WO2020077657A1 - Polyphenylene sulfide/carbon fiber composite material with good bonding force to metal - Google Patents

Polyphenylene sulfide/carbon fiber composite material with good bonding force to metal Download PDF

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WO2020077657A1
WO2020077657A1 PCT/CN2018/111591 CN2018111591W WO2020077657A1 WO 2020077657 A1 WO2020077657 A1 WO 2020077657A1 CN 2018111591 W CN2018111591 W CN 2018111591W WO 2020077657 A1 WO2020077657 A1 WO 2020077657A1
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carbon fiber
polyphenylene sulfide
resin
composite material
weight
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PCT/CN2018/111591
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French (fr)
Chinese (zh)
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郎鸣华
严兵
赵清新
何定军
刘成
钱馨馨
唐许
张林强
刘圣强
刘腾达
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江苏澳盛复合材料科技有限公司
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Publication of WO2020077657A1 publication Critical patent/WO2020077657A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the invention relates to a carbon fiber composite material, especially a polyphenylene sulfide / carbon fiber composite material with good adhesion to metal.
  • Polyphenylene sulfide is a thermoplastic resin with a phenylsulfide group in the main chain of the molecule. It has high temperature resistance, corrosion resistance, radiation resistance, flame retardancy, balanced physical and mechanical properties, excellent dimensional stability, and excellent electrical properties. The characteristic of performance is a special engineering plastic with excellent comprehensive performance. Carbon fiber has excellent characteristics such as low density, high specific strength and specific modulus, high temperature resistance, chemical corrosion resistance, high thermal conductivity, and low thermal expansion. Carbon fiber reinforced polyphenylene sulfide can further increase the tensile strength and impact strength of polyphenylene sulfide, improve its toughness, and expand its scope of application.
  • carbon fiber reinforced polyphenylene sulfide needs to be used in combination with metal materials, such as injection molding of carbon fiber reinforced polyphenylene sulfide onto metal parts.
  • metal materials such as injection molding of carbon fiber reinforced polyphenylene sulfide onto metal parts.
  • CN201711166435.3 By compounding ternary chlorinated vinegar resin and fluorine resin in PPS, the adhesion to the metal is improved, and the tensile shear strength of the same metal can be increased by nearly 70%, and compared with the original PPS composite material, It can be achieved by simply changing the formula of the resin, without changing the existing process, without adding equipment, and it is simple and easy to implement.
  • the ternary chlorinated vinegar resin used in this method has poor heat resistance, and will be partially decomposed during processing, resulting in increased processing difficulty and unstable product performance.
  • the present invention provides a polyphenylene sulfide / carbon fiber composite material with good adhesion to metals, and at the same time provides a metal resin composite body made of the composite material.
  • a polyphenylene sulfide / carbon fiber composite material including polyphenylene sulfide, carbon fiber short fiber, epoxy resin and novolac resin, and based on 100 parts by weight of the total polyphenylene sulfide and carbon fiber short fiber 65 to 95 parts by weight of sulfide and 5 to 35 parts by weight of carbon fiber staple fiber.
  • Polyphenylene sulfide is a polymer with a phenyl sulfide group in the molecular main chain, including homopolymers, copolymers of p-phenyl sulfide and / or m-phenyl sulfide, and mixtures thereof.
  • Carbon fiber staple fiber is made by short-cutting carbon fiber filament by fiber cutting machine.
  • the reinforcing fiber of polyphenylene sulfide composite material the tensile strength, bending strength and impact resistance of polyphenylene sulfide can be improved.
  • Epoxy resin refers to a compound containing two or more epoxy groups in the molecule. It is a polymer prepolymer with aliphatic, alicyclic or aromatic segments as the main chain, and is an important class of thermosetting resin. Common epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, and glycidyl ester epoxy resin. Resin, glycidylamine epoxy resin, epoxidized olefin compound, etc. Epoxy resin can improve the adhesion of polyphenylene sulfide / carbon fiber composite materials to metals.
  • Novolac resin also known as novolac resin, is a type of phenolic resin that can be dissolved in an organic solvent, can be melted by heating, and will not be cured for a long time.
  • Novolak resin can be cured with epoxy resin to improve the adhesion of polyphenylene sulfide / carbon fiber composite materials to metals.
  • Common novolak resins include bisphenol A novolak resins, cresol novolak resins, and phenol novolak resins.
  • the total amount of polyphenylene sulfide and carbon fiber short fibers is 100 parts by weight, and the total amount of epoxy resin and novolak resin is 5 to 30 parts by weight.
  • the effect of improving the adhesion of polyphenylene sulfide / carbon fiber composite material to metal is obvious, and it is easy to process.
  • the total amount of polyphenylene sulfide and carbon fiber short fibers is 100 parts by weight, and the total amount of epoxy resin and novolak resin is 10 to 20 parts by weight.
  • Epoxy equivalent refers to the number of grams of epoxy resin containing one equivalent of epoxy groups, and the unit is grams per equivalent, which is an important physical property index indicating the number of epoxy groups contained in the epoxy resin.
  • Hydroxyl equivalent refers to the grams of novolak resin containing one equivalent of hydroxyl groups, and the unit is grams / equivalent, which is an important physical property index indicating the number of hydroxyl groups contained in the novolak resin.
  • Weight ratio of epoxy resin and novolac resin (epoxy equivalent of epoxy resin / hydroxyl equivalent of novolac resin) ⁇ ⁇ formula 1
  • the weight ratio range of the epoxy resin and the novolak resin is preferably in the range of ⁇ in Formula 1 between 0.8 and 1. It has obvious effect on improving the adhesion between polyphenylene sulfide / carbon fiber composite and metal.
  • ⁇ is greater than 1, or less than 0.8, it is not conducive to the improvement of the adhesion between the epoxy resin and the novolac resin to the polyphenylene sulfide / carbon fiber composite material to the metal. More preferably, ⁇ is between 0.85 and 0.95.
  • the melting point of the epoxy resin is 90 ° C or higher, preferably 120 ° C or higher, and most preferably 140 ° C or higher.
  • This type of epoxy resin has good heat resistance, and it is not easy to cause side reactions such as decomposition at the processing temperature of the composite material, and the curing temperature of the epoxy resin and the novolak phenol resin is high, and it is easy to control the curing reaction during the processing process .
  • the novolak resin is one or more of bisphenol A novolak resin and cresol novolak resin. These two novolac resins have better matching with epoxy resins, and are more effective for improving the adhesion of polyphenylene sulfide / carbon fiber composite materials to metals.
  • the novolak resin is two types of bisphenol A novolak resin and cresol novolak resin, and the parts by weight of the two The number ratio is 1: 1 to 1: 3, preferably 1: 1.5 to 1:25.
  • the melting point of the novolak resin is between 90 and 120 ° C, and most preferably between 95 and 115 ° C. Similar to epoxy resin, the noble phenolic resin with higher melting point has better heat resistance, side reactions such as decomposition are not easy to occur at the processing temperature of the composite material, and the curing temperature is high, it is easy to control the curing reaction during the processing ; However, the compatibility of the novolak resin with a melting point greater than 120 °C with epoxy resin is not good, which is not conducive to the improvement of the adhesion of the composite material to the metal.
  • the polyphenylene sulfide / carbon fiber composite material according to the present invention contains 0.2 to 10 parts by weight of a silane coupling agent based on 100 parts by weight of the total polyphenylene sulfide and carbon fiber short fibers.
  • Silane coupling agent is a type of organosilicon compound containing two different chemical groups in the molecule. Its molecule has chemical reaction with inorganic materials (such as glass, metal, etc.) and organic materials (such as synthetic resin). Etc.) The ability of chemical reaction, which can enhance the adhesion between polyphenylene sulfide, epoxy resin, novolak resin, carbon fiber, and improve the performance of the composite material.
  • the silane coupling agent include siloxanes containing one or more of amine groups, epoxy groups, vinyl groups, isocyanate groups, and mercapto groups.
  • the silane coupling agent contains one or more of epoxy groups or isocyanate groups, which are combined with epoxy resins and novolac resins.
  • the compatibility and reactivity are better, which has obvious effect on improving the adhesion of the composite material to the metal and the stability of the mechanical properties of the composite material.
  • the epoxy group-containing silane coupling agent is most preferred.
  • the invention also provides a metal-resin composite body made of the polyphenylene sulfide / carbon fiber composite material according to the invention, which comprises the polyphenylene sulfide / carbon fiber composite material and metal parts to which the invention belongs.
  • the polyphenylene sulfide / carbon fiber composite material of the present invention improves the adhesion with metals, and the raw materials used have good heat resistance and will not be decomposed during processing, so it is easy to process performance and product performance stability is good. In addition, the tensile strength and impact strength of the composite material are also improved to a certain extent.
  • a polyphenylene sulfide / carbon fiber composite material with good adhesion to metals The raw materials used in the examples and comparative examples are as follows:
  • A1 TORAYCAA630T-30V produced by Toray Industries, 30 parts by weight of carbon-containing short fibers and 70 parts by weight of polyphenylene sulfide.
  • the melting point of polyphenylene sulfide is 278 ° C.
  • EPICLON 2050 produced by DIC Corporation, bisphenol A epoxy resin, melting point 85 ° C, epoxy equivalent 700g / eq.
  • EPICLON 4050 produced by DIC Corporation, bisphenol A epoxy resin, melting point 100 ° C, epoxy equivalent 900g / eq.
  • EPICLON HM-091 produced by DIC Corporation, bisphenol A type epoxy resin, melting point 145 °C, epoxy equivalent 2600g / eq.
  • D1 Glycidylpropyltriethoxysilane, Shin-Etsu Chemical Co., Ltd. KBM-403.
  • D2 Isocyanopropyl triethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. KBE-9007.
  • D3 3-Mercaptopropyltriethoxysilane, KBM-803 produced by Shin-Etsu Chemical Co., Ltd.
  • the raw materials and parts by weight according to Table 1 were thoroughly mixed, added to an extruder and extruded and pelletized to obtain composite resin pellets, and the temperature of the extruder was set to 300 ° C.
  • Example 5 Based on the raw material formula of Example 5, according to the formula shown in Table 2, two types of novolak resins are mixed and used to replace the original novolak resin. After the raw materials are thoroughly mixed, they are added to an extruder and extruded to obtain composite resin pellets. The temperature of the extruder is set to 300 ° C.
  • the silane coupling agent was added according to the formula shown in Table 3. After the raw materials are thoroughly mixed, they are added to an extruder and extruded to obtain composite resin pellets.
  • the temperature of the extruder is set to 300 ° C.
  • Carbon fiber short fiber reinforced polyphenylene sulfide resin A1 Carbon fiber short fiber reinforced polyphenylene sulfide resin A1.
  • Composite resin particles were prepared according to Example 6 of CN201711166435.3.
  • the above-mentioned surface-treated aluminum alloy plate was embedded in an injection mold, and the composite material prepared in the examples and the comparative examples was injected into an aluminum alloy plate using an injection molding machine. ⁇ 5 mm aluminum alloy resin composite, and the tensile shear strength of the aluminum alloy resin composite was measured.
  • Tensile strength According to GB / T1447-2005, the composite material is cut into type I specimens with a length of 200mm and a test speed of 10mm / min. Test 5 splines and calculate the average and standard deviation.
  • Tensile shear strength The metal and resin ends of the metal-resin composite are clamped with a tensile tester for measurement, the distance between the clamps is 60 mm, and the test speed is 10 mm / min. Test 5 splines and calculate the average and standard deviation.

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
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Abstract

Disclosed is a polyphenylene sulfide/carbon fiber composite material with a good bonding force to a metal, which material includes polyphenylene sulfide, carbon fiber staple fibers, an epoxy resin and a novolac resin, and contains 65-95 parts by weight of polyphenylene sulfide and 5-35 parts by weight of carbon fiber staple fibers based on 100 parts by weight of the total of polyphenylene sulfide and carbon fiber staple fibers. The composite material improves the bonding force to a metal, and the raw materials used have a good thermal resistance and cannot be decomposed during processing, such that the composite material is easy to process and has a good product stability. In addition, the tensile strength and impact strength of the composite material are also improved to some extent.

Description

一种与金属粘结性好的聚苯硫醚/碳纤维复合材料Polyphenylene sulfide / carbon fiber composite material with good adhesion to metal 技术领域Technical field
本发明涉及一种碳纤维复合材料，特别是一种与金属粘结性好的聚苯硫醚/碳纤维复合材料。The invention relates to a carbon fiber composite material, especially a polyphenylene sulfide / carbon fiber composite material with good adhesion to metal.
背景技术Background technique
聚苯硫醚(PPS)是分子主链中带有苯硫基的热塑性树脂，具有耐高温、耐腐蚀、耐辐射、阻燃、均衡的物理机械性能、极好的尺寸稳定性以及优良的电性能的特点，是一种综合性能优异的特种工程塑料。碳纤维具有低密度、高比强度和比模量、耐高温、抗化学腐蚀、高热导、低热膨胀等优良特性。碳纤维增强聚苯硫醚可以进一步提高聚苯硫醚的拉伸强度和冲击强度，改善它的韧性，扩大其应用范围。Polyphenylene sulfide (PPS) is a thermoplastic resin with a phenylsulfide group in the main chain of the molecule. It has high temperature resistance, corrosion resistance, radiation resistance, flame retardancy, balanced physical and mechanical properties, excellent dimensional stability, and excellent electrical properties. The characteristic of performance is a special engineering plastic with excellent comprehensive performance. Carbon fiber has excellent characteristics such as low density, high specific strength and specific modulus, high temperature resistance, chemical corrosion resistance, high thermal conductivity, and low thermal expansion. Carbon fiber reinforced polyphenylene sulfide can further increase the tensile strength and impact strength of polyphenylene sulfide, improve its toughness, and expand its scope of application.
在汽车、电子电器等用途中，需要将碳纤维增强聚苯硫醚同金属材料复合使用，比如将碳纤维增强聚苯硫醚注塑到金属件上。相对于其他工程塑料，PPS同金属的粘结性虽然较好，但在某些应用场合下，仍然存在界面容易剥离和脱落的问题，需要进一步提高PPS同金属的粘结性。In applications such as automobiles and electronic appliances, carbon fiber reinforced polyphenylene sulfide needs to be used in combination with metal materials, such as injection molding of carbon fiber reinforced polyphenylene sulfide onto metal parts. Compared with other engineering plastics, although the adhesion between PPS and metal is better, in some applications, there is still the problem that the interface is easy to peel and fall off, and it is necessary to further improve the adhesion between PPS and metal.
CN201711166435.3通过在PPS中复配三元氯醋树脂和氟树脂，提高了同金属的粘结性，同金属的拉伸剪切强度可以提高近70％，且与原PPS复合材料相比，只需更改树脂的配方即可实现，不需更改现有的工艺，不需增添设备，简单易行。CN201711166435.3 By compounding ternary chlorinated vinegar resin and fluorine resin in PPS, the adhesion to the metal is improved, and the tensile shear strength of the same metal can be increased by nearly 70%, and compared with the original PPS composite material, It can be achieved by simply changing the formula of the resin, without changing the existing process, without adding equipment, and it is simple and easy to implement.
但是，该方法中使用的三元氯醋树脂耐热性不佳，在加工过程中，会部分发生分解，造成加工难度增大以及产品性能不稳定。However, the ternary chlorinated vinegar resin used in this method has poor heat resistance, and will be partially decomposed during processing, resulting in increased processing difficulty and unstable product performance.
为此，需要一种加工性能好、产品性能稳定、能够改善同金属的粘结力的聚苯硫醚/碳纤维复合材料。For this reason, a polyphenylene sulfide / carbon fiber composite material with good processing performance, stable product performance, and improved adhesion to metals is needed.
发明内容Summary of the invention
为解决上述问题，本发明提供了一种与金属粘结性好的聚苯硫醚/碳纤维复合材料，同时提供一种根据本复合材料制成的金属树脂复合体。In order to solve the above problems, the present invention provides a polyphenylene sulfide / carbon fiber composite material with good adhesion to metals, and at the same time provides a metal resin composite body made of the composite material.
一种聚苯硫醚/碳纤维复合材料，包含聚苯硫醚、碳纤维短纤、环氧树脂和线型酚醛树脂，且以聚苯硫醚和碳纤维短纤合计为100重量份计，含聚苯硫醚65～95重量份、碳纤维短纤5～35重量份。A polyphenylene sulfide / carbon fiber composite material, including polyphenylene sulfide, carbon fiber short fiber, epoxy resin and novolac resin, and based on 100 parts by weight of the total polyphenylene sulfide and carbon fiber short fiber 65 to 95 parts by weight of sulfide and 5 to 35 parts by weight of carbon fiber staple fiber.
聚苯硫醚是分子主链中带有苯硫基的聚合物，包含对苯硫醚和/或间苯硫醚的均聚物、共聚物，及它们的混合物。Polyphenylene sulfide is a polymer with a phenyl sulfide group in the molecular main chain, including homopolymers, copolymers of p-phenyl sulfide and / or m-phenyl sulfide, and mixtures thereof.
碳纤维短纤是由碳纤维长丝经纤维切断机短切而成。作为聚苯硫醚的复合材料的增强 纤维，可以提高聚苯硫醚的拉伸强度、弯曲强度和耐冲击强度。Carbon fiber staple fiber is made by short-cutting carbon fiber filament by fiber cutting machine. As the reinforcing fiber of polyphenylene sulfide composite material, the tensile strength, bending strength and impact resistance of polyphenylene sulfide can be improved.
以聚苯硫醚和碳纤维短纤合计为100重量份计，当聚苯硫醚多于95重量份，碳纤维短纤少于5重量份，碳纤维对聚苯硫醚的增强作用不明显；当聚苯硫醚少于65重量份，碳纤维短纤多于35重量份，碳纤维在聚苯硫醚基体中的分散变差，性能均匀性降低。Taking the total of polyphenylene sulfide and carbon fiber short fiber as 100 parts by weight, when polyphenylene sulfide is more than 95 parts by weight and carbon fiber short fiber is less than 5 parts by weight, the reinforcing effect of carbon fiber on polyphenylene sulfide is not obvious; The phenylene sulfide is less than 65 parts by weight, and the carbon fiber staple fiber is more than 35 parts by weight. The dispersion of the carbon fiber in the polyphenylene sulfide matrix becomes poor, and the performance uniformity decreases.
环氧树脂是指分子中含有两个或两个以上环氧基的化合物，是以脂肪族、脂环族或芳香链段为主链的高分子预聚物，是一类重要的热固性树脂。常见的环氧树脂，可以列举出双酚A型环氧树脂、双酚F型环氧树脂、多酚型缩水甘油醚环氧树脂、脂肪族缩水甘油醚环氧树脂、缩水甘油酯型环氧树脂、缩水甘油胺型环氧树脂、环氧化烯烃化合物等。环氧树脂能够提高聚苯硫醚/碳纤维复合材料对金属的粘结性。Epoxy resin refers to a compound containing two or more epoxy groups in the molecule. It is a polymer prepolymer with aliphatic, alicyclic or aromatic segments as the main chain, and is an important class of thermosetting resin. Common epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, and glycidyl ester epoxy resin. Resin, glycidylamine epoxy resin, epoxidized olefin compound, etc. Epoxy resin can improve the adhesion of polyphenylene sulfide / carbon fiber composite materials to metals.
线型酚醛树脂，又称线性酚醛树脂，是能够溶解于有机溶剂、加热能够熔融、且长期加热也不会固化的一类酚醛树脂。线型酚醛树脂能够与环氧树脂固化，一同提高聚苯硫醚/碳纤维复合材料对金属的粘结性。常见的线型酚醛树脂，可以列举出双酚A型线型酚醛树脂、甲酚型线型酚醛树脂、苯酚型线型酚醛树脂等。Novolac resin, also known as novolac resin, is a type of phenolic resin that can be dissolved in an organic solvent, can be melted by heating, and will not be cured for a long time. Novolak resin can be cured with epoxy resin to improve the adhesion of polyphenylene sulfide / carbon fiber composite materials to metals. Common novolak resins include bisphenol A novolak resins, cresol novolak resins, and phenol novolak resins.
进一步，本发明所述的聚苯硫醚/碳纤维复合材料中，以聚苯硫醚和碳纤维短纤合计为100重量份计，环氧树脂和线型酚醛树脂合计为5～30重量份，对提高聚苯硫醚/碳纤维复合材料同金属的粘结力效果明显，且易于加工。若偏离此范围，则提高聚苯硫醚/碳纤维复合材料同金属的粘结力无效或效果不明显，且不易于加工，尤其是线型酚醛树脂含量较多时，容易在基体中形成凝胶状异物，对复合材料力学性能的稳定性不利。Further, in the polyphenylene sulfide / carbon fiber composite material of the present invention, the total amount of polyphenylene sulfide and carbon fiber short fibers is 100 parts by weight, and the total amount of epoxy resin and novolak resin is 5 to 30 parts by weight. The effect of improving the adhesion of polyphenylene sulfide / carbon fiber composite material to metal is obvious, and it is easy to process. If it deviates from this range, the adhesion between the polyphenylene sulfide / carbon fiber composite and the metal is invalid or the effect is not obvious, and it is not easy to process, especially when the content of the novolak resin is large, it is easy to form a gel in the matrix Foreign matter is detrimental to the stability of the mechanical properties of the composite material.
进一步优选为，以聚苯硫醚和碳纤维短纤合计为100重量份计，环氧树脂和线型酚醛树脂合计为10～20重量份。More preferably, the total amount of polyphenylene sulfide and carbon fiber short fibers is 100 parts by weight, and the total amount of epoxy resin and novolak resin is 10 to 20 parts by weight.
环氧当量是指含有一当量环氧基的环氧树脂的克数，单位为克/当量，是表示环氧树脂所含环氧基数量的重要物性指标。Epoxy equivalent refers to the number of grams of epoxy resin containing one equivalent of epoxy groups, and the unit is grams per equivalent, which is an important physical property index indicating the number of epoxy groups contained in the epoxy resin.
羟基当量是指含有一当量羟基的线型酚醛树脂的克数，单位为克/当量，是表示线型酚醛树脂所含羟基数量的重要物性指标。Hydroxyl equivalent refers to the grams of novolak resin containing one equivalent of hydroxyl groups, and the unit is grams / equivalent, which is an important physical property index indicating the number of hydroxyl groups contained in the novolak resin.
当体系中同时含有两种或两种以上的环氧树脂(或线型酚醛树脂)时，环氧当量(或羟基当量)按这几种环氧树脂(或线型酚醛树脂)的环氧当量的重量平均值计算，即环氧当量(或羟基当量)＝树脂1的环氧当量(或羟基当量)×树脂1的重量百分含量+……+树脂n的环氧当量(或羟基当量)×树脂n的重量百分含量。When the system contains two or more epoxy resins (or novolac resins) at the same time, the epoxy equivalent (or hydroxyl equivalent) is equivalent to the epoxy equivalents of these epoxy resins (or novolac resins) Calculate the weight average value, that is, epoxy equivalent (or hydroxyl equivalent) = epoxy equivalent of resin 1 (or hydroxyl equivalent) × weight percentage of resin 1 + ... + epoxy equivalent of resin n (or hydroxyl equivalent) × Weight percentage of resin n.
当环氧树脂和线型酚醛树脂的重量份数比为环氧树脂的环氧当量/线型酚醛树脂羟基当量时，理论上环氧树脂中的环氧基和线型酚醛树脂中的羟基能够反应完全。环氧树脂和线型 酚醛树脂的重量份数比可以写为如下式1，其中α为无单位量。When the weight ratio of epoxy resin and novolac resin is epoxy equivalent of epoxy resin / hydroxyl equivalent of novolac resin, theoretically the epoxy group in epoxy resin and the hydroxyl group in novolac resin can The reaction is complete. The weight ratio of the epoxy resin and the novolac resin can be written as the following formula 1, where α is a unitless quantity.
环氧树脂和线型酚醛树脂的重量份数比＝(环氧树脂的环氧当量/线型酚醛树脂的羟基当量)×α式1Weight ratio of epoxy resin and novolac resin = (epoxy equivalent of epoxy resin / hydroxyl equivalent of novolac resin) × α formula 1
进一步，本发明所述的聚苯硫醚/碳纤维复合材料中，环氧树脂和线型酚醛树脂的重量份数比范围优选为式1中的α取值为0.8～1之间的范围，这对提高聚苯硫醚/碳纤维复合材料同金属的粘结力效果较明显。当α大于1，或小于0.8时，都不利于环氧树脂和线型酚醛树脂对提高聚苯硫醚/碳纤维复合材料同金属的粘结力的提高。进一步优选，α为0.85～0.95之间。Further, in the polyphenylene sulfide / carbon fiber composite material according to the present invention, the weight ratio range of the epoxy resin and the novolak resin is preferably in the range of α in Formula 1 between 0.8 and 1. It has obvious effect on improving the adhesion between polyphenylene sulfide / carbon fiber composite and metal. When α is greater than 1, or less than 0.8, it is not conducive to the improvement of the adhesion between the epoxy resin and the novolac resin to the polyphenylene sulfide / carbon fiber composite material to the metal. More preferably, α is between 0.85 and 0.95.
进一步，本发明所述的聚苯硫醚/碳纤维复合材料中，所述环氧树脂的熔点为90℃以上，优选120℃以上，最优选为140℃以上。此类环氧树脂具有较好的耐热性，在复合材料的加工温度下不易发生分解等副反应，且环氧树脂同线型酚醛树脂的固化温度较高，在加工过程中容易控制固化反应。Furthermore, in the polyphenylene sulfide / carbon fiber composite material according to the present invention, the melting point of the epoxy resin is 90 ° C or higher, preferably 120 ° C or higher, and most preferably 140 ° C or higher. This type of epoxy resin has good heat resistance, and it is not easy to cause side reactions such as decomposition at the processing temperature of the composite material, and the curing temperature of the epoxy resin and the novolak phenol resin is high, and it is easy to control the curing reaction during the processing process .
进一步，本发明所述的聚苯硫醚/碳纤维复合材料中，所述线型酚醛树脂是双酚A型线型酚醛树脂、甲酚型线型酚醛树脂中的一种或多种。这两种线型酚醛树脂与环氧树脂的匹配度更佳，对提高聚苯硫醚/碳纤维复合材料同金属的粘结力更有效。Further, in the polyphenylene sulfide / carbon fiber composite material of the present invention, the novolak resin is one or more of bisphenol A novolak resin and cresol novolak resin. These two novolac resins have better matching with epoxy resins, and are more effective for improving the adhesion of polyphenylene sulfide / carbon fiber composite materials to metals.
进一步，本发明所述的聚苯硫醚/碳纤维复合材料中，所述线型酚醛树脂是双酚A型线型酚醛树脂和甲酚型线型酚醛树脂中的两种，两者的重量份数比1:1～1:3，优选为1:1.5～1:25.。Further, in the polyphenylene sulfide / carbon fiber composite material of the present invention, the novolak resin is two types of bisphenol A novolak resin and cresol novolak resin, and the parts by weight of the two The number ratio is 1: 1 to 1: 3, preferably 1: 1.5 to 1:25.
进一步，本发明所述的聚苯硫醚/碳纤维复合材料中，所述线型酚醛树脂的熔点在90～120℃之间，最优选为95～115℃之间。同环氧树脂类似，较高熔点的线型酚醛树脂具有较好的耐热性，在复合材料的加工温度下不易发生分解等副反应，且固化温度较高，在加工过程中容易控制固化反应；但是，具有大于120℃熔点的线型酚醛树脂同环氧树脂的相容性不佳，不利于复合材料同金属的粘结力的提高。Furthermore, in the polyphenylene sulfide / carbon fiber composite material of the present invention, the melting point of the novolak resin is between 90 and 120 ° C, and most preferably between 95 and 115 ° C. Similar to epoxy resin, the noble phenolic resin with higher melting point has better heat resistance, side reactions such as decomposition are not easy to occur at the processing temperature of the composite material, and the curing temperature is high, it is easy to control the curing reaction during the processing ; However, the compatibility of the novolak resin with a melting point greater than 120 ℃ with epoxy resin is not good, which is not conducive to the improvement of the adhesion of the composite material to the metal.
进一步，本发明所述的聚苯硫醚/碳纤维复合材料中，以聚苯硫醚和碳纤维短纤合计为100重量份计，还含有硅烷偶联剂0.2～10重量份。硅烷偶联剂是一类在分子中同时含有两种不同化学性质基团的有机硅化合物，其分子同时具有与无机质材料(如玻璃、金属等)发生化学反应、与有机质材料(如合成树脂等)发生化学反应的能力，从而可以增强聚苯硫醚、环氧树脂、线型酚醛树脂、碳纤维相互之间的粘结力，改善复合材料的性能。硅烷偶联剂可以列举出含有胺基、环氧基、乙烯基、异氰酸酯基、巯基中的一种或多种的硅氧烷。Furthermore, the polyphenylene sulfide / carbon fiber composite material according to the present invention contains 0.2 to 10 parts by weight of a silane coupling agent based on 100 parts by weight of the total polyphenylene sulfide and carbon fiber short fibers. Silane coupling agent is a type of organosilicon compound containing two different chemical groups in the molecule. Its molecule has chemical reaction with inorganic materials (such as glass, metal, etc.) and organic materials (such as synthetic resin). Etc.) The ability of chemical reaction, which can enhance the adhesion between polyphenylene sulfide, epoxy resin, novolak resin, carbon fiber, and improve the performance of the composite material. Examples of the silane coupling agent include siloxanes containing one or more of amine groups, epoxy groups, vinyl groups, isocyanate groups, and mercapto groups.
进一步，本发明所述的聚苯硫醚/碳纤维复合材料中，所述的硅烷偶联剂含环氧基或异氰酸酯基中的一种或多种，它们与环氧树脂、线型酚醛树脂的相容性、反应性较佳，对提高 复合材料同金属的粘结力，以及复合材料力学性能的稳定性效果明显。最优选含环氧基的硅烷偶联剂。Further, in the polyphenylene sulfide / carbon fiber composite material described in the present invention, the silane coupling agent contains one or more of epoxy groups or isocyanate groups, which are combined with epoxy resins and novolac resins. The compatibility and reactivity are better, which has obvious effect on improving the adhesion of the composite material to the metal and the stability of the mechanical properties of the composite material. The epoxy group-containing silane coupling agent is most preferred.
本发明还提供一种利用本发明所述的聚苯硫醚/碳纤维复合材料制成的金属树脂复合体，其包含本发明所属的聚苯硫醚/碳纤维复合材料和金属件。The invention also provides a metal-resin composite body made of the polyphenylene sulfide / carbon fiber composite material according to the invention, which comprises the polyphenylene sulfide / carbon fiber composite material and metal parts to which the invention belongs.
本发明的效果：The effect of the invention:
本发明的聚苯硫醚/碳纤维复合材料，改善了同金属的粘结力，且所用的原料耐热性好，不会在加工中分解，所以易于加工性能，产品性能的稳定性好。另外，对复合材料的拉伸强度和冲击强度也有一定的改善。The polyphenylene sulfide / carbon fiber composite material of the present invention improves the adhesion with metals, and the raw materials used have good heat resistance and will not be decomposed during processing, so it is easy to process performance and product performance stability is good. In addition, the tensile strength and impact strength of the composite material are also improved to a certain extent.
具体实施方式detailed description
一种与金属粘结性好的聚苯硫醚/碳纤维复合材料，实施例和对比例中使用的原料如下：A polyphenylene sulfide / carbon fiber composite material with good adhesion to metals. The raw materials used in the examples and comparative examples are as follows:
【碳纤维短纤增强聚苯硫醚树脂】【Carbon fiber short fiber reinforced polyphenylene sulfide resin】
A1：东丽株式会社产TORAYCAA630T-30V，含碳纤维短纤30重量份、聚苯硫醚70重量份。聚苯硫醚熔点为278℃。A1: TORAYCAA630T-30V produced by Toray Industries, 30 parts by weight of carbon-containing short fibers and 70 parts by weight of polyphenylene sulfide. The melting point of polyphenylene sulfide is 278 ° C.
【环氧树脂】【Epoxy resin】
B1：DIC株式会社产EPICLON 2050，双酚A型环氧树脂，熔点85℃，环氧当量700g/eq。B1: EPICLON 2050 produced by DIC Corporation, bisphenol A epoxy resin, melting point 85 ° C, epoxy equivalent 700g / eq.
B2：DIC株式会社产EPICLON4050，双酚A型环氧树脂，熔点100℃，环氧当量900g/eq。B2: EPICLON 4050 produced by DIC Corporation, bisphenol A epoxy resin, melting point 100 ° C, epoxy equivalent 900g / eq.
B3：DIC株式会社产EPICLON HM-091，双酚A型环氧树脂，熔点145℃，环氧当量2600g/eq。B3: EPICLON HM-091 produced by DIC Corporation, bisphenol A type epoxy resin, melting point 145 ℃, epoxy equivalent 2600g / eq.
【线型酚醛树脂】【Novolak resin】
C1：DIC株式会社产PHENOLITE TD-2091，苯酚型线型酚醛树脂，熔点110℃，羟基当量100g/eq。C1: PHENOLITE TD-2091 produced by DIC Corporation, phenol novolak resin, melting point 110 ° C, hydroxyl equivalent 100g / eq.
C2：DIC株式会社产PHENOLITE VH-4170，双酚A型线型酚醛树脂，熔点105℃，羟基当量120g/eq。C2: PHENOLITE VH-4170 manufactured by DIC Corporation, bisphenol A novolak resin, melting point 105 ° C, hydroxyl equivalent 120g / eq.
C3：DIC株式会社产PHENOLITEKA-1163，甲酚型线型酚醛树脂，熔点110℃，羟基当量120g/eq。C3: PHENOLITEKA-1163 manufactured by DIC Corporation, cresol novolak resin, melting point 110 ° C, hydroxyl equivalent 120g / eq.
C4：DIC株式会社产PHENOLITEKA-1160，甲酚型线型酚醛树脂，熔点85℃，羟基当量120g/eq。C4: PHENOLITEKA-1160 manufactured by DIC Corporation, cresol novolak resin, melting point 85 ° C, hydroxyl equivalent 120g / eq.
【硅烷偶联剂】【A silane coupling agent】
D1：缩水甘油基丙基三乙氧基硅烷，信越化学工业株式会社产KBM-403。D1: Glycidylpropyltriethoxysilane, Shin-Etsu Chemical Co., Ltd. KBM-403.
D2：异氰酸丙基三乙氧基硅烷，信越化学工业株式会社产KBE-9007。D2: Isocyanopropyl triethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. KBE-9007.
D3：3-巯基丙基三乙氧基硅烷，信越化学工业株式会社产KBM-803。D3: 3-Mercaptopropyltriethoxysilane, KBM-803 produced by Shin-Etsu Chemical Co., Ltd.
实施例1～13Examples 1 to 13
按照表1的原料和重量份充分混合，添加到挤出机中挤出切粒得到复合材料树脂颗粒，挤出机温度设定为300℃。The raw materials and parts by weight according to Table 1 were thoroughly mixed, added to an extruder and extruded and pelletized to obtain composite resin pellets, and the temperature of the extruder was set to 300 ° C.
表1Table 1
Figure PCTCN2018111591-appb-000001
Figure PCTCN2018111591-appb-000001
备注：α的定义见式1。Remarks: See definition 1 for α.
实施例14～19Examples 14-19
在实施例5的原料配方基础上，按照表2所示的配方，将两个品种的线型酚醛树脂混合使用，以替代原线型酚醛树脂。原料充分混合后，添加到挤出机中挤出切粒得到复合材料树脂颗粒，挤出机温度设定为300℃。Based on the raw material formula of Example 5, according to the formula shown in Table 2, two types of novolak resins are mixed and used to replace the original novolak resin. After the raw materials are thoroughly mixed, they are added to an extruder and extruded to obtain composite resin pellets. The temperature of the extruder is set to 300 ° C.
表2Table 2
Figure PCTCN2018111591-appb-000002
Figure PCTCN2018111591-appb-000002
Figure PCTCN2018111591-appb-000003
Figure PCTCN2018111591-appb-000003
实施例20～24Examples 20-24
在实施例16的原料配方基础上，按照表3所示的配方，增加硅烷偶联剂。原料充分混合后，添加到挤出机中挤出切粒得到复合材料树脂颗粒，挤出机温度设定为300℃。Based on the raw material formula of Example 16, the silane coupling agent was added according to the formula shown in Table 3. After the raw materials are thoroughly mixed, they are added to an extruder and extruded to obtain composite resin pellets. The temperature of the extruder is set to 300 ° C.
表3table 3
Figure PCTCN2018111591-appb-000004
Figure PCTCN2018111591-appb-000004
对比例1Comparative Example 1
碳纤维短纤增强聚苯硫醚树脂A1。Carbon fiber short fiber reinforced polyphenylene sulfide resin A1.
对比例2Comparative Example 2
按CN201711166435.3的实施例6制备复合材料树脂颗粒。Composite resin particles were prepared according to Example 6 of CN201711166435.3.
将实施例和对比例制得的复合材料树脂分别在300℃熔融，用注塑机注塑，得到长×宽×厚度＝200mm×100mm×4mm的复合材料板，并测定复合材料的拉伸强度和冲击强度。The composite resins prepared in the examples and comparative examples were melted at 300 ° C and injected with an injection molding machine to obtain composite plates with length × width × thickness = 200 mm × 100 mm × 4 mm, and the tensile strength and impact of the composite materials were measured. strength.
将市售1mm厚的5052铝合金板，切割成长×宽＝45mm×18mm长方形片，放入丙酮溶液中，超声波清洗15min后，用纯净水清洗干净；再将其作为阳极放入体积比1:3的高氯酸乙醇混合溶液中，在40V电压下常温电解3min；随后继续将其作为阳极放入1mol/L的磷酸溶液中，在40V电压下继续电解40min；再浸泡在2mol/L的磷酸中30min，取出用纯净水清洗干净并烘干得到表面处理的铝合金板。A commercially available 5052 aluminum alloy plate with a thickness of 1 mm was cut into rectangular pieces with a length × width = 45 mm × 18 mm, and placed in an acetone solution. After ultrasonic cleaning for 15 min, it was cleaned with purified water; 3 Perchloric acid ethanol mixed solution, electrolysis at room temperature for 3min at 40V voltage; then continue to use it as an anode into 1mol / L phosphoric acid solution, continue electrolysis at 40V voltage for 40min; then soak in 2mol / L phosphoric acid In 30 minutes, take out cleaned with purified water and dried to obtain the surface-treated aluminum alloy plate.
将上述的表面处理铝合金板嵌入到注塑模具中，用注塑机将实施例与对比例制备的复合材料注塑到得到铝合金板上，得到复合材料尺寸为45mm×10mm×5mm，接合面为10mm× 5mm的铝合金树脂复合体，并测定铝合金树脂复合体的拉伸剪切强度。The above-mentioned surface-treated aluminum alloy plate was embedded in an injection mold, and the composite material prepared in the examples and the comparative examples was injected into an aluminum alloy plate using an injection molding machine. × 5 mm aluminum alloy resin composite, and the tensile shear strength of the aluminum alloy resin composite was measured.
实施例和对比例的性能测定方法如下：The performance measurement methods of the examples and comparative examples are as follows:
1、拉伸强度：按GB/T1447-2005进行，将复合材料裁剪成Ⅰ型试样，长为200mm，测试速度为10mm/min。测试5个样条，计算平均值和标准偏差。1. Tensile strength: According to GB / T1447-2005, the composite material is cut into type I specimens with a length of 200mm and a test speed of 10mm / min. Test 5 splines and calculate the average and standard deviation.
2、冲击强度：按GB/T1043-1993进行，将复合材料裁剪成1型试样，缺口类型为A。测试5个样条，计算平均值和标准偏差。2. Impact strength: According to GB / T1043-1993, the composite material is cut into type 1 samples, and the notch type is A. Test 5 splines and calculate the average and standard deviation.
3、拉伸剪切强度：用拉力试验机夹住金属树脂复合体的金属和树脂端进行测定，夹具间距离为60mm，测试速度为10mm/min。测试5个样条，计算平均值和标准偏差。3. Tensile shear strength: The metal and resin ends of the metal-resin composite are clamped with a tensile tester for measurement, the distance between the clamps is 60 mm, and the test speed is 10 mm / min. Test 5 splines and calculate the average and standard deviation.
测试结果如表4所示。The test results are shown in Table 4.
表4Table 4
Figure PCTCN2018111591-appb-000005
Figure PCTCN2018111591-appb-000005
Figure PCTCN2018111591-appb-000006
Figure PCTCN2018111591-appb-000006
从表4中可以看出，与对比例1相比，本发明实施例的拉伸强度和冲击性能良好，与金属的粘结力有很大的提高，粘结性能更好，且对拉伸强度和冲击强度也有一定程度的改善；与对比例2相比，粘结性能相近或更佳，且由于改善了加工性能，产品性能更稳定，标准偏差更小，运用领域更加广泛。As can be seen from Table 4, compared with Comparative Example 1, the tensile strength and impact performance of the examples of the present invention are good, the adhesion to metal is greatly improved, the bonding performance is better, and the tensile strength The strength and impact strength have also been improved to a certain extent; compared with Comparative Example 2, the bonding performance is similar or better, and due to the improved processing performance, the product performance is more stable, the standard deviation is smaller, and the application field is more extensive.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据技术方案及发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above is only the preferred embodiment of the present invention, but the scope of protection of the present invention is not limited to this, any person skilled in the art in the technical field within the technical scope disclosed by the present invention, according to the technical solutions and inventive concepts Equivalent substitutions or changes should be covered within the protection scope of the present invention.

Claims (10)

  1. 一种与金属粘结性好的聚苯硫醚/碳纤维复合材料，其特征在于，包含聚苯硫醚、碳纤维短纤、环氧树脂和线型酚醛树脂，且以聚苯硫醚和碳纤维短纤合计为100重量份计，含聚苯硫醚65～95重量份、碳纤维短纤5～35重量份。A polyphenylene sulfide / carbon fiber composite material with good adhesion to metal, characterized in that it contains polyphenylene sulfide, carbon fiber short fiber, epoxy resin and novolac resin, and the polyphenylene sulfide and carbon fiber short The total amount of fibers is 100 parts by weight, containing 65 to 95 parts by weight of polyphenylene sulfide and 5 to 35 parts by weight of carbon fiber short fibers.
  2. 根据权利要求1所述的一种与金属粘结性好的聚苯硫醚/碳纤维复合材料，其特征在于，以聚苯硫醚和碳纤维短纤合计为100重量份计，环氧树脂和线型酚醛树脂合计为5～30重量份。The polyphenylene sulfide / carbon fiber composite material with good adhesion to metal according to claim 1, characterized in that the total amount of polyphenylene sulfide and carbon fiber short fiber is 100 parts by weight, epoxy resin and thread The total amount of phenolic resin is 5 to 30 parts by weight.
  3. 根据权利要求2所述的一种与金属粘结性好的聚苯硫醚/碳纤维复合材料，其特征在于，环氧树脂和线型酚醛树脂的重量份数比为(环氧树脂的环氧当量/线型酚醛树脂的羟基当量)×0.8～环氧树脂的环氧当量/线型酚醛树脂的羟基当量之间。The polyphenylene sulfide / carbon fiber composite material with good adhesion to metal according to claim 2, wherein the weight ratio of epoxy resin and novolac resin is (epoxy resin epoxy resin) Equivalent / hydroxyl equivalent of novolac resin) × 0.8 to epoxy equivalent of epoxy resin / hydroxyl equivalent of novolac resin.
  4. 根据权利要求3所述的一种与金属粘结性好的聚苯硫醚/碳纤维复合材料，其特征在于，所述环氧树脂的熔点为90℃以上。The polyphenylene sulfide / carbon fiber composite material with good adhesion to metal according to claim 3, wherein the melting point of the epoxy resin is above 90 ° C.
  5. 根据权利要求1-4任一项所述的一种与金属粘结性好的聚苯硫醚/碳纤维复合材料，其特征在于，所述线型酚醛树脂是双酚A型线型酚醛树脂、甲酚型线型酚醛树脂中的一种或多种。The polyphenylene sulfide / carbon fiber composite material with good adhesion to metal according to any one of claims 1 to 4, characterized in that the novolak resin is a bisphenol A novolak resin, One or more of cresol novolak resins.
  6. 根据权利要求5所述的一种与金属粘结性好的聚苯硫醚/碳纤维复合材料，其特征在于，所述线型酚醛树脂是双酚A型线型酚醛树脂和甲酚型线型酚醛树脂中的两种，两者的重量份数比1:1～1:3。The polyphenylene sulfide / carbon fiber composite material with good adhesion to metal according to claim 5, wherein the novolak resin is bisphenol A novolak resin and cresol novolak resin Two types of phenolic resins, the weight ratio of the two is 1: 1 to 1: 3.
  7. 根据权利要求1-6任一项所述的一种与金属粘结性好的聚苯硫醚/碳纤维复合材料，其特征在于，所述线型酚醛树脂的熔点在90～120℃之间。The polyphenylene sulfide / carbon fiber composite material with good metal adhesion according to any one of claims 1 to 6, wherein the melting point of the novolak resin is between 90 and 120 ° C.
  8. 根据权利要求1-7任一项所述的一种与金属粘结性好的聚苯硫醚/碳纤维复合材料，其特征在于，以聚苯硫醚和碳纤维短纤合计为100重量份计，还含有硅烷偶联剂0.2～10重量份。The polyphenylene sulfide / carbon fiber composite material with good adhesion to metal according to any one of claims 1-7, characterized in that the total amount of polyphenylene sulfide and carbon fiber short fiber is 100 parts by weight, It also contains 0.2 to 10 parts by weight of silane coupling agent.
  9. 根据权利要求8所述的一种与金属粘结性好的聚苯硫醚/碳纤维复合材料，其特征在于，所述的硅烷偶联剂含环氧基或异氰酸酯基中的一种或多种。A polyphenylene sulfide / carbon fiber composite material with good adhesion to metals according to claim 8, wherein the silane coupling agent contains one or more of epoxy groups or isocyanate groups .
  10. 一种利用权利要求1～9任一项所述的聚苯硫醚/碳纤维复合材料制成的金属树脂复合体。A metal-resin composite body made of the polyphenylene sulfide / carbon fiber composite material according to any one of claims 1 to 9.
PCT/CN2018/111591 2018-10-18 2018-10-24 Polyphenylene sulfide/carbon fiber composite material with good bonding force to metal WO2020077657A1 (en)

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