CN1103410A - Process for production of saturated hydroxy polyester resin and powder paint of polyurethane synthesized with its resultant - Google Patents
Process for production of saturated hydroxy polyester resin and powder paint of polyurethane synthesized with its resultant Download PDFInfo
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- CN1103410A CN1103410A CN 94108846 CN94108846A CN1103410A CN 1103410 A CN1103410 A CN 1103410A CN 94108846 CN94108846 CN 94108846 CN 94108846 A CN94108846 A CN 94108846A CN 1103410 A CN1103410 A CN 1103410A
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- Prior art keywords
- polyester resin
- hydroxy polyester
- saturated hydroxy
- acid
- weight part
- 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.)
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 30
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 22
- 239000004645 polyester resin Substances 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 title claims abstract description 22
- 239000004814 polyurethane Substances 0.000 title claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title abstract description 15
- 239000003973 paint Substances 0.000 title abstract description 5
- 239000006085 branching agent Substances 0.000 claims abstract description 7
- 230000032050 esterification Effects 0.000 claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- 230000004927 fusion Effects 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 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
- 230000035484 reaction time Effects 0.000 claims 1
- 239000004566 building material Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- -1 dicarboxylic acid compound Chemical class 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000675108 Citrus tangerina Species 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The process for producing saturated hydroxy polyester resin used to synthesize powdered paint of polyurethane for domestic electric appliances, building material, car, agricultural machinery, etc. includes direct fusion esterification of polyacid and polylol in the presence of catalyst and chain-branching agent and ordinary-temp. condensation polymerization and features high quality and excellent performance of product, safe production, and easy control of process. The synthesized powder paint has good weatherability, better decorative performance and stable nature.
Description
The invention belongs to organic high molecular compound preparation and paint field.
Saturated hydroxy polyester resin is mainly used in the synthetic of blocked isocyanate solidified polyurethane powder coating.Hydroxy polyester resin generally is that polycondensation-separate the method for contracting synthesizes the employing vacuum.
U.S. Pat 4264751 discloses the transesterify one vacuum condensation reaction method of producing vibrin, this method is that dibasic alcohol and dicarboxylic acid compound carry out transesterify one vacuum polycondensation in the presence of chain branching agent, and synthetic saturated hydroxy polyester also is used to make polyurethane powder coating.The shortcoming that adopts this method is that facility investment is big, and product mechanical property instability easily produces a large amount of inflammable toxic gas methyl alcohol in building-up process, produce dangerously, the disposal of waste gas, water and industrial residue expense is big, the product cost height, do not have competitive power, and Technology is difficult to assurance etc.
U.S. Pat 4124570 has been described a kind of saturated hydroxy polyester resin of synthesis of polyurethane powder coating, its acid number is controlled at 10～30MgkoH/g, synthetic powder coating gel time is obviously shortened, the tangerine peel of filming that forms is serious, gloss is low, and the solvent resistance and the shock resistance of filming simultaneously are poor.
U.S. Pat 4054681 discloses a kind of saturated hydroxy polyester resin that is used for the synthesis of polyurethane powder coating, its shortcoming is that easily caking is agglomerating in the storage at normal temperature transportation for the synthetic polyurethane powder coating, package stability is poor, should not be as the starting material of polyurethane powder coating.
The saturated hydroxy polyester resin synthetic polyurethane powder coating that the purpose of this invention is to provide a kind of production method of saturated hydroxy polyester resin and utilize this method to generate, the feasible saturated hydroxy polyester resin excellent property of utilizing this method to generate, lighter color, transparency is good, can overcome the deficiency of prior art with its synthetic polyurethane powder coating, having formation films plentiful, light and good toughness, anti-resistance to marring reaches good weathering resistance by force, processing is preferably arranged, construction property, satisfactory stability is arranged when storing transportation, the good surface appearance of having filmed during application is ornamental, favorable mechanical performance and heat-resisting, advantages such as weather resistance.
The production method of saturated hydroxy polyester resin provided by the present invention realizes by following measure.
By polyvalent alcohol and polyprotonic acid in the presence of catalyzer, chain branching agent, direct fusion esterification, the normal pressure polycondensation is synthetic.Its reaction formula is as follows:
Direct esterification becomes the low polymerization degree polyester
Polycondensation becomes the polyester of high-polymerization degree
Total expressivity structure is
Wherein: the G-polyvalent alcohol, the A-polyprotonic acid, n 〉=2, PE is the low polymerization degree vibrin.
Polyprotonic acid content is the 30-65%(weight part), polyvalent alcohol content is the 20-40%(weight part), catalyzer is a Dibutyltin oxide, its content is the 0.01-1.2%(weight part).
In esterification, also can add 1～10%(weight part) longer chain fatty acid or Fatty Alcohol(C12-C14 and C12-C18), with the effect of De Gengjia.
The synthetic technical process is as follows:
Polyprotonic acid+polyvalent alcohol (catalyzer)/(normal pressure, heating) esterification becomes low polymerization degree polyester (polycondensation)/() to be condensed into polymer → cooling, decompression → cooling → fragmentation → packing
The synthetic need of saturated hydroxy polyester resin 10～16 hours, esterifying polycondensation temperature are controlled at 190 ℃～240 ℃, use good heating system, vacuum, tightness system, accurate measuring apparatus, separation column adopts the efficient conjugate ring filler of stainless steel, has advantages such as separation efficiency height, operation balance.
Concrete operating process is; in the polyester synthesis reaction vessel, drop into the polyprotonic acid of metering; polyvalent alcohol and catalyzer; under protection of inert gas, slowly be warming up to 190 ℃-240 ℃ of temperature of reaction by heating; constant temperature when aquifer yield reaches theoretical aquifer yield, is tested its acid number, hydroxyl value; when index reaches acid number (mgkoH/g) respectively: 3～8, hydroxyl value (mgkoH/g): can lower the temperature in 30～45 o'clock, decompression, cooling, discharge, pulverizing and packing.
The over-all properties of polyurethane powder coating depends on the kind of hydroxy polyester resin, solidifying agent, filling material and proportioning, fine raw material, scientific formula.Advanced technology is the assurance that obtains the good over-all properties of polyurethane powder coating.Polyurethane powder coating of the present invention, it is the saturated hydroxy polyester resin of being produced with saturated hydroxy polyester resin production method provided by the invention, and blocked isocyanate curing agent is base-material, adds flow agent, and color stuffing fusion, is extruded, pulverized and form through mixing.
The present invention compared with prior art has following advantage:
1, synthetic saturated hydroxy polyester resin of the present invention have lighter color, control indexes rationally, the characteristics of steady quality, excellent performance, by this resin synthetic polyurethane powder coating, good processing and construction property are not only arranged, and filming of formation has good decorative appearance, excellent physical and mechanical properties, more comprehensively chemical proofing and typical weathering resistance.
2, the every performance index control of saturated hydroxy polyester resin rationally among the present invention, have lower acid number (3-8mgkoH/g) and suitable hydroxyl value (30-45mgkoH/g), molecular weight is to be controlled at 2500～5000, second-order transition temperature is controlled at 55 ℃～65 ℃, make the synthetic polyurethane powder coating have long gelation time, in the polyurethane powder coating prescription, can reduce hardener dose, at the condition decline lower crosslink density that guarantees mechanical property, thereby make filming of formation smooth smooth, give film excellent solvent-resistance energy and mechanical property (snappiness, shock resistance).Synthetic vibrin normal temperature prevented from caking by this polyester synthetic Polyurethane powder coating, has good storage stability.
3, the present invention adopts good heating installation, vacuum sealing system, accurate measuring apparatus, separation column has adopted the efficient conjugate ring of advanced stainless steel to replace traditional Raschig ring filler simultaneously, have the separation efficiency height, distinguishing features such as smooth operation can and shift out reactor with the moisture absorption that generates in the reaction process, and the loss of alcohol seldom, guaranteed the accuracy of metering; Simultaneously efficient conjugate ring can significantly reduce the packing tower height, reduces the process cost of facility investment and saving technological process.
Below in conjunction with embodiment the production method of saturated hydroxy polyester resin is further described in detail.
Selecting terephthalic acid for use is polyprotonic acid, and neopentyl glycol is a polyvalent alcohol, and TriMethylolPropane(TMP) is a chain branching agent.In reactor, drop into 525 parts of neopentyl glycol, 150 parts of glycol ethers, 1000 parts of terephthalic acids, 450 parts of TriMethylolPropane(TMP)s, fusion, intensification, and feed N
2Protection; slowly be warming up to 240 ℃ of maximum temperature; separation column adopts the insulation of water and steam azeotropic simultaneously, and the water of generation is successively told, and insulation is about 10-16 hour with this understanding; measure its acid number, hydroxyl value; when index reaches acid number 3-8mbkoH/g respectively, during hydroxyl value 30-45mgkoH/g, then to reaction mirror system decompression, vacuumize; cooling then, discharge, crushing packing get final product.
Mid-chain branched agent of the present invention can also be selected trimellitic acid 1,2-anhydride for use.
Below in conjunction with embodiment polyurethane powder coating of the present invention is further described.
100 parts of saturated hydroxy polyester resins provided by the present invention, 18～25 parts of blocked isocyanate curing agents, 1.2～2.0 parts of flow agents, 0.8～1.0 part of st-yrax, TIO
250～60 parts through mixed melting, and extrude, pulverize by twin screw extruder, 115 ℃-125 ℃ of extrusion temperatures, powder size is no more than 90um.
The preparation method of above-mentioned blocked isocyanate curing agent is: adopt active hydrogen atom reaction in vulcabond and the ∈-hexanolactam earlier, temperature of reaction is controlled at 120 ℃-150 ℃, add then dibutyl tin laurate carry out trimerization reaction or with the polyvalent alcohol addition, the group content of the isocyanic ester isocyanide of part trimerization sealing is controlled at 7.0-14.0%, the ratio control of affixture type blocked isocyanate curing agent NCO/OH is between 2.0-4.0, measure free NCO content, if it less than 0.8%, gets final product discharging.
Claims (4)
1, a kind of production method of saturated hydroxy polyester resin, comprise reactor, heating system, vacuum, tightness system and measuring apparatus, it is characterized in that by polyprotonic acid and polyvalent alcohol at catalyzer, chain branching agent exists down, direct fusion esterification, the normal pressure polycondensation is synthetic, and wherein, polyprotonic acid content is 30-65% (weight part), polyvalent alcohol content is 20-40% (weight part), chain branching agent content is 1-10% (weight part), catalyzer Dibutyltin oxide content 0.01-1.2% (weight part), and the esterifying polycondensation temperature is controlled at 190 °-240 ℃, reaction times 10-16 hour, adopt the efficient conjugate ring separation column of stainless steel, the acid number of resultant is controlled at 3-8MgkoH/g, and hydroxyl value is controlled at 30-45MgkoH/g.
2, the production method of saturated hydroxy polyester according to claim 1 is characterized in that in esterification adding the 1-10%(weight part) longer chain fatty acid or Fatty Alcohol(C12-C14 and C12-C18).
3, the production method of saturated hydroxy polyester resin according to claim 1 and 2 is characterized in that polyprotonic acid selects terephthalic acid for use, and polyvalent alcohol is selected neopentyl glycol for use, and chain branching agent is selected TriMethylolPropane(TMP) or trimellitic acid 1,2-anhydride for use.
4, a kind of polyurethane powder coating is characterized in that the saturated hydroxy polyester resin with claim 1 or 2 or 3 described production method preparations is that base-material is synthetic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108846A CN1060484C (en) | 1994-07-22 | 1994-07-22 | Process for production of saturated hydroxy polyester resin and powder paint of polyurethane synthesized with its resultant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108846A CN1060484C (en) | 1994-07-22 | 1994-07-22 | Process for production of saturated hydroxy polyester resin and powder paint of polyurethane synthesized with its resultant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1103410A true CN1103410A (en) | 1995-06-07 |
| CN1060484C CN1060484C (en) | 2001-01-10 |
Family
ID=5033680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94108846A Expired - Fee Related CN1060484C (en) | 1994-07-22 | 1994-07-22 | Process for production of saturated hydroxy polyester resin and powder paint of polyurethane synthesized with its resultant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1060484C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406494C (en) * | 2006-12-06 | 2008-07-30 | 上海振华造漆厂 | Epoxy-modified polyester resin for coil back paint and preparation method thereof |
| CN101481578B (en) * | 2009-02-03 | 2011-01-19 | 广州慧谷化学有限公司 | Capacitor coating with deep drawing resistant performance and high temperature yellowing resistance and preparation thereof |
| CN102250514A (en) * | 2011-01-19 | 2011-11-23 | 一可油墨涂料（深圳）有限公司 | Solvent-resistant halogen-free two-component screen printing ink |
| CN102408820A (en) * | 2011-07-29 | 2012-04-11 | 哈尔滨理工大学 | Preparation method of water-soluble low-contact-angle semi-inorganic silicon steel sheet paint |
| CN105367767A (en) * | 2015-12-07 | 2016-03-02 | 浙江传化天松新材料有限公司 | Saturated middle hydroxyl value polyester resin for high flexibility powder coating and preparation method thereof |
| CN108822285A (en) * | 2018-07-11 | 2018-11-16 | 广东美涂士建材股份有限公司 | The low thinning of the low hydroxyl of high-solid lower-viscosity is than alkyd resin and its preparation method and application |
| CN109180925A (en) * | 2018-09-07 | 2019-01-11 | 安徽恒隆新材料有限公司 | A kind of high glaze powdery paints hydroxy polyester resin and the preparation method and application thereof |
| CN113308184A (en) * | 2021-06-18 | 2021-08-27 | 佛山市南海嘉多彩粉末涂料有限公司 | Bending-resistant weather-resistant powder coating composition for stainless steel and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4359554A (en) * | 1973-09-06 | 1982-11-16 | Ford Motor Company | Powder paint with epoxy and hydroxy copolymer and dicarboxylic acids |
| GB9205137D0 (en) * | 1992-03-10 | 1992-04-22 | Scott Bader Co | Anti-popping agents for powder coating compositions |
-
1994
- 1994-07-22 CN CN94108846A patent/CN1060484C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406494C (en) * | 2006-12-06 | 2008-07-30 | 上海振华造漆厂 | Epoxy-modified polyester resin for coil back paint and preparation method thereof |
| CN101481578B (en) * | 2009-02-03 | 2011-01-19 | 广州慧谷化学有限公司 | Capacitor coating with deep drawing resistant performance and high temperature yellowing resistance and preparation thereof |
| CN102250514A (en) * | 2011-01-19 | 2011-11-23 | 一可油墨涂料（深圳）有限公司 | Solvent-resistant halogen-free two-component screen printing ink |
| CN102250514B (en) * | 2011-01-19 | 2014-02-26 | 深圳市美丽华油墨涂料有限公司 | Solvent-resistant halogen-free two-component screen printing ink |
| CN102408820A (en) * | 2011-07-29 | 2012-04-11 | 哈尔滨理工大学 | Preparation method of water-soluble low-contact-angle semi-inorganic silicon steel sheet paint |
| CN105367767A (en) * | 2015-12-07 | 2016-03-02 | 浙江传化天松新材料有限公司 | Saturated middle hydroxyl value polyester resin for high flexibility powder coating and preparation method thereof |
| CN105367767B (en) * | 2015-12-07 | 2017-06-23 | 浙江传化天松新材料有限公司 | Hydroxy polyester resin and preparation method thereof in high-flexibility saturation used for powder coating |
| CN108822285A (en) * | 2018-07-11 | 2018-11-16 | 广东美涂士建材股份有限公司 | The low thinning of the low hydroxyl of high-solid lower-viscosity is than alkyd resin and its preparation method and application |
| CN108822285B (en) * | 2018-07-11 | 2020-12-25 | 广东美涂士建材股份有限公司 | Alkyd resin with high solid content, low viscosity, low hydroxyl content and low dilution ratio as well as preparation method and application thereof |
| CN109180925A (en) * | 2018-09-07 | 2019-01-11 | 安徽恒隆新材料有限公司 | A kind of high glaze powdery paints hydroxy polyester resin and the preparation method and application thereof |
| CN109180925B (en) * | 2018-09-07 | 2020-12-18 | 安徽恒隆新材料有限公司 | Hydroxyl polyester resin for high-gloss powder coating and preparation method and application thereof |
| CN113308184A (en) * | 2021-06-18 | 2021-08-27 | 佛山市南海嘉多彩粉末涂料有限公司 | Bending-resistant weather-resistant powder coating composition for stainless steel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1060484C (en) | 2001-01-10 |
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