20 carbon atoms, and n is an integer of 1-10.
It is understood that R 2 may be an alkyl or cycloalkyl group having 2 to 20 carbon atoms, meaning that the number of carbon atoms of the alkyl or cycloalkyl group includes 2, 3,4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20; n includes 1,2, 3,4,5, 6, 7, 8, 9, 10.
In some of these examples, n is 1, 2, 3, 4, or 5 in the two-component polyurethane varnish.
In some examples, the two-component polyurethane varnish comprises, in parts by mass, the preparation monomers of the first acrylic resin and the second acrylic resin, each independently comprising:
0-30 parts of hydroxyl alkyl acrylate;
10-90 parts of hydroxyalkyl methacrylate;
5-50 parts of caprolactone modified hydroxyethyl (meth) acrylate;
0-50 parts of vinyl aromatic hydrocarbon;
0-5 parts of other ethylenically unsaturated carboxylic acid; and
0-50 Parts of other alkyl esters of ethylenically unsaturated carboxylic acids.
It is understood that the hydroxyalkyl acrylates include, but are not limited to, 0,1,2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30 parts by mass; hydroxyalkyl methacrylates include, but are not limited to, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 55 parts, 60 parts, 62 parts, 68 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts; caprolactone-modified hydroxyethyl (meth) acrylate includes, but is not limited to, 5 parts, 10 parts, 15 parts, 18 parts, 20 parts, 25 parts, 28 parts, 30 parts, 35 parts, 38 parts, 40 parts, 45 parts, 48 parts, 50 parts; vinyl aromatic hydrocarbons include, but are not limited to, 0, 5, 10, 15, 18, 20, 25, 28, 30, 35, 38, 40, 45, 48, 50; other ethylenically unsaturated carboxylic acids include, but are not limited to, 0 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts; other alkyl esters of ethylenically unsaturated carboxylic acids include, but are not limited to, 0, 5, 10, 15, 18, 20, 25, 28, 30, 35, 38, 40, 45, 48, 50 parts.
In some examples, the two-component polyurethane varnish comprises, in parts by mass, the preparation monomers of the first acrylic resin and the second acrylic resin, each independently comprising:
20-60 parts of hydroxyalkyl methacrylate;
5-20 parts of caprolactone modified hydroxyethyl (meth) acrylate;
10-30 parts of vinyl aromatic hydrocarbon;
0.5-2 parts of other ethylenically unsaturated carboxylic acid; and
20-30 Parts of an alkyl ester of another ethylenically unsaturated carboxylic acid.
It is understood that the weight average molecular weights Mw of the first acrylic resin and the second acrylic resin can be controlled by blending parameters such as the ratio of each monomer, the kind of initiator, the amount of use, and the like.
It is also understood that caprolactone-modified hydroxyethyl (meth) acrylate is synthesized from caprolactone by ring opening reaction with hydroxyethyl (meth) acrylate, which has the structure of formula (I) above.
It is further understood that other ethylenically unsaturated carboxylic acids and alkyl esters of other ethylenically unsaturated carboxylic acids are different from the caprolactone-modified hydroxyethyl (meth) acrylate and vinyl aromatic hydrocarbon described above.
In some of these examples, the two-part polyurethane varnish includes at least one of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxybutyl acrylate, and 4-hydroxybutyl acrylate.
In some examples, the two-part polyurethane varnish includes at least one of 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate, and 4-hydroxybutyl methacrylate.
In some of these examples, the caprolactone-modified hydroxyethyl (meth) acrylate comprises at least one of hydroxyethyl caprolactone acrylate and hydroxyethyl caprolactone methacrylate in the two-component polyurethane varnish.
It will be appreciated that the CAS number for hydroxyethyl caprolactone acrylate is 110489-05-9, which is of formula (I) above, R 1 is H, R 2 is ethyl, and n is 1; the CAS number of the hydroxyethyl caprolactone methacrylate is 85099-10-1, the structure of the hydroxyethyl caprolactone methacrylate is the formula (I), R 1 is CH 3,R2, ethyl, and n is 1.
In some of these examples, the vinyl aromatic hydrocarbon comprises styrene in the two-component polyurethane varnish.
In some of these examples, the other ethylenically unsaturated carboxylic acid comprises an acrylic monomer in the two-component polyurethane varnish.
In some of these examples, the other ethylenically unsaturated carboxylic acid comprises acrylic acid in the two-component polyurethane varnish.
In some of these examples, the alkyl esters of other ethylenically unsaturated carboxylic acids comprise alkyl acrylate monomers in the two-component polyurethane varnish.
In some of these examples, the alkyl ester of the other ethylenically unsaturated carboxylic acid in the two-component polyurethane varnish includes at least one of n-butyl methacrylate and n-butyl acrylate.
In some examples, the hydroxyl number of the first acrylic resin and the second acrylic resin are each independently 100 KOH/g to 200 mg KOH/g.
It is understood that the hydroxyl number of the first acrylic resin and the second acrylic resin includes, but is not limited to 100 KOH/g、110 KOH/g、120 KOH/g、130 KOH/g、140 KOH/g、150 KOH/g、160 KOH/g、170 KOH/g、180 KOH/g、190 KOH/g、200 mg KOH/g.
In some examples, the hydroxyl number of the first acrylic resin and the second acrylic resin are each independently 110 KOH/g to 190 mg KOH/g.
In some examples, the hydroxyl number of the first acrylic resin and the second acrylic resin are each independently 130 KOH/g to 180 mg KOH/g.
In some examples, the acid values of the first acrylic resin and the second acrylic resin are each independently 0 KOH/g to 30 mg KOH/g in the two-component polyurethane varnish.
It is understood that the acid numbers of the first acrylic resin and the second acrylic resin include, but are not limited to, 0 KOH/g, 1 KOH/g, 5 KOH/g, 10 KOH/g, 15 KOH/g, 20 KOH/g, 25 KOH/g, 30 mg KOH/g.
In some examples, the acid values of the first acrylic resin and the second acrylic resin are each independently 0 KOH/g to 20 mg KOH/g.
In some examples, the acid values of the first acrylic resin and the second acrylic resin are each independently 0 KOH/g to 10 mg KOH/g.
In some examples, the Tg values of the first acrylic resin and the second acrylic resin are each independently-40 ℃ to 50 ℃ in the two-component polyurethane varnish.
It is understood that the Tg values of the first acrylic resin and the second acrylic resin include, but are not limited to, -40 ℃, -30 ℃, -20 ℃, -10 ℃,0 ℃,10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃.
In some examples, the Tg values of the first acrylic resin and the second acrylic resin are each independently-30 ℃ to 40 ℃ in the two-component polyurethane varnish.
In some examples, the Tg values of the first acrylic resin and the second acrylic resin are each independently-10 ℃ to 30 ℃ in the two-component polyurethane varnish.
In some of these examples, the amino resin comprises a melamine-based compound in the two-component polyurethane varnish.
In some examples, the two-component polyurethane varnish includes at least one of hexamethoxymethyl melamine, tetramethoxymethyl benzoguanamine, tetramethoxymethyl urea, and butoxy/methoxy combination substituted melamine.
In some examples, the two-component polyurethane varnish further comprises 5-30 parts by weight of a second solvent.
It is understood that the second solvent includes, but is not limited to, 5 parts, 10 parts, 20 parts, 30 parts by mass.
In some of these examples, the second solvent comprises an aprotic solvent in the two-component polyurethane varnish.
It will be appreciated that aprotic solvents are chemically inert with respect to the other components of the two-component polyurethane varnish and do not react when cured.
In some examples, the second solvent comprises at least one of an aromatic aprotic solvent, a ketone aprotic solvent, an aprotic-like solvent, an ester aprotic solvent, and an ether aprotic solvent.
In some examples, the aromatic aprotic solvent includes, but is not limited to, at least one of toluene, xylene, trimethylbenzene, solvesso 100, solentnaphtha, and Hydrsol (ARAL).
In some examples, the ketone aprotic solvent includes, but is not limited to, at least one of acetone, methyl ethyl ketone, and methyl amyl ketone.
In some examples, the ester aprotic solvent includes, but is not limited to, at least one of butyl glycol acetate, ethyl acetate, butyl acetate, amyl acetate, and ethyl ethoxypropionate.
In some examples, the ether aprotic solvent includes, but is not limited to, at least one of diethyl ether, tetrahydrofuran, and dioxane.
In some examples, the second solvent comprises ethylene glycol butyl ether acetate, ethyl acetate, and trimethylbenzene in the two-component polyurethane varnish.
In some examples, the ratio of the water content in the second solvent to the total mass of the second solvent is less than or equal to 0.5%.
It is understood that the a-component may also include additives commonly used in two-component polyurethane varnishes in the art, including but not limited to at least one of antioxidants, water scavengers (Wasserf ä nger), rheology additives, sag resins, light stabilizers, defoamers, leveling agents, catalysts and the like.
In some examples, the two-component polyurethane varnish further comprises 10-50 parts of an additive in parts by mass, wherein the additive comprises at least one of anti-sagging resin, light stabilizer, defoamer, leveling agent and catalyst.
It is understood that additives include, but are not limited to, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts by weight.
In some examples, the two-component polyurethane varnish further comprises, by mass, 5-15 parts of anti-sagging resin, 1-5 parts of light stabilizer, 0.1-1 part of defoamer, 0.1-1 part of leveling agent and 2-8 parts of catalyst.
It is understood that anti-sagging resins include, but are not limited to, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts by mass; light stabilizers include, but are not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts; defoamers include, but are not limited to, 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part; leveling agents include, but are not limited to, 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part; catalysts include, but are not limited to, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts.
It is understood that the anti-sagging resin includes, but is not limited to, at least one of crosslinked polymer particles, inorganic layered silicate (e.g., montmorillonite-type aluminum magnesium silicate, layered sodium magnesium silicate, and layered sodium magnesium fluorine lithium silicate), silica (e.g., aerosil), synthetic polymer having ionic groups and/or groups that act as an association (e.g., polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinylpyrrolidone, styrene-maleic anhydride copolymer, or ethylene-maleic anhydride copolymer, and derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates thereof); light stabilizers include, but are not limited to, at least one of ultraviolet light absorbers (UVA), hindered amine radical traps (HLSA); defoamers include, but are not limited to, at least one of silicone oils, polyacrylates, polyurethanes, polyethers, mineral oils; leveling agents include, but are not limited to, at least one of acrylic type, polyester type, silicone type; the catalyst includes, but is not limited to, sulfuric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, acetic acid, trifluoroacetic acid, phosphoric acid monoesters, phosphoric acid diesters, or at least one of the above components blocked by the corresponding amine.
In some examples, the sag resistant resin comprises at least one of Setalux 81198 SS-55 YA and Setal 82166 SS-64 in a two-component polyurethane varnish.
In some of these examples, the light stabilizer comprises at least one of Tinuvin 1130 and Tinuvin 292 in the two-component polyurethane varnish.
In some of these examples, the defoamer comprises VK DF-0301 in a two-component polyurethane varnish.
In some of these examples, the leveling agent comprises at least one of BYK 331 and BYK-3760 in the two-component polyurethane varnish.
In some of these examples, the catalyst comprises at least one of Nacure 4167 and Nacure 5528.
It is understood that the polyisocyanate includes, but is not limited to, at least one of aliphatic, alicyclic, or heterocyclic polyisocyanates, and the like.
In some of these examples, the two-part polyurethane varnish includes a Hexamethylene Diisocyanate (HDI) oligomer.
In some examples, the two-part polyurethane varnish includes at least one of HDI dimer, HDI trimer, HDI pentamer, and HDI heptamer.
It will be appreciated that the first solvent is better soluble in the polyisocyanate compound but does not react with the isocyanate.
In some examples, the two-component polyurethane varnish includes at least one of acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, isobutyl acetate, 3-methoxybutyl acetate, butyl acetate, sec-butyl acetate, isopropyl acetate, ethyl 3-ethoxypropionate, methyl isobutyl ketone, methyl amyl ketone, trimethylbenzene, tetramethylbenzene, propylene glycol methyl ether acetate, toluene, xylene, ethylbenzene, diethyl carbonate, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 1, 3-dioxolane, and ethylene glycol diethyl ester.
In some examples, the molar ratio of hydroxyl groups in the A component to isocyanate groups in the B component is (0.9-1.5): 1.
It is understood that the molar ratio of hydroxyl groups in the A component to isocyanate groups in the B component includes, but is not limited to, 0.9:1, 0.92:1, 0.95:1, 0.98:1, 1:1, 1.02:1, 1.05:1, 1.08:1, 1.1:1, 1.2:1, 1.5:1.
In some examples, the molar ratio of hydroxyl groups in the A component to isocyanate groups in the B component is (0.95-1.25): 1.
It will be appreciated that the A-component is stored separately from the B-component; when the components are mixed, the molar ratio of hydroxyl groups in the component A to isocyanate groups in the component B can be controlled by controlling the weight ratio of the component A to the component B.
In some examples, the weight ratio of the A component to the B component in the two-component polyurethane varnish is (2-5): 1.
It is understood that the weight ratio of the A component to the B component includes, but is not limited to, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1.
In some examples, the VOC is 420 g/L or less after the A component is mixed with the B component in the two-component polyurethane varnish.
The application provides a preparation method of a two-component polyurethane varnish, which comprises the following steps:
Step S10: the raw materials are provided according to the components of the two-component polyurethane varnish.
In some examples thereof, in step S10, the preparation of the first acrylic resin and the second acrylic resin each independently includes the steps of:
Adding a third solvent into a four-neck flask provided with a thermometer and a stirrer, and raising the temperature to a reflux temperature; after the reflux temperature was stabilized, the monomer forming the first acrylic resin or the second acrylic resin, the initiator, and the third solvent were mixed, and added dropwise to a four-necked flask, maintaining reflux.
After the reaction, the mixture is diluted with a fourth solvent and cooled to obtain a first acrylic resin or a second acrylic resin.
In some examples thereof, in step S10, the third solvent comprises at least one of Solvesso 100 and ethyl acetate; the fourth solvent comprises propylene glycol methyl ether acetate PMA.
Step S20: and mixing the raw materials corresponding to the component A to obtain the component A.
And mixing the first acrylic resin, the second acrylic resin and the amino resin to obtain the component A.
In some of these examples, step S20 includes the steps of:
and mixing the first acrylic resin, the second acrylic resin, the amino resin and the additive to obtain the component A.
Step S30: and mixing the raw materials corresponding to the component B to obtain the component B.
In some examples, in step S30, the polyisocyanate and the first solvent are mixed to provide the B component.
In some of these examples, in step S30, mixing is performed under nitrogen blanket.
The application provides a paint layer, wherein the paint layer is prepared from the two-component polyurethane varnish.
The application provides a preparation method of a paint layer, which comprises the steps of mixing and coating an A component and a B component by adopting the double-component polyurethane varnish, and curing to obtain the paint layer.
It will be appreciated that the application is not limited in the manner of application and is applicable in the art. Further, the manner of curing includes, but is not limited to, baking. Further, the baking temperature is 140-160 ℃. It is understood that the baking temperature includes, but is not limited to 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃.
When the component A and the component B are mixed and cured, hydroxyl groups of the first acrylic resin and the second acrylic resin in the component A react with isocyanate groups of isocyanate to generate polyurethane, and amino resin or hydroxyl groups and carboxyl groups of the acrylic resin react with each other in a polycondensation manner.
The paint layer formed by the two-component polyurethane varnish has the advantages of good appearance, high hardness and good scratch resistance.
An embodiment of the present application provides a paint layer article comprising the paint layer described above.
In some examples, the paint layer article includes, but is not limited to, an automobile.
The present application will be described in further detail with reference to the following specific embodiments, but the embodiments of the present application are not limited thereto.
The methacrylates used in the following examples and comparative examples were prepared as follows:
the preparation steps of the acrylic resin C1 are as follows:
Into a four-necked flask equipped with a thermometer and a stirrer, 45.00 parts by weight of Solvesso 100 and 15.00 parts by weight of ethyl acetate were injected, and the temperature was raised to a reflux temperature of 150 ℃. After the reflux temperature was stabilized, 30.00 parts by weight of hydroxypropyl methacrylate, 10.00 parts by weight of hydroxyethyl methacrylate, 15.00 parts by weight of hydroxyethyl caprolactone acrylate, 1.00 parts by weight of acrylic acid, 25.00 parts by weight of styrene monomer, 5.00 parts by weight of n-butyl methacrylate and 24.00 parts by weight of n-butyl acrylate, 2.60 parts by weight of an initiator (di-t-butyldtbp peroxide) and 3.00 parts by weight of Solvesso 100 were uniformly mixed in a beaker, added dropwise to the four-necked flask uniformly over 180 minutes, and then after heat preservation reflux at 150 ℃ for 90 minutes, cooled at room temperature, and the reaction was completed. The reaction product was diluted with propylene glycol methyl ether acetate PMA and cooled to 60 ℃ to give acrylic resin C1 having tg=5 ℃, ohv=170 mgKOH/g, mw=13000 daltons, av=8 mg KOH/g.
The preparation steps of the acrylic resin C2 are as follows:
Into a four-necked flask equipped with a thermometer and a stirrer, 17.50 parts by weight of Solvesso 100 and 12.00 parts by weight of ethyl acetate were injected, and the temperature was raised to a reflux temperature of 150 ℃. After the reflux temperature was stabilized, 22.00 parts by weight of hydroxypropyl methacrylate, 6.50 parts by weight of hydroxyethyl caprolactone acrylic acid, 0.65 part by weight of acrylic acid, 13.00 parts by weight of styrene monomer, 7.00 parts by weight of n-butyl methacrylate and 15.50 parts by weight of n-butyl acrylate, 3.00 parts by weight of an initiator (dtex amyl peroxide DTAP) and 3 parts by weight of Solvesso 100 were uniformly mixed in a beaker, added dropwise to the four-necked flask uniformly over 180 minutes, and then after heat preservation and reflux for 90 minutes at 150 ℃, cooled at room temperature, and the reaction was completed. The reaction product was diluted with propylene glycol methyl ether acetate PMA and cooled to 60 ℃ to give acrylic resin C2 having tg=4 ℃, ohv=150 mgKOH/g, mw=5500 daltons, av=8 mg KOH/g.
The proportions of the respective production monomers were adjusted, and an acrylic resin C3 having tg=4 ℃, ohv=140 mgKOH/g, mw=18000 daltons, av=7 mg KOH/g was produced according to the above-described method.
The proportions of the respective production monomers were adjusted, and an acrylic resin C4 having tg= -1 ℃, ohv=160 mgKOH/g, mw=3000 daltons, av=8 mg KOH/g was produced according to the above-described method.
Acrylic resin C5 was prepared as described above, with tg=5 ℃, ohv=150 mgKOH/g, mw=11000 daltons, av=6.5 mg KOH/g.
Acrylic resin C6 was prepared as described above, with tg=3 ℃, ohv=135 mgKOH/g, mw=7000 daltons, av=7.5 mg KOH/g.
The preparation steps of the acrylic resin C7 are as follows:
Into a four-necked flask equipped with a thermometer and a stirrer, 30.00 parts by weight of Solvesso 100 and 20.00 parts by weight of ethyl acetate were injected, and the temperature was raised to a reflux temperature of 150 ℃. After the reflux temperature was stabilized, 35.00 parts by weight of hydroxypropyl methacrylate, 10.00 parts by weight of hydroxyethyl acrylate, 24.00 parts by weight of isobornyl acrylate, 1.00 parts by weight of acrylic acid, 28.00 parts by weight of styrene monomer, 1.00 parts by weight of isobutyl acrylate, 6.00 parts by weight of DTAP and 5 parts by weight of Solvesso 100 were uniformly mixed in a beaker, added dropwise to the four-necked flask uniformly over 180 minutes, and then after heat preservation and reflux at 150℃for 90 minutes, the reaction was cooled at room temperature. The reaction product was diluted with propylene glycol methyl ether acetate PMA and cooled to 60 ℃ to give a hydroxy functional polyacrylic resin C7 having tg=35 ℃, ohv=140 mgKOH/g, mw=4000 daltons, av=8 mg KOH/g.
Example 1
(1) A component
Sequentially adding 10 Kg acrylic resin C1, 50 Kg acrylic resin C2, 10 Kg Cymel 325 (amino resin), 10 Kg Setal 82166 SS-64 (anti-sagging resin), 0.3 Kg VK DF-0301 (defoamer), 0.3 Kg Nacure 4167 (acid catalyst), 3 Kg Nacure 5528 (acid catalyst), 1.5 Kg Tinuvin 1130 (ultraviolet light absorber), 0.8 Kg Tinuvin 292 (light stabilizer), 0.2 Kg BYK 331 (flatting agent), 0.4 Kg BYK-3760 (flatting agent), 3 Kg n-butyl acetate and 2.5 Kg trimethylbenzene into a container with a stirrer under stirring condition, and uniformly stirring to obtain a polyurethane varnish A component; the ratio of the mass of the amino resin to the total mass of the acrylic resin C1 and the acrylic resin C2 was 1:6.
(2) Polyurethane varnish B component
And (3) sequentially adding 80Kg Desmodur N3300 (isocyanate curing agent), 10Kg n-butyl acetate and 10Kg Solvesso 100 into a container with a stirrer under the protection of nitrogen, and uniformly stirring to obtain a polyurethane varnish B component.
Example 2
(1) Polyurethane varnish A component
In a container with a stirrer, 15 Kg acrylic resin C1, 45 kg acrylic resin C2、10 Kg Cymel 238、10 kg Setalux 81198 SS-55 YA、0.3 Kg VK DF-0301、0.3 Kg Nacure 4167、3 Kg Nacure 5528、1.5 Kg Tinuvin 1130、0.8 Kg Tinuvin 292、0.2 Kg BYK 331、0.4 Kg BYK-3760, 3 Kg n-butyl acetate and 2.5 Kg trimethylbenzene are sequentially added under stirring, and the polyurethane varnish A component is obtained.
(2) Polyurethane varnish B component
And (3) sequentially adding 80 Kg Desmodur N3300, 10 Kg n-butyl acetate and 10 Kg Solvesso 100 into a container with a stirrer under the protection of nitrogen, and uniformly stirring to obtain a polyurethane varnish B component.
Example 3
(1) Polyurethane varnish A component
In a container with a stirrer, 20 Kg acrylic resin C1, 40 kg acrylic resin C2、10 Kg Cymel 238、10 kg Setal 82166 SS-64、0.3 Kg VK DF-0301、0.3 Kg Nacure 4167、3 Kg Nacure 5528、1.5 Kg Tinuvin 1130、0.8 Kg Tinuvin 292、0.2 Kg BYK 331、0.4 Kg BYK-3760 , 3 Kg n-butyl acetate and 2.5 Kg trimethylbenzene are sequentially added under stirring, and the polyurethane varnish A component is obtained.
(2) Polyurethane varnish B component
And (3) sequentially adding 60 Kg Desmodur N3300, 20 Kg Desmodur N3900, 10Kg of n-butyl acetate and 10Kg Solvesso 100 into a container with a stirrer under the protection of nitrogen, and uniformly stirring to obtain a polyurethane varnish B component.
Example 4
(1) Polyurethane varnish A component
In a container with a stirrer, 15 Kg acrylic resin C1, 45 kg acrylic resin C2、8 Kg Cymel 238、2 Kg Cymel 325、10 kg Setalux 81198 SS-55 YA、0.3 Kg VK DF-0301、0.3 Kg Nacure 4167、3Kg Nacure 5528、1.5 Kg Tinuvin 1130、0.8 Kg Tinuvin 292、0.2 Kg BYK 331、0.4 Kg BYK-3760 , 3 Kg n-butyl acetate and 2.5 Kg trimethylbenzene are sequentially added under stirring, and the polyurethane varnish A component is obtained.
(2) Polyurethane varnish B component
And (3) sequentially adding 80 Kg Desmodur N3900, 10Kg of n-butyl acetate and 10Kg Solvesso 100 into a container with a stirrer under the protection of nitrogen, and uniformly stirring to obtain a polyurethane varnish B component.
Example 5
Substantially the same as in example 1, except that in example 5, the acrylic resin C1 (mw=13000 daltons) in example 1 was replaced with an acrylic resin C3 (mw=18000 daltons) of equal mass, and the acrylic resin C2 (mw=5500 daltons) was replaced with an acrylic resin C4 (mw=3000 daltons) of equal mass.
Example 6
Substantially the same as in example 1, except that in example 6, the acrylic resin C1 (mw=13000 daltons) in example 1 was replaced with an acrylic resin C5 (mw=11000 daltons) of equal mass, and the acrylic resin C2 (mw=5500 daltons) was replaced with an acrylic resin C6 (mw=7000 daltons) of equal mass.
Example 7
Substantially the same as in example 1, except that in example 7, the addition amount of the acrylic resin C1 was 11 Kg, the addition amount of the acrylic resin C2 was 54 kg, the addition amount of the amino resin Cymel 325 was 5 Kg, and the ratio of the mass of the amino resin to the total mass of the acrylic resin C1 and the acrylic resin C2 was 13:1.
Comparative example 1
(1) Polyurethane varnish A component
In a container with a stirrer, 60 Kg acrylic resin C1、10 Kg Cymel 238、10 kg Setalux 81198 SS-55 YA、0.3 Kg VK DF-0301、0.3 Kg Nacure 4167、3 Kg Nacure 5528、1.5 Kg Tinuvin 1130、0.8 Kg Tinuvin 292、0.2 Kg BYK 331、0.4 Kg BYK-3760, 3 Kg n-butyl acetate and 2.5 Kg trimethylbenzene are sequentially added under stirring, and the mixture is stirred uniformly to obtain a polyurethane varnish A component.
(2) Polyurethane varnish B component
And (3) sequentially adding 80 Kg Desmodur N3300, 10 Kg n-butyl acetate and 10 Kg Solvesso 100 into a container with a stirrer under the protection of nitrogen, and uniformly stirring to obtain a polyurethane varnish B component.
Comparative example 2
(1) Polyurethane varnish A component
In a container with a stirrer, 25 Kg acrylic resin C1, 45 Kg acrylic resin C2、10 kg Setal 82166 SS-64、0.3 Kg VK DF-0301、0.3 Kg Nacure 4167、3 Kg Nacure 5528、1.5 Kg Tinuvin 1130、0.8 Kg Tinuvin 292、0.2 Kg BYK 331、0.4 Kg BYK-3760 , 3 Kg n-butyl acetate and 2.5 Kg trimethylbenzene are sequentially added under stirring, and the polyurethane varnish A component is obtained.
(2) Polyurethane varnish B component
And (3) sequentially adding 80 Kg Desmodur N3300, 10 Kg n-butyl acetate and 10 Kg Solvesso 100 into a container with a stirrer under the protection of nitrogen, and uniformly stirring to obtain a polyurethane varnish B component.
Comparative example 3
(1) Polyurethane varnish A component
In a container with a stirrer, 60 Kg acrylic resin C7、10 Kg Cymel 238、10 kg Setalux 81198 SS-55 YA、0.3 Kg VK DF-0301、0.3 Kg Nacure 4167、3 Kg Nacure 5528、1.5 Kg Tinuvin 1130、0.8 Kg Tinuvin 292、0.2 Kg BYK 331、0.4 Kg BYK-3760, 3 Kg n-butyl acetate and 2.5 Kg trimethylbenzene are sequentially added under stirring, and the mixture is stirred uniformly to obtain a polyurethane varnish A component.
(2) Polyurethane varnish B component
And (3) sequentially adding 80 Kg Desmodur N3300, 10K g n-butyl acetate and 10 Kg Solvesso 100 into a container with a stirrer under the protection of nitrogen, and uniformly stirring to obtain a polyurethane varnish B component.
Comparative example 4
(1) Polyurethane varnish A component
In a container with a stirrer, 60 Kg acrylic resin C2、10 Kg Cymel 325、10 kg Setalux 81198 SS-55 YA、0.3 Kg VK DF-0301、0.3 Kg Nacure 4167、3 Kg Nacure 5528、1.5 Kg Tinuvin 1130、0.8 Kg Tinuvin 292、0.2 Kg BYK 331、0.4 Kg BYK-3760, 3 Kg n-butyl acetate and 2.5 Kg trimethylbenzene are sequentially added under stirring, and the mixture is stirred uniformly to obtain a polyurethane varnish A component.
(2) Polyurethane varnish B component
And (3) sequentially adding 80 Kg Desmodur N3300, 10 Kg n-butyl acetate and 10 Kg Solvesso 100 into a container with a stirrer under the protection of nitrogen, and uniformly stirring to obtain a polyurethane varnish B component.
Comparative example 5
Substantially the same as in example 1, except that the acrylic resin C1 (mw=13000 daltons) in example 1 was replaced with an acrylic resin C6 (mw=7000 daltons) of equal mass in comparative example 5.
Comparative example 6
Substantially the same as in example 1, except that in comparative example 6, the addition amount of acrylic resin C1 was 50 Kg and the addition amount of acrylic resin C2 was 10 kg.
Comparative example 7
Substantially the same as in example 1, except that comparative example 7 was conducted to remove the B component, an amino resin was used as a curing agent.
The components and parts of the polyurethane varnishes provided in the examples and comparative examples are shown in table 1.
TABLE 1
Wherein, C1-C7 respectively refer to acrylic resin C1-acrylic resin C7, and the unit of Mw is daltons.
According to the coating mode known by the person skilled in the art, the electrophoretic ED plate is coated with the intermediate coating and the colored paint of Xiangjiang Guangxi in turn, and the varnish samples of the examples or the comparative examples are respectively coated (the component A and the component B are mixed according to the weight ratio of 3.5:1), and according to the test plate preparation and the evaluation method known by the person skilled in the art, the coating liquid parameters, the coating application property and the coating film performance are respectively evaluated.
Scratch resistance is a test for dry scratch resistance by the following method:
1. Experimental facilities and model: SDL ATLAS M238BB Model CM-5 friction color fastness meter;
2. sandpaper for experiment: siC material back adhesive sand paper with granularity of 2400 meshes and round diameter of 30 mm;
3. Experimental procedure and evaluation of results:
3.1 Marking scratch test positions and 3 positions for measuring glossiness on the test plate, wherein the positions for measuring glossiness divide the scratch test positions into 4 equal parts;
3.2 Using a glossiness meter to measure the glossiness of the mark, and recording 20 DEG glossiness G0;
3.3 Setting the wiping times to 15 times;
3.4 The sand paper is stuck to the instrument, and the sand paper is not allowed to be stuck in a skew, a wrinkling and other anomalies;
3.5 Placing the sample plate on an operation table, wherein the test surface faces upwards, fixing the sample plate by two hands, and preventing the sample plate from shaking or moving in the test process;
3.6 Starting a test, measuring the glossiness of the position of the mark for measuring the glossiness by using a glossiness meter after the test is finished, and recording 20-degree glossiness G1;
3.7 A total of three experiments were performed, and if one of the three results deviates by more than 10% from the average, the result was removed and retested. If there are 2 results that deviate from the average by 10%, the test must be re-performed.
3.8 Calculate light retention = G1/g0 x 100%
4. Other requirements are:
4.1 The panels were subjected to a temperature (23.+ -. 2) ℃ and relative humidity (50.+ -. 5)% for at least 24 hours prior to testing.
4.2 The experimental conditions were temperature (23.+ -. 2) ℃ and relative humidity (50.+ -. 5%).
4.3 Note that the experimental procedure was observed for anomalies and recorded.
4.4 The test panel surface is not allowed to have defects such as particles, scratches, etc. that affect the measurement results.
VOC: GB 38597-2009; pencil hardness: GB/T6739-2006; horizontal long-wave value L and vertical long-wave value L: BYK orange peel instrument; sag performance: GB/T9264-2012.
The test results are shown in Table 2.
TABLE 2
As can be seen from table 2, the appearance properties, hardness and scratch resistance of the polyurethane varnishes provided in each example were all better than those of the comparative examples, with the overall properties of example 1 being relatively better; in contrast, comparative example 1 was free from the addition of the low molecular weight acrylic resin C2, and the mass of the acrylic resin C1 was 60 Kg, and the C1 resin was introduced in large amounts, causing difficulty in horizontal flow, resulting in deterioration of the horizontal appearance (long wave L value); the comparative example 2 was free of amino resin, and the mass of acrylic resin C1 and acrylic resin C2 were increased by 5 Kg, respectively, and the pencil hardness thereof was significantly reduced; comparative example 3 the substitution of acrylic resin C1 and acrylic resin C2 with 60 Kg of low molecular weight acrylic resin C7 free of hydroxyethylcaprolactone acrylate monomer resulted in a significant decrease in scratch resistance, sag resistance; comparative example 4 without the addition of high molecular weight acrylic resin C1, the mass of acrylic resin C2 containing only hydroxyethylcaprolactone (meth) acrylate monomer was 60 Kg, resulting in a significant decrease in sag resistance; comparative example 5 the acrylic resin C1 of example 1 was replaced with an acrylic resin C6 of equal mass, which resulted in a significant decrease in sag resistance compared to example 1 due to a decrease in molecular weight; comparative example 6 the addition amount of acrylic resin C1 was 50 Kg and the addition amount of acrylic resin C2 was 10 kg, since C1 resin was introduced in a large amount, the sagging property was drastically improved, but the horizontal flow was difficult and the horizontal plate long wave L value was high, resulting in deterioration of the appearance of the coating film; comparative example 7 uses an amino resin as a crosslinking agent, which removes the B component containing the crosslinking group isocyanate group, compared with example 1, resulting in insufficient crosslinking reaction to cause a decrease in the hardness of the coating film, and also, due to lack of urethane bonds, resulting in insufficient chain elasticity in the molecules of the coating film to cause a decrease in scratch resistance.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. It should be understood that, based on the technical solutions provided by the present application, those skilled in the art may obtain technical solutions through logical analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent of the application should therefore be determined with reference to the appended claims, which are to be construed as in accordance with the doctrines of claim interpretation.
Claims (13)
1. A two-component polyurethane varnish is characterized by comprising a component A and a component B;
The component A comprises the following components in parts by weight:
8-25 parts of a first acrylic resin;
36-55 parts of a second acrylic resin; and
5-20 Parts of amino resin;
The first acrylic resin and the second acrylic resin each contain hydroxyl groups; the weight average molecular weight Mw of the first acrylic resin is 10000-20000 daltons, and the weight average molecular weight Mw of the second acrylic resin is 2000-9000 daltons;
The component B comprises the following components in parts by weight:
70-90 parts of polyisocyanate; and
10-30 Parts of a first solvent.
2. The two-component polyurethane varnish of claim 1, wherein the two-component polyurethane varnish satisfies at least one of the following characteristics:
The mass ratio of the first acrylic resin to the second acrylic resin is 1 (2-5);
the ratio of the mass of the amino resin to the total mass of the first acrylic resin and the second acrylic resin is 1 (6-13).
3. The two-part polyurethane varnish of claim 1, wherein the preparation monomers of the first acrylic resin and the second acrylic resin each independently comprise a structure of the following formula (I):
（Ⅰ）
wherein R 1 is H or CH 3,R2 is alkyl or cycloalkyl having 2-20 carbon atoms, and n is an integer of 1-10.
4. The two-component polyurethane varnish according to claim 1, wherein the preparation monomers of the first acrylic resin and the second acrylic resin each independently include, in parts by mass:
0-30 parts of hydroxyl alkyl acrylate;
10-90 parts of hydroxyalkyl methacrylate;
5-50 parts of caprolactone modified hydroxyethyl (meth) acrylate;
0-50 parts of vinyl aromatic hydrocarbon;
0-5 parts of other ethylenically unsaturated carboxylic acid; and
0-50 Parts of other alkyl esters of ethylenically unsaturated carboxylic acids.
5. The two-component polyurethane varnish of claim 4, wherein the two-component polyurethane varnish independently satisfies at least one of the following characteristics:
The hydroxyl alkyl acrylate comprises at least one of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxybutyl acrylate and 4-hydroxybutyl acrylate;
the hydroxyalkyl methacrylate comprises at least one of 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate and 4-hydroxybutyl methacrylate;
the caprolactone-modified hydroxyethyl (meth) acrylate comprises at least one of hydroxyethyl caprolactone acrylate and hydroxyethyl caprolactone methacrylate;
The vinylarenes include styrene;
The other ethylenically unsaturated carboxylic acids include acrylic monomers;
The other ethylenically unsaturated carboxylic acids include acrylic acid;
The alkyl esters of other ethylenically unsaturated carboxylic acids include alkyl acrylate monomers;
The alkyl esters of other ethylenically unsaturated carboxylic acids include at least one of n-butyl methacrylate and n-butyl acrylate.
6. The two-component polyurethane varnish according to claim 1, wherein the hydroxyl value of the first acrylic resin and the second acrylic resin is 100 KOH/g to 200 mg KOH/g, the acid value is 0 KOH/g to 30 mg KOH/g, and the Tg value is-40 ℃ to 50 ℃.
7. The two-component polyurethane varnish according to any one of claims 1 to 6, wherein the amino resin satisfies at least one of the following characteristics:
the amino resin comprises melamine compounds;
the amino resin includes at least one of hexamethoxymethyl melamine, tetramethoxymethyl benzoguanamine, tetramethoxymethyl urea, and butoxy/methoxy combination substituted melamine.
8. The two-component polyurethane varnish according to any one of claims 1 to 6, wherein the B component satisfies at least one of the following characteristics:
the polyisocyanate includes a hexamethylene diisocyanate oligomer;
The first solvent includes at least one of acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, isobutyl acetate, 3-methoxybutyl acetate, butyl acetate, sec-butyl acetate, isopropyl acetate, ethyl 3-ethoxypropionate, methyl isobutyl ketone, methyl amyl ketone, trimethylbenzene, tetramethylbenzene, propylene glycol methyl ether acetate, toluene, xylene, ethylbenzene, diethyl carbonate, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 1, 3-dioxolane, and ethylene glycol diethyl ester.
9. The two-component polyurethane varnish according to any one of claims 1 to 6, wherein the component a further comprises 10 to 50 parts by mass of an additive, and the additive comprises at least one of an anti-sagging resin, a light stabilizer, an antifoaming agent, a leveling agent, a catalyst and a second solvent.
10. The two-component polyurethane varnish according to claim 1 to 6, wherein the molar ratio of the hydroxyl groups in the A component to the isocyanate groups in the B component is (0.9 to 1.5): 1.
11. A method for preparing a two-component polyurethane varnish, which is characterized by comprising the following steps:
The component providing raw material of a two-component polyurethane varnish according to any one of claims 1 to 10;
mixing the raw materials corresponding to the component A to obtain the component A;
and mixing the raw materials corresponding to the component B to obtain the component B.
12. A paint layer, characterized in that the paint layer is prepared from the two-component polyurethane varnish as defined in any one of claims 1 to 10.
13. A paint article comprising the paint layer of claim 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410334181.5A CN118146709A (en) | 2024-03-22 | 2024-03-22 | Double-component polyurethane varnish, preparation method thereof, paint layer and paint layer product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410334181.5A CN118146709A (en) | 2024-03-22 | 2024-03-22 | Double-component polyurethane varnish, preparation method thereof, paint layer and paint layer product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118146709A true CN118146709A (en) | 2024-06-07 |
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ID=91284964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410334181.5A Pending CN118146709A (en) | 2024-03-22 | 2024-03-22 | Double-component polyurethane varnish, preparation method thereof, paint layer and paint layer product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118146709A (en) |
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2024
- 2024-03-22 CN CN202410334181.5A patent/CN118146709A/en active Pending
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