WO2023071795A1 - 一种pc复合材料及其制备方法和应用 - Google Patents

一种pc复合材料及其制备方法和应用 Download PDF

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Publication number
WO2023071795A1
WO2023071795A1 PCT/CN2022/124850 CN2022124850W WO2023071795A1 WO 2023071795 A1 WO2023071795 A1 WO 2023071795A1 CN 2022124850 W CN2022124850 W CN 2022124850W WO 2023071795 A1 WO2023071795 A1 WO 2023071795A1
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Prior art keywords
composite material
butyl acrylate
acrylate
core
polyethylene
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PCT/CN2022/124850
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English (en)
French (fr)
Inventor
李红刚
陈平绪
叶南飚
艾军伟
杨燕
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金发科技股份有限公司
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Publication of WO2023071795A1 publication Critical patent/WO2023071795A1/zh

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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
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • 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

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to a PC composite material and its preparation method and application.
  • PC Polycarbonate
  • PC is an engineering resin with excellent comprehensive performance. It has been widely used in the fields of automobile industry, electrical and electronic, and office equipment due to its outstanding impact strength, dimensional stability, transparency, and weather resistance. Applications.
  • polycarbonate materials have low hardness and poor wear resistance, so when they are used in some wear-prone scenes (such as consumer electronic product casings), special surface treatment (such as spraying treatment) is usually required to prevent the surface of the product from being easily damaged during use. Scratches and damages, but because the polycarbonate molecular chain is relatively rigid, the internal stress after molding is relatively large, and the spraying treatment will easily lead to poor toughness of the material and affect the use.
  • fabric electronic products such as mobile phone cases, speakers, wireless charging boards, data cables, etc.
  • glue to bond the fabric, or using fabric weaving, etc., to wrap a layer of fabric (such as cotton cloth, linen) on the surface of the product. , cotton, polyester or spandex, etc.), which can protect the product and scratch resistance, and solve the problem of poor wear resistance and easy wear of PC materials.
  • the cloth will have better use than plastic Hand feel and richer appearance style options can meet the market's diverse needs for electronic product appearance styles.
  • this type of product requires additional fabric processing, which is low in efficiency and high in cost, and cannot meet the requirements of extensive use; moreover, it adopts the glue bonding method, which is prone to glue aging and bonding due to the heat emitted by electronic products during use. The performance is reduced, the fabric is peeled and blistered, which affects the use of the product and the appearance of the product.
  • the existing PC material has poor adhesion to fabrics, and it cannot be directly bonded to fabrics without glue, and the fabric weaving method is only suitable for linear products such as data cables, so it is not suitable for fabric products such as mobile phone cases and speakers. At present, only glue bonding can be used. It can be seen that the application and development of polycarbonate materials in fabric electronic products is still limited by technology.
  • the object of the present invention is to provide a PC composite material with excellent cloth bonding performance, which can be directly injected into the cloth (that is, using a similar in-mold decoration process, placing the cloth In the mold, the PC composite material is injected again, and the mold is closed for injection molding), so that the cloth is directly adhered to the surface of the product, and the direct bonding between the material and the cloth is realized, and the bonding strength is high.
  • Another object of the present invention is to provide a method for preparing the above-mentioned PC composite material.
  • Another object of the present invention is to provide the application of the above-mentioned PC composite material
  • a PC composite material in parts by weight, comprises the following components:
  • the toughening agent of the present invention is selected from any one of the core-shell structure polymers with methyl methacrylate or polystyrene acrylonitrile as the shell and polyacrylate or polyacrylate grafted silicone composition as the core.
  • the toughening agent is selected from any one of the core-shell structure polymers with methyl methacrylate as the shell and polyacrylate or polyacrylate grafted silicone composition as the core one or more; more preferably, the toughening agent is selected from the core-shell structure with methyl methacrylate as the shell, polybutylacrylate grafted dimethylsiloxane or polyoctyl acrylate as the core Any one or more of the polymers.
  • the present invention finds through research that by adding polyethylene-butyl acrylate grafted glycidyl acrylate and a core-shell structure toughening agent of specific components to the polycarbonate material, the cloth bonding performance and toughness of the material can be significantly improved .
  • the surface of the fabric contains more active groups of hydroxyl and amine groups.
  • Polyethylene-butyl acrylate grafted glycidyl acrylate will react with the hydroxyl and amine groups on the surface of the fabric, and because of its good flexibility of molecular chains, With better fluidity, the material is easier to inject into the cloth, so that the material can be effectively bonded with the cloth, and the impact strength of the material can be improved at the same time; and the toughening agent has better compatibility with polycarbonate, and its Belonging to flexible molecules, the chain segment easily enters the tiny gaps in the fabric during the injection molding process with the fabric, which can further improve the bonding strength between the material and the fabric; through the synergistic effect of the two, the fabric bonding performance and toughness of the material are effectively improved.
  • the cloth described in the present invention includes cotton cloth, linen cloth, cotton linen, polyester or spandex blended weaving and the like.
  • the content of butyl acrylate in the polyethylene-butyl acrylate grafted glycidyl acrylate is 20%-40%, and the content of glycidyl acrylate is 5%-10%.
  • the higher the butyl acrylate content the more supple the molecular chain, which is conducive to maintaining high toughness of the material, but the high content of butyl acrylate will cause the material to be too soft and lose the rigidity of the material; the content of glycidyl acrylate is too low, and the required fabric viscosity cannot be achieved.
  • the content of glycidyl acrylate is too high, the cloth bonding performance of the material will not be improved significantly, and it will react with the end group of polycarbonate instead, which will increase the viscosity of the material, which is not conducive to injection molding. More preferably, the content of butyl acrylate in the polyethylene-butyl acrylate grafted glycidyl acrylate is 25%-30%, and the content of glycidyl acrylate is 6%-8%.
  • the weight ratio of the polyethylene-butyl acrylate grafted glycidyl ester to the toughening agent is 0.5-2; more preferably, the polyethylene-butyl acrylate grafted glycidyl ester and the toughening agent
  • the weight ratio of the agent is 0.6-1.4; further preferably, the weight ratio of the polyethylene-butyl acrylate grafted glycidyl ester to the toughening agent is 0.8-1.
  • the number average molecular weight of the polycarbonate in the present invention is 15000-30000; more preferably, the number average molecular weight of the polycarbonate is 20000-25000.
  • the PC composite material of the present invention also includes 0.2-1 part of antioxidant and 0.2-1 part of lubricant in parts by weight.
  • the antioxidant is selected from any one or more of phenolic antioxidants or phosphite antioxidants;
  • the phenolic antioxidant is selected from ⁇ -(4-hydroxyl-3, 5-Di-tert-butylphenyl) propanoic acid n-octadecyl alcohol ester (trade name: antioxidant 1076), tetrakis (methyl-(3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ) pentaerythritol ester (trade name Antioxidant 1010) or triethylene glycol ether-di(3-tert-butyl-4-hydroxy-methylphenyl) propionate (trade name Antioxidant 245) Any one or more;
  • the phosphite antioxidant is selected from three (2,4-di-tert-butylphenyl) phosphite (trade name antioxidant 168), dioctadecyl pentaerythritol bis Any one or more of
  • the lubricant is selected from any one or more of pentaerythritol stearate, ethylene wax, montan wax.
  • the present invention also provides the preparation method of above-mentioned PC composite material, comprises the following steps:
  • the twin-screw extruder put each component into the mixer and mix for 10-20 minutes; after mixing evenly, put it in the twin-screw extruder, melt extrude, granulate, and make PC composite material; among them, the twin-screw extruder
  • the machine temperature is set to 200-280°C.
  • the present invention also provides the application of the above-mentioned PC composite material in cloth art electronic products. Preferably, it can be used to prepare mobile phone casings or speaker casings.
  • the present invention can adopt a similar in-mold decoration process to produce a fabric product in which the fabric is directly bonded to the PC composite material, that is, the fabric is placed in a mold, then injected into the PC composite material, and molded for injection molding.
  • the following two processes can be used: one is to make the cloth into a circular roller roll belt, install it in the injection molding machine and the injection mold, inject it into the PC composite material, close the mold for injection molding, and fully automatically circulate the belt. Produced to achieve continuous production; the other is to shape the cloth through a molding machine, then cut it and place it in an injection mold, inject it into PC composite materials, and mold it to produce it.
  • the present invention has the following beneficial effects:
  • the bonding performance of the material and the cloth can be significantly improved, while maintaining Good toughness.
  • the PC composite material of the present invention does not need to add additional binders, and can be directly injected into the cloth through a process of injection molding (i.e., using a similar in-mold transfer process, placing the cloth in the mold, injecting the PC composite material, and closing the mold for injection molding) ), which can make the cloth directly adhere to the surface of the product, realize the direct bonding between the material and the cloth, and the bonding strength is high, while maintaining a high impact strength (up to 650J/m or more), which can meet the requirements of the actual application process. Requirements for product toughness.
  • the application of the polycarbonate material is further broadened, and it is especially suitable for preparing fabric electronic products such as fabric mobile phone shells and fabric speaker shells.
  • Polycarbonate 1 The number average molecular weight is 20000; Samyang 3020PJ;
  • Polycarbonate 2 Number average molecular weight is 15000; Idemitsu FN1500;
  • Polycarbonate 3 The number average molecular weight is 30000; Samyang 3030PJ;
  • Polycarbonate 4 The number average molecular weight is 25000; Samyang 2025PJ;
  • Polyethylene-butyl acrylate grafted glycidyl acrylate 1 25% butyl acrylate, 8% glycidyl acrylate, Arkema AX8700;
  • Polyethylene-butyl acrylate grafted glycidyl acrylate 2 30% butyl acrylate, 6% glycidyl acrylate, DuPont PTW;
  • Polyethylene-butyl acrylate grafted glycidyl acrylate 3 25% butyl acrylate, 5% glycidyl acrylate, Arkema AX8750;
  • Polyethylene-butyl acrylate grafted glycidyl acrylate 4 butyl acrylate content 15%, glycidyl acrylate content 4.5%, Arkema AX8820;
  • Toughener 1 Mitsubishi S-2001 with a core-shell structure with methyl methacrylate as the shell and polybutylacrylate grafted with dimethylsiloxane as the core;
  • Toughener 2 Mitsubishi SRK200A with a core-shell structure with polystyrene acrylonitrile as the shell and polybutylacrylate grafted dimethylsiloxane as the core;
  • Toughener 3 has a core-shell structure with methyl methacrylate as the shell and polyoctyl acrylate as the core, Rohm and Haas 2390;
  • Toughener 4 Polydimethylsiloxane, Zhongyuan MR-01;
  • Toughener 5 Terpolymer of polyacrylate-acrylonitrile-styrene, XC 500A.
  • Toughener 6 has a core-shell structure with methyl methacrylate as the shell and polybutadiene styrene as the core, Rohm and Haas 2620;
  • Antioxidant 1076 and Antioxidant 168 are compounded at a weight ratio of 1:2;
  • Lubricant Montan wax, commercially available.
  • the twin-screw extruder includes ten temperature control zones, the temperature of the temperature control zone 1-2 is 200-250°C, the temperature of the temperature control zone 3-4 is 260-280°C, and the temperature control zone 5-6 The temperature of the temperature control zone is 260-270°C, the temperature of the temperature control zone 7-8 is 240-260°C, and the temperature of the temperature control zone 9-10 is 250-260°C.
  • the preparation method is: using a similar in-mold decoration process, the cotton cloth is shaped by a molding machine, then cut and placed in an injection mold, and injected into the PC composite material , closed mold injection molding, and made fabric mobile phone case products, which were subjected to the following performance tests, and the test results are shown in Table 1-3.
  • 1 Hundred-grid test Use a hundred-grid knife to draw 10 ⁇ 10 (100) small square grids with a side length of 1mm on the surface of the test sample fabric layer. Each line should be as deep as the bottom layer of the fabric to the surface of the PC composite material;
  • the 3M adhesive tape adheres to the surface of the product to be tested in the small grid area.
  • the angle is the direction of 60 °, and the adhesive tape is torn off smoothly in 0.5-1.0S; the same embodiment is carried out 2 times the same test, and the situation of the cloth falling off in the grid (the cloth is peeled off) is observed, and the evaluation is based on the following criteria: Grade 5B: There is no shedding of the incision, its edge, and the intersection of the lattice;
  • Grade 4B There is partial shedding at the intersection of the incision or at the edge, 0 ⁇ the shedding area of the cross-cut area ⁇ 5%;
  • Grade 3B There is partial shedding at the intersection of the incision or at the edge, 5% ⁇ the shedding area of the cross-cut area ⁇ 15%;
  • Grade 2B There is partial fall off at the intersection of the cuts or the edge, and/or part of the grid falls off as a whole, 15% ⁇ the fall off area of the crossed area ⁇ 35%;
  • Grade 1B Partial fall-off at the intersection of the cuts or the edge, and/or part of the entire grid falls off, 35% ⁇ the fall-off area of the cross-cut area ⁇ 65%;
  • Grade 0B There is partial fall-off at the intersection of the cuts or the edge, and/or part of the entire grid falls off, and the fall-off area of the cross-cut area is > 65%;
  • 2Boiling test Boil the test sample in water at 80°C for 12 hours, and observe whether there are bubbles on the surface of the sample (bubbles will appear when the fabric and material are peeled off).
  • Notched impact strength Tested with reference to the standard ASTM D256-2010, and the thickness of the sample tested is 3.2mm.
  • Table 1 The distribution ratio of each component (by weight) and the performance test results of Examples 1 to 8
  • Table 2 The distribution ratio of each component (by weight) and the performance test results of Examples 9 to 16
  • the present invention adds polyethylene-butyl acrylate grafted glycidyl acrylate to the polycarbonate material, and adds the core-shell structure toughening agent of specific components simultaneously, can significantly improve
  • the bonding performance between the material and the cloth can be directly bonded between the material and the cloth through the direct injection molding process with the cloth, and the bonding strength is high (it can still maintain a good bond after the 100-grid test and the boiling test), and has High toughness (impact strength can reach more than 650J/m).
  • Comparative example 1 compares with embodiment 1, the content of butyl acrylate and glycidyl acrylate of polyethylene-butyl acrylate grafted glycidyl acrylate is not within the required range, and the hundred grid test level only reaches 3B, and the cloth bonding performance of the material Difference.
  • Example 2 Compared Example 2/3/4, compared with Example 1, the use of other types of toughening agents has a poor effect on improving the cloth adhesion performance of the material, and the 100-grid test grade only reaches 3B.
  • Comparative example 5/6 is compared with Example 1, without adding polyethylene-butyl acrylate grafted with glycidyl acrylate or without adding a toughening agent, the material has poor cloth bonding performance and poor toughness.

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Abstract

本发明公开了一种PC复合材料及其制备方法和应用。所述的PC复合材料，按重量份数计，包括组分：聚碳酸酯100份；聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯1-5份；增韧剂2-6份；所述增韧剂选自以甲基丙烯酸甲酯或聚苯乙烯丙烯腈为壳、以丙烯酸酯或丙烯酸酯接枝有机硅组成为核的核-壳结构聚合物中的任意一种或几种。本发明通过在聚碳酸酯材料中添加聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯，同时加入特定组分的核-壳结构增韧剂，能够显著提高材料与布料的粘接性能，同时保持良好的韧性；实现了材料与布料的直接粘接，且粘接强度高。进一步拓宽了聚碳酸酯材料的应用，可用于制备布艺手机壳、布艺音箱外壳等布艺类电子产品。

Description

一种PC复合材料及其制备方法和应用 技术领域
本发明涉及工程塑料技术领域，具体涉及一种PC复合材料及其制备方法和应用。
背景技术
聚碳酸酯(PC)是一种综合性能卓越的工程树脂，以其突出的冲击强度、尺寸稳定性、透明性、耐候性等特性，在汽车行业、电子电气、办公设备等领域内得到了普遍的应用。然而，聚碳酸酯材料硬度低、耐磨性差，故在应用于一些易磨损场景(如消费电子产品外壳)时通常需要对表面进行特殊处理(如喷涂处理)，防止产品在使用过程中表面容易刮花、受损，但是由于聚碳酸酯分子链比较刚性，成型后内应力比较大，喷涂处理容易导致材料韧性变差，影响使用。
目前已有一些布艺类电子产品，如手机壳、音箱、无线充电板、数据线等，通过使用胶水粘接布料，或者使用布艺编织等方式，在产品表面包裹上一层布料(例如棉布、麻布、棉麻、涤纶或氨纶混织等)，可起到保护产品、耐刮擦的作用，很好的解决PC材料耐磨性差、易磨损的问题，同时布料相对于塑料会具有更好的使用手感和更丰富的外观风格选择，能够满足市场对电子产品外观风格的多样化需求。但是这类产品需要再增加额外的布艺加工，效率低且成本高，无法满足广泛性使用要求；而且采用胶水粘接的方式，在使用过程中由于电子产品散发热量导致容易出现胶水老化、粘接性下降，使布料剥离起泡，影响产品使用和产品美观的问题。然而，现有的PC材料与布料的粘结性差，若不采用胶水无法将其与布料直接粘结，而布艺编制方式只适用于数据线等线条型产品，故对于手机壳、音箱等布艺产品目前只能采用胶水粘接的方式。由此可见，目前聚碳酸酯材料在布艺类电子产品的应用发展仍然是受到技术限制。
发明内容
为了克服上述现有技术存在的不足，本发明的目的在于提供一种PC复合材料，具有优异的布料粘结性能，可以通过与布料直接注塑成型工艺(即采用类似模内装饰工艺，将布料放置在模具内，再注射入PC复合材料，合模注塑成型)，使布料直接粘附在产品表面，实现材料与布料的直接粘结，且粘结强度高。
本发明的另一目的在于提供上述PC复合材料的制备方法。
本发明的再一目的在于提供上述PC复合材料物的应用
本发明是通过以下技术方案实现的：
一种PC复合材料，按重量份数计，包括以下组分：
聚碳酸酯      100份；
聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯  1-5份；
增韧剂        2-6份。
本发明所述增韧剂选自以甲基丙烯酸甲酯或聚苯乙烯丙烯腈为壳、以聚丙烯酸酯或聚丙烯酸酯接枝有机硅组成为核的核-壳结构聚合物中的任意一种或几种；优选的，所述增韧剂选自以甲基丙烯酸甲酯为壳、以聚丙烯酸酯或聚丙烯酸酯接枝有机硅组成为核的核-壳结构聚合物中的任意一种或几种；更优选的，所述增韧剂选自以甲基丙烯酸甲酯为壳、以聚丙烯酸丁酯接枝二甲基硅氧烷或聚丙烯酸辛酯为核的核-壳结构聚合物中的任意一种或几种。
本发明经研究发现，在聚碳酸酯材料中通过添加聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯和特定组分的核-壳结构增韧剂，能够显著改善材料的布料粘接性能和韧性。一般的，布料表面含有较多的羟基、胺基活性基团，聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯会与布料表面的羟基、胺基反应，且由于其分子链段柔顺性好，有较好的流动性，材料更容易与布料注塑成型，从而使材料能够与布料有效粘结，同时提高材料冲击强度；而所述增韧剂与聚碳酸酯具有较好的相容性，其属于柔性分子，在与布料注塑过程中链段容易进入布料的微小空隙，能够进一步提高材料与布料粘结强度；通过二者协同作用，使材料的布料粘结性能和韧性得到有效提升。本发明所述的布料包括棉布、麻布、棉麻、涤纶或氨纶混织等。
优选的，所述聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯中的丙烯酸丁酯含量为20％-40％，丙烯酸缩水甘油酯含量为5％-10％。丙烯酸丁酯含量越高分子链越柔顺，有利于材料保持较高韧性，但丙烯酸丁酯含量过高会导致材料过软、损失材料刚性；丙烯酸缩水甘油酯含量过低，无法达到要求的布料粘结效果，丙烯酸缩水甘油酯含量过高，对材料的布料粘结性能提升不明显，而且反而会与聚碳酸酯的端基反应，使材料的粘度提高，不利于注塑。更优选的，所述聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯中的丙烯酸丁酯含量为25％-30％，丙烯酸缩水甘油酯含量为6％-8％。
优选的，所述的聚乙烯-丙烯酸丁酯接枝缩水甘油酯和增韧剂的重量比为0.5-2；更优选的，所述的聚乙烯-丙烯酸丁酯接枝缩水甘油酯和增韧剂的重量比为0.6-1.4；进一步优选的，所述的聚乙烯-丙烯酸丁酯接枝缩水甘油酯和增韧剂的重量比为0.8-1。
优选的，本发明所述的聚碳酸酯的数均分子量为15000-30000；更优选的，所述的聚碳酸酯的数均分子量为20000-25000。
根据材料性能需求，本发明所述的PC复合材料，按重量份数计，还包括0.2-1份抗氧 剂；0.2-1份润滑剂。
优选的，所述抗氧剂选自酚类抗氧剂或亚磷酸酯类抗氧剂中的任意一种或几种；所述酚类抗氧剂选自β-(4-羟基-3，5-二叔丁基苯基)丙酸正十八碳醇酯(商品名为抗氧剂1076)、四(甲基-(3，5-二叔丁基-4-羟基苯基)丙酸)季戊四醇酯(商品名为抗氧剂1010)或三乙二醇醚-二(3-叔丁基-4-羟基-甲基苯基)丙酸酯(商品名为抗氧剂245)中的任意一种或几种；所述亚磷酸酯抗氧剂选自三(2，4-二叔丁基苯基)亚磷酸酯(商品名为抗氧剂168)、双十八烷基季戊四醇双亚磷酸酯(商品名为抗氧剂618)或季戊四醇四(3-月桂基硫代丙酸酯)中的任意一种或几种。
优选的，所述润滑剂选自季戊四醇硬脂酸酯类、乙烯蜡、蒙旦蜡中的任意一种或几种。
本发明还提供上述PC复合材料的制备方法，包括以下步骤：
按照配比，将各组分投入混合器中混合10-20分钟；混合均匀后投置于双螺杆挤出机中，熔融挤出，造粒，制得PC复合材料；其中，双螺杆挤出机温度设置为200-280℃。
本发明还提供上述PC复合材料在布艺类电子产品中的应用。优选的，可用于制备手机壳或音箱外壳等。
本发明可采用类似模内装饰工艺制得布料与PC复合材料直接粘合的布艺产品，即：将布料放置在模具内，再注射入PC复合材料，合模注塑成型。
具体的，可采用以下两种工艺：一种是把布料制作成循环滚筒卷状带，安装到注塑机和注塑模具内，注射入PC复合材料，合模注塑成型，全自动地循环带移动式生产出来，实现连续化生产；另一种是把布料经过成型机成型，再经过剪切后放置到注塑模具内，注射入PC复合材料，合模注塑成型生产出来的。
本发明与现有技术相比，具有如下有益效果：
本发明通过在聚碳酸酯材料中添加聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯，同时加入特定组分的核-壳结构增韧剂，能够显著提高材料与布料的粘结性能，同时保持良好的韧性。本发明的PC复合材料不需再另外加入粘结剂，通过与布料直接注塑成型工艺(即采用类似模内转印工艺，将布料放置在模具内，再注射入PC复合材料，合模注塑成型)，即可使布料直接粘附在产品表面，实现材料与布料的直接粘结，且粘结强度高，同时保持较高的冲击强度(达到650J/m以上)，能够满足实际应用过程中对产品韧性的要求。进一步拓宽了聚碳酸酯材料的应用，特别适用于制备布艺手机壳、布艺音箱外壳等布艺类电子产品。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进 一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
对本发明实施例及对比例所用的原材料做如下说明，但不限于这些材料：
聚碳酸酯1：数均分子量为20000；三养3020PJ；
聚碳酸酯2：数均分子量为15000；出光FN1500；
聚碳酸酯3：数均分子量为30000；三养3030PJ；
聚碳酸酯4：数均分子量为25000；三养2025PJ；
聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯1：丙烯酸丁酯含量为25％，丙烯酸缩水甘油酯含量为8％，阿科玛AX8700；
聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯2：丙烯酸丁酯含量为30％，丙烯酸缩水甘油酯含量为6％，杜邦PTW；
聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯3：丙烯酸丁酯含量为25％，丙烯酸缩水甘油酯含量为5％，阿科玛AX8750；
聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯4：丙烯酸丁酯含量15％，丙烯酸缩水甘油酯含量为4.5％，阿科玛AX8820；
增韧剂1：具有以甲基丙烯酸甲酯为壳、以聚丙烯酸丁酯接枝二甲基硅氧烷为核的核-壳结构三菱S-2001；
增韧剂2：具有以聚苯乙烯丙烯腈为壳、以聚丙烯酸丁酯接枝二甲基硅氧烷为核的核-壳结构三菱SRK200A；
增韧剂3：具有以甲基丙烯酸甲酯为壳、以聚丙烯酸辛酯为核的核-壳结构，罗门哈斯2390；
增韧剂4：聚二甲基硅氧烷，钟渊MR-01；
增韧剂5：聚丙烯酸酯-丙烯腈-苯乙烯的三元共聚物，XC 500A。
增韧剂6：具有以甲基丙烯酸甲酯为壳、以聚丁二烯苯乙烯为核的核-壳结构，罗门哈斯2620；
抗氧剂：抗氧剂1076与抗氧剂168按重量比1：2复配；
润滑剂：蒙旦蜡，市售。
实施例和对比例的PC复合材料的制备方法：
按照表1/表2/表3配比，将各组分投入混合器中混合10-20分钟；混合均匀后投置于双螺杆挤出机中，熔融挤出，造粒，制得PC复合材料；其中，双螺杆挤出机包括十个温控区， 温控1-2区的温度为200～250℃，温控3-4区的温度为260-280℃，温控5-6区的温度为260～270℃，温控7-8区的温度为240～260℃，温控9-10区的温度为250～260℃。
使用实施例和对比例的PC复合材料制备布艺手机壳产品，制备方法为：采用类似模内装饰工艺，把棉布经过成型机成型，再经过剪切后放置到注塑模具内，注射入PC复合材料，合模注塑成型，制得布艺手机壳产品，将其进行以下各项性能测试，测试结果如表1-3所示。
各项性能测试方法：
(1)粘结性能测试：
①百格测试：用百格刀在测试样品布料层表面划10×10个(100个)边长为1mm的正方形小网格，每一条划线应深及布料底层至PC复合材料表面；用3M胶粘带粘附产品表面被测试小网格区域，用橡皮擦用力擦拭胶粘带表面使其牢牢粘住被测试小网格，拿住胶粘带悬空一段，并在与样品表面夹角为60°的方向，在0.5-1.0S内平稳地撕离胶粘带；同一实施例进行2次相同试验，观察网格内布料脱落(布料被剥离材料)的情况，评价基于以下标准：5B等级：切口及其边缘、格子交叉点无任何脱落；
4B等级：在切口相交处或边缘有部分脱落，0＜划格区域脱落面积≤5％；
3B等级：在切口相交处或边缘有部分脱落，5％＜划格区域脱落面积≤15％；
2B等级：在切口相交处或边缘有部分脱落，及/或部分格子整片脱落，15％＜划格区域脱落面积≤35％；
1B等级：在切口相交处或边缘有部分脱落，及/或部分格子整片脱落，35％＜划格区域脱落面积≤65％；
0B等级：在切口相交处或边缘有部分脱落，及/或部分格子整片脱落，划格区域脱落面积＞65％；
②水煮测试：将测试样品于80℃水温水煮12小时，观察样品表面是否起泡(布料与材料剥离会出现气泡)。
(2)缺口冲击强度：参照标准ASTM D256-2010进行测试，样品测试厚度为3.2mm。
表1：实施例1～8各组分配比(按重量份数计)及各项性能测试结果
Figure PCTCN2022124850-appb-000001
表2：实施例9～16各组分配比(按重量份数计)及各项性能测试结果
Figure PCTCN2022124850-appb-000002
表3：对比例1～6各组分配比(按重量份数计)及各项性能测试结果
Figure PCTCN2022124850-appb-000003
由上述实施例和对比例可以看出，本发明在聚碳酸酯材料中添加聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯，同时加入特定组分的核-壳结构增韧剂，能够显著提高材料与布料的粘结性能，可通过与布料直接注塑成型工艺，实现材料与布料的直接粘结，粘结强度高(经百格测试和水煮测试后仍能保持良好粘结)，且具有较高的韧性(冲击强度能够达到650J/m以上)。
对比例1与实施例1比较，聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯的丙烯酸丁酯、丙烯酸缩水甘油酯含量不在要求范围内，百格测试等级仅达到3B，材料的布料粘结性能差。
对比例2/3/4与实施例1比较，使用其他类型的增韧剂，对于材料的布料粘接性能改善效果差，百格测试等级仅达到3B。
对比例5/6与实施例1比较，不添加聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯或不添加增韧剂，材料的布料粘结性能差，且韧性也较差。

Claims (10)

  1. 一种PC复合材料，其特征在于，按重量份数计，包括以下组分：
    聚碳酸酯    100份；
    聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯  1-5份；
    增韧剂      2-6份。
  2. 根据权利要求1所述的PC复合材料，其特征在于，所述增韧剂选自以甲基丙烯酸甲酯或聚苯乙烯丙烯腈为壳、以聚丙烯酸酯或聚丙烯酸酯接枝有机硅组成为核的核-壳结构聚合物中的任意一种或几种；优选的，所述增韧剂选自以甲基丙烯酸甲酯为壳、以聚丙烯酸酯或聚丙烯酸酯接枝有机硅组成为核的核-壳结构聚合物中的任意一种或几种；更优选的，所述增韧剂选自以甲基丙烯酸甲酯为壳、以聚丙烯酸丁酯接枝二甲基硅氧烷或聚丙烯酸辛酯为核的核-壳结构聚合物中的任意一种或几种。
  3. 根据权利要求1所述的PC复合材料，其特征在于，所述聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯中的丙烯酸丁酯质量含量为20％-40％，丙烯酸缩水甘油酯质量含量为5％-10％；优选的，所述聚乙烯-丙烯酸丁酯接枝丙烯酸缩水甘油酯中的丙烯酸丁酯质量含量为25％-30％，丙烯酸缩水甘油酯质量含量为6％-8％。
  4. 根据权利要求1所述的PC复合材料，其特征在于，所述的聚乙烯-丙烯酸丁酯接枝缩水甘油酯和增韧剂的重量比为0.5-2；优选的，所述的聚乙烯-丙烯酸丁酯接枝缩水甘油酯和增韧剂的重量比为0.6-1.4；更优选的，所述的聚乙烯-丙烯酸丁酯接枝缩水甘油酯和增韧剂的重量比为0.8-1。
  5. 根据权利要求1所述的PC复合材料，其特征在于，所述的聚碳酸酯的数均分子量为15000-30000；优选的，所述的聚碳酸酯的数均分子量为20000-25000。
  6. 根据权利要求1所述的PC复合材料，其特征在于，按重量份数计，还包括0.2-1份抗氧剂；0.2-1份润滑剂。
  7. 根据权利要求6所述的PC复合材料，其特征在于，所述抗氧剂选自酚类抗氧剂或亚磷酸酯类抗氧剂中的任意一种或几种；所述酚类抗氧剂选自β-(4-羟基-3，5-二叔丁基苯基)丙酸正十八碳醇酯、四(甲基-(3，5-二叔丁基-4-羟基苯基)丙酸)季戊四醇酯或三乙二醇醚-二(3-叔丁基-4-羟基-甲基苯基)丙酸酯中的任意一种或几种；所述亚磷酸酯抗氧剂选自三(2，4-二叔丁基苯基)亚磷酸酯、双十八烷基季戊四醇双亚磷酸酯或季戊四醇四(3-月桂基硫代丙酸酯)中的任意一种或几种；所述润滑剂选自季戊四醇硬脂酸酯类、乙烯蜡、蒙旦蜡中的任意一种或几种。
  8. 根据权利要求1-7任一项所述的PC复合材料的制备方法，其特征在于，包括以下步骤： 按照配比，将各组分投入混合器中混合10-20分钟；混合均匀后投置于双螺杆挤出机中，熔融挤出，造粒，制得PC复合材料；其中，双螺杆挤出机温度设置为200-280℃。
  9. 根据权利要求1-7任一项所述的PC复合材料在布艺类电子产品中的应用。
  10. 根据权利要求9所述的PC复合材料在布艺类电子产品中的应用，其特征在于，用于制备手机壳或音箱外壳。
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