CN101260271A - Transparent cover light powder paint composition and preparation method thereof - Google Patents
Transparent cover light powder paint composition and preparation method thereof Download PDFInfo
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- CN101260271A CN101260271A CNA2008100695700A CN200810069570A CN101260271A CN 101260271 A CN101260271 A CN 101260271A CN A2008100695700 A CNA2008100695700 A CN A2008100695700A CN 200810069570 A CN200810069570 A CN 200810069570A CN 101260271 A CN101260271 A CN 101260271A
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Abstract
The invention relates to a transparent finish powder coating compound and a preparation method thereof, wherein, the compound of the invention comprises curing agent (B) 10-30 percent, flatting agent (D) 0.1-5 percent, degasifying agent (E) 0-5 percent and light stabilizer (F) 0-5 percent. The invention is characterized in that: the invention also comprises a copolymer (A) 50-85 percent and modifying agent (C) 5-20 percent. The preparation method of the compound is as follows: the curing agent (B), the flatting agent (D), the degasifying agent (E), the light stabilizer (F), the copolymer (A) and the modifying agent (C) are mixed for three to five minutes; the mixed material is added into an extruding machine for melt extrusion, the temperature of a feeding section is between 90 and 110 DEG C, the temperature of a banburying section is between 105 and 130 DEG C, and the average detention time of the material does not exceed 50 seconds; an extruded liquid melt tablet is grinded in a grinding mill and passes through a 180-mesh sieve. The compound has better storage stability; the coating has good anti-impact performance and is suitable for transparent coating of automobile parts and automobile external layers.
Description
Technical field
The present invention relates to a kind of transparent cover light powder paint composition and preparation method thereof.
Background technology
Powder coating is the few environment-friendly type coating of solvent output.At present, particularly the America and Europe that there are strict requirements of the discharge to volatile organic compounds, it uses is constantly increasing, and the transparent powder of vinylformic acid also is a powder coating development in future trend.Because therefore advantages such as acrylic acid series coating has high-weatherability, anti-zonedly spends, transparency is good are generally used for car surface Lacquer finish and automobile aluminium wheel and spray.
In general, the acrylic ester thermosetting powder coating(s) is meant and uses the material of acrylate resin as main resin glue, the kind of the reactive base that contains according to them, be broadly divided into three kinds, promptly contain hydroxyl acrylate resin, contain acidic group (carboxyl) acrylate resin, contain the acrylic resin of glycidyl.
Such according to what CN1462781A put down in writing, contain the comparison of acrylate resin under same molecular weight, same Heating temperature of glycidyl, with respect to the acrylate resin that contains hydroxyl, contain the acrylate resin of acidic group, melt viscosity reduces, and filming of obtaining in roasting process is smoothly the most excellent.And, make this acrylate resin that contains glycidyl form firm filming as the thermosetting powder coating(s) that the polynary carboxylic compound combination of solidifying agent obtains, contain the promptly excellent weathering resistance of the original speciality of acrylic resin, can form cured coating film with excellent appearance characteristics (smoothness, high gloss etc.), physical property (shock resistance, scuff resistance etc.), chemical property (acid resistance, solvent resistance etc.).
But, have its fatal shortcoming with the acrylic ester thermosetting powder coating(s) of the acrylic resin manufacturing that contains glycidyl.The acrylate resin that contains glycidyl, its be with glycidyl as the crosslinked functional group of thermofixation, the size of glycidyl content can determine the crosslinking degree of paint film, and then influences shock strength.The second-order transition temperature of resin can be regulated by the consumption of different monomers.In order to improve the resistance to impact shock that coating varnish is filmed, general way is to introduce flexible side-chains on the main chain of polymkeric substance, but such consequence will cause the glass transition temperature Tg of resin to reduce.Because transparent powder paint is in order to keep its transparency, filler and additive are had the requirement of strict amount, so the package stability of transparent powder paint directly depends on the character of resin.Therefore, in order to improve the package stability of powder coating, it is high that the Tg of general requirement resin wants, but this shock resistance of again influence being filmed.
Summary of the invention
The present invention will solve above-mentioned problem of filming between shock resistance and the powder coating package stability, and its purpose is to provide a kind of excellent storage stability, film suitable trolley part with superperformance and the outer clear-coated a kind of transparent cover light powder paint composition of automobile and preparation method thereof.
In order to achieve the above object, transparent cover light powder paint composition of the present invention comprises solidifying agent (B) 10-30%, flow agent (D) 0.1-5%, air release agent (E) 0-5%, photostabilizer (F) 0-5%, it is characterized in that: also comprise multipolymer (A) 50-85%, properties-correcting agent (C) 5-20%.
Described multipolymer (A) comprises glycidyl methacrylate and/or methacrylic acid Beta-methyl glycidyl ester (A1) 20-50%, also comprise ethylene unsaturated monomer, the therein ethylene unsaturated monomer is selected from esters of acrylic acid (A2) 0-20%, methyl acrylic ester (A3) 0-50%, ethyl propylene acid esters class (A4) 0-20%, hydroxymethyl acrylate class (A5) 0-20%.
Described solidifying agent composition is that carbonatoms is the aliphatic dibasic acid of 10-18 or their mixture.
Described properties-correcting agent composition is that carbonatoms is acid of monobasic representative examples of saturated aliphatic or their mixture of 10-30.
Described flow agent is selected from polyacrylic acid lipoid substance and/or acetate butyl fibre chlorins compound;
Described air release agent is selected from the polymerizable compound and/or the fluorocarbon of organosilicon and modified compound and/or inorganic silicon.
Described photostabilizer is selected from benzophenone and/or benzotriazole category and/or hindered amines derivative.
The preparation method of this product is, a, with described glycidyl methacrylate and/or methacrylic acid Beta-methyl glycidyl ester (A1) 20-50%, esters of acrylic acid (A2) 0-20%, methyl acrylic ester (A3) 0-50%, ethyl propylene acid esters class (A4) 0-20%, hydroxymethyl acrylate class (A5) 0-20% mix and obtain mix monomer; Add inert solvent again in reaction vessel, start stirring and temperature control at 100-160 ℃, pressure-controlling is at 0.8-1.4 normal atmosphere, drip mix monomer and initiator then, dripped off in 120-180 minute, be incubated 100-150 minute, add initiator, be incubated 100-150 minute at last; Solvent is removed in underpressure distillation, promptly gets bright copolymer A; B, with solidifying agent (B) 10-30%, flow agent (D) 0.1-5%, air release agent (E) 0-5%, photostabilizer (F) 0-5%, multipolymer (A) 50-85%, properties-correcting agent (C) 5-20% mixing 3-5 minute; C, mixture is added forcing machine melt extrude, the feeding section temperature is 90-110 ℃, and banburying section temperature is 105-130 ℃, and the material average retention time is no more than 50 seconds; F, with the extrusion melt compressing tablet, abrasive dust in pulverizing mill is crossed 180 purposes sieve.
Described inert solvent is selected from a kind of in the following solvents: the mixture of benzene,toluene,xylene, vinyl acetic monomer, N-BUTYL ACETATE, capryl acetate, acetic acid heptyl ester, tetrahydrofuran (THF), acetone, methylethylketone, mibk, MAK, methyl isoamyl ketone and these solvents.
The present invention's advantage compared with prior art is, because the glass transition temperature Tg of synthetic multipolymer is more than 40 ℃, powder coating promptly has package stability preferably, has introduced properties-correcting agent again, make the shock resistance of filming improve, it is clear-coated to be fit to trolley part and automobile skin.Its performance is as shown in the table.
The performance of transparent cover light powder paint
| Test event | Test result | Examination criteria |
| Powder stability in storage (15 ~ 25 ℃, six months) | Not conglomeration | Range estimation |
| The transparency | Transparent clear, not yellowing is not hazed | Range estimation |
| Appearance of film | Smooth smooth, fullness ratio is good | Range estimation |
| Glossiness (60 ° of incident) | ≥97.7％ | GB/T 9754-88 |
| Shock strength | ≥50kg·cm 2 | GB/T 1732-93 |
| Snappiness | ≤2mm | GB/T 1731-93 |
| Surface hardness | ≥3H | GB/T 6739-96 |
| Sticking power | 0 grade | GB/T 9286-98 |
| QUV tests (1000h) | Protect light rate 〉=90.8% | GB/T 14522-93 |
| Salt-fog resistant test | ≤2mm | GB/T 1771-91 |
The major influence factors that influences the powder coating package stability is the glass transition temperature Tg of resin, under the following conditions, promptly the Tg that is measured by differential scanning calorimeter (DSC, the DSC100 of TA company) is more than 40 ℃, and powder coating promptly has package stability preferably.
The performance of acrylic resin is decided by used monomeric kind and consumption, and the monomer of synthesizing propylene acid resin is divided into cross-linking monomer, soft monomer and hard monomer.The second-order transition temperature (Tg) of resin raises when hard monomer content increases, and the hardness of filming increases snappiness and reduces, the shock resistance variation; Otherwise when increasing as if soft monomer content, the Tg of resin reduces snappiness and improves, and shock resistance improves; Simultaneously, the melt viscosity of the low more resin of Tg is low more, and the levelling property of filming is good more, but the hardness of filming, stain resistance and water tolerance reduce.
As mentioned above, the shock resistance that obtain filming reaches the transparent cover light powder paint of powder excellent storage stability well, and it is irrealizable relying on the prescription that changes multipolymer separately.The present invention is solved this problem by introducing the method for properties-correcting agent.Specific practice is that at first synthetic multipolymer with higher Tg uses long-chain monobasic saturated fatty acid (properties-correcting agent) to introduce flexible side group then.These two kinds of materials keep unreactiveness in the storage stage, only when the paint film crosslinking curing hydroxyl of long-chain monobasic saturated fatty acid (properties-correcting agent) just with resin matrix in epoxide group react, flexible side-chains is introduced in the copolymer molecule structure.Because the synthetic copolymer A has higher Tg, selected solidifying agent (B), properties-correcting agent (C) fusing point are higher, and chemical stability is better, so powder coating has package stability preferably.Simultaneously, in solidification process, introduce flexible side-chains, make the shock resistance of filming improve.
Because institute adds monomeric reactive behavior difference, under same temperature condition, if next reacts at initiator with all monomers, because unexpectedly poly-rate differs, the molecular structure of polymkeric substance is uncontrollable, and causes the performance of copolymer instability.In order to address this problem, introduce the method that drips among this preparation method, simultaneously solvent, temperature of reaction, reaction pressure there are certain control, to make the multipolymer of molecular weight and moderate molecular weight distribution.
In the powder production process, should control processing conditions well, to prevent transparent cover light powder paint generation xanthochromia and because the reaction of the too high multipolymer that causes of local temperature and solidifying agent or properties-correcting agent.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description:
Embodiment 1
The prescription of copolymer A is as shown in table 1:
The prescription of table 1 copolymer A
| Name of material | Mass percent |
| Glycidyl methacrylate (A1) | 36.4 |
| Methyl acrylate (A2) | 9.5 |
| Jia Jibingxisuanyizhi (A3) | 40.3 |
| Ethylacrylic acid methyl esters (A4) | 5.8 |
| Methylol butyl acrylate (A5) | 8.0 |
| Initiator | 3.0 |
By prescription, above-mentioned A1-A5 monomer is mixed earlier, initiator is dissolved in the above-mentioned monomer solution again; Inert solvent is made up of toluene, N-BUTYL ACETATE, and the weight ratio of toluene and N-BUTYL ACETATE is 6: 4; The assembling reaction unit, after checking that heating, stirring, temperature control system are errorless, in reaction vessel, drop into inert solvent, start and stir and intensification, the reaction vessel temperature control is at 140 ℃, pressure-controlling is at 1.1 normal atmosphere, and constant adding contains the monomer solution of initiator in reaction vessel, and this process was finished in 180 minutes; Be incubated 150 minutes, add initiator, be incubated 100 minutes at last; Underpressure distillation desolventizes, and emits resin after the degassing while hot, and cooling obtains water white copolymer resin.Described inert solvent is selected from a kind of in the following solvents: the mixture of benzene,toluene,xylene, vinyl acetic monomer, N-BUTYL ACETATE, capryl acetate, acetic acid heptyl ester, tetrahydrofuran (THF), acetone, methylethylketone, mibk, MAK, methyl isoamyl ketone and these solvents
By the multipolymer that above-mentioned prescription and method obtain, its glass transition temperature Tg is 45 ℃, and softening temperature is 102 ℃, and number-average molecular weight is at 1000-6000.
Again with multipolymer 60kg, solidifying agent 20kg, properties-correcting agent 20kg, air release agent 3kg, photostabilizer 1kg, flow agent 5kg high-speed mixing 3 minutes adds forcing machine with mixture and melt extrudes, the feeding section temperature is 90 ℃, banburying section temperature is 130 ℃, and the material average retention time is no more than 50 seconds, with extrusion melt compressing tablet, cooling, abrasive dust in pulverizing mill is crossed 180 purposes sieve and is promptly got transparent cover light powder paint composition.Product granularity control: the following powder of 62 μ m≤3%.Described solidifying agent composition is that carbonatoms is the aliphatic dibasic acid of 10-18 or their mixture.Described properties-correcting agent composition is that carbonatoms is acid of monobasic representative examples of saturated aliphatic or their mixture of 10-30.Described flow agent is selected from polyacrylic acid lipoid substance and/or acetate butyl fibre chlorins compound.Described air release agent is selected from the polymerizable compound and/or the fluorocarbon of organosilicon and modified compound and/or inorganic silicon.Described photostabilizer is selected from benzophenone and/or benzotriazole category and/or hindered amines derivative.
Embodiment 2
For improving the flow leveling of coating, the content of the hard monomer in the minimizing prescription that can be suitable, adjusted prescription is as shown in table 2.Other is identical with embodiment 1.
The prescription of table 2 copolymer A
| Name of material | Mass percent |
| Methacrylic acid Beta-methyl glycidyl ester (A1) | 38.2 |
| Ethyl propenoate (A2) | 18.9 |
| Methyl methacrylate (A3) | 28.3 |
| Ethylacrylic acid methyl esters (A4) | 6.6 |
| Methylol ethyl propenoate (A5) | 8.0 |
| Initiator | 2.6 |
Its second-order transition temperature of multipolymer that is obtained by above-mentioned prescription is 34 ℃, and softening temperature is 92 ℃.
By above-mentioned prescription the mixing of A1-A5 monomer is obtained mix monomer; Add inert solvent again in reaction vessel, start stirring and temperature control at 100 ℃, pressure-controlling drips mix monomer and initiator then at 0.8 normal atmosphere, drips off in 180 minutes, is incubated 150 minutes, adds initiator, is incubated 100 minutes at last; Solvent is removed in underpressure distillation, promptly gets bright multipolymer.Described inert solvent is selected from a kind of in the following solvents: the mixture of benzene,toluene,xylene, vinyl acetic monomer, N-BUTYL ACETATE, capryl acetate, acetic acid heptyl ester, tetrahydrofuran (THF), acetone, methylethylketone, mibk, MAK, methyl isoamyl ketone and these solvents.
With multipolymer 60kg, solidifying agent 20kg, properties-correcting agent 20kg, air release agent 3kg, photostabilizer 1kg, flow agent 5kg high-speed mixing 3 minutes adds forcing machine with mixture and melt extrudes, the feeding section temperature is 90 ℃, banburying section temperature is 130 ℃, and the material average retention time is no more than 50 seconds, with extrusion melt compressing tablet, cooling, abrasive dust in pulverizing mill is crossed 180 purposes sieve and is promptly got transparent cover light powder paint composition.Product granularity control: the following powder of 62 μ m≤3%.Described solidifying agent composition is that carbonatoms is the aliphatic dibasic acid of 10-18 or their mixture.Described properties-correcting agent composition is that carbonatoms is acid of monobasic representative examples of saturated aliphatic or their mixture of 10-30.Described flow agent is selected from polyacrylic acid lipoid substance and/or acetate butyl fibre chlorins compound.Described air release agent is selected from the polymerizable compound and/or the fluorocarbon of organosilicon and modified compound and/or inorganic silicon.Described photostabilizer is selected from benzophenone and/or benzotriazole category and/or hindered amines derivative.
Embodiment 3
For improving the package stability of powder coating, can suitably increase the content of hard monomer, adjusted prescription is as shown in table 3.Other is identical with embodiment.
The prescription of table 3 copolymer A
| Name of material | Mass percent |
| Glycidyl methacrylate (A1) | 44.3 |
| Butyl acrylate (A2) | 10.9 |
| Methyl methacrylate (A3) | 30.2 |
| Ethylacrylic acid methyl esters (A4) | 6.6 |
| Methylol butyl acrylate (A5) | 8.0 |
| Initiator | 2.6 |
Its second-order transition temperature of multipolymer that is obtained by above-mentioned prescription is 52 ℃, and softening temperature is 118 ℃.
A, by above-mentioned prescription the A1-A5 monomer is mixed and to obtain mix monomer; Add inert solvent again in reaction vessel, start stirring and temperature control at 130 ℃, pressure-controlling drips mix monomer and initiator then at 1.1 normal atmosphere, drips off in 150 minutes, is incubated 130 minutes, adds initiator, is incubated 130 minutes at last; Solvent is removed in underpressure distillation, promptly gets bright copolymer A.Described inert solvent is selected from a kind of in the following solvents: the mixture of benzene,toluene,xylene, vinyl acetic monomer, N-BUTYL ACETATE, capryl acetate, acetic acid heptyl ester, tetrahydrofuran (THF), acetone, methylethylketone, mibk, MAK, methyl isoamyl ketone and these solvents.
With solidifying agent (B) 15.0, flow agent (D) 2.0, air release agent (E) 2.0, multipolymer 71.0, properties-correcting agent (C) 10.0 mixed 3-5 minute; C, mixture is added forcing machine melt extrude, the feeding section temperature is 100 ℃, and banburying section temperature is 115 ℃, and the material average retention time is no more than 50 seconds; F, with the extrusion melt compressing tablet, abrasive dust in pulverizing mill is crossed 180 purposes sieve.In order to improve the anti-ultraviolet property of coating, can add photostabilizer, adjusted prescription is as shown in table 3.Described solidifying agent composition is that carbonatoms is the aliphatic dibasic acid of 10-18 or their mixture.Described properties-correcting agent composition is that carbonatoms is acid of monobasic representative examples of saturated aliphatic or their mixture of 10-30.Described flow agent is selected from polyacrylic acid lipoid substance and/or acetate butyl fibre chlorins compound.Described air release agent is selected from the polymerizable compound and/or the fluorocarbon of organosilicon and modified compound and/or inorganic silicon.Described photostabilizer is selected from benzophenone and/or benzotriazole category and/or hindered amines derivative.
Embodiment 4
For improving the anti-ultraviolet property of coating, can in powder coating, add photostabilizer, it is as shown in table 4 to fill a prescription.
The prescription of table 4 transparent powder paint
| Name of material | Mass percent |
| Multipolymer | 65.0 |
| Solidifying agent | 12.0 |
| Properties-correcting agent | 18.0 |
| Flow agent | 2.0 |
| Air release agent | 2.0 |
| Photostabilizer | 1.0 |
Claims (9)
1, a kind of transparent cover light powder paint composition comprises solidifying agent (B) 10-30%, flow agent (D) 0.1-5%, and air release agent (E) 0-5%, photostabilizer (F) 0-5% is characterized in that: also comprise multipolymer (A) 50-85%, properties-correcting agent (C) 5-20%.
2, transparent cover light powder paint composition according to claim 1, it is characterized in that: described multipolymer (A) comprises glycidyl methacrylate and/or methacrylic acid Beta-methyl glycidyl ester (A1) 20-50%, also comprise ethylene unsaturated monomer, the therein ethylene unsaturated monomer is selected from esters of acrylic acid (A2) 0-20%, methyl acrylic ester (A3) 0-50%, ethyl propylene acid esters class (A4) 0-20%, hydroxymethyl acrylate class (A5) 0-20%.
3, transparent cover light powder paint composition according to claim 1 is characterized in that: described solidifying agent composition is that carbonatoms is the aliphatic dibasic acid of 10-18 or their mixture.
4, transparent cover light powder paint composition according to claim 1 is characterized in that: described properties-correcting agent composition is that carbonatoms is acid of monobasic representative examples of saturated aliphatic or their mixture of 10-30.
5, transparent cover light powder paint composition according to claim 1 is characterized in that: described flow agent is selected from polyacrylic acid lipoid substance and/or acetate butyl fibre chlorins compound.
6, transparent cover light powder paint composition according to claim 1 is characterized in that: described air release agent is selected from the polymerizable compound and/or the fluorocarbon of organosilicon and modified compound and/or inorganic silicon.
7, transparent cover light powder paint composition according to claim 1 is characterized in that: described photostabilizer is selected from benzophenone and/or benzotriazole category and/or hindered amines derivative.
8, a kind of preparation method of transparent cover light powder paint composition, it is characterized in that: a, with described glycidyl methacrylate and/or methacrylic acid Beta-methyl glycidyl ester (A1) 20-50%, esters of acrylic acid (A2) 0-20%, methyl acrylic ester (A3) 0-50%, ethyl propylene acid esters class (A4) 0-20%, hydroxymethyl acrylate class (A5) 0-20% mix and obtain mix monomer; Add inert solvent again in reaction vessel, start stirring and temperature control at 100-160 ℃, pressure-controlling is at 0.8-1.4 normal atmosphere, drip mix monomer and initiator then, dripped off in 120-180 minute, be incubated 100-150 minute, add initiator, be incubated 100-150 minute at last; Solvent is removed in underpressure distillation, promptly gets bright copolymer A; B, with solidifying agent (B) 10-30%, flow agent (D) 0.1-5%, air release agent (E) 0-5%, photostabilizer (F) 0-5%, multipolymer (A) 50-85%, properties-correcting agent (C) 5-20% mixing 3-5 minute; C, mixture is added forcing machine melt extrude, the feeding section temperature is 90-110 ℃, and banburying section temperature is 105-130 ℃, and the material average retention time is no more than 50 seconds; F, with the extrusion melt compressing tablet, abrasive dust in pulverizing mill is crossed 180 purposes sieve.
9, the preparation method of transparent cover light powder paint composition according to claim 8 is characterized in that: described inert solvent is selected from a kind of in the following solvents: the mixture of benzene,toluene,xylene, vinyl acetic monomer, N-BUTYL ACETATE, capryl acetate, acetic acid heptyl ester, tetrahydrofuran (THF), acetone, methylethylketone, mibk, MAK, methyl isoamyl ketone and these solvents.
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|---|---|---|---|
| CN2008100695700A CN101260271B (en) | 2008-04-14 | 2008-04-14 | Transparent cover light powder paint composition and preparation method thereof |
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| CN101260271B CN101260271B (en) | 2010-06-09 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980787A (en) * | 2014-04-30 | 2014-08-13 | 张家港江南粉末涂料有限公司 | Acrylic acid transparent powdery paint for glazing and preparation method thereof |
| CN104109453A (en) * | 2014-07-28 | 2014-10-22 | 漳州三德利油漆涂料有限公司 | Compound functional agricultural machinery finishing powder coating and production process thereof |
| CN105949859A (en) * | 2016-05-23 | 2016-09-21 | 黄山华惠科技有限公司 | Luster-enhancing agent for powder coating as well as preparation method and application of luster-enhancing agent |
| CN106366809A (en) * | 2016-08-30 | 2017-02-01 | 安徽美佳新材料股份有限公司 | High-impact-resistance automotive finishing powder coating |
| CN112430413A (en) * | 2020-10-21 | 2021-03-02 | 浙江喜泽荣制漆有限公司 | Outdoor transparent finishing powder and preparation method thereof |
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2008
- 2008-04-14 CN CN2008100695700A patent/CN101260271B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980787A (en) * | 2014-04-30 | 2014-08-13 | 张家港江南粉末涂料有限公司 | Acrylic acid transparent powdery paint for glazing and preparation method thereof |
| CN104109453A (en) * | 2014-07-28 | 2014-10-22 | 漳州三德利油漆涂料有限公司 | Compound functional agricultural machinery finishing powder coating and production process thereof |
| CN104109453B (en) * | 2014-07-28 | 2016-06-22 | 漳州三德利油漆涂料有限公司 | Composite functional type agricultural machinery clear top powder coatings and production technology thereof |
| CN105949859A (en) * | 2016-05-23 | 2016-09-21 | 黄山华惠科技有限公司 | Luster-enhancing agent for powder coating as well as preparation method and application of luster-enhancing agent |
| CN106366809A (en) * | 2016-08-30 | 2017-02-01 | 安徽美佳新材料股份有限公司 | High-impact-resistance automotive finishing powder coating |
| CN112430413A (en) * | 2020-10-21 | 2021-03-02 | 浙江喜泽荣制漆有限公司 | Outdoor transparent finishing powder and preparation method thereof |
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| CN101260271B (en) | 2010-06-09 |
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