CN111087587A - Bifunctional polyester resin for super-weather-resistant heat transfer printing powder coating and preparation method thereof - Google Patents
Bifunctional polyester resin for super-weather-resistant heat transfer printing powder coating and preparation method thereof Download PDFInfo
- Publication number
- CN111087587A CN111087587A CN201811244394.XA CN201811244394A CN111087587A CN 111087587 A CN111087587 A CN 111087587A CN 201811244394 A CN201811244394 A CN 201811244394A CN 111087587 A CN111087587 A CN 111087587A
- Authority
- CN
- China
- Prior art keywords
- polyester resin
- powder coating
- heat transfer
- koh
- transfer powder
- 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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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 89
- 239000004645 polyester resin Substances 0.000 title claims abstract description 89
- 239000000843 powder Substances 0.000 title claims abstract description 74
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000010023 transfer printing Methods 0.000 title description 7
- 229920000728 polyester Polymers 0.000 claims abstract description 62
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002253 acid Substances 0.000 claims abstract description 44
- 238000012546 transfer Methods 0.000 claims abstract description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 239000008199 coating composition Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000005886 esterification reaction Methods 0.000 claims description 33
- 238000006068 polycondensation reaction Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 230000032050 esterification Effects 0.000 claims description 31
- 229920005862 polyol Polymers 0.000 claims description 29
- 150000003077 polyols Chemical class 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000006085 branching agent Substances 0.000 claims description 14
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 12
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 230000014759 maintenance of location Effects 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000007519 polyprotic acids Polymers 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 23
- 239000000178 monomer Substances 0.000 description 21
- 239000003963 antioxidant agent Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 230000003078 antioxidant effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 9
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 238000006136 alcoholysis reaction Methods 0.000 description 5
- -1 hydroxyl-carboxyl Chemical group 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- ZBSOGTZYMVJKTF-UHFFFAOYSA-K 4-trichlorostannylbutane-1,1-diol Chemical compound OC(O)CCC[Sn](Cl)(Cl)Cl ZBSOGTZYMVJKTF-UHFFFAOYSA-K 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- KCFOLUKWAIAKFB-UHFFFAOYSA-N CCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Br Chemical compound CCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Br KCFOLUKWAIAKFB-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- UYDJAHJCGZTTHB-UHFFFAOYSA-N cyclopentane-1,1-diol Chemical compound OC1(O)CCCC1 UYDJAHJCGZTTHB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a bifunctional polyester resin for an ultra-weather-resistant heat transfer powder coating and a preparation method thereof, wherein the bifunctional polyester resin has an acid value of at least 10 and less than 28mg KOH/g polyester and a hydroxyl value of 10 to 40mg KOH/g polyester, and at least 88 mol% of polybasic acid structural units in the bifunctional polyester resin are derived from isophthalic acid. The invention also relates to an ultra-weatherable heat transfer powder coating comprising the difunctional polyester resin and a coated article.
Description
Technical Field
The invention relates to bifunctional polyester resin for super weather-proof heat transfer printing powder coating and a preparation method thereof. The invention also relates to coating compositions comprising the difunctional polyester resins of the invention and coated articles.
Background
In recent years, weather-resistant powder coatings have become more and more popular in the market. At present, the weather-resistant powder coating applied to metal materials is mainly polyester and polyurethane type powder coating. Although the weather-resistant polyester resin powder coating currently known has certain weather resistance, the weather resistance still cannot meet the outdoor high weather resistance coating requirement. Furthermore, the existing weather-resistant polyester resins are generally carboxyl-terminated polyesters, which have a high acid value.
With the development of society, people seek more colorful appearance patterns while seeking powder coatings with higher weather resistance. The requirement can be well met by adopting a thermal transfer printing technology. In the powder coating thermal transfer technique, a powder coating is sprayed on a metal material and cured to form a film, and then a grained paper is attached to the coating film to thermally transfer the pattern of the grained paper to the coating film. After the step of thermal transfer printing, the wood grain effect on the coating film is clear and vivid. The transfer image obtained by the heat transfer technology has bright color, clear and vivid pattern and rich layers. The transfer effect is comparable to that of a printed matter.
Therefore, there is a need in the industry for super weatherable polyester powder coatings with both higher weatherability and thermal transfer properties.
Disclosure of Invention
One aspect of the invention provides a bifunctional polyester resin for an ultra-weather-resistant heat transfer printing powder coating. The difunctional polyester resin of the present invention has an acid number of at least 10 and less than 28mg KOH/g polyester and a hydroxyl number of from 10 to 40mg KOH/g polyester. In the difunctional polyester resin of the present invention, at least 88 mole percent of the polyacid structural units are derived from isophthalic acid.
Another aspect of the present invention provides a method for preparing a difunctional polyester resin for an ultraweatherable heat transfer powder coating, comprising heating a reaction mixture containing a polyol component, a polyacid component, a branching agent, and optionally an esterification catalyst, to effect a reaction until a product within a given acid and hydroxyl value range is obtained, wherein the reaction mixture comprises: 28.0 to 50.0 wt.% of a polyol component, 45.0 to 70.0 wt.% of a polyacid component, wherein at least 88 mole% of the polyacid component is isophthalic acid, 0.5 to 4.7 wt.% of a branching agent, 0 to 0.3 wt.% of an esterification catalyst, said wt.% being based on the total weight of all material charges.
Another aspect of the present invention provides an ultraweatherable heat transfer powder coating composition comprising the difunctional polyester resin described herein and a curing agent TGIC and a blocked isocyanate, and optionally additives.
The present invention also provides a coated article comprising a substrate having coated thereon a difunctional polyester resin or powder coating composition according to the present invention.
The inventors have surprisingly found that the difunctional polyester resins of the present invention are capable of significantly improving the weatherability of powder coatings. Moreover, powder coating compositions formulated with the difunctional polyester resins of the present invention also provide good thermal transfer performance and/or leveling. The bifunctional polyester resin can be used for preparing powder coating, and the dosage of the curing agent can be reduced, so that the requirement of the market on reducing the dosage of the toxic curing agent is well met.
The details of one or more embodiments of the invention are set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and from the claims.
Definition of
As used herein, unless otherwise indicated, "a", "an", "the", "at least one" and "one or more" and instances where no numerical word is used, are used interchangeably. Thus, for example, a coating composition that includes "a" pigment can be interpreted to mean that "one or more" pigments are included in the coating composition. The use of a singular form herein is intended to include the plural form as well, unless the context clearly indicates otherwise.
Where a composition is described as including or comprising a particular component, optional components not contemplated by the present invention are not contemplated as being excluded from the composition and it is contemplated that the composition may consist of or consist of the recited component or where a method is described as including or comprising a particular process step, optional process steps not contemplated by the present invention are not contemplated as being excluded from the method and it is contemplated that the method may consist of or consist of the recited process step.
The term "polyacid structural unit" when used in reference to a difunctional polyester refers to the portion of the structural unit used to form a part of the repeating unit of the polyester resin and formed from the polyacid component. In general, the repeating unit of the polyester resin is composed of a polybasic acid structural unit and a polyhydric alcohol structural unit.
In the context of the present invention, the term "gloss retention" is an effective parameter for measuring the weatherability of a coating. According to the invention, the gloss retention of a coating is the ratio of the gloss at 60 ℃ after a certain period of time in the QUV-B ageing test at 50 ℃ for 4 hours under UV light and at 40 ℃ for 4 hours under the water vapor cycle test at 60 ℃ of the initially formed coating.
Unless otherwise indicated, the glass transition temperature (Tg) of a polyester resin is the measured Tg of the resin. According to the invention, the glass transition temperature of the polyesters is measured according to ISO11357 using DSC differential scanning calorimetry.
"viscosity" or equivalently "melt viscosity" herein means the melt viscosity (in pa.s) at 160 ℃. Viscosity measurements were performed on a Brookfield CAP 2000+ H Viscometer at 160 ℃. The shear rate applied was 21s-1And a 19.05mm rotor (spindle) (conical rotor CAP-S-05(19.05mm,1.8 °)) was used.
By "composition" is meant herein: combinations and/or mixtures of different chemicals and/or components, which form an integral whole.
By "powder" is meant herein: a solid substance which is substantially dry at room temperature and atmospheric pressure, reduced to a fine, loose particulate state, wherein the maximum particle size of the individual particles at 23 ℃ and atmospheric pressure is preferably at most 200 μm, more preferably at most 180 μm, even more preferably at most 160 μm, most preferably at most 150 μm, in particular at most 140 μm, more in particular at most 130 μm, most in particular at most 120 μm, such as at most 110 μm, such as at most 100 μm, such as at most 90 μm; the minimum particle size of the individual particles at 23 ℃ and atmospheric pressure is preferably at least 10 μm, more preferably at least 15 μm, even more preferably at least 20 μm, most preferably at least 25 μm, in particular at least 30 μm, more in particular at least 35 μm, most in particular at least 40 μm, such as at least 45 μm, such as at least 50 μm, such as at least 60 μm, such as at least 70 μm. A particle is defined as a small object as follows: a) having an average linear dimension as described herein below and b) behaves as a whole in terms of its transport and performance. The method used to measure the particle size of the powder coating composition of the present invention is sieve analysis.
"curing" means herein: the process of becoming "fixed" to form an irreversible crosslinked network (a so-called "cured form" or "cured composition") in which the material no longer flows, melts or dissolves. The terms "cure" and "crosslinking" are used interchangeably herein.
By "powder coating" is meant herein a cured powder coating composition in the form of a coating. The powder coating is obtained after curing the powder coating composition.
In the present invention, the numerical ranges defined by endpoints include all any number within the range, for example, a range of 1 to 5 encompasses the numbers 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like. Moreover, the disclosed numerical ranges include all sub-ranges within the broader range, for example, a range of 1 to 5 includes sub-ranges of 1 to 4, 1.5 to 4.5, 1 to 2, etc.
The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
Detailed Description
Bifunctional polyester resin
In one aspect, the invention provides a bifunctional polyester resin for an ultra-weather-resistant heat transfer printing powder coating. The bifunctional polyester resin of the invention is hydroxyl-carboxyl bifunctional polyester resin. By hydroxy-carboxyl difunctional polyester resin is meant that the polyester resin not only contains hydroxyl functional groups with a certain reactivity, but also carboxyl functional groups with a certain reactivity, the reactivity being characterized by a hydroxyl value and an acid value. Polyester resins having generally lower hydroxyl numbers (e.g., less than 10mg KOH/g) or lower acid numbers (e.g., less than 10mg KOH/g) cannot be considered hydroxyl-reactive or carboxyl-reactive.
The carboxyl functional group and hydroxyl functional group content of the resin can be determined by methods well known in the art. For example, the acid value and the hydroxyl value of the polyester resin are measured by KOH titration. The acid number of the polyester can be determined using ISO 2114. The hydroxyl number of the polyester can be determined using ISO 2554.
In some embodiments, the difunctional polyester resin of the present invention has an acid number of at least 10mg KOH/g polyester. The difunctional polyester resin of the present invention has an acid number of less than 28mg KOH/g polyester. In a preferred embodiment, the difunctional polyester resin of the present invention has an acid number of from 10 to 27mg KOH/g polyester, more preferably from 12 to 26mg KOH/g polyester. For example, the bifunctional polyester resin of the present invention has an acid value of 10mg KOH/g polyester, 12mg KOH/g polyester, 14mg KOH/g polyester, 15mg KOH/g polyester, 16mg KOH/g polyester, 17mg KOH/g polyester, 18mg KOH/g polyester, 19mg KOH/g polyester, 20mg KOH/g polyester, 21mg KOH/g polyester, 22mg KOH/g polyester, 23mg KOH/g polyester, 24mg KOH/g polyester, 25mg KOH/g polyester, 26mg KOH/g polyester, 27mg KOH/g polyester.
In some embodiments, the difunctional polyester resin of the present invention has a hydroxyl number of 10 to 40mg KOH/g polyester. In a preferred embodiment, the difunctional polyester resin of the present invention has a hydroxyl number of from 10 to 35mg KOH/g polyester, more preferably from 10 to 32mg KOH/g polyester, even more preferably from 12 to 30mg KOH/g polyester. For example, the bifunctional polyester resin of the present invention has a hydroxyl value of 11mg KOH/g polyester, 14mg KOH/g polyester, 16mg KOH/g polyester, 17mg KOH/g polyester, 18mg KOH/g polyester, 19mg KOH/g polyester, 20mg KOH/g polyester, 21mg KOH/g polyester, 22mg KOH/g polyester, 23mg KOH/g polyester, 24mg KOH/g polyester, 25mg KOH/g polyester, 26mg KOH/g polyester, 27mg KOH/g polyester, 28mg KOH/g polyester.
In some embodiments, a substantial portion of the polyacid structural units in the difunctional polyester resins of the present invention are derived from isophthalic acid. Preferably, at least 88 mole percent of the polyacid structural units are derived from isophthalic acid. More preferably, at least 90 mole percent of the polyacid structural units are derived from isophthalic acid. Even more preferably, at least 92 mole percent of the polyacid structural units are derived from isophthalic acid. For example, at least 91 mole%, at least 93 mole%, at least 95 mole%, 96 mole%, 98 mole% of the polyacid structural units are derived from isophthalic acid. Most preferably, all (100 mole%) of the polyacid structural units in the difunctional polyester resin are derived from isophthalic acid.
In some embodiments, the difunctional polyester resins of the present invention have a glass transition temperature, Tg, in the range of 40 to 80 ℃. Preferably, the Tg is in the range of 45-75 deg.C, more preferably in the range of 50-65 deg.C. In one exemplary embodiment, Tg can be determined by Differential Scanning Calorimetry (DSC) using a scan rate of 5 ℃/min.
In some embodiments, the difunctional polyester resin of the present invention has a melt viscosity in the range of 20 to 90 pas at 160 ℃. Preferably, the melt viscosity at 160 ℃ is in the range of 25-80 pas, such as 28, 30, 35, 40, 50, 60, 70 pas.
While several prior patent applications have mentioned the use of isophthalic acid to improve weatherability, none of the patents disclose or teach the use of isophthalic acid to form a polyester that is synthesized with most or all of the polyacid components to achieve the weatherability of the present invention. Moreover, the powder coating compositions reported in the prior patents, after film formation, reach a gloss retention of only up to 88% for 500 hours in the QUV-B ageing test, which clearly does not meet the weather resistance requirements of current coatings. The inventors have surprisingly found that with the present hydroxy-carboxyl difunctional polyester resin having an acid number of at least 10 and less than 28mg KOH/g polyester and a hydroxyl number of from 10 to 40mg KOH/g polyester and at least 88 mole% of the polyacid structural units in the difunctional polyester resin are derived from isophthalic acid, the powder coatings formulated to form are capable of achieving ultra-high weatherability. For example, the light retention at 800-. It is particularly important that the difunctional polyester resin of the present invention results in coatings that maintain ultra-high weatherability for extended periods of time. For example, coatings comprising the polyester resins of the present invention have a gloss retention of at least 88%, even at least 90%, as measured in a QUV-B weathering test for 600 hours. Such further improvement in weatherability would not be expected by one of ordinary skill in the art.
Preparation method of bifunctional polyester resin
The difunctional polyester resins described above may be prepared by a variety of methods. For example, one exemplary method of preparation includes the steps of: mixing and heating a polyol, a polyacid, a branching agent, and optionally an esterification catalyst to effect an esterification polycondensation reaction; then adding an acidolysis agent or an alcoholysis agent under the condition of controlling the reaction system at a given temperature to perform further esterification reaction; controlling the acid value within a given range, and then carrying out vacuum polycondensation until a resin product within a predetermined range of acid value and hydroxyl value is obtained; optionally, additives such as antioxidants are added.
Accordingly, another aspect of the present invention also relates to a process for the preparation of a difunctional polyester resin according to the present invention comprising:
reacting the reaction mixture until a product within the given acid and hydroxyl value ranges is obtained;
wherein the reaction mixture comprises:
i)28.0 to 50.0 wt.% of a polyol component,
ii)45.0 to 70.0 wt% of a polyacid component, wherein at least 88 mole% of the polyacid component is isophthalic acid,
iii)0.5 to 4.7% by weight of a branching agent, and
iv)0 to 0.3% by weight of an esterification catalyst,
the weight percents are based on the total weight of all material charges.
In the process of the present invention, mainly esterification polycondensation reactions, further esterification (alcoholysis/acidolysis) reactions and vacuum polycondensation reactions are involved. Generally, in the esterification polycondensation reaction, a polybasic acid component and a polyol component are mixed and heated to perform the reaction. In the further esterification reaction, an alcoholysis agent or an acid hydrolysis agent is added to the reaction mixture to control the acid value within a suitable range. Subsequently, the polycondensation was carried out while keeping the reaction mixture under vacuum until the acid value and the hydroxyl value were within the set ranges.
In the method of the present invention, in order to obtain the objective hydroxycarboxyl-difunctional polyester resin, it is necessary to control the amount ratio of the components of the reaction mixture.
In some preferred embodiments, the amount of polyol component is 30.0 to 45.0 wt.%, more preferably 32.0 to 42.0 wt.%, even more preferably 34.0 to 40.0 wt.%, based on the total weight of all material charges. For example, the amount of polyol component is 35.0 wt.%, 36.0 wt.%, 37.0 wt.%, 38.0 wt.%, or 39.0 wt.%, based on the total weight of all material charges.
In the process of the present invention, the polyol is preferably a diol. Examples of diols include ethylene glycol, monoethylene glycol, propylene glycol, methyl propylene glycol, cyclopentanediol, neopentyl glycol, and 1, 4-cyclohexanedimethanol, and any combination thereof. Preferably, the polyol is neopentyl glycol, 1, 4-cyclohexanedimethanol or a combination thereof. Particularly preferably, the polyol is neopentyl glycol. One or more of the polyols described hereinabove may also be used as alcoholysis agent.
In some preferred embodiments, the amount of polyacid component is from 48.0 to 68.0 weight percent, more preferably from 50.0 to 65.0 weight percent, even more preferably from 53.0 to 63.0 weight percent, based on the total weight of all material charges. For example, the amount of polyacid component is 46.0, 52.0, 54.0, 56.0, 57, 58.0, 59.0, 60.0, 61.0, 62.0, 64.0, or 66.0 weight percent based on the total weight of all material charges.
In the method of the present invention, examples of the polybasic acid include isophthalic acid, terephthalic acid, phthalic anhydride, adipic acid, sebacic acid, trimellitic anhydride, and combinations thereof. To obtain better weatherability, at least 88 mole%, preferably at least 90 mole%, more preferably 92 mole%, even more preferably 95 mole%, at least 99 mole% of the polyacid component is isophthalic acid. Most preferably, isophthalic acid (i.e., essentially 100 mole% of the polyacid component) is employed entirely as the polyacid component. Preferably, one or more of the polyacids described above can also be used as acidolysis agent.
In the process of the present invention, when more than one polyacid is used, each polyacid may be added in different ways and orders. In some embodiments, a homogeneous mixture of two or more polyacids may be added. In other embodiments, two or more separate polyacids may be added simultaneously. In some embodiments, the isophthalic acid may be added first, followed by the addition of additional polyacid at a different stage.
In some preferred embodiments, the amount of branching agent is 1.0 to 4.0 wt%, preferably 1.5 to 3.8 wt%, more preferably 2.0 to 3.5 wt%, based on the total weight of all material charges. For example, the amount of branching agent is 2.2 wt.%, 2.4 wt.%, 2.6 wt.%, 2.8 wt.%, 3.0 wt.%, or 3.2 wt.%, based on the total weight of all material charges. Examples of branching agents include trimethylolpropane, trimethylolethane, ditrimethylolpropane and pentaerythritol and any combination thereof. Preferably, trimethylolpropane is used as branching agent. Trimethylolpropane may also be used as the alcoholysis agent.
In the method of the present invention, the branching agent may be added to the reaction system before the start of the polycondensation reaction, or may be added to the reaction system during or after the polycondensation reaction. In some embodiments, the branching agent may be mixed with the polyol component prior to addition of the polyacid component. In other embodiments, the branching agent may be added after the esterification polycondensation reaction of the polyacid component and the polyol component.
In some embodiments, the reaction system may comprise an esterification catalyst. The preferable esterification catalyst is tetrabutyl titanate or a tin catalyst, and is selected from one or more of butylstannoic acid, dibutyltin oxide, tributyltin oxide, dihydroxybutyltin chloride and stannous oxalate. The amount of esterification catalyst is in the range of about 0 to 0.2 wt.%, preferably in the range of about 0.01 wt.% to 0.15 wt.%, more preferably in the range of about 0.02 wt.% to 0.12 wt.%, based on the total weight of all material charges. For example, the amount of esterification catalyst is about 0.03 wt.%, about 0.04 wt.%, about 0.05 wt.%, 0.08 wt.%, or 0.1 wt.%, based on the total weight of all material charges.
In some embodiments, the reaction system may comprise antioxidant a. The antioxidant A is selected from the group consisting of hindered phenol antioxidants and phosphite antioxidants. In a preferred embodiment, pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (2, 4-di-t-butylphenyl) phosphite or a combination thereof is used as antioxidant A. The amount of antioxidant A can vary within wide limits. The amount of antioxidant A can be determined reasonably by the person skilled in the art according to the actual requirements. For example, the amount of antioxidant a may be from 0.01 to 0.3 wt%, preferably from 0.05 to 0.2 wt%, for example about 0.08 wt%, 0.1 wt%, 0.15 wt%, relative to the total weight of all material charges.
In some embodiments, the method of the present invention may further comprise the step of adding an additive. Additives for weather-resistant polyester resins are known in the art, such as antioxidant B, curing accelerators, and the like.
In a preferred embodiment, 2, 6-di-tert-butyl-4-methylphenol, 2' -methylene-bis (4-methyl-6-tert-butylphenol), pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (2, 4-di-tert-butylphenyl) phosphite or combinations thereof are used as antioxidant B, for example, Irganox1010 and/or SONGNOX6180 can be used in a wide range of amounts.
Examples of cure accelerators include the use of triphenyl phosphine bromide, methyl triphenyl phosphine bromide, ethyl triphenyl phosphine bromide, and combinations thereof. The amount of curing accelerator may be 0.01 to 0.2 wt%, preferably 0.05 to 0.1 wt%, for example about 0.08 wt%, relative to the total weight of all material charges.
In some preferred embodiments, the reaction in the present invention comprises an esterification polycondensation reaction conducted at a temperature in the range of 240 ℃ to 260 ℃. Preferably, the esterification polycondensation is conducted at a temperature in the range of 245 ℃ and 255 ℃. More preferably, the esterification polycondensation is conducted at a temperature of about 250 ℃.
In some preferred embodiments, the reaction in the present invention comprises a vacuum polycondensation reaction conducted at a temperature in the range of 220-240 ℃. Preferably, the vacuum polycondensation is conducted at a temperature in the range of 225-. More preferably, the vacuum polycondensation is conducted at a temperature of about 230 ℃. Preferably, the time of vacuum polycondensation may be controlled so that a polyester resin having a desired acid value and/or hydroxyl value is obtained.
The bifunctional polyester resin synthesized by the method can be directly used for preparing an ultra-weather-resistant thermal transfer powder coating composition.
Powder coating composition
Another aspect of the present invention provides an ultraweatherable heat transfer powder coating composition comprising the difunctional polyester resin described herein and a curing agent, and optionally additives.
The amount of difunctional polyester resin is 40 to 70 weight percent based on the total weight of the ultra weatherable heat transfer powder coating composition. Preferably, the amount of difunctional polyester resin is 45 to 65 wt-%, more preferably 50 to 60 wt-%, such as 48 wt-%, 52 wt-%, 53 wt-%, 54 wt-%, 55 wt-% or 58 wt-%, based on the total weight of the powder coating composition.
In the polyester type powder coating system, examples of the curing agent mainly include triglycidyl isocyanurate (TGIC), blocked isocyanate, hydroxyalkylamide (Primid), polyepoxy compound, amino resin, tetramethoxyglycoluril, and the like.
The inventors have found that better coating results (e.g. best levelling) can be obtained with TGIC and blocked isocyanates as curing agents compared to other curing agents. Thus, in some preferred embodiments, TGIC and blocked isocyanate are employed as curing agents. An example of a blocked isocyanate is B1530 (caprolactam blocked polyisocyanate). In a particularly preferred embodiment, TGIC and B1530 are used as curing agents.
The amount of TGIC is 0.5 to 10 wt%, preferably 0.08 to 8 wt%, more preferably 1 to 6 wt%, based on the total weight of the ultra weatherable heat transfer powder coating composition. For example, the amount of TGIC is 1.2 wt.%, 1.5 wt.%, 1.8 wt.%, 2.0 wt.%, or 2.5 wt.%, based on the total weight of the powder coating composition.
The amount of blocked isocyanate is 1 to 15 wt%, preferably 2 to 10 wt%, more preferably 3 to 8 wt%, based on the total weight of the super weatherable heat transfer powder coating composition. For example, the amount of blocked isocyanate is 4, 4.5, 5, 5.5, or 6 weight percent based on the total weight of the powder coating composition.
In some embodiments, the ultraweatherable thermal transfer powder coating compositions of the present invention may further comprise one or more additives. Examples of additives include, but are not limited to, pigments, fillers, adjuvants, and any combination thereof. The person skilled in the art will be able to select suitable additives and amounts thereof according to the actual requirements.
Suitable pigments include inorganic pigments such as titanium dioxide, zinc sulfide, barium sulfate, calcium carbonate, iron oxide, carbon black, and chromium oxide; and organic pigments such as azo compounds, phthalocyanine blue and phthalocyanine green. The amount of pigment used can vary within wide limits and can be adjusted to the actual requirements. For example, the pigment is used in an amount of 0 to 50 wt%, preferably 10 to 45 wt%, more preferably 20 to 40 wt%, e.g., 25 wt%, 30 wt%, 35 wt%.
Suitable fillers include, for example, metal oxides, silicates, carbonates, and sulfates. Suitable examples of fillers include, but are not limited to, barium sulfate, kaolin, mica powder, and silica powder.
Examples of suitable auxiliaries include degassing agents, leveling agents, matting agents and stabilizers and combinations thereof. A suitable example of a degassing agent is benzoin. Preferably, a leveling agent may be used to improve the leveling of the coating composition. Examples of leveling agents include, but are not limited to, the leveling agent GLP503/588 from Ningbo south sea, the leveling agent Modaflow Powder III/2000 from Konno, the leveling agent PV88/P67 from Worlee-chemie, and the like.
The skilled person will be able to determine the kind of auxiliaries and their amounts, depending on the desired product properties (e.g. coating colour, hardness, roughness, etc.). The amount of auxiliaries can be varied within wide limits and is adjusted according to the actual requirements. In some exemplary embodiments, the adjuvant is used in an amount of 0 to 10 wt%, preferably 0.5 to 8 wt%, more preferably 0.8 to 5 wt%, for example 1 wt%, 1.5 wt%, 2 wt%, 3 wt%, or 5 wt%.
The powder coating composition according to the invention may be applied to a suitable substrate in any suitable manner. Suitable coating methods include, but are not limited to, electrostatic coating, fluidized bed coating, electrophoretic coating, and hot melt spray coating.
Coated articles
The present invention also provides a coated article comprising a substrate having coated thereon a powder coating composition formulated with the difunctional polyester resin of the present invention. Examples of suitable substrates include metals, such as steel, cast iron, aluminum, other alloys; glass; a ceramic; wood; a brick block; and combinations thereof. The difunctional polyester resin and powder coating compositions of the present invention are particularly suitable for coating metal substrates, more preferably aluminum materials.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available and can be used directly without further treatment.
Test method
Table 1: the properties of the resin or coating are measured in the present invention using the methods shown in the following table.
Table 2: the materials used
| Material | Suppliers of goods |
| Neopentyl glycol | Sigma-Aldrich |
| Trimethylolpropane | Sigma-Aldrich |
| Isophthalic acid | Sigma-Aldrich |
| Adipic acid | Sigma-Aldrich |
| TGIC (triglycidyl isocyanurate) | Sigma-Aldrich |
| B1530 (caprolactam blocked polyisocyanate) | Winning and creating specialty Chemicals (Shanghai) Co., Ltd |
| Titanium white powder | Kemu chemical (Shanghai) Co Ltd |
| Barium sulfate | Shahar Ben chemical (Shanghai) Co., Ltd |
| Leveling agent | Sigma-Aldrich |
| Benzoinum | Sigma-Aldrich |
| Butyl Stannoic acid (catalyst) | Sigma-Aldrich |
| Pentaerythritol diphosphite | Sigma-Aldrich |
| Antioxidant agent | Sigma-Aldrich |
Synthesis examples:
difunctional polyester resin 1
1903.6 g of neopentyl glycol, 123.7 g of trimethylolpropane, 2.25 g of catalyst butyl stannoic acid and 3.83 g of pentaerythritol diphosphite are added into a 6L reactor under nitrogen environment, the temperature is raised and heated to about 150 ℃, 2943 g of isophthalic acid monomer is added after the polyol monomer in the reactor is observed to be completely molten, and the mixture is stirred uniformly. Heating to 250 deg.c, esterification and polycondensation of polyol and polybasic acid monomer, and maintaining the acid value of the reaction system below 15 mgKOH/g. The heating was stopped, the temperature of the reaction system was controlled to 205 ℃ and 225.8 g of adipic acid was added for further esterification. The acid value was controlled to be lower than 35mg KOH/g, and then polycondensation was carried out in vacuo until the acid value and the hydroxyl value were within the set ranges. Stopping heating, reducing the temperature of the reaction system from 205 ℃ to 195 ℃, then adding 4.5 g of antioxidant, mixing for 30 minutes, and discharging to obtain the resin 1.
Difunctional polyester resin 2
1894 g of neopentyl glycol, 127.6 g of trimethylolpropane, 2.25 g of catalyst butyl stannoic acid and 3.83 g of pentaerythritol diphosphite are added into a 6L reactor under nitrogen environment, the temperature is raised and heated to about 150 ℃, after the polyol monomer in the reactor is observed to be completely melted, 3036 g of isophthalic acid monomer is added, and the mixture is stirred uniformly. Heating to 250 ℃, carrying out esterification polycondensation reaction on the polyhydric alcohol and the polybasic acid monomer under the reaction condition, and keeping the temperature until the acid value of the reaction system is lower than 20mg KOH/g. The heating was stopped, the temperature of the reaction system was controlled to 205 ℃ and 137 g of adipic acid was added for further esterification. The acid value was controlled to be lower than 30mg KOH/g, and then polycondensation was carried out in vacuo until the acid value and the hydroxyl value were within the set ranges. Stopping heating, reducing the temperature of the reaction system from 205 ℃ to 195 ℃, then adding 4.5 g of antioxidant, mixing for 30 minutes, and discharging to obtain the resin 2.
Difunctional polyester resin 3
1889 g of neopentyl glycol, 129.8 g of trimethylolpropane, 2.25 g of catalyst butyl stannoic acid and 3.83 g of pentaerythritol diphosphite are added into a 6-liter reactor under nitrogen environment, the temperature is raised and heated to about 150 ℃, 3089 g of isophthalic acid monomer is added after the polyol monomer in the reactor is observed to be completely melted, and the mixture is stirred uniformly. Heating to 250 ℃, carrying out esterification polycondensation reaction on the polyhydric alcohol and the polybasic acid monomer under the reaction condition, and keeping the temperature until the acid value of the reaction system is lower than 20mg KOH/g. The heating was stopped, the temperature of the reaction system was controlled to 205 ℃ and 86 g of adipic acid was added for further esterification. The acid value was controlled to be lower than 30mg KOH/g, and then polycondensation was carried out in vacuo until the acid value and the hydroxyl value were within the set ranges. Stopping heating, reducing the temperature of the reaction system from 205 ℃ to 195 ℃, then adding 4.5 g of antioxidant, mixing for 30 minutes, and discharging to obtain the resin 3.
Difunctional polyester resin 4
1884 g of neopentyl glycol, 2.25 g of a catalyst butyl stannic acid and 3.83 g of pentaerythritol diphosphite are added into a 6L reactor under nitrogen atmosphere, the temperature is raised and heated to about 150 ℃, 3179 g of isophthalic acid monomer is added after the polyol monomer in the reactor is observed to be completely melted, and the mixture is stirred uniformly. Heating to 250 deg.c, esterification and polycondensation of polyol and polybasic acid monomer, and maintaining the acid value of the reaction system below 50mg KOH/g. The heating was stopped, the temperature of the reaction system was controlled to 220 ℃ and 129.5 g of trimethylolpropane was added for further esterification. The acid value was controlled to be lower than 35mg KOH/g, and then polycondensation was carried out in vacuo until the acid value and the hydroxyl value were within the set ranges. Stopping heating, reducing the temperature of the reaction system from 220 ℃ to 195 ℃, then adding 4.5 g of antioxidant, mixing for 30 minutes, and discharging to obtain resin 4.
Difunctional polyester resin 5
1831 g of neopentyl glycol, 2.25 g of a catalyst butyl stannoic acid and 3.83 g of pentaerythritol diphosphite are added into a 6L reactor under nitrogen atmosphere, the temperature is raised and heated to about 150 ℃, 3177 g of isophthalic acid monomer is added after the polyol monomer in the reactor is observed to be completely melted, and the mixture is stirred uniformly. Heating to 250 deg.c, esterification and polycondensation of polyol and polybasic acid monomer, and maintaining the acid value of the reaction system below 60mg KOH/g. The heating was stopped, the temperature of the reaction system was controlled to 210 ℃ and 163.6 g of trimethylolpropane was added for further esterification. The acid value was controlled to be lower than 45mg KOH/g, and then polycondensation was carried out in vacuo until the acid value and the hydroxyl value were within the set ranges. Stopping heating, reducing the temperature of the reaction system from 210 ℃ to 195 ℃, then adding 4.5 g of antioxidant, mixing for 30 minutes, and discharging to obtain the resin 5.
Hydroxy-functional polyester resin A
1959 g of neopentyl glycol, 143.8 g of trimethylolpropane, 2.25 g of catalyst butyl stannoic acid and 3.83 g of pentaerythritol diphosphite are added into a 6L reactor under nitrogen environment, the temperature is raised and heated to about 150 ℃, 3092 g of isophthalic acid monomer is added after the polyol monomer in the reactor is observed to be completely melted, and the mixture is stirred uniformly. Heating to 250 deg.c, esterification and polycondensation of polyol and polybasic acid monomer, and maintaining the acid value of the reaction system below 15mg KOH/g. The heating was stopped, the temperature of the reaction system was controlled to 230 ℃ and then polycondensation was carried out in vacuum until the acid value and the hydroxyl value were within the set ranges. Stopping heating, reducing the temperature of the reaction system from 230 ℃ to 195 ℃, then adding 4.5 g of antioxidant, mixing for 30 minutes, and discharging to obtain the resin A.
Carboxyl-functional polyester resin B
1776 g of neopentyl glycol, 138.2 g of trimethylolpropane, 2.25 g of catalyst butyl stannoic acid and 3.83 g of pentaerythritol diphosphite are added into a 6L reactor under nitrogen environment, the temperature is raised and heated to about 150 ℃, after the polyol monomer in the reactor is observed to be completely melted, 3269 g of isophthalic acid monomer is added, and the mixture is stirred uniformly. Heating to 250 deg.c, esterification and polycondensation of polyol and polybasic acid monomer, and maintaining the acid value of the reaction system below 50mg KOH/g. The heating was stopped, the temperature of the reaction system was controlled to 240 ℃ and then polycondensation was carried out in vacuum until the acid value was within the set range. Stopping heating, reducing the temperature of the reaction system from 240 ℃ to 195 ℃, then adding 4.5 g of antioxidant, mixing for 30 minutes, and discharging to obtain the resin B.
The raw material composition and physical properties of each resin are shown in table 3 below.
Examples 1-2 and comparative examples A-C: powder coating composition
The powder coating is prepared by the following steps:
1. premixing all raw materials such as polyester, a curing agent, a flatting agent, pigment, a defoaming agent and the like for manufacturing the powder coating in a premixer;
2. melting and extruding the premixed raw materials through an extruder;
3. cooling and tabletting the melt-extruded material;
4. and crushing and sieving the flaky object by a crusher to obtain powder particles with proper particle size, namely the powder coating.
Powder coatings were prepared using resin 1, resin 2, comparative resin 1, comparative resin 2, and comparative resin 3 (1: 1 mixture of comparative resin 1 and comparative resin 2), respectively, as raw material polyesters, and the properties of the coatings were measured.
From the above results, it can be seen that coating compositions formulated with the difunctional polyester resins of the present invention result in coatings having both excellent leveling and thermal transfer properties.
In order to verify the weathering resistance of the powder coating compositions according to the invention, the coatings obtained in examples 1 and 2 were also subjected to a QUV-B ageing test. The aging time of the coating is related to the gloss retention as shown in the table below.
| Test time (h) | 60 ℃ gloss retention (%) | |
| Example 1 | 300h | 98.0％ |
| 600h | 90.0％ | |
| 800h | 73.8％ | |
| Example 2 | 300h | 98.7％ |
| 600h | 92.8％ | |
| 800h | 75.5％ |
It is evident from the table that powder coating compositions formulated with the difunctional polyester resins of the present invention can give coatings with ultra-high weatherability. In particular, the gloss retention measured after 600 hours of cycling in a QUV-B weathering tester is as high as 90.0% or even higher. It is known that powder coating compositions formulated with the existing weather-resistant polyester resins have a gloss retention after 500 hours in the QUV-B ageing test of up to 88%, which is significantly lower than that of the powder coating compositions according to the invention. It would not be expected by those skilled in the art that powder coating compositions having such high weatherability could be formulated using the difunctional polyester resins of the present invention.
While the invention has been described with reference to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the invention as disclosed herein.
Claims (22)
1. A difunctional polyester resin for an ultraweatherable heat transfer powder coating, wherein the difunctional polyester resin has an acid value of at least 10 and less than 28mg KOH/g polyester and a hydroxyl value of 10 to 40mg KOH/g polyester, and at least 88 mole% of the polyacid structural units in the difunctional polyester resin are derived from isophthalic acid.
2. The difunctional polyester resin for the super weatherable heat transfer powder coating according to claim 1, wherein the difunctional polyester resin has an acid value of 12 to 27mg KOH/g polyester.
3. The difunctional polyester resin for the ultra-weatherable heat transfer powder coating of claim 1, wherein the difunctional polyester resin has a hydroxyl value of 12 to 30mg KOH/g polyester.
4. The difunctional polyester resin for the ultra-weatherable heat transfer powder coating of claim 1, wherein all of the polyacid structural units in the difunctional polyester resin are derived from isophthalic acid.
5. The difunctional polyester resin for the super weatherable heat transfer powder coating according to any one of claims 1 to 4, wherein the difunctional polyester resin has a glass transition temperature Tg in the range of 40 to 80 ℃.
6. The bifunctional polyester resin for the super weather-resistant heat transfer powder coating according to any one of claims 1 to 4, wherein the bifunctional polyester resin has a melt viscosity at 160 ℃ in the range of 20 to 90 Pa-s.
7. The bifunctional polyester resin for the super weather-resistant heat transfer powder coating according to any one of claims 1 to 4, wherein the bifunctional polyester resin is obtained by:
reacting the reaction mixture until a product within the given acid and hydroxyl value ranges is obtained;
wherein the reaction mixture comprises:
i)28.0 to 50.0 wt.% of a polyol component,
ii)45.0 to 70.0 wt% of a polyacid component, wherein at least 88 mole% of the polyacid component is isophthalic acid,
iii)0.5 to 4.7% by weight of a branching agent, and
iv)0 to 0.3% by weight of an esterification catalyst,
the weight% is relative to the total weight of all material charges.
8. The difunctional polyester resin for the ultra weatherable heat transfer powder coating according to any one of claims 1 to 4, wherein said difunctional polyester resin is capable of providing a coating that retains at least 88% of gloss retention after 600 hours in QUV-B aging under UV light for 4 hours at 50 ℃ and water vapor cycle test for 4 hours at 40 ℃.
9. Process for the preparation of a difunctional polyester resin according to any of the preceding claims comprising:
reacting the reaction mixture until a product within the given acid and hydroxyl value ranges is obtained;
wherein the reaction mixture comprises:
i)28.0 to 50.0 wt.% of a polyol component,
ii)45.0 to 70.0 wt% of a polyacid component, wherein at least 88 mole% of the polyacid component is isophthalic acid,
iii)0.5 to 4.7% by weight of a branching agent, and
iv)0 to 0.3% by weight of an esterification catalyst,
the weight percents are based on the total weight of all material charges.
10. The method of claim 9, wherein the amount of the polyol component is 30.0 to 45.0 wt% based on the total weight of all material charges.
11. The method of claim 9, wherein the amount of the polyacid component is from 50.0 to 65.0 percent by weight, based on the total weight of all material charges.
12. The process of claim 9, wherein the amount of branching agent is 1.0-4.0 wt% based on the total weight of all material charges.
13. The process as claimed in claim 9, wherein the reaction comprises an esterification polycondensation carried out at a temperature in the range of 240-260 ℃.
14. The process as claimed in claim 9, wherein the reaction comprises vacuum polycondensation conducted at a temperature in the range of 220-240 ℃.
15. The method according to claim 14, wherein the time of the vacuum polycondensation is controlled so that the obtained polyester resin has an acid value of 12 to 27mg KOH/g polyester and a hydroxyl value of 12 to 30mg KOH/g polyester.
16. The method of any one of claims 9 to 14, wherein the polyol is neopentyl glycol, 1, 4-cyclohexanedimethanol, or a combination thereof.
17. An ultraweatherable heat transfer powder coating composition comprising the difunctional polyester resin of any one of claims 1 to 8 or prepared by the process of any one of claims 9 to 16, further comprising TGIC, blocked isocyanate and optional additives.
18. The ultraweatherable heat transfer powder coating composition of claim 17, wherein the polyester resin is present in an amount of 40 to 70 weight percent based on the total weight of the ultraweatherable heat transfer powder coating composition.
19. The ultraweatherable heat transfer powder coating composition of claim 17, wherein the TGIC is in an amount of 0.5 to 10 weight percent based on the total weight of the ultraweatherable heat transfer powder coating composition.
20. The superweatherable heat transfer powder coating composition of claim 17, wherein the blocked isocyanate is present in an amount of 1-15 wt% based on the total weight of the superweatherable heat transfer powder coating composition.
21. The ultraweatherable thermal transfer powder coating composition of any one of claims 17-20, wherein a coating formed therefrom retains at least 88% gloss after 600 hours in a QUV-B aging test with 50 ℃ UV light for 4 hours and a 40 ℃ water vapor cycle test for 4 hours.
22. A coated article comprising a substrate having coated thereon the ultraweatherable thermal transfer powder coating composition of any one of claims 17-21.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124701A (en) * | 2022-08-10 | 2022-09-30 | 浙江超浪新材料有限公司 | Bifunctional polyester resin, powder coating and application |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6706794B1 (en) * | 1999-10-04 | 2004-03-16 | Daikin Industries, Ltd. | Powder coating composition having high weather resistance |
| CN1821327A (en) * | 2004-10-12 | 2006-08-23 | 拜尔材料科学有限责任公司 | A flexible,weather resistant powder coating composition |
| CN103739831A (en) * | 2014-01-16 | 2014-04-23 | 帝兴树脂(昆山)有限公司 | Preparation method of polyester resin for high temperature resistant powder coating and high temperature resistant powder coating |
| CN106633012A (en) * | 2016-12-30 | 2017-05-10 | 帝兴树脂(昆山)有限公司 | Polyester resin for heat transfer printing powder coating and preparation method of polyester resin |
| CN107266665A (en) * | 2017-04-20 | 2017-10-20 | 浙江传化天松新材料有限公司 | A kind of TGIC solidifications high tenacity, superelevation weather-resistance powder coatings polyester resin and preparation method thereof |
| CN107868235A (en) * | 2017-10-30 | 2018-04-03 | 广州擎天材料科技有限公司 | A kind of powdery paints difunctional polyester resin and preparation method thereof |
| CN108084415A (en) * | 2017-12-22 | 2018-05-29 | 安徽神剑新材料股份有限公司 | A kind of terminal hydroxy group-carboxyl difunctional saturated polyester resin and preparation method thereof |
-
2018
- 2018-10-24 CN CN201811244394.XA patent/CN111087587A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6706794B1 (en) * | 1999-10-04 | 2004-03-16 | Daikin Industries, Ltd. | Powder coating composition having high weather resistance |
| CN1821327A (en) * | 2004-10-12 | 2006-08-23 | 拜尔材料科学有限责任公司 | A flexible,weather resistant powder coating composition |
| CN103739831A (en) * | 2014-01-16 | 2014-04-23 | 帝兴树脂(昆山)有限公司 | Preparation method of polyester resin for high temperature resistant powder coating and high temperature resistant powder coating |
| CN106633012A (en) * | 2016-12-30 | 2017-05-10 | 帝兴树脂(昆山)有限公司 | Polyester resin for heat transfer printing powder coating and preparation method of polyester resin |
| CN107266665A (en) * | 2017-04-20 | 2017-10-20 | 浙江传化天松新材料有限公司 | A kind of TGIC solidifications high tenacity, superelevation weather-resistance powder coatings polyester resin and preparation method thereof |
| CN107868235A (en) * | 2017-10-30 | 2018-04-03 | 广州擎天材料科技有限公司 | A kind of powdery paints difunctional polyester resin and preparation method thereof |
| CN108084415A (en) * | 2017-12-22 | 2018-05-29 | 安徽神剑新材料股份有限公司 | A kind of terminal hydroxy group-carboxyl difunctional saturated polyester resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 汤明麟等: ""超耐候粉末涂料用聚酯树脂的研究"", 《涂料工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124701A (en) * | 2022-08-10 | 2022-09-30 | 浙江超浪新材料有限公司 | Bifunctional polyester resin, powder coating and application |
| CN115124701B (en) * | 2022-08-10 | 2023-12-22 | 浙江超浪新材料有限公司 | Difunctional polyester resin, powder coating and application |
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