WO2019056547A1 - Complexe de polyamide pour l'électroplacage écologique et son procédé de préparation - Google Patents

Complexe de polyamide pour l'électroplacage écologique et son procédé de préparation Download PDF

Info

Publication number
WO2019056547A1
WO2019056547A1 PCT/CN2017/112365 CN2017112365W WO2019056547A1 WO 2019056547 A1 WO2019056547 A1 WO 2019056547A1 CN 2017112365 W CN2017112365 W CN 2017112365W WO 2019056547 A1 WO2019056547 A1 WO 2019056547A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamide
environmentally friendly
coupling agent
polyamide composite
electroplating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/112365
Other languages
English (en)
Chinese (zh)
Inventor
金良文
梁永华
郑红专
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangmen Dengzhongtai Engineering Plastics Co Ltd
Original Assignee
Jiangmen Dengzhongtai Engineering Plastics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangmen Dengzhongtai Engineering Plastics Co Ltd filed Critical Jiangmen Dengzhongtai Engineering Plastics Co Ltd
Publication of WO2019056547A1 publication Critical patent/WO2019056547A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—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
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Definitions

  • the invention belongs to the technical field of polymer materials, and in particular relates to a polyamide composite used for environmental protection electroplating and a preparation method thereof.
  • Plastic plating can make the surface of plastic products have metallic luster, beautiful appearance, play a decorative role, improve the mechanical strength of the surface of the product, and prolong the service life; make the plastic products have high stability to external factors such as light and atmosphere, and are not easy to aging; Plastics are electrically conductive, magnetically conductive and weldable. Plastic electroplated products can be used in aerospace, shipbuilding, automotive, electronic appliances, architectural decoration, toys and household goods industries, and are widely used.
  • Vacuum plating mainly includes several types of vacuum evaporation, sputtering plating and ion plating. They are all used to deposit various metal and non-metal films on the surface of plastic parts by distillation or sputtering under vacuum conditions. In this way, very thin surface coatings can be obtained, and the protrusions with fast adhesion are good.
  • the main process of water electroplating is to put the products to be electroplated into an electroplating bath for electroplating.
  • the water electroplating process is relatively simple, and the requirements from the equipment to the environment are not as severe as vacuum ion plating, and thus it is widely used. It can be used for water plating plastics including: ABS, nylon, polycarbonate and polystyrene. Among them, ABS is the largest, electroplating effect is the best, and the process is the most mature.
  • Polyamide commonly known as nylon (Nylon), is a general term for heterochain polymers containing repeating structural unit amide groups (NHCO-) in macromolecular chains of polymers, mainly composed of dibasic acids and binary Amine or amino acid lactam is obtained by polycondensation and self-polymerization. It is the earliest and most used thermoplastic engineering plastic.
  • PA varieties and the aromatic ring can be classified into an aromatic ring-containing polyamide and an aliphatic polyamide according to whether the main chain structure contains an aromatic ring, and the aromatic ring-containing polyamide is the same as the amine or the acid of the nylon raw material.
  • the aromatic ring-containing polyamides include semi-aromatic polyamides and copolymers thereof, such as PA6T/66, PA6/6T, PA9T, PA10T, PA12T, etc.; also include wholly aromatic polyamides such as aramid 1313, aramid 1414 and the like.
  • the aromatic ring-containing polyamide has an aromatic ring in its molecular chain compared to the aliphatic polyamide, and can significantly improve the heat resistance, rigidity, solvent resistance, and the like of the nylon.
  • the aromatic ring-containing polyamide products which can be used for water electroplating have not been reported.
  • Thermoplastic elastomer is a block copolymer composed of a glassy or semi-crystalline thermoplastic resin and a soft elastomer. It combines the high elasticity of rubber with the thermoplastic processability of thermoplastic resins.
  • the third generation of synthetic rubber The structural feature is that the chemical bond constitutes different resin segments and rubber segments, and the resin segment forms a physical "crosslinking" by the force between the segments.
  • the rubber segment is a high elastic segment with a large free rotation capability, and the plastic and rubber segments are Arrange and join in proper order stand up.
  • thermoplastic elastomer Due to the structural characteristics of the polymer chain and the reversibility of the crosslinked state, the thermoplastic elastomer exhibits physical and mechanical properties such as elasticity, strength and deformation characteristics of the vulcanized rubber at normal temperature, and the physical cross-linking of the plastic segment changes with temperature at a high temperature. Reversible change, showing the processing characteristics of thermoplastics.
  • industrially produced TPE mainly includes: styrenes, olefins, polyurethanes, polyesters, polyvinyl chlorides, decylamines, dienes and organic fluorines.
  • a styrenic thermoplastic elastomer refers to a triblock copolymer (SDS) or a multi-block composed of a polystyrene segment as a hard segment (S) and a polybutadiene chain as a soft segment (D). Copolymer.
  • the main products are block copolymer (SBS) with polybutadiene (B) as soft segment, block copolymer (SIS) with polyisoprene as soft segment and SBS hydrogenation product (SEBS). )Wait.
  • SBS thermoplastic elastomer, a block copolymer of styrene and butadiene is known as the third generation of synthetic rubber.
  • the SIS production process is basically the same as that of SBS, so many SBS devices in the world have the ability to produce SIS at the same time. However, from the production process, the production SIS is more difficult than SBS, so not all SBS devices can produce SIS at the same time, and the variety number is significantly less than SBS.
  • the polyolefin-based thermoplastic elastomer is composed of rubber and polyolefin, and the rubber components are usually ethylene propylene diene monomer (EPDM), nitrile rubber (NBR), and butyl rubber.
  • the polyolefin component is mainly polypropylene (PP) and polyethylene (PE).
  • TPO exhibits rubber elasticity at room temperature, low density, high flexural modulus, good fluidity, excellent weather resistance, ozone resistance, UV resistance, good high temperature resistance, low temperature impact resistance, etc. Easy processing and cost Low, reusable, is a combination of good performance materials.
  • Polyurethane-based thermoplastic elastomer (TPU)
  • the polyurethane-based thermoplastic elastomer is a type of urethane rubber and is classified into a polyester type and a polyether type.
  • the structure of its macromolecular chain is composed of alternating polar polyurethane or polyurea segments (hard segments) and aliphatic polyester or polyether segments (soft segments).
  • the hydrogen bond cross-linking formed between the molecules and the light cross-linking structure between the macromolecular chains make the polymer material plasticity with changes in temperature. High hardness, good wear resistance and good elasticity are the most prominent features of this type of elastomer.
  • Polyester thermoplastic elastomers are a class of block copolymers containing an aromatic polyester hard segment and an aliphatic polyester or polyether soft segment. The ratio of hard and soft segments determines the hardness and physical and mechanical properties of the thermoplastic polyester elastomer.
  • the hard segment forms a physical cross-linking point, which is subjected to stress, and the soft segment is a freely distributed high-elastic segment that contributes elasticity.
  • TPEE has good elasticity, wear resistance, excellent flex resistance, excellent heat resistance, good low temperature flexibility and high low temperature impact strength.
  • Plastic plating refers to a process of applying a metal plating layer on a plastic surface by electroless plating and electroplating. After the electroplated metal layer, the plastic product retains the characteristics of light plastic parts, high production efficiency and large design flexibility; Decorative, wear-resistant and thermal conductivity, plastic plating processes are widely used in electronics, optical instruments, machine tool buttons and light industrial products. Replacing metals with plastic-plated metal layers is of great significance in engineering applications, not only achieving weight reduction, but also reducing costs.
  • ABS is an amorphous polymer material with an ivory appearance, opaque, odorless, tasteless, non-toxic, and excellent in electroplating properties. It is an excellent non-metal plating material.
  • the content of butadiene in ABS plastic has a great influence on the electroplating effect.
  • the ABS of electroplating should not exceed 10% of butadiene, and should generally be 18% to 24%.
  • the elastomer phase also known as the rubber phase
  • This bottleneck-shaped hole can greatly enhance the coating. The combination of strength.
  • the electroplating process of ABS plastic includes the following steps: the first step of stress removal, the purpose is to reduce the deformation of the object after electroplating due to the internal stress generated by injection molding; the second step is degreasing, most of which are removed by alkaline or acidic degreaser. Oil stains, mold release agents and some debris that may affect subsequent operations during processing or transportation.
  • the main purpose of degreasing is to degrease and degrease while reducing the surface tension and imparting hydrophilicity to the surface.
  • the third step is to roughen, the purpose of roughening is to increase the surface roughness, increase the surface area, to increase the bonding force between the metal plating layer and the plastic, so that the plastic surface changes from hydrophobic to hydrophilic, and the parts are uniformly wetted by water.
  • metal ions There are two kinds of chemical roughening formula widely used in ABS parts: one is Cr0 3 -H 2 S0 4 -H 2 O etching system; the other is Cr0 3 -H 2 S0 4 -H 3 P0 4 etching system They all contain hexavalent chromium. Hexavalent chromium is a toxic poison/inhalation of extremely toxic substances.
  • the fourth step is sensitization, that is, adsorption of reducing divalent tin ions on the surface of the material to prepare for activation; the fifth step is activation and reduction, first adsorbing a layer of catalytically active precious metal such as Ag on the surface of the material, Then reduce it, which can improve the surface activity and accelerate the deposition speed. It should be noted that the activation liquid on the surface of the material should be cleaned to prevent the subsequent process from being stained.
  • the sixth step is electroless plating, that is, uniform plating is formed on the surface of the material. The metal plating with good continuity provides protection for electroplating; the seventh step is electroplating. Usually, three metals of copper, nickel and chromium are compositely plated on the surface of the material to form the final surface decorative layer.
  • the conventional electroplated grade nylon material is mainly made of an aliphatic polyamide (PA6-based) resin, and is filled with a certain proportion of inorganic ore powder to be electroplated and modified.
  • PA6-based aliphatic polyamide
  • the electroplating solution first swells the aliphatic polyamide resin, and then infiltrates into the interior to corrode the inorganic ore powder in the material to form a surface roughening effect, which is used to increase the surface bonding force between the electroplated metal layer and the nylon substrate.
  • the surface treatment of the polyamide is usually carried out using a sulfuric acid solution and chromic acid, as in U.S. Patent No. 5,324,766.
  • the use of heavy metal chromic acid is extremely hazardous to workers and can also cause significant pollution to the environment.
  • the organic components contained in the expansion system and other chemicals added will remove some of the filler in the nylon plastic, and because not all of the filler can be removed, some nylon plastics are difficult or impossible to plate.
  • the roughening and expansion process is the key factor affecting the appearance quality and bonding force of the coating.
  • the uniform roughening effect on the surface of the workpiece can lay a solid foundation for obtaining the decorative coating with good adhesion. Whether the surface roughening is uniform or not directly determines the plating quality of the surface of the nylon workpiece.
  • the existing electroplated grade nylon materials have major defects: 1. Need to use special nylon electroplating syrup; 2.
  • the substrate plating bonding strength is not high, and can not meet the requirements of metal plating products adhesion; 3.
  • the production is not flexible and the cost is high.
  • the cost of the traditional nylon electroplating process is about 2.4 yuan / DM, and the cost of the ABS plating process is about 1.2 yuan / dm. Therefore, its market application is not as broad as ABS.
  • a polyamide composite for environmentally friendly plating which uses an aliphatic polyamide resin and a semi-aromatic polyamide resin as a host resin by adding a special thermoplastic elasticity.
  • the body is uniformly distributed on the surface of the resin during the mixing modification process.
  • the polyamide composite of the present invention can also be used for electroplating treatment without adding mineral powder, and is subjected to surface metallization coating by electroplating to obtain a product with high strength, high temperature resistance, low water absorption and dimensional stability, in particular, Excellent substrate plating adhesion.
  • Another object of the present invention is to provide a method for preparing a polyamide composite for environmentally friendly plating.
  • a polyamide composite for environmentally friendly plating comprising the following raw materials by weight:
  • thermoplastic elastomer has a melt index higher than a melt index of the aromatic ring-containing polyamide resin.
  • the aliphatic polyamide means that the polyamide is derived from one or more aliphatic diamines (eg, aliphatic C 6 -C 20 alkylenediamines, alicyclic diamines, preferably diamines) Including bis(p-aminocyclohexyl)methane, 1,6-hexanediamine, 2-methylpentanediamine, 2-methyloctanediamine, trimethyl 1,6-hexanediamine, 1,8-octyl Diamine, 1,9-nonanediamine, 1,10-nonanediamine, 1,12-dodecanediamine, and m-xylylenediamine) and one or more dicarboxylic acids (eg, Adipic acid, sebacic acid, sebacic acid, dodecanedioic acid or derivatives thereof, and/or one or more aliphatic lactams, amino acids (such as 11-aminododecanoic acid, caprolactam and
  • the aliphatic polyamide is selected from the group consisting of PA6, PA66, PA6/66, PA56, PA 46, PA 610, PA 612, PA 11, PA 12, PA 910, PA 912, PA 913, PA 914, PA 915, PA 616, PA 936, PA 1010, PA 1012, PA 1013, PA 1014, PA 1210, PA 1212, PA 1213, PA 1214, PA 1313, PA 614, PA 613, PA 615, PA 616, and PA 613 One or more.
  • the aliphatic polyamide is selected from one or more of PA6, PA66, PA6/66, PA56, PA610, PA612, PA1010, PA1212, PA11, PA12, PA1313.
  • the aromatic ring-containing polyamide resin may be composed of an aromatic dibasic acid such as terephthalic acid and an aliphatic dibasic acid (eg It has been obtained by polycondensation of a diamine) or polycondensation of an aromatic diamine such as p-phenylenediamine with an aliphatic diamine such as adipic acid.
  • an aromatic dibasic acid such as terephthalic acid and an aliphatic dibasic acid (eg It has been obtained by polycondensation of a diamine) or polycondensation of an aromatic diamine such as p-phenylenediamine with an aliphatic diamine such as adipic acid.
  • the aromatic ring-containing polyamide resin is one or more of PA4T, PA6T/66, PA6T/6I, PA9T, PA10T, PA12T, PA12T/12I, PA13T, PA13T/13I, MXD6.
  • the thermoplastic elastomer is at least one of a polyolefin elastomer, a polyester elastomer, and a polystyrene elastomer.
  • the thermoplastic elastomer may be used by chemical modification of maleic anhydride, silicone (silane), chlorine, amine, acrylic acid, epoxy compound or the like.
  • the polyolefin elastomer is a material obtained by homopolymerizing or copolymerizing an olefin such as ethylene, propylene or butadiene or a diene monomer.
  • the polyolefin elastomer is selected from the group consisting of ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), or a blend of EPDM and EPM, ethylene- ⁇ -olefin copolymer, modification
  • EPM ethylene-propylene-diene rubber
  • the ethylene- ⁇ -olefin copolymer and the reactor directly prepare one or more of thermoplastic polyolefins (reactor TPO).
  • Examples of the ethylene- ⁇ -olefin copolymer include ethylene and propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, and 1- a copolymer of an ⁇ -olefin such as a terpene.
  • examples of the modified ethylene- ⁇ -olefin copolymer include maleic anhydride, silicone (silane), chlorine, and amine in the polymer side chain or polymer terminal of the ethylene- ⁇ -olefin copolymer.
  • a substance obtained by chemical modification such as acrylic acid or epoxy compound.
  • the polystyrene elastomer is selected from the group consisting of styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene butylene-styrene block copolymer (SEBS), styrene- One or more of isobutylene block copolymer (SIB), styrene-isobutylene-styrene block copolymer (SIBS), styrene-ethylene propylene-styrene block copolymer (SEPS).
  • SBS styrene-butadiene-styrene block copolymer
  • SEBS styrene-ethylene butylene-styrene block copolymer
  • SIB isobutylene block copolymer
  • SIBS styrene-isobutylene-styrene block copolymer
  • SEPS styren
  • the polyester elastomer is a polyether-ester block copolymer or a polyester-ester block copolymer.
  • the polyester elastomer is selected from the group consisting of dimethyl terephthalate, 1,4-butanediol, and polytetramethylene ether glycol (PTMG), which are obtained by transesterification and polycondensation. Wait.
  • the polyester elastomer is a polybutylene naphthalate (PBN)-based elastomer, a polybutylene terephthalate (PBT)-based elastomer, or the like.
  • thermoplastic elastomer has a melt index of > 2 g/10 min, test conditions: 220 ° C, 2.16 kg; the thermoplastic elastomer has a melt index higher than that of the aliphatic polyamide and the aromatic ring-containing polyamide resin, It is advantageous for the thermoplastic elastomer to migrate outward when mixed and modified, and distributed on the surface layer of the polyamide composite.
  • the inorganic ore powder is at least one selected from the group consisting of alumina, silica, talc, titanium oxide, zinc oxide, demontbromite and kaolin. Further preferably, the inorganic ore powder is at least one selected from the group consisting of talc, alumina, silica, zinc oxide, and demineralized soil.
  • the inorganic ore fines have a particle size of more than 1500 mesh. Particularly preferably, the inorganic ore fine powder has an average particle diameter of 0.1 to 1 ⁇ m, and the particle diameter herein refers to a median diameter (D50) measured by a laser particle size analyzer, and the inorganic oxide ore powder The particle size distribution is normally distributed.
  • the particle size of the above-mentioned inorganic ore fine powder cannot satisfy the distribution requirement, it needs to be depolymerized, and the depolymerization treatment should ensure the depolymerization between the ore particles while avoiding causing the fracture thereof, because after the crushing In the inorganic ore fines, due to the presence of a large number of fine particles, the specific surface area will further increase, resulting in an increase in agglomeration between the inorganic mineral powders, which is not conducive to Uniform dispersion in the polyamide composite, the inorganic mineral powder mainly plays a role in increasing the mechanical strength and temperature resistance of the material.
  • the inorganic ore powder is an inorganic ore powder modified by a coupling agent, wherein a weight ratio of the coupling agent to the inorganic ore powder is 1:20 to 1:100.
  • the coupling agent contains a reactive group, one end of which can form a covalent bond or a hydrogen bond with the hydroxyl group of the inorganic material, and the other end forms a hydrogen bond with the organic material or generates a covalent bond.
  • the interface between the inorganic material and the organic material is organically connected to improve various properties of the composite material.
  • the coupling agent is selected from the group consisting of an epoxy silane coupling agent, an amino silane coupling agent, a fluorenyl silane coupling agent, a ureido silane coupling agent, an isocyanate silane coupling agent, and a titanate.
  • a coupling agent a borate coupling agent, an aluminum-titanium composite coupling agent, and an aluminate coupling agent, which modifies the inorganic ore fine powder.
  • the coupling agent-modified inorganic ore fine powder is carried out by a usual dipping method, a shower method, a spray method, or the like, and the modification method thereof is not particularly limited in the present invention. According to the process design, a method in which the inorganic ore fine powder and the solution containing the coupling agent are more uniformly contacted and adsorbed can be used arbitrarily.
  • the impregnation method is to put the mineral powder into the solution containing the coupling agent, and the capillary pressure is generated due to the surface tension, so that the liquid penetrates into the inside of the capillary, and the coupling agent gradually diffuses and adsorbs on the surface of the ore powder and the micropores. After the impregnation is equilibrated, the remaining solution is removed by drying or baking.
  • the spray method and the spray method directly spray the liquid containing the coupling agent on the surface of the ore powder. Due to the different nozzle outlets, the spray method has larger droplets, which are generally suitable for bulk materials and granular materials, and the spray method is suitable for spraying. For powder materials.
  • the advantage of the impregnation method is that the active component has high utilization rate, low cost and simple production method, but the drying process may lead to migration of the active component, while the spray method and the spray method have higher efficiency and are easier to dry. But need to add extra equipment.
  • epoxy silane coupling agent examples include vinyltrimethoxysilane, vinylphenyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, and ⁇ -glycidoxy Propyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane.
  • the amino-based silane coupling agent includes ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- 3-(4-(3-Aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane.
  • the isocyanate-based silane coupling agent includes ⁇ -isocyanatepropyltriethoxysilane, isocyanatepropyltrimethoxysilane.
  • the ureido-based silane coupling agent includes ⁇ -ureidopropyltriethoxysilane, ⁇ -ureidopropyltrimethoxysilane.
  • the titanate coupling agent comprises a compound of isopropyl triisostearate isopropyl titanate, isopropyl tristearate bis, di(dioctyloxy pyrophosphate) ethylene titanate Ester, isopropyl tris(dioctylpyrophosphate) titanate, isopropyl tris(dodecylbenzenesulfonyl) titanate, isopropyl trioleate acyl titanate, Isopropyl tris(dioctylphosphoryloxy) titanate, isopropyl dioleic acid acyloxy (dioctylphosphoryloxy) titanate.
  • the aliphatic polyamide composite further comprises a fiber reinforced material, a flame retardant, a nucleating agent and an antioxidant One or more.
  • the fiber reinforcing material includes one or more of glass fiber, carbon fiber, aramid fiber, and wollastonite.
  • the fiber reinforcing material is added in an amount of not more than 40% by weight based on the total weight of the aliphatic polyamide composite.
  • the glass fiber has a non-circular cross section, and refers to a glass fiber whose long axis is in a state perpendicular to the longitudinal direction of the fiber and which corresponds to the longest straight line in the cross section.
  • the non-circular cross section has a short axis with the longest linear distance in the corresponding cross section in a direction perpendicular to the long axis.
  • the non-circular cross section of the fibers can have a variety of shapes including a dome (number eight) shape, a rectangular shape, an elliptical shape, a semi-elliptical shape, a rough triangular shape, a polygonal shape, and a rectangular shape. Those skilled in the art will appreciate that the cross section can have other shapes.
  • the ratio of the major axis length to the minor axis length is preferably between about 1.5:1 and about 6:1.
  • the ratio is more preferably between 2:1 and 5:1, but more preferably between 3:1 and about 4:1.
  • the glass fibers can be in the form of long glass fibers, chopped fibers, comminuted short glass fibers, or other suitable forms known to those skilled in the art.
  • the carbon fiber is one or more of acrylonitrile-based carbon fiber, pitch-based carbon fiber, viscose-based carbon fiber, or phenolic carbon fiber.
  • the atomic structure of the carbon fiber is similar to that of graphite, and the carbon atom layers are arranged in a regular hexagonal pattern, and the interlayer spacing between the layers is 0.344 nm due to the presence of sp3 bonds.
  • the carbon fiber has a tensile strength of 2 to 7 GPa, an elastic modulus of 200 to 900 GPa, and a density of 1.78 g/cm 3 .
  • the carbon fiber may be T300, T700, T800, T1000 of Toray Corporation, or P-1002K, P-100S2K, P-1202K, P-120S2K, etc. of CytecThronel series.
  • the aramid fiber is polyphthaloylbenzenediamine, which is a novel synthetic fiber mainly classified into para-aramid fiber (PPTA) and meta-aramid fiber (PMIA).
  • PPTA para-aramid fiber
  • PMIA meta-aramid fiber
  • the wollastonite is a non-toxic natural mineral, and the wollastonite produced in nature is generally a fibrous, needle-like or radial aggregate, and the single crystal has a plate shape or a plate column extending along the b-axis.
  • Wollastonite has low solubility in neutral water, low oil absorption, no crystallization water, low hygroscopicity, no dehydration during heating, high melting point, low thermal expansion coefficient, good heat resistance, corrosion resistance and weathering resistance. Good mechanical and electrical properties. After filling the resin, it has good dimensional stability, abrasion resistance and smoothness. Compared with flaky fillers such as talc and mica, it has surface scratch resistance.
  • Wollastonite has good dispersibility in the resin, a small degree of strength reduction, and a low melt strength after filling the material.
  • the molding processability of the material is also improved due to the decrease in hygroscopicity and viscosity.
  • the wollastonite has a particle size of from 200 to 800 mesh; more preferably from 400 to 600 mesh.
  • the wollastonite of the present invention is a silane coupling agent-modified wollastonite.
  • the flame retardant comprises one or more of a halogen-based flame retardant, a halogen-free flame retardant, and a flame retardant synergist.
  • the flame retardant is added in an amount not exceeding 20% by weight based on the total weight of the polyamide composite.
  • Halogenated flame retardants are effective for both unreinforced and reinforced nylons and can be used in conjunction with synergistic metal oxides, metal salts, phosphorus containing compounds or char formers. However, halogenated flame retardants can also cause the nylon chain to crack into combustible monomers or similar things initiated or catalyzed by hydrogen halide (HX).
  • Halogenated flame retardants usually use chlorinated flame retardants and brominated flame retardants; chlorinated flame retardants are mainly produced by Diels-Alder reaction of hexachlorocyclopentadiene and cyclooctadiene. A meta-addition product, bis(hexachlorocyclopentadienyl)cyclooctane, which is most commonly used in nylon. Brominated flame retardant The commonly used agent is decabromodiphenylethane. The effect is not obvious when used alone, but the effect is very obvious after the synergistic action of antimony trioxide.
  • the halogen-free flame retardant additive is mainly composed of a phosphorus compound and a metal hydroxide.
  • the halogen-free flame retardant of the present invention is a phosphorus-nitrogen flame retardant, preferably one or more of melamine cyanurate, hypophosphite or ammonium polyphosphate, further preferably ammonium polyphosphate, wherein phosphorus The content is not less than 19%.
  • the flame retardant synergist includes siloxane, metal oxide (such as silica, boehmite, alumina, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, Cobalt oxide, cerium oxide, chromium oxide, tin oxide, cerium oxide, nickel oxide, copper oxide, tungsten oxide, antimony trioxide, ferric oxide, metal powder (such as aluminum, iron, titanium, manganese, zinc, Molybdenum, cobalt, cerium, chromium, tin, antimony, nickel, copper and tungsten), and metal salts (such as barium metaborate, zinc carbonate, zinc borate, magnesium carbonate, calcium carbonate and barium carbonate).
  • metal oxide such as silica, boehmite, alumina, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, Cobalt oxide, cerium oxide, chrom
  • the antioxidant is added in an amount not exceeding 2% by weight based on the total weight of the polyamide composite.
  • the antioxidant can be divided into a primary antioxidant and a secondary antioxidant.
  • the primary antioxidant refers to a compound such as an aromatic amine and a hindered phenol capable of eliminating free radicals, and a derivative thereof
  • the auxiliary antioxidant refers to decomposition of hydrogen peroxide.
  • the primary antioxidant is selected from the group consisting of tetrakis[methyl- ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester, ⁇ -(3,5-di-tert-butyl) -4-hydroxyphenyl)propionic acid n-octadecyl alcohol ester, N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl) hexamethylenediamine Or a variety.
  • the auxiliary antioxidant is selected from one or both of tris[2.4-di-tert-butylphenyl]phosphite, pentaerythritol distearyl diphosphate.
  • the nucleating agent is added in an amount not exceeding 1% by weight based on the total weight of the polyamide composite.
  • the nucleating agent is an ethylene acrylic acid copolymer, preferably a sodium ion derivative of an ethylene-methacrylic acid copolymer.
  • the main role of the nucleating agent is to increase the crystallization rate of the nylon material, increase the tensile strength and flexural modulus of the material, and enhance the strength.
  • the above preparation method of the polyamide composite for environmental protection plating comprises the following steps:
  • step (3) The blend obtained in the step (1) is added to a twin-screw extruder, and at the same time, the inorganic ore powder treated by the step (2) is added, and after mixing, the pellets are extruded and obtained.
  • the polyamide composite of the invention has better electroplating property and mechanical property than the existing electroplated grade nylon, and no blistering, pitting, orange peel and the like appear in the electroplating process, and the surface of the material is smooth; The temperature resistance is improved, and the material is not easily deformed at high temperature plating, and meets the requirements of high temperature plating;
  • the polyamide composite of the invention can be processed by the existing ABS plastic electroplating process, and the equipment investment is small, the electroplating cost is low, and the product competitiveness is greatly improved;
  • the polyamide elastomer of the present invention has a small amount of thermoplastic elastomer added and is distributed on the surface layer of the polyamide resin to maintain the basic characteristics of the polyamide resin substrate. Further, the thermoplastic elastomer is easily corroded by the plating solution to produce an ABS-like substance. The hole of the "bait" function, thereby improving the bonding strength of the coating;
  • the polyamide composite of the present invention can be electroplated by using the existing ABS electroplating hexavalent chromium roughening solution, and can also be treated with an environmentally-friendly potassium permanganate roughening liquid, which is suitable for the development of environmentally friendly electroplating;
  • the electroplating bonding force with the surface of the electroplating coating layer reaches 10N or more, which ensures the safety of use;
  • This product has excellent high temperature resistance and can withstand up to 280 °C in the short term, which can broaden the range of use of electroplating products.
  • Tensile strength was measured according to "Standard Test Method for Plastic Tensile Properties of ASTM D 638-2008", and a dumbbell-shaped sample was prepared with a size of 160*10*4 mm, a gauge length of 50 mm, a tensile speed of 50 m/min, and a longitudinal axis stretching. .
  • the tensile strength at break of the specimen and the corresponding elongation at break were recorded.
  • the sample should be placed under conditions of 23 ⁇ 2 ° C (73.4 ⁇ 3.6 ° F) and 50 ⁇ 5% relative humidity before the test, and adjusted for not less than 40 hours. During the tensile test, the sample is stretched until it breaks, and the percentage of the distance from which the gauge length is recorded is the elongation at break.
  • the impact strength test was carried out in accordance with "Standard Test Method for Cantilever Beam Impact Property Testing of ASTM D256 Plastics".
  • the standard sample was broken by the swing of the standard pendulum, and the energy absorbed by the recorded sample fracture was its impact strength.
  • the standard sample molding material has a width in the range of 3.17 to 12.7 mm (0.125 to 0.500 in).
  • all specimens with dimensions less than 12.7 mm (0.500 in) should be notched on the shorter side. All stamper specimens shall be notched in a plane parallel to the direction in which the stamp is applied.
  • the parallelism of one side of the notch to the other is within 0.025 mm (0.001 in) by removing a small amount of material during processing to maintain the tolerance of the depth of the sample.
  • the test shall be carried out under conditions of 23 ⁇ 2 ° C (73.4 ⁇ 3.6 ° F) and 50 ⁇ 5% relative humidity.
  • the plating bonding force refers to the bonding strength of the plating layer to the base resin or the intermediate plating layer, that is, the force required to peel the plating layer per unit surface area from the base resin or the intermediate plating layer.
  • the material was injection molded into a square product of 120*60*2 mm, then electroplated, and a 10*80 mm strip was cut on the plate with a knife. Applying 3M adhesive tape to the width of the strip coating, and then using the universal testing machine to test the maximum force required to separate the coating from the resin is the bonding strength of the coating.
  • the bending performance test was carried out in accordance with "ISO 178-2010 Determination of Plastic Bending Properties".
  • the bending strength is the maximum stress that the material bears when it breaks under the bending load or reaches the specified deflection.
  • the bending modulus is the ability of the material to resist bending deformation within the elastic limit, and the bending strength and the flexural modulus are both MPa.
  • the load heat distortion temperature test was carried out according to "ISO 75-2-2013 Plastics. Determination of deflection temperature under load”. The test pressure was 1.8 MPa, and the temperature at which the deformation degree reached 0.34 mm was the heat distortion temperature.
  • PA6T/66 D3000 resin of Jiangmen Dezhongtai Engineering Plastic Technology Co., Ltd.;
  • PA6 M2500I of Xinhui Meida Nylon Co., Ltd.;
  • PA12T T3000 resin of Jiangmen Dezhongtai Engineering Plastic Technology Co., Ltd.
  • Glass fiber 301HP of Chongqing International Composites
  • Carbon fiber Type-45 of Toray, Japan
  • Silane coupling agent KH550 A-1100 of American United Carbon Corporation
  • Titanate coupling agent KR-238S of Kenrich Petroleum Company of the United States;
  • TPE G4774 of DuPont Co., Ltd.
  • TPU WHT-2195 of Yantai Wanhua Polyurethane Co., Ltd.;
  • TPO ExxonMobil Chemical's CMV241;
  • Talc powder Hangzhou Fuyang Xintianlong Mine Powder Co., Ltd., 2000 mesh;
  • Alumina ALuna-100 of Guangzhou Ji Bi Sheng Technology Industrial Co., Ltd.;
  • Antioxidant SEED of Clariant Chemicals (China) Co., Ltd.
  • a polyamide composite for environmentally friendly plating comprising the following raw materials by weight (total weight of raw materials: 10KG):
  • the above preparation method of the polyamide composite for environmental protection plating comprises the following steps:
  • the PA6T/66 and TPE were fed into a twin-screw extruder through a main feeder for melt polymerization, and the pelletized pellets obtained the polyamide composite of the present invention.
  • a polyamide composite for environmentally friendly plating comprising the following raw materials by weight (total weight of raw materials: 10KG):
  • the above preparation method of the polyamide composite for environmental protection plating comprises the following steps:
  • PA6T/66 and TPE are added to a twin-screw extruder through a main feeder for melt polymerization, and the pellets are granulated to obtain a blend, which is ready for use;
  • step (3) adding the blend obtained in the step (1) and the SEED to the twin-screw extruder through the main feeder, and adding the inorganic mineral powder alumina treated in the step (2) to the side feeder.
  • the temperature was controlled to melt extrusion at 315 ° C, and the pellet was milled at a twin screw speed of 350 RPM to obtain the polyamide composite of the present invention.
  • a polyamide composite for environmentally friendly plating comprising the following raw materials by weight (total weight of raw materials: 10KG):
  • the above preparation method of the polyamide composite for environmental protection plating comprises the following steps:
  • PA12T and TP0 are added to a twin-screw extruder through a main feeder for melt polymerization, and the pellets are granulated to obtain a blend, which is ready for use;
  • step (3) adding the blend obtained in the step (1) and the SEED to the twin-screw extruder through the main feeder, and adding the inorganic mineral powder alumina treated by the step (2) to the side feeder.
  • the temperature was controlled to melt extrusion at 305 ° C, and the pellet was milled at a twin screw rotation speed of 250 RPM to obtain the polyamide composite of the present invention.
  • a polyamide composite for environmentally friendly plating comprising the following raw materials by weight (total weight of raw materials: 10KG):
  • the above preparation method of the polyamide composite for environmental protection plating comprises the following steps:
  • PA12T, PA6 and TPU are melt-polymerized in an internal mixer, and the pellets are granulated to obtain a blend, which is ready for use;
  • step (3) adding the blend obtained in the step (1) and the SEED to the twin-screw extruder through the main feeder, and adding the inorganic ore powder talc treated by the step (2) to the side feeder.
  • the temperature was controlled to melt extrusion at 295 ° C, and the pellets were milled at a twin screw speed of 300 RPM to obtain the polyamide composite of the present invention.
  • a polyamide composite for environmentally friendly plating comprising the following raw materials by weight (total weight of raw materials: 10KG):
  • the above preparation method of the polyamide composite for environmental protection plating comprises the following steps:
  • PA12T, PA6 and TPU are melt-polymerized in an internal mixer, and the pellets are granulated to obtain a blend, which is ready for use;
  • step (3) adding the blend obtained in the step (1) and the SEED to the twin-screw extruder through the main feeder, and adding the inorganic ore powder talc powder subjected to the step (2) to the side feeder, Alumina, after mixing, melt-extruded at a temperature controlled at 295 ° C, pelletizing, and a twin-screw rotation speed of 300 RPM, to obtain a polyamide composite of the present invention.
  • An aliphatic polyamide composite for environmentally friendly plating comprising the following raw materials by weight (total weight of raw materials: 10KG):
  • the above preparation method of the polyamide composite for environmental protection plating comprises the following steps:
  • PA6T/66 and TPU, TPO are melt-polymerized in an autoclave to obtain a blend, which is ready for use;
  • step (3) adding the blend obtained in the step (1) and the SEED to the twin-screw extruder through the main feeder, and adding the inorganic ore powder talc treated by the step (2) to the side feeder.
  • a polyamide composite comprising the following raw materials by weight (total weight of raw materials: 10KG):
  • the preparation method of the above polyamide composite comprises the following steps:
  • a polyamide composite comprising the following raw materials by weight (total weight of raw materials: 10KG):
  • the preparation method of the above polyamide composite comprises the following steps:
  • the polyamide composites obtained in Examples 1-3 and Comparative Example 1 were subjected to electroplating after treatment with a potassium permanganate roughening liquid, and the plating layer formed after electroplating was subjected to a plating adhesion test.
  • the polyamide composites obtained in Examples 4 to 6 and Comparative Example 2 were subjected to electroplating after treatment with a chromic acid roughening liquid, and the plating layer formed after electroplating was subjected to a plating adhesion test. The test results are shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un complexe de polyamide pour l'électroplacage écologique, le complexe comprenant les matières premières suivantes en pourcentage en poids : de 40 % à 90 % d'une résine polyamide contenant des cycles aromatiques, de 3 % à 20 % d'un élastomère thermoplastique, de 0 % à 20 % d'un polyamide aliphatique, de 0 % à 2 % d'un agent de couplage, et de 0 % à 40 % d'une poudre minérale inorganique, l'indice de fluidité de l'élastomère thermoplastique étant supérieur à celui de la résine polyamide contenant des cycles aromatiques et à celui du polyamide aliphatique. L'invention concerne également un procédé pour la préparation du complexe de polyamide pour l'électroplacage écologique. Le complexe de polyamide de la présente invention présente de meilleures propriétés mécaniques et d'électroplacage, peut être traité avec un liquide de rugosification écologique au permanganate de potassium, et est approprié pour le développement de l'électroplacage écologique, et après électroplacage, la force de liaison d'électroplacage de celui-ci avec la surface d'une couche revêtue par électroplacage peut atteindre au moins 10 N, garantissant la sécurité pendant l'utilisation.
PCT/CN2017/112365 2017-09-19 2017-11-22 Complexe de polyamide pour l'électroplacage écologique et son procédé de préparation Ceased WO2019056547A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710844128.XA CN107663372B (zh) 2017-09-19 2017-09-19 一种用于环保电镀的聚酰胺复合物及其制备方法
CN201710844128.X 2017-09-19

Publications (1)

Publication Number Publication Date
WO2019056547A1 true WO2019056547A1 (fr) 2019-03-28

Family

ID=61097284

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/112365 Ceased WO2019056547A1 (fr) 2017-09-19 2017-11-22 Complexe de polyamide pour l'électroplacage écologique et son procédé de préparation

Country Status (2)

Country Link
CN (1) CN107663372B (fr)
WO (1) WO2019056547A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109553966B (zh) * 2018-10-16 2021-04-20 成霖企业股份有限公司 可电镀的高密度塑料组合物和高密度塑料制品及制备方法
CN109722018A (zh) * 2018-12-21 2019-05-07 金旸（厦门）新材料科技有限公司 一种高刚性低吸水性pa/abs合金材料及其制备方法
CN114507441B (zh) * 2021-12-24 2025-04-29 金发科技股份有限公司 一种聚酰胺复合材料及其制备方法和应用
CN116218205B (zh) * 2023-03-03 2024-03-29 金旸（厦门）新材料科技有限公司 一种可电镀导热尼龙复合材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1863874A (zh) * 2003-08-16 2006-11-15 通用电气公司 聚(芳基醚)/聚酰胺组合物
CN1925890A (zh) * 2004-02-27 2007-03-07 索维高级聚合物股份有限公司 保护穿戴者的包含芳香族聚酰胺组合物的防护装置以及适用于制备所述防护装置的芳香族聚酰胺组合物
CN1993425A (zh) * 2004-07-29 2007-07-04 索维高级聚合物股份有限公司 抗冲改性的聚酰胺组合物
CN104662094A (zh) * 2012-10-12 2015-05-27 尤尼吉可株式会社 半芳香族聚酰胺膜
WO2017034295A1 (fr) * 2015-08-24 2017-03-02 롯데첨단소재(주) Composition de résine thermoplastique et article moulé produit à partir de cette dernière

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100575419C (zh) * 2006-12-28 2009-12-30 深圳市科聚新材料有限公司 一种聚酰胺材料及其制备方法
CN101418097B (zh) * 2007-10-23 2011-05-11 广州金发科技股份有限公司 一种可电镀的聚丙烯复合物及其制备方法
CN102276897A (zh) * 2011-06-29 2011-12-14 广州市聚赛龙工程塑料有限公司 一种聚乙烯/尼龙合金复合材料及其制备方法
CN106046781B (zh) * 2016-07-12 2019-01-04 江门市德众泰工程塑胶科技有限公司 用于电镀处理的芳香族聚酰胺复合物及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1863874A (zh) * 2003-08-16 2006-11-15 通用电气公司 聚(芳基醚)/聚酰胺组合物
CN1925890A (zh) * 2004-02-27 2007-03-07 索维高级聚合物股份有限公司 保护穿戴者的包含芳香族聚酰胺组合物的防护装置以及适用于制备所述防护装置的芳香族聚酰胺组合物
CN1993425A (zh) * 2004-07-29 2007-07-04 索维高级聚合物股份有限公司 抗冲改性的聚酰胺组合物
CN104662094A (zh) * 2012-10-12 2015-05-27 尤尼吉可株式会社 半芳香族聚酰胺膜
WO2017034295A1 (fr) * 2015-08-24 2017-03-02 롯데첨단소재(주) Composition de résine thermoplastique et article moulé produit à partir de cette dernière

Also Published As

Publication number Publication date
CN107663372B (zh) 2019-11-19
CN107663372A (zh) 2018-02-06

Similar Documents

Publication Publication Date Title
WO2019056548A1 (fr) Complexe de polyamide aliphatique pour l'électroplacage écologique et son procédé de préparation
WO2019056546A1 (fr) Complexe de polysulfure de phénylène pour l'électroplacage écologique et son procédé de préparation
CA2874759C (fr) Composition de moulage de polyamide thermoplastique
KR101825589B1 (ko) 개선된 도금 성능을 갖는 높은 탄성률 레이저 직접 구조화 폴리카보네이트 조성물들 및 반사 첨가제들에 의한 넓은 레이저 윈도우
WO2019056547A1 (fr) Complexe de polyamide pour l'électroplacage écologique et son procédé de préparation
CN107674416B (zh) 用于环保电镀的液晶聚合物材料及其制备方法
KR20140029130A (ko) 폴리아미드 성형 조성물 및 이의 용도
EP3795642A1 (fr) Article moulé en résine renforcée de fibres de verre
KR20160100935A (ko) 플라스틱 몰딩 컴파운드 및 이의 용도
KR20110110217A (ko) 금속 도금을 위한 열가소성 기재의 컨디셔닝 및 에칭의 무크롬 방법
JP2015066735A (ja) ポリフェニレンスルフィド樹脂組成物からなる成形品と金属箔を接合した複合成形品および複合成形品の製造方法
KR20060012608A (ko) 급속 결정화 폴리에스테르 조성물
EP0888880A1 (fr) Piece soufflee multicouche conductrice et composition de resine conductrice
KR100910342B1 (ko) 폴리페닐렌술피드 수지 구조체
CN1165583C (zh) 聚亚芳基硫醚树脂组合物
JPH11106647A (ja) ポリアミド樹脂組成物
US6723400B1 (en) Laminates for making electroconductive fuel tubes
JP4207436B2 (ja) ポリアミド樹脂組成物
WO2007069769A1 (fr) Moulage en resine plaque
Verma et al. An introduction to high-performance advanced polymers composites, their types, processing, and applications in automotive industries
JP2024513073A (ja) 静電気防止ポリアミド組成物及びそれを含む物品
JP3915213B2 (ja) 導電性樹脂組成物
JP2005248170A (ja) ポリフェニレンスルフィド樹脂組成物
KR101424324B1 (ko) 금속과 폴리머 복합재 부품, 특히 자동차 분야에 있어서의 용도
CN118459897A (zh) 一种聚丙烯复合材料及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17926154

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17926154

Country of ref document: EP

Kind code of ref document: A1