WO2018036374A1 - 一种pc合金材料及其制备方法和应用 - Google Patents

一种pc合金材料及其制备方法和应用 Download PDF

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WO2018036374A1
WO2018036374A1 PCT/CN2017/096147 CN2017096147W WO2018036374A1 WO 2018036374 A1 WO2018036374 A1 WO 2018036374A1 CN 2017096147 W CN2017096147 W CN 2017096147W WO 2018036374 A1 WO2018036374 A1 WO 2018036374A1
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alloy material
copper
aluminum
zirconium
ppm
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English (en)
French (fr)
Inventor
杨燕
李明昆
何继辉
佟伟
谢修好
刘奇祥
丁超
叶南飚
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • C08K2201/002—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
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a PC alloy material and a preparation method and application thereof.
  • PC Polycarbonate
  • PC is an engineering plastic with excellent performance. It has good comprehensive properties, high mechanical strength, good impact toughness, dimensional stability and good electrical insulation. However, PC also has high melt viscosity, poor fluidity and solvent resistance. Poor property, stress cracking and swelling in solvent and alkaline environment, sensitivity to notch, stress cracking during processing, and high processing temperature. It is a more effective and simple modification method to select special polyester to improve PC performance and obtain composite materials with excellent comprehensive performance.
  • Polyethylene terephthalate-1,4-cyclohexanedimethanol ester has high impact strength, outstanding transparency, high gloss, good heat resistance, no bending, scratch resistance, aging resistance, and anti-aging Excellent in static electricity, chemical resistance, hydrolysis resistance, good fluidity, strong tinting strength, easy molding, and good hygiene (according to FDA).
  • the object of the present invention is to solve the deficiencies of the prior art and provide a PC alloy material which has good fluidity, warpage property, internal stress property, mold release property and color, and is particularly suitable for forming thin walls. product.
  • Another object of the present invention is to provide a method of preparing the PC alloy material.
  • Another object of the invention is to provide an application of the PC alloy material.
  • a PC alloy material comprising the following components by weight:
  • Fibrous filler 0 ⁇ 32 parts
  • the PC alloy material comprises the following components by weight:
  • Fibrous filler 0 ⁇ 32 parts
  • the PC alloy material contains aluminum element, copper element and zirconium element, the content of the aluminum element is 0.1 to 500 ppm, the content of the copper element is 0.1 to 500 ppm, and the content of the zirconium element is 0.1 to 500 ppm.
  • the inventors have unexpectedly discovered that in the above formulation, the addition of aluminum, copper and zirconium elements and controlling the content thereof within a certain range can further enhance polyethylene terephthalate-1,4-cyclohexane. Warpage properties, internal stress properties, release properties, and color of PC modified by dimethanol ester.
  • the content of the aluminum element in the PC alloy material is preferably from 1 to 300 ppm, more preferably from 1 to 100 ppm. Further, the aluminum element is preferably contained in an amount of 10 to 90 ppm, more preferably 20 to 70 ppm.
  • the content of the copper element in the PC alloy material is preferably from 1 to 300 ppm, more preferably from 1 to 100 ppm. Further, the copper element is preferably contained in an amount of 10 to 90 ppm, more preferably 20 to 70 ppm.
  • the content of the zirconium element in the PC alloy material is preferably from 1 to 300 ppm, more preferably from 1 to 100 ppm. Further, the zirconium element is preferably contained in an amount of 6 to 80 ppm, more preferably 12 to 60 ppm.
  • the aluminum element is present in the PC alloy material in the form of an aluminum salt or an oxide of aluminum.
  • the aluminum salt includes, but is not limited to, aluminum chloride, aluminum sulfate, aluminum nitrate or aluminum phosphate, and the like.
  • the oxide of aluminum includes, but is not limited to, aluminum oxide.
  • the copper element is present in the PC alloy material in the form of a copper salt or an oxide of copper.
  • the copper salts include, but are not limited to, copper chloride, copper nitrate, copper sulfate, copper phosphate.
  • the oxide of copper includes, but is not limited to, copper oxide or cuprous oxide.
  • the zirconium element is present in the PC alloy material in the form of an oxide of zirconium or zirconium.
  • the zirconium salts include, but are not limited to, zirconium chloride, zirconium nitrate, zirconium sulfate, zirconium phosphate.
  • the zirconium oxides include, but are not limited to, zirconia.
  • the polyethylene terephthalate-1,4-cyclohexanedimethanol ester has a melting point of 290 to 310 °C.
  • the 1,4-cyclohexanedimethylene in the polyethylene terephthalate-1,4-cyclohexanedimethanol ester is from 80:20 to 20:80.
  • the 1,4-cyclohexanedimethanol structural unit (CHDM) and the ethylene glycol structural unit (EG) in the polyethylene terephthalate-1,4-cyclohexane dimethanol ester The molar ratio is 60:40 to 70:30 or 30:70 to 40:60.
  • the addition of a fibrous filler can further enhance its mechanical properties. Therefore, it is preferred that the content of the fibrous filler in the PC alloy material is more than 0 parts.
  • the fibrous filler may be one or more of metal fiber, carbon fiber, plastic fiber, glass fiber; preferably glass fiber; wherein the glass fiber is selected from one of a roving fiber, a long glass fiber, and a short glass fiber. Or a few, preferably one or more of M-glass, E-glass, A-glass, S-glass, R-glass, C-glass, more preferably E-glass, A-glass, C -glass.
  • the above glass fiber may be surface-treated by a slurry and an adhesion promoter, or may be partially covered with a surface treatment, or may be subjected to no treatment on the surface; the diameter of the glass fiber is 1 um to 25 um, preferably 3 um. ⁇ 20 um, most preferably 4 um to 15 um.
  • the content of aluminum element, copper element and zirconium element contained therein is tested as follows:
  • the PC alloy material of the present invention may further include other auxiliaries such as antioxidants, light stabilizers, impact modifiers, flame retardants, fluorescent whitening agents, lubricants, plasticizers, etc., depending on the needs of different uses. Toughener, thickener, antistatic agent, mold release agent, pigment, etc.
  • the antioxidant may be an antioxidant commonly used in the art, and may be selected from one or more of a hindered amine antioxidant, a hindered phenol antioxidant, or a phosphite antioxidant, such as 1010, 168. One of, 1076, 445, 1098 or a mixture of two or more.
  • the toughening agent may be a toughening agent commonly used in the art, such as an EVA type toughening agent, an EMA type toughening agent, an ASA type toughening agent, an AES type toughening agent, a SAS type toughening agent, and an acrylate type.
  • a toughening agent commonly used in the art, such as an EVA type toughening agent, an EMA type toughening agent, an ASA type toughening agent, an AES type toughening agent, a SAS type toughening agent, and an acrylate type.
  • the light stabilizer may be a light stabilizer commonly used in the art, such as a mixture of one or more of a hindered amine or an ultraviolet absorber, and specifically, UV-944, UV-234, 770DF, 328, 531 , one of the 5411 or a mixture of two or more.
  • the impact modifier may be an impact modifier commonly used in the art, such as one or a mixture of two of PTW, styrene-ethylene/butylene-styrene block copolymer SEBS.
  • the flame retardant may be a flame retardant commonly used in the art, such as a phosphorus flame retardant, and specifically may be bisphenol A bis(diphenyl phosphate) BDP, RDP, dimethyl methylphosphonate (DMMP). And one or a mixture of two or more of diethyl diethylphosphonate (DEEP).
  • a flame retardant commonly used in the art such as a phosphorus flame retardant, and specifically may be bisphenol A bis(diphenyl phosphate) BDP, RDP, dimethyl methylphosphonate (DMMP).
  • DMMP dimethyl methylphosphonate
  • DEEP diethyl diethylphosphonate
  • the fluorescent whitening agent can be a fluorescent whitening agent commonly used in the art, such as bistriazinylaminostilbene.
  • the lubricant may be a lubricant commonly used in the art, such as one or a mixture of two or more of pentaerythritol ester, montan wax, silicone oil.
  • the plasticizer may be a plasticizer commonly used in the art, such as one or a mixture of two or more of glycerin, citric acid, butyl citrate, epoxidized soybean oil and the like.
  • the thickener may be a thickener commonly used in the art, such as an inorganic thickener, a polyacrylate thickener.
  • the antistatic agent is a permanent antistatic agent and may be a permanent antistatic agent commonly used in the art, such as one of PELESTAT-230, PELESTAT-6500, SUNNICO ASA-2500, or a mixture of two or more thereof.
  • the release agent may be a release agent commonly used in the art, such as one of silicone oil, paraffin wax, white mineral oil, petrolatum or a mixture of two or more.
  • the pigment may be a pigment commonly used in the art, such as one or a mixture of two or more of carbon black, titanium white powder, black species, phthalocyanine blue, fluorescent orange, and the like.
  • the warpage of the PC alloy material is measured by a secondary element, and the maximum warpage ⁇ is less than 100, the surface tension is greater than 44 dynes, and the color deviation is less than 1.5%.
  • the surface tension test can be carried out by referring to the following methods: different dyne solution prepared by using ethanol and water, and applying a dash solution to a flat plate surface (coating area>3 cm 2 ), as in 2 If it does not shrink in seconds, it can be re-tested with a higher value of the solvent; if it shrinks within 2 seconds, it breaks into many small droplets, indicating that the number of the last used Dyne solvent is the surface of the plate. tension.
  • the color test can be carried out by referring to the following method: using a color difference meter, measuring three sets of data of color L, a, b and Four sets of color difference data of ⁇ E, ⁇ L, ⁇ a, and ⁇ b after colorimetry are calculated.
  • the preparation method of the PC alloy material of the present invention comprises the following steps:
  • the zirconium or zirconium oxide is passed through the main feed port, and the fibrous filler is fed into the twin-screw extruder through the main feed port or the side feed port.
  • the temperature setting temperature of the twin-screw extruder is 200 ° C. ⁇ 280 ° C;
  • the method for preparing the PC alloy material comprises the following steps:
  • the zirconium or zirconium oxide is passed through the main feed port, and the fibrous filler is fed into the twin-screw extruder through the main feed port or the side feed port.
  • the temperature setting temperature of the twin-screw extruder is 200 ° C. ⁇ 280°C, wherein at least one vacuum is set, and the vacuum may be located at the end of the conveying section, the front end of the melting section and the metering section;
  • the melt is passed through the die, and the number of die holes is in the range of 4 to 30, so that the molten strip of the strip composition having a diameter of 0.5 mm to 10 mm can be obtained; the molten strip passes through the temperature of 20 ° C to 25 ° C
  • the water tank cooling port is introduced into the pelletizer for homogenization pelletization, and the obtained particles are dehumidified by sieve empty to obtain the final PC. alloy.
  • the present invention has the following beneficial effects:
  • the invention adopts polyester to modify the PC alloy, so that the obtained PC alloy material overcomes the shortage of the existing PC alloy material, and at the same time has good fluidity, warpage property, internal stress property, demolding performance and color. Particularly suitable for making thin-walled products.
  • the warpage property, internal stress property, mold release property and color of the obtained PC alloy material are further improved.
  • each performance is tested according to the following scheme:
  • Fluidity test MFR According to the measurement ASTM D1238, the test conditions were 260 ° C, 5 kg.
  • h is the maximum distance between the workpiece and the reference object
  • l is the projection length of the workpiece at the reference object
  • a is the length of the workpiece perpendicular to the direction of the reference object.
  • Acetone soak test PC alloy material was immersed in acetone solvent at room temperature for 1 hour, and air cracking was taken out to observe cracking.
  • the evaluation method is that when the surface tension ⁇ 44 dynes is judged to be poor, when the surface tension is > 44 dynes, it is judged as good.
  • the test method is as follows:
  • the change in surface tension is reflected in whether it is easy to cause paint stripping when painting PC alloy material products.
  • the greater the surface tension the stronger the bond between the paint and the PC alloy material, and it is not easy to fall off the paint.
  • the cross-lattice method is used to test the paint film.
  • GB/T 9286 the width of the knife edge is about 10mm ⁇ 12mm, and the interval is from 1mm to 1.2mm. There are 10 grids.
  • the line is drawn down, there will be 10 straight line marks with the same interval.
  • the vertical position of the straight knife mark is drawn down, it becomes a square of 100 squares of 10*10.
  • the 100-grain knife is drawn down, it should be cut to the bottom of the material. It should not be cut only on the paint, otherwise the test will not be established.
  • the Baige knife is finished, it will not fall off with the tape test.
  • the tape is attached to the position of the hundred grid, the tape is pressed tightly with the finger pressed, and the tape is torn up with an instant force, visually on the material. Whether the paint is detached or not, in addition to the JIS standard, the 3D Transparent Tape 600 is specified.
  • the injection temperature is 280 ° C, and when the injection speed is 50%, the cooling time is 10 s, and whether the material and the mold can be directly separated. Easy to remove is judged to be good, and manual picking is required to be judged as poor.
  • the color method adopts the following method: under the standard C light source, the magnesium oxide standard whiteboard is used as a reference, and the value calculated from the reflectance of the red, green and blue light of the sample is evaluated, and the degree of yellowing is evaluated. The smaller the value, the better. .
  • Polycarbonate is an aromatic polycarbonate (brand: PC L-1250Y).
  • Polyethylene terephthalate-1,4-cyclohexanedimethanol ester is Eastman product:
  • the sources of the aluminum elements used were all commercially available aluminum salts or aluminum oxides. Place The source of the copper element used is a commercially available copper salt or copper oxide. The source of the zirconium element used is a commercially available zirconium salt or zirconium oxide, and other unspecified raw materials are generally commercially available products.
  • the preparation method of the PC alloy material comprises the following steps:
  • the zirconium or zirconium oxide is passed through the main feed port, and the fibrous filler is fed into the twin-screw extruder through the main feed port or the side feed port.
  • the temperature setting temperature of the twin-screw extruder is 200 ° C. ⁇ 280 ° C;
  • the amount of the aluminum oxide or aluminum oxide, the copper salt or the copper oxide, the zirconium salt or the zirconium oxide is adjusted by detecting the content of the aluminum element and the copper element in the pellet.
  • the PC alloy materials of Examples 0 to 32 and Comparative Examples 1 to 3 were prepared according to the formulations of Tables 1 to 6, and their performance tests are shown in Table 7. It can be seen from Examples 1 to 32 that the warpage, internal stress, mold release property and color performance of the PC alloy material are significantly improved when the aluminum alloy, the zirconium element and the copper element are added to the PC alloy material. From In Comparative Examples 1 to 3, it can be seen that when the content of any of the added aluminum element, copper element, and zirconium element is too high, the warpage, internal stress, and color properties of the PC alloy material are significantly affected.
  • Example 18 Example 19 Example 20 Example 21 Example 22 Polycarbonate resin / kg 70 70 70 70 70 Polyester A/kg 30 Polyester B/kg 30 Polyester C/kg 30 Polyester D/kg 30 Polyester E/kg 30 Source of zirconium Zirconia Zirconia Zirconia Zirconia Source of copper Copper oxide Copper oxide Copper oxide Copper oxide Source of aluminum Aluminum oxide Aluminum oxide Aluminum oxide Aluminum oxide Aluminum oxide Zirconium content / ppm 25 25 25 25 25 25 25 Copper content / ppm 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33 33
  • Example 23 Example 24 Example 25 Example 26 Polycarbonate resin / kg 54 91 70 70 Polyester A/kg 30 30 4 61 Source of zirconium Zirconia Zirconia Zirconia Source of copper Copper oxide Copper oxide Copper oxide Copper oxide Source of aluminum Aluminum oxide Aluminum oxide Aluminum oxide Aluminum oxide Zirconium content / ppm 25 25 25 25 25 25
  • Comparative example 1 Comparative example 2 Comparative example 3 Polycarbonate resin / serving 70 70 70 Polyester A / serving 30 30 30 Source of zirconium Zirconia Zirconia Source of copper Copper oxide Copper oxide Copper oxide Source of aluminum Aluminum oxide Aluminum oxide Aluminum oxide Aluminum oxide Aluminum oxide

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Abstract

一种PC合金材料，其包括如下按重量份计算的组分：聚碳酸酯54～91份；聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯4～61份；纤维状填料0～32份；其他助剂0～6份。采用聚酯对PC合金进行改性，使获得的PC合金材料克服了现有PC合金材料的不足，其同时具有良好的流动性、翘曲性能、内应力性能、脱模性能、色泽，特别适用于制成薄壁制品。

Description

一种PC合金材料及其制备方法和应用 技术领域
本发明涉及高分子材料技术领域，特别涉及一种PC合金材料及其制备方法和应用。
背景技术
聚碳酸酯(PC)是性能优异的工程塑料，具有良好的综合性能，机械强度高、耐冲击韧性好、尺寸稳定、电绝缘性好；但PC同时也有熔体粘度大、流动性差、耐溶剂性差，在溶剂和碱性环境下易发生应力开裂和溶胀，对缺口的敏感性较大，加工时容易发生应力开裂，且加工温度较高。选择特殊聚酯改善PC性能，获得综合性能优异的复合材料，是一种较为有效、简便的改性途径。
聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯具有冲击强度高、突出的透明度、高光泽、耐热性好、弯曲不泛白、耐划痕、耐老化、防静电、耐化学性优异、耐水解、流动性好、着色力强、易于成型加工、卫生性好(符合FDA)等优点。
虽然现有技术有采用聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯对PC进行改性，但是其制品在流动性、翘曲性能、内应力性能、脱模性能、色泽等方面未能达到很好的效果，特别是作为薄壁制品方面，上述性能的不足尤其明显。
发明内容
本发明的目的是为了解决现有技术的不足，提供一种PC合金材料，该材料同时具有良好的流动性、翘曲性能、内应力性能、脱模性能、色泽，特别适用于制成薄壁制品。
本发明的另一目的在于提供所述PC合金材料的制备方法。
本发明的另一目的在于提供所述PC合金材料的应用。
本发明的上述目的通过如下技术方案予以实现。
一种PC合金材料，包括如下按重量份计算的组分：
聚碳酸酯54～91份；
聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯4～61份；
纤维状填料             0～32份；
其他助剂             0～6份。
优选地，所述PC合金材料包括如下按重量份计算的组分：
聚碳酸酯54～91份；
聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯4～61份；
纤维状填料             0～32份；
其他助剂             0～6份；
所述PC合金材料中，含有铝元素、铜元素及锆元素，铝元素的含量为0.1～500ppm；铜元素的含量为0.1～500ppm；锆元素的含量为0.1～500ppm。
发明人意外发现，在上述配方中，额外地添加铝元素、铜元素和锆元素，并控制其含量在某范围内，能进一步提升聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯改性PC的翘曲性能、内应力性能、脱模性能、色泽。
当添加的铝元素、铜元素或锆元素中任一种元素含量过高时，无法起到上述效果。
优选地，所述PC合金材料中，铝元素的含量优选为1～300ppm，更优选为1～100ppm。更进一步地，铝元素的优选含量为10～90ppm，更优选为20～70ppm。
优选地，所述PC合金材料中，铜元素的含量优选为1～300ppm，更优选为1～100ppm。更进一步地，铜元素的优选含量为10～90ppm，更优选为20～70ppm。
优选地，所述PC合金材料中，锆元素的含量优选为1～300ppm，更优选为1～100ppm。更进一步地，锆元素的优选含量为6～80ppm，更优选为12～60ppm。
优选地，铝元素以铝盐或铝的氧化物的形式存在于PC合金材料中。所述铝盐包括但不限于氯化铝、硫酸铝、硝酸铝或磷酸铝等。所述铝的氧化物包括但不限于三氧化二铝。
优选地，铜元素以铜盐或铜的氧化物的形式存在于PC合金材料中。所述铜盐包括但不限于氯化铜、硝酸铜、硫酸铜、磷酸铜。所述铜的氧化物包括但不限于氧化铜或氧化亚铜。
优选地，锆元素以锆盐或锆的氧化物的形式存在于PC合金材料中。所述锆盐包括但不限于氯化锆、硝酸锆、硫酸锆、磷酸锆。所述锆的氧化物包括但不限于氧化锆。
优选地，所述聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯的熔点为290～310℃。
更优选地，所述聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯中1,4-环己烷二甲 醇结构单元(CHDM)和乙二醇结构单元(EG)的摩尔比为80:20～20:80。
更优选地，所述聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯中1,4-环己烷二甲醇结构单元(CHDM)和乙二醇结构单元(EG)的摩尔比为60:40～70:30或30:70～40:60。
在合金组合物中，添加纤维状填料可以进一步提升其力学性能。因此，优选所述PC合金材料中纤维状填料的含量大于0份。
所述纤维状填料可以是金属纤维、碳纤维、塑料纤维、玻璃纤维中的一种或几种；优选玻璃纤维；其中，所述玻璃纤维选自粗纺纤维、长玻璃纤维、短玻璃纤维中的一种或几种，优选为M-玻璃、E-玻璃、A-玻璃、S-玻璃、R-玻璃、C-玻璃中的一种或几种，更优选为E-玻璃、A-玻璃、C-玻璃。以上玻璃纤维可以是经过浆料和粘合促进剂进行表面处理的，也可以是对表面部分覆盖处理，还可以是表面不进行任何处理；所述玻璃纤维的直径为1um～25um，优选为3um～20um，最优选为4um～15um。
优选地，当所述PC合金材料含有铝元素、铜元素及锆元素时，其所含的铝元素、铜元素及锆元素的含量按照如下方法进行测试：
在分析天平中精确称量PC合金材料的颗粒2g，倒入100ml消解瓶中，然后加入97％的浓硫酸5ml，在预设温度300℃铁板加热仪器中加热10分钟，然后再加入68％的硝酸5ml，再保持加热20分钟，使颗粒物完全分解后冷却至室温，加入20ml的双氧水中和酸性至pH值为7后，用去离子水稀释上述液体，将液体通过进样管导入ICP检测仪器中测定铝元素、铜元素及锆元素的含量。
根据不同的用途需要，本发明的PC合金材料还可以进一步包括其他助剂，如抗氧化剂、光稳定剂、抗冲改性剂、阻燃剂、荧光增白剂、润滑剂、增塑剂、增韧剂、增稠剂、抗静电剂、脱模剂、颜料等。
所述抗氧化剂可以是本领域常用的抗氧化剂，其可选自受阻胺类抗氧剂、受阻酚类抗氧剂或亚磷酸酯类抗氧剂中的一种或几种，例如1010、168、1076、445、1098中的一种或者两种及以上的混合物。
所述增韧剂可以是本领域常用的增韧剂，例如EVA型增韧剂、EMA型增韧剂、ASA型增韧剂、AES型增韧剂、SAS型增韧剂、丙烯酸酯类增韧剂、有机硅增韧剂中的一种或多种混合物。
所述光稳定剂可以是本领域常用的光稳定剂，例如受阻胺类或紫外线吸收剂中的一种或几种的混合,具体可以列举出UV-944、UV-234、770DF、328、531、5411中的一种或者两种及以上的混合物。
所述抗冲改性剂可以是本领域常用的抗冲改性剂，例如PTW、苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物SEBS中的一种或者两种的混合物。
所述阻燃剂可以是本领域常用的阻燃剂，例如磷系阻燃剂，具体可以为双酚A双(二苯基磷酸酯)BDP、RDP、甲基膦酸二甲酯(DMMP)和乙基膦酸二乙酯(DEEP)中的一种或者两种及以上的混合物。
所述荧光增白剂可以是本领域常用的荧光增白剂，例如双三嗪氨基二苯乙烯。
所述润滑剂可以是本领域常用的润滑剂，例如季戊四醇酯、蒙旦蜡、硅油中的一种或者两种及以上的混合物。
所述增塑剂可以是本领域常用的增塑剂，例如甘油、柠檬酸、柠檬酸丁酯、环氧大豆油等中的一种或者两种及以上的混合物。
所述增稠剂可以是本领域常用的增稠剂，例如无机增稠剂、聚丙烯酸酯增稠剂。
所述抗静电剂为永久性抗静电剂，可以是本领域常用的永久性抗静电剂，例如PELESTAT-230、PELESTAT-6500、SUNNICO ASA-2500中的一种或者两种及以上的混合物。
所述脱模剂可以是本领域常用的脱模剂，例如硅油、石蜡、白矿油、凡士林中的一种或者两种及以上的混合物。
所述颜料可以是本领域常用的颜料，例如炭黑、钛白粉、黑种、酞菁蓝、荧光橙等中的一种或者两种及以上的混合物。
所述PC合金材料的翘曲性采用二次元观察偏离距离，最大翘曲度γ小于100，表面张力大于44达因，色泽偏差小于1.5％。
表面张力测试可以参照如下方法进行：采用乙醇和水配制好的不同达因溶液，用棉签蘸某一达因溶液在平放的方板表面涂布(涂布面积＞3cm2)，如在2秒钟内不收缩，可再使用标值较高达因溶剂重试；若在2秒钟内发生收缩，破裂成许多小液滴，则表明上一次使用的达因溶剂所标的数字就是该板表面张力。
色泽测试可以参照如下方法进行：采用色差仪，测颜色L、a、b三组数据并 计算比色后的△E、△L、△a、△b四组色差数据。
计算色差△E＝(△L2+△a2+△b2)1/2。
本发明所述PC合金材料的制备方法，包括如下步骤：
1)按照配方含量称量各组分，并将需要预烘干处理的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、纤维状填料、其他助剂进行120℃～130℃预烘干处理；
2)将预烘干处理的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、纤维状填料、其他助剂、分别经过高混机混合均匀；
3)将混合均匀的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、其他助剂，铝盐或铝的氧化物、铜盐或铜的氧化物及锆盐或锆的氧化物分别通过主喂料口，纤维状填料通过主喂料口或侧喂料口，加入到双螺杆挤出机中，双螺杆挤出机的温控设置温度为200℃～280℃；
4)冷却、切粒。
优选地，所述PC合金材料的制备方法，包括如下步骤：
1)按照配方含量称量各组分，并将需要预烘干处理的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、纤维状填料、其他助剂进行120℃～130℃预烘干处理，预烘干时间设定为4h～6h，得到预烘干处理的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、纤维状填料、其他助剂；
2)将预烘干处理的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、纤维状填料、其他助剂、分别经过高混机混合均匀，混合温度为30℃～50℃，混合时间设定在5min～15min；
3)将混合均匀的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、其他助剂，铝盐或铝的氧化物、铜盐或铜的氧化物及锆盐或锆的氧化物分别通过主喂料口，纤维状填料通过主喂料口或侧喂料口，加入到双螺杆挤出机中，双螺杆挤出机的温控设置温度为200℃～280℃，其中并设置至少1个抽真空，抽真空可以位于输料段的末端，熔融段的前端以及计量段部分；
4)将得到熔体经过模头，模头孔数量范围为4～30个，因此可以得到直径为0.5mm～10mm的条状组合物的熔融长条；熔融长条通过20℃～25℃的水槽冷却口，引入到切粒机中进行均化切粒，得到的粒子通过筛空输送除湿后得到最终的PC 合金材料。
与现有技术相比，本发明具有如下有益效果：
本发明采用聚酯对PC合金进行改性，使获得的PC合金材料克服了现有PC合金材料的不足，其同时具有良好的流动性、翘曲性能、内应力性能、脱模性能、色泽，特别适用于制成薄壁制品。特别的，在PC合金材料添加特定含量的铝元素、铜元素和锆元素后，所得PC合金材料的翘曲性能、内应力性能、脱模性能、色泽得到进一步的提升。
具体实施方式
以下结合具体实施例对本发明进行阐述，然而本发明的保护范围并非仅仅局限于以下实施例，实施例的说明只是用于帮助理解本发明的方法及其核心思想。凡在本专利的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明要求的保护范围之内。
实施例中，各性能按照如下方案进行测试：
(1)流动性测试MFR：根据测定ASTM D1238，测试条件为260℃，5kg。
(2)翘曲性能
采用二次元观察偏离距离，用最大翘曲度表征
γ＝h/l*a。
h为制件与参考对象制件的最大距离，l为制件在参考对象的投影长度，a为制件垂直于参考对象方向的长度。
(3)内应力测试
丙酮浸泡试验：PC合金材料在常温下的丙酮溶剂中浸泡1小时，取出风干后进行观察开裂情况。
无可见裂纹评价为好，有裂缝判为差。
(4)粘附力，表面张力测试
评估方法为，当表面张力≤44达因判定为差，当表面张力＞44达因判定为好
测试方法如下：
采用乙醇和水配制好的不同达因溶液，用棉签蘸某一达因溶液在平放的合金方板表面涂布(涂布面积＞3cm2)，如在2秒钟内不收缩，可再使用标值较高达因溶剂重试；若在2秒钟内发生收缩，破裂成许多小液滴，则表明上一次使用的 达因溶剂所标的数字就是该板表面张力。
是否容易脱漆：
表面张力的变化，体现在对PC合金材料制品上漆时，是否容易造成脱漆。表面张力越大，漆与PC合金材料的结合度更牢固，不容易掉漆。
采用十字画格法测试漆膜情况，GB/T 9286，刀口宽度约为10mm～12mm，每1mm～1.2mm为间隔，共有10格，直线划下时会出现10条间隔相同的直线刀痕，于直线刀痕的垂直位置划下，便成为10*10的100格的正方形，百格刀划下去的时候应该割到见到底材，不可只割在涂料上，否则测试便不成立。当百格刀划完之后，用胶带测试会不会脱落，首先，胶带贴于百格位置，以手指压下将胶带紧密贴附，再以瞬间的力道将胶带撕起，目视素材上的涂料是否有脱落现象此外，以JIS标准而言，指定厂牌与型号3M的Transparent Tape 600。
(5)脱模性，注塑温度在280℃，在注射速度50％时，冷却时间10s，材料与模具能否直接脱离。易脱除判定为好，需要手动取件判定为差。
(6)色泽采用以下方法：在标准C光源下氧化镁标准白板作为基准，从试样对红、绿、蓝三色光的反射率计算所得的数值，评价其偏黄程度，数值越小越好。
聚碳酸酯为芳香族聚碳酸酯(牌号：PC L-1250Y)。
聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯为Eastman产品：
聚酯A为聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯，其熔点为290℃，n(CHDM):n(EG)＝80:20。
聚酯B为聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯，其熔点为295℃，n(CHDM):n(EG)＝65:35。
聚酯C为聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯，其熔点为300℃，n(CHDM):n(EG)＝50:50。
聚酯D为聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯，其熔点为305℃，n(CHDM):n(EG)＝35:65。
聚酯E为聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯，其熔点为310℃，n(CHDM):n(EG)＝20:80。
实施例及对比例中，所用的铝元素的来源均为市售的铝盐或铝的氧化物。所 用的铜元素的来源均为市售的铜盐或铜的氧化物。所用的锆元素的来源均为市售的锆盐或锆的氧化物，其他未特别指明的原料均为普通市售产品。
实施例及对比例中，所述PC合金材料的制备方法，包括如下步骤：
1)按照配方含量称量各组分，并将需要预烘干处理的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、纤维状填料、其他助剂进行120℃～130℃预烘干处理；
2)将预烘干处理的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、纤维状填料、其他助剂分别经过高混机混合均匀；
3)将混合均匀的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、其他助剂，铝盐或铝的氧化物、铜盐或铜的氧化物、锆盐或锆的氧化物分别通过主喂料口，纤维状填料通过主喂料口或侧喂料口，加入到双螺杆挤出机中，双螺杆挤出机的温控设置温度为200℃～280℃；
4)冷却、切粒。通过检测粒料中铝元素和铜元素的含量，从而调节铝盐或铝的氧化物、铜盐或铜的氧化物、锆盐或锆的氧化物的加入量。
例如：
1)取70Kg聚碳酸酯树脂，30Kg聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯，进行120℃～130℃预烘干处理；
2)预烘干处理后的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯经过高混机混合均匀；
3)将混合均匀的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、分别通过主喂料口，加入到双螺杆挤出机中，双螺杆挤出机的温控设置温度为200℃～280℃；取相对于聚碳酸酯树脂和聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯总重量0.06％的三氧化二铝、0.04％的氧化铜、0.05％的氧化锆在主喂料口加入；
4)冷却、切粒。对粒料中铝元素的含量进行检测，测得其中铝元素含量为310ppm，铜元素含量为305ppm，锆元素含量为312ppm。
实施例0～32及对比例1～3
按表1至表6的配方，制备实施例0～32及对比例1～3的PC合金材料，其性能测试，见表7。从实施例1～32可以看出，当PC合金材料中添加铝元素、锆元素和铜元素后PC合金材料的翘曲、内应力、脱模性、色泽性能明显提升。从 对比例1～3可以看出，当添加的铝元素、铜元素、锆元素任意之一的含量过高时，PC合金材料的翘曲、内应力、色泽性能会受到明显的影响。
表1
Figure PCTCN2017096147-appb-000001
表2
Figure PCTCN2017096147-appb-000002
Figure PCTCN2017096147-appb-000003
表3
  实施例18 实施例19 实施例20 实施例21 实施例22
聚碳酸酯树脂/kg 70 70 70 70 70
聚酯A/kg 30        
聚酯B/kg   30      
聚酯C/kg     30    
聚酯D/kg       30  
聚酯E/kg         30
锆元素来源 氧化锆 氧化锆 氧化锆 氧化锆 氧化锆
铜元素来源 氧化铜 氧化铜 氧化铜 氧化铜 氧化铜
铝元素来源 三氧化二铝 三氧化二铝 三氧化二铝 三氧化二铝 三氧化二铝
锆元素含量/ppm 25 25 25 25 25
铜元素含量/ppm 33 33 33 33 33
铝元素含量/ppm 33 33 33 33 33
表4
  实施例23 实施例24 实施例25 实施例26
聚碳酸酯树脂/kg 54 91 70 70
聚酯A/kg 30 30 4 61
锆元素来源 氧化锆 氧化锆 氧化锆 氧化锆
铜元素来源 氧化铜 氧化铜 氧化铜 氧化铜
铝元素来源 三氧化二铝 三氧化二铝 三氧化二铝 三氧化二铝
锆元素含量/ppm 25 25 25 25
铜元素含量/ppm 33 33 33 33
铝元素含量/ppm 33 33 33 33
表5
Figure PCTCN2017096147-appb-000004
表6
  对比例1 对比例2 对比例3
聚碳酸酯树脂/份 70 70 70
聚酯A/份 30 30 30
锆元素来源 氧化锆 氧化锆 氧化锆
铜元素来源 氧化铜 氧化铜 氧化铜
铝元素来源 三氧化二铝 三氧化二铝 三氧化二铝
锆元素含量/ppm 88 532 117
铜元素含量/ppm 92 99 125
铝元素含量/ppm 549 107 543
表7
Figure PCTCN2017096147-appb-000005
Figure PCTCN2017096147-appb-000006

Claims (10)

  1. 一种PC合金材料，包括如下按重量份计算的组分：
    聚碳酸酯 54～91份；
    聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯 4～61份；
    纤维状填料       0～32份；
    其他助剂         0～6份。
  2. 根据权利要求1所述PC合金材料，包括如下按重量份计算的组分：
    聚碳酸酯 54～91份；
    聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯 4～61份；
    纤维状填料       0～32份；
    其他助剂         0～6份；
    所述PC合金材料中，含有铝元素、锆元素和铜元素，铝元素的含量为0.1～500ppm，优选为1～300ppm，更优选为1～100ppm；铜元素的含量为0.1～500ppm，优选为1～300ppm，更优选为1～100ppm；锆元素的含量为0.1～500ppm，优选为1～300ppm，更优选为1～100ppm。
  3. 根据权利要求2所述PC合金材料，其特征在于，铝元素以铝盐或铝的氧化物的形式存在于PC合金材料中；铜元素以铜盐或铜的氧化物的形式存在于PC合金材料中；锆元素以锆盐或锆的氧化物的形式存在于PC合金材料中。
  4. 根据权利要求2或3所述PC合金材料，其特征在于，铝元素以氯化铝、硝酸铝、硫酸铝、磷酸铝或三氧化二铝的形式存在于PC合金材料中；铜元素以氯化铜、硝酸铜、硫酸铜、磷酸铜、氧化铜或氧化亚铜的形式存在于PC合金材料中；锆元素以氯化锆、硝酸锆、硫酸锆、磷酸锆、氧化锆的形式存在于PC合金材料中。
  5. 根据权利要求1或2所述PC合金材料，其特征在于，所述聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯的熔点为290～310℃。
  6. 根据权利要求5所述PC合金材料，其特征在于，所述聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯中1,4-环己烷二甲醇酯结构单元和对苯二甲酸乙二醇酯结构单元的摩尔比为80:20～20:80，优选为60:40～70:30或30:70～40:60。
  7. 根据权利要求2所述PC合金材料，其特征在于，所述PC合金材料中，铝元素、铜元素及锆元素的含量按照如下方法进行测试：在分析天平中精确称量PC合金材料的颗粒2g，倒入100ml消解瓶中，然后加入97％的浓硫酸5ml，在预设温度300℃铁板加热仪器中加热10分钟，然后再加入68％的硝酸5ml，再保持加热20分钟，使颗粒物完全分解后冷却至室温，加入20ml的双氧水中和酸性至pH值为7后，用去离子水稀释上述液体，将液体通过进样 管导入ICP检测仪器中测定铝元素、铜元素及锆元素的浓度。
  8. 根据权利要求2所述PC合金材料，其特征在于，所述PC合金材料的翘曲性采用二次元观察偏离距离，最大翘曲度γ小于100，表面张力大于44达因，色泽偏差小于1.5％。
  9. 权利要求2～8任意一项所述PC合金材料的制备方法，包括如下步骤：
    1)按照配方含量称量各组分，并将需要预烘干处理的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、纤维状填料、其他助剂进行120℃～130℃预烘干处理；
    2)将预烘干处理的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、纤维状填料、其他助剂分别经过高混机混合均匀；
    3)将混合均匀的聚碳酸酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、其他助剂，铝盐或铝的氧化物、铜盐或铜的氧化物及锆盐或锆的氧化物分别通过主喂料口，纤维状填料通过主喂料口或侧喂料口，加入到双螺杆挤出机中，双螺杆挤出机的温控设置温度为200℃～280℃；
    4)冷却、切粒。
  10. 权利要求1～8任意一项所述PC合金材料在制备薄壁制品中的应用。
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