Scratch-resistant thermoplastic composite material and method of making and use thereof

Abstract

The application discloses a kind of scratch-resistant thermoplastic composite and its preparation method and application.The scratch-resistant thermoplastic composite includes inner layer material and at least one outer layer material, the inner layer material is the core layer including fiber bundle, first thermoplastic resin and first auxiliary agent, at least one outer layer material is wrapped the core layer and is the resin layer including second thermoplastic resin and second auxiliary agent, wherein, the fiber bundle continuously extends from one end of the core layer to its opposite end, and the second auxiliary agent includes scratch-resistant auxiliary agent.The scratch-resistant thermoplastic composite of the application is based on multi-component material system design, can make the performance synergy effect between each component, while having excellent scratch resistance, can realize the on-line addition of scratch-resistant auxiliary agent of thermoplastic composite.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of polymer composites, and particularly relates to a scratch-resistant thermoplastic composite material and a preparation method and application thereof. BACKGROUND

[0002] Long fiber reinforced thermoplastic composite material is a common thermoplastic composite material, which is one of the fastest growing materials in today's composite material market. As a semi-structural material and a structural material, the development goal of long fiber reinforced thermoplastic composite material is in various fields of industry and civil use, including automobile, appliance, entertainment, food processing, communication, electronic and electrical appliances, power tools, gardening, etc.

[0003] The fiber length of long fiber reinforced thermoplastic material is equivalent to the particle length, the fiber orientation is highly consistent, and the material has the characteristics of low density, easy molding, high specific strength, high modulus, good fatigue resistance and non-water absorption. In addition, the material has good dimensional stability, excellent impact resistance, chemical stability (salt resistance, oil resistance, fuel resistance, etc.) and recyclable advantages, and is especially suitable for use in high and low temperature alternating occasions. It can be injection molded on a general injection molding machine, and can also be molded into a shape, and is an ideal candidate for metal replacement materials. In the total amount of long fiber reinforced thermoplastic composite material, the application amount of automobile material accounts for 80%-90%.

[0004] However, with the continuous improvement of long fiber reinforced thermoplastic composite material technology and the continuous expansion of application cases, and the further improvement of people's awareness of health, safety and environmental protection and the continuous advancement of automobile process, more and higher requirements are put forward for the performance of the material. In addition to the requirements of excellent mechanical properties and functionalization, the processing performance and the performance requirements of the molded parts after molding are also considered. For example, for large and complex automobile parts and high-precision electronic and electrical components, the prepared material is required to have scratch resistance, easy molding, high dimensional stability, high surface quality and processing and molding requirements.

[0005] In addition, with the continuous improvement of people's aesthetic, people's requirements for the scratch resistance of the material surface are getting higher and higher. The common method to improve the scratch resistance of thermoplastic materials is to add a scratch-resistant additive during the melt blending process of the thermoplastic material, so as to endow the thermoplastic composite with scratch resistance. The common scratch-resistant agent has low surface energy and poor compatibility with the thermoplastic composite, and the scratch-resistant additive can also deteriorate the impregnation effect of long fibers in the thermoplastic composite. At the same time, the addition of conventional scratch-resistant additives and melt blending of thermoplastic composites can cause different degrees of fiber breakage and poor impregnation effect of long fibers. Therefore, the improvement of scratch resistance and the impregnation effect of long fibers are mutually exclusive, and it is difficult to obtain a thermoplastic composite with good scratch resistance and good impregnation effect of long fibers by conventional methods. It is particularly important to solve the problem of good impregnation effect of long glass fibers in the thermoplastic composite and effectively improve the scratch resistance of the surface of the composite.

[0006] For the above problems, the prior art still far fails to meet the needs of practical applications. SUMMARY

[0007] In view of the above problems existing in the prior art, the present application provides a scratch-resistant thermoplastic composite material and a preparation method and application thereof. The scratch-resistant thermoplastic composite material of the present application is designed based on a multi-component material system, which can achieve performance synergy between components, has excellent scratch resistance, and can realize online addition of scratch-resistant additives to the thermoplastic composite. Further, the scratch-resistant thermoplastic composite material of the present application can greatly improve the flowability of fibers in the resin melt, greatly improve the surface performance of the composite material, and expand the application range.

[0008] The first aspect of the present application provides a scratch-resistant thermoplastic composite material, which comprises an inner layer material and at least one outer layer material. The inner layer material is a core layer comprising a fiber bundle, a first thermoplastic resin and a first additive. The at least one outer layer material wraps the core layer and is a resin layer comprising a second thermoplastic resin and a second additive. The fiber bundle continuously extends from one end of the core layer to the opposite end. The second additive comprises a scratch-resistant additive.

[0009] The present inventors have found that a continuous fiber bundle is impregnated with a first component including a first thermoplastic resin and a first additive to form a core layer, and a second component including a second thermoplastic resin is uniformly coated on the outside of the core layer, thereby forming a scratch-resistant thermoplastic composite material having a continuous fiber-reinforced resin as a core layer (inner layer material) and a resin layer coated on the outside of the core layer as an outer layer material, which has excellent scratch resistance and enables on-line addition of a scratch-resistant additive to the thermoplastic composite material. In addition, by adjusting the properties and functions of the first thermoplastic resin in the core layer and the second thermoplastic resin in the resin layer, the scratch-resistant thermoplastic composite material can have different properties and functions.

[0010] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, the outer layer material (resin layer) can substantially continuously coat the inner layer material (core layer). Although not preferred, in the scratch-resistant thermoplastic composite material of the present application, the outer layer material (resin layer) coats the inner layer material (core layer) by at least 80%, for example, 80-99%, 85-95%.

[0011] In the present application, the terms "one end" and / or "opposite end" are generally with respect to the longitudinal direction of the scratch-resistant thermoplastic composite material.

[0012] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, the scratch-resistant thermoplastic composite material can be in the form of a strip, a rod, or a particle. Of course, the scratch-resistant thermoplastic composite material of the present application can also be in other shapes, for example, a continuous filament. In the present application, the scratch-resistant thermoplastic composite material in the form of a strip, a rod, or a particle can be cut from a continuous filament of the scratch-resistant thermoplastic composite material.

[0013] In some embodiments, the scratch-resistant thermoplastic composite material is in the form of a strip, a rod, or a particle. The length (longitudinal dimension) of the scratch-resistant thermoplastic composite material in the form of a strip, a rod, or a particle can be 5-30 mm, preferably 5-25 mm, and more preferably 6-15 mm.

[0014] In other embodiments, although not preferred, the scratch-resistant thermoplastic composite material can also have a relatively small length dimension. For example, the scratch-resistant thermoplastic composite material is in the form of a particle, and the particle size (length) of the scratch-resistant thermoplastic composite material in the form of a particle can also be 2-5 mm, and preferably 3-4 mm.

[0015] According to some embodiments of the scratch-resistant thermoplastic composite according to the present application, the present application does not have a special requirement for the cross-sectional shape of the scratch-resistant thermoplastic composite. In some embodiments, the cross-section of the scratch-resistant thermoplastic composite in the form of a particle or a rod is circular or quasi-circular. In other embodiments, the cross-section of the scratch-resistant thermoplastic composite in the form of a particle or a rod can be rectangular or square.

[0016] According to some embodiments of the scratch-resistant thermoplastic composite according to the present application, the amount of the first thermoplastic resin in the inner layer material is 1-90 parts by weight, and the amount of the fiber bundle is 10-110 parts by weight.

[0017] In some specific embodiments, the amount of the first thermoplastic resin in the inner layer material can be 1 part by weight, 10 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, or a range consisting thereof; and in some specific embodiments, the amount of the fiber bundle can be 1 part by weight, 10 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, or a range consisting thereof.

[0018] In some preferred embodiments, the amount of the first thermoplastic resin in the inner layer material can be 20-70 parts by weight, preferably 20-55 parts by weight, more preferably 24-45 parts by weight; and / or the amount of the fiber bundle can be 20-110 parts by weight, more preferably 25-110 parts by weight.

[0019] According to some embodiments of the scratch-resistant thermoplastic composite according to the present application, the amount of the second thermoplastic resin in the outer layer material is 1-110 parts by weight.

[0020] In some specific embodiments, the amount of the second thermoplastic resin in the outer layer material can be 1 part by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, 100 parts by weight, 105 parts by weight, 110 parts by weight, or a range consisting thereof.

[0021] In some preferred embodiments, the amount of the second thermoplastic resin in the outer layer material can be 10-99 parts by weight, more preferably 10-90 parts by weight, preferably 40-90 parts by weight.

[0022] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, in the inner layer material, the amount of the first thermoplastic resin is 1-90 parts by weight, preferably 20-70 parts by weight, more preferably 20-55 parts by weight, and further preferably 24-45 parts by weight; and / or the amount of the fiber bundle is 10-99 parts by weight, preferably 20-80 parts by weight, and more preferably 25-50 parts by weight.

[0023] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, in the inner layer material, the amount of the first thermoplastic resin is 1-90 parts by weight, preferably 20-70 parts by weight, more preferably 20-55 parts by weight, and further preferably 24-45 parts by weight; and / or the amount of the fiber bundle is 10-99 parts by weight, preferably 20-80 parts by weight, and more preferably 25-50 parts by weight.

[0024] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, in the inner layer material, the weight ratio of the fiber bundle to the first thermoplastic resin is 0.25-6:1. For example, in the inner layer material, the weight ratio of the fiber bundle to the first thermoplastic resin is 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.2:1, 1.5:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 6:1, or ranges consisting of the foregoing.

[0025] In some preferred embodiments, in the inner layer material, the weight ratio of the fiber bundle to the first thermoplastic resin can be 0.35-4.5:1, preferably 1.7-4.5:1.

[0026] The amounts of the first and second auxiliary agents are limited in the present application for the purpose of achieving the effects of the relevant auxiliary agents.

[0027] In different embodiments of the present application, the number of layers of the outer layer material is not limited, and the outer layer material can be one layer or multiple layers. When the outer layer material is multiple layers, the multiple layers of the outer layer material can be formed by one outer layer material or by multiple outer layer materials.

[0028] According to some embodiments of the scratch resistant thermoplastic composite material of the present application, the first and second thermoplastic resins are the same or different, each independently selected from at least one of polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyacrylonitrile-butadiene-styrene copolymer, polyacrylonitrile-styrene copolymer, polyoxymethylene, polyamide, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polycarbonate, polyphenylene ether, polyurethane, polyether ether ketone, and polyphenylene sulfide, and alloy polymers thereof.

[0029] According to preferred embodiments of the scratch resistant thermoplastic composite material of the present application, the first and second thermoplastic resins are each independently selected from at least one of polypropylene, polyethylene, polyamide (also known as nylon), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene sulfide, polyurethane, and polyether ether ketone (PEEK).

[0030] According to preferred embodiments of the scratch resistant thermoplastic composite material of the present application, the first and second thermoplastic resins are each independently selected from at least one of homopolymer polypropylene, copolymer polypropylene, a mixture of homopolymer polypropylene and copolymer polypropylene, nylon 6 (PA6), nylon 66 (PA66), and a mixture of nylon 6 and nylon 66.

[0031] According to other embodiments of the scratch resistant thermoplastic composite material of the present application, the first and second thermoplastic resins can also be selected from thermoplastic polyurethane elastomer (TPU) and / or high performance nylon (PPA).

[0032] According to some embodiments of the scratch resistant thermoplastic composite material of the present application, the first thermoplastic resin has a melt flow rate at 230 °C under a load of 2.16 kg of 60-8000 g / 10 min. For example, the first thermoplastic resin can have a melt flow rate at 230 °C under a load of 2.16 kg of 60 g / 10 min, 100 g / 10 min, 200 g / 10 min, 450 g / 10 min, 500 g / 10 min, 1000 g / 10 min, 1500 g / 10 min, 2000 g / 10 min, 3000 g / 10 min, 4000 g / 10 min, 5000 g / 10 min, 6000 g / 10 min, 7000 g / 10 min, 7500 g / 10 min, 8000 g / 10 min, or a range comprised therebetween.

[0033] In some preferred embodiments, the first thermoplastic resin can have a melt flow rate at 230°C under a load of 2.16 kg of 100-8000 g / 10 min, preferably 1000-7500 g / 10 min, more preferably 1900-7500 g / 10 min.

[0034] According to some embodiments of the scratch resistant thermoplastic composite of the present application, the second thermoplastic resin has a melt flow rate at 230°C under a load of 2.16 kg of 0.1-8000 g / 10 min. For example, the second thermoplastic resin can have a melt flow rate at 230°C under a load of 2.16 kg of 0.1 g / 10 min, 1 g / 10 min, 1.5 g / 10 min, 3 g / 10 min, 10 g / 10 min, 20 g / 10 min, 30 g / 10 min, 40 g / 10 min, 45 g / 10 min, 50 g / 10 min, 55 g / 10 min, 60 g / 10 min, 70 g / 10 min, 80 g / 10 min, 90 g / 10 min, 100 g / 10 min, 450 g / 10 min, 500 g / 10 min, 800 g / 10 min, 1000 g / 10 min, 1500 g / 10 min, 1900 g / 10 min, 2500 g / 10 min, 3000 g / 10 min, 4000 g / 10 min, 5000 g / 10 min, 6000 g / 10 min, 7000 g / 10 min, 8000 g / 10 min, or a range consisting thereof.

[0035] In some preferred embodiments, the second thermoplastic resin can have a melt flow rate at 230°C under a load of 2.16 kg of 3-55 g / 10 min or 450-8000 g / 10 min, preferably 3-45 g / 10 min or 1900-8000 g / 10 min.

[0036] In different embodiments of the present application, the melt flow rate of the first thermoplastic resin and the second thermoplastic resin is not particularly specified, and the melt flow rate of the first thermoplastic resin and the second thermoplastic resin can be selected according to the desired properties.

[0037] In particular, the present inventors have found that the parameters according to the present application (e.g. melt flow rate) allow to prepare scratch-resistant thermoplastic composites having both high surface quality properties and overall properties. For example, the melt flow rate of the first thermoplastic resin is higher than the melt flow rate of the second thermoplastic resin, thereby allowing to obtain scratch-resistant thermoplastic composites having improved mechanical properties; conversely, the melt flow rate of the second thermoplastic resin is higher than the melt flow rate of the first thermoplastic resin, thereby allowing to obtain scratch-resistant thermoplastic composites having improved gloss.

[0038] According to some preferred embodiments of the scratch-resistant thermoplastic composite according to the present application, the first thermoplastic resin has a melt flow rate at 230°C under a load of 2.16 kg of 60-450 g / 10 min, for example 60-200 g / 10 min, and the second thermoplastic resin has a melt flow rate at 230°C under a load of 2.16 kg of 3-55 g / 10 min or 450-8000 g / 10 min. In some particular embodiments, the first thermoplastic resin has a melt flow rate at 230°C under a load of 2.16 kg of 60-450 g / 10 min and the second thermoplastic resin has a melt flow rate at 230°C under a load of 2.16 kg of 800-8000 g / 10 min.

[0039] According to other preferred embodiments of the scratch-resistant thermoplastic composite according to the present application, the first thermoplastic resin has a melt flow rate at 230°C under a load of 2.16 kg of more than 450 g / 10 min, in particular more than 450 g / 10 min, and the second thermoplastic resin has a melt flow rate at 230°C under a load of 2.16 kg of less than 100 g / 10 min, preferably 1.5-55 g / 10 min, more preferably 3-50 g / 10 min.

[0040] According to some embodiments of the scratch-resistant thermoplastic composite according to the present application, the weight ratio of the second thermoplastic resin to the first thermoplastic resin is 0.05-12.5:1. For example, the weight ratio of the second thermoplastic resin to the first thermoplastic resin can be 0.05:1, 0.1:1, 0.14:1, 0.15:1, 0.18:1, 0.2:1, 0.25:1, 0.3:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.3:1, 1.4:1, 1.7:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 5:1, 8:1, 10:1, 12.5:1 or ranges consisting of these values.

[0041] In some preferred embodiments, the weight ratio of the second thermoplastic resin to the first thermoplastic resin can be 0.1-4:1, preferably 0.14-3.5:1.

[0042] According to preferred embodiments of the scratch-resistant thermoplastic composite material of the present application, when the melt flow rate of the second thermoplastic resin at 230℃ and under a load of 2.16kg is 800-8000g / 10min, the weight ratio of the second thermoplastic resin to the first thermoplastic resin is less than 0.25:1, preferably less than 0.18:1, more preferably less than 0.15:1.

[0043] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, when the first thermoplastic resin and the second thermoplastic resin are selected from at least one of nylon 6, nylon 66, and a mixture of nylon 6 and nylon 66, the viscosity of the selected nylon 6 and nylon 66 is 1.8-3.5. Herein, the viscosity of the nylon is the relative viscosity determined according to the Enslin Viscosity Determination Method GB / T266-88.

[0044] According to specific embodiments of the scratch-resistant thermoplastic composite material of the present application, the first thermoplastic resin and the second thermoplastic resin can be self-made or commercially available.

[0045] For example, the polypropylene resin with the trade name of PPB-M100-GH available from Sinopec Yangzi Petrochemical Co., Ltd., the polypropylene resin with the trade name of M60RHC available from Sinopec East China Branch, and the nylon 6 with the trade name of PA6-BL3200H available from Sinopec Baling Branch can be used as the first thermoplastic resin.

[0046] For example, the polypropylene resin with the trade name of PPB-M100-GH available from Sinopec Yangzi Petrochemical Co., Ltd., the polypropylene resin with the trade name of PPH-T03 available from Sinopec Maoming Branch, the polypropylene resin with the trade name of M50RH available from Sinopec East China Branch, the polypropylene resin with the trade name of K8303 available from Yanshan Petrochemical Co., Ltd., the polypropylene resin with the trade name of PF1500 available from Hunan Shengjin New Material Co., Ltd., or the polypropylene resin with the trade name of PPH-Y450 available from Sinopec Shijiazhuang Refinery Branch, and the nylon 6 with the trade name of PA6-BL3200H available from Sinopec Baling Branch can be used as the second thermoplastic resin.

[0047] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, the fiber bundle is selected from at least one of glass fiber, carbon fiber, basalt fiber, aramid fiber, stainless steel fiber, synthetic resin fiber, and mineral fiber.

[0048] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, the glass fibers are continuous glass fibers and / or chopped glass fibers.

[0049] Suitable fiber bundles for use in the present application can be alkali-free glass fibers of the trade designation SE4805 available from Owens Corning (Shanghai) Fiberglass Co., Ltd., alkali-free glass fibers of the trade designation ER4301H available from Chongqing International Composite Material Co., Ltd., carbon fibers of the trade designation T700SC available from Toray Industries, Inc., and basalt fibers available from Mudanjiang Jinshi Basalt Fibers Co., Ltd.

[0050] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, the core layer and the resin layer are arranged in sequence from inside to outside in a transverse cross-section of the scratch-resistant thermoplastic composite material; and the fiber bundles are oriented along the longitudinal direction of the scratch-resistant thermoplastic composite material. Preferably, the length of the fiber bundles is substantially the same as the length (longitudinal dimension) of the scratch-resistant thermoplastic composite material, whereby the fiber bundles continuously extend from one end to the opposite end of the core layer in the longitudinal direction.

[0051] In some preferred embodiments, the fiber bundles can be subjected to a dispersion treatment. Such dispersion treatment methods are known in the art and are not specifically limited in the present application.

[0052] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, the inner layer material is free of short fibers, in particular, free of non-oriented short fibers.

[0053] In some specific embodiments, the inner layer material is composed of fiber bundles, a first thermoplastic resin, and a first auxiliary agent.

[0054] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, the outer layer material is free of fibers. In some preferred embodiments, the outer layer material is composed of a second thermoplastic resin and a second auxiliary agent.

[0055] According to other embodiments of the scratch-resistant thermoplastic composite material of the present application, the outer layer material contains fibers, such as short fibers.

[0056] In some specific embodiments, the weight ratio of the fibers to the second thermoplastic resin in the outer layer material is 1-50:100, preferably 5-50:100, and more preferably 20-45:100.

[0057] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, the scratch-resistant auxiliary agent is a silicone masterbatch, preferably BONDYRAM 1001 from BASF, MB50 from Dow Corning, and the like.

[0058] In some embodiments, the amount of the scratch resistant aid is 1-6 parts by weight, preferably 1-3.5 parts by weight, based on 100 parts by weight of the second thermoplastic resin.

[0059] According to some embodiments of the scratch resistant thermoplastic composite material of the present application, the first and second aids each independently comprise at least one of 0.5-15 parts by weight of a compatibilizer, 0.05-3 parts by weight of an antioxidant and 0.05-2.5 parts by weight of a lubricant, based on 100 parts by weight of the first and second thermoplastic resins, respectively. Preferably, the first and second aids each independently comprise at least one of 1-15 parts by weight, preferably 1-6 parts by weight, more preferably 3-6 parts by weight of a compatibilizer, 0.1-1 parts by weight, preferably 0.1-0.5 parts by weight of an antioxidant and 0.5-2.5 parts by weight of a lubricant.

[0060] According to some embodiments of the scratch resistant thermoplastic composite material of the present application, the compatibilizer is selected from at least one of a polar monomer grafted polymer. Preferably, the polar monomer is selected from at least one of maleic anhydride, maleic anhydride derivatives, acrylic acid and acrylic ester derivatives. Preferably, the polymer is selected from at least one of polyethylene, polypropylene, ethylene-a-olefin copolymer and propylene-a-olefin (a-olefin other than propylene) copolymer.

[0061] According to specific embodiments of the scratch resistant thermoplastic composite material of the present application, maleic anhydride grafted polypropylene (PP-g-MAH) available from Plirang Plastic Industrial Co., Ltd. under the trade designation BONDYRAM 1001, maleic anhydride grafted ethylene-octene copolymer (POE-g-MAH) available from Shanghai Risheng Technology Co., Ltd. under the trade designation CMG9805, titanate coupling agent available from Nanjing Shuguang Chemical Group Co., Ltd. under the trade designation NDZ12 or aluminates coupling agent available from Nanjing Youpu Chemical Co., Ltd. under the trade designation XHY-501 can be used as the compatibilizer.

[0062] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, the antioxidant is selected from at least one of tetrakis [beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester (antioxidant 1010), tris[2,4-di-tert-butylphenyl] phosphite (antioxidant 168), n-octadecyl beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (antioxidant 2246), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane (antioxidant CA), and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant 626).

[0063] According to specific embodiments of the scratch-resistant thermoplastic composite material of the present application, antioxidant 1010 and / or antioxidant 168 available from BASF can be used as the antioxidant.

[0064] According to some embodiments of the scratch-resistant thermoplastic composite material of the present application, the lubricant is selected from at least one of ethylene bis-stearamide, calcium stearate, polyethylene wax, pentaerythritol stearate, silicone, polyethylene glycol, and fluorine-containing resin.

[0065] According to specific embodiments of the scratch-resistant thermoplastic composite material of the present application, an oxidized polyethylene wax available from Xianghe Paint Group with trade name XH-201 can be used as the lubricant.

[0066] In different embodiments of the present application, the first additive can further include at least one of a slip agent, an antistatic agent, and a plasticizer, and / or the second additive can further include at least one of a slip agent, an antistatic agent, a plasticizer, a nucleating agent, a scratch-resistant additive, a heat stabilizer, a color master, an antistatic agent, and a filler, and the specific types and amounts of these additives are not limited and can have a wide range of selection.

[0067] The present application provides in a second aspect a method for preparing a scratch-resistant thermoplastic composite material, the method comprising the following steps:

[0068] Step A, melting the mixture of the first thermoplastic resin and the first additive to obtain a first component melt;

[0069] Step B, performing a first impregnation treatment on the continuous fiber bundle with the first component melt to form a filamentous core layer product;

[0070] Step C, melting the mixture of the second thermoplastic resin and the second additive to obtain a second component melt;

[0071] Step D, subjecting the filamentous core layer article to a second impregnation process with the second component melt to form a resin layer continuously wrapping the core layer.

[0072] According to some embodiments of the preparation method of the present application, the preparation method can be carried out continuously in line to obtain a continuous filamentous article, which can be directly stored or used, or cut into a strip, rod or granular article with a certain length.

[0073] According to some embodiments of the preparation method of the present application, the mixing conditions of step A include a temperature of 40-60℃ and a time of 0.5-20min, preferably 1-10min, and more preferably 3-5min.

[0074] According to some embodiments of the preparation method of the present application, the melting temperature in step A is 200-380℃. In the present application, the melting time can have a wide selection range, for the purpose of fully melting the first thermoplastic resin and the first auxiliary agent to obtain a melt.

[0075] According to some embodiments of the preparation method of the present application, preferably, before the first impregnation process of the continuous fiber with the first component melt in step B, the continuous fiber is further subjected to a dispersion process and a preheating process, and the preheating temperature is preferably 80-250℃. The dispersion process in the present application adopts a conventional fiber dispersion process in the art.

[0076] According to some embodiments of the preparation method of the present application, the mixing conditions of step C include a temperature of 40-60℃ and a time of 0.5-20min, preferably 1-10min, and more preferably 3-5min.

[0077] According to some embodiments of the preparation method of the present application, the melting temperature in step C is 200-380℃. In the present application, the melting time can have a wide selection range, for the purpose of fully melting the second thermoplastic resin and the optional second auxiliary agent.

[0078] According to some embodiments of the preparation method of the present application, the first impregnation process in step B can be carried out in a first impregnation mold, and the first impregnation mold is an adjustable impregnation mold, which includes a fiber inlet, a fiber outlet and a melt flow channel, and at least one first godet is arranged in the mold cavity of the first impregnation mold; the first godet can move between the fiber inlet and the fiber outlet; and / or the first godet can move in a direction perpendicular to the connecting line of the fiber inlet and the fiber outlet.

[0079] According to some embodiments of the preparation method of the present application, the first impregnation treatment in step B can be performed in a second impregnation mold, which is a combined impregnation mold comprising a first module, an intermediate module and a second module connected in sequence, the first module being provided with a fiber inlet and a first module flow channel, the second module being provided with a fiber outlet and a second module flow channel, and the intermediate module being provided with an intermediate module flow channel; after the first module, the intermediate module and the second module are connected in sequence, the first module flow channel, the intermediate module flow channel and the second module flow channel are connected to form a combined flow channel for the fibers to pass through.

[0080] According to some embodiments of the preparation method of the present application, the first impregnation treatment in step B can also be performed in a third impregnation mold, which is a strong turbulence impregnation mold comprising a fiber inlet channel, an impregnation outlet and a melt slit flow channel, all of which are connected to a mold cavity inside the third impregnation mold; wherein the mold cavity of the third impregnation mold is provided with a second godet, which comprises at least one driven godet, and the driven godet is driven to rotate by a driving device.

[0081] The first impregnation mold, the second impregnation mold and the third impregnation mold used in the present application are described in Chinese patent applications CN 202011193483.3, 202011191450.5 and 202011199839.4, which are incorporated herein by reference in their entirety.

[0082] It should be noted that the first impregnation mold, the second impregnation mold and the third impregnation mold described above can be applied to any existing manufacturing system and preparation technology of scratch-resistant thermoplastic composites, especially any existing manufacturing system and preparation technology of continuous fiber reinforced intumescent flame-retardant thermoplastic composites.

[0083] According to some embodiments of the preparation method of the present application, the second impregnation treatment in step D can be performed in a forming mold. The forming mold is composed of a core, a sleeve and a sleeve die plate. The core is located inside the sleeve to form a forming cavity with the sleeve, and the resin melt can enter the cavity from the bottom or top or both sides of the sleeve. The core can move forward and backward in the sleeve, and the pressure of the melt in the cavity can be determined by adjusting the size of the cavity space formed. The pressure of the melt in the cavity can also be adjusted by the angle between the core and the sleeve.

[0084] The working principle of the forming die is as follows: the strip formed with the inner layer impregnated material after impregnating the die is guided to pass through the hole in the middle of the core, and then the inner and outer layer material composite structure is formed in the cavity filled with the mixed melt formed by the core and the outer sleeve, and finally is guided out through the outer sleeve die plate.

[0085] According to some embodiments of the preparation method, after step D, the obtained scratch-resistant thermoplastic composite material is subjected to pulling out, stretching, cooling, drying and granulation treatment. The process conditions of the pulling out, stretching, cooling, drying and granulation treatment are not particularly limited, and are in a wide selection range, so as to obtain the scratch-resistant thermoplastic composite material meeting different specifications.

[0086] According to some embodiments of the preparation method, in the inner layer material, the amount of the first thermoplastic resin is 1-90 parts by weight, and the amount of the fiber bundle is 10-110 parts by weight.

[0087] In some specific embodiments, in the inner layer material, the amount of the first thermoplastic resin can be 1 part by weight, 10 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, or a range consisting of the foregoing; and in some specific embodiments, the amount of the fiber bundle can be 1 part by weight, 10 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, or a range consisting of the foregoing.

[0088] In some preferred embodiments, in the inner layer material, the amount of the first thermoplastic resin can be 20-70 parts by weight, preferably 20-55 parts by weight, and more preferably 24-45 parts by weight; and / or the amount of the fiber bundle can be 20-110 parts by weight, preferably 25-110 parts by weight.

[0089] According to some embodiments of the preparation method, in the outer layer material, the amount of the second thermoplastic resin is 1-110 parts by weight.

[0090] In some specific embodiments, in the outer layer material, the amount of the second thermoplastic resin can be 1 part by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, 100 parts by weight, 105 parts by weight, 110 parts by weight, or a range consisting of the foregoing.

[0091] In some preferred embodiments, the amount of the second thermoplastic resin in the outer layer material can be 10-90 parts by weight, preferably 40-90 parts by weight.

[0092] According to some embodiments of the preparation method of the present application, the amount of the first thermoplastic resin in the inner layer material is 1-90 parts by weight, preferably 20-70 parts by weight, more preferably 20-55 parts by weight, and further preferably 24-45 parts by weight; and / or the amount of the fiber bundle is 10-99 parts by weight, preferably 20-80 parts by weight, and more preferably 25-50 parts by weight.

[0093] According to some embodiments of the preparation method of the present application, the amount of the first thermoplastic resin in the inner layer material is 1-90 parts by weight, preferably 20-70 parts by weight, more preferably 20-55 parts by weight, and further preferably 24-45 parts by weight; and / or the amount of the fiber bundle is 10-99 parts by weight, preferably 20-80 parts by weight, and more preferably 25-50 parts by weight.

[0094] According to some embodiments of the preparation method of the present application, the weight ratio of the fiber to the first thermoplastic resin in the inner layer material is 0.25-6:1. For example, the weight ratio of the fiber bundle to the first thermoplastic resin in the inner layer material is 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.2:1, 1.5:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 6:1, or ranges consisting of the foregoing.

[0095] In some preferred embodiments, the weight ratio of the fiber bundle to the first thermoplastic resin in the inner layer material can be 0.35-4.5:1, preferably 0.43-4.5:1.

[0096] In different embodiments of the present application, the number of layers of the outer layer material is not limited, and the outer layer material can be one layer or multiple layers. When the outer layer material is multiple layers, the multiple layers of the outer layer material can be formed by one outer layer material or by multiple outer layer materials.

[0097] According to some embodiments of the manufacturing method of the present application, the first and second thermoplastic resins are the same or different, each independently selected from at least one of polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyacrylonitrile- butadiene-styrene copolymer, polyacrylonitrile-styrene copolymer, polyoxymethylene, polyamide, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polycarbonate, polyphenylene ether, polyurethane, polyether ether ketone, and polyphenylene sulfide, and alloy polymers thereof.

[0098] According to preferred embodiments of the manufacturing method of the present application, the first and second thermoplastic resins are each independently selected from at least one of polypropylene, polyethylene, polyamide (also known as nylon), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene sulfide, polyurethane, and polyether ether ketone (PEEK).

[0099] According to preferred embodiments of the manufacturing method of the present application, the first and second thermoplastic resins are each independently selected from at least one of homopolymer polypropylene, copolymer polypropylene, a mixture of homopolymer polypropylene and copolymer polypropylene, nylon 6 (PA6), nylon 66 (PA66), and a mixture of nylon 6 and nylon 66.

[0100] According to other embodiments of the manufacturing method of the present application, the first and second thermoplastic resins can also be selected from thermoplastic polyurethane elastomer (TPU) and / or high-performance nylon (PPA).

[0101] According to some embodiments of the manufacturing method of the present application, the first thermoplastic resin has a melt flow rate of 60-8000 g / 10 min at 230 °C under a load of 2.16 kg. For example, the first thermoplastic resin can have a melt flow rate of 60 g / 10 min, 100 g / 10 min, 200 g / 10 min, 450 g / 10 min, 500 g / 10 min, 1000 g / 10 min, 1500 g / 10 min, 2000 g / 10 min, 3000 g / 10 min, 4000 g / 10 min, 5000 g / 10 min, 6000 g / 10 min, 7000 g / 10 min, 7500 g / 10 min, 8000 g / 10 min, or a range consisting of any two of the foregoing values, at 230 °C under a load of 2.16 kg.

[0102] In some preferred embodiments, the first thermoplastic resin can have a melt flow rate at 230°C under a load of 2.16 kg of 100-8000 g / 10 min, preferably 1000-7500 g / 10 min, more preferably 1900-7500 g / 10 min.

[0103] According to some embodiments of the method of manufacture of the present application, the second thermoplastic resin has a melt flow rate at 230°C under a load of 2.16 kg of 0.1-8000 g / 10 min. For example, the second thermoplastic resin can have a melt flow rate at 230°C under a load of 2.16 kg of 0.1 g / 10 min, 1 g / 10 min, 1.5 g / 10 min, 3 g / 10 min, 10 g / 10 min, 20 g / 10 min, 30 g / 10 min, 40 g / 10 min, 45 g / 10 min, 50 g / 10 min, 55 g / 10 min, 60 g / 10 min, 70 g / 10 min, 80 g / 10 min, 90 g / 10 min, 100 g / 10 min, 450 g / 10 min, 500 g / 10 min, 800 g / 10 min, 1000 g / 10 min, 1500 g / 10 min, 1900 g / 10 min, 2500 g / 10 min, 3000 g / 10 min, 4000 g / 10 min, 5000 g / 10 min, 6000 g / 10 min, 7000 g / 10 min, 8000 g / 10 min, or a range consisting thereof.

[0104] In some preferred embodiments, the second thermoplastic resin can have a melt flow rate at 230°C under a load of 2.16 kg of 3-55 g / 10 min or 450-8000 g / 10 min, preferably 3-45 g / 10 min or 1900-8000 g / 10 min.

[0105] In different embodiments of the present application, the melt flow rate of the first thermoplastic resin and the second thermoplastic resin is not particularly limited, and can be selected according to the desired performance. In particular, the present inventors have found that the preparation conditions (e.g., melt flow rate) according to the present application can produce a scratch-resistant thermoplastic composite material with high surface quality performance and comprehensive performance. For example, the melt flow rate of the first thermoplastic resin is higher than that of the second thermoplastic resin, so that the scratch-resistant thermoplastic composite material can have improved mechanical properties; conversely, the melt flow rate of the second thermoplastic resin is higher than that of the first thermoplastic resin, so that the scratch-resistant thermoplastic composite material can have improved gloss.

[0106] According to some preferred embodiments of the preparation method of the present application, the melt flow rate of the first thermoplastic resin at 230°C under a load of 2.16 kg is 60-450 g / 10 min, for example, 60-200 g / 10 min, and the melt flow rate of the second thermoplastic resin at 230°C under a load of 2.16 kg is 3-55 g / 10 min or 450-8000 g / 10 min. In some specific embodiments, the melt flow rate of the first thermoplastic resin at 230°C under a load of 2.16 kg is 60-450 g / 10 min, and the melt flow rate of the second thermoplastic resin at 230°C under a load of 2.16 kg is 800-8000 g / 10 min.

[0107] According to other preferred embodiments of the preparation method of the present application, the melt flow rate of the first thermoplastic resin at 230°C under a load of 2.16 kg is greater than 450 g / 10 min, in particular greater than 450 g / 10 min, and the melt flow rate of the second thermoplastic resin at 230°C under a load of 2.16 kg is less than 100 g / 10 min, preferably 1.5-55 g / 10 min, more preferably 3-50 g / 10 min.

[0108] According to some embodiments of the preparation method of the present application, the weight ratio of the second thermoplastic resin to the first thermoplastic resin is 0.05-12.5:1. For example, the weight ratio of the second thermoplastic resin to the first thermoplastic resin can be 0.05:1, 0.1:1, 0.14:1, 0.15:1, 0.18:1, 0.2:1, 0.25:1, 0.3:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.3:1, 1.4:1, 1.7:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 5:1, 8:1, 10:1, 12.5:1 or a range consisting of the above.

[0109] In some preferred embodiments, the weight ratio of the second thermoplastic resin to the first thermoplastic resin can be 0.14-4:1, preferably 0.14-3.5:1.

[0110] According to preferred embodiments of the preparation method of the present application, when the melt flow rate of the second thermoplastic resin at 230℃ and under a load of 2.16kg is 800-8000g / 10min, the weight ratio of the second thermoplastic resin to the first thermoplastic resin is less than 0.25:1, preferably less than 0.18:1, more preferably less than 0.15:1.

[0111] According to some embodiments of the preparation method of the present application, when the first thermoplastic resin and the second thermoplastic resin are selected from at least one of nylon 6, nylon 66, a mixture of nylon 6 and nylon 66, the viscosity of the selected nylon 6 and nylon 66 is 1.8-3.5.

[0112] According to specific embodiments of the preparation method of the present application, the first thermoplastic resin and the second thermoplastic resin can be self-made or commercially available.

[0113] For example, the polypropylene resin with the trade name of PPB-M100-GH available from Sinopec Yangzi Petrochemical Co., Ltd., the polypropylene resin with the trade name of M60RHC available from Sinopec East China Branch, and the nylon 6 with the trade name of PA6-BL3200H available from Sinopec Baling Branch can be used as the first thermoplastic resin.

[0114] For example, a polypropylene resin of a brand PPB-M100-GH available from Sinopec Yangzi Petrochemical Co., Ltd., a brand PPH-T03 available from Sinopec Maoming Branch Co., Ltd., a brand M50RH available from Sinopec East China Branch Co., Ltd., a brand K8303 available from Yanshan Petrochemical Co., Ltd., a brand PF1500 available from Hunan Shengjin New Material Co., Ltd., or a brand PPH-Y450 available from Sinopec Shijiazhuang Refinery Branch Co., Ltd., and a nylon 6 of a brand PA6-BL3200H available from Sinopec Baling Branch Co., Ltd. can be used as the second thermoplastic resin.

[0115] According to some embodiments of the preparation method of the present application, the fiber bundle is selected from at least one of glass fiber, carbon fiber, basalt fiber, aramid fiber, stainless steel fiber, synthetic resin fiber, and mineral fiber.

[0116] According to preferred embodiments of the preparation method of the present application, the glass fiber is continuous glass fiber and / or fixed-length glass fiber.

[0117] According to some embodiments of the preparation method of the present application, each of the first and second auxiliary agents independently includes at least one of 0.5-15 parts by weight of a compatibilizer, 0.05-3 parts by weight of an antioxidant, and 0.05-2.5 parts by weight of a lubricant, with the mass of the first and second thermoplastic resins being 100 parts by weight. Preferably, each of the first and second auxiliary agents independently includes 1-15 parts by weight, preferably 1-6 parts by weight, more preferably 3-6 parts by weight of at least one of a compatibilizer, 0.1-1 parts by weight, preferably 0.1-0.5 parts by weight of an antioxidant, and 0.5-2.5 parts by weight of a lubricant.

[0118] According to some embodiments of the preparation method of the present application, the compatibilizer is selected from at least one of a polar monomer grafted modified polymer. Preferably, the polar monomer is selected from at least one of maleic anhydride, maleic anhydride derivative, acrylic acid, and acrylic ester derivative. Preferably, the polymer is selected from at least one of polyethylene, polypropylene, ethylene-α-olefin copolymer, and propylene-α-olefin (α-olefin other than propylene).

[0119] According to some embodiments of the preparation method of the present application, the lubricant is selected from at least one of ethylene bis-stearamide, calcium stearate, polyethylene wax, pentaerythritol stearate, silicone, polyethylene glycol, and fluorine-containing resin.

[0120] In different embodiments of the present application, the first auxiliary agent can further include at least one of a slip agent, an antistatic agent and a plasticizer, the second auxiliary agent can further include at least one of a slip agent, an antistatic agent, a plasticizer, a nucleating agent, a scratch-resistant auxiliary agent, a flame retardant, a thermal stabilizer, a color masterbatch, an antistatic agent and a filler, and the specific types and amounts of the auxiliary agents are not limited and can be selected within a wide range.

[0121] In some embodiments of the present application, the preparation method of the present application is carried out in a scratch-resistant thermoplastic composite manufacturing system as shown in Figure 2 or Figure 3 The specific structure and connection mode of the scratch-resistant thermoplastic composite manufacturing system are described in the specific embodiments section.

[0122] The third aspect of the present application provides the above-mentioned scratch-resistant thermoplastic composite, the scratch-resistant thermoplastic composite prepared by the above-mentioned preparation method, and the application of the scratch-resistant thermoplastic composite in the fields of automobile industry, mechanical manufacturing, electronics and electrical appliances, chemical industry and environmental protection, aerospace communication and construction industry, preferably in large automobile parts and / or high-precision electronic and electrical components, and more preferably in automobile front-end modules and / or all-plastic tailgate inner panels. However, it is not limited thereto.

[0123] Advantages of the present application:

[0124] 1. The scratch-resistant thermoplastic composite prepared by the present application has a core layer and an outer layer composite structure. Based on the composite system design of the multiple materials, the performance synergy effect between the inner layer material and the outer layer material can be achieved, the processing performance of the scratch-resistant thermoplastic composite and the lubricity between the fibers and the resin matrix during injection molding can be effectively improved, the flowability of the fibers in the resin matrix melt can be improved, and thus the bonding state between the two can be improved and the separation state between the two can be reduced. The inner layer structure ensures that the long glass fibers are fully impregnated in the thermoplastic resin, and the outer functional layer ensures good dispersibility of the scratch-resistant auxiliary agent. At the same time, the flowability of the entire material system can also be improved, the comprehensive performance and surface quality of the prepared scratch-resistant thermoplastic composite are greatly improved, the requirements of the injection molding process are reduced, the application range of the scratch-resistant thermoplastic composite is expanded, and it has broad application prospects and economic significance.

[0125] 2. The scratch-resistant thermoplastic composite of the present application has excellent scratch resistance. By adding a small amount of high molecular weight scratch-resistant auxiliary agent in the outer layer material, the scratch resistance of the composite material surface can be greatly improved, and the addition amount of the scratch-resistant auxiliary agent can be reduced by not adding it in the core layer material. The scratch-resistant auxiliary agent is only in the outer layer material, which is more conducive to the effect of improving the scratch resistance of the composite material by enriching the surface of the scratch-resistant auxiliary agent.

[0126] 3、The scratch-resistant thermoplastic composite material of the present application has low cost, short injection molding cycle, high part dimensional stability, high material strength, no need for secondary mixing during use, and wide applicability. Further, the outer layer material of the scratch-resistant thermoplastic composite material of the present application can be free of fibers, has good surface quality performance, no floating fibers on the surface, and improved gloss. BRIEF DESCRIPTION OF DRAWINGS

[0127] The accompanying drawings are included to provide a further understanding of the present application, and are incorporated in and constitute a part of the specification, illustrate embodiments of the present application and, together with the description, serve to explain the principles of the present application. In the drawings:

[0128] Figure 1 Structure diagram of the scratch-resistant thermoplastic composite material according to an embodiment of the present application;

[0129] Figure 2 Structure diagram of the manufacturing system of the scratch-resistant thermoplastic composite material according to an embodiment of the present application;

[0130] Figure 3 Structure diagram of the manufacturing system of the scratch-resistant thermoplastic composite material according to another embodiment of the present application;

[0131] Figure 4 Cross-sectional view of the first impregnation mold according to an embodiment of the present application;

[0132] Figure 5 Cross-sectional view of the second impregnation mold according to an embodiment of the present application;

[0133] Figure 6 Cross-sectional view of the third impregnation mold according to an embodiment of the present application;

[0134] Figure 7 Diagram of the second impregnation process according to an embodiment of the present application;

[0135] Figure 8 Cross-sectional view of the molding mold used in the second impregnation process according to an embodiment of the present application.

[0136] Explanation of reference signs:

[0137] 0-1, core layer; 0-2, fiber bundle; 0-3, resin layer;

[0138] 1, fiber rack and fiber guiding device; 2, fiber pretreatment device; 3, first impregnation mold; 4, molten plasticizing feeding device; 5, molding mold; 6, cooling water tank; 7, drying machine; 8, traction machine; 9, pelletizer; 10, collection box;

[0139] A300, first impregnation die head; A1, fiber inlet; A2, second runner; A3, melt channel; A4, first runner; A5, upper die cover; A6, fiber outlet; A7, impregnation die body; A8, first godet;

[0140] B300, second impregnation die head; B1, fiber inlet; B2, melt channel; B3, first module; B31, first module channel; B4, combined channel; B5, standardization joint; B6, intermediate module; B61, intermediate module channel; B7, second module; B71, second module channel; B8, fiber outlet;

[0141] C300, third impregnation die head; C1, melt split channel; C2, impregnation die outer body; C3, fiber inlet channel; C4, driving godet; C5, driven godet; C6, impregnation outlet;

[0142] 4-1, extruder I; 4-2, extruder II;

[0143] 5-1, core; 5-2, sheath; 5-3, sheath die plate; 5-4, strand; 5-5, second resin inlet. DETAILED DESCRIPTION

[0144] In order to make the present application more easily understood, the present application will be described in detail below in conjunction with examples, which are only illustrative and do not limit the scope of application of the present application.

[0145] The test method of the present application and the equipment used in the test are as follows:

[0146] (1) The tensile strength test is detected according to the ISO527-2 standard, and the tensile speed is 5 mm / min.

[0147] (2) The bending strength test is detected according to the ISO178 standard, and the bending speed is 2 mm / min.

[0148] (3) The notched impact strength test is detected according to the ISO179 standard.

[0149] (4) The surface glossiness test is detected according to the ISO2813 standard.

[0150] (5) The scratch resistance test is detected according to the PV3952 standard.

[0151] Part of the reagents used in the present application are from:

[0152] (1) PPB-M100-GH, melt flow rate 100 g / 10 min, test condition 230 °C, 2.16 Kg load, produced by SINOPEC Yangzi Petrochemical Co., Ltd.

[0153] (2) PF1500, melt flow rate 1500 g / 10 min, produced by Hunan Shengjin New Material Co., Ltd.

[0154] (3) PPH-Y450, melt flow rate 450 g / 10 min, produced by SINOPEC Shijiazhuang Refinery Branch Co., Ltd.

[0155] (4) BL3200H, viscosity 1.8, produced by SINOPEC Baling Branch Co., Ltd.

[0156] (5) SE4805, E-glass fiber, diameter 17 μm, linear density 2400 tex, produced by Owens Corning (Shanghai) Fiberglass Co., Ltd.

[0157] (6) ER4301H, E-glass fiber, diameter 17 μm, linear density 2400 tex, produced by Chongqing International Composite Material Co., Ltd.

[0158] (7) T700SC, carbon fiber, tow 1200-50C, produced by Toray Industries, Inc.

[0159] (8) Basalt fiber, single fiber diameter 12 μm, produced by Mudanjiang Jinshi Basalt Fiber Co., Ltd.

[0160] (9) PP-g-MAH, trade name BONDYRAM 1001, produced by Plirama Plastic Industry Co., Ltd.

[0161] (10) POE-g-MAH, trade name CMG9805, produced by Shanghai Richstar Technology Co., Ltd.

[0162] (11) NDZ12, produced by Nanjing Shuguang Chemical Group Co., Ltd.

[0163] (12) XHY-501, produced by Nanjing Youpu Chemical Co., Ltd.

[0164] (13) Antioxidant 1010, produced by BASF.

[0165] (14) Antioxidant 168, produced by BASF.

[0166] (15) Scratch resistance aid SR100, produced by BASF.

[0167] (16) XH-201, produced by Xianghe Paint Group.

[0168] (17) Scratch-resistant additive MB50, Dow Corning.

[0169] The invention will now be further described with reference to the accompanying drawings.

[0170] Figure 1 The structure of the scratch-resistant thermoplastic composite material of the present invention is shown. For example... Figure 1 As shown, the cross-section of the scratch-resistant thermoplastic composite material of the present invention is circular, and from the inside out, it includes a core layer 0-1 and a resin layer 0-3. Fiber bundles 0-2 are distributed in the core layer 0-1 with longitudinal orientation, and the fiber bundles 0-2 are uniformly dispersed in the core layer 0-1.

[0171] like Figure 2 and Figure 3 As shown, the manufacturing system of the present invention includes a fiber rack and fiber guiding device 1, a fiber pretreatment device 2, a first impregnation mold 3, a melt plasticizing feeding device 4, a molding mold 5, a cooling water tank 6, a dryer 7, a traction machine 8, a pelletizer 9, a collection box 10, and an electrical control system (not shown in the figure), which are connected in sequence.

[0172] In the manufacturing system, molding die 5 is used for molding the inner and outer layer composite material, and its structure is as follows: Figure 8 As shown.

[0173] In the manufacturing system, the first impregnation mold 3 is used for impregnating the fiber with the resin melt.

[0174] like Figure 4 As shown, in one embodiment, the first impregnation mold is an impregnation device with an adjustable guide roller position, including a first impregnation mold head A300. The first impregnation mold head A300 includes an impregnation mold body A7, a fiber inlet A1, a fiber outlet A6, and a melt flow channel A3. At least one first guide roller A8 is provided in the mold cavity, wherein the first guide roller A8 is movable between the fiber inlet A1 and the fiber outlet A6, or the first guide roller A8 is movable along a direction perpendicular to the line connecting the fiber inlet A1 and the fiber outlet A6; or, the first guide roller A8 is movable both between the fiber inlet A1 and the fiber outlet A6 and along a direction perpendicular to the line connecting the fiber inlet A1 and the fiber outlet A6.

[0175] Taking a rectangular first impregnation mold head A300 as an example, the first impregnation mold head A300 is provided with a plurality of first guide rollers A8. The axial direction of each first guide roller A8 is the width direction of the first impregnation mold head A300. Therefore, each first guide roller A8 can move along the length direction of the first impregnation mold head A300 or along the height direction, thereby changing the position of the first guide roller A8 within the first impregnation mold head A300.

[0176] It can be understood that the axial direction of the first guide roller A8 can also be the length direction of the first impregnation die head A300, at this time each first guide roller A8 can move along the width direction of the first impregnation die head A300, and can also move along the height direction of the first impregnation die head A300, so as to change the position of the first guide roller A8 in the first impregnation die head A300.

[0177] Since the fiber (fiber bundle) needs to pass the first guide roller A8 in the mold cavity in the first impregnation die head A300 when walking in the mold cavity, by changing the position (horizontal position, vertical position, etc.) of the first guide roller A8 in the first impregnation die head A300, the walking path of the fiber in the mold cavity can be changed, so that when the required impregnation condition of the fiber changes, it is not necessary to replace a new die, but only to adjust the position of the first guide roller A8 in the first impregnation die head A300, thereby improving the production efficiency and the continuity of production. At the same time, the number of first impregnation die heads A300 can be reduced, and the production cost can be saved.

[0178] Specifically, the inventive concept of the present application is to achieve the purpose of adjusting the position of the first guide roller A8 by slotting the inner wall of the mold cavity of the first impregnation die head A300.

[0179] The first inner wall of the first impregnation die head A300 is provided with a first sliding groove A4, and the first sliding groove A4 extends between the fiber inlet A1 and the fiber outlet A6 (i.e. Figure 4 The first guide roller A8 moves along the first sliding groove A4 to change its horizontal position in the first impregnation die head A300.

[0180] Further, the first inner wall of the first impregnation die head A300 is also provided with a second sliding groove A2, and the second sliding groove extends in a direction perpendicular to the first sliding groove A4 (i.e. Figure 4 The first guide roller A8 moves along the second sliding groove A2 to change its vertical position in the die head.

[0181] It should be noted that the first sliding groove A4 and the second sliding groove A2 can be connected. Therefore, the first guide roller A8 can be arbitrarily moved in the longitudinal direction or the transverse direction, so that its position is changed.

[0182] Among them, the cross section of the first sliding groove A4 and the second sliding groove A2 can be trapezoidal, circular, arc-shaped or rectangular, etc., and the present application does not limit this.

[0183] The first guide roller A8 is provided with an adjusting device (not shown in the figure) at both ends, which is used to adjust the axial length of the first guide roller A8, wherein the minimum axial length of the first guide roller A8 is smaller than the distance between the first inner wall and the second inner wall, and the maximum axial length of the first guide roller A8 is greater than the distance between the first inner wall and the second inner wall.

[0184] As shown in Figure 5 In another embodiment of the present application, the second impregnation die is a combined impregnation die, which comprises a second impregnation die head B300, and the second impregnation die head B300 comprises a first module B3, an intermediate module B6 and a second module B7 connected in sequence. Wherein the first module B3 is provided with a fiber inlet B1 and a first module flow channel B31, the second module B7 is provided with a fiber outlet B8 and a second module flow channel B71, and the intermediate module B6 is provided with an intermediate module flow channel B61.

[0185] After the first module B3, the intermediate module B6 and the second module B7 are connected in sequence, the first module flow channel B31, the intermediate module flow channel B61 and the second module flow channel B71 are connected in communication to form a combined flow channel B4 for the fiber to pass through, wherein the number of intermediate modules B6 is at least one. That is, the first module B3 is the first module, the second module B7 is the last module, and there is one or more intermediate modules B6 between them. It should be noted that these intermediate modules B6 are also connected in sequence.

[0186] That is, the number of intermediate modules B6 can be increased or decreased as needed, so that when the impregnation requirements change, different intermediate modules B6 are selected to form a combined second impregnation die head B300, thereby improving the continuity and production efficiency of the production and saving the cost of additional mold opening.

[0187] Furthermore, by selecting different intermediate modules B6, the shape parameters (such as curvature, etc.) of the combined flow channel B4 formed can be changed, so that the flow path of the fiber and the melt can be changed, and then the fiber impregnation angle and fiber tension in different stations of the die can be changed, ultimately achieving the purpose of adjusting and optimizing the whole fiber impregnation process, and improving the adaptability of the second impregnation die head B300 to different resin matrices and fibers.

[0188] The above-mentioned first module B3, intermediate module B6 and second module B7 are placed in the mold frame, and the constraint action of the mold frame makes them in close contact with each other, thereby ensuring the sealing property of the combined flow channel B4 formed.

[0189] As shown in Figure 5 An embodiment with 2 intermediate modules B6 is shown. In Figure 5In the embodiment shown, the downstream end of the first module flow channel B31 is connected to the upstream end of one of the intermediate module flow channels B61, the two intermediate module flow channels B61 are connected to each other, and the downstream end of the other intermediate module flow channel B61 is connected to the upstream end of the second intermediate module flow channel B71, thereby forming a combined flow channel B4 extending from the fiber inlet B1 to the fiber outlet B8.

[0190] It can be understood that different combined flow channels B4 can be obtained by selecting different intermediate modules B6.

[0191] As shown in the drawings, Figure 5 The downstream end of the first module flow channel B31, the upstream end of the second module flow channel B71, and the two ends of the intermediate module flow channel B61 are all located in the same plane and are configured with standardized joints B5. In other words, the connections between the first module flow channel B31, the intermediate module flow channel B61, and the second module B71 are connected by standardized joints B5. Since the standardized joints B5 are all located in the same plane and have the same shape and size, it is convenient to connect different modules.

[0192] As shown in the drawings, Figure 6 In another embodiment of the present application, the third impregnation die is a strong turbulent impregnation die, which includes a third impregnation die head C300, and the third impregnation die head C300 includes an impregnation die outer body C2, a fiber inlet passage C3, an impregnation outlet C6, and a melt slit flow channel C1 are arranged on the impregnation die outer body C2, and the fiber inlet passage C3, the impregnation outlet C6, and the melt slit flow channel C1 are all connected to the die cavity inside the impregnation die outer body C2.

[0193] The second godet includes at least one driving godet C4, and the driving godet C4 is driven to rotate by a driving device (not shown in the drawings). Since the rotation of the driving godet C4 is driven by the driving device rather than being driven by the traction of the fiber, when the fiber passes through the driving godet C4, the driving godet C4 helps to reduce the traction tension of the fiber and the friction between the fiber and the driving godet C4, thereby reducing the breaking amount of the fiber, ensuring the integrity of the fiber, avoiding the fiber being pulled off, and improving the mechanical properties of the material. Preferably, the second godet further includes at least one driven godet C5, and the driven godet C5 is driven by the fiber passing through the driving godet C4; or the driven godet C5 is connected to the driving godet C4 through a belt mechanism, a gear mechanism, or a chain mechanism. Figure 6As shown, an example is shown with one active godet C4 and two driven godets C5, wherein the two driven godets C5 are arranged one above the other to extend the impregnation path of the fiber passing therethrough. The active godet C4 and the driven godets C5 can have the same height within the die cavity or different heights.

[0194] Further, the driving device can be an electric motor, a hydraulic mechanism or a reduction gearbox or the like capable of driving the active godet C4 to rotate.

[0195] According to the running speed vl of the fiber entering the die cavity of the impregnation die outer body C2, the tangential speed v2 of the corresponding active godet C4 can be selected, for example, to be the same as the running speed vl of the fiber, i.e. vl = v2, so as to reduce the breakage and abrasion of the fiber, thereby ensuring the integrity of the fiber and promoting the impregnation degree of the fiber, shortening the impregnation time and improving the production efficiency.

[0196] As shown in FIG. 1, the fiber pretreatment device 2 is arranged at the upstream of the impregnation die outer body C2, and the impregnation die outer body C2 is arranged at the downstream of the fiber pretreatment device 2. Figure 2 As shown in FIG. 2, the melt plasticizing feeding device 4 is composed of one twin-screw extruder for melt plasticizing the material. The twin-screw extruder is a co-rotating twin-screw extruder with a screw diameter of 25-95 mm and a length-diameter ratio of 36:1-65:1. When the melt plasticizing feeding device 4 is composed of one extruder 4, the melt plasticized melt in the extruder is divided by a melt distributor to enter the impregnation die and the forming die, respectively, and the melt flow control valve is used to control the flow of each.

[0197] As shown in FIG. 3, the melt plasticizing feeding device 4 is composed of two extruders 4-1 and 4-2 for melt plasticizing the material. The melt plasticized melt of each extruder is respectively introduced into the impregnation die and the forming die. Figure 3 As shown in FIG. 3, the melt plasticizing feeding device 4 is composed of two extruders 4-1 and 4-2 for melt plasticizing the material. The melt plasticized melt of each extruder is respectively introduced into the impregnation die and the forming die.

[0198] The fiber pretreatment device 2 is composed of a combination of a tension roller and a hot oven. This combination allows the tension on the fiber to be released when the fiber enters the hot oven, thereby adapting to different strengths of the fiber and avoiding breakage of the fiber with small strength before entering the impregnation die. The surface of the tension roller in the fiber pretreatment device 2 needs to be treated with ceramic plating to increase the surface roughness and reduce the friction on the fiber.

[0199] In the manufacturing system, the fiber frame and fiber guiding device 1 is used for the guiding and untwisting of the fiber, and the device is equipped with an automatic control untwisting device, which is connected with the traction machine 8 and is electrically connected with the electric control system (such as the PLC control device).

[0200] In the manufacturing system, the cooling water tank 6, the drying machine 7, the traction machine 8, the pelletizer 9 and the collection box 10 are conventional devices or apparatuses known to those skilled in the art, and will not be described here.

[0201] Figure 7 A schematic diagram of the second impregnation treatment using a forming die is shown, Figure 8 A cross-sectional view of the forming die used in the second impregnation treatment is shown.

[0202] As Figure 8 shown, in one embodiment, the forming die 5 is composed of a core 5-1, an outer sleeve 5-2 and an outer sleeve die plate 5-3. The core 5-1 is located inside the outer sleeve 5-2, forming a cavity with the outer sleeve 5-2, and the resin melt can enter the cavity from the bottom or top or both sides of the outer sleeve 5-2. The core 5-1 can move forward and backward in the outer sleeve 5-2, and the pressure of the melt in the cavity can be adjusted by adjusting the size of the cavity space formed. The pressure of the melt in the cavity can also be adjusted by the angle between the core 5-1 and the outer sleeve 5-2. The working principle of the forming die 5 is as follows: the strand formed after the impregnation die 3 forms the inner layer of the impregnated material, is guided through the hole in the middle of the core 5-1, and then realizes the forming of the inner and outer layer material composite structure in the cavity filled with mixed melt formed by the core 5-1 and the outer sleeve 5-2, and finally is guided out through the outer sleeve die plate 5-3.

[0203] As Figure 7 shown, the strand 5-4 enters the cavity formed by the core (not shown) and the outer sleeve 5-2 filled with the second component melt, wherein the second component melt is fed into the cavity from the second resin inlet 5-5.

[0204] In the following examples and comparative examples, the manufacturing system shown in Figure 3 is used to prepare the scratch-resistant thermoplastic composite material, wherein the first impregnation treatment uses the first impregnation die shown in Figure 4 , and the second impregnation treatment uses the forming die shown in Figure 8 .

[0205]

Example 1

[0206] (1) Take 50 parts by weight of dry PPB-M100-GH polypropylene resin (melt flow rate 100 g / 10 min), 3 parts by weight of BONDYRAM 1001, 0.1 part by weight of antioxidant 1010, 0.5 part by weight of XH-201, stir in a high-speed mixer at 50°C for 3 min to obtain a first component melt, and send it into a first impregnation mold.

[0207] (2) 30 parts by weight of glass fiber SE4805 enters the first impregnation mold under the action of a traction machine, where it is infiltrated and dispersed with the first component melt to form a strip, which is used as an inner layer material.

[0208] (3) Take 49 parts by weight of dry PPH-Y450 polypropylene resin (melt flow rate 450 g / 10 min), 2.5 parts by weight of BONDYRAM 1001, 1.03 parts by weight of MB50, 0.1 part by weight of antioxidant 1010, 0.5 part by weight of XH-201, stir in a high-speed mixer at 50°C for 3 min, use it as an outer layer material, and send it into a double-screw extruder connected to a molding mold to obtain a second component melt.

[0209] (4) The inner layer material enters the molding mold under the action of the traction machine, is guided through the hole in the middle of the core, and realizes the molding of the inner and outer layer material composite structure in the cavity filled with the second component melt formed by the core and the outer sleeve. Finally, it is guided out through the mold outlet.

[0210] (5) Adjust the amount of extrusion of the extruder for the outer layer material and the diameter of the die outlet of the mold to adjust the amount of coating of the outer layer material, so that it is coated according to the amount defined in step (3). Adjust the cutter speed of the granulator to control the length of the prepared scratch-resistant thermoplastic composite material to 61.1 mm. In the composite material, the proportion of glass fiber SE4805 is 22% by weight.

[0211] (6) The polypropylene composite material prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0212]

Example 2

[0213] (1) Take 20 parts by weight of self-made high-flow polypropylene (melt flow rate 1000 g / 10 min), 0.6 parts by weight of BONDYRAM 1001, 0.1 part by weight of antioxidant 1010, 0.5 part by weight of XH-201, stir in a high-speed mixer at 50°C for 3 min to obtain a first component melt, and send it into a first impregnation mold.

[0214] (2) 50 parts by weight of glass fiber SE4805 under the action of the traction machine enters the first impregnation mold, where it is infiltrated and dispersed with the melt to form a strip, which is used as the inner layer material.

[0215] (3) 59 parts by weight of dry PPH-T03 polypropylene resin (melt flow rate 3 g / 10 min), 3 parts by weight of BONDYRAM 1001, 0.61 parts by weight of MB50, 0.1 parts by weight of antioxidant 1010, 0.5 parts by weight of XH-201 are weighed, stirred in a high-speed mixer at 50°C for 3 min, used as the outer layer material, and fed into the double-screw extruder connected to the molding mold to obtain the second component melt.

[0216] (4) The inner layer material enters the molding mold under the action of the traction machine, is guided through the hole in the middle of the core, and realizes the molding of the inner and outer layer material composite structure in the cavity filled with the second component melt formed by the core and the outer sleeve. Finally, it is guided out through the mold outlet.

[0217] (5) The amount of outer layer material is adjusted by adjusting the amount of extrusion of the extruder for the outer layer material and the diameter of the die outlet of the mold. The amount of coating is adjusted to the amount defined in step (3), and the cutter speed of the granulator is adjusted to control the length of the prepared scratch-resistant thermoplastic composite material to 15 mm. In the composite material, the proportion of glass fiber SE4805 is 37% by weight.

[0218] (6) The polypropylene composite material prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0219]

Example 3

[0220] (1) 20 parts by weight of dry self-made high-flow polypropylene (melt flow rate 7500 g / 10 min), 0.6 parts by weight of BONDYRAM 1001, 0.1 parts by weight of antioxidant 1010, 0.5 parts by weight of XH-201 are weighed, stirred in a high-speed mixer at 50°C for 3 min to obtain a first component melt, and fed into a first impregnation mold.

[0221] (2) 80 parts by weight of glass fiber SE4805 under the action of the traction machine enters the first impregnation mold, where it is infiltrated and dispersed with the melt to form a strip, which is used as the inner layer material.

[0222] (3) Take 69 parts by weight of dry K8303 polypropylene resin (melt flow rate 1.5 g / 10 min), 3 parts by weight of BONDYRAM 1001, 2.2 parts by weight of MB50, 0.1 part by weight of antioxidant 1010, 0.5 part by weight of XH-201, stir in a high-speed mixer at 50°C for 3 min, take it as the outer layer material, and send it into the double screw extruder connected with the forming mold to obtain the second component melt.

[0223] (4) The inner layer material enters the forming mold under the action of the traction machine, is guided to pass through the hole in the middle of the core, and realizes the molding of the inner and outer layer material composite structure in the cavity filled with the second component melt formed by the core and the outer sleeve. Finally, it is guided out through the mold outlet.

[0224] (5) Adjust the amount of the outer layer material by adjusting the extrusion amount of the extruder for the outer layer material and the diameter of the die outlet of the mold, so that the amount of the outer layer material is coated according to the amount defined in step (3). Adjust the cutter rotating speed of the cutter granulator, so that the length of the prepared scratch-resistant thermoplastic composite material is controlled to be 18 mm. In the composite material, the proportion of glass fiber SE4805 is 45.4% by weight.

[0225] (6) The polypropylene composite material prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0226]

Example 4

[0227] (1) Take 70 parts by weight of dry PPB-M100-GH (melt flow rate 100 g / 10 min), 3 parts by weight of BONDYRAM 1001, 0.1 part by weight of antioxidant 1010, and 0.5 part by weight of XH-201, stir in a high-speed mixer at 50°C for 3 min to obtain a first component melt, and send it into a first impregnation mold.

[0228] (2) 25 parts by weight of glass fiber SE4805 enters the first impregnation mold under the action of the traction machine, is impregnated and dispersed with the melt there, and forms a strip, which is taken as the inner layer material.

[0229] (3) Take 69 parts by weight of dry K8303 polypropylene resin (melt flow rate 1.5 g / 10 min), 3 parts by weight of BONDYRAM 1001, 2.2 parts by weight of MB50, 0.1 part by weight of antioxidant 1010, 0.5 part by weight of XH-201, stir in a high-speed mixer at 50°C for 3 min, take it as the outer layer material, and send it into the double screw extruder connected with the forming mold to obtain the second component melt.

[0230] (4) The inner layer material is guided to pass through the hole in the middle of the core under the action of the traction machine, and realizes the molding of the composite structure of the inner and outer layer materials in the cavity formed by the core and the outer sleeve filled with the second component melt, and finally is guided out through the mold outlet.

[0231] (5) The amount of the outer layer material is adjusted by adjusting the amount of extrusion of the extruder for the outer layer material and the diameter of the die outlet of the mold, so that the outer layer material is coated according to the amount defined in step (3), and the cutter rotating speed of the cutter is adjusted, so that the length of the prepared scratch-resistant thermoplastic composite material is controlled to be 5 mm. In the composite material, the proportion of glass fiber SE4805 is 22.7% by weight.

[0232] (6) The polypropylene composite material prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0233]

Example 5

[0234] (1) 57 parts by weight of dry M60RHC polypropylene resin (melt flow rate 60 g / 10 min), 2.5 parts by weight of BONDYRAM 1001, 0.5 parts by weight of NDZ12, 0.1 parts by weight of antioxidant 168, and 0.25 parts by weight of XH-201 were weighed, stirred in a high-speed mixer at 50°C for 3 min to obtain a first component melt, and sent into a first impregnation mold.

[0235] (2) 40 parts by weight of glass fiber SE4805 was guided into the first impregnation mold under the action of the traction machine, and was impregnated and dispersed with the melt to form a strip, which was used as the inner layer material.

[0236] (3) 97 parts by weight of dry M50RH polypropylene resin (melt flow rate 50 g / 10 min), 4 parts by weight of BONDYRAM 1001, 2.04 parts by weight of SR100, 0.8 parts by weight of NDZ12, 0.1 parts by weight of antioxidant 168, and 0.8 parts by weight of XH-201 were weighed, stirred in a high-speed mixer at 50°C for 3 min, used as the outer layer material, and sent into a double-screw extruder connected with a molding mold to obtain a second component melt.

[0237] (4) The inner layer material is guided to pass through the hole in the middle of the core under the action of the traction machine, and realizes the molding of the composite structure of the inner and outer layer materials in the cavity formed by the core and the outer sleeve filled with the second component melt, and finally is guided out through the mold outlet.

[0238] (5) Adjust the amount of the outer layer material by adjusting the extrusion amount of the extruder for the outer layer material and the die head outlet diameter, so that the outer layer material is coated according to the amount defined in step (3), and adjust the cutter rotating speed of the cutter granulator, so that the length of the prepared scratch-resistant thermoplastic composite material is controlled to be 10 mm. In the composite material, the proportion of glass fiber SE4805 is 19.5% by weight.

[0239] (6) The polypropylene composite material prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0240]

Example 6

[0241] (1) Weigh 57 parts by weight of dry PA6-BL3200H, 3 parts by weight of CMG9805, 0.1 parts by weight of antioxidant 1010, and 0.5 parts by weight of XH-201, and stir in a high-speed mixer at 50°C for 3 min to obtain a first component melt, and then send it into the first impregnation mold.

[0242] (2) ER4301H enters the first impregnation mold under the action of the traction machine, and infiltrates and disperses with the first component melt to form a strip, which is used as the inner layer material.

[0243] (3) Weigh 97 parts by weight of dry PA6-BL3200H, 3 parts by weight of CMG9805, 0.1 parts by weight of antioxidant 1010, 2.04 parts by weight of MB50, and 0.5 parts by weight of XH-201, and stir in a high-speed mixer at 50°C for 3 min, and then send it into the double-screw extruder connected with the forming mold to obtain a second component melt.

[0244] (4) The inner layer material enters the forming mold under the action of the traction machine, is guided to pass through the hole in the middle of the core, and realizes the forming of the composite structure of the inner and outer layer materials in the cavity filled with the second component melt formed by the core and the outer sleeve, and finally is guided out through the mold outlet.

[0245] (5) Adjust the amount of the outer layer material by adjusting the extrusion amount of the extruder for the outer layer material and the die head outlet diameter, so that the outer layer material is coated according to the amount defined in step (3), and adjust the cutter rotating speed of the cutter granulator, so that the length of the prepared scratch-resistant thermoplastic composite material is controlled to be 12 mm. In the composite material, the proportion of ER4301H is 40% by weight.

[0246] (6) The long glass fiber reinforced PA6 composite material prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0247]

Example 7

[0248] (1) Take 57 parts by weight of dry PPB-M100-GH, 3 parts by weight of BONDYRAM 1001, 0.5 parts by weight of XHY-501, 0.1 parts by weight of antioxidant 1010, and 0.5 parts by weight of XH-201, and stir in a high-speed mixer at 50°C for 3 min to obtain a first component melt, and send it into a first impregnation mold.

[0249] (2) The continuous basalt fiber enters the first impregnation mold under the action of the traction machine, and is infiltrated and dispersed with the first component melt here to form a strip, which is used as an inner layer material.

[0250] (3) Take 97 parts by weight of dry PPB-M100-GH, 3 parts by weight of BONDYRAM 1001, 0.5 parts by weight of XHY-501, 0.1 parts by weight of antioxidant 1010, 2.04 parts by weight of MB50, and 0.5 parts by weight of XH-201, and stir in a high-speed mixer at 50°C for 3 min, which is used as an outer layer material, and is sent into a double-screw extruder connected with a forming mold to obtain a second component melt.

[0251] (4) The inner layer material enters the forming mold under the action of the traction machine, is guided to pass through the hole in the middle of the core, and realizes the forming of the composite structure of the inner and outer layer materials in the cavity filled with the second component melt formed by the core and the outer sleeve, and is finally guided out through the mold outlet.

[0252] (5) The amount of the outer layer material is adjusted by adjusting the amount of the extruder for the outer layer material and the diameter of the die outlet of the mold, so that it is coated according to the amount defined in step (3), and the cutter rotating speed of the granulator is adjusted to control the length of the prepared scratch-resistant thermoplastic composite material to 12 mm. In the composite material, the proportion of continuous basalt fiber is 40% by weight.

[0253] (6) The basalt fiber reinforced PP composite material prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0254]

Example 8

[0255] (1) Take 57 parts by weight of dry PPB-M100-GH, 3 parts by weight of BONDYRAM 1001, 0.5 parts by weight of XHY-501, 0.1 parts by weight of antioxidant 1010, and 0.5 parts by weight of XH-201, and stir in a high-speed mixer at 50°C for 3 min to obtain a first component melt, and send it into a first impregnation mold.

[0256] (2) The continuous basalt fiber enters the first impregnation mold under the action of the traction machine, and is infiltrated and dispersed with the first component melt here to form a strip, which is used as an inner layer material.

[0257] (3) Take 97 parts of dry PA6-BL3200H, 3 parts of BONDYRAM 1001, 0.5 parts of NDZ12, 0.1 parts of antioxidant 1010, 2.04 parts of MB50, and 0.5 parts of XH-201 by weight, stir them in a high-speed mixer at 50°C for 3 minutes, take them as the outer layer material, and send them into the double-screw extruder connected with the forming mold to obtain the second component melt.

[0258] (4) The inner layer material enters the forming mold under the action of the traction machine, is guided to pass through the hole in the middle of the core, and realizes the molding of the inner and outer layer material composite structure in the cavity formed by the core and the outer sleeve filled with the second component melt, and finally is guided out through the mold outlet.

[0259] (5) Adjust the amount of the outer layer material by adjusting the extrusion amount of the extruder for the outer layer material and the diameter of the die outlet of the mold, so that the outer layer material is coated according to the amount defined in step (3), and adjust the cutter speed of the cutter to control the length of the prepared scratch-resistant thermoplastic composite material to 12 mm. In the composite material, the proportion of continuous carbon fibers is 40% by weight.

[0260] (6) The long carbon fiber reinforced PA6 composite material prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0261]

Example 9

[0262] The preparation process is the same as that of Example 1, except that 70 parts of PPB-M100-GH by weight are taken in step (1), and 85 parts of PPH-Y450 by weight are taken in step (3). The prepared composite material is tested for performance, and the test results are shown in Table 1. In the composite material, the proportion of glass fiber SE4805 is 15.5% by weight.

[0263]

Example 10

[0264] The preparation process is the same as that of Example 1, except that 45 parts of PPB-M100-GH by weight, 2.5 parts of BONDYRAM 1001 by weight, 0.08 parts of antioxidant 1010 by weight, and 0.4 parts of XH-201 by weight are taken in step (1), and 65 parts of PPH-Y450 by weight are taken in step (3). The prepared composite material is tested for performance, and the test results are shown in Table 1. In the composite material, the proportion of glass fiber SE4805 is 20.2% by weight.

[0265]

Example 11

[0266] The preparation process of Example 1 is followed, except that in step (1), 25 parts by weight of PPB-M100-GH, 1.5 parts by weight of BONDYRAM 1001, 0.05 parts by weight of antioxidant 1010, and 0.25 parts by weight of XH-201 are weighed, and in step (3), 45 parts by weight of PPH-Y450 are weighed. The performance of the prepared composite material is tested, and the test results are shown in Table 1. In the composite material, the proportion of glass fiber SE4805 is 27.7% by weight.

[0267]

Example 12

[0268] The preparation process of Example 1 is followed, except that in step (1), 55 parts by weight of PPB-M100-GH are weighed, and in step (3), 70 parts by weight of PPH-Y450 are weighed. The performance of the prepared composite material is tested, and the test results are shown in Table 1. In the composite material, the proportion of glass fiber SE4805 is 18.3% by weight.

[0269]

Example 13

[0270] (1) 50 parts by weight of dry PPB-M100-GH polypropylene resin (melt flow rate 100 g / 10 min), 3 parts by weight of BONDYRAM 1001, 0.1 parts by weight of antioxidant 1010, and 0.5 parts by weight of XH-201 are weighed, stirred in a high-speed mixer at 50°C for 3 min to obtain a first component melt, and fed into a first impregnation mold.

[0271] (2) 30 parts by weight of glass fiber SE4805 is introduced into the first impregnation mold under the action of a traction machine, where it is infiltrated and dispersed with the first component melt to form a strip, which is used as an inner layer material.

[0272] (3) 49 parts by weight of dry M60RHC polypropylene resin (melt flow rate 60 g / 10 min), 20 parts by weight of short glass fibers cut from glass fiber SE4805 with a length of 3 mm, 2.5 parts by weight of BONDYRAM 1001, 0.1 parts by weight of antioxidant 1010, 1.03 parts by weight of MB50, and 0.5 parts by weight of XH-201 are weighed, stirred in a high-speed mixer at 50°C for 3 min, used as an outer layer material, and fed into a double-screw extruder connected to a molding mold to obtain a second component melt.

[0273] (4) The inner layer material is introduced into the molding mold under the action of the traction machine, guided through the hole in the middle of the core, and realizes the molding of the composite structure of the inner and outer layer materials in the cavity filled with the second component melt formed by the core and the outer sleeve, and finally guided out through the mold outlet.

[0274] (5) Adjust the amount of the outer layer material by adjusting the amount of extrusion of the extruder for the outer layer material and the diameter of the die head outlet, so that the outer layer material is coated in the amount defined in step (3), and adjust the cutter speed of the cutter granulator, so that the length of the granules of the prepared scratch-resistant thermoplastic composite material is controlled to be 6.1 mm. In the composite material, the proportion of glass fiber SE4805 is 32% by weight.

[0275] (6) The polypropylene composite material prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0276]

Example 1

[0277] (1) Weigh 57 parts by weight of dry PPB-M100-GH, 3 parts by weight of BONDYRAM 1001, 0.1 part by weight of antioxidant 1010, and 0.5 part by weight of XH-201, and stir them in a high-speed mixer at 50°C for 3 minutes to obtain a melt, and then send it into the impregnation mold.

[0278] (2) SE4805 enters the impregnation mold under the action of the traction machine, and is infiltrated and dispersed with the melt. The content of SE4805 in the composite material is adjusted by selecting the size (6 mm) of the sizing die plate of the impregnation mold, and the content of SE4805 is controlled to be 22% by weight. The cutter speed of the cutter granulator is adjusted, so that the length of the granules of the prepared polypropylene composite material is controlled to be 12 mm.

[0279] (3) The polypropylene composite material prepared by the above method is injection molded into a standard sample bar for performance testing. The test results are shown in Table 1.

[0280]

Example 2

[0281] (1) Weigh 50 parts by weight of dry PPB-M100-GH polypropylene resin (melt flow rate 100 g / 10 min), 30 parts by weight of short glass fibers cut from glass fiber SE4805 with a length of 3 mm, 3 parts by weight of BONDYRAM 1001, 0.1 part by weight of antioxidant 1010, and 0.5 part by weight of XH-201, and stir them in a high-speed mixer at 50°C for 3 minutes as an inner layer resin;

[0282] (2) Weigh 49 parts by weight of M60RHC polypropylene resin (melt flow rate 60 g / 10 min), 20 parts by weight of short glass fibers cut from glass fiber SE4805 with a length of 3 mm, 3 parts by weight of BONDYRAM 1001, 0.1 part by weight of antioxidant 1010, and 0.5 part by weight of XH-201, and stir them in a high-speed mixer at 50°C for 3 minutes as an outer layer material;

[0283] (3) respectively, the inner layer material is added to the No. 1 extruder, the outer layer material is added to the No. 2 extruder, the two extruders are extruded at the same time, and the continuous filament with the inner layer being the short glass fiber-containing resin layer and the outer layer being the short glass fiber-containing resin layer is obtained through the die extrusion of the two extruders with the inner and outer layer structure, and the continuous filament is cut into granules to obtain the raw material of the comparative example. The performance test is shown in Table 1.

[0284] Table 1

[0285]

[0286] Note: D1 and D2 in Table 1 are Comparative Example 1 and Comparative Example 2 respectively, and S1-S13 are Example 1-Example 13.

[0287] By comparing Comparative Examples 1-5 and 9-13 with Comparative Examples 1-2, it is concluded that the tensile strength, bending strength, notched Charpy impact strength and surface gloss of the long glass fiber reinforced polypropylene material prepared by the present application are obviously higher than those of the material prepared by Comparative Example 1, and the surface quality of the product is higher.

[0288] According to Examples 6-8 of the present application, it is known that the preparation method proposed by the present application is not only suitable for long glass fiber reinforced polypropylene composite material, but also suitable for the preparation of continuous glass fiber reinforced PA6, continuous basalt fiber reinforced polypropylene and continuous carbon fiber reinforced PA6 composite material.

[0289] Further, according to the data in Table 1, it can be seen that the thermoplastic composite material of the present application has good scratch resistance, and the melt flow rate of the thermoplastic resin selected as the inner layer material and the outer layer material can make the prepared composite material have ideal surface gloss.

[0290] The preparation method of the present application is simple to operate, can realize online continuous production, can ensure high production capacity and low energy consumption, and is suitable for industrial production and application.

[0291] The above is only the preferred example of the present application. It should be noted that for ordinary skilled persons in the art, under the technical inspiration provided by the present application, other equivalent variants and improvements as the common knowledge in the art can also be made, and should be regarded as the protection scope of the present application.

Claims

1. A scratch-resistant thermoplastic composite material, comprising an inner layer material and at least one outer layer material, wherein the inner layer material is a core layer comprising fiber bundles, a first thermoplastic resin, and a first additive, and the at least one outer layer material encapsulates the core layer and is a resin layer comprising a second thermoplastic resin and a second additive, wherein, The fiber bundle extends continuously from one end of the core layer to its opposite end, and the second additive includes a scratch-resistant additive. In the cross-section of the scratch-resistant thermoplastic composite material, from the inside out, there are a core layer and a resin layer, and the first thermoplastic resin and the second thermoplastic resin are of the same type. The melt flow rate of the first thermoplastic resin at 230°C and a load of 2.16 kg is 60-8000 g / 10 min. The melt flow rate of the second thermoplastic resin at 230°C and a load of 2.16 kg is 0.1-8000 g / 10 min; The melt flow rate of the first thermoplastic resin is higher than the melt flow rate of the second thermoplastic resin, or the melt flow rate of the second thermoplastic resin is higher than the melt flow rate of the first thermoplastic resin. In the inner layer material, the amount of the first thermoplastic resin is 1-90 parts by weight, and the amount of the fiber bundle is 10-110 parts by weight; in the outer layer material, the amount of the second thermoplastic resin is 1-110 parts by weight. Wherein, the second thermoplastic resin is 100 parts by weight, and the scratch-resistant additive is 1-6 parts by weight.

2. The scratch-resistant thermoplastic composite material according to claim 1, characterized in that, The scratch-resistant thermoplastic composite material is in the form of strips, rods, or granules.

3. The scratch-resistant thermoplastic composite material according to claim 2, characterized in that, The length of the scratch-resistant thermoplastic composite material is 5-30 mm.

4. The scratch-resistant thermoplastic composite material according to claim 2, characterized in that, The length of the scratch-resistant thermoplastic composite material is 5-25 mm.

5. The scratch-resistant thermoplastic composite material according to claim 2, characterized in that, The scratch-resistant thermoplastic composite material has a length of 6-15 mm.

6. The scratch-resistant thermoplastic composite material according to claim 1, characterized in that, In the inner layer material, the amount of the first thermoplastic resin is 20-70 parts by weight; the amount of the fiber bundle is 20-110 parts by weight; and / or, In the inner layer material, the weight ratio of the fiber bundle to the first thermoplastic resin is 0.25-6:1; and / or, In the outer layer material, the amount of the second thermoplastic resin is 10-99 parts by weight.

7. The scratch-resistant thermoplastic composite material according to claim 6, characterized in that, In the inner layer material, the amount of the first thermoplastic resin is 20-55 parts by weight; the amount of the fiber bundle is 25-110 parts by weight; and / or, In the inner layer material, the weight ratio of the fiber bundle to the first thermoplastic resin is 0.35-4.5:1; and / or, In the outer layer material, the amount of the second thermoplastic resin is 40-90 parts by weight.

8. The scratch-resistant thermoplastic composite material according to claim 6, characterized in that, In the inner layer material, the amount of the first thermoplastic resin is 24-45 parts by weight; and / or, In the inner layer material, the weight ratio of the fiber bundle to the first thermoplastic resin is 0.43-4.5:

1.

9. The scratch-resistant thermoplastic composite material according to claim 1, characterized in that, In the inner layer material, the amount of the first thermoplastic resin is 1-90 parts by weight; the amount of the fiber bundle is 10-99 parts by weight; or, In the inner layer material, the amount of the first thermoplastic resin is 50-70 parts by weight; the amount of the fiber bundle is 90-110 parts by weight; and / or in the outer layer material, the amount of the second thermoplastic resin is 90-110 parts by weight.

10. The scratch-resistant thermoplastic composite material according to claim 9, characterized in that, In the inner layer material, the amount of the first thermoplastic resin is 20-70 parts by weight; and / or the amount of the fiber bundle is 20-80 parts by weight; or, In the inner layer material, the amount of the first thermoplastic resin is 50-60 parts by weight; and / or the amount of the fiber bundle is 100-110 parts by weight; and / or in the outer layer material, the amount of the second thermoplastic resin is 95-105 parts by weight.

11. The scratch-resistant thermoplastic composite material according to claim 10, characterized in that, In the inner layer material, the amount of the first thermoplastic resin is 20-55 parts by weight; and / or the amount of the fiber bundle is 25-50 parts by weight.

12. The scratch-resistant thermoplastic composite material according to claim 11, characterized in that, In the inner layer material, the amount of the first thermoplastic resin is 24-45 parts by weight.

13. The scratch-resistant thermoplastic composite material according to any one of claims 1-12, characterized in that, The inner layer material does not contain non-oriented short fibers.

14. The scratch-resistant thermoplastic composite material according to any one of claims 1-12, characterized in that, The inner layer material is composed of fiber bundles, a first thermoplastic resin, and a first additive.

15. The scratch-resistant thermoplastic composite material according to any one of claims 1-12, characterized in that, The outer layer material does not contain fibers; or The outer layer material contains fibers.

16. The scratch-resistant thermoplastic composite material according to claim 15, characterized in that, The outer layer material is composed of a second thermoplastic resin and a second additive; or The outer layer material contains short fibers.

17. The scratch-resistant thermoplastic composite material according to claim 15, characterized in that, In the outer layer material, the weight ratio of the fiber to the second thermoplastic resin is 1-50:

100.

18. The scratch-resistant thermoplastic composite material according to claim 15, characterized in that, In the outer layer material, the weight ratio of the fiber to the second thermoplastic resin is 5-50:

100.

19. The scratch-resistant thermoplastic composite material according to claim 15, characterized in that, In the outer layer material, the weight ratio of the fiber to the second thermoplastic resin is 20-45:

100.

20. The scratch-resistant thermoplastic composite material according to any one of claims 1-12, characterized in that, The first thermoplastic resin and the second thermoplastic resin are selected from at least one of polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyacrylonitrile-butadiene-styrene copolymer, polyacrylonitrile-styrene copolymer, polyoxymethylene, polyamide, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, and their alloy polymers; and / or, The fiber bundle is selected from at least one of glass fiber, carbon fiber, stainless steel fiber, synthetic resin fiber, and mineral fiber.

21. The scratch-resistant thermoplastic composite material according to any one of claims 1-12, characterized in that, The first thermoplastic resin and the second thermoplastic resin are selected from at least one of polypropylene, polyethylene, polyamide, polyethylene terephthalate, and polybutylene terephthalate; and / or, The fiber bundle is selected from at least one of basalt fiber and aromatic polyamide fiber.

22. The scratch-resistant thermoplastic composite material according to any one of claims 1-12, characterized in that, The first thermoplastic resin and the second thermoplastic resin are selected from at least one of homopolymer polypropylene, copolymer polypropylene, a mixture of homopolymer polypropylene and copolymer polypropylene, nylon 6, nylon 66, and a mixture of nylon 6 and nylon 66.

23. The scratch-resistant thermoplastic composite material according to any one of claims 1-12, characterized in that, The melt flow rate of the first thermoplastic resin at 230°C and a load of 2.16 kg is 100-8000 g / 10 min; the melt flow rate of the second thermoplastic resin at 230°C and a load of 2.16 kg is 3-55 g / 10 min or 450-8000 g / 10 min. And / or, the weight ratio of the second thermoplastic resin to the first thermoplastic resin is 0.05-12.5:

1.

24. The scratch-resistant thermoplastic composite material according to claim 23, characterized in that, The melt flow rate of the first thermoplastic resin at 230°C and a load of 2.16 kg is 1000-7500 g / 10 min; the melt flow rate of the second thermoplastic resin at 230°C and a load of 2.16 kg is 3-45 g / 10 min or 1900-8000 g / 10 min. And / or, the weight ratio of the second thermoplastic resin to the first thermoplastic resin is 0.1-4:

1.

25. The scratch-resistant thermoplastic composite material according to claim 24, characterized in that, The melt flow rate of the first thermoplastic resin at 230°C and a load of 2.16 kg is 1900-7500 g / 10 min. And / or, the weight ratio of the second thermoplastic resin to the first thermoplastic resin is 0.14-3.5:

1.

26. The scratch-resistant thermoplastic composite material according to any one of claims 1-12, characterized in that, The first thermoplastic resin has a melt flow rate of 60-450 g / 10 min at 230°C and a load of 2.16 kg, and the second thermoplastic resin has a melt flow rate of 3-55 g / 10 min or 450-8000 g / 10 min at 230°C and a load of 2.16 kg; or The first thermoplastic resin has a melt flow rate of 450-8000 g / 10 min at 230°C and a load of 2.16 kg, and the second thermoplastic resin has a melt flow rate of 0.1 g / 10 min to less than 100 g / 10 min at 230°C and a load of 2.16 kg.

27. The scratch-resistant thermoplastic composite material according to claim 26, characterized in that, The melt flow rate of the first thermoplastic resin at 230°C and a load of 2.16 kg is 60-200 g / 10 min; or The first thermoplastic resin has a melt flow rate of greater than 450 g / 10 min to less than 8000 g / 10 min at 230°C and a load of 2.16 kg, and the second thermoplastic resin has a melt flow rate of 1.5-55 g / 10 min at 230°C and a load of 2.16 kg.

28. The scratch-resistant thermoplastic composite material according to claim 26, characterized in that, The first thermoplastic resin has a melt flow rate of 60-450 g / 10 min at 230°C and a load of 2.16 kg, and the second thermoplastic resin has a melt flow rate of 800-8000 g / 10 min at 230°C and a load of 2.16 kg; or The first thermoplastic resin has a melt flow rate of greater than 450 g / 10 min to less than 8000 g / 10 min at 230°C and a load of 2.16 kg, and the second thermoplastic resin has a melt flow rate of 3-50 g / 10 min at 230°C and a load of 2.16 kg.

29. The scratch-resistant thermoplastic composite material according to claim 23, characterized in that, When the melt flow rate of the second thermoplastic resin is 800-8000 g / 10 min at 230°C and a load of 2.16 kg, the weight ratio of the second thermoplastic resin to the first thermoplastic resin is 0.05:1 to less than 0.25:1; and / or, When the first thermoplastic resin and the second thermoplastic resin are selected from at least one of nylon 6, nylon 66, and a mixture of nylon 6 and nylon 66, the viscosity of nylon 6 and nylon 66 is 1.8-3.

5.

30. The scratch-resistant thermoplastic composite material according to claim 23, characterized in that, When the melt flow rate of the second thermoplastic resin is 800-8000 g / 10min at 230°C and a load of 2.16 kg, the weight ratio of the second thermoplastic resin to the first thermoplastic resin is 0.05:1 to less than 0.18:

1.

31. The scratch-resistant thermoplastic composite material according to claim 23, characterized in that, When the melt flow rate of the second thermoplastic resin is 800-8000 g / 10min at 230°C and a load of 2.16 kg, the weight ratio of the second thermoplastic resin to the first thermoplastic resin is 0.05:1 to less than 0.15:

1.

32. The scratch-resistant thermoplastic composite material according to any one of claims 1-12, characterized in that, The scratch-resistant additive is a silicone masterbatch; And / or, based on 100 parts by weight of the first thermoplastic resin and the second thermoplastic resin respectively, the first additive and the second additive each independently include at least one of 0.5-15 parts by weight of compatibilizer, 0.05-3 parts by weight of antioxidant and 0.05-2.5 parts by weight of lubricant.

33. The scratch-resistant thermoplastic composite material according to claim 32, characterized in that, With 100 parts by weight of the second thermoplastic resin, the amount of the scratch-resistant additive is 1-3.5 parts by weight; And / or, based on 100 parts by weight of the first thermoplastic resin and the second thermoplastic resin respectively, the first additive and the second additive each independently include 1-15 parts by weight of a compatibilizer. At least one of an antioxidant (0.1-1 parts by weight) and a lubricant (0.5-2.5 parts by weight); and / or, The compatibilizer is selected from at least one of polar monomer-grafted modified polymers; and / or, The antioxidant is selected from at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris[2,4-di-tert-butylphenyl] phosphite, octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and bis(2,4-di-tert-butylphenol) pentaerythritol diphosphite; and / or The lubricant is selected from at least one of ethylene bis-stearamide, calcium stearate, polyethylene wax, pentaerythritol stearate, silicone, polyethylene glycol, and fluorinated resins; and / or, The first additive further includes at least one of a slip agent, an antistatic agent, and a plasticizer; and / or, The second additive also includes at least one of slip agents, antistatic agents, plasticizers, nucleating agents, scratch-resistant additives, flame retardants, heat stabilizers, color masterbatches, and fillers.

34. The scratch-resistant thermoplastic composite material according to claim 33, characterized in that, Based on 100 parts by weight of the first thermoplastic resin and the second thermoplastic resin respectively, the first additive and the second additive each independently comprise at least one selected from 1-6 parts by weight of a compatibilizer, 0.1-0.5 parts by weight of an antioxidant, and 0.5-2.5 parts by weight of a lubricant; and / or, The polar monomer is selected from at least one of maleic anhydride, maleic anhydride derivatives, acrylic acid and acrylate derivatives; and / or the polymer is selected from at least one of polyethylene, polypropylene, ethylene-α-octene copolymer and propylene-α-olefin copolymer.

35. The scratch-resistant thermoplastic composite material according to claim 34, characterized in that, Based on 100 parts by weight of the first thermoplastic resin and the second thermoplastic resin respectively, the first additive and the second additive each independently include 3-6 parts by weight of compatibilizer.

36. A method for preparing the scratch-resistant thermoplastic composite material according to any one of claims 1-35, characterized in that, The method includes the following steps: Step A: The first thermoplastic resin and the first additive are mixed and melted to obtain the first component melt; Step B: The continuous fiber bundle is subjected to a first impregnation treatment with the first component melt to form a filamentous core layer product; Step C: The second thermoplastic resin and the second additive are mixed and melted to obtain the second component melt; Step D: The filamentous core layer product is subjected to a second impregnation treatment with the second component melt to form a resin layer that encapsulates the core layer.

37. The preparation method according to claim 36, characterized in that, The mixing conditions in step A include: a temperature of 40-60℃ and a time of 0.5-20 min; a melting temperature of 200-380℃ in step A; and / or, The mixing conditions in step C include: a temperature of 40-60℃ and a time of 0.5-20 min; the melting temperature in step C is 200-380℃.

38. The preparation method according to claim 37, characterized in that, The mixing conditions for step A include: a time of 1-10 minutes; and / or, The mixing conditions for step C include a time of 1-10 minutes.

39. The preparation method according to claim 37, characterized in that, The mixing conditions for step A include: a time of 3-5 minutes; and / or, The mixing conditions for step C include a time of 3-5 minutes.

40. The preparation method according to any one of claims 36-39, characterized in that, In step B, the first impregnation process is performed in a first impregnation mold. The first impregnation mold is an adjustable impregnation mold, which includes a fiber inlet, a fiber outlet, and a melt flow channel. At least one first guide roller is provided in the mold cavity of the first impregnation mold. The first guide roller is movable between the fiber inlet and the fiber outlet, and / or the first guide roller is movable along a direction perpendicular to the line connecting the fiber inlet and the fiber outlet.

41. The preparation method according to any one of claims 36-39, characterized in that, In step B, the first impregnation process is carried out in the second impregnation mold. The second impregnation mold is a combined impregnation mold, which includes a first module, an intermediate module, and a second module connected in sequence. The first module is provided with a fiber inlet and a first module flow channel. The second module is provided with a fiber outlet and a second module flow channel. The intermediate module is provided with an intermediate module flow channel. After the first module, the intermediate module, and the second module are connected in sequence, the first module flow channel, the intermediate module flow channel, and the second module flow channel are connected to form a combined flow channel for the fiber to pass through.

42. The preparation method according to any one of claims 36-39, characterized in that, In step B, the first impregnation process is carried out in a third impregnation mold, which is a strong turbulent impregnation mold. The third impregnation mold includes a fiber inlet channel, an impregnation outlet, and a melt gap channel. The fiber inlet channel, the impregnation outlet, and the melt gap channel are all connected to the mold cavity inside the third impregnation mold. A second guide roller is provided inside the mold cavity of the third impregnation mold. The second guide roller includes at least one active guide roller, which is driven to rotate by a driving device.

43. The application of a scratch-resistant thermoplastic composite material according to any one of claims 1-35 or a scratch-resistant thermoplastic composite material prepared by any one of claims 36-42 in the fields of automotive industry, machinery manufacturing, electronics and electrical appliances, chemical and environmental protection, aerospace and communications and construction industry.

44. The application according to claim 43, characterized in that, The application is in large automotive parts and / or high-precision electronic and electrical components.

45. The application according to claim 43, characterized in that, The application is in the automotive front-end module and / or the all-plastic tailgate inner panel.

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