WO2016101507A1 - 一种具有良好热稳定性的lds用聚碳酸酯组合物 - Google Patents

一种具有良好热稳定性的lds用聚碳酸酯组合物 Download PDF

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WO2016101507A1
WO2016101507A1 PCT/CN2015/079002 CN2015079002W WO2016101507A1 WO 2016101507 A1 WO2016101507 A1 WO 2016101507A1 CN 2015079002 W CN2015079002 W CN 2015079002W WO 2016101507 A1 WO2016101507 A1 WO 2016101507A1
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lds
parts
mixture
antioxidant
polycarbonate
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PCT/CN2015/079002
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English (en)
French (fr)
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曹艳霞
赖华林
秦勇
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深圳华力兴新材料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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
    • 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
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Definitions

  • the present invention relates to the field of LDS technology, and more particularly to a polycarbonate composition for LDS having good thermal stability.
  • 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
  • Laser direct structuring uses a computer to control the movement of a laser according to the trajectory of a conductive pattern.
  • the laser is projected onto a molded three-dimensional plastic device and is lived in a few seconds.
  • the circuit pattern is formed.
  • the emergence of laser direct structuring technology has ended the history of complicated three-dimensional circuit device molding process and high manufacturing cost.
  • 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. Due to the excellent mechanical properties of polycarbonate (PC), toughness and rigidity Sexual equilibrium, often used as an antenna carrier for mobile phones and wireless communications 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 in the composition system. Or atoms, which are catalysts which catalyze the degradation of the polycarbonate composition; at the same time, the inorganic metal compound or mixture of organic metals is alkaline to varying degrees, which 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 thermal stability, improves mechanical properties and processing properties, and does not affect the plating performance, and has excellent comprehensive performance.
  • a polycarbonate composition for LDS in parts by mass, comprising the following components:
  • the antioxidant is composed of a hindered phenolic antioxidant and a phosphite antioxidant
  • the heat stabilizer is composed of a metal compound, a layered double hydroxide and an ultraviolet light absorber.
  • 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 heat stabilizer may be 0.1 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 3 parts, 4 parts or 5 parts, etc.
  • the antioxidant may be 0.3 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts, etc.
  • the invention optimizes the content of each component of the polycarbonate composition for LDS, in particular, the combination of the metal compound, the layered double metal hydroxide and the ultraviolet light absorber in the heat stabilizer, so that each A synergistic effect occurs between the components, so that it has good thermal stability, inhibits thermal degradation of the polycarbonate composition of LDS, and improves the mechanical properties and processing properties of the polycarbonate composition for LDS;
  • a combination of a hindered phenolic antioxidant, a phosphite antioxidant, and a heat stabilizer causes a synergistic effect between the components to have good oxidation resistance and processing properties, and inhibits the polycarbonate combination for LDS.
  • Thermal degradation and oxidative degradation improve 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.
  • 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 hindered phenolic antioxidant, the phosphite antioxidant and the metal compound have a mass ratio of 1:2 to 5:1 to 4, and may be 1:2:1, 1:3:2, 1 : 4:3 or 1:5:4, preferably 1:2 to 4:1 to 3.
  • the mass ratio thereof is optimized, so that the thermodynamic properties and processing properties of the polycarbonate composition for LDS are remarkably enhanced. .
  • 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 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], bis(3,5-tris-butyl-4-hydroxyphenyl) sulfide or tetra[ ⁇ -(3,5-tributyl) a mixture of one or at least two of -4-hydroxyphenyl)propionic acid] pentaerythritol ester.
  • 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 heat stabilizer consists of a metal compound, a layered double hydroxide and an ultraviolet light absorber.
  • the metal compound, the layered double metal hydroxide and the ultraviolet light absorber have a mass ratio of 1:1 to 6:0.1 to 4, and may be 1:1:1:1, 1:2:0.5, 1: 3:1, 1:4:2, 1:5:3 or 1:6:4, etc., preferably 1:1 to 4:0.2 to 2.
  • a metal compound, a layered double metal hydroxide, and an ultraviolet light absorber are used in combination, and the mass ratio thereof is optimized to cause a synergistic effect between the components to make it have a good effect.
  • the thermal stability can further inhibit the thermal degradation of the polycarbonate composition of LDS, and significantly improve the mechanical properties and processability of the polycarbonate composition for LDS.
  • the metal compound is one or a mixture of at least two of an inorganic compound of magnesium, an inorganic compound of calcium, an inorganic compound of cerium or an inorganic compound of zinc, and preferably the metal compound is an inorganic compound of zinc.
  • the inorganic compound of zinc is one or a mixture of at least two of zinc oxide, zinc phosphide or zinc sulfide, and preferably the zinc inorganic compound is zinc oxide, active zinc oxide, nanometer. a mixture of one or a mixture of zinc oxide, zinc sulfide, zinc phosphate, zinc metaphosphate or zinc dialkyl dithiophosphate.
  • the layered double metal hydroxide is a hydrotalcite or hydrotalcite-like compound, or a mixture of the two.
  • the ultraviolet light absorber is a benzophenone ultraviolet light absorber or a benzotriazole ultraviolet light absorber, or a mixture of the two, preferably the ultraviolet light absorber is a benzotriazole ultraviolet light. Light absorber.
  • the ultraviolet light absorber is a mixture of one or at least two of the commercial brands 360DD, 234, 329, 328, 327 or 326 ultraviolet light absorbers, preferably the commercial brands 329, 234, 5411, 2777, 360DD One or a mixture of at least two of the ultraviolet light absorbers.
  • the polycarbonate is one of an aliphatic carbonate, an alicyclic carbonate or an aromatic carbonate or There are two less mixtures.
  • 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 a low molecular weight (1000-2000 Mw) polyethylene wax, oxidized polyethylene a wax, an ester wax, a montan wax, an EBS and a modified compound thereof, a silicone powder and a modification thereof, or a mixture of at least two, preferably the dispersing agent is an oxidized polyethylene wax, an ester wax, a silicone One or a mixture of at least two of the powder and its modifications.
  • 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 thermal stability, is resistant to precipitation during the molding process, is resistant to solvent extraction, and is resistant to salting, and does not affect the plating.
  • a method of preparing the above polycarbonate composition for LDS comprising the steps of:
  • the antioxidant comprises a hindered phenolic antioxidant, a phosphite antioxidant and a metal compound;
  • 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.
  • the polyurethane composition for LDS of the present invention comprises, in parts by mass, 60 to 90 parts of polycarbonate, 5 to 20 parts of LDS additive, 0.1 to 5 parts of heat stabilizer, and 0.3 to 3 parts of antioxidant.
  • the antioxidant is composed of a hindered phenolic antioxidant and a phosphite antioxidant
  • the heat stabilizer is composed of a metal compound, a layered double hydroxide and an ultraviolet light absorber.
  • the invention optimizes the content of each component of the polycarbonate composition for LDS, in particular, the combination of the metal compound, the layered double metal hydroxide and the ultraviolet light absorber in the heat stabilizer, so that the components occur
  • the synergistic effect makes it have good thermal stability, inhibits the thermal degradation of the polycarbonate composition of LDS, and improves the mechanical properties and processing properties of the polycarbonate composition for LDS; especially the hindered phenolic antioxidant, phosphorous acid
  • the ester antioxidant and the heat stabilizer are used in combination to achieve synergistic effect between the components, have good oxidation resistance and processing property, inhibit thermal degradation and oxidative degradation of the polycarbonate composition for LDS, and improve the polymerization of LDS.
  • the mechanical properties and processability of the carbonate composition, while the polycarbonate composition of LDS 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, 8 parts of MBS core-shell copolymer toughening agent, 3 parts of maleic anhydride graft copolymer compatibilizer, 12 parts of LDS additive, 2 parts of heat stabilizer ZnS, hydrotalcite 2 parts, 0.2 parts of ultraviolet light absorber 5411, 0.5 parts of antioxidant 1076, 1 part of antioxidant 627A, and 0.2 parts of silicone powder were pre-mixed uniformly, and put into a heating and melting of a twin-screw extruder to obtain a melt and a squeeze.
  • the polycarbonate composition for LDS was obtained by cooling, and a powder of LDS material was obtained.
  • 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.
  • silicone core-shell copolymer toughening agent 90 parts by weight of polycarbonate, 4 parts of silicone core-shell copolymer toughening agent, 2 parts of ethylene acrylic acid graft copolymer compatibilizer, 5 parts of LDS additive, 2 parts of hydrotalcite, ultraviolet light absorber 329 0.3 parts, antioxidant 1076 0.3 parts, antioxidant 168 1 part, and 0.2 parts of silicone powder are pre-mixed uniformly, and put into a twin-screw extruder for heating and melting to obtain a melt, extrusion, cooling, and LDS.
  • Comparative Example 2 The polycarbonate composition for LDS of the present example, in parts by mass, including components:
  • the MFR of the polycarbonate was 12 g/10 min, 300 ° C / 1.5 Kg.
  • Comparative Example 3 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, 8 parts of MBS core-shell copolymer toughening agent, 3 parts of maleic anhydride graft copolymer compatibilizer, 12 parts of LDS additive, 2 parts of heat stabilizer ZnS, hydrotalcite 2 parts, 1076 parts of antioxidant, 0.5 part of antioxidant 627A, and 0.2 part of silicone powder were pre-mixed uniformly, and heated and melted in a twin-screw extruder to obtain a melt, extrusion, and cooling to obtain a polycondensation for LDS.
  • the carbonate composition, pulverized, produces granules of LDS material.
  • Comparative Example 1 lacked the component metal compound as compared with Example 1.
  • the mechanical properties, thermal stability and plating performance of the polycarbonate composition for LDS of Example 1 were significantly better than the comparative examples. 1 is good;
  • Comparative Example 2 The composition of Comparative Example 2 was compared with Example 3: mass ratio of hindered phenolic antioxidant, phosphite antioxidant and metal compound was 2:1:7, metal compound, layered double hydroxide The mass ratio of the ultraviolet light absorber to the ultraviolet light absorber is 4.2:1:1. It can be seen from the above table that the mechanical properties, thermal stability and plating performance of the polycarbonate composition for LDS of Example 3 are significantly better than those of Comparative Example 2;
  • Comparative Example 3 lacked the ultraviolet light absorber as compared with Example 2.
  • the mechanical properties, thermal stability and chemical conversion properties of the polycarbonate composition for LDS of Example 2 were significantly compared. Proportion 3 is good.
  • the polycarbonate composition for LDS of the invention has good thermodynamic properties, the impact strength is even 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 not affected. 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 combination of the metal compound, the layered double metal hydroxide and the ultraviolet light absorber in the heat stabilizer, so that the components occur
  • the synergistic effect makes it have good thermal stability, inhibits thermal degradation of the polycarbonate composition of LDS, and improves the mechanical properties and processing properties of the polycarbonate composition for LDS.
  • hindered phenolic antioxidants phosphite antioxidants and heat stabilizers are used in combination to achieve a synergistic effect between the components, having good oxidation resistance and processing properties, and inhibiting polycarbons for LDS.
  • the acid ester composition is thermally degraded and oxidatively degraded to improve the mechanical properties and processing properties of the polycarbonate composition for LDS, and the polycarbonate composition of LDS is resistant to precipitation, solvent extraction, salting resistance and no influence during the molding process.
  • Plating is used in combination to achieve a synergistic effect between the components, having good oxidation resistance and processing properties, and inhibiting polycarbons for LDS.
  • the acid ester composition is thermally degraded and oxidatively degraded to improve the mechanical properties and processing properties of the polycarbonate composition for LDS, and the polycarbonate composition of LDS is resistant to precipitation, solvent extraction, salting resistance and no influence during the molding process. Plating.
  • 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.

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Abstract

一种具有良好热稳定性的LDS用聚碳酸酯组合物，按质量份计，其包括聚碳酸酯60～90份、LDS添加剂2～30份、热稳定剂0.1～5份、抗氧剂0.3～3份；其中，抗氧剂由受阻酚类抗氧剂和亚磷酸酯类抗氧剂组成，热稳定剂由金属化合物、层状双金属氢氧化物和紫外光吸收剂组成。此外，对LDS用聚碳酸酯组合物各组分含量进行优化处理，特别是对金属化合物、层状双金属氢氧化物、紫外光吸收剂进行组合使用，和对受阻酚类抗氧剂、亚磷酸酯类抗氧剂和热稳定剂进行进一步组合使用，使各组分间发生协同效应，极大抑制LDS用聚碳酸酯组合物热降解，提高了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。

Description

一种具有良好热稳定性的LDS用聚碳酸酯组合物 技术领域
本发明涉及LDS技术领域，尤其涉及一种具有良好热稳定性的LDS用聚碳酸酯组合物。
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热稳定性，提高了力学性能、加工性能，且不影响化镀性能，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：
Figure PCTCN2015079002-appb-000001
其中，所述抗氧剂由受阻酚类抗氧剂和亚磷酸酯类抗氧剂组成，所述热稳定剂由金属化合物、层状双金属氢氧化物和紫外光吸收剂组成。
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，热稳定剂可以为0.1份、0.5份、1份、1.5份、2份、3份、4份或5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，特别是热稳定剂中对金属化合物、层状双金属氢氧化物、紫外光吸收剂进行组合使用，使各 组分间发生协同效应，使其具有良好的热稳定性能，抑制LDS用聚碳酸酯组合物热降解，提高了LDS用聚碳酸酯组合物的力学性能和加工性能；
尤其是对受阻酚类抗氧剂、亚磷酸酯类抗氧剂和热稳定剂进行组合使用，使各组分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。
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、亚磷酸酯类抗氧剂和金属化合物质量比为1∶2～5∶1～4，可以为1∶2∶1、1∶3∶2、1∶4∶3或1∶5∶4，优选为1∶2～4∶1～3。
本发明的受阻酚类抗氧剂、亚磷酸酯类抗氧剂和金属化合物一起配合使用时，并对其质量比进行优化处理，使得LDS用聚碳酸酯组合物的热力学性能、加工性能明显增强。
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。
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 PCTCN2015079002-appb-000002
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、亚磷酸三环已酯、亚磷酸一丁基二苯酯、亚磷酸一辛基二苯酯等。
优选地，所述热稳定剂由金属化合物、层状双金属氢氧化物和紫外光吸收剂组成。
优选地，所述金属化合物、层状双金属氢氧化物和紫外光吸收剂的质量比为1∶1～6∶0.1～4，可以为1∶1∶0.1、1∶2∶0.5、1∶3∶1、1∶4∶2、1∶5∶3或1∶6∶4等，优选为1∶1～4∶0.2～2。
本发明的热稳定剂中对金属化合物、层状双金属氢氧化物、紫外光吸收剂进行组合使用，并对其质量比进行优化处理，使各组分间发生协同效应，使其具有良好的热稳定性能，进一步抑制LDS用聚碳酸酯组合物热降解，显著提高了LDS用聚碳酸酯组合物的力学性能和加工性能。
优选地，所述金属化合物为镁的无机化合物、钙的无机化合物、钡的无机化合物或锌的无机化合物中一种或至少两种的混合物，优选所述金属化合物为锌的无机化合物。
优选地，所述锌的无机化合物为锌的氧化物、锌的磷化物或锌的硫化物中一种或至少两种的混合物，优选所述锌的无机化合物为氧化锌、活性氧化锌、纳米氧化锌、硫化锌、磷酸锌、偏磷酸锌或二烷基二硫代磷酸锌中一种或至少两种的混合物。
优选地，所述层状双金属氢氧化物为水滑石或类水滑石化合物，或两者的混合物。
优选地，所述紫外光吸收剂为二苯甲酮类紫外光吸收剂或苯并三唑类紫外光吸收剂，或者两者的混合物，优选所述紫外光吸收剂为苯并三唑类紫外光吸收剂。
优选地，所述紫外光吸收剂为商品牌号360DD、234、329、328、327或326紫外光吸收剂中一种或至少两种的混合物，优选为商品牌号329、234、5411、2777、360DD紫外光吸收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 PCTCN2015079002-appb-000003
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热稳定性能，在成型过程中耐析出、耐溶剂萃取、耐盐化，且不影响化镀。
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、热稳定剂0.1～5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、亚磷酸酯类抗氧剂和金属化合物；
(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：本发明的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、热稳定剂0.1～5份和抗氧剂0.3～3份；其中，所述抗氧剂由受阻酚类抗氧剂和亚磷酸酯类抗氧剂组成，所述热稳定剂由金属化合物、层状双金属氢氧化物和紫外光吸收剂组成。本发明对LDS用聚碳酸酯组合物各组分含量进行优化处理，特别是热稳定剂中对金属化合物、层状双金属氢氧化物、紫外光吸收剂进行组合使用，使各组分间发生协同效应，使其具有良好的热稳定性能，抑制LDS用聚碳酸酯组合物热降解，提高了LDS用聚碳酸酯组合物的力学性能和加工性能；尤其是受阻酚类抗氧剂、亚磷酸酯类抗氧剂和热稳定剂再进行组合使用，使各组分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。
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 PCTCN2015079002-appb-000004
Figure PCTCN2015079002-appb-000005
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4份、乙烯丙烯酸接枝共聚物相容剂2份、LDS添加剂5份、热稳定剂ZnO 0.5份、水滑石2份、紫外光吸收剂329 0.3份、抗氧剂1076 0.3份、抗氧剂168 1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。
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 PCTCN2015079002-appb-000006
Figure PCTCN2015079002-appb-000007
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8份、马来酸酐接枝共聚物相容剂3份、LDS添加剂12份、热稳定剂ZnS 2份、水滑石2份、紫外光吸收剂5411 0.2份、抗氧剂1076 0.5份、抗氧剂627A 1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。
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 PCTCN2015079002-appb-000008
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4份、LDS添加剂20份、热稳定剂纳米氧化锌1份、类水滑石3份、紫外光吸收剂234 0.2份、抗氧剂1790 0.3份、抗氧剂S-9228T 0.7份、改性硅酮粉0.3份、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 PCTCN2015079002-appb-000009
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4份、乙烯丙烯酸接枝共聚物相容剂2份、LDS添加剂5份、水滑石2份、紫外光吸收剂329 0.3份、抗氧剂1076 0.3份、抗氧剂168 1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。
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 PCTCN2015079002-appb-000010
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4份、LDS添加剂20份、热稳定剂纳米氧化锌2.1份、类水滑石0.5份、紫外光吸收剂2340.5份、抗氧剂1790 0.6份、抗氧剂S-9228T 0.3份、改性硅酮粉0.3份、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 PCTCN2015079002-appb-000011
Figure PCTCN2015079002-appb-000012
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8份、马来酸酐接枝共聚物相容剂3份、LDS添加剂12份、热稳定剂ZnS 2份、水滑石2份、抗氧剂1076 1份、抗氧剂627A 0.5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1～3得到的LDS用聚碳酸酯组合物按照ISO标准进行以下性能测试，结果如下表：
Figure PCTCN2015079002-appb-000013
Figure PCTCN2015079002-appb-000014
对比例1中组分与实施例1相比缺少组分金属化合物，从上表可以看出实施例1的LDS用聚碳酸酯组合物的机械性能、热稳定性能和化镀性能明显比对比例1好；
对比例2中的组分与实施例3相比：受阻酚类抗氧剂、亚磷酸酯类抗氧剂和金属化合物质量比为2∶1∶7，金属化合物、层状双金属氢氧化物和紫外光吸收剂质量比为4.2∶1∶1，从上表可以看出实施例3的LDS用聚碳酸酯组合物的机械性能、热稳定性能和化镀性能明显比对比例2好；
对比例3中的组分与实施例2相比缺少紫外光吸收剂，从上表可以看出实施例2的LDS用聚碳酸酯组合物的机械性能、热稳定性能和化镀性能明显比对比例3好。
从上表可以看出本发明的LDS用聚碳酸酯组合物具有良好的热力学性能，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，特别是热稳定剂中对金属化合物、层状双金属氢氧化物、紫外光吸收剂进行组合使用，使各组分间发生协同效应，使其具有良好的热稳定性能，抑制LDS用聚碳酸酯组合物热降解，提高了LDS用聚碳酸酯组合物的力学性能和加工性能，
尤其是受阻酚类抗氧剂、亚磷酸酯类抗氧剂和热稳定剂再进行组合使用，使各组分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：
    Figure PCTCN2015079002-appb-100001
    其中，所述抗氧剂由受阻酚类抗氧剂和亚磷酸酯类抗氧剂组成，所述热稳定剂由金属化合物、层状双金属氢氧化物和紫外光吸收剂组成。
  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。
  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、亚磷酸酯类抗氧剂和金属化合物质量比为1∶2～5∶1～4，优选为1∶2～4∶1～3。
  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 PCTCN2015079002-appb-100002
    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。
  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，所述热稳定剂由金属化合物、层状双金属氢氧化物和紫外光吸收剂组成；
    优选地，所述金属化合物、层状双金属氢氧化物和紫外光吸收剂的质量比为1∶1～6∶0.1～4，优选为1∶1～4∶0.2～2；
    优选地，所述金属化合物为镁的无机化合物、钙的无机化合物、钡的无机化合物或锌的无机化合物中一种或至少两种的混合物，优选所述金属化合物为锌的无机化合物；
    优选地，所述锌的无机化合物为锌的氧化物、锌的磷化物或锌的硫化物中一种或至少两种的混合物，优选所述锌的无机化合物为氧化锌、活性氧化锌、纳米氧化锌、硫化锌、磷酸锌、偏磷酸锌或二烷基二硫代磷酸锌中一种或至少两种的混合物；
    优选地，所述层状双金属氢氧化物为水滑石或类水滑石化合物，或两者的混合物；
    优选地，所述紫外光吸收剂为二苯甲酮类紫外光吸收剂或苯并三唑类紫外光吸收剂，或者两者的混合物，优选所述紫外光吸收剂为苯并三唑类紫外光吸收剂；
    优选地，所述紫外光吸收剂为商品牌号329、234、5411或360DD紫外光吸收剂中一种或至少两种的混合物。
  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 PCTCN2015079002-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；
    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、热稳定剂0.1～5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，所述抗氧剂由受阻酚类抗氧剂和亚磷酸酯类抗氧剂组成，所述热稳 定剂由金属化合物、层状双金属氢氧化物和紫外光吸收剂组成；
    (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。
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