CN107603214A - A kind of preparation method and application of flame-retardant polyamide composition, Flameproof polyamide - Google Patents
A kind of preparation method and application of flame-retardant polyamide composition, Flameproof polyamide Download PDFInfo
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- CN107603214A CN107603214A CN201610545635.9A CN201610545635A CN107603214A CN 107603214 A CN107603214 A CN 107603214A CN 201610545635 A CN201610545635 A CN 201610545635A CN 107603214 A CN107603214 A CN 107603214A
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- polyamide
- daiamid composition
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Abstract
The present invention relates to a kind of flame-retardant polyamide composition, and it includes：(A) polyamide, and (B) fire retardant 5 40%, the percentage are the mass percent relative to polyamide；The polyamide is 25,000 40000 with more than 230 DEG C of fusing point and weight average molecular weight.The daiamid composition of the present invention can reduce the dosage of fire retardant, obtain suitable with other daiamid compositions or more preferable flame retardant effect, environmental pollution will not be caused because of the decomposition of a large amount of fire retardants, while the mechanical performance of polyamide is excellent, has a wide range of application.
Description
Technical field
The present invention relates to the preparation method and application of a kind of flame-retardant polyamide composition, Flameproof polyamide.
Background technology
Polyamide is a kind of polymer composite of good performance, in mechanical strength, the opering characteristic of electric apparatus and antifriction scouring
Consumption etc. all shows excellent characteristic, can be used as engineering plastics, be widely used in component of machine, electronics, electrical equipment portion
The fields such as part, it is even more further to develop into the numerous areas such as sheet for interior material and building materials in recent years.Above-mentioned application is to polyamides
The fire resistance of amine has higher requirements.
In the prior art, for the polyamide of existing large-scale use, such as nylon 6 or nylon66 fiber, typically pass through
Fire retardant is added to improve the fire resistance of polyamide.Nylon 6 or nylon66 fiber largely add halogen/antimony fire retardant, realize its resistance
Fuel efficiency fruit, but halogen/antimony fire retardant cost is high, the halide-containing released during burning, not only produces injury to the person, and directly
Pollute environment.Also, along with the addition of fire retardant, not only cost increases, while polyamide mechanical strength, such as：Draftability
Energy, extension at break amount, impact strength etc. gradually reduce.On this basis, it is low and with excellent to study a kind of fire retardant addition
Different flame retardant effect, while the polyamide product that mechanical strength is good, have become urgent problem to be solved in industry.
The content of the invention
According to an aspect of the present invention, there is provided a kind of daiamid composition, it includes：
(A) polyamide, and,
(B) fire retardant 5-40%, preferably 8-30%, more preferably 15-25%；
The polyamide includes more than 230 DEG C of fusing point and weight average molecular weight 25000-40000 polyamide；The percentage
For relative to polyamide (component (A)) mass percent.
According to the specific embodiment of the present invention, the limited oxygen index of the polyamide be preferably 30% (V/V) with
On, more preferably 31-36% (V/V), further preferably 32-35% (V/V).
According to the specific embodiment of the present invention, the preferred 280-330 of initial pyrolyzation temperature Td of the polyamide
DEG C, further preferably 290-320 DEG C, more preferably 300-315 DEG C.Initial pyrolyzation temperature described herein, it is defined as polymer weightlessness 1%
When temperature, can use Td (1%loss) represent.
Preferred 380-450 DEG C of heat decomposition temperature during the decomposition mechanism of the polyamide, further preferably 390-430 DEG C,
More preferably 400-430 DEG C.Heat decomposition temperature T during decomposition mechanismDecomposition mechanismRepresent.
According to the specific embodiment of the present invention, the terminal amino group content of the polyamide is preferably 45-60meq/kg,
More preferably 48-57meq/kg.
According to the specific embodiment of the present invention, the preferred glass transition temperature of polyamide is preferably 45-60
DEG C, more preferably 48-55 DEG C.
According to the specific embodiment of the present invention, the fusing point of the polyamide is preferably 240-270 DEG C, more preferably
250-260℃。
Preferably, the polyamide (component (A)) includes poly hexamethylene adipamide pentanediamine, i.e. polyamide 56.
The specific embodiment of the present invention, the component (A) also includes other polymer beyond polyamide, described
It is sub- that other polymers include polyolefin, polyester, makrolon, polyacrylate, polymethacrylates, polyacrylonitrile, polyamides
One kind or more in amine, epoxy resin, polyurethane, polyvinyl acetate, phenolic resin, Lauxite or other polyamide etc.
Kind.
The polyolefin include polyethylene, polyvinyl chloride, polypropylene, polybutene, polystyrene, ABS, ethylene-propylene copolymer,
One or more in polytetrafluoroethylene (PTFE), Kynoar and ethylene/vinyl acetate copolymer.The polyester include PET and/or
PBT.Other polyamide include any known polyamide, such as polyamide 6, polyamide 66, polyamide 610, polyamide 1010
With the one or more in polyamide 1414.
Preferably, the weight of the polyamide and other polymers ratio is preferred (70-99)：(30-1), more preferably (80-
90)：(20-10).
The specific embodiment of the present invention, the fire retardant include organic fire-retardant, preferably include phosphonium flame retardant.
The specific embodiment of the present invention, the phosphonium flame retardant include but are not limited to monophosphate aryl phosphoric acids
Ester, bis phosphoric acid aryl phosphate ester, the bony dimethyl phthalate of alkyl, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester,
One or more in propyl benzene system phosphate, butylbenzene system phosphate and hypophosphites；It is preferred that hypophosphites.
Further, daiamid composition of the invention, reinforcing agent, toughener, chemical crosslinking auxiliary agent, profit can also be added
One kind in lubrication prescription, heat stabilizer, antioxidant, ultraviolet light degradation inhibitor, releasing agent, colouring agent, nucleator and plasticizer
It is or a variety of.Mentioned component is present in amount usually used in this field in the daiamid composition of the present invention.
The reinforcing agent preferably includes calcium carbonate, has circular or non-circular cross sections glass fibre, sheet glass, glass
Pearl, carbon fiber, talcum, mica, wollastonite, calcined clay, kaolin, diatomite, magnesium sulfate, magnesium silicate, barium sulfate, titanium dioxide
Any one or a few combination in titanium, sodium carbonate aluminium, barium ferrite and potassium titanate.The addition of the reinforcing agent is 1-
20%, the percentage is the mass percent for accounting for component (A).
The toughener preferably includes the metal salt of active function groups and/or carboxylic acid, preferably includes Glycidyl methacrylate
The copolymer of glyceride and methacrylate, the ethene of unsaturated carboxylic acid acid anhydrides and copolymer, the ethene of alpha-olefin of grafting
Diene copolymer, alkene methacrylic acid -2- isocyanato ethyls and more than one methacrylate with alpha-olefin
The ionomer that copolymer, alkene methacrylic acid -2- isocyanato ethyls generate with the reaction of zinc, lithium, magnesium or manganese compound respectively.
The addition of the toughener is 1-10%, and the percentage is the mass percent for accounting for component (A).
The chemical crosslinking auxiliary agent (crosslinking agent) preferably includes to aoxidize diisopropylbenzene (DIPB), dibenzoyl peroxide or 2,5- diformazans
Any one or a few combination in base -2,5- double (t-butylperoxy hexane or di-t-butyl peroxides).The chemistry
The addition of crosslinking coagent is 0.1-5%, and the percentage is the mass percent for accounting for component (A).
The lubricant preferably includes fatty acid metal salts, fatty acid alkali metal salt, fatty acid alkali salt, aliphatic acid
It is any one or a few combination in ester and fatty acid amide, more preferably calcium stearate, montanic acid calcium, aluminum stearate, two hard
Glycerol, glyceryl tristearate, ethylenediamine distearate, monopalmitin, laurin, Dan Shan
Any one or a few combination in Yu acid glyceride and pentaerythritol tetrastearate.Aliphatic acid is carboxylic acid, preferably one
First carboxylic acid or dicarboxylic acids, the more preferably aliphatic acid with 10-44 carbon atom, more preferably with 14-44 carbon
The aliphatic acid of atom, it is still more preferably the aliphatic acid with 30-40 carbon atom；For example, aliphatic acid can be preferably nonyl
Acid, palmitic acid, laurate, Heptadecanoic acide, dodecanedioic acid or behenic acid, more preferably stearic acid, capric acid and montanic acid.Metal
For Al, Ca or Mg.Fatty acid ester is aliphatic acid and fatty alcohol reaction gained.Fatty alcohol is monohydric alcohol to tetrahydroxylic alcohol, preferably positive fourth
Alcohol, n-octyl alcohol, stearyl alcohol, ethylene glycol, propane diols, neopentyl glycol, pentaerythrite, further preferred glycerine and pentaerythrite.
Fatty acid amide is aliphatic acid and aliphatic amine reaction gained.Aliphatic amine can be monoamine to tertiary amine, preferably stearmide, second two
Amine, propane diamine, hexamethylene diamine, two (6- Aminohexyls) amine, further preferred ethylenediamine and hexamethylene diamine.The increasing
The addition of strong agent is 0.1-5%, and the percentage is the mass percent for accounting for component (A).
The heat stabilizer preferably includes copper compound.The preferred cuprous halide of copper compound, more preferably cuprous halide and alkali
The combination of any one or two kinds in metal halide.The preferred KI of alkali halide.When copper compound be cuprous halide and
During the combination of alkali halide, the mass ratio of cuprous halide and alkali halide is 1:4.The addition of the heat stabilizer
For 0.2-5%, the percentage is the mass percent for accounting for component (A).
The antioxidant preferably includes steric hindrance phenolic antioxidant, steric hindrance aliphatic amine antioxidant and aromatic amine
Any one or a few combination in antioxidant.Steric hindrance aliphatic amine antioxidant has preferable applicability.When anti-
When oxidant is steric hindrance phenolic antioxidant, the mass percent that steric hindrance phenolic antioxidant accounts for component (A) is 0.05-
3%, preferably 0.1-1.5%, more preferably 0.1-1%；When antioxidant is space bit aliphatic amine antioxidant, space bit aliphatic series
The mass percent that amine antioxidant accounts for component (A) is 0-3%, preferably 0.01-2%, more preferably 0.05-1.5%, the percentage
Than to account for component (A) mass percent.
The ultraviolet light degradation inhibitor preferably includes various substituted resorcinols, salicylate, BTA and two
Any one or a few combination in Benzophenone.The addition of the ultraviolet light degradation inhibitor is less than 2%, such as 0.1-
1.5%, the percentage is the mass percent for accounting for component (A).
The colouring agent preferably includes dyestuff or pigment.Pigment is inorganic pigment or organic pigment.Inorganic pigment is preferably
Titanium dioxide or ultramarine blue；Organic pigment be phthalocyanine, quinacridone and in any one or a few combination.Dyestuff is benzene
Amido black or anthraquinone.The addition of the colouring agent is less than 2%, such as 0.1-1.5%, and the percentage is to account for component (A)
Mass percent.
The nucleator preferably includes any one or a few the group in phenyl-phosphonite sodium, alumina, silica and talcum
Close.The addition of the nucleator is less than 2%, such as 0.1-1.5%, the percentage are the quality percentages for accounting for component (A)
Than.
A kind of engineering plastics, its raw material include daiamid composition as described above.
The preparation method of the engineering plastics preferably includes following steps：By daiamid composition melting mixing, according to this
Field conventional method, such as injection, injection/blowing, extrusion or extrusion blow moulding are molded, engineering plastics are made.
Beneficial effects of the present invention：The daiamid composition of the present invention can reduce the dosage of fire retardant, obtain and other
Daiamid composition is suitable or more preferable flame retardant effect, will not cause environmental pollution because of the decomposition of a large amount of fire retardants, gather simultaneously
The mechanical performance of acid amides is excellent, has a wide range of application.
Embodiment
By the following specific examples further illustrate the invention.
1st, the measure of limited oxygen index
Limited oxygen index (LOI) refers to the volume fraction of oxygen when polymer can support its burning in oxygen and nitrogen mixture gas
Concentration, to characterize the index for the difficulty or ease burnt when material combustion behavior, judgement material and flame contact.Limited oxygen index can be with
Lit up with combustion and test measure, burning is measured downwards under given conditions by a polymer rods.In the present invention, limited oxygen index
Detection method determines with reference to ISO 4589-2 methods.
2nd, relative viscosity η r detection method
ISO 307.1157.1628
3rd, the measure of fusing point (Tm)
ISO 3146ISO 11357
4th, tensile strength, elongation at break detection method
ISO 527-2
5th, bending strength
ISO 527-2
6th, Izod notched impact strength
ISO 179/leA
7th, UL-94 flammability ratings (Underwriters Laboratory)：
ISO 4589-2
Plastic flame grade includes：HB, V-2, V-1 and V-0；
HB：3-13mm sample, burning velocity are less than 40mm/min；Sample less than 3mm, burning velocity are less than 70mm/
min；Or extinguish before 10mm mark；
V-2：The combustion testing of 10s twice is carried out to sample, flame extinguishes in 60s；There can be comburant to fall down.
V-1：After carrying out 10s combustion testing twice to sample, flame extinguished in 60 seconds；There can not be comburant to fall down.
V-0：After carrying out 10s combustion testing twice to sample, flame extinguished in 30 seconds；There can not be comburant to fall down.
8th, terminal amino group content detection method
ASTM D2074
9th, glass transition temperature
ISO 11357
10th, heat decomposition temperature (Tdegradation)
Thermogravimetric analysis (Thermogravimetric Analysis, TGA)：Testing sample is measured under programed temperature
Quality and temperature change relation, with the heat endurance and component of research material.Sample is placed in baking oven, in 80 DEG C of dryings
12h, take 5-10mg samples to be placed in alumina crucible afterwards, while use empty crucible as control.Under a nitrogen atmosphere, by sample
Product are heated to 700 DEG C with 20 DEG C/min speed from 30 DEG C.
Td (1%loss)：Initial pyrolyzation temperature, it is defined as temperature during polymer weightlessness 1%.
TDecomposition mechanism：Heat decomposition temperature during decomposition mechanism.
Embodiment 1
By 100 parts by weight PA56 (Tm254 DEG C, Mw32000), 12 parts by weight of flame retardant OP1312,10 parts by weight GF, 0.4
Parts by weight of crosslinking agent, 0.4 parts by weight lubricant, 0.6 parts by weight heat stabilizer, 0.3 parts by weight antioxidant, 0.3 parts by weight are purple
Outside line decomposing inhibitor, the melting mixing at about 255 DEG C, extrusion molding, wire rod is obtained, for following experiments.
Embodiment 2- embodiments 5 and comparative example 1- comparative examples 8
Carry out similarly to Example 1, simply change component and its content as shown in table 1-3, under gained polyamide is used for
State experiment.The PA6 and PA66 used in comparative example is commercially available.
Wherein, OP1312：Organic hypophosphite fire retardant；
MCA：Chemical formula C6H9N9O3, melamine cyanurate flame retardant；
GF：Glass Fiber Reinforcement；
MBS：MBS terpolymer toughener.
The daiamid composition composition of table 1 and its content (digital unit is parts by weight)
The daiamid composition composition of table 2 and its content
The daiamid composition composition of table 3 and its content
The material obtained using embodiment 1-5 and comparative example 1-8 be used to carrying out tensile strength test, bending strength test,
Izod notched impact strength experiment, the evaluation of UL-94 flammability ratings.As a result as shown in table 4- tables 6.
The performance parameter of the embodiment 1-6 of table 4 daiamid composition
| Group | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Tensile strength MPa | 96 | 116 | 160 | 74 | 68 |
| Bending strength MPa | 142 | 147 | 164 | 88 | 76 |
| Izod notched impact strength | 5.1 | 5.6 | 5.3 | 4.0 | 3.9 |
| UL-94 flammability ratings (0.8mm) | V-0 | V-0 | V-0 | V-0 | V-0 |
| LOI | 36.6 | 34.1 | 35.2 | 35.3 | 34.1 |
The performance parameter of the comparative example 1-6 of table 5 daiamid composition
| Group | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Tensile strength | 94 | 120 | 156 | 71 | 66 |
| Bending strength | 125 | 148 | 163 | 82 | 72 |
| Izod notched impact strength | 5.2 | 5.8 | 4.8 | 3.8 | 3.4 |
| UL-94 flammability ratings (0.8mm) | V-2 | V-2 | V-2 | V-2 | V-2 |
| LOI | 26.0 | 28.1 | 25.9 | 28.5 | 27.4 |
The performance parameter of the comparative example 6-8 of table 6 daiamid composition
| Group | Comparative example 6 | Comparative example 7 | Comparative example 8 |
| Tensile strength | 95 | 113 | 110 |
| Bending strength | 129 | 138 | 130 |
| Izod notched impact strength | 4.5 | 5.1 | 4.1 |
| UL-94 flammability ratings (0.8mm) | V-2 | V-2 | V-2 |
| LOI | 26.0 | 27.1 | 27.1 |
Claims (10)
1. a kind of daiamid composition, it includes：
(A) polyamide, and,
(B) fire retardant 5-40%, preferably 8-30%, more preferably 15-25%；The percentage is the quality hundred relative to polyamide
Divide ratio；
The polyamide includes more than 230 DEG C of fusing point and weight average molecular weight 25000-40000 polyamide.
2. daiamid composition according to claim 1, wherein, the limited oxygen index of the polyamide is 30% (V/V)
More than, more preferably 31-36% (V/V), further preferably 32-35% (V/V)；And/or
The initial pyrolyzation temperature of the polyamide is 280-330 DEG C, preferably 290-320 DEG C, more preferably 300-315 DEG C；With/
Or,
The heat decomposition temperature during decomposition mechanism of the polyamide is 380-450 DEG C, preferably 390-430 DEG C, more preferably
400-430℃；And/or
The terminal amino group content of the polyamide is 45-60meq/kg, preferably 48-57meq/kg；And/or
The glass transition temperature of the polyamide is 45-60 DEG C, preferably 48-55 DEG C；And/or
The fusing point of the polyamide is 240-270 DEG C, preferably 250-260 DEG C.
3. daiamid composition according to claim 1 or 2, wherein, the polyamide includes polyamide 56.
4. according to the daiamid composition any one of claim 1-3, wherein, component (A) is also wrapped in addition to polyamides
Other polymer are included, the other polymers include polyolefin, polyester, makrolon, polyacrylate, polymethylacrylic acid
Ester, polyacrylonitrile, polyimides, epoxy resin, polyurethane, polyvinyl acetate, phenolic resin, Lauxite and other polyamides
One or more in amine；
The weight of the polyamide and other polymers ratio is preferably (70-99)：(30-1), more preferably (80-90)：(20-10).
5. daiamid composition according to claim 4, wherein, the polyolefin includes polyethylene, polyvinyl chloride, poly- third
Alkene, polybutene, polystyrene, ABS, ethylene-propylene copolymer, polytetrafluoroethylene (PTFE), Kynoar and ethylene/vinyl acetate copolymer
In one or more；
The polyester includes PET and/or PBT；
Other polyamide include one in polyamide 6, polyamide 66, polyamide 610, polyamide 1010 and polyamide 1414
Kind is a variety of.
6. according to the daiamid composition any one of claim 1-5, wherein, the fire retardant includes organic fire-resisting
Agent, preferably include phosphonium flame retardant.
7. according to the daiamid composition any one of claim 1-6, wherein, the phosphonium flame retardant includes monophosphate
Aryl phosphate ester, bis phosphoric acid aryl phosphate ester, the bony dimethyl phthalate of alkyl, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (two
Toluene) one or more in ester, propyl benzene system phosphate, butylbenzene system phosphate and hypophosphites.
8. according to the daiamid composition any one of claim 1-7, it further comprises reinforcing agent, toughener, change
Learn crosslinking coagent, lubricant, heat stabilizer, antioxidant, ultraviolet light degradation inhibitor, releasing agent, colouring agent, nucleator and increasing
Mould the one or more in agent.
9. a kind of engineering plastics, its raw material includes the daiamid composition as any one of claim 1-8.
10. a kind of preparation method of engineering plastics, it comprises the following steps：By the polyamides any one of claim 1-8
Amine composition melting mixing, by being molded, injection/blowing, extrusion or extrusion blow moulding and be made engineering plastics.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109486182A (en) * | 2018-10-22 | 2019-03-19 | 滁州吉胜新材料科技有限公司 | A kind of high temperature resistant aramid fiber 56 and preparation method thereof |
| CN110903642A (en) * | 2018-09-18 | 2020-03-24 | 上海凯赛生物技术股份有限公司 | Halogen-free flame-retardant resin and preparation method thereof |
| CN111117218A (en) * | 2019-12-31 | 2020-05-08 | 会通新材料(上海)有限公司 | Polyamide composition with improved color fastness after hot baking and application thereof |
| CN112694744A (en) * | 2020-12-10 | 2021-04-23 | 苏州恒坤精密电子有限公司 | Preparation method of high-temperature-resistant insulating material for power battery shell |
| CN115948050A (en) * | 2022-08-12 | 2023-04-11 | 苏州润佳高分子材料有限公司 | Anti-warping glass fiber reinforced nylon material |
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| CN104861648A (en) * | 2015-05-21 | 2015-08-26 | 浙江新力塑料股份有限公司 | Special halogen-free flame retardant reinforced PA (polyamide) 56 composite material for casing of low-voltage circuit breaker |
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| US3793289A (en) * | 1971-10-13 | 1974-02-19 | Allied Chem | Flame retardant nylon compositions |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903642A (en) * | 2018-09-18 | 2020-03-24 | 上海凯赛生物技术股份有限公司 | Halogen-free flame-retardant resin and preparation method thereof |
| CN110903642B (en) * | 2018-09-18 | 2022-03-18 | 上海凯赛生物技术股份有限公司 | Halogen-free flame-retardant resin and preparation method thereof |
| CN109486182A (en) * | 2018-10-22 | 2019-03-19 | 滁州吉胜新材料科技有限公司 | A kind of high temperature resistant aramid fiber 56 and preparation method thereof |
| CN111117218A (en) * | 2019-12-31 | 2020-05-08 | 会通新材料(上海)有限公司 | Polyamide composition with improved color fastness after hot baking and application thereof |
| CN112694744A (en) * | 2020-12-10 | 2021-04-23 | 苏州恒坤精密电子有限公司 | Preparation method of high-temperature-resistant insulating material for power battery shell |
| CN115948050A (en) * | 2022-08-12 | 2023-04-11 | 苏州润佳高分子材料有限公司 | Anti-warping glass fiber reinforced nylon material |
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Effective date of registration: 20181226 Address after: Fourth Floor, Building 5, No. 1690 Cailun Road, Zhangjiang High-tech Park, Pudong New Area, Shanghai Applicant after: CATHAY R&D CENTER Co.,Ltd. Applicant after: CATHAY INDUSTRIAL BIOTECH Ltd. Applicant after: CATHAY (JINXIANG) BIOMATERIAL Co.,Ltd. Address before: No.5 Building, 1690 Cailun Road, Zhangjiang High-tech Park, Pudong New Area, Shanghai, 200120 Applicant before: CATHAY R&D CENTER Co.,Ltd. Applicant before: CATHAY INDUSTRIAL BIOTECH Ltd. |
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Address after: 201203 floor 4, building 5, No. 1690, Cailun Road, Shanghai pilot Free Trade Zone Applicant after: CATHAY R&D CENTER Co.,Ltd. Applicant after: CATHAY INDUSTRIAL BIOTECH Ltd. Applicant after: CATHAY (JINXIANG) BIOMATERIAL Co.,Ltd. Address before: 201203 Shanghai Zhangjiang High Tech Park of Pudong New Area Cailun Road No. 1690 Building 5 Floor 4 Applicant before: CATHAY R&D CENTER Co.,Ltd. Applicant before: CATHAY INDUSTRIAL BIOTECH Ltd. Applicant before: CATHAY (JINXIANG) BIOMATERIAL Co.,Ltd. |
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Effective date of registration: 20191029 Address after: 201203 floor 4, building 5, No. 1690, Cailun Road, Shanghai pilot Free Trade Zone Applicant after: CATHAY R&D CENTER Co.,Ltd. Applicant after: CIBT USA Applicant after: CATHAY (JINXIANG) BIOMATERIAL Co.,Ltd. Address before: 201203 floor 4, building 5, No. 1690, Cailun Road, Shanghai pilot Free Trade Zone Applicant before: CATHAY R&D CENTER Co.,Ltd. Applicant before: CATHAY INDUSTRIAL BIOTECH Ltd. Applicant before: CATHAY (JINXIANG) BIOMATERIAL Co.,Ltd. |
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