CN109971157A - A kind of TPU composite material and preparation method of alternative plating and coating - Google Patents
A kind of TPU composite material and preparation method of alternative plating and coating Download PDFInfo
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- CN109971157A CN109971157A CN201910239069.2A CN201910239069A CN109971157A CN 109971157 A CN109971157 A CN 109971157A CN 201910239069 A CN201910239069 A CN 201910239069A CN 109971157 A CN109971157 A CN 109971157A
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
Abstract
The present invention relates to a kind of high molecular material, in particular to a kind of TPU composite material and preparation method of alternative plating and coating；Wherein, a kind of TPU composite material of alternative plating and coating, including following components: 60-99 parts of TPU resin；0.1-20 parts of sphere powder, 0.1-20 parts of metal powder；0.1-5 parts of dispersing agent；0.1-1 parts of antioxidant；0.1-1 parts of light stabilizer；Wherein metal powder and spherical powder are handled using chemisorption, can greatly improve the compatibility with TPU resin；TPU composite material is obtained by double screw extruder melting, mixing, cooling and pelletizing again.The present invention provides the TPU composite material of a kind of alternative plating and coating, which can cut down light weld bond in injection molding and eliminate the open defects such as current mark, and have strong metal-like, the market application of alternative some plating and coating.
Description
Technical field
The present invention relates to a kind of high molecular material, in particular to the TPU composite material of a kind of alternative plating and coating and
Preparation method.
Background technique
Current governmental payes attention to environmental protection further, plating and key industry of the coating as water pollution, most related enterprises
Industry ordered to rectify and improve, as can Part Substitution plating and coating plastic products exempt from sprayed on material, have environment-friendly and green, recyclable
The characteristics of, while avoiding and volatilizing the poisonous and hazardous chemicals such as benzene, formaldehyde, dimethylbenzene in plating and coating process outward
Matter avoids and causes the symptoms such as headache, Nausea and vomiting to operator, injures liver, kidney, nervous system and the note of human body
Recall the serious consequences such as power decline.
Currently, the preparation method for exempting from sprayed on material is to add the pearl with particular color effect in matrix resin mostly
The special powder of light powder, metal powder, glass powder etc. and other processing aids are formed finely dispersed by extrusion machining
Material.Because special powder is mostly laminated structure, radius-thickness ratio is in 10-1000, special in the product injection moulding process of product structure complexity
Different powder can flow direction along resin melt and be orientated, while phenomena such as also can turn to melt, invert, converge, sheet knot
The special powder of structure can then form the different shapes such as parallel, flip angle, vertical along melt flows direction with product surface, this
If sample, light is reflected on the special powder of sheet the reflected light for then forming different angle, causes to flow in product surface
The open defects such as trace and weld bond affect the market application for exempting from sprayed on material and promote.
Summary of the invention
To solve the problems in above-mentioned background technique, the present invention provides the TPU composite wood of a kind of alternative plating and coating
Material, by weight, including following component:
Wherein, the spherical powder is at least one of spherical powder of basic anhydride.
On the basis of above scheme, further, the basic anhydride are magnesia, in calcium oxide, sodium oxide molybdena
At least one, partial size are 10~200 μm.
On the basis of above scheme, further, the spherical powder is handled using following methods: using two fourths
Base hydroxy-methylbenzene, 2-hydroxy-4-n-octoxybenzophenone add spherical after isopropyl triisostearoyltitanate mixing
Powder, using 100-300rpm/min, and under 120 DEG C of -150 DEG C of environment, heating, drying is obtained；
Preferably, the dibutyl hydroxy toluene, 2-hydroxy-4-n-octoxybenzophenone, three isostearoyl base metatitanic acids
Isopropyl ester is mixed according to the ratio of 1:2:3.In the present solution, using dibutyl hydroxy toluene, 2- hydroxyl -4- n-octyloxy hexichol first
Ketone, isopropyl triisostearoyltitanate are modified basic anhydride after being mixed using specific ratio, make spherical
Compatibility between powder and other raw materials and TPU resin significantly improves, and improves mobility of the metal powder in matrix resin,
The open defect that TPU product can significantly be mitigated, such as current mark and weld bond.
On the basis of above scheme, further, the metal powder is carried out using isopropyl triisostearoyltitanate
Surface treatment, processing method are as follows: it is 0.5%- that isopropyl triisostearoyltitanate alcohol or water, which are diluted to mass fraction,
Metal powder is placed in the solution by 20% concentration, after stirring 1-30min, up to the surface treated gold after heating, drying
Belong to powder.In the present solution, after being handled using isopropyl triisostearoyltitanate metal powder surface, it can not only be further
Reinforce mobility of the metal powder in matrix resin, moreover it is possible to make metal powder in the mixing of other raw materials and resin, guarantee metal
Glossiness.
On the basis of above scheme, further, the metal powder be bronze powder, red copper powder, silver powder, silver powder, nickel powder,
One or more of stainless steel powder, zinc powder, iron powder.
On the basis of above scheme, further, the partial size of the metal powder after the surface treatment is 10~200 μm；
The shape of metal powder after the surface treatment is one of ball-type, cylindrical type, dendritic, square or a variety of.
On the basis of above scheme, further, the dispersing agent is polyethylene wax, polypropylene wax, EVA wax, tristearin
Acid, stearmide, ethylene bis stearamide, butyl stearate, zinc stearate, calcium stearate, dimethyl silicone polymer, poly- methyl
One of phenyl siloxane is a variety of.
On the basis of above scheme, further, the antioxidant is four [β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, three [the tertiary fourths of 2.4- bis-
Base phenyl] phosphite ester, triethylene-glycol it is bis- [one of β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic ester or
It is a variety of.
On the basis of above scheme, further, the light stabilizer is 2- [(1, the 1- dimethyl of 2- hydroxyl -3,5- bis-
Propyl phenyl)] -2H- benzotriazole, 2-hydroxy-4-n-octoxybenzophenone, N, the bis- (2,2,6,6- tetramethyl -4- piperazines of N'-
Piperidinyl)-N, one or more of N'- dialdehyde-based hexamethylene diamine.
The present invention also provides the TPU of a kind of as above any alternative plating and coating and presentation metal-like is compound
The preparation method of material, comprising the following steps:
Step a, TPU, dispersing agent, antioxidant, light stabilizer are placed in high-speed mixer, high-speed stirred 1-5min；
Step b, after spherical powder and surface treatment after treatment is added in the premix of the preparation into step a
Metal powder takes out after stirring at low speed 1-5min；
Step c, pelletizing, packaging after being placed in double screw extruder melting by the step b premix prepared, be kneaded, be cooling.
The TPU composite material of the alternative plating of one kind provided by the invention and coating compared with prior art, have with
Under effect:
1, by being modified processing to spherical powder, make compatible between spherical powder and other raw materials and TPU resin
Property significantly improves, and improves mobility of the metal powder in matrix resin, can significantly mitigate the open defect of TPU product, such as
Current mark and weld bond；
2, by being surface-treated to metal powder, mobility of the metal powder in matrix resin is further strengthened, is reduced
The severity of current mark and weld bond；It can also make metal powder in the mixing of other raw materials and resin, guarantee the glossiness of metal；
3, it can directly be molded, without spraying that is, being not only able to satisfy environmental regulation, protection human health, but also can save for enterprise
Cost.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, without
It is whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not before making creative work
Every other embodiment obtained is put, shall fall within the protection scope of the present invention.
The present invention also provides the formula of embodiment and comparative example as follows (units: parts by weight), as shown in Table 1 and Table 2:
Table 1
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| TPU | 87 | 92.5 | 87 | 92.5 | 87 | 92.5 |
| The metal powder of surface treatment | 4 | 1.5 | / | / | 4 | 1.5 |
| Untreated metal powder | / | / | / | / | / | / |
| Dispersing agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Antioxidant | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Light stabilizer | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Treated spherical powder | / | / | / | / | 8 | 5 |
| Untreated spherical powder | / | / | 8 | 5 | / | / |
Wherein,
Metal powder in embodiment and comparative example is aluminium powder, wherein the content 80% of aluminium element, and other elements are zinc member
Element；Spherical powder in embodiment and comparative example is made of content for 35% magnesia, 35% calcium oxide and 30% sodium oxide molybdena.
When being surface-treated in comparative example and embodiment to the metal powder, processing method are as follows: by three isostearoyl bases
Isopropyl titanate alcohol or water be diluted to mass fraction be 0.5%-20% concentration, metal powder is placed in the solution, solution and
The mass ratio of metal-powder is 10, after stirring 1-30min, up to the surface treated metal powder, grain after heating, drying
Diameter is 10~200 μm.
It when handling in the embodiment of table 1 the spherical powder, is handled using following methods: using dibutyl
Hydroxy-methylbenzene, 2-hydroxy-4-n-octoxybenzophenone, isopropyl triisostearoyltitanate are mixed according to the ratio of 1:2:3
Afterwards, add spherical powder, the mass ratio of mixed liquor and spherical powder is 10, using 100-300rpm/min, and 120 DEG C-
Heating, drying obtains under 150 DEG C of environment, and partial size is 10~200 μm.
Spherical powder described in the comparative example 5 of table 2 and the use of comparative example 6 is identical with the processing method of metal powder, using three
Isostearoyl base isopropyl titanate is surface-treated, processing method are as follows: by isopropyl triisostearoyltitanate alcohol or water
Being diluted to mass fraction is 0.5%-20% concentration, and metal powder and spherical powder are placed in the solution, after stirring 1-30min,
Up to the surface treated metal powder after heating, drying.
Dispersing agent in embodiment and comparative example is ethylene bis stearamide；
Antioxidant in embodiment and comparative example is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi
Alcohol ester is commonly called as 1010；
Light stabilizer in embodiment and comparative example is 2- [2- hydroxyl -3,5- two (1,1- dimethyl propyl phenyl)] -
2H- benzotriazole, is commonly called as UV-328；
The present invention provides following preparation method also according to the formula of above-described embodiment and comparative example, has including following step
It is rapid:
Step a, TPU, dispersing agent, antioxidant, light stabilizer are placed in high-speed mixer, high-speed stirred 1-5min；
Step b, it is added in the premix of the preparation into step a, after spherical powder after treatment and surface treatment
Metal powder, taken out after stirring at low speed 1-5min；
Step c, pelletizing, packaging after being placed in double screw extruder melting by the step b premix prepared, be kneaded, be cooling,
The draw ratio of middle twin screw extruder is 40；Temperature is 190-220 DEG C；Revolution speed of screw is 300-500rpm/min, and feeding turns
Speed is 10-30Hz.
According to the formula making material of Tables 1 and 2, injection molding obtains product, will be obtained by the various embodiments described above and comparative example
To product be tested for the property and observe its current mark and weld bond state, and evaluate.Table 3 and table 4 be respectively embodiment 1-6 and
The appearance results contrast table of comparative example 1-6.
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Glossiness | 92 | 90 | 84 | 81 | 79 | 77 |
| Current mark | - | - | ○ | - | ○ | ○ |
| Weld bond | - | - | * | * | * | * |
Table 4
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Glossiness | 85 | 83 | 69 | 65 | 83 | 80 |
| Current mark | ○○ | ○○ | ○○○○ | ○○○○ | ○ | ○○ |
| Weld bond | * * | * | * * * | * * * | * | * |
Zero, * have respectively represented the severity of current mark and weld bond ,-then indicate not finding.
Comparing embodiment 3 and comparative example 1 and comparing embodiment 4 and comparative example 2, it can be seen that after adding spherical powder,
The severity of material weld bond and current mark can be reduced.
Comparing embodiment 1 and 3 and comparing embodiment 2 and 4, it can be seen that after addition treated spherical powder, material
Weld bond the case where improved, substantially without current mark and weld bond.
Comparing embodiment 1 and comparative example 5 and comparing embodiment 2 and comparative example 6, it can be seen that dibutyl is passed through in addition
Hydroxy-methylbenzene, 2-hydroxy-4-n-octoxybenzophenone, isopropyl triisostearoyltitanate are mixed according to the ratio of 1:2:3
Spherical powder after post-processing is than adding the spherical powder being surface-treated merely through isopropyl triisostearoyltitanate, material
The case where current mark and weld bond of material, is more preferable, substantially without current mark and weld bond.
Comparing embodiment 3, embodiment 5 and comparative example 3 and comparing embodiment 4, embodiment 6 and comparative example 4, can see
Out, addition metal powder can guarantee the glossiness of material, and the gloss of material can further be promoted by adding surface-treated metal powder
Spend and mitigate the severity of current mark and weld bond.
Comparing embodiment 1 and comparative example 3 and comparing embodiment 2 and comparative example 4, it can be seen that addition is different hard by three
The metal powder that fatty acyl group isopropyl titanate is surface-treated has greatly improved to the glossiness of material, while also further
It demonstrates, after adding processed spherical powder and surface-treated metal powder, the case where weld bond of material obtains very big
Improvement, substantially without current mark and weld bond.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of TPU composite material of alternative plating and coating, it is characterised in that: by weight, including following component:
Wherein, the spherical powder is at least one of spherical powder of basic anhydride.
2. the TPU composite material of alternative plating according to claim 1 and coating and presentation metal-like, feature exists
In: the basic anhydride select at least one of magnesia, calcium oxide, sodium oxide molybdena.
3. the TPU composite material of one kind alternative plating and coating according to claim 1, it is characterised in that:
The spherical powder is handled using following methods: using dibutyl hydroxy toluene, 2- hydroxyl -4- n-octyloxy hexichol
Ketone adds spherical powder, using 100-300rpm/min, and 120 after isopropyl triisostearoyltitanate mixing
Heating, drying obtains under DEG C -150 DEG C of environment.
4. the TPU composite material of one kind alternative plating and coating according to claim 1, it is characterised in that:
The metal powder is surface-treated using isopropyl triisostearoyltitanate, processing method are as follows: by three isostearoyls
It is 0.5%-20% concentration that base isopropyl titanate alcohol or water, which are diluted to mass fraction, and metal powder is placed in the solution, is stirred
After 1-30min, obtained after heating, drying.
5. the TPU composite material of one kind alternative plating and coating according to claim 1, it is characterised in that: the gold
Category powder is one or more of bronze powder, red copper powder, silver powder, silver powder, nickel powder, stainless steel powder, zinc powder, iron powder.
6. the TPU composite material of one kind alternative plating and coating according to claim 4, it is characterised in that: the table
The partial size of metal powder after surface treatment is 10~200 μm；The shape of metal powder after the surface treatment be ball-type, cylindrical type,
One of dendritic, square are a variety of.
7. the TPU composite material of one kind alternative plating and coating according to claim 1, it is characterised in that: described point
Powder is polyethylene wax, polypropylene wax, EVA wax, stearic acid, stearmide, ethylene bis stearamide, butyl stearate, tristearin
One of sour zinc, calcium stearate, dimethyl silicone polymer, polymethylphenylsiloxane are a variety of.
8. the TPU composite material of one kind alternative plating and coating according to claim 1, it is characterised in that: described anti-
Oxygen agent is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid n-octadecyl alcohol ester, three [2.4- di-tert-butyl-phenyl] phosphite esters, bis- [β-(the 3- tert-butyls-of triethylene-glycol
4- hydroxy-5-methyl base phenyl) one of propionic ester or a variety of.
9. the TPU composite material of one kind alternative plating and coating according to claim 1, it is characterised in that: the light
Stabilizer is 2- [2- hydroxyl -3,5- two (1,1- dimethyl propyl phenyl)] -2H- benzotriazole, 2- hydroxyl -4- n-octyloxy two
Benzophenone, N, bis- (2,2,6,6- tetramethyl -4- the piperidyl)-N of N'-, one or more of N'- dialdehyde-based hexamethylene diamine.
10. a kind of preparation method of the TPU composite material of alternative plating and coating described in -9 according to claim 1, special
Sign is: including following preparation step:
Step a, TPU, dispersing agent, antioxidant, light stabilizer are placed in high-speed mixer, high-speed stirred 1-5min；
Step b, the metal after spherical powder and surface treatment after treatment is added in the premix of the preparation into step a
Powder takes out after stirring at low speed 1-5min；
Step c, pelletizing, packaging after being placed in double screw extruder melting by the step b premix prepared, be kneaded, be cooling.
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| CN201910239069.2A CN109971157B (en) | 2019-03-27 | 2019-03-27 | TPU composite material capable of replacing electroplating and coating and preparation method thereof |
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| JPS59191748A (en) * | 1983-04-15 | 1984-10-30 | Hitachi Ltd | Corrosionproof member |
| US6013723A (en) * | 1996-12-03 | 2000-01-11 | Fuji Photo Film Co., Ltd. | Injection molded article used with a photosensitive material |
| CN104177760A (en) * | 2014-07-31 | 2014-12-03 | 青岛吉顺隆商贸有限公司 | Environment-friendly metal imitating plastic |
| CN104629343A (en) * | 2013-11-06 | 2015-05-20 | 天津金发新材料有限公司 | Spraying-free TPU composition having special aesthetic effects and preparation method and application thereof |
| CN107840976A (en) * | 2017-05-05 | 2018-03-27 | 东莞市正程新材料有限公司 | A kind of TPU film and preparation method thereof |
| CN107868438A (en) * | 2016-09-27 | 2018-04-03 | 湖北创鑫聚氨酯材料有限公司 | A kind of preparation method of compound polyurethane material |
-
2019
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59191748A (en) * | 1983-04-15 | 1984-10-30 | Hitachi Ltd | Corrosionproof member |
| US6013723A (en) * | 1996-12-03 | 2000-01-11 | Fuji Photo Film Co., Ltd. | Injection molded article used with a photosensitive material |
| CN104629343A (en) * | 2013-11-06 | 2015-05-20 | 天津金发新材料有限公司 | Spraying-free TPU composition having special aesthetic effects and preparation method and application thereof |
| CN104177760A (en) * | 2014-07-31 | 2014-12-03 | 青岛吉顺隆商贸有限公司 | Environment-friendly metal imitating plastic |
| CN107868438A (en) * | 2016-09-27 | 2018-04-03 | 湖北创鑫聚氨酯材料有限公司 | A kind of preparation method of compound polyurethane material |
| CN107840976A (en) * | 2017-05-05 | 2018-03-27 | 东莞市正程新材料有限公司 | A kind of TPU film and preparation method thereof |
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