CN104559691B - Polymer composite for heat transfer printing low-temperature crosslinking and preparation method thereof - Google Patents
Polymer composite for heat transfer printing low-temperature crosslinking and preparation method thereof Download PDFInfo
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- 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
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- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to the field of chemical coatings, and provides a polymer composite for heat transfer printing low-temperature crosslinking. The polymer composite comprises the following components in percentage by weight: 55-58% of a polyester resin, 4.5-5.2% of a curing agent, 30-36% of a pigment and a filler, 2.7-7% of an assistant, 0.15- 0.4% of a curing accelerator, and 1-1.5% of a nano material. The preparation method comprises the following steps: (1) previously dispersing the nano materials and barium sulfate, then pouring the dispersed materials into absolute ethyl alcohol, and dispersing the dispersed materials and the absolute ethyl alcohol by using a cohesive energy ultrasonic emulsifier; (2) pouring the dispersed materials, the absolute ethyl alcohol and other components into a material mixing kettle to be mixed according to a formula, melting, extruding and mixing the mixed materials through an extruder, breaking the materials after the materials are cooled, and finally, performing screening in a classification manner by a rotary screen so as to obtain the polymer composite. For the polymer composite, under the action of the curing accelerator, films are formed in a crosslinking manner, and the impact resistance, the flexibility, the adhesive force, the salt spray resistance, boiling water resistance, damp and hot resistance and the like are good.
Description
Technical field
The present invention relates to chemistry painting industry field, is that one kind is coated on aluminium section bar outer surface, aluminium is protected and is decorated,
Simultaneously user can as needed can be in the polymer composite of the various patterns of surface heat-transferring.
Background technology
The processing method of aluminium shape surface is relatively more at present, has electrophoresis, oxidation, electrostatic powder coating etc., wherein electrostatic powder
Last coating is because of environmental protection and color rich color, more and more welcomed by the people.The powdery paints for transferring is can be especially useful for, because
Material surface that can be after spray coating prints various textures and pattern, meets the demand of individual character, increasingly receives an acclaim.But
Existing powdery paints has that baking temperature is high, and the time is long, and weather resistance it is not good the problems such as, such as change weather resistance into excellent
Extra-weather-proof resin or fluorocarbon coating, there is selling at exorbitant prices user again and be difficult to receive, the problems such as promote difficult.
The content of the invention
The present invention be a kind of polymer composite that thermal transfer can be carried out for being coated in aluminium shape surface, the macromolecule
The film-forming temperature of composite is low, can energy saving, improve production efficiency, ageing-resistant performance be excellent, polymer composite into
In the surface various textures of thermal transfer and pattern as needed, the color and decorative pattern of aluminium section bar decoration can be greatly enriched after film.
The technical solution adopted in the present invention is：It is a kind of for thermal transfer can crosslinked at low temperature polymer composite, its
Component and weight/mass percentage composition are：Polyester resin 55～58%, firming agent 4.5～5.2%, pigment and filler 30～36%, help
Agent 2.7～7%, curing accelerator 0.15～0.4%, nano material 1～1.5%.
Further, described polyester resin is the terminal carboxyl polyester resin that polyhydric alcohol and polybasic carboxylic acid are polymerized, its
Acid number is 30～38mgKOH/g, and Tg is 60～67 DEG C, and softening point is 100～125 DEG C.
Further, described firming agent is isocyanuric acid three-glycidyl ester, the epoxide equivalent of the firming agent is 105～
110g/mol, 95～125 DEG C of melting range, fugitive constituent≤0.5%.
Preferably, described filler mean diameter≤10 μm, specially barium sulfate, Kaolin or silicon powder one of which
Or it is various.
Preferably, described curing accelerator is tetradecyltrimethylammonium amine bromide or benzyltriphenylphosphonium bromide phosphorus, its
D50 is≤40 μm.
Further, described nano material is nano zine oxide, nano silicon, nano titanium oxide one of which
Or it is various.
Further, described auxiliary agent includes levelling agent, dispersant, degasser, fluffy powder, sand streak agent, delustering agent, described
Levelling agent include acrylate copolymer, dispersant includes methacrylic acid and cinnamic copolymer, and degasser includes peace
Breath perfume or amide waxe, fluffy powder include aerosil or aluminium oxide C, and sand streak agent includes politef wax powder, delustering agent
Non-reactive delustering agent such as SA206, A9, A8, PW176, XG605W, SA2067A commonly used including powdery paints etc..
It is above-mentioned for thermal transfer can crosslinked at low temperature polymer composite preparation method, comprise the steps：
(1) nano material is pre-dispersed：Nano material and filler are carried out pre-dispersed, then will be thrown to nothing with scattered material
In water-ethanol, disperseed using energy-collecting ultrasonic ripple emulsator, the horn of ultrasonic emulsator is directly immersed in pre-dispersed molten
In liquid, make acoustic energy be directly entered dispersion, the material after dispersion utilizes vacuum filtration, dry stand-by；
(2) material obtained in step (1) and other components are mixed by formula input mixing kettle, by the thing for mixing
Material carries out melting extrusion mixing by extruder, extrusion mixing material is cooled down, is crushed material with disintegrating machine, then
Finely divided and classification is carried out with air classification mill, is finally sieved with rotation sieve classification and is obtained product.
Further, described sieve number used of sieving is 180 mesh.
The invention has the beneficial effects as follows, the isocyanuric acid three-glycidyl ester firming agent that the present invention is adopted promotes in solidification
In the presence of agent, epoxide group is reacted with the carboxyl of polyester resin, is crosslinked film forming.Gained polymer composite belongs to low temperature
Cross-linking type, general condition of cure are 180 DEG C/10min, can adjust most as little as 160 DEG C/10min hardening time according to user's request,
Up to 50kg/cm, pliability 1mm, 0 grade of adhesive force, salt fog resistance can reach polymer composite impact strength after crosslinking
More than 500h, the 2h of resistance to boiling water, wet-heat resisting 1000h, the physical and mechanical propertiess and ageing-resistant performance of organic double compound are excellent, prepare work
Skill is simple, is remarkably improved labor productivity, is adapted to industrialized production.
Description of the drawings
Fig. 1 is polymer composite preparation method process chart of the present invention.
Specific embodiment
Specific embodiment
In following embodiment, polyester resin is the terminal carboxyl polyester resin that polyhydric alcohol and polybasic carboxylic acid are polymerized, ginseng
Number is 30～38mgKOH/g for the acid number of resin, and Tg is 60～67 DEG C, and softening point is 100～125 DEG C；Firming agent used is different
Cyanuric acid three-glycidyl ester, the epoxide equivalent of the firming agent is 105～110g/mol, 95～125 DEG C of melting range, fugitive constituent≤
0.5%；Pigment reaches more than 180 DEG C for thermostability, and light resistance reaches 7～8 grades, weatherability reach 4～5 grades it is various without weight
The coloring pigment and Rutile type titanium dioxide of metal.
Embodiment 1
It is a kind of for thermal transfer can crosslinked at low temperature polymer composite, with following formula, (each group is divided into quality hundred
Divide content)：58 parts of NH3395 polyester resin, 4.7 parts of isocyanuric acid three-glycidyl ester, 14 parts of coloring pigment, 18 parts of barium sulfate,
Nano material (nano zine oxide, nano titanium oxide, nano silicon three 1：1：1 mixture) 1.5 parts, myristyl three
0.2 part of methyl bromide ammonium (through micronization, D50 is 40 μm), 2.0 parts of levelling agent, 1.0 parts of dispersant, Benzoinum degasser 0.5
Part, 0.1 part of fluffy powder.
Embodiment 2
It is a kind of for thermal transfer can crosslinked at low temperature polymer composite, with following formula, (each group is divided into quality hundred
Divide content)：55 parts of NH3395 polyester resin, 5.2 parts of isocyanuric acid three-glycidyl ester, 14 parts of coloring pigment, barium sulfate 20.5
Part, nano material (nano zine oxide, nano titanium oxide, the two 1：1 mixture) 1.5 parts, benzyltriphenylphosphonium bromide phosphorus 0.15
Part (without micronization, D50 is 30 μm), 2.0 parts of levelling agent, 1.0 parts of dispersant, 0.5 part of Benzoinum degasser, fluffy powder
0.15 part.
Embodiment 3
It is a kind of for thermal transfer can crosslinked at low temperature polymer composite, with following formula, (each group is divided into quality hundred
Divide content)：55 parts of NH3395 polyester resin, 4.7 parts of isocyanuric acid three-glycidyl ester, 14 parts of coloring pigment, 18 parts of barium sulfate,
Nano material (nano zine oxide, nano titanium oxide, nano silicon three 1：1：1 mixture) 1.5 parts, myristyl three
0.2 part of methyl bromide ammonium (through micronization, D50 is 32 μm), 2 parts of levelling agent, 0.7 part of dispersant, Benzoinum degasser 0.5
Part, 3.4 parts of SA206 delustering agents.
Embodiment 4
It is a kind of for thermal transfer can crosslinked at low temperature polymer composite, with following formula, (each group is divided into quality hundred
Divide content)：55 parts of NH3395 polyester resin, 4.7 parts of isocyanuric acid three-glycidyl ester, 14 parts of coloring pigment, 18 parts of barium sulfate,
Nano material (nano zine oxide, nano titanium oxide, nano silicon three 1：1：1 mixture) 1.2 parts, myristyl three
0.2 part of methyl bromide ammonium (through micronization, D50 is 32 μm), 1.2 parts of levelling agent, 0.7 part of dispersant, Benzoinum degasser 0.3
Part, 4.7 parts of SA2067A delustering agents.
Embodiment 5
It is a kind of for thermal transfer can crosslinked at low temperature polymer composite, with following formula, (each group is divided into quality hundred
Divide content)：55 parts of NH3395 polyester resin, 4.7 parts of isocyanuric acid three-glycidyl ester, 20 parts of coloring pigment, 11 parts of barium sulfate,
5 parts of Kaolin, nano material (nano zine oxide, nano titanium oxide, nano silicon three 1：1：1 mixture) 1.2 parts,
0.4 part of benzyltriphenylphosphonium bromide phosphorus (through micronization, D50 is 30 μm), 0.6 part of SA207 sand streaks agent, 1.2 parts of dispersant, rest in peace
0.6 part of fragrant degasser, 0.3 part of fluffy powder.
In the various embodiments described above for thermal transfer can crosslinked at low temperature polymer composite preparation method it is as follows：
(1) nano material is pre-dispersed：Nano material and filler are carried out pre-dispersed, then pre-dispersed material is thrown to nothing
In water-ethanol, disperseed using energy-collecting ultrasonic ripple emulsator, the horn of ultrasonic emulsator is directly immersed in pre-dispersed molten
In liquid, make acoustic energy be directly entered dispersion, the material after dispersion utilizes vacuum filtration, dry stand-by；
(2) various raw materials (including pre-dispersed nano material) are mixed by formula input mixing kettle, incorporation time 3
The material for mixing is carried out melting extrusion mixing, extrusion mixing material chill roll and cooling zone by extruder by～5min
Cooled down, material is crushed to into thick below 2.5mm, long and width below 20mm with disintegrating machine, then is carried out carefully with air classification mill
Crush and be classified, finally sieved with rotation sieve classification and obtain product, sieve number is 180 mesh.
Comparative example 1
Curing accelerator in embodiment 1 is replaced with without micronization, D50 is 50 μm of tetradecyltrimethylammonium bromination
Ammonium.
Comparative example 2
Curing accelerator in embodiment 2 is replaced with without micronization, D50 is 60 μm of tetradecyltrimethylammonium bromination
Ammonium.
Comparative example 3
Benzyltriphenylphosphonium bromide phosphorus addition in embodiment 5 is revised as into 0.5 part, other conditions are with embodiment 5.
Comparative example 4
Benzyltriphenylphosphonium bromide phosphorus addition in embodiment 5 is revised as into 0.1 part, other conditions are with embodiment 5.
Technical performance
Table 1
The data in contrast table 1 are it is recognized that while only by curing accelerator in comparative example 1 and comparative example 2
Particle diameter has somewhat made and has changed, but on final performance in terms of affect very big, such as gloss, salt spray resistance, impact property, resistance to
Effect and outward appearance after boiling water, transfer has large effect, and this is likely due to the curing accelerator employed in the application
Impact, due to its fusing point relatively be up to more than 240 DEG C, cannot melt during the product manufacturing and use, be easier to out
The situation of existing pinprick, under the application formulation condition, chooses proper settings accelerator and performance is greatly improved；Additionally,
The addition of delustering agent in formula can change the pass pool of product, and the addition of sand streak agent can change the outward appearance of product, be have product
Frosted finish effect.
Claims (6)
1. it is a kind of for thermal transfer can crosslinked at low temperature polymer composite, it is characterised in that：Its component and quality percentage contain
Measure and be：Terminal carboxyl polyester resin 55～58%, the firming agent 4.5～5.2%, pigment containing epoxide group and filler 30～36%,
Auxiliary agent 2.7～7%, curing accelerator 0.15～0.4%, nano material 1～1.5%；Described terminal carboxyl polyester resin is many
First alcohol and polybasic carboxylic acid are polymerized, and its acid number is 30～38mgKOH/g, and Tg is 60～67 DEG C, and softening point is 100～125 DEG C；
The described firming agent containing epoxide group is isocyanuric acid three-glycidyl ester, and the epoxide equivalent of the firming agent is 105～110g/
Mol, 95～125 DEG C of melting range, fugitive constituent≤0.5%；Described curing accelerator is Tetradecyl Trimethyl Ammonium Bromide or benzyl
Tri-phenyl-phosphorus bromide, its D50 are≤40 μm.
2. it is according to claim 1 for thermal transfer can crosslinked at low temperature polymer composite, it is characterised in that：It is described
Filler mean diameter≤10 μm, specially barium sulfate, Kaolin or silicon powder one or more of which.
3. it is according to claim 1 for thermal transfer can crosslinked at low temperature polymer composite, it is characterised in that：It is described
Nano material be nano zine oxide, nano silicon, nano titanium oxide wherein two or more.
4. it is according to claim 1 for thermal transfer can crosslinked at low temperature polymer composite, it is characterised in that：It is described
Auxiliary agent include levelling agent, dispersant, degasser, fluffy powder, delustering agent, sand streak agent, described levelling agent includes acrylate
Copolymer, dispersant include methacrylic acid and cinnamic copolymer, and degasser includes Benzoinum or amide waxe, fluffy powder bag
Aerosil or aluminium oxide C are included, sand streak agent includes politef wax powder, and delustering agent is non-reactive delustering agent, including
SA206, A9, A8, PW176, KT3309, SA2067A one or more of which.
5. according to any one of Claims 1 to 4 for thermal transfer can crosslinked at low temperature polymer composite preparation
Method, it is characterised in that：
(1) nano material is pre-dispersed：Nano material and filler are carried out pre-dispersed, then pre-dispersed material is thrown to anhydrous second
In alcohol, disperseed using energy-collecting ultrasonic ripple emulsator, the horn of ultrasonic emulsator be directly immersed in pre-dispersed solution,
Make acoustic energy be directly entered dispersion, the material after dispersion utilizes vacuum filtration, dry stand-by；
(2) material obtained in step (1) and other components are mixed by formula input mixing kettle, the material for mixing is led to
Crossing extruder carries out melting extrusion mixing, extrusion mixing material is cooled down, is crushed material with disintegrating machine, then with sky
Gas grading mill carries out finely divided and classification, is finally sieved with rotation sieve classification and obtains product.
6. it is according to claim 5 for thermal transfer can crosslinked at low temperature polymer composite preparation method, which is special
Levy and be：Described sieves sieve number used for 180 mesh.
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| CN201410819689.0A CN104559691B (en) | 2014-12-25 | 2014-12-25 | Polymer composite for heat transfer printing low-temperature crosslinking and preparation method thereof |
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| CN109266185A (en) * | 2018-10-16 | 2019-01-25 | 上海国丽粉体涂料有限公司 | A kind of powdery paints and application thereof |
| CN109651937A (en) * | 2018-12-12 | 2019-04-19 | 东莞市爱粤金属粉末有限公司 | Powdery paints and preparation method thereof |
| CN112831258A (en) * | 2021-03-04 | 2021-05-25 | 四川和乐门业有限公司 | Environment-friendly hot-press-resistant transparent finishing powder and preparation method thereof |
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| CN101851460A (en) * | 2010-06-04 | 2010-10-06 | 江苏兰陵高分子材料有限公司 | Polyester powder coating for solar water heater |
| CN103687892A (en) * | 2011-08-04 | 2014-03-26 | 阿克佐诺贝尔国际涂料股份有限公司 | Thermosetting durable powder coating composition |
| CN102516855B (en) * | 2011-12-13 | 2014-02-19 | 广东华江粉末科技有限公司 | Powdery paint for aluminum profile and preparation method thereof |
| CN103304790A (en) * | 2013-06-06 | 2013-09-18 | 广东伊诗德新材料科技有限公司 | Polyester resin for outdoor aluminum profile heat transfer printing powder coating and preparation method thereof |
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