CN111171564A - Polyamide composition with increased laser transmissivity and improved molding defects and application thereof - Google Patents
Polyamide composition with increased laser transmissivity and improved molding defects and application thereof Download PDFInfo
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- CN111171564A CN111171564A CN201911415030.8A CN201911415030A CN111171564A CN 111171564 A CN111171564 A CN 111171564A CN 201911415030 A CN201911415030 A CN 201911415030A CN 111171564 A CN111171564 A CN 111171564A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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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
-
- 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
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention discloses a polyamide composition with the functions of increasing laser transmissivity and improving molding defects, which comprises the following raw materials in parts by weight: 24.5-44.5 parts of polyamide 66 resin; 14.5-44.5 parts of polyamide 56 resin; 10-50 parts of glass fiber; additive: 0-1 part; wherein the sum of the weight parts of the raw materials is 100 parts. The invention also discloses application of the polyamide composition with the functions of increasing laser transmissivity and improving molding defects in extruded products and injection-molded products. The present invention significantly increases laser transmission and achieves lower material surface roughness while reducing the probability of white emissions occurring near the pour point of the injection molded part, as compared to conventional PA66 compositions.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyamide composition with functions of increasing laser transmissivity and improving molding defects and application thereof.
Background
The plastic laser welding technique is a technique in which a laser beam penetrates a layer of plastic and is absorbed by a plastic of a mating layer, and the contact surface of the plastic is melted by the heat generated by the laser, thereby bonding thermoplastic sheets, films, or molded parts together.
Advantages of laser welding applied to the fusion of plastic parts include: the welding is precise and firm; the seal is airtight and watertight, resin degradation is less during welding, debris generated is less, and the surfaces of the products can be tightly connected together around the weld; plastic residues can not be generated by laser welding, so that the laser welding method is more suitable for the pharmaceutical product industry, electronic sensors and the like; the laser welding process can be applied to workpieces with small size or complex appearance structure. Because the laser is convenient for the control of computer software, and the output of the fiber laser can flexibly reach each fine part of the part, the laser welding can be adopted to weld the regions which are not easy to reach by other welding methods, and the products with complex shapes and even three-dimensional geometric shapes are welded. Laser welding significantly reduces the vibrational and thermal stresses of the article as compared to other welding methods. This means that the article or the internal components of the device age more slowly and can be applied to a fragile article. Many different kinds of materials can be welded. Almost all thermoplastics and thermoplastic elastomers can be laser welded. Commonly used welding materials are polypropylene (PP), Polystyrene (PS), Polycarbonate (PC), styrene-butadiene-acrylonitrile copolymer (ABS), Polyamide (PA), acryl (PMMA), Polyoxymethylene (POM), polyester (PET or PBT), and the like.
The quality of laser welding of plastics is significantly affected by the crystalline nature of the material of the laser penetration layer, and it is well known to those skilled in the art that the higher the crystallinity of the material, the stronger the absorption of the laser, resulting in insufficient energy absorption at the penetration layer-absorption layer region, and thus in poor weld quality, which is described in detail in CN101065428A and CN 100369962C. Unfortunately, the glass fiber reinforced polyamide 66 (hereinafter referred to as PA66) composition is very susceptible to nucleation by the filled glass fibers, and the polyamide 66 resin still obtains a significantly higher degree of crystallinity during cooling of the injection molding process than the glass fiber reinforced polyamide 6 composition, and thus, conventional glass fiber reinforced polyamide 66 compositions are not suitable for laser welding, and the black version of the material will exacerbate this problem.
In addition, also due to the problem of rapid crystallization, cooling and solidification, the glass fiber reinforced PA66 modified resin often has defects in the molding process, and it is often foreseeable that agglomerated white matter is generated near the runner inlet, which causes appearance defects of parts and thus reduces the production yield, and the white matter is a glass fiber-resin combination, and is well known to those skilled in the art, and the cooling cannot enter a 'cold material well' near the runner inlet.
Disclosure of Invention
In view of the technical problems of the background art, the present invention provides a polyamide composition with increased laser transmission and improved molding defects and applications thereof, which significantly increases laser transmission and achieves lower material surface roughness while reducing the probability of white emissions occurring near the pour point of injection molded parts, compared to conventional PA66 compositions.
The invention provides a polyamide composition capable of increasing laser transmissivity and improving molding defects, which comprises the following raw materials in parts by weight:
24.5-44.5 parts of polyamide 66 resin;
14.5-44.5 parts of polyamide 56 resin;
10-50 parts of glass fiber;
additive: 0-1 part;
wherein the sum of the weight parts of the raw materials is 100 parts.
The improvement of the molding defects refers to the reduction of the probability of generating white emissions near the pouring point in the molding process, and the white emissions are characterized by cooling substances caused by accidental cooling of the polymer melt at the pouring point in the molding process.
The PA66 resin is not particularly limited, and its relative viscosity is preferably 2.4 to 3.2, more preferably 2.4 to 2.7; preferably, the content of terminal amino groups is 70mmol/kg or less.
Preferably, the relative viscosity of the polyamide 56 resin is 2.4 to 3.2.
Preferably, the relative viscosity of the polyamide 56 resin is 2.4 to 2.7.
The detection method of the relative viscosity comprises the following steps: the polyamide 56 resin is dissolved in a sulfuric acid solution with the mass fraction of 96% for detection, wherein the mass fraction of the polyamide 56 resin is 1%, and the detection method refers to the standard ISO 307.
The content of the terminal amino group of the polyamide 56 resin is not particularly required, the preferable content of the terminal amino group is more than or equal to 50mmol/kg, the preferable content of the terminal amino group is more than or equal to 60mmol/kg, and the more preferable content of the terminal amino group is more than or equal to 80 mmol/kg.
The polyamide 56 resin belongs to a semi-bio-based synthetic polymer, and is obtained by performing polycondensation reaction on pentanediamine (obtained by a biological fermentation method) and adipic acid (obtained by conventional chemical synthesis).
The synthesis process of the polyamide 56 resin is similar to that of the polyamide 66, and the specific method comprises the following steps: firstly, mixing 1, 5-pentanediamine and adipic acid according to a molar ratio of 1:1-1.05, adding an antioxidant, carrying out a salt forming reaction at a temperature of 10-130 ℃ and a pressure of 0.1-0.3MPa, pumping the solution into a tubular continuous reactor or a prepolymerization reactor at a temperature of 230-290 ℃ and a pressure of 1-5MPa, and reacting for 30-300min to obtain a prepolymer. Further flashing the obtained prepolymer to remove water, continuously pumping the dewatered prepolymer into a polycondensation reactor, setting the reaction temperature to be 250-300 ℃ under the protection of nitrogen, reacting for 30-200min to obtain polyamide 56, extruding and granulating the melt of the polyamide 56 to obtain a final finished product, wherein the detailed synthesis steps can refer to patents CN105885038A, CN103145979A, CN104031263A and the like.
The glass fiber described in the present invention is not particularly limited, and functions to improve mechanical strength, such as tensile strength, flexural strength, impact strength, etc., of the polyamide composition.
Preferably, the glass fibers are grade E alkali-free glass fibers.
The diameter of the glass fiber is not particularly limited, and is preferably 7 to 17 micrometers, more preferably 10 to 13 micrometers.
The length of the glass fiber is not particularly limited, and continuous uncut glass fiber filaments may be used, and cut glass chopped fibers may also be used, the chopped glass fibers preferably having a length of 2 to 5 mm.
The cross section of the glass fiber has no special requirement and can be round or rectangular. The rectangular cross section is vertical to the longitudinal direction of the fiber, the longest straight line distance in the rectangular cross section is a long axis, the shortest straight line distance in the rectangular cross section is a short axis, the length of the long axis and the short axis is 1.5-10:1, and the preferable ratio is 3-4: 1.
And the glass fiber is treated by a surface sizing agent.
The surface sizing agent comprises a coupling agent, such as: epoxy group-containing compounds, acrylic acid-containing compounds, polyurethane-containing compounds, and the like, and preferably, the coupling agent is a silane coupling agent-containing compound.
The general formula of the silane coupling agent is as follows:
(X-(CH2)n)k-Si-(0-CmH2m+1)4-k；
wherein, X is amino, ethylene oxide, hydroxyl, etc.;
n is an integer from 2 to 10, preferably from 3 to 4;
m is an integer from 2 to 10, preferably from 3 to 4;
k is an integer from 1 to 3, preferably 1.
The silane coupling agent is used in an amount of 0.025 to 1%, preferably 0.05 to 0.5%, by weight of the glass fiber.
Preferably, the additive includes, but is not limited to, at least one of an antioxidant, a lubricant, an organic dye.
Preferably, the additive has no nucleating effect on neither the polyamide 56 resin nor the polyamide 66 resin.
Preferably, antioxidants include, but are not limited to: at least one of hindered phenol antioxidant, hindered amine antioxidant and organic phosphite ester auxiliary antioxidant.
The hindered amine antioxidant is a free radical scavenger.
preferably, the hindered phenol antioxidant is at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and bis (2,2,6, 6-tetramethyl-3-piperidinylamino) -isophthalamide.
preferably, the hindered amine-based antioxidant is at least one of 4,4 '-bis (. α',. α '-dimethylbenzyl) diphenylamine, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, poly { [6- [ (1,1,3, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2,2,6,6, -tetramethyl-piperidyl) imino ] -1, 6-hexadiene [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] }.
Preferably, lubricants include, but are not limited to: at least one of fatty acid ester, olefin wax, acidified olefin wax, oxidized olefin wax, and silicone.
Preferably, the olefin wax, the acidified olefin wax, and the oxidized olefin wax all have a molecular weight of 3000g/mol or less.
Preferably, the olefin wax, the acidified olefin wax, and the oxidized olefin wax all have a molecular weight greater than the molecular weight of the white oil.
The olefin wax, acidified olefin wax and oxidized olefin wax are obtained by a series of cracking reactions, and are in a solid state.
The acidified olefin WAX and the oxidized olefin WAX are obtained by further modifying the olefin WAX, and the common brands are oxidized WAX PED521 of Germany Kelaien and acidified WAX Hi-WAX 4202E of Mitsui chemistry.
Preferably, the organic dye does not include aniline black dyes.
The organic dye is at least one of a perinone red dye, an ultramarine green dye, an ultramarine blue dye and an anthraquinone yellow dye.
Additives useful in the present invention do not include: kaolin, talc, mica, wollastonite, solid and/or hollow glass microspheres, boron nitride, nano-silica, nano-carbon black, inorganic phosphites (e.g., sodium hypophosphite), and organic nucleating agents (e.g., phenyl hypophosphite, polyamide oligomer).
The invention also provides the application of the polyamide composition with the functions of increasing the laser transmissivity and improving the molding defects in extruded products and injection molded products.
The invention can be used for preparing any products formed by extrusion molding and injection molding; such as: electrical and electronic products, automobile components, office equipment parts, building materials, parts for conveyor belts, parts for medical devices, parts for toys and sporting goods, and the like.
The automobile component is, for example: engine compartment components, intake manifolds, front compartment components, radiator components, instrument panel assemblies, and the like; electrical and electronic articles such as: sensor housings, personal computers, liquid crystal projectors, mobile computing devices, mobile phones, and the like. Office equipment parts such as: parts of printers, copiers, facsimile machines, and the like.
Has the advantages that:
the object of the present invention is to provide a polyamide composition with increased laser transmission and improved molding defects, which surprisingly has a significantly increased laser transmission and a substantially reduced probability of white emissions near the gate, when polyamide 56 resin is added to a glass fiber reinforced PA66 composition at a level that is surprisingly high.
The present invention significantly increases laser transmission and achieves lower material surface roughness while reducing the probability of white emissions occurring near the pour point of the injection molded part, as compared to conventional PA66 compositions.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Examples E1-E5 and comparative examples C1-C7 in the present invention use the following starting materials:
component A
PA66, brand EPR27, relative viscosity 2.7, terminal amino group content less than or equal to 70mmol/kg, purchased from Hill-Sharpse Amazon engineering plastics Limited;
component B
PA56, designation 1270W, relative viscosity 2.7, terminal amino content 54mmol/kg, purchased from Shanghai Kaiser Biotech Co., Ltd;
component C
Alkali-free E-grade glass fiber, grade: ECS 301HP, available from Chongqing International composite materials corporation;
component D
D1: antioxidant 1098, CAS accession No.: 23128-74-7, trade name IGNANOX 1098, available from BASF;
d2: antioxidant agent
P-EPQ, CAS registry number: 119345-01-6, available from Special Chemicals, Inc., of Kelain, Germany;
d3: oxidized high-density polyethylene wax, grade: PED521, acid number 17mgKOH/g, available from Claien specialty Chemicals, Inc., Germany;
d4: solvent Red 179, trademark MACROLEX RED E2G, available from Langshen, Germany;
d5: solvent BLUE 97, under the designation MacroLEX BLUE RR, available from Lansheng, Germany;
d6: solvent YELLOW 114, trademark MACROLEX YELLOW G, available from Langshen, Germany.
Examples E1-E5 and comparative examples C1-C7 in the present invention were prepared by: according to the proportion of each embodiment and comparative example, A, C, D is premixed, and then added into a first main hopper of a double-screw extruder produced by Nanjing Ruiya equipment Limited company with the screw diameter of 35mm, the length-diameter ratio of the screw is 48:1, the whole extruder is divided into 12 sections of barrels, a component B is fed from a second measuring feeding hopper which is arranged at the 8 th barrel, and the extrusion temperature is set as follows from a first area: 200-280 ℃, the head temperature is set to be 260 ℃, the screw rotating speed is set to be 300rpm, and the composition is obtained through melting plasticization, extrusion and grain cutting. (it is worth emphasizing that examples E1-E5 and comparative examples C1-C7 all give compositions which are black)
The resulting composition was dried and then injection molded according to the following process to obtain a stepped block having a thickness of 1mm and 2mm, the injection molding conditions being shown in Table 1:
TABLE 1 injection parameters
The detection method comprises the following steps:
and (3) laser transmittance testing:
the step block is placed in a constant temperature and humidity box (23 ℃, 50% humidity) to be stored for 48 hours and then taken out to be tested for laser transmissivity, and the sample transmissivity adopts near-infrared laser beams with the wavelength of 1064 nm; the stepped blocks of different thicknesses were measured with a spectrophotometer (NIRS-6500 by Foss NIRS system).
White emissions test:
continuously injecting plastic on a special mold, wherein a near sprue of the mold is arranged at the central part of a part, the diameter of the sprue is 0.5mm, the sprue is directly connected with a mold cavity of the mold, the part is a rectangular flat plate, the size of the mold cavity is 3 multiplied by 5 multiplied by 1.5mm, the number of the cavities of the mold cavity is one mold and 4 cavities, the injection molding conditions are shown in table 1, continuously injecting 200 molds after the injection molding is stable, and counting the frequency of white emissions at the edge of the near sprue.
The formulations and performance test results for examples E1-E5 and comparative examples C6-C7 are shown in Table 2.
TABLE 2 formulations and results of Performance tests for examples E1-E5 and comparative examples C6-C7
The formulations and performance test results for comparative examples C1-C5 are shown in Table 3.
TABLE 3 formulation and Performance test results for comparative examples C1-C5
From comparison of comparative examples C1-C5 with examples E1-E5, the addition of PA56 resin to PA66 resin at the same glass fiber loading significantly improved laser transmission while the frequency of white emissions was reduced to almost an unobvious level. From the comparison of comparative examples C6-C7 with example E5, the laser transmission begins to decrease and the frequency of white emissions begins to increase as the PA56 content decreases, therefore, the PA56 content is preferably equal to or greater than the PA56 addition level in comparative example C6.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A polyamide composition with the functions of increasing laser transmissivity and improving molding defects is characterized by comprising the following raw materials in parts by weight:
24.5-44.5 parts of polyamide 66 resin;
14.5-44.5 parts of polyamide 56 resin;
10-50 parts of glass fiber;
additive: 0-1 part;
wherein the sum of the weight parts of the raw materials is 100 parts.
2. The polyamide composition having an increased laser transmissivity and improved molding defects according to claim 1, wherein the polyamide 56 resin has a relative viscosity of 2.4 to 3.2; preferably, the relative viscosity of the polyamide 56 resin is 2.4 to 2.7.
3. Polyamide composition with increased laser light transmission and improved molding defects according to claim 1 or 2, characterized in that the additive comprises at least one of an antioxidant, a lubricant, an organic dye.
4. Polyamide composition with increased laser light transmission and improved molding defects according to any one of claims 1 to 3, characterized in that the antioxidant comprises: at least one of hindered phenol antioxidant, hindered amine antioxidant and organic phosphite ester auxiliary antioxidant.
5. the polyamide composition having an increased laser transmittance and an improved molding defect according to claim 4, wherein the hindered phenolic antioxidant is at least one of pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] and bis (2,2,6, 6-tetramethyl-3-piperidinylamino) -isophthalamide.
6. the polyamide composition having an increased laser light transmittance and an improved molding defect according to claim 4, wherein the hindered amine-based antioxidant is at least one of 4,4 ' -bis (α, α ' -dimethylbenzyl) diphenylamine, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, N ' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, poly { [6- [ (1,1,3, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2,2,6,6, -tetramethyl-piperidyl) imino ] -1, 6-hexadi-ylene [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] }.
7. Polyamide composition with increased laser light transmission and improved moulding defects according to any of claims 1 to 6, characterized in that the lubricant comprises: at least one of fatty acid ester, olefin wax, acidified olefin wax, oxidized olefin wax, and silicone.
8. The polyamide composition having an increased laser transmittance and an improved molding defect according to claim 7, wherein the olefin wax, the acidified olefin wax and the oxidized olefin wax each have a molecular weight of 3000g/mol or less; preferably, the olefin wax, the acidified olefin wax, and the oxidized olefin wax all have a molecular weight greater than the molecular weight of the white oil.
9. Polyamide composition with increased laser light transmission and improved moulding defects according to any of claims 1 to 8, characterized in that the organic dye does not comprise aniline black dyes.
10. Use of a polyamide composition according to any one of claims 1 to 9 having increased laser light transmission and improved molding defects in extruded articles, injection molded articles.
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| WO2021129503A1 (en) * | 2019-12-26 | 2021-07-01 | 上海金发科技发展有限公司 | Polyamide composite for improving laser weldability |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017159418A1 (en) * | 2016-03-16 | 2017-09-21 | 三菱エンジニアリングプラスチックス株式会社 | Polyamide resin composition and molded article |
| CN110591350A (en) * | 2019-09-03 | 2019-12-20 | 会通新材料(上海)有限公司 | Smoke-inhibiting polyamide composition and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017159418A1 (en) * | 2016-03-16 | 2017-09-21 | 三菱エンジニアリングプラスチックス株式会社 | Polyamide resin composition and molded article |
| CN110591350A (en) * | 2019-09-03 | 2019-12-20 | 会通新材料(上海)有限公司 | Smoke-inhibiting polyamide composition and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021129503A1 (en) * | 2019-12-26 | 2021-07-01 | 上海金发科技发展有限公司 | Polyamide composite for improving laser weldability |
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Application publication date: 20200519 |
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| RJ01 | Rejection of invention patent application after publication |