CN114231135A - Outdoor mirror powder coating, preparation method thereof and coating formed by same - Google Patents
Outdoor mirror powder coating, preparation method thereof and coating formed by same Download PDFInfo
- Publication number
- CN114231135A CN114231135A CN202111591387.9A CN202111591387A CN114231135A CN 114231135 A CN114231135 A CN 114231135A CN 202111591387 A CN202111591387 A CN 202111591387A CN 114231135 A CN114231135 A CN 114231135A
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- 238000000576 coating method Methods 0.000 title claims abstract description 65
- 239000011248 coating agent Substances 0.000 title claims abstract description 59
- 239000000843 powder Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920001225 polyester resin Polymers 0.000 claims abstract description 29
- 239000004645 polyester resin Substances 0.000 claims abstract description 29
- 229920006038 crystalline resin Polymers 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract 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 abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000000049 pigment Substances 0.000 claims abstract description 5
- 239000011256 inorganic filler Substances 0.000 claims abstract description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 16
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- 150000007519 polyprotic acids Polymers 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 7
- 239000006085 branching agent Substances 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims description 5
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 4
- UVHLUYZMNUCVJN-UHFFFAOYSA-N 3-methyloctane-4,4-diol Chemical compound CCCCC(O)(O)C(C)CC UVHLUYZMNUCVJN-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- 229940100573 methylpropanediol Drugs 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 229940051250 hexylene glycol Drugs 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005452 bending Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000009472 formulation Methods 0.000 description 8
- 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 6
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ZBSOGTZYMVJKTF-UHFFFAOYSA-K 4-trichlorostannylbutane-1,1-diol Chemical compound OC(O)CCC[Sn](Cl)(Cl)Cl ZBSOGTZYMVJKTF-UHFFFAOYSA-K 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000013035 low temperature curing Methods 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
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000000080 wetting agent Substances 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
- 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
- C09D5/033—Powdery paints characterised by the additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses an outdoor mirror surface powder coating, a preparation method thereof and a coating formed by the same, wherein the outdoor mirror surface powder coating comprises the following raw materials in percentage by weight: the carboxyl-terminated polyester resin A65-85%; hydroxyl-terminated crystalline resin B6-15%; 5-8.5% of triglycidyl isocyanurate; 1.5-4% of closed isocyanate; 0.8-1.2% of a leveling agent; 0.5-10% of pigment; 0-3% of inorganic filler; 0-1 wt% of an auxiliary agent; the mirror surface powder coating for outdoor use is prepared by adopting a co-extrusion mode of the low-viscosity carboxyl-terminated polyester resin A and the low-viscosity hydroxyl-terminated crystalline resin B, the leveling PCI on the surface of the coating after baking and curing is in a range of 9-10, the leveling effect is close to the mirror surface effect, the bending and impact properties are excellent, and the substitution of paint and water-based paint is realized.
Description
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to an outdoor mirror surface powder coating, a preparation method thereof and a coating formed by the same.
Background
The powder coating is a solid powder synthetic resin coating composed of solid resin, pigment, filler, auxiliary agent and the like. Unlike conventional solvent-based coatings and water-based coatings, the dispersion medium is not a solvent and water, but air. The paint has the characteristics of no solvent pollution, 100 percent film forming and low energy consumption, so that the paint is replaced in many fields such as building materials, engineering machinery, furniture and household appliances at present.
However, since the powder coating needs to be subjected to a high-temperature melting crosslinking curing process, the leveling property of the powder coating is lower than that of the paint, and the powder coating is difficult to replace in a part of fields with requirements on leveling property. Therefore, the development and preparation of the mirror powder coating and the polyester resin thereof are one of the directions which are seriously attacked by the industry.
Disclosure of Invention
The invention aims to provide an outdoor mirror surface powder coating and a preparation method thereof.
The invention also aims to provide a coating formed by the outdoor mirror surface powder coating, wherein the surface leveling grade (PCI) of the coating obtained after the outdoor mirror surface powder coating is baked for 10min at 200 ℃ is 9-10, the coating is close to a mirror surface effect, conical bending is not cracked by 3mm, the impact performance is not cracked by 30inch.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the outdoor mirror surface powder coating comprises the following raw materials in percentage by weight:
carboxyl-terminated polyester resin a: 65-85%;
hydroxyl-terminated crystalline resin B: 6-15%;
triglycidyl isocyanurate: 5-8.5%;
blocked isocyanate: 1.5-4%;
0.8-1.2% of a leveling agent;
0.5-10% of pigment;
0-3% of inorganic filler;
0-1% of an auxiliary agent.
The carboxyl-terminated polyester resin A has an acid value of 30-36 mgKOH/g and a viscosity of 1500-2500 mPa.S/200 ℃.
The hydroxyl-terminated crystalline resin B has an acid value of 0 to 5mgKOH/g, a hydroxyl value of 30 to 50mgKOH/g, a crystal melting temperature of 105 to 120 ℃ and a viscosity of 500 to 1000mPa.S/200 ℃.
The mass ratio of the carboxyl-terminated polyester resin A to the hydroxyl-terminated crystalline resin B is 10: 1-7: 1, and if the amount of the hydroxyl-terminated crystalline resin B is too high, the powder coating can be blocked in the storage process.
The weight ratio of the carboxyl-terminated polyester resin A to triglycidyl isocyanurate (TGIC) is 93: 6.5-7.5.
The weight ratio of the hydroxyl-terminated crystalline resin B to the blocked isocyanate is 4: 1.
the leveling agent is a GLP588 series silicon dioxide adsorbed polyacrylate leveling agent.
The inorganic filler is any one or more of barium sulfate, mica and calcium carbonate.
The auxiliary agent is any one or more of benzoin, a wetting agent 701B, a coupling agent or an electrifying agent.
The pigment is inorganic material, such as one or more of titanium dioxide, iron oxide yellow and carbon black.
The carboxyl-terminated polyester resin A is prepared from the following raw materials in percentage by weight: polyol: 32-45% wt; polybasic acid: 46-55% wt; acid hydrolysis agent: 8-13% wt; 0.03-0.15 wt% of esterification catalyst.
The polyhydric alcohol in the carboxyl-terminated polyester resin A is one or more of neopentyl glycol, ethylene glycol, diethylene glycol, ethylbutylpropanediol, cyclohexanedimethanol and methylpropanediol, preferably a mixture of neopentyl glycol, ethylene glycol, diethylene glycol, ethylbutylpropanediol and methylpropanediol according to any proportion, more preferably a mixture of neopentyl glycol, ethylene glycol, diethylene glycol, ethylbutylpropanediol and methylpropanediol according to a mass ratio of 20-30: 2-5: 1-5: 1, in a mixture of the components.
The polybasic acid in the carboxyl-terminated polyester resin A is a mixture of isophthalic acid and terephthalic acid according to any proportion, preferably a mixture of isophthalic acid and terephthalic acid according to any mass ratio of 4-6: 1.
The acid hydrolysis agent in the carboxyl-terminated polyester resin A is any one or more of isophthalic acid, fumaric acid, adipic acid, succinic acid, sebacic acid and dodecanedioic acid, preferably a mixture of isophthalic acid, fumaric acid, adipic acid and dodecanedioic acid in any proportion, and more preferably a mixture of isophthalic acid, fumaric acid, adipic acid and dodecanedioic acid in a mass ratio of 5-8:1.5-3.0:0.5-1.5: 1.
The catalyst in the carboxyl-terminated polyester resin A is a tin catalyst, preferably one or more of dibutyltin oxide, tributyltin oxide, dihydroxybutyltin chloride, stannous oxalate and monobutyltin oxide, preferably a mixture of monobutyltin oxide and stannous oxalate in any proportion, and more preferably a mixture of monobutyltin oxide and stannous oxalate in a mass ratio of 1: 2-5.
The preparation method of the carboxyl-terminated polyester resin A comprises the following steps:
1) putting the polyol, the polyacid and the catalyst in a formula amount into a reaction kettle at the same time, slowly heating to 235-255 ℃ in an inert atmosphere, and maintaining until the system is clear and the acid value reaches 5-20 mgKOH/g;
2) adding an acidolysis agent with the formula amount, and carrying out acidolysis on the end-capped materials at 235-250 ℃ for 1.5-2 h;
3) and when the acid value of the system is 38-42 mgKOH/g, cooling to 215-230 ℃, carrying out vacuum polycondensation until the acid value of the system reaches 28-34 mgKOH/g of resin, the viscosity reaches 1500-2500 mPa.S/200 ℃, cooling to 180-225 ℃, and discharging.
The hydroxyl-terminated crystalline resin B is prepared from the following raw materials in percentage by weight: polyol: 40-55%; branching agent: 1-5%; polybasic acid: 40-58%; 0.03-0.15% of esterification catalyst.
The polyhydric alcohol in the hydroxyl-terminated crystalline resin B is a mixture of neopentyl glycol, ethylene glycol, hexanediol, cyclohexanedimethanol and butanediol according to any proportion, and more preferably a mixture of neopentyl glycol, ethylene glycol, hexanediol, cyclohexanedimethanol and butanediol according to a mass ratio of 1.5-2.5:1:3-4:4-5: 5-6.
The branching agent in the hydroxyl-terminated crystalline resin B is any one or more of trimethylolpropane, trimethylolethane, trimesic acid, trimellitic anhydride and pentaerythritol, preferably a mixture of trimethylolpropane, trimethylolethane and trimesic acid according to any proportion, and more preferably a mixture of trimethylolpropane, trimethylolethane and trimesic acid according to a mass ratio of 1:1-3: 1-3.
The polybasic acid in the hydroxyl-terminated crystalline resin B is a mixture of terephthalic acid, isophthalic acid, adipic acid and dodecanedioic acid according to any proportion, and more preferably a mixture of terephthalic acid, isophthalic acid, adipic acid and dodecanedioic acid according to the mass ratio of 2-4:0.5-1.5:2-5: 1.
The catalyst in the hydroxyl-terminated crystalline resin B is a tin catalyst, preferably one or more of dibutyltin oxide, tributyltin oxide, dihydroxybutyltin chloride, stannous oxalate and monobutyltin oxide, preferably a mixture of monobutyltin oxide and stannous oxalate in any proportion, and more preferably a mixture of monobutyltin oxide and stannous oxalate in a mass ratio of 1: 1-3.
The preparation method of the hydroxyl-terminated crystalline resin B comprises the following steps:
(1) putting the polyol, the polybasic acid, the bronzing agent and the catalyst into a reaction kettle at the same time, slowly heating to 235-255 ℃ in an inert atmosphere, and maintaining until the system is clear and the acid value reaches 5-20 mgKOH/g;
(2) cooling to 215-230 ℃, and carrying out vacuum polycondensation until the acid value of the system reaches 0-5 mgKOH/g, the hydroxyl value is 30-50 mgKOH/g, and the viscosity is 500-1000 mPa.S/200 ℃.
The preparation method of the outdoor mirror surface powder coating provided by the invention comprises the following steps: the formula amount of the raw materials are fully premixed in a mixing tank → extruded by an extruder → pressed → crushed → ground → sieved → packaged.
The leveling grade of the coating formed by the outdoor mirror surface powder coating is 9-10, the coating is close to a mirror surface effect, conical bending is not cracked for 3mm, impact performance is not cracked for 30inch.
According to the outdoor mirror surface powder coating, the low-viscosity carboxyl-terminated polyester resin A with the acid value of 30-36 mgKOH/g and the viscosity of 1500-2500 mPa.S/200 ℃ is prepared by taking the polyalcohol, the polybasic acid, the acidolysis agent and the esterification catalyst as raw materials, and the low viscosity is beneficial to improving the leveling grade; and a crystalline polyester resin B having an acid value of 0 to 5mgKOH/g, a hydroxyl value of 30 to 50mgKOH/g, and a viscosity of 500 to 1000mPa.S/200 ℃ and having terminal hydroxyl groups with a low viscosity is synthesized synchronously by using a polyol, a polybasic acid, a branching agent, and an esterification catalyst as raw materials. Then, the low-viscosity carboxyl-terminated polyester resin A and the low-viscosity hydroxyl-terminated crystalline polyester resin B are used as main body resins, and are matched with a specific amount of triglycidyl isocyanurate and blocked isocyanate as curing agents to obtain the outdoor mirror powder coating, the low viscosity of the main body resins in the formula is favorable for improving the leveling grade of the powder lifting coating, the ultralow viscosity and the mechanical property of the low-viscosity hydroxyl-terminated crystalline polyester resin B near the curing temperature are good, and the blocked isocyanate can react only by deblocking in the curing and heating processes, so that the slow reaction activity is realized, and the leveling property and the mechanical property of the powder coating are further remarkably improved.
Detailed Description
The present invention will be described in detail with reference to examples.
Examples
Polyester resin A
The method comprises the steps of putting the polyhydric alcohol, the aromatic acid and the catalyst in the formula amount shown in the table 1 into a reaction kettle at the same time, slowly heating to 235-255 ℃ in a nitrogen atmosphere, maintaining, after the system is clarified, sampling, detecting that the Acid Value (AV) reaches 5-20 mgKOH/g of resin, adding a secondary acidolysis agent, and maintaining the temperature at 235-250 ℃ for acidolysis and end capping for about 1.5-2 hours. Cooling to 215-230 ℃ when the acid value of the polyester is 38-42 mgKOH/g resin, and carrying out vacuum (0.1 MPA) polycondensation for a period of time to ensure that the acid value of the polyester reaches 28-34 mgKOH/g resin and the viscosity is 1500-2500 mPa.S/200 ℃. Then cooling to 180-225 ℃ and discharging. Wherein resins a, b and c are examples and d is a comparative example.
TABLE 1 polyester resin A raw Material formulation, control of acid number and Properties during production
Crystalline resin B
The method comprises the steps of putting the polyol, the polybasic acid, the branching agent and the catalyst in the formula amount shown in the table 2 into a reaction kettle at the same time, slowly heating to 235-255 ℃ in a nitrogen atmosphere and maintaining, cooling to 215-230 ℃ when the Acid Value (AV) of the system is detected to reach 5-20 mgKOH/g of resin after the system is clarified, and carrying out vacuum (-0.1 MPA) polycondensation for a period of time to ensure that the acid value of the polyester reaches 0-5 mgKOH/g of resin, the hydroxyl value is 30-50 mgKOH/g of resin, and the viscosity is 500-1000 mPa.S/200 ℃.
TABLE 2 crystalline resin B raw material formulation, control of acid number and properties during production
Table 3 shows the formulations of the low-temperature-curing powder coatings prepared using the polyester resin A and the crystalline resin B, formulation 8 being a comparative example (unit: g)
TABLE 3
Weighing the different raw materials according to the formulation in table 3 → premixing sufficiently in a mixing tank → co-extruding by an extruder → tabletting → crushing → grinding → sieving by a 200 mesh sieve → packaging the finished product to obtain the mirror powder coating for outdoor use of the invention. The parameters of the extruder for melt extrusion are as follows: the screw rotating speed is 45Hz, the temperature of the zone I is 95-105 ℃, the temperature of the zone II is 105-115 ℃, and the powder coatings corresponding to the formulas 1-8 are produced under the same process flow and process parameters.
The powder coating was then sprayed onto the iron plate after surface phosphating, cured by baking at 200 ℃ for 10min to give a coating, and the coating was tested for different properties, the results of which are given in table 4.
Table 4 summary of the properties of the powder coatings for the different formulations.
Remarks that the leveling grade PCI from 1 to 10 represents the improvement of the leveling performance, wherein PCI-10 represents the leveling performance as same as a mirror, and a commercial standard board is used for evaluating the PCI grade at present.
From Table 3, it can be seen that when the mass ratio of the polyester resin A to the polyester resin B is 5:1 (formulation 3), the powder coating obtained was agglomerated after storage at 42 ℃ for 3 days, which was not favorable for the end-user. From formulation 8 (comparative) it can be seen that the coating leveling rating after baking, PCI, is 5.4 when the powder coating is prepared directly with the conventional polyester resin and curing agent TGIC. As is evident from formulas 1-2 and 3-7, the powder coating provided by the invention has the advantages of mirror-like level, excellent bending and impact properties, and can replace paints and water-based paints in more fields.
The above detailed description of an outdoor mirror powder coating and its preparation method and coating layer formed thereby with reference to the embodiments is illustrative and not restrictive, and several embodiments can be enumerated within the limits of the invention, so that changes and modifications that do not depart from the general concept of the present invention are intended to be within the scope of the present invention.
Claims (16)
1. The outdoor mirror surface powder coating is characterized by comprising the following raw materials in percentage by weight:
carboxyl-terminated polyester resin a: 65-85%;
hydroxyl-terminated crystalline resin B: 6-15%;
triglycidyl isocyanurate: 5-8.5%;
blocked isocyanate: 1.5-4%;
0.8-1.2% of a leveling agent;
0.5-10% of pigment;
0-3% of inorganic filler;
0-1% of an auxiliary agent.
2. The outdoor mirror powder coating according to claim 1, wherein the carboxyl-terminated polyester resin A has an acid value of 30 to 36mgKOH/g and a viscosity of 1500 to 2500mPa.S/200 ℃; the hydroxyl-terminated crystalline resin B has an acid value of 0 to 5mgKOH/g, a hydroxyl value of 30 to 50mgKOH/g, a crystal melting temperature of 105 to 120 ℃ and a viscosity of 500 to 1000mPa.S/200 ℃.
3. The outdoor mirror powder coating according to claim 1, wherein the carboxyl-terminated polyester resin A is prepared from the following raw materials in percentage by weight: polyol: 32-45% wt; polybasic acid: 46-55% wt; acid hydrolysis agent: 8-13% wt; 0.03-0.15 wt% of esterification catalyst.
4. The outdoor mirror powder coating according to claim 3, wherein the polyol is any one or more of neopentyl glycol, ethylene glycol, diethylene glycol, ethylbutylpropanediol, cyclohexanedimethanol and methylpropanediol.
5. A mirror powder coating for outdoor use according to claim 3, wherein said polybasic acid is a mixture of isophthalic acid and terephthalic acid in any ratio.
6. A mirror powder coating for outdoor use according to claim 3, wherein said acid decomposer is any one or more of isophthalic acid, fumaric acid, adipic acid, succinic acid, sebacic acid, dodecanedioic acid.
7. The outdoor mirror powder coating for outdoor use according to claim 3, wherein the preparation method of the carboxyl-terminated polyester resin A comprises the steps of:
1) putting the polyol, the polyacid and the catalyst in a formula amount into a reaction kettle at the same time, slowly heating to 235-255 ℃ in an inert atmosphere, and maintaining until the system is clear and the acid value reaches 5-20 mgKOH/g;
2) adding an acidolysis agent with the formula amount, and carrying out acidolysis on the end-capped materials at 235-250 ℃ for 1.5-2 h;
3) when the acid value of the system is 38-42 mgKOH/g, cooling to 215-230 ℃, carrying out vacuum polycondensation until the acid value of the system reaches 28-34 mgKOH/g, the viscosity reaches 1500-2500 mPa.S/200 ℃, cooling to 180-225 ℃, and discharging.
8. The outdoor mirror powder coating according to claim 1, wherein the hydroxyl-terminated crystalline resin B is prepared from the following raw materials in percentage by weight: polyol: 40-55%; branching agent: 1-5%; polybasic acid: 40-58%; 0.03-0.15% of esterification catalyst.
9. A mirror powder coating for outdoor use according to claim 8, wherein said polyol is a mixture of neopentyl glycol, ethylene glycol, hexylene glycol, cyclohexanedimethanol, and butanediol in any ratio.
10. A mirror powder coating for outdoor use according to claim 8, wherein said branching agent is any one or more of trimethylolpropane, trimethylolethane, trimesic acid, trimellitic anhydride, pentaerythritol.
11. The outdoor mirror powder coating of claim 8, wherein the polybasic acid is a mixture of terephthalic acid, isophthalic acid, adipic acid, and dodecanedioic acid in any ratio.
12. The outdoor mirror powder coating according to claim 3 or 8, wherein the catalyst is a tin-based catalyst.
13. The outdoor mirror powder coating for outdoor use according to claim 8, wherein the method for preparing the hydroxyl-terminated crystalline resin B comprises the steps of:
(1) putting the polyol, the polybasic acid, the bronzing agent and the catalyst into a reaction kettle at the same time, slowly heating to 235-255 ℃ in an inert atmosphere, and maintaining until the system is clear and the acid value reaches 5-20 mgKOH/g;
(2) cooling to 215-230 ℃, and carrying out vacuum polycondensation until the acid value of the system reaches 0-5 mgKOH/g, the hydroxyl value is 30-50 mgKOH/g, and the viscosity is 500-1000 mPa.S/200 ℃.
14. The outdoor mirror powder coating of claim 1, wherein the weight ratio of the carboxyl-terminated polyester resin A to triglycidyl isocyanurate (TGIC) is 93: 6.5-7.5; the weight ratio of the hydroxyl-terminated crystalline resin B to the blocked isocyanate is 4: 1.
15. a method for preparing an outdoor mirror powder coating according to any one of claims 1 to 14, comprising the steps of: the formula amount of the raw materials are fully premixed in a mixing tank → extruded by an extruder → pressed → crushed → ground → sieved → packaged.
16. The outdoor coating formed with a mirror-like powder coating according to any one of claims 1 to 14.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115926603A (en) * | 2022-11-17 | 2023-04-07 | 广东银洋环保新材料有限公司 | Anti-bending transparent matte high-hardness powder coating and preparation method thereof |
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