CN102108181A - Thermoplastic alloy and preparation method thereof - Google Patents

Thermoplastic alloy and preparation method thereof Download PDF

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Publication number
CN102108181A
CN102108181A CN2010106138996A CN201010613899A CN102108181A CN 102108181 A CN102108181 A CN 102108181A CN 2010106138996 A CN2010106138996 A CN 2010106138996A CN 201010613899 A CN201010613899 A CN 201010613899A CN 102108181 A CN102108181 A CN 102108181A
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thermoplastic alloy
alloy
compatilizer
mixture
abs
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CN102108181B (en
Inventor
郭涛
程庆
王亮
胡志华
胡浩
叶南飚
王林
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SICHUAN KINGFA TECHNOLOGY DEVELOPMENT CO., LTD.
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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MIANYANG CHANGXIN NEW MATERIAL DEVELOPMENT Co Ltd
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a thermoplastic alloy. The thermoplastic alloy comprises the following components in percentage by weight: 25 to 80 percent of acrylonitrile-butadiene-styrene (ABS) resin, 15 to 70 percent of copolyester, 1 to 5 percent of compatilizer, 0.5 to 1.5 percent of weathering resistant agent and 0.5 to 1.5 percent of processing aid. The preparation method of the thermoplastic alloy comprises the following steps of: pre-mixing the components in a highly mixing machine; adding the mixture into a double-screw extruder; plastifying, mixing and extruding at the temperature of between 170 and 250 DEG C; and cooling and pelleting the mixture to obtain the finished product. The thermoplastic alloy has the advantages of the ABS and the copolyester, high toughness and high weather resistance and can be applied in the field having no requirement on fire resistance but having relatively high requirement on the toughness and the weather resistance of materials.

Description

A kind of thermoplastic alloy and preparation method thereof
Technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of thermoplastic alloy and preparation method thereof.
Background technology
ABS belongs to the fifth-largest general-purpose plastics in the world, also is the macromolecular material that a kind of demand is big, development is fast between engineering plastics and general-purpose plastics.The ABS resin has rigidity, the thermotolerance of vinyl cyanide concurrently, and the toughness of divinyl and cinnamic glossiness and processing fluidity are widely used in aspects such as electronics, electrical equipment, automobile, textile equipment, building and daily necessities.Though ABS resin has excellent comprehensive performances,, thereby limited its application because the toughness of ABS resin is low than some engineering plastics.
Adding rubber toughening agent, ABS is carried out blending and modifying is the main method of improving its performance, but the effect of improving especially the amplitude that improves of toughness is limited, and cause the loss of other performances easily.With preparation alloy among other kind macromolecular materials addings ABS is another main direction of present modification, as ABS/ nylon, ABS/PVC, ABS/PC, ABS/PMMA etc.It is the product of complying with polyblend trend that copolyesters is added among the ABS preparation ABS/ copolyesters alloy.
Copolyesters is meant with acid and diol reaction and carries out copolymerization and the polyester material for preparing, mainly contains PETG, PCTG, PCTA and PCCE etc.Compare with traditional polyester material, the physical and mechanical properties and the processing characteristics of copolyesters are greatly improved.Goods height by copolyesters preparation is bright thoroughly, and excellent shock resistance has very high rigidity, hardness and good toughness, even also keeps due toughness when low temperature, and can adopt traditional extrude, forming methods such as injection moulding, blowing and plastic uptake process.ABS and copolyesters are carried out blending and modifying prepare alloy material, can merge both advantages, more excellent performance is arranged at aspects such as weathering resistance, solvent resistance and physical and mechanical propertiess.JinFa Science Co., Ltd once carried out blending and modifying with ABS resin and polyester or copolyesters, and added a certain amount of fire retardant, had prepared flame-retardant alloy (application number: 200810218436.2).This class alloy has flame retardant resistance, but not outstanding aspect toughness and weathering resistance.
Summary of the invention
The objective of the invention is to improve the performance of existing thermoplastic alloy, a kind of superhigh tenacity that has is provided, have thermoplastic alloy of good weatherability properties and preparation method thereof concurrently.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A kind of thermoplastic alloy, form by the component that following percentage ratio by weight calculates:
ABS resin 25～80%
Copolyesters 15～70%
Compatilizer 1～5%
Weather resisting agent 0.5～1.5%
Processing aid 0.5～1.5%;
Described copolyesters is PCTG, PETG or PCTA;
Described compatilizer is one or more the mixture in oxazoline multipolymer (OZ), SIS/SEBS (SEBS), the ethylene-methyl methacrylate glycidyl ester grafted polystyrene (EGMA-g-PS).
Described compatilizer is preferably ethylene-methyl methacrylate glycidyl ester grafted polystyrene (EGMA-g-PS).
Described ABS resin is made up of the grafting polybutadiene rubber of 5 ~ 80 weight % and grafted polystyrene-acrylonitrile copolymer of 95 ~ 20 weight %.Described ABS resin can be synthetic by emulsion graft polymerization method or substance law, also can be got by grafting polybutadiene rubber and the direct blend of Styrene-Acrylnitrile Copolymer.
Described PCTG and PETG have structure shown in formula I:
Figure 324708DEST_PATH_IMAGE001
（Ⅰ）
The add-on of cyclohexanedimethyleterephthalate alcohol was PCTG greater than 50% o'clock in the formula I, less than 50% o'clock be PETG, m in the formula〉1;
Described PCTA has structure shown in the formula II:
Figure 972727DEST_PATH_IMAGE002
（Ⅱ）
M in the formula II, n〉1.
Described weather resisting agent is one or more the mixture in benzotriazole category (for example CHISORB P), hindered amines (for example CHISORB 770), the phenol (for example CHISORB 5431).
Described processing aid is one or more the mixture in ethylene bis stearic acid amide (EBS), erucicamide, Zinic stearas, the organic silicone oil.
A kind of preparation method of described thermoplastic alloy comprises the steps: each component process high mixer pre-mixing is joined in the twin screw extruder, extrudes through the plasticizing mixing under 170 ~ 250 ℃, and cooling granulation obtains finished product.
Compared with prior art, the present invention has following beneficial effect:
(1) uses ABS resin and copolyesters as material matrix, combine both advantages,, make alloy have superhigh tenacity, compare original technology or patent and have a clear superiority in by adding appropriate compatilizer;
(2) by adding the weather-proof system that is fit to, ABS/ copolyesters alloy has good weathering resistance, especially compares flame-proof ABS/copolyesters alloy and has clear superiority;
(3) by regulating the ratio of two kinds of main components in the alloy, can obtain the material of a series of different physical and mechanical propertiess;
(4) composite by compatilizer and weather-proof system, the physical and mechanical properties and the weather resistance of alloy significantly promote, and are applicable to no fire-retardant requirement but field that toughness of material and weathering resistance are had higher requirements.
 
Embodiment
Further explain the present invention below in conjunction with embodiment, but embodiment does not do any type of qualification to the present invention.
Embodiment 1:
Accurate weighing 25kg ABS resin, 70kg PCTG, 3kg EGMA-g-PS, 0.7kg CHISORB P, 0.7kg CHISORB 770,0.6kg EBS; Through the high mixer thorough mixing, use parallel dual-screw extruding machine to adopt melt blending one to go on foot the method for extruding (extrusion temperature: 170 ~ 250 ℃), promptly get novel thermoplastic alloy of the present invention.Being injection molded into test by standard size with injection moulding machine with the material of this embodiment preparation, to use standard batten, the physicals after the test be (iso standard): tensile strength 47MPa, IZOD notched Izod impact strength 66kJ/m 2, flexural strength 68MPa; Melting index 5g/10min(220 ℃/10kg), glossiness (60 degree angle incident): 96.Weathering resistance adopts the ISO4892-2 standard to carry out, and the aberration changing value Δ E that shines material after 300 hours is 1.3.
Embodiment 2:
Accurate weighing 60kg ABS resin, 36kg PCTG, 2kg EGMA-g-PS, 0.7kg CHISORB P, 0.7kg CHISORB 770,0.6kg EBS; Through the high mixer thorough mixing, use parallel dual-screw extruding machine to adopt melt blending one to go on foot the method for extruding (extrusion temperature: 170 ~ 250 ℃), promptly get novel thermoplastic alloy of the present invention.Being injection molded into test by standard size with injection moulding machine with the material of this embodiment preparation, to use standard batten, the physicals after the test be (iso standard): tensile strength 45MPa, IZOD notched Izod impact strength 52kJ/m 2, flexural strength 63MPa; Melting index 14g/10min(220 ℃/10kg), glossiness (60 degree angle incident): 93.Aberration changing value Δ E is that the 1.8(testing method is with embodiment 1).
Embodiment 3:
Accurate weighing 70kg ABS resin, 27kg PETG, 1kg EGMA-g-PS, 0.7kg CHISORB P, 0.7kg CHISORB 770,0.4kg EBS, 0.2kg organic silicone oil; Through the high mixer thorough mixing, use parallel dual-screw extruding machine to adopt melt blending one to go on foot the method for extruding (extrusion temperature: 170 ~ 250 ℃), promptly get novel thermoplastic alloy of the present invention.Being injection molded into test by standard size with injection moulding machine with the material of this embodiment preparation, to use standard batten, the physicals after the test be (iso standard): tensile strength 43MPa, IZOD notched Izod impact strength 45kJ/m 2, flexural strength 62MPa; Melting index 16g/10min(220 ℃/10kg), glossiness (60 degree angle incident): 91.Aberration changing value Δ E is that the 2.2(testing method is with embodiment 1).
Embodiment 4:
Accurate weighing 75kg ABS resin, 21kg PETG, 2kg OZ, 0.7kg CHISORB P, 0.7kg CHISORB 770,0.6kg EBS; Through the high mixer thorough mixing, use parallel dual-screw extruding machine to adopt melt blending one to go on foot the method for extruding (extrusion temperature: 170 ~ 250 ℃), promptly get novel thermoplastic alloy of the present invention.Being injection molded into test by standard size with injection moulding machine with the material of this embodiment preparation, to use standard batten, the physicals after the test be (iso standard): tensile strength 42MPa, IZOD notched Izod impact strength 35kJ/m 2, flexural strength 61MPa; Melting index 18g/10min(220 ℃/10kg), glossiness (60 degree angle incident): 89.Aberration changing value Δ E is that the 2.3(testing method is with embodiment 1).
Embodiment 5:
Accurate weighing 80kg ABS resin, 15kg PCTA, 3kg SEBS, 0.7kg CHISORB P, 0.7kg CHISORB 5431,0.6kg EBS; Through the high mixer thorough mixing, use parallel dual-screw extruding machine to adopt melt blending one to go on foot the method for extruding (extrusion temperature: 170 ~ 250 ℃), promptly get novel thermoplastic alloy of the present invention.Being injection molded into test by standard size with injection moulding machine with the material of this embodiment preparation, to use standard batten, the physicals after the test be (iso standard): tensile strength 40MPa, IZOD notched Izod impact strength 28kJ/m 2, flexural strength 59MPa; Melting index 19g/10min(220 ℃/10kg), glossiness (60 degree angle incident): 87.Aberration changing value Δ E is that the 2.5(testing method is with embodiment 1).
From embodiment 1 ~ 5, it can also be seen that to have the compatilizer of different structure, the toughness that improves the ABS/ polyester there is tangible difference, appropriate compatilizer when interpolation is more a spot of, still can make product have high toughness.With the relatively poor compatilizer of raw material consistency,, also little to the tough property improvement of product even add bigger consumption.
Comparative Examples 1:
Adopt " a kind of thermoplastic flame-retardant alloy and preparation method thereof (application number: 200810218436.2) embodiment 3 " compare.Material is formed: 100kg ABS resin, 25kgPETG, 25kgPCTG, 10kg tetrabromo-bisphenol, 5kg bromination epoxy, 8kgCPE, 3kg antimonous oxide, 0.5kg tetramethylolmethane (anti-photo-thermal oxygenant), 2kg vinyl bis-stearamides, 0.5kg perfluor polyethylene.The performance of this material is (iso standard): IZOD notched Izod impact strength 30KJ/m 2, flexural strength 63MPa; Glossiness (60 degree angle incident) 89; Flame retardant rating (UL94): 1.5mm V-0.Weathering resistance also adopts the ISO4892-2 standard to carry out, and the aberration changing value Δ E that shines material after 300 hours is 7.8.
From the detected result of embodiment 1 and Comparative Examples as seen, embodiment 1 is not owing to add fire retardant, and used the weather-proof system that is fit to, and the relative Comparative Examples of its aberration changing value has clear superiority, thereby can be applicable to a lot of weather-proof demanding fields.In addition, embodiment 1 has added compatilizer, and its IZOD notched Izod impact strength reaches 66kJ/m 2, compare the 30KJ/m of ratio 2Have a clear superiority in.

Claims (6)

1. thermoplastic alloy is characterized in that being made up of the component that following percentage ratio by weight calculates:
ABS resin 25～80%
Copolyesters 15～70%
Compatilizer 1～5%
Weather resisting agent 0.5～1.5%
Processing aid 0.5～1.5%;
Described copolyesters is PCTG, PETG or PCTA;
Described compatilizer is one or more the mixture in oxazoline multipolymer, SIS/SEBS, the ethylene-methyl methacrylate glycidyl ester grafted polystyrene.
2. according to the described thermoplastic alloy of claim 1, it is characterized in that described ABS resin is made up of the grafting polybutadiene rubber of 5 ~ 80 weight % and grafted polystyrene-acrylonitrile copolymer of 95 ~ 20 weight %.
3. according to the described thermoplastic alloy of claim 1, it is characterized in that described weather resisting agent is one or more the mixture in benzotriazole category, hindered amines, the phenol.
4. according to the described thermoplastic alloy of claim 1, it is characterized in that described processing aid is one or more the mixture in ethylene bis stearic acid amide, erucicamide, Zinic stearas, the organic silicone oil.
5. according to the described thermoplastic alloy of claim 1, it is characterized in that described compatilizer is an ethylene-methyl methacrylate glycidyl ester grafted polystyrene.
6. the preparation method of the described thermoplastic alloy of claim 1 is characterized in that comprising the steps: each component process high mixer pre-mixing is joined in the twin screw extruder, extrudes through the plasticizing mixing under 170 ~ 250 ℃, and cooling granulation obtains finished product.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702633A (en) * 2011-12-30 2012-10-03 天津金发新材料有限公司 In-situ fiber-forming toughened regenerated polystyrene material and preparation method
CN105670210A (en) * 2016-03-31 2016-06-15 山东同道电源科技有限公司 High-strength oil-resistant storage battery case material and preparation method thereof
CN106221116A (en) * 2016-08-16 2016-12-14 苏州市云林电子有限公司 A kind of chemical resistance modified ABS rubber
CN107793691A (en) * 2016-08-29 2018-03-13 合肥杰事杰新材料股份有限公司 A kind of bloom chemicals-resistant ABS/ copolyester alloy materials and preparation method thereof
CN108314869A (en) * 2018-02-12 2018-07-24 金发科技股份有限公司 A kind of ASA/ polyester alloys material and its preparation method and application
CN109535634A (en) * 2017-09-21 2019-03-29 博富科技股份有限公司 Exempt from spray antimicrobial ABS/PETG alloy and preparation method thereof
CN109651769A (en) * 2017-10-12 2019-04-19 天津星瑞包装科技有限公司 A kind of ABS/PETG composite material and preparation method that high heat resistance enhancing is modified
CN110305440A (en) * 2019-06-17 2019-10-08 金发科技股份有限公司 A kind of environment-friendly flame-resistant ABS composite material and preparation method
CN110317435A (en) * 2019-06-20 2019-10-11 上海金发科技发展有限公司 The multi-functional low smell composite material and preparation method that resists cold
CN114456566A (en) * 2022-01-27 2022-05-10 上海金山锦湖日丽塑料有限公司 Transparent ultrahigh-hardness PC/PS resin composition and preparation method and application thereof

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CN101265404A (en) * 2007-03-12 2008-09-17 深圳市科净科技有限公司 Permanent antistatic copolymer material and processing method thereof
CN101649094A (en) * 2009-08-26 2010-02-17 四川大学 Flame retarding ABS/PVC/PETG alloy with low cost and high performance and preparation method thereof
CN101831136A (en) * 2010-04-21 2010-09-15 深圳市科聚新材料有限公司 High-strength high-toughness flame-resistant ABS (Acrylonitrile Butadiene Styrene) composite material and preparation method thereof

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CN101265404A (en) * 2007-03-12 2008-09-17 深圳市科净科技有限公司 Permanent antistatic copolymer material and processing method thereof
CN101649094A (en) * 2009-08-26 2010-02-17 四川大学 Flame retarding ABS/PVC/PETG alloy with low cost and high performance and preparation method thereof
CN101831136A (en) * 2010-04-21 2010-09-15 深圳市科聚新材料有限公司 High-strength high-toughness flame-resistant ABS (Acrylonitrile Butadiene Styrene) composite material and preparation method thereof

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102702633B (en) * 2011-12-30 2014-07-23 天津金发新材料有限公司 In-situ fiber-forming toughened regenerated polystyrene material and preparation method
CN102702633A (en) * 2011-12-30 2012-10-03 天津金发新材料有限公司 In-situ fiber-forming toughened regenerated polystyrene material and preparation method
CN105670210A (en) * 2016-03-31 2016-06-15 山东同道电源科技有限公司 High-strength oil-resistant storage battery case material and preparation method thereof
CN106221116A (en) * 2016-08-16 2016-12-14 苏州市云林电子有限公司 A kind of chemical resistance modified ABS rubber
CN107793691A (en) * 2016-08-29 2018-03-13 合肥杰事杰新材料股份有限公司 A kind of bloom chemicals-resistant ABS/ copolyester alloy materials and preparation method thereof
CN109535634A (en) * 2017-09-21 2019-03-29 博富科技股份有限公司 Exempt from spray antimicrobial ABS/PETG alloy and preparation method thereof
CN109651769A (en) * 2017-10-12 2019-04-19 天津星瑞包装科技有限公司 A kind of ABS/PETG composite material and preparation method that high heat resistance enhancing is modified
WO2019153988A1 (en) * 2018-02-12 2019-08-15 金发科技股份有限公司 Asa/polyester alloy material, preparation method therefor and application thereof
CN108314869A (en) * 2018-02-12 2018-07-24 金发科技股份有限公司 A kind of ASA/ polyester alloys material and its preparation method and application
CN108314869B (en) * 2018-02-12 2020-09-29 金发科技股份有限公司 ASA/polyester alloy material and preparation method and application thereof
CN110305440A (en) * 2019-06-17 2019-10-08 金发科技股份有限公司 A kind of environment-friendly flame-resistant ABS composite material and preparation method
WO2020253483A1 (en) * 2019-06-17 2020-12-24 金发科技股份有限公司 Environment-friendly flame-retardant abs composite material and preparation method therefor
CN110305440B (en) * 2019-06-17 2021-07-13 金发科技股份有限公司 Environment-friendly flame-retardant ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof
CN110317435A (en) * 2019-06-20 2019-10-11 上海金发科技发展有限公司 The multi-functional low smell composite material and preparation method that resists cold
CN114456566A (en) * 2022-01-27 2022-05-10 上海金山锦湖日丽塑料有限公司 Transparent ultrahigh-hardness PC/PS resin composition and preparation method and application thereof
CN114456566B (en) * 2022-01-27 2024-02-13 上海金山锦湖日丽塑料有限公司 Transparent ultra-high hardness PC/PS resin composition, and preparation method and application thereof

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Address after: 510520 Guangdong city of Guangzhou province high tech Industrial Development Zone No. 33 Ke Feng Lu

Patentee after: Kingfa Technology Co., Ltd.

Patentee after: Shanghai Kingfa Science and Technology Development Co., Ltd.

Patentee after: SICHUAN KINGFA TECHNOLOGY DEVELOPMENT CO., LTD.

Address before: 510520 Guangdong city of Guangzhou province high tech Industrial Development Zone No. 33 Ke Feng Lu

Patentee before: Kingfa Technology Co., Ltd.

Patentee before: Shanghai Kingfa Science and Technology Development Co., Ltd.

Patentee before: Mianyang Changxin New Material Development Co., Ltd.

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Application publication date: 20110629

Assignee: GUANGDONG JINFA TECHNOLOGY CO., LTD.

Assignor: Blond Polytron Technologies Inc| Shanghai golden hair Technology Development Co., Ltd.|Sichuan golden hair science and Technology Development Co., Ltd.

Contract record no.: 2014440000493

Denomination of invention: Thermoplastic alloy and preparation method thereof

Granted publication date: 20130220

License type: Exclusive License

Record date: 20141210

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