CN110511528B - ABS cable sheath material and processing technology thereof - Google Patents
ABS cable sheath material and processing technology thereof Download PDFInfo
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- CN110511528B CN110511528B CN201910787531.2A CN201910787531A CN110511528B CN 110511528 B CN110511528 B CN 110511528B CN 201910787531 A CN201910787531 A CN 201910787531A CN 110511528 B CN110511528 B CN 110511528B
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/307—Other macromolecular compounds
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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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
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Insulated Conductors (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of cable sheaths, in particular to an ABS cable sheath material and a processing technology thereof, wherein the ABS cable sheath material is prepared from the following raw materials in parts by weight: 72-90 parts of ABS resin, 6-15 parts of PC resin, 3-8 parts of organosilicon flame retardant, 5-12 parts of inorganic flame retardant, 3-10 parts of compatilizer, 1-5 parts of polyethylene wax, 1-3 parts of vinyl tri (b-methoxyethoxy) silane, 20-40 parts of silicon micropowder and 0.7-1.6 parts of antioxidant; the invention improves the heat resistance and the flame retardant property of the material, and simultaneously improves the notch impact strength and the tensile strength of the ABS cable sheath material.
Description
Technical Field
The invention relates to the technical field of cable sheaths, in particular to an ABS cable sheath material and a processing technology thereof.
Background
The ABS resin is a terpolymer consisting of styrene, butadiene and acrylonitrile, integrates the high fluidity of the styrene, the rubber toughness of the butadiene and the chemical resistance of the acrylonitrile, has excellent processability, low temperature resistance, electric insulation performance, chemical corrosion resistance, high gloss and excellent electroplating performance, has the excellent characteristics of good creep resistance, high dimensional stability, small molding shrinkage and the like, can be used as a cable sheath material, and plays an insulation protection role on a cable core.
On the one hand, however, the oxygen index of the ABS resin is only 18%, and the ABS resin belongs to flammable materials; on the other hand, ABS resin itself has low heat resistance, and the heat distortion temperature is 82-84 ℃ (ASTM D648, 1.82 MPa); therefore, when the ABS resin is used for cable sheath materials, flame retardance and heat resistance modification are mostly needed to meet the use requirement of safety and fire resistance.
At present, flame retardant is added to flame retardant modification of ABS resin to achieve the purpose of flame retardance, and the ABS resin is of a sea-island structure, so that the heat-resistant temperature of the ABS resin can be further reduced by adding the flame retardant. Chinese patent CN200910110381.8 discloses a high heat-resistant, high-gloss and flame-retardant ABS modified material and a preparation method thereof, wherein the material comprises ABS, SAN, a flame retardant, a heat-resistant agent, a compatilizer, an antioxidant and a lubricant, the method has the advantages of high heat resistance, high flame retardance and high gloss, but the method has very limited effect on improving the heat resistance of the flame-retardant ABS, the thermal deformation temperature does not exceed 90 ℃, meanwhile, the mechanical property is greatly influenced by adding the heat-resistant agent, and particularly, the notch impact strength is generally reduced to below 10.
Disclosure of Invention
The first purpose of the invention is to provide an ABS cable sheath material, which improves the notch impact strength and tensile strength of the ABS cable sheath material while improving the heat resistance and flame retardant property of the material.
The first purpose of the invention is realized by the following technical scheme:
an ABS cable sheath material is prepared from the following raw materials in parts by weight: 72-90 parts of ABS resin, 6-15 parts of PC resin, 3-8 parts of organosilicon flame retardant, 5-12 parts of inorganic flame retardant, 3-10 parts of compatilizer, 1-5 parts of polyethylene wax, 1-3 parts of vinyl tri (b-methoxy ethoxy) silane, 20-40 parts of silicon micropowder and 0.7-1.6 parts of antioxidant.
By adopting the technical scheme, the PC resin, namely polycarbonate, is colorless and transparent, heat-resistant and impact-resistant, and has UL 94V-2 grade flame retardant property without additives. And adding PC resin into the ABS resin, and mixing to obtain the ABS cable sheath material with better heat resistance and flame retardance. Polyethylene wax (PE wax), also known as high molecular wax, is widely used because of its excellent cold resistance, heat resistance, chemical resistance and wear resistance; the polyethylene wax can increase the gloss of the cable sheath, improve the fluidity of ABS resin and the demolding property of PC resin, and increase the processing performance of the cable sheath. The main component of the silicon micro powder is silicon dioxide, and the silicon micro powder has the excellent performances of good temperature resistance, acid and alkali corrosion resistance, high heat conductivity coefficient, high insulation, low expansion, stable chemical performance, high hardness and the like. Vinyl tri (b-methoxyethoxy) silane, a bifunctional molecule that reacts with both inorganic fillers and organic polymers; once the vinyl tri (b-methoxyethoxy) silane is combined with the silicon micropowder, the surface of the silicon micropowder is hydrophobized, and the compatibility of the silicon micropowder and an organic polymer can be improved, so that the share of the silicon micropowder can be increased, and the temperature resistance, the flame retardance and the tensile strength of the ABS cable sheath material are improved.
Preferably, the feed additive is prepared from the following raw materials in parts by weight: 75-85 parts of ABS resin, 8-13 parts of PC resin, 4-6 parts of organic silicon flame retardant, 7-10 parts of inorganic flame retardant, 5-8 parts of compatilizer, 2-4 parts of polyethylene wax, 1.5-2.5 parts of vinyl tri (b-methoxy ethoxy) silane, 25-35 parts of silicon micropowder and 1.0-1.3 parts of antioxidant.
Preferably, the organic silicon flame retardant is an organic silicon liquid flame retardant DC-8008.
By adopting the technical scheme, the DC-8008 is colorless transparent liquid, is an efficient organic silicon flame retardant additive, is mainly applied to flame retardant modification of PC, PC/ABS, PPO, LCP, PS, PA6 and the like, and has a good flame retardant effect.
Preferably, the inorganic flame retardant comprises antimony trioxide and also comprises one or more of magnesium hydroxide and aluminum hydroxide.
By adopting the technical scheme, the magnesium hydroxide and the aluminum hydroxide can be modified by the vinyl tri (b-methoxyethoxy) silane, so that the problem of nonuniform dispersion caused by easy coalescence of magnesium hydroxide and aluminum hydroxide powder particles can be avoided, the inorganic flame retardant can be uniformly dispersed in the cable sheath material, and the flame retardant property of the cable sheath material is improved.
Preferably, the compatibilizer is a methyl methacrylate-butadiene-styrene terpolymer.
By adopting the technical scheme, the Methyl methacrylate-Butadiene-Styrene terpolymer, namely Methyl methacrylate-Butadiene-Styrene, abbreviated as MBS, is a leading impact modifier and can improve the impact resistance of the sheath material.
Preferably, the antioxidant comprises a main antioxidant and an antioxidant 168, and the main antioxidant comprises an antioxidant 1010 or/and an antioxidant 1076.
By adopting the technical scheme, the antioxidant 168 is tris (2, 4-di-tert-butyl) phenyl phosphite with a chemical name, is a phosphite antioxidant, and is widely applied to synthesis and processing of various plastics such as polypropylene, polyethylene, ABS, polycarbonate fiber, polyester resin and the like. The antioxidant 1010 is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester with a chemical name, and is white crystalline powder. The chemical name of the antioxidant 1076 is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, white powder or particles. The antioxidant 168 has excellent synergistic effects with both primary antioxidants.
Preferably, the weight ratio of the acrylonitrile to the butadiene to the styrene in the ABS resin is 15: 30: 55.
By adopting the technical scheme, the relationship between the components and the performance of the ABS resin is as follows: the content of acrylonitrile is increased, and the chemical resistance and oil resistance of ABS can be improved; the content of butadiene is increased, so that the impact strength and the toughness are improved, but the fluidity, the heat resistance and the weather resistance are reduced; the increase in styrene content increases the gloss and flowability, but decreases the impact strength. A large number of tests prove that the impact strength and the heat resistance of the sheath material can reach the best after the ABS resin is applied to the cable sheath under the three component proportions of the invention.
The second purpose of the invention is to provide a processing technology of the ABS cable sheath material, which comprises the following processing steps:
(1) banburying ABS resin, PC resin, an organic silicon flame retardant, an inorganic flame retardant, a compatilizer, polyethylene wax, vinyl tri (b-methoxyethoxy) silane and an antioxidant to obtain a mixture A;
(2) and adding silica powder into the mixture A, and banburying to obtain the ABS cable sheath material.
By adopting the technical scheme, the raw materials except the silica powder are mixed, then the silica powder is added for mixing, the mixture A is reinforced, and the temperature resistance and the tensile strength of the ABS cable sheath material are further improved.
Preferably, in the step (1), the banburying temperature is 200-.
Preferably, in the step (2), the banburying temperature is 215-240 ℃, and the banburying time is 30-50 min.
In conclusion, the invention has the following beneficial effects:
(1) according to the invention, the PC resin is used for modifying the ABS resin, so that the flame retardant property of the ABS sheath material is improved; through the synergistic effect of WD-72 silane and inorganic hydroxide, the inorganic hydroxide is more uniformly dispersed in the sheath material, so that the flame retardant property of the cable sheath material is further improved, and the flammability detection result reaches the V-0 standard;
(2) through the synergistic effect of WD-72 silane and the silica powder, the compatibility of the silica powder and an organic polymer is improved, the share of the silica powder is increased, the thermal deformation temperature of the ABS cable sheath material is increased to be more than 110 ℃, and the tensile strength is up to 64 MPa;
(3) by selecting ABS resin with proper components and adopting MBS compatilizer, the flame retardance of the ABS sheath material is improved, and the notch impact strength of the sheath material is improved to 22kJ/m at most2。
Detailed Description
The present invention will be further described with reference to the following specific examples.
The weight ratio of acrylonitrile, butadiene and styrene in the ABS resin is 12: 30: 58; the PC resin is DuPont PC 2000; the organosilicon flame retardant is organosilicon liquid flame retardant DC-8008; the compatilizer is MBS EXL 2620; the granularity of the silicon micropowder is 1500 meshes.
Example 1
An ABS cable sheath material is obtained by the following processing steps:
(1) according to the mixing amount of the raw materials in the table 1, adding ABS resin, PC resin, an organic silicon flame retardant, an inorganic flame retardant, a compatilizer, polyethylene wax, vinyl tri (b-methoxyethoxy) silane (WD-72 silane) and an antioxidant into an internal mixer to be internally mixed for 15min at 200 ℃ to obtain a mixture A;
(2) adding silica powder into the mixture A, and continuously banburying at 215 ℃ for 50min to obtain the ABS cable sheath material of example 1.
Example 2
An ABS cable sheath material is obtained by the following processing steps:
(1) according to the mixing amount of the raw materials in the table 1, adding ABS resin, PC resin, an organic silicon flame retardant, an inorganic flame retardant, a compatilizer, polyethylene wax, vinyl tri (b-methoxyethoxy) silane and an antioxidant into an internal mixer to be internally mixed for 11min at 214 ℃ to obtain a mixture A;
(2) adding silica powder into the mixture A, and continuously banburying at 223 ℃ for 47min to obtain the ABS cable sheath material of example 2.
Example 3
An ABS cable sheath material is obtained by the following processing steps:
(1) according to the mixing amount of the raw materials in the table 1, adding ABS resin, PC resin, an organic silicon flame retardant, an inorganic flame retardant, a compatilizer, polyethylene wax, vinyl tri (b-methoxyethoxy) silane and an antioxidant into an internal mixer to be internally mixed for 10min at 222 ℃ to obtain a mixture A;
(2) adding silica powder into the mixture A, and continuously banburying at 232 ℃ for 40min to obtain the ABS cable sheath material of the embodiment 3.
Example 4
An ABS cable sheath material is obtained by the following processing steps:
(1) according to the mixing amount of the raw materials in the table 1, adding ABS resin, PC resin, an organic silicon flame retardant, an inorganic flame retardant, a compatilizer, polyethylene wax, vinyl tri (b-methoxyethoxy) silane and an antioxidant into an internal mixer to be internally mixed for 8min at 230 ℃ to obtain a mixture A;
(2) adding silica powder into the mixture A, and continuously banburying at 240 ℃ for 30min to obtain the ABS cable sheath material of example 4.
Examples 5 to 8
The ABS cable sheath materials of examples 5-8 were processed in the same manner as the ABS cable sheath material of example 3, except that the raw materials were added in the amounts shown in Table 1, and the remainder was the same as example 3.
TABLE 1 ABS Cable sheathing materials of examples 1 to 8 with respect to the respective raw material contents (units/g)
Comparative example 1
Comparative example 1 was the same as example 6 except that no fine silica powder was contained in the raw material, and the contents of the remaining raw materials were added as shown in table 2.
Comparative example 2
Comparative example 2 the same processing procedure as in example 6, except that the inorganic flame retardants in the raw materials were all antimony trioxide without magnesium hydroxide and/or aluminum hydroxide, and the contents of the remaining raw materials were added as shown in table 2.
Comparative example 3
Comparative example 3 was the same as example 6 except that the starting materials were free of vinyltris (b-methoxyethoxy) silane and the remaining starting materials were added in amounts as shown in table 2.
Comparative example 4
Comparative example 4 is the same as example 6 except that the ABS resin has acrylonitrile, butadiene and styrene in a weight ratio of 15: 25: 60, and the raw materials are added in amounts shown in Table 2.
Comparative example 5
Comparative example 5 is the same as example 6 except that the ABS resin has acrylonitrile, butadiene and styrene in a weight ratio of 25: 30: 45, and the raw materials are added in amounts shown in Table 2.
Comparative example 6
Comparative example 6 is the same as example 6 except that the ABS resin has acrylonitrile, butadiene and styrene in a weight ratio of 20: 30: 50, and the raw materials are added in amounts shown in Table 2.
Comparative example 7
Comparative example 7 is the same as example 6 except that the ABS resin has acrylonitrile, butadiene and styrene in a weight ratio of 30: 15: 55, and the raw materials are added in amounts shown in Table 2.
Comparative example 8
Comparative example 8 is the same in type and content of each raw material as example 6, except that it is prepared by the following processing operations: according to the mixing amount of each raw material in the table 2, adding ABS resin, PC resin, organic silicon flame retardant, inorganic flame retardant, compatilizer, polyethylene wax, vinyl tri (b-methoxyethoxy) silane, silica powder and antioxidant into an internal mixer, and internally mixing for 10min at 222 ℃; and then continuously banburying at 232 ℃ for 40min to obtain the ABS cable sheath material of the comparative example 8.
TABLE 2 blending amounts (unit/g) of respective raw materials for ABS cable sheathing materials of comparative examples 1 to 8
Performance detection
The tensile strength and elongation at break of the jacket material were measured according to GB1040, Izod notched impact strength according to GB1843, flexural strength and flexural modulus according to GB9341, flame retardancy according to UL94 standard, heat distortion temperature of the material according to ASTM D648, and the results of the jacket materials of the examples and comparative examples are shown in Table 3.
Table 3 results of performance test of each cable sheathing material of examples 1 to 8 and comparative examples 1 to 8
As can be seen from Table 3, the ABS cable sheath material of the present invention has good impact resistance, heat resistance and flame retardancy. The results of the comparative example 1 and the example 6 show that the silicon micro powder has positive effects on the temperature resistance and the tensile strength of the cable sheath material; the results of comparative example 2 and example 6 show that the inorganic hydroxide has a large positive correlation with the flame retardant property and the heat resistance of the cable sheath material; as shown by the results of comparative example 3 and example 6, WD-72 silane has an influence on the heat resistance, flame retardancy and tensile strength of the cable jacket of the present invention; the results of the comparative examples 1 to 3 show that the silicon micropowder and WD-72 silane, magnesium hydroxide and aluminum hydroxide have synergistic effects. As shown by the results of comparative examples 4 to 7, the optimum weight ratio of the three components in the ABS resin in the system of the present invention was 12: 30: 58. The results of the comparative example 8 prove that in the processing technology, the two-step banburying is adopted, the banburying temperature of the second step is controlled to be higher than that of the first step, the time is longer than that of the first step, and the silica powder is added in the second step for banburying, so that the cable sheath material obtained has the best flame retardant property, tensile strength, heat resistance and the like.
The above-mentioned embodiments are merely illustrative and not restrictive, and those skilled in the art can modify the embodiments without inventive contribution as required after reading this specification, but only fall within the scope of the claims of the present invention.
Claims (6)
1. The ABS cable sheath material is characterized by being prepared from the following raw materials in parts by weight: 72-90 parts of ABS resin, 6-15 parts of PC resin, 3-8 parts of organosilicon flame retardant, 5-12 parts of inorganic flame retardant, 3-10 parts of compatilizer, 1-5 parts of polyethylene wax, 1-3 parts of vinyl tri (b-methoxyethoxy) silane, 20-40 parts of silicon micropowder and 0.7-1.6 parts of antioxidant;
the inorganic flame retardant comprises antimony trioxide, and also comprises a mixture of magnesium hydroxide and aluminum hydroxide;
the ABS resin comprises acrylonitrile, butadiene and styrene in a weight ratio of 12: 30: 58;
a processing technology of an ABS cable sheath material comprises the following processing steps:
(1) banburying ABS resin, PC resin, an organic silicon flame retardant, an inorganic flame retardant, a compatilizer, polyethylene wax, vinyl tri (b-methoxyethoxy) silane and an antioxidant to obtain a mixture A;
(2) adding silica powder into the mixture A, and banburying to obtain an ABS cable sheath material;
the compatilizer is methyl methacrylate-butadiene-styrene terpolymer.
2. The ABS cable sheath material of claim 1, which is prepared from the following raw materials in parts by weight: 75-85 parts of ABS resin, 8-13 parts of PC resin, 4-6 parts of organic silicon flame retardant, 7-10 parts of inorganic flame retardant, 5-8 parts of compatilizer, 2-4 parts of polyethylene wax, 1.5-2.5 parts of vinyl tri (b-methoxy ethoxy) silane, 25-35 parts of silicon micropowder and 1.0-1.3 parts of antioxidant.
3. The ABS cable jacket material of claim 1, wherein: the organosilicon flame retardant is organosilicon liquid flame retardant DC-8008.
4. The ABS cable jacket material of claim 1, wherein: the antioxidant comprises a main antioxidant and an antioxidant 168, and the main antioxidant comprises an antioxidant 1010 or/and an antioxidant 1076.
5. The processing technology of the ABS cable sheath material of claim 1, wherein the processing technology comprises the following steps: in the step (1), the banburying temperature is 200 ℃ and 230 ℃, and the banburying time is 8-15 min.
6. The processing technology of the ABS cable sheath material of claim 1, wherein the processing technology comprises the following steps: in the step (2), the banburying temperature is 215-240 ℃, and the banburying time is 30-50 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104277411A (en) * | 2014-05-27 | 2015-01-14 | 安徽宁国市高新管业有限公司 | Cable glass fiber reinforced plastic sheath material |
| CN104479281A (en) * | 2014-12-10 | 2015-04-01 | 杭州金州高分子科技有限公司 | High-impact-resistance flame-retardant ABS (acrylonitrile-butadiene-styrene) alloy material |
| CN107641286A (en) * | 2017-11-03 | 2018-01-30 | 成都乐维斯科技有限公司 | A kind of insulating materials with high intensity cable |
| CN108485226A (en) * | 2018-04-23 | 2018-09-04 | 合肥仁德电子科技有限公司 | A kind of high intensity shock-absorbing composite material for mouse manufacture |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080033083A1 (en) * | 2006-08-01 | 2008-02-07 | Gang Li | Flame retardant thermoplastic compositions having emi shielding |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277411A (en) * | 2014-05-27 | 2015-01-14 | 安徽宁国市高新管业有限公司 | Cable glass fiber reinforced plastic sheath material |
| CN104479281A (en) * | 2014-12-10 | 2015-04-01 | 杭州金州高分子科技有限公司 | High-impact-resistance flame-retardant ABS (acrylonitrile-butadiene-styrene) alloy material |
| CN107641286A (en) * | 2017-11-03 | 2018-01-30 | 成都乐维斯科技有限公司 | A kind of insulating materials with high intensity cable |
| CN108485226A (en) * | 2018-04-23 | 2018-09-04 | 合肥仁德电子科技有限公司 | A kind of high intensity shock-absorbing composite material for mouse manufacture |
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