WO2016101508A1 - 一种lds用聚碳酸酯组合物及其制备方法 - Google Patents

一种lds用聚碳酸酯组合物及其制备方法 Download PDF

Info

Publication number
WO2016101508A1
WO2016101508A1 PCT/CN2015/079003 CN2015079003W WO2016101508A1 WO 2016101508 A1 WO2016101508 A1 WO 2016101508A1 CN 2015079003 W CN2015079003 W CN 2015079003W WO 2016101508 A1 WO2016101508 A1 WO 2016101508A1
Authority
WO
WIPO (PCT)
Prior art keywords
antioxidant
lds
parts
polycarbonate
mixture
Prior art date
Application number
PCT/CN2015/079003
Other languages
English (en)
French (fr)
Inventor
曹艳霞
赖华林
秦勇
Original Assignee
深圳华力兴新材料股份有限公司
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 深圳华力兴新材料股份有限公司 filed Critical 深圳华力兴新材料股份有限公司
Publication of WO2016101508A1 publication Critical patent/WO2016101508A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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

Definitions

  • the invention relates to the technical field of LDS, in particular to a polycarbonate composition for LDS and a preparation method thereof.
  • LDS Laser-directing-structuring
  • the LDS process uses a thermoplastic material as a raw material, but an inorganic metal oxide or an organic metal mixture having a special crystal structure is added to the thermoplastic.
  • the laser is used to "fire" the high-resolution circuit diagram on the three-dimensional part.
  • the copper, nickel and/or gold circuitry is then plated in the activated area in a chemically plated metal bath.
  • MID Three-dimensional interconnect device
  • MID Three-dimensional interconnect device
  • the laser direct structuring technology uses a computer to control the movement of the laser according to the trajectory of the conductive pattern, and the laser is projected onto the molded three-dimensional plastic device to activate the circuit pattern in a few seconds.
  • LDS technology uses a computer to control the movement of the laser according to the trajectory of the conductive pattern, and the laser is projected onto the molded three-dimensional plastic device to activate the circuit pattern in a few seconds.
  • the emergence of laser direct molding technology has ended the three-dimensional circuit device molding process Miscellaneous, high manufacturing costs.
  • LDS technology provides a wider range of forms of fine circuit structure, which makes the circuit design more flexible, can be easily corrected by computer control data changes, and no need Modifications to the internal structure of the equipment, the components produced have a full three-dimensional interconnection function; this flexibility allows the rapid use of laser direct structuring technology in the production development process, avoiding the existence of the early stage of evaluating the feasibility of the production process Complex conversion, very suitable for the production of different types of antennas and sensors;
  • LDS technology can directly engrave the three-dimensional circuit such as antenna and sensor directly on the plastic shell of the device, not only avoiding the internal metal interference of the device, but also reducing the volume of the device;
  • Adopt LDS technology with high production efficiency, short product production cycle, durable and low maintenance of laser system, suitable for continuous uninterrupted production, low failure rate and high production efficiency.
  • laser direct structuring technology is mainly used in wireless communication products in three-dimensional interconnects, especially in antennas for smartphones and wireless mobile communication devices.
  • Internationally renowned antenna manufacturers such as Laird, Molex, Tyco, and Kailu have already used LDS technology to mass produce antenna products.
  • Almost all known smartphone companies such as Apple, Samsung, SEMC, HTC, Huawei, and ZTE have already been used.
  • the model uses an antenna produced by laser direct structuring technology.
  • Laser direct-forming technology antennas will become the mainstream of antennas and sensors in the 4G communication information era.
  • PC Polycarbonate
  • PC has outstanding impact resistance, creep resistance, dimensional stability and chemical resistance, low heat resistance, low water absorption, non-toxicity, excellent dielectric properties, self-extinguishing, easy to enhance resistance Good performance such as flammability.
  • bisphenol A polycarbonate is the largest and most widely used polycarbonate, and one of the fastest growing engineering plastics. Because polycarbonate (PC) has excellent mechanical properties, balance of toughness and rigidity, it is often used as an antenna carrier for mobile phones and wireless communication in the era of 2G communication and 3G communication.
  • the frequency band of the mobile phone signal is higher and wider, such as the TD-LTE frequency band is 2.5 to 2.69Ghz, but the ordinary PC and its alloy resin have large electromagnetic loss when the frequency is above 2.4G, the mobile phone antenna The signal loss is serious, and the need for mobile communication materials suitable for transmitting high-speed electromagnetic waves is extremely urgent.
  • the world's largest companies capable of producing LDS mobile phone antenna materials are large multinational companies in Europe, the United States and Japan, such as RTP, Sabic and Ticona in the US; DSM in the Netherlands, LANXESS in Germany, BASF and EVONIK. And Japan's Mitsubishi Engineering Plastics Co., Ltd., but the material prices are high, and the production costs of related companies are high.
  • the domestic LDS mobile phone antenna materials have different degrees of poor performance, poor plating performance, and low yield of finished products.
  • the present invention has been developed in the context of such a demand.
  • the impact toughness of the material decreases from 60-70 KJ/m 2 to 10 KJ/m 2 or even lower, and the melt flow index (MFR) increases by 5 times or more.
  • laser direct molding additive is a metal oxide or metal complex with a special crystal structure, so there is a certain amount of free metal ions or atoms in the composition system, which are catalytic polycarbonate combinations. Catalyst for degradation of the substance; at the same time, inorganic metal compound The organic or organometallic mixture is alkaline to varying degrees and further exacerbates the degree of degradation of the polycarbonate composition. Thereby the material loses its practical value. Therefore, studying and solving the influence of laser direct molding additive (LDS additive) on the thermodynamics and processing properties of PC system in the composition system is the core and key issue in the preparation of the material.
  • LDS additive laser direct molding additive
  • an aspect of the present invention provides a polycarbonate composition for LDS.
  • the polycarbonate composition for LDS has good mechanical properties, processability and plating performance, and is excellent in overall performance.
  • a polycarbonate composition for LDS in parts by mass, comprising the following components:
  • Antioxidant 0.3 to 3 parts
  • the antioxidant is composed of a hindered phenol antioxidant, a phosphite antioxidant, a thioester antioxidant, and a benzofuranone antioxidant.
  • the polycarbonate in the present invention may be 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts or 90 parts, etc.
  • the LDS additive may be 5 parts, 8 parts, 10 parts, 12 parts, 15 parts or 20 parts.
  • the antioxidant may be 0.3 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts, and the like.
  • the invention optimizes the content of each component of the polycarbonate composition for LDS, in particular, the hindered phenolic antioxidant, the phosphite antioxidant, the thioester antioxidant and the benzofuranone antioxidation
  • the combination of the agents has a synergistic effect between the antioxidants, has good oxidation resistance and processing properties, inhibits thermal degradation and oxidative degradation of the polycarbonate composition for LDS, and improves the mechanical properties and processability of the polycarbonate composition for LDS.
  • the polycarbonate composition of LDS is resistant to precipitation, solvent extraction, salting resistance and does not affect the plating during the molding process.
  • the same effect can be obtained by replacing the thioester antioxidant with a thioether antioxidant.
  • it contains a combination of 3 to 25 parts of a toughening agent, 1 to 10 parts of a compatibilizing agent, 1 to 8 parts of a lubricant, 0.1 to 2 parts of a dispersing agent, or 0.1 to 10 parts of a filler, or a combination of at least two.
  • the mass ratio of the hindered phenol antioxidant, the phosphite antioxidant, the thioester antioxidant, and the benzofuranone antioxidant is from 1 to 3:1:0.3 to 1:0.2.
  • ⁇ 1 may be 1:1:0.3:0.2, 2:1:1:1 or 3:1:0.5:0.5, etc., preferably 1 to 2:1:0.5 to 1:0.3-0.7.
  • the component of the present invention contains one or a combination of at least two of a toughening agent, a compatibilizing agent, a dispersing agent or a filler, and further optimizes the content of each component of the antioxidant agent, and fully utilizes the components.
  • the combination of performance makes the antioxidant capacity and processing performance of the antioxidant significantly improved, greatly inhibiting the thermal degradation and oxidative degradation of the polycarbonate composition for LDS, and at the same time helping to enhance the mechanical properties and processing of polycarbonate for LDS.
  • the performance, LDS polycarbonate composition is more resistant to precipitation, solvent extraction and salt resistance during the molding process, and does not affect the plating.
  • the hindered phenolic antioxidant is a sulfur-containing hindered phenolic antioxidant or an asymmetric hindered phenolic antioxidant, or a mixture of the two.
  • the hindered phenolic antioxidant is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine- 2,4,6-(1H,3H,5H)-trione, diethylene glycol bis[ ⁇ -(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], One or at least one of bis(3,5-tris-butyl-4-hydroxyphenyl) sulfide or tetrakis[ ⁇ -(3,5-tris-butyl-4-hydroxyphenyl)propanoate]pentaerythritol ester a mixture of two.
  • the hindered phenolic antioxidant is a mixture of one or at least two of commercially available brand numbers 1076, 1098, 1010, CA, 330, 1790, 3114, AO-80 or 245, preferably said hindered
  • the phenolic antioxidant is one or a mixture of at least two of the commercial brands 1076, 1010, 1790, AO-80 or 245 antioxidants.
  • the phosphite antioxidant has the structural formula shown in Formula I:
  • R' in the formula I is an alkyl group and/or an aryl group.
  • R' is a C1 to C25 alkyl group and/or a C6 to C12 aryl group.
  • the phosphite antioxidant is one or at least two of the commercial brand number 618, 168, 626, 627, 627A, P-EPQ, PEP-36, S-9228, S9228T or S9960C antioxidant.
  • the phosphite antioxidant is one or a mixture of at least two of the commercial brands 168, 626, P-EPQ, PEP-36, S-9228 or S9960C antioxidants.
  • phosphites include: phosphite triesters, phosphite diesters, phosphite monoesters, etc., such as triphenyl phosphite, tridecyl phenyl phosphite, tris(2,4-di-tert-butylphenyl) Phosphite, tridecyl phosphite, tridecyl phosphite, trioctyl phosphite, tri-octadecyl phosphite, dioctadecyl pentaerythritol diphosphite, tricyclohexyl phosphite , monobutyl diphenyl phosphite, monooctyl diphenyl phosphite, and the like.
  • triphenyl phosphite tridecyl phenyl phosphite, tris(2,
  • the thioester antioxidant is dilauryl thiodipropionate, dioctadecyl thiodipropionate, di(tetradecyl) thiodipropionate or pentathiopropane of pentaerythritol.
  • the esters One or a mixture of at least two of the esters.
  • the thioester antioxidant is one or a mixture of at least two of the commercial brand number 800, 802, 412, 412S, SE4 or SE10.
  • the polycarbonate is one or a mixture of at least two of an aliphatic carbonate, an alicyclic carbonate or an aromatic carbonate.
  • the polycarbonate is a polycarbonate containing a bisphenol A structure as shown in Formula II;
  • the polycarbonate has a melt index of 2 to 25 g/1 min at 300 ° C / 1.2 kg, and a viscosity average molecular weight of 10,000 to 40,000.
  • the melt index of the selected polycarbonate is 300 ° C / 1.2 kg. 5 to 15 g / 1 min, the viscosity average molecular weight is 15,000 to 30,000.
  • polycarbonates of the present invention enhance the thermodynamic properties of the LDS polycarbonate end products while also ensuring process fluidity, with polycarbonate being most preferred.
  • the LDS additive is an inorganic metal oxide or an organometallic complex, or a mixture of the two.
  • the metal oxide is one or a mixture of at least two of cadmium, zinc, copper, cobalt, magnesium, tin, titanium, iron, aluminum, nickel, manganese or chromium.
  • the ligand of the organometallic complex is an olefin- ⁇ complex, an ⁇ 6-aromatic complex, a ⁇ -propylene complex, a cyclopentadienyl complex, a metallocene complex, a metal carbene complex. a mixture of one or at least two of a metal carbamide complex or a carbonyl transition metal complex.
  • the toughening agent is a mixture of one or at least two of ABS, MBS, SBS, SEBS, SIS, POE, silicone core-shell polymer, high rubber powder, EBA or EMA.
  • the lubricant is one or a mixture of at least two of polyfunctional stearates, silicones, low molecular weight oxidized polyethylene waxes, stearates or EBSs.
  • the dispersing agent is one of a low molecular weight (1000 to 2000 Mw) polyethylene wax, an oxidized polyethylene wax, an ester wax, a montan wax, an EBS and a modified compound thereof, a silicone powder, and a modification thereof. a mixture of at least two, preferably the dispersant is an oxidized polyethylene wax, an ester wax, a silicone powder, and a modification thereof One or a mixture of at least two.
  • the filler is one or a mixture of at least two of glass fiber, hollow glass microbead, barium sulfate, kaolin, diatomaceous earth, talc or mica powder.
  • the filler of the present invention improves the heat resistance of the polycarbonate composition for LDS, and the hydrotalcite can also improve the plating performance.
  • the compatibilizer is a compatibilizer in which a fatty acid anhydride functional group, an epoxy functional group or a carboxyl functional group is grafted in a molecular structure.
  • the fatty acid anhydride functional group is one or a combination of at least two of maleic anhydride, succinic anhydride, acrylic anhydride or methacrylic anhydride functional groups, preferably maleic anhydride functional groups and/or acrylic anhydride functional groups.
  • the compatibilizer is a maleic anhydride graft compatibilizer, an acrylic graft compatibilizer or a methacrylic epoxy graft compatibilizer.
  • Another aspect of the present invention provides a method for preparing the above polycarbonate composition for LDS, which is simple and easy to handle, improves the processing stability of the polycarbonate composition for LDS in the preparation process, and simultaneously prepares LDS for preparation.
  • the polyurethane composition has good mechanical properties, processing properties and plating properties, and is resistant to precipitation, solvent extraction, salting resistance, and does not affect the plating during the molding process.
  • a method of preparing the above polycarbonate composition for LDS comprising the steps of:
  • the antioxidant includes a hindered phenol antioxidant, a phosphite antioxidant, a thioester antioxidant, and a benzofuranone antioxidant;
  • the LDS was pulverized with a polycarbonate composition to obtain granules of LDS material.
  • the heating temperature in the extruder is as follows: one zone 147-150 ° C, two zones 220-270 ° C, three zones 240-290 ° C, four zones 240-300 ° C, five zones 250 ⁇ 300 ° C, six zones 250 ⁇ 300 ° C, seven zones 240 ⁇ 280 ° C, eight zones 240 ⁇ 280 ° C, nine zones 240 ⁇ 280 ° C and the head 240 ⁇ 280 ° C.
  • a polyurethane composition for LDS comprising, in parts by mass, 60 to 90 parts of polycarbonate, 5 to 20 parts of an LDS additive, and 0.3 to 3 parts of an antioxidant; wherein the antioxidant includes hindered A phenolic antioxidant, a phosphite antioxidant, a thioester antioxidant, and a benzofuranone antioxidant.
  • the invention optimizes the content of each component of the polycarbonate composition for LDS, in particular, the hindered phenolic antioxidant, the phosphite antioxidant, the thioester antioxidant and the benzofuranone antioxidation
  • the combination of the agents causes a synergistic effect between the antioxidants, greatly inhibits thermal degradation and oxidative degradation of the polycarbonate composition for LDS, and has good oxidation resistance and processing properties, and improves the polycarbonate composition for LDS.
  • Mechanical properties, processing properties and plating properties, while LDS polycarbonate composition is resistant to precipitation, solvent extraction, salting resistance and does not affect the plating during the molding process.
  • Figure 1 is a process flow diagram of the present invention.
  • Example 1 The polycarbonate composition for LDS of the present example, in parts by mass, includes components:
  • the MFR of the polycarbonate in this example was 5 g/10 min, 300 ° C / 1.5 kg.
  • Example 2 The polycarbonate composition for LDS of the present example, in parts by mass, including components:
  • the MFR of the polycarbonate is 10 g/10 min, 300 ° C / 1.5 Kg.
  • 80 parts by weight of polycarbonate, 10 parts of MBS core-shell copolymer toughening agent, maleic anhydride, by mass part 5 parts of graft copolymer compatibilizer, 12 parts of LDS additive, 0.5 part of antioxidant 627A, 0.5 part of antioxidant 802, 0.5 part of benzofuranone antioxidant and 0.2 part of silicone powder are pre-mixed uniformly.
  • the mixture was heated and melted in a twin-screw extruder to obtain a melt, extruded, cooled, and a polycarbonate composition for LDS was obtained, which was pulverized to obtain granules of LDS material.
  • Example 3 The polycarbonate composition for LDS of the present example, in parts by mass, includes components:
  • the MFR of the polycarbonate was 12 g/10 min, 300 ° C / 1.5 Kg.
  • Comparative Example 1 The polycarbonate composition for LDS of the present example, in parts by mass, includes components:
  • the MFR of the polycarbonate is 5 g/10 min, 300 ° C / 1.5 Kg.
  • Comparative Example 2 The polycarbonate composition for LDS of the present example, in parts by mass, including components:
  • the MFR of the polycarbonate is 10 g/10 min, 300 ° C / 1.5 Kg.
  • the polycarbonate composition for LDS of the present invention has stable thermodynamic properties, and the impact strength is as high as 60 KJ/m 2 ; the processing property is excellent, the processing heat resistance is good; and the plating performance is not affected, and the comprehensive performance is excellent.
  • the polycarbonate composition for LDS of the present invention has good laser laser engraving performance, high yield of finished plating, and resistance to precipitation, solvent extraction, and salting resistance during molding.
  • the invention optimizes the content of each component of the polycarbonate composition for LDS, in particular, the hindered phenolic antioxidant, the phosphite antioxidant, the thioester antioxidant and the benzofuranone antioxidation
  • the combination of the agents causes a synergistic effect between the antioxidants, greatly inhibits thermal degradation and oxidative degradation of the polycarbonate composition for LDS, and has good oxidation resistance and processing properties, and improves the polycarbonate composition for LDS.
  • Mechanical properties, processing properties and plating properties, while LDS polycarbonate composition is resistant to precipitation, solvent extraction, salting resistance and does not affect the plating during the molding process.
  • the invention solves the problem that the thermal oxygen stability and the mechanical processing property of the polycarbonate are greatly reduced due to the addition of the laser direct molding additive component, the practical application value, the thermodynamic processing property and the balance with the laser laser engraving performance are solved. Insulation is good, and it has broad market prospects in the era of 4G communication.
  • the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Landscapes

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

Abstract

公开了一种LDS用聚碳酸酯组合物及其制备方法。该LDS用聚碳酸酯组合物按质量份计包括：聚碳酸酯60～90份、LDS添加剂2～30份、抗氧剂0.3～3份；其中，抗氧剂由受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫酯类抗氧剂和苯并呋喃酮类抗氧剂组成，极大地抑制了LDS用聚碳酸酯组合物热降解和氧化降解，提高了LDS用聚碳酸酯组合物的力学性能、加工性能，且不影响化镀性能，该LDS用聚碳酸酯组合物综合性能优异。

Description

一种LDS用聚碳酸酯组合物及其制备方法 技术领域
本发明涉及LDS技术领域，尤其涉及一种LDS用聚碳酸酯组合物及其制备方法。
背景技术
随着现代社会的技术进步和通讯信息业的迅猛发展，制造商需要将复杂部件通过功能一体化将部件逐渐变得更小，这可以通过三维立体互连件器件(也称为模内互联装置，MID)实现。激光直接线路成形技术(laser-directing-structuring，LDS)是制造MID的特殊创新技术。利用该技术可以灵活、方便地以较低的成本在三维MID上制造印刷电路，不使用化学蚀刻的方法。LDS工艺采用热塑性塑料为原材料，但是该热塑性塑料中加入具有特殊晶型结构的无机金属氧化物或者有机金属混合物。注塑后，用激光在三维部件上“烧制”高分辨的电路图。继而在化学电镀金属浴中，在经活化的区域镀覆铜、镍和/或金电路。
三维立体互连件器件(MID)可以应用于通讯信息和电子行业，医疗行业、军事与国防业、航空航天业、汽车零部件行业、精密传感器行业、印制电路板行业、电子通讯与元器件行业、大型装备制造业、电池制造业等领域。但在很长一段时间里，三维立体互连件器件被分为两部分模塑(双注塑技术)，通过表面化学活化和选择性电镀，但这是一种只有对大批量零件有经济意义的高成本的工艺。
激光直接成型技术(LDS技术)是利用计算机按照导电图形的轨迹控制激光的运动，将激光投照到模塑成型的三维塑料器件上，在几秒钟的时间内，活化出电路图案。激光直接成型技术的出现结束了三维立体电路器件成型工艺复 杂、制造成本高的历史。
LDS技术具有以下优点：
1)、相较于传统的工艺，LDS技术在形成精细电路结构方面提供更广泛的范围，它使电路设计具有较大的灵活性，通过电脑控制数据改变可以很容易的对其修正，而且无需对设备内部结构进行修改，所生产的部件具备完全的三维立体互连功能；这种灵活性使得可以采用激光直接成型技术迅速用于生产开发过程，能够避免在评估生产工艺可行性的前期阶段存在的复杂转换，非常适合生产不同种类的天线及传感器；
2)、LDS技术可将天线及传感器等三维立体电路直接镭雕在器件塑料外壳上，不仅避免器件的内部金属干扰，更可以缩小器件的体积；
3)、采用LDS技术生产效率高，产品生产周期短，激光系统耐用、少维护，适用于连续不间断生产，并且故障率低，生产效率高。
在通讯和信息行业，激光直接成型技术(LDS技术)在三维立体互连件的主要为无线通讯产品，特别是在智能手机和无线移动通讯设备的天线中。国际上知名的天线厂商Laird、Molex、Tyco、启碁等目前均已使用LDS技术大量生产天线产品，几乎所有已知的智能手机公司如Apple、Samsung、SEMC、HTC、华为、中兴等均已有机型使用激光直接成型技术技术生产的天线。激光直接成型技术天线将会成为4G通讯信息时代天线及传感器的主流。
聚碳酸酯(PC)具有突出的抗冲击能力，耐蠕变，尺寸稳定性好及耐化学腐蚀性，耐热、吸水率低、无毒、介电性能优良，还有自熄、易增强阻燃性等优良性能。其中双酚A型聚碳酸酯是目前产量最大、用途最广的一种聚碳酸酯，也是发展最快的工程塑料之一。由于聚碳酸酯(PC)力学性能优异，韧性和刚性均衡，常在2G通讯和3G通讯时代作为手机及无线通讯的天线载体。
然而，进入4G通讯时代后，手机信号的频段频率更高更宽，如TD-LTE频段在2.5～2.69Ghz，但普通的PC及其合金树脂在2.4G频段以上时电磁损耗很大，手机天线的信号损失严重，对适合传导高速电磁波的手机类通讯材料的需要迫在眉睫。
据报道，世界上能够生产LDS手机天线材料的公司主要是欧洲、美国和日本的大型跨国公司，例如美国的RTP公司、Sabic公司和Ticona公司；荷兰DSM公司、德国LANXESS公司、BASF公司、EVONIK公司和日本的三菱工程塑料公司，但材料价格高昂，相关企业生产成本很高。而国内LDS手机天线材料均程度不同的存在着材料性能均衡性差、化镀效果不良、成品良率低等问题。本发明正是在这样需求背景下研发而成的。
研究和实验发现，当聚合物体系中含有激光直接成型添加剂(LDS添加剂)时，即使聚合物中添加大量的受阻酚类抗氧剂，也不能抑制该组合物体系的力学性能大幅度下降从而使得材料失去实用价值。根据我司TGA(热失重分析)测试的结果，在常规抗氧条件下，添加了激光直接成型添加剂(LDS添加剂)的PC的玻璃化转变温度Tg和开始热失重的温度比普通PC塑料的相应温度低50℃甚至100℃以上，材料的冲击韧性从60-70KJ/m2下降到10KJ/m2甚至更低，熔体流动指数(MFR)上升了5倍甚至更多。这些数据表明材料发生了严重的降解反应，推测是由于LDS添加剂与PC间直接发生反应或者成为了PC分子链发生降解反应的催化剂，最终的结果使PC大分子链易于断裂，力学强度大幅度下降，熔体粘度大幅度下降。
从理论分析，激光直接成型添加剂(LDS添加剂)是具有特殊晶型结构的金属氧化物或金属配合物，因此该组合物体系中存在一定含量的游离金属离子或原子，它们是催化聚碳酸酯组合物发生降解的催化剂；同时，无机金属化合 物或有机金属混合物不同程度上具有碱性，也进一步加剧了聚碳酸酯组合物的降解反应程度。从而使得材料失去实用价值。因此，该组合物体系中研究并解决激光直接成型添加剂(LDS添加剂)对PC体系热力学和加工性能的影响是制备该材料的核心和关键问题。
发明内容
有鉴于此，本发明一方面提供一种LDS用聚碳酸酯组合物。该LDS用聚碳酸酯组合物具有良好的力学性能、加工性能和化镀性能，综合性能优异。
本发明采用以下技术方案：
一种LDS用聚碳酸酯组合物，按质量份计，包括以下组分：
聚碳酸酯    60～90份；
LDS添加剂   2～30份；
抗氧剂      0.3～3份；
其中，所述抗氧剂由受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫酯类抗氧剂和苯并呋喃酮类抗氧剂组成。
本发明中聚碳酸酯可以为60份、65份、70份、75份、80份、85份或90份等，LDS添加剂可以为5份、8份、10份、12份、15份或20份等，抗氧剂可以为0.3份、0.5份、1份、1.5份、2份、2.5份或3份等。
本发明对LDS用聚碳酸酯组合物各组分含量进行优化处理，特别是对受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫酯类抗氧剂和苯并呋喃酮类抗氧剂进行组合使用，使抗氧化剂间发生协同效应具有良好的抗氧化能力和加工性能，抑制LDS用聚碳酸酯组合物热降解和氧化降解，提高LDS用聚碳酸酯组合物的力学性能和加工性能，同时LDS用聚碳酸酯组合物在成型过程中耐析出、耐溶剂萃取、耐盐化且不影响化镀。
本发明中将硫酯类抗氧剂替换为硫醚类抗氧剂，也可以达到同样效果。
还含有增韧剂3～25份、相容剂1～10份、润滑剂1～8份、分散剂0.1～2份或填充剂0.1～10份中一种或至少两种的组合。
优选地，所述受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫酯类抗氧剂和苯并呋喃酮类抗氧剂的质量比为1～3∶1∶0.3～1∶0.2～1，可以为1∶1∶0.3∶0.2、2∶1∶1∶1或3∶1∶0.5∶0.5等，优选为1～2∶1∶0.5～1∶0.3～0.7。
本发明的组分中含有增韧剂、相容剂、分散剂或填充剂中一种或至少两种的组合，并对抗氧剂的各组分含量进行进一步优化处理，充分利用各组分的性能进行配合使用，使得抗氧剂的抗氧化能力和加工性能明显提高，极大抑制LDS用聚碳酸酯组合物热降解和氧化降解，同时有助于增强LDS用聚碳酸酯的力学性能和加工性能，LDS用聚碳酸酯组合物在成型过程中耐析出、耐溶剂萃取、耐盐化性能也得到进一步提高，且不影响化镀。
所述受阻酚类抗氧剂为含硫受阻酚类抗氧剂或不对称受阻酚类抗氧剂，或者两者的混合物。
优选地，所述受阻酚类抗氧剂为1，3，5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)-1，3，5-三嗪-2，4，6-(1H，3H，5H)-三酮、二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]、双(3，5-三级丁基-4-羟基苯基)硫醚或四[β-(3，5-三级丁基-4-羟基苯基)丙酸]季戊四醇酯中一种或至少两种的混合物。
优选地，所述受阻酚类抗氧剂为商品牌号1076、1098、1010、CA、330、1790、3114、AO-80或245抗氧剂中一种或至少两种的混合物，优选所述受阻酚类抗氧剂为商品牌号1076、1010、1790、AO-80或245抗氧剂中一种或至少两种的混合物。
优选地，所述亚磷酸酯类抗氧剂结构式如式I所示：
Figure PCTCN2015079003-appb-000001
其中，式I中R’为烷基和/或芳基。
优选地，R’为C1～C25烷基和/或C6～C12芳基。
优选地，所述亚磷酸酯类抗氧剂为商品牌号618、168、626、627、627A、P-EPQ、PEP-36、S-9228、S9228T或S9960C抗氧剂中一种或至少两种的混合物，优选所述亚磷酸酯类抗氧剂为商品牌号168、626、P-EPQ、PEP-36、S-9228或S9960C抗氧剂中一种或至少两种的混合物。
亚磷酸酯的实例包括：亚磷酸三酯、亚磷酸二酯、亚磷酸单酯等，例如亚磷酸三苯酯、亚磷酸三壬基苯酯、三(2，4-二叔丁基苯基)亚磷酸酯、亚磷酸三壬酯、亚磷酸三癸酯、亚磷酸三辛酯、三-十八烷基亚磷酸酯、双十八烷基季戊四醇双亚磷酸酯、亚磷酸三环己酯、亚磷酸一丁基二苯酯、亚磷酸一辛基二苯酯等。
优选地，所述硫酯类抗氧剂为硫代二丙酸二月桂酯、硫代二丙酸双十八酯、硫代二丙酸二(十四)酯或季戊四醇类十二硫代丙酯中一种或至少两种的混合物。
优选地，所述硫酯类抗氧剂为商品牌号800、802、412、412S、SE4或SE10抗氧剂中一种或至少两种的混合物。
所述聚碳酸酯为脂肪族碳酸酯、脂环族碳酸酯或芳香族碳酸酯中一种或至少两种的混合物。
优选地，所述聚碳酸酯为含有如式II所示双酚A结构的聚碳酸酯；
Figure PCTCN2015079003-appb-000002
优选地，所述聚碳酸酯在300℃/1.2kg条件下熔融指数为2～25g/1min，粘均分子量为10,000～40,000，优选所选聚碳酸酯在300℃/1.2kg条件下熔融指数为5～15g/1min，粘均分子量为15,000～30,000。
本发明中聚碳酸酯增强了LDS聚碳酸酯终端产品的热力学性能，同时也保证了加工流动性，其中最优选地聚碳酸酯效果最好。
优选地，所述LDS添加剂为无机金属氧化物或有机金属配合物，或两者的混合物。
优选地，所述金属氧化物为镉、锌、铜、钴、镁、锡、钛、铁、铝、镍、锰或铬的氧化物中一种或者至少两种的混合物。
优选地，所述有机金属配合物的配体为烯烃-π配合物、η6-芳烃配合物、π-丙烯基配合物、环戊二烯基配合物、茂金属配合物、金属卡宾络合物、金属卡拜络合物或羰基过渡金属配合物中一种或者至少两种的混合物。
优选地，所述增韧剂为ABS、MBS、SBS、SEBS、SIS、POE、有机硅核壳聚合物、高胶粉、EBA或EMA中一种或至少两种的混合物。
优选地，所述润滑剂为多官能团硬脂酸酯类、硅酮类、低分子量氧化聚乙烯蜡类，硬脂酸盐类或EBS类中一种或至少两种的混合物。
优选地，所述分散剂为低分子量(1000～2000Mw)聚乙烯蜡、氧化聚乙烯蜡、酯蜡、蒙旦蜡、EBS及其改性化合物、硅酮粉及其改性物中一种或者至少两种的混合物，优选所述分散剂为氧化聚乙烯蜡、酯蜡、硅酮粉及其改性物中 一种或者至少两种的混合物。
优选地，所述填充剂为玻璃纤维、空心玻璃微珠、硫酸钡、高岭土、硅藻土、滑石粉或云母粉中一种或者至少两种的混合物。
本发明的填充剂，提高了LDS用聚碳酸酯组合物的耐热性、其中水滑石还可以提高化镀性能。
优选地，所述相容剂为分子结构中接枝有脂肪酸酐官能团、环氧官能团或羧基官能团的相容剂。
优选地，脂肪酸酐官能团为马来酸酐、丁二酸酐、丙烯酸酐或甲基丙烯酸酐的官能团中一种或至少两种组合，优选为马来酸酐官能团和/或丙烯酸酐官能团。
优选地，所述相容剂为马来酸酐接枝相容剂、丙烯酸接枝相容剂或甲基丙烯酸环氧接枝相容剂。
本发明另一方面提供一种制备上述LDS用聚碳酸酯组合物的方法，该制备方法简单易操作，提高了LDS用聚碳酸酯组合物在制备过程中的加工稳定性，同时制备的LDS用聚氨酯组合物具有良好的力学性能、加工性能和化镀性能，在成型过程中耐析出、耐溶剂萃取、耐盐化、不影响化镀。
一种制备上述LDS用聚碳酸酯组合物的方法，包括以下步骤：
(1)按质量份计，将聚碳酸酯60～90份、LDS添加剂2～30份和抗氧剂0.3～3份预混合均匀，投入到双螺杆挤出机中加热熔融，得到熔融物；
其中，所述抗氧剂包括受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫酯类抗氧剂和苯并呋喃酮类抗氧剂；
(2)将所述熔融物挤出、冷却，得到LDS用聚碳酸酯组合物；
(3)将所述LDS用聚碳酸酯组合物进行粉粹，制得LDS材料颗粒。
优选地，步骤(1)中，所述挤出机中加热温度如下：一区147～150℃、二区220～270℃、三区240～290℃、四区240～300℃、五区250～300℃、六区250～300℃、七区240～280℃、八区240～280℃、九区240～280℃和机头240～280℃。
本发明的有益效果：一种LDS用聚氨酯组合物，按质量份计，包括聚碳酸酯60～90份、LDS添加剂5～20份和抗氧剂0.3～3份；其中，抗氧剂包括受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫酯类抗氧剂和苯并呋喃酮类抗氧剂。本发明对LDS用聚碳酸酯组合物各组分含量进行优化处理，特别是对受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫酯类抗氧剂和苯并呋喃酮类抗氧剂进行组合使用，使抗氧化剂间发生协同效应，极大抑制LDS用聚碳酸酯组合物热降解和氧化降解，使其具有良好的抗氧化能力和加工性能，提高LDS用聚碳酸酯组合物的力学性能、加工性能和化镀性能，同时LDS用聚碳酸酯组合物在成型过程中耐析出、耐溶剂萃取、耐盐化且不影响化镀。
附图说明
图1为本发明的工艺流程图。
具体实施方式
下面结合具体实施例来进一步说明本发明的技术方案。
实施例1：本实施例的LDS用聚碳酸酯组合物，按质量份计，包括组分：
Figure PCTCN2015079003-appb-000003
Figure PCTCN2015079003-appb-000004
本实施例中聚碳酸酯的MFR为5g/10min，300℃/1.5Kg。
本实施例中的LDS用聚碳酸酯组合物制备方法如下：
按质量份计，将聚碳酸酯90份、有机硅核壳共聚物增韧剂3份、乙烯丙烯酸接枝共聚物相容剂3份、LDS添加剂6份、抗氧剂1076 0.3份、抗氧剂168 0.3份、抗氧剂800 0.3份、苯并呋喃酮类抗氧剂0.3份和硅酮粉0.2份预混合均匀，投入到双螺杆挤出机的加热熔融、得到熔融物、挤出、冷却、得到LDS用聚碳酸酯组合物，粉粹，制得LDS材料颗粒。
实施例2：本实施例的LDS用聚碳酸酯组合物，按质量份计，包括组分：
Figure PCTCN2015079003-appb-000005
其中，聚碳酸酯的MFR为10g/10min，300℃/1.5Kg。
本实施例中的LDS用聚碳酸酯组合物制备方法如下：
按质量份计，将聚碳酸酯80份、MBS核壳共聚物增韧剂10份、马来酸酐 接枝共聚物相容剂5份、LDS添加剂12份、抗氧剂627A 0.5份、抗氧剂802 0.5份、苯并呋喃酮类抗氧剂0.5份和硅酮粉0.2份预混合均匀，投入到双螺杆挤出机的加热熔融，得到熔融物、挤出、冷却、得到LDS用聚碳酸酯组合物，粉粹，制得LDS材料颗粒。
实施例3：本实施例的LDS用聚碳酸酯组合物，按质量份计，包括组分：
Figure PCTCN2015079003-appb-000006
其中，聚碳酸酯的MFR为12g/10min，300℃/1.5Kg。
本实施例中的LDS用聚碳酸酯组合物制备方法如下：
按质量份计，将聚碳酸酯60份、ABS增韧剂15份、PTW相容剂5份、LDS添加剂20份、抗氧剂1790 0.3份、抗氧剂S-9228T 0.2份、抗氧剂412 0.2份、苯并呋喃酮类抗氧剂0.2份、改性硅酮粉0.3份和氧化聚乙烯蜡0.5份预混合均匀，投入到双螺杆挤出机的加热熔融，得到熔融物、挤出、冷却，得到LDS用聚碳酸酯组合物，粉粹，制得LDS材料颗粒。
对比例1：本实施例的LDS用聚碳酸酯组合物，按质量份计，包括组分：
Figure PCTCN2015079003-appb-000007
其中，聚碳酸酯的MFR为5g/10min，300℃/1.5Kg。
本实施例中的LDS用聚碳酸酯组合物制备方法如下：
按质量份计，将聚碳酸酯90份、有机硅核壳共聚物增韧剂3份、乙烯丙烯酸接枝共聚物相容剂3份、LDS添加剂6份、抗氧剂1076 0.3份、抗氧剂168 1份、抗氧剂800 1份、苯并呋喃酮类抗氧剂0.6份和硅酮粉0.2份预混合均匀，投入到双螺杆挤出机的加热熔融、得到熔融物、挤出、冷却、得到LDS用聚碳酸酯组合物，粉粹，制得LDS材料颗粒。
对比例2：本实施例的LDS用聚碳酸酯组合物，按质量份计，包括组分：
Figure PCTCN2015079003-appb-000008
Figure PCTCN2015079003-appb-000009
其中，聚碳酸酯的MFR为10g/10min，300℃/1.5Kg。
本实施例中的LDS用聚碳酸酯组合物制备方法如下：
按质量份计，将聚碳酸酯80份、MBS核壳共聚物增韧剂10份、马来酸酐接枝共聚物相容剂5份、LDS添加剂12份、抗氧剂1076 0.7份、抗氧剂627A 0.5份、抗氧剂802 1.5份、苯并呋喃酮类抗氧剂2.5份、硅酮粉0.2份预混合均匀，投入到双螺杆挤出机的加热熔融，得到熔融物、挤出、冷却，得到LDS用聚碳酸酯组合物，粉粹，制得LDS材料颗粒。
将实施例1～3、对比例1～2得到的LDS用聚碳酸酯组合物和目前市场上LDS用聚碳酸酯组合物(对比例3)按照ISO标准进行以下性能测试，结果如下表：
Figure PCTCN2015079003-appb-000010
从上表可以看出本发明的LDS用聚碳酸酯组合物热力学性能稳定，冲击强度甚至高达60KJ/m2；加工性能优异，加工耐热性好；同时不影响化镀性能，综合性能优异。
另外，本发明的LDS用聚碳酸酯组合物具有良好的激光镭雕性能，成品化镀良率高，成型过程中耐析出、耐溶剂萃取、耐盐化。
本发明对LDS用聚碳酸酯组合物各组分含量进行优化处理，特别是对受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫酯类抗氧剂和苯并呋喃酮类抗氧剂进行组合使用，使抗氧化剂间发生协同效应，极大抑制LDS用聚碳酸酯组合物热降解和氧化降解，使其具有良好的抗氧化能力和加工性能，提高LDS用聚碳酸酯组合物的力学性能、加工性能和化镀性能，同时LDS用聚碳酸酯组合物在成型过程中耐析出、耐溶剂萃取、耐盐化且不影响化镀。
本发明解决了由于添加了激光直接成型添加剂成分而引起的聚碳酸酯的热氧稳定性、机械加工性能大幅度下降失去实际应用价值以及热力学加工性能及与激光镭雕化镀性能的平衡问题，绝缘性好，在4G通讯时代具有广阔的市场前景。
应该注意到并理解，在不脱离后附的权利要求所要求保护的本发明的精神和范围的情况下，能够对上述详细描述的本发明做出各种修改和改进。因此，要求保护的技术方案的范围不受所给出的任何特定示范教导的限制。
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种LDS用聚碳酸酯组合物，其特征在于，按质量份计，包括以下组分：
    聚碳酸酯   60～90份；
    LDS添加剂  2～30份；
    抗氧剂     0.3～3份；
    其中，所述抗氧剂由受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫酯类抗氧剂和苯并呋喃酮类抗氧剂组成。
  2. 根据权利要求1所述的LDS用聚碳酸酯组合物，其特征在于，还含有增韧剂3～25份、相容剂1～10份、润滑剂1～8份、分散剂0.1～2份或填充剂0.1～10份中一种或至少两种的组合；
    优选地，将所述硫酯类抗氧剂替换为硫醚类抗氧剂。
  3. 根据权利要求1或2所述的LDS用聚碳酸酯组合物，其特征在于，所述受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫酯类抗氧剂和苯并呋喃酮类抗氧剂的质量比为1～3∶1∶0.3～1∶0.2～1，优选为1～2∶1∶0.5～1∶0.3～0.7。
  4. 根据权利要求1～3之一所述的LDS用聚碳酸酯组合物，其特征在于，所述受阻酚类抗氧剂为含硫受阻酚类抗氧剂或不对称受阻酚类抗氧剂，或者两者的混合物；
    优选地，所述受阻酚类抗氧剂为1，3，5-三(4-叔丁基-3-羟基-2，6-二甲基苄基)-1，3，5-三嗪-2，4，6-(1H，3H，5H)-三酮、二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]、双(3，5-三级丁基-4-羟基苯基)硫醚或四[β-(3，5-三级丁基-4-羟基苯基)丙酸]季戊四醇酯中一种或至少两种的混合物；
    优选地，所述受阻酚类抗氧剂为商品牌号1076、1098、1010、CA、330、1790、3114、AO-80或245抗氧剂中一种或至少两种的混合物，优选所述受阻 酚类抗氧剂为商品牌号1076、1010、1790、AO-80或245抗氧剂中一种或至少两种的混合物。
  5. 根据权利要求1～4之一所述的LDS用聚碳酸酯组合物，其特征在于，所述亚磷酸酯类抗氧剂结构式如式I所示：
    Figure PCTCN2015079003-appb-100001
    其中，式I中R’为烷基和/或芳基；
    优选地，R’为C1～C25烷基和/或C6～C12芳基；
    优选地，所述亚磷酸酯类抗氧剂为商品牌号618、168、626、627、627A、P-EPQ、PEP-36、S-9228、S9228T或S9960C抗氧剂中一种或至少两种的混合物，优选所述亚磷酸酯类抗氧剂为商品牌号168、626、P-EPQ、PEP-36、S-9228或S9960C抗氧剂中一种或至少两种的混合物；
    优选地，所述硫酯类抗氧剂为硫代二丙酸二月桂酯、硫代二丙酸双十八酯、硫代二丙酸二(十四)酯或季戊四醇类十二硫代丙酯中一种或至少两种的混合物。
  6. 根据权利要求1～5之一所述的LDS用聚碳酸酯组合物，其特征在于，所述聚碳酸酯为脂肪族碳酸酯、脂环族碳酸酯或芳香族碳酸酯中一种或至少两种的混合物；
    优选地，所述聚碳酸酯为含有如式II所示双酚A结构的聚碳酸酯；
    Figure PCTCN2015079003-appb-100002
    Figure PCTCN2015079003-appb-100003
    优选地，所述聚碳酸酯在300℃/1.2kg条件下熔融指数为2～25g/1min，粘均分子量为10,000～40,000，优选所选聚碳酸酯在300℃/1.2kg条件下熔融指数为5～15g/1min，粘均分子量为15,000～30,000。
  7. 根据权利要求1～6之一所述的LDS用聚碳酸酯组合物，其特征在于，所述LDS添加剂为无机金属氧化物或有机金属配合物，或两者的混合物；
    优选地，所述无机金属氧化物为镉、锌、铜、钴、镁、锡、钛、铁、铝、镍、锰或铬的氧化物中一种或者至少两种的混合物；
    优选地，所述有机金属配合物的配体为烯烃-π配合物、η6-芳烃配合物、π-丙烯基配合物、环戊二烯基配合物、茂金属配合物、金属卡宾络合物、金属卡拜络合物或羰基过渡金属配合物中一种或者至少两种的混合物。
  8. 根据权利要求2～7之一所述的LDS用聚碳酸酯组合物，其特征在于，所述增韧剂为ABS、MBS、SBS、SEBS、SIS、POE、有机硅核壳聚合物、高胶粉、EBA或EMA中一种或至少两种的混合物；
    优选地，所述分散剂为低分子量聚乙烯蜡、氧化聚乙烯蜡、酯蜡、蒙旦蜡、EBS及其改性化合物、硅酮粉及其改性物中一种或者至少两种的混合物，优选所述分散剂为氧化聚乙烯蜡、酯蜡、硅酮粉及其改性物中一种或者至少两种的混合物；
    优选地，所述填充剂为玻璃纤维、空心玻璃微珠、硫酸钡、高岭土、硅藻土、滑石粉或云母粉中一种或者至少两种的混合物；
    优选地，所述相容剂为分子结构中接枝有脂肪酸酐官能团、环氧官能团或羧基官能团的相容剂；
    优选地，脂肪酸酐官能团为马来酸酐、丁二酸酐、丙烯酸酐或甲基丙烯酸 酐的官能团中一种或至少两种组合，优选为马来酸酐官能团和/或丙烯酸酐官能团；
    优选地，所述相容剂为马来酸酐接枝相容剂、丙烯酸接枝相容剂或甲基丙烯酸环氧接枝相容剂。
  9. 一种制备如权利要求1所述的LDS用聚碳酸酯组合物的方法，其特征在于，包括以下步骤：
    (1)按质量份计，将聚碳酸酯60～90份、LDS添加剂2～30份和抗氧剂0.3～3份预混合均匀，投入到挤出机中加热熔融，得到熔融物；
    其中，所述抗氧剂包括受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫酯类抗氧剂和苯并呋喃酮类抗氧剂；
    (2)将所述熔融物挤出、冷却，得到LDS用聚碳酸酯组合物。
  10. 根据权利要求9所述的制备方法，其特征在于，步骤(1)中，所述挤出机中加热温度如下：一区147～150℃、二区220～270℃、三区240～290℃、四区240～300℃、五区250～300℃、六区250～300℃、七区240～280℃、八区240～280℃、九区240～280℃和机头240～280℃；
    优选地，步骤(2)之后，还包括步骤(3)将所述LDS用聚碳酸酯组合物进行粉粹，制得LDS材料颗粒。
PCT/CN2015/079003 2014-12-26 2015-05-14 一种lds用聚碳酸酯组合物及其制备方法 WO2016101508A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410830568.6 2014-12-26
CN201410830568.6A CN104497537B (zh) 2014-12-26 2014-12-26 一种lds用聚碳酸酯组合物及其制备方法

Publications (1)

Publication Number Publication Date
WO2016101508A1 true WO2016101508A1 (zh) 2016-06-30

Family

ID=52939000

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/079003 WO2016101508A1 (zh) 2014-12-26 2015-05-14 一种lds用聚碳酸酯组合物及其制备方法

Country Status (2)

Country Link
CN (1) CN104497537B (zh)
WO (1) WO2016101508A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112300555A (zh) * 2019-07-29 2021-02-02 广州合成材料研究院有限公司 一种激光打标的阻燃聚碳酸酯材料及其制备方法和应用
CN112759818A (zh) * 2020-12-25 2021-05-07 深圳力越新材料有限公司 一种手机天线用的lds功能母粒及其制备方法
CN113121972A (zh) * 2019-12-30 2021-07-16 江苏派锐电子有限公司 一种新型易散热耐老化电子元器件塑料外壳材料
CN116144145A (zh) * 2021-11-19 2023-05-23 广东中塑新材料有限公司 聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯组合物及其制备方法

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104497537B (zh) * 2014-12-26 2016-08-31 深圳华力兴新材料股份有限公司 一种lds用聚碳酸酯组合物及其制备方法
CN104497535B (zh) * 2014-12-26 2016-08-31 深圳华力兴新材料股份有限公司 一种具有良好热稳定性的lds用聚碳酸酯组合物
CN105713231A (zh) * 2016-02-17 2016-06-29 黄秀茹 一种用于聚合物的添加剂及其制备方法以及由其组成的聚合物组合物
CN105601993A (zh) * 2016-02-17 2016-05-25 黄秀茹 一种用于聚合物的添加剂及其制备方法以及由其组成的聚合物组合物
CN105848422B (zh) * 2016-06-08 2017-03-22 上海安费诺永亿通讯电子有限公司 一种电路制作方法
KR102013020B1 (ko) * 2016-12-30 2019-08-21 롯데첨단소재(주) 레이저 직접 구조화 공정용 열가소성 수지 조성물 및 이를 포함하는 복합체
JP7381232B2 (ja) * 2019-07-16 2023-11-15 Ｍｃｐｐイノベーション合同会社 レーザーダイレクトストラクチャリング用熱可塑性樹脂組成物及び成形体
CN111995856A (zh) * 2020-07-16 2020-11-27 天津金发新材料有限公司 一种pc组合物
CN112063014A (zh) * 2020-08-10 2020-12-11 上海奇克氟硅材料有限公司 抗烧芯、抗黄变的抗氧剂组合物及其制备和应用
CN112341666A (zh) * 2020-11-09 2021-02-09 中广核高新核材科技（苏州）有限公司 一种改性lds镭雕助剂的制备方法和lds复合材料
CN112341784B (zh) * 2020-11-16 2022-06-28 金发科技股份有限公司 一种聚碳酸酯组合物及其制备方法和应用
CN112662159B (zh) * 2020-12-19 2022-10-14 杭州本松新材料技术股份有限公司 一种镀覆性、耐降解性好的聚碳酸酯激光直接成型材料及制备方法和制品

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102762658A (zh) * 2010-02-08 2012-10-31 三菱化学欧洲合资公司 聚合物组合物
CN102770491A (zh) * 2009-12-21 2012-11-07 三菱化学欧洲合资公司 芳族聚碳酸酯组合物
CN103450675A (zh) * 2012-05-31 2013-12-18 金发科技股份有限公司 具有激光直接成型功能的树脂组合物、其制备方法以及该树脂组合物的应用
US20140296410A1 (en) * 2013-04-01 2014-10-02 Sabic Innovative Plastics Ip B.V. High modulus laser direct structuring polycarbonate composites with enhanced plating performance and broad laser window and methods for the manufacture and use thereof
CN104497537A (zh) * 2014-12-26 2015-04-08 深圳华力兴新材料股份有限公司 一种lds用聚碳酸酯组合物及其制备方法
CN104583317A (zh) * 2012-09-14 2015-04-29 三菱工程塑料株式会社 激光直接成型用树脂组合物、树脂成型品及具有镀层的树脂成型品的制造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101659759B (zh) * 2009-09-22 2011-09-07 四川大学 有机-无机复合光热稳定剂及由其制备的聚氯乙烯与制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102770491A (zh) * 2009-12-21 2012-11-07 三菱化学欧洲合资公司 芳族聚碳酸酯组合物
CN102762658A (zh) * 2010-02-08 2012-10-31 三菱化学欧洲合资公司 聚合物组合物
CN103450675A (zh) * 2012-05-31 2013-12-18 金发科技股份有限公司 具有激光直接成型功能的树脂组合物、其制备方法以及该树脂组合物的应用
CN104583317A (zh) * 2012-09-14 2015-04-29 三菱工程塑料株式会社 激光直接成型用树脂组合物、树脂成型品及具有镀层的树脂成型品的制造方法
US20140296410A1 (en) * 2013-04-01 2014-10-02 Sabic Innovative Plastics Ip B.V. High modulus laser direct structuring polycarbonate composites with enhanced plating performance and broad laser window and methods for the manufacture and use thereof
CN104497537A (zh) * 2014-12-26 2015-04-08 深圳华力兴新材料股份有限公司 一种lds用聚碳酸酯组合物及其制备方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112300555A (zh) * 2019-07-29 2021-02-02 广州合成材料研究院有限公司 一种激光打标的阻燃聚碳酸酯材料及其制备方法和应用
CN112300555B (zh) * 2019-07-29 2022-11-15 广州合成材料研究院有限公司 一种激光打标的阻燃聚碳酸酯材料及其制备方法和应用
CN113121972A (zh) * 2019-12-30 2021-07-16 江苏派锐电子有限公司 一种新型易散热耐老化电子元器件塑料外壳材料
CN112759818A (zh) * 2020-12-25 2021-05-07 深圳力越新材料有限公司 一种手机天线用的lds功能母粒及其制备方法
CN112759818B (zh) * 2020-12-25 2022-09-30 深圳力越新材料有限公司 一种手机天线用的lds功能母粒及其制备方法
CN116144145A (zh) * 2021-11-19 2023-05-23 广东中塑新材料有限公司 聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯组合物及其制备方法

Also Published As

Publication number Publication date
CN104497537A (zh) 2015-04-08
CN104497537B (zh) 2016-08-31

Similar Documents

Publication Publication Date Title
WO2016101508A1 (zh) 一种lds用聚碳酸酯组合物及其制备方法
WO2016101507A1 (zh) 一种具有良好热稳定性的lds用聚碳酸酯组合物
CN109735060B (zh) 一种用于激光直接成型技术的热塑性复合材料及其制备方法
CN102532853B (zh) 一种高硬度抗划伤改性pc材料及其制备方法
CN102020833B (zh) 高成型速率、高流动的增强阻燃聚酯及其生产方法
CN103665817B (zh) 一种高抗冲聚碳酸酯复合材料及其制备方法
CN101784607A (zh) 芳族聚碳酸酯组合物
CN108034204A (zh) 一种耐低温冲击聚酯组合物及其制备方法
CN108219460B (zh) 一种nmt技术用pps/sps工程塑料及制备方法
CN103087456A (zh) 一种耐热abs材料及其制备方法
CN114479410B (zh) 一种低介电损耗lds工程塑料及其制备方法
CN106928682A (zh) 一种具有良好综合性能的激光直接成型材料及其制备方法
CN110283441B (zh) 介孔分子筛复配激光直接成型材料及其应用
CN110951236B (zh) 基于聚苯醚的激光直接成型材料及其制备方法
CN109627665B (zh) 一种用于激光直接成型的热塑性树脂组合物及其制备方法
CN107501746A (zh) 一种替代abs用于园林工具的低收缩、高耐候聚丙烯复合材料及其制备方法
CN106280012A (zh) 一种电镀聚丙烯合金材料及其制备方法
CN110467811B (zh) 一种耐弯折的激光直接成型材料及其制备方法
CN105713336A (zh) 一种高性能电镀abs合金材料及其制备方法
CN105754141B (zh) 含铋敏化助剂在制备可激光直接成型的树脂组合物中的应用
CN110872436B (zh) 一种生物基激光直接成型材料及其制备方法
CN104119590A (zh) 一种玻纤增强聚烯烃-硅橡胶复合材料及其制备方法
CN103709710A (zh) 加工性能优异的pc/abs合金材料及其制备方法
CN104163982A (zh) 一种环保发泡聚丙烯材料及其制备方法
CN110066504B (zh) 一种低气味阻燃pc/pbt合金及其制备方法

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: 15871584

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: 15871584

Country of ref document: EP

Kind code of ref document: A1