Polyamide long glass fiber reinforced composite material and its manufacturing method

Abstract

To provide a polyamide glass long fiber-reinforced composite material, and a method for producing the same.SOLUTION: A composite material contains an impregnation material and a glass fiber material. The impregnation material contains a polyamide resin, a toughening agent, and a compatibilizer. The toughening agent is an elastomer which is composed of a first polyolefin material, and is modified with a maleic acid anhydride, the compatibilizer is a resin material which is composed of a second polyolefin material and is modified with a maleic acid anhydride. A first melt index of the toughening agent is lower than a second melt index of the compatibilizer. The glass fiber material is impregnated and covered with an impregnation material. The glass fiber material contains a glass long fiber modified with a hydroxyl group and / or a carboxyl group thereon.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a polymer composite material, and more particularly to a polyamide long glass fiber reinforced composite material and a method for producing the same. [Background technology]

[0002] The molecular structure of polyamide resin (nylon plastic) contains many hydrophilic amide groups, but polyamide resin has poor mechanical properties such as toughness and abrasion resistance, so its applications are limited. In response to this, polyamide resin is sometimes modified industrially using processes such as copolymerization, blend reinforcement, and reinforcement. The glass fiber reinforcement process is often used to modify polyamide resin, and can effectively increase the abrasion resistance, mechanical properties, hardness, and dimensional stability of polyamide resin.

[0003] As the length of the glass fiber increases, the effect of the glass fiber in reinforcing the polyamide resin is greatly improved. The impact strength of the long glass fiber reinforced material can be doubled compared with that of the short glass fiber. The polyamide long glass fiber reinforced composite material has the advantages of high strength, high rigidity, high notch impact strength, short-term heat resistance and fatigue resistance, and the polyamide long glass fiber reinforced composite material maintains excellent mechanical properties even in high temperature and high humidity environments, and can replace metal as a structural material.

[0004] However, the toughness of the polyamide long glass fiber reinforced composite materials of the prior art is still poor, and there is room for improvement due to the poor impregnation effect of the polyamide resin on the long glass fiber during the production process. Summary of the Invention [Problem to be solved by the invention]

[0005] The technical problem to be solved by the present invention is to provide a polyamide long glass fiber reinforced composite material and a manufacturing method thereof in response to the shortcomings of the prior art. [Means for solving the problem]

[0006] In order to solve the above technical problems, one technical means adopted by the present invention provides a method for producing a long polyamide glass fiber reinforced composite material, which includes a supplying step of feeding raw materials to an extruder to mix and melt them to form a mixed plastic melt, an impregnation step of feeding the mixed plastic melt to an impregnation device to feed continuous long glass fibers to the impregnation device to sufficiently impregnate the long glass fibers with the mixed plastic melt, and the surfaces of the long glass fibers are modified with hydroxyl groups and / or carboxyl groups, and a molding step of molding, cooling and granulating the long glass fibers impregnated with the mixed plastic melt to obtain a long polyamide glass fiber reinforced composite material. The raw materials include a polyamide resin, a toughening agent, and a compatibilizer, the toughening agent being an elastomer comprised of a first polyolefin material and modified with maleic anhydride, the compatibilizer being a resin material comprised of a second polyolefin material and modified with maleic anhydride, and the first melt index of the toughening agent being lower than the second melt index of the compatibilizer.

[0007] Preferably, the extruder is a twin-screw extruder, the processing temperature of the extruder is 250° C.-400° C., and the screw speed is 200 rpm-300 rpm.

[0008] Preferably, the first polyolefin material constituting the toughening agent is at least one selected from the group consisting of ethylene propylene diene rubber (EPDM), thermoplastic polyolefin (TPO), polyolefin elastomer (POE), and ethylene-methyl acrylate-glycidyl methacrylate terpolymer (E-MA-GMA).

[0009] Preferably, the graft ratio of the first maleic anhydride of the toughening agent is 0.3% to 1.5%, and the first melt index of the toughening agent is 1 g / 10 min to 20 g / 10 min.

[0010] Preferably, the second polyolefin material constituting the compatibilizer is at least one selected from the group consisting of polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymer.

[0011] Preferably, the graft ratio of the second maleic anhydride of the compatibilizer is 0.3% to 1.5%, and the second melt index of the compatibilizer is 100 to 600 g / 10 min.

[0012] Preferably, when the toughener and the compatibilizer are mixed and melted with the polyamide resin in the extruder, an active acid anhydride group of the modified maleic anhydride of the toughener and / or the compatibilizer reacts with an amino group at the end of a polymer chain of the polyamide resin to form an amide bond first, and then an imide bond is formed after a ring-closing reaction, thereby forming a graft copolymer.

[0013] Preferably, the raw material further comprises a flow modifier which is a polyolefin hyperdispersant having a number average molecular weight of 1000 g / mol to 10,000 g / mol.

[0014] Preferably, in the impregnation step, the long glass fibers are supplied to a stretching device via a bobbin device, and after undergoing a preheating operation and a stretching operation, are introduced into the impregnation device, whereby the long glass fibers are impregnated with the mixed plastic melt in a preheated and stretched state.

[0015] Preferably, the long glass fibers impregnated with the mixed plastic melt are bundled and covered by a die head of the impregnation device, and are discharged from the impregnation device, and the long glass fibers are glass fibers having a length of 5 mm to 30 mm.

[0016] In order to solve the above technical problems, another technical means adopted by the present invention provides a polyamide long glass fiber reinforced composite material. The polyamide long glass fiber reinforced composite material includes an impregnating material and a glass fiber material. The impregnating material includes a polyamide resin, a toughening agent and a compatibilizer, the toughening agent is an elastomer composed of a first polyolefin material and modified with maleic anhydride, the compatibilizer is a resin material composed of a second polyolefin material and modified with maleic anhydride, and the first melt index of the toughening agent is lower than the second melt index of the compatibilizer. The glass fiber material is impregnated and covered with the impregnating material, and the glass fiber material includes long glass fibers modified on the surface with hydroxyl groups and / or carboxyl groups.

[0017] Preferably, the first polyolefin material for constituting the toughening agent is at least one selected from the group consisting of ethylene propylene diene rubber (EPDM), thermoplastic polyolefin (TPO), polyolefin elastomer (POE), and ethylene-methyl acrylate-glycidyl methacrylate terpolymer (E-MA-GMA). The graft ratio of the first maleic anhydride of the toughening agent is 0.3% to 1.5%, and the first melt index of the toughening agent is 1g / 10min to 20g / 10min.

[0018] Preferably, the second polyolefin material for constituting the compatibilizer is at least one selected from the group consisting of polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymer. The graft ratio of the second maleic anhydride of the compatibilizer is 0.3% to 1.5%, and the second melt index of the compatibilizer is 100g / 10min to 600g / 10min.

[0019] Preferably, the impregnating material further comprises a flow modifier which is a polyolefin hyperdispersant having a number average molecular weight of 1000 g / mol to 10,000 g / mol.

[0020] Preferably, the total weight of all materials in the impregnating material is 100 parts by weight, and the content of the polyamide resin is 50 parts by weight to 97 parts by weight, the content of the toughening agent is 0.1 parts by weight to 20 parts by weight, the content of the compatibilizer is 0.1 parts by weight to 20 parts by weight, and the content of the flowability modifier is 10 parts by weight or less.

[0021] Preferably, the weight ratio of the glass fiber material to the impregnating material (glass fiber material: impregnating material) is 5:95 to 65:35. Effect of the Invention

[0022] The advantageous effects of the present invention are that the long glass fiber reinforced polyamide composite material and its manufacturing method according to the present invention have the following technical features: "the toughener is an elastomer made of a first polyolefin material and modified with maleic anhydride, the compatibilizer is a resin material made of a second polyolefin material and modified with maleic anhydride, and the first melt index of the toughener is lower than the second melt index of the compatibilizer" and "the long glass fiber material is sufficiently impregnated and covered with an impregnation material, and the surface of the long glass fiber material is modified with hydroxyl groups and / or carboxyl groups". This improves the toughness of polyamide (nylon plastic) and solves the problem of poor impregnation effect in the process. [Brief description of the drawings]

[0023] [Figure 1] 1 is a flowchart of a method for producing a long polyamide glass fiber reinforced composite material according to an embodiment of the present invention. [Diagram 2] FIG. 1 is a schematic diagram of an apparatus for producing a long polyamide glass fiber reinforced composite material according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] In order to better understand the features and technical contents of the present invention, please refer to the following detailed description of the present invention and the accompanying drawings, which are provided for reference and explanation only and are not intended to limit the scope of the present invention.

[0025] Hereinafter, the present invention will be described in terms of certain specific embodiments, and those skilled in the art can understand the advantages and effects of the present invention based on the contents disclosed in this specification. The present invention can be implemented or applied in other different specific embodiments, and each detail in this specification can be modified and changed in various ways based on different perspectives and applications, without departing from the concept of the present invention.

[0026] In addition, as described above, the accompanying drawings of the present invention are for simple schematic illustrations and are not drawn based on actual size. The technical contents of the present invention will be described in more detail based on the following embodiments, but the scope of protection of the present invention is not limited by the disclosed contents.

[0027] It should be understood that although the present specification may use terms such as "first," "second," and "third" to describe various elements or signals, these elements or signals are not limited by these terms, but are primarily used to distinguish one element from another element or one signal from another signal.

[0028] Furthermore, the term "or" as used herein may include any one or more combinations of the associated listed items, depending on the actual circumstances.

[0029] [Method of manufacturing reinforced composite materials] As shown in Figures 1 and 2, in an embodiment of the present invention, a method for producing a polyamide long glass fiber reinforced composite material is provided, which includes steps S110 to S130. It should be noted that the order and operation method of each step in this embodiment can be adjusted according to needs and are not limited thereto. In the production method according to the present invention, other operations may be provided before, between, or after each step, and some of the operations described can also be replaced, deleted, or rearranged to carry out the production method.

[0030] The step S110 includes a feeding step of feeding the raw material RM to an extruder 1 to mix and melt the raw material RM to form a mixed plastic melt. Here, the raw material RM includes at least a polyamide resin (PA resin), a toughener, a compatibilizer, and a flow modifier. The toughener can be introduced into the polyamide resin to improve the toughness of the plastic. Also, the compatibility between the toughener and the polyamide resin can be improved by introducing the compatibilizer and the flow modifier. The raw material RM may further include an antioxidant, a lubricant, and a colorant.

[0031] In one embodiment of the present invention, the extruder 1 may be, for example, a twin screw extruder. In order to melt the polymer material in the raw material RM, the processing temperature of the extruder 1 is, for example, 250°C to 400°C, and preferably 250°C to 350°C. It should be noted that the processing temperature is the temperature control of each element (e.g., the feed section, compression section, melting section, metering section, head, mold) in the extruder 1, and the temperature control of each element may be the same or different from each other, and the present invention is not limited thereto.

[0032] The screw speed of the extruder 1 is controlled to 200 to 300 revolutions per minute (rpm), and preferably 240 to 260 revolutions per minute, although the present invention is not limited thereto.

[0033] In the raw material RM, the polyamide resin may be called a nylon resin, which is formed by polymerization of a carboxyl-containing monomer and an amino-containing monomer through an amide bond.

[0034] The toughening agent is an elastomer made of a first polyolefin material, and the first polyolefin material is at least one selected from the group consisting of ethylene propylene diene monomer rubber (EPDM), thermoplastic polyolefin (TPO), polyolefin elastomer (POE), and ethylene-methyl acrylate-glycidyl methacrylate terpolymer (E-MA-GMA).

[0035] Here, the ethylene propylene diene rubber (EPDM) is an elastomer and belongs to synthetic rubber. EPDM is a copolymer of ethylene and propylene, or a terpolymer of ethylene, propylene and a small amount of a third monomer (e.g., diene). Here, the thermoplastic polyolefin (TPO) is an elastomer. TPO is a mixture of ethylene propylene rubber (EPM) or ethylene propylene diene rubber (EPDM) with an olefin material such as polyethylene (PE) and / or polypropylene (PP), that is, TPO belongs to a rubber-plastic blend. Here, the polyolefin elastomer (POE) is an elastomer. POE is a material based on ethylene and / or polypropylene. To be more specific, POE is a polymer synthesized by introducing a monomer such as 1-butene or 1-octene in the process of polymerizing ethylene and / or polypropylene, and its structure is similar to that of ethylene propylene diene rubber (EPDM).

[0036] The four materials (EPDM, TPO, POE, E-MA-GMA) are similar in chemical structure or properties, but slightly different in definition. Those skilled in the art will understand that the four materials are not in a superior or inferior relationship to each other, but belong to the same rank of materials. In addition, elastomers in this specification are polymers with viscoelasticity, and have a relatively low Young's modulus and a relatively high breaking strain.

[0037] More specifically, in this embodiment, the toughening agent is preferably a material modified with maleic anhydride (MAH). Here, the maleic anhydride may be, for example, grafted onto the toughening agent (the elastomer composed of the first polyolefin material). More specifically, the maleic anhydride may be, for example, melt-grafted onto the toughening agent. The melt-grafting may be, for example, performed in a single screw extruder, a twin screw extruder, or a rheometer. Preferably, the melt-grafting is performed in a twin screw extruder.

[0038] In one embodiment of the present invention, the grafting ratio of the first maleic anhydride to the maleic anhydride toughening agent is preferably 0.3% to 1.5%, and particularly preferably 0.5% to 1.3%.

[0039] It should be noted that the "grafting rate of maleic anhydride" in this specification can be analyzed, for example, by a Fourier transform infrared spectrometer (FTIR). The Fourier transform infrared spectrometer can perform a qualitative analysis of whether maleic anhydride is grafted to the molecular chain of a polyolefin material, and can also quantify the grafting rate of maleic anhydride. According to the infrared absorption spectrum, maleic anhydride grafts can be detected at 1780 cm -1 , 1830cm -1 The maleic anhydride has a significant absorption peak at 1000 nm, which is a characteristic peak of the carboxyl group in the maleic anhydride. The quantitative analysis of the graft ratio of the maleic anhydride can be performed based on, for example, the Beer-Lambert law.

[0040] More specifically, in one embodiment of the present invention, the toughening agent has a first melt index, which is preferably 1 g / 10 min to 20 g / 10 min, and particularly preferably 3 / 10 min to 15 g / 10 min.

[0041] It should be noted that the melt index in this specification is the weight of a polyolefin material extruded from an opening of an extrusion plastometer in 10 minutes. The unit is g / 10 min. The melt index indicates the fluidity in a molten state. The higher the melt index, the lower the number average molecular weight and the better the fluidity. Conversely, the lower the melt index, the higher the number average molecular weight and the worse the fluidity. In this embodiment, the melt index is measured at 230°C and a load of 2.16 kg based on ASTM D1238.

[0042] The compatibilizer is a resin material composed of a second polyolefin material. The second polyolefin material may be at least one selected from the group consisting of polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymer. The compatibilizer is also a polyolefin material modified with maleic anhydride (MAH). For example, the compatibilizer may be polyethylene modified with maleic anhydride, polypropylene modified with maleic anhydride, or ethylene-propylene copolymer modified with maleic anhydride. It is noteworthy that the compatibilizer is a polyolefin material that is not an elastomer. In a molten state, the compatibilizer has a higher fluidity (melt index) than the toughening agent. In one embodiment of the present invention, the second grafting ratio of the maleic anhydride to the compatibilizer is preferably 0.3% to 1.5%, and particularly preferably 0.5% to 1.3%.

[0043] The compatibilizer has a second melt index, which is preferably 100 g / 10 min to 600 g / 10 min, and particularly preferably 200 g / 10 min to 500 g / 10 min.

[0044] The method for grafting maleic anhydride onto a polyolefin material has been described in the preceding detailed description of the invention, and the definitions of the graft ratio and melt index have been described in the preceding detailed description of the invention, so that they will not be described here again.

[0045] It is worth noting that in an embodiment of the present invention, the toughener is a material modified with maleic anhydride, and the compatibilizer is also a material modified with maleic anhydride. Thus, when the toughener and the compatibilizer are mixed and melted with a polyamide resin (PA resin), the organic acid anhydride grafted to the toughener and the organic acid anhydride grafted to the compatibilizer react with the amino functional group at the end of the polymer chain of the polyamide resin to form an amide bond (-NH-CO-, amide bond), and then after a ring-closing reaction, an imide bond (-N-(C=O)2, imide bond) is formed to form a graft copolymer, i.e., the toughener and / or compatibilizer are grafted to the polyamide resin (toughener / compatibilizer-g-PA).

[0046] As a result, the graft copolymer at the phase interfaces increases the bonding strength between the phase interfaces through covalent bonds, expanding the dispersion range of the dispersed phase (toughener and compatibilizer) in the continuous phase and effectively improving the properties of the graft copolymer (e.g., toughness, low-temperature impact resistance).

[0047] More specifically, the flow modifier is a hyperdispersant (polymer dispersant), which is a highly efficient polymer dispersant having a number average molecular weight of 1,000 to 10,000. More specifically, the flow modifier is a polyolefin hyperdispersant. In one embodiment of the present invention, the flow modifier is Solplus TM Solplus is a superdispersant. TM A hyperdispersant is a 100% active polymeric dispersant that can improve the dispersion and stability of fillers in thermoplastics, although the invention is not limited thereto.

[0048] The introduction of the flow modifier can improve the problem of insufficient flowability of the polyolefin material in the molten state, so that the mixed plastic melt can have a better impregnation effect on the glass fiber material.

[0049] The antioxidant is an antioxidant used for polyamide resin. The antioxidant may be, for example, at least one selected from the group consisting of tetrakis(3,5-di-tert-butyl-4-hydroxy)pentaerythritol phenylpropionate, tris(2,4-di-tert-butyl)phenyl phosphite, and n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. Preferably, it is tetrakis(3,5-di-tert-butyl-4-hydroxy)pentaerythritol phenylpropionate. The lubricant is a lubricant used for polyamide resin. The lubricant may be, for example, at least one selected from the group consisting of vinyl bisstearamide, erucamide, polyethylene wax, paraffin, stearic acid, zinc stearate, and calcium stearate. Preferably, it is vinyl bisstearamide. The colorant is one that imparts color to the polymer material. The colorant may be at least one selected from the group consisting of titanium dioxide, carbon black, and other inorganic or organic colorants, and is preferably titanium dioxide. The antioxidant, lubricant, and colorant are well-known techniques, and will not be described here.

[0050] Regarding the range of the amount used, the content of the polyamide resin is preferably 50 parts by weight to 97 parts by weight, and particularly preferably 75 parts by weight to 96 parts by weight, with the total weight of the raw material RM being 100 parts by weight. The content of the toughening agent is preferably 0.1 parts by weight to 20 parts by weight, and particularly preferably 4 parts by weight to 20 parts by weight. The content of the compatibilizer is preferably 0.1 parts by weight to 20 parts by weight, and particularly preferably 3 parts by weight to 15 parts by weight. The content of the flowability modifier is preferably 10 parts by weight or less, and particularly preferably 2.0 parts by weight to 5.0 parts by weight. The content of the antioxidant is preferably 0.1 parts by weight to 3.0 parts by weight, and particularly preferably 0.1 parts by weight to 1.5 parts by weight. The content of the lubricant is preferably 0.01 parts by weight to 3.0 parts by weight, and particularly preferably 0.01 parts by weight to 1.5 parts by weight. The content of the colorant is preferably 0.5 to 5.0 parts by weight, and particularly preferably 1.0 to 2.0 parts by weight.

[0051] The step S120 includes an impregnation step in which the mixed plastic melt formed in the step S110 is fed to an impregnation device 2, and continuous long glass fibers GF are fed to the impregnation device 2 to sufficiently impregnate the long glass fibers GF with the mixed plastic melt, and then the long glass fibers GF impregnated with the mixed plastic melt are discharged from the impregnation device 2.

[0052] More specifically, the long glass fiber GF is supplied to a spreading device 4 through a bobbin device 3, and the long glass fiber GF is preheated (the preheating temperature is 110°C to 130°C) and spread, and then introduced into the impregnation device 2, whereby the long glass fiber GF is impregnated with the mixed plastic melt in a preheated and spread state. After the impregnation operation is completed, the long glass fiber GF impregnated with the mixed plastic melt is bundled and covered by a trumpet-shaped die head of the impregnation device 2, and is led out of the impregnation device. It should be noted that the long glass fiber is preferably a glass fiber having a length of 5 millimeters (mm) to 30 mm, and particularly preferably 6 mm to 25 mm.

[0053] In one embodiment of the present invention, the weight ratio of the long glass fiber GF to the mixed plastic melt (glass fiber material:mixed plastic melt) is 5:95 to 65:35, and preferably 40:60 to 60:40, so that the long glass fiber GF has a better impregnation effect.

[0054] Also, the surface of the long glass fiber GF is preferably modified with functional groups such as hydroxyl groups (-OH) and / or carboxyl groups (-COOH). For example, the surface of the long glass fiber GF is treated with a silane coupling agent to provide the functional groups, but the present invention is not limited thereto. Thus, when the long glass fiber GF is impregnated with the mixed plastic melt, the maleic anhydride-modified toughener and the maleic anhydride-modified compatibilizer in the mixed plastic melt react with the hydroxyl groups and / or carboxyl groups on the surface of the long glass fiber GF to improve the degree of impregnation of the long glass fiber GF with the mixed plastic melt.

[0055] It is worth noting that if the toughening agent or compatibilizer is not modified with maleic anhydride, materials such as EPDM, TPO, POE, PP, and PE have poor compatibility with PA, resulting in two-phase separation. Furthermore, when a toughening agent or compatibilizer that is not modified with maleic anhydride is mixed with glass fiber, the glass fiber may break at the die head of the impregnation device, and the fiber may clog the extrusion port of the impregnation device.

[0056] The step S130 includes a shaping step in which the long glass fibers GF impregnated with the mixed plastic melt are shaped and cooled (the cooling temperature is 15°C to 35°C) through a molding device 5. The shaping step further includes guiding the long glass fibers GF through a guide device 6 to a granulator 7 for granulation, thereby obtaining a product P of a granulated polyamide long glass fiber reinforced composite material.

[0057] [Polyamide long glass fiber reinforced composite material] In the above-mentioned embodiment, the method for producing a long polyamide glass fiber reinforced composite material has been described in detail. In the embodiment of the present invention, a long polyamide glass fiber reinforced composite material is also provided. The long polyamide glass fiber reinforced composite material can be produced by the above-mentioned production method, but the present invention is not limited thereto.

[0058] Specifically, the polyamide long glass fiber reinforced composite material includes an impregnating material and a glass fiber material covered with the impregnating material.

[0059] The impregnating material includes a polyamide resin, a toughening agent, a compatibilizer, a flow modifier, an antioxidant, a lubricant, and a colorant, that is, the composition of the impregnating material corresponds to the raw material RM in the manufacturing method.

[0060] The polyamide resin may be, for example, a nylon resin. The toughening agent is an elastomer composed of a first polyolefin material. The toughening agent is at least one selected from the group consisting of ethylene propylene diene rubber (EPDM), thermoplastic olefin (TPO), polyolefin elastomer (POE), and ethylene-methyl acrylate-glycidyl methacrylate terpolymer (E-MA-GMA).

[0061] To explain further, in this embodiment, the toughening agent is preferably a material modified with maleic anhydride (MAH). Here, the maleic anhydride may be grafted to the toughening agent (elastomer composed of polyolefin material), for example. In one embodiment of the present invention, the graft ratio of the first maleic anhydride in the toughening agent of the maleic anhydride is preferably 0.3% to 1.5%, and particularly preferably 0.5% to 1.3%. The toughening agent has a first melt index. The first melt index is preferably 1g / 10min to 20g / 10min, and particularly preferably 3 / 10min to 15g / 10min.

[0062] The compatibilizer is a resin material composed of a second polyolefin material. The second polyolefin material is at least one selected from the group consisting of polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymer. The compatibilizer is also a material modified with maleic anhydride. In one embodiment of the present invention, the graft ratio of the second maleic anhydride in the maleic anhydride compatibilizer is preferably 0.3% to 1.5%, and particularly preferably 0.5% to 1.3%. The compatibilizer has a second melt index. The second melt index is preferably 100g / 10min to 600g / 10min, and particularly preferably 200g / 10min to 500g / 10min.

[0063] The flow modifier is a hyperdispersant (polymer dispersant) and is a highly efficient polymer dispersant having a number average molecular weight of 1,000 to 10,000. More specifically, the flow modifier is a polyolefin hyperdispersant. In one embodiment of the present invention, the flow modifier is Solplus TM Although a hyperdispersant, the invention is not limited thereto.

[0064] The characteristics of the antioxidant, lubricant, and colorant have already been described in the above-mentioned embodiment of the manufacturing method, so they will not be described here again.

[0065] Regarding the range of the amount used, the total weight of all materials in the impregnated material (corresponding to the raw material RM) is 100 parts by weight, and the content of the polyamide resin is preferably 50 parts by weight to 97 parts by weight, and particularly preferably 75 parts by weight to 96 parts by weight. The content of the toughening agent is preferably 0.1 parts by weight to 20 parts by weight, and particularly preferably 4 parts by weight to 20 parts by weight. The content of the compatibilizer is preferably 0.1 parts by weight to 20 parts by weight, and particularly preferably 3 parts by weight to 15 parts by weight. The content of the flowability modifier is preferably 10 parts by weight or less, and particularly preferably 2.0 parts by weight to 5.0 parts by weight. The content of the antioxidant is preferably 0.1 parts by weight to 3.0 parts by weight, and particularly preferably 0.1 parts by weight to 1.5 parts by weight. The content of the lubricant is preferably 0.01 parts by weight to 3.0 parts by weight, and particularly preferably 0.1 parts by weight to 1.5 parts by weight. The content of the colorant is preferably 0.5 to 5.0 parts by weight, and particularly preferably 1.0 to 2.0 parts by weight.

[0066] More specifically, the glass fiber material is made of long glass fibers, and the length of the long glass fibers is preferably 5 millimeters (mm) to 30 mm, and particularly preferably 6 mm to 25 mm.

[0067] In one embodiment of the present invention, the weight ratio of the glass fiber material (long glass fiber) to the impregnating material (glass fiber material: impregnating material) is 5:95 to 65:35, and preferably 40:60 to 60:40. The surface of the long glass fiber is preferably modified with a functional group such as a hydroxyl group (-OH) and / or a carboxyl group (-COOH). This allows the long glass fiber to have a better impregnation effect.

[0068] Regarding technical effects, the technical method according to the embodiment of the present invention involves preheating and extending glass fibers, mixing polyamide resin (also called nylon plastic) with polymer modifiers such as tougheners, compatibilizers and flow modifiers, and then melt-plasticizing the mixture through an extruder. The melt is then fed into an impregnation device to impregnate the glass fibers.

[0069] The technical method according to the embodiment of the present invention can produce a long glass fiber reinforced composite material by controlling the melt viscosity of the mixed plastic melt by the modifier to a range suitable for impregnation of the long glass fiber, and impregnating the fiber in an impregnation device. The technical method according to the embodiment of the present invention can effectively solve the problem that the polyamide resin is difficult to impregnate into the glass fiber by introducing the toughening agent, the compatibilizer, and the flowability modifier.

[0070] To explain further, in the embodiment of the present invention, by using an elastomer such as EPDM, TPO or POE, the toughness of the polyamide resin can be improved, and in particular, the toughness under low temperature conditions (e.g., low-temperature impact strength) can be improved.

[0071] By grafting the above-mentioned elastomers onto maleic anhydride, the low temperature impact resistance of the elastomers can be imparted to the polyamide resins. In an embodiment of the present invention, the introduction of a flow modifier (active solid polymer dispersant) can improve the dispersion and stability of discontinuous phases (e.g., tougheners, lubricants, colorants) in thermoplastics.

[0072] To explain further, in order to improve the toughness of the entire polyamide glass fiber reinforced composite material, the embodiment of the present invention mainly adds a maleic anhydride (MAH) grafted toughener (EPDM, TPO, POE, E-MA-GMA) and a compatibilizer (PP, PE, PP / PE) grafted with maleic anhydride (MAH) to a polyamide resin to form a polyamide glass fiber reinforced composite material. It is also noteworthy that in the embodiment of the present invention, the graft ratio of the first maleic anhydride in the toughener is preferably 0.3% to 1.5%. The graft ratio of the second maleic anhydride in the compatibilizer is preferably 0.3% to 1.5%. The technical effect of controlling the graft ratio of maleic anhydride within the above range is to improve the compatibility between different resin materials and the adhesion between the resin material and glass fiber. If the graft rate of maleic anhydride is less than 0.3%, the compatibility between different resin materials is poor, and phase separation is easily caused, resulting in poor physical properties of the final product. If the graft rate of maleic anhydride is more than 1.5%, the manufacturing cost is too high. More specifically, the first melt index of the toughening agent is 1g / 10min to 20g / 10min. The technical effect is that the toughening agent effectively improves the toughness of the composite material in the melt index range. If the first melt index is less than 1g / 10min, the fluidity of the mixed plastic melt is too low and extrusion processing cannot be performed. If the first melt index is more than 20g / 10min, the toughening effect of the toughening agent cannot be exerted. The second melt index of the compatibilizer is 100g / 10min to 600g / 10min. The technical effect is that the compatibilizer improves the dispersibility of the toughening agent in the polyamide resin. If the second melt index is less than 100 g / 10 min, the dispersibility of the toughening agent in the polyamide resin deteriorates, whereas if the second melt index is more than 600 g / 10 min, the compatibility effect cannot be significantly improved.

[0073] Due to the above-mentioned constitution, the polyamide glass fiber reinforced composite material according to the present invention is provided with excellent heat resistance, rigidity, mechanical strength, chemical resistance and surface glossiness, and also has relatively low water absorption and good dimensional stability.

[0074] The long glass fiber reinforced polyamide composite material according to the embodiment of the present invention can be widely applied in fields such as electronic devices, automobiles, military industries, and other fields.

[0075] [Experimental data and results] In order to prove the technical effects of the long polyamide glass fiber reinforced composite material and the manufacturing method thereof of the present invention, the experimental data and results are described below, however, the following examples and comparative examples are provided for the purpose of understanding the present invention, and the scope of protection of the present invention is not limited to these examples.

[0076] In Examples 1 to 7, a plurality of raw materials, such as polyamide, toughening agent (e.g., POE-g-MA, TPO-g-MA, EPDM-g-MA, E-MA-GMA-g-MA), compatibilizer (e.g., PE-g-MA, PP-g-MA, PE / PP-g-MA), flow modifier (e.g., polyolefin superdispersant), and other additives (e.g., antioxidant, lubricant, colorant, etc.), based on the formulation in Table 1A, were fed to a twin-screw extruder and mixed and melted to form a mixed plastic melt. The mixed plastic melt was fed to an impregnation device, and continuous long glass fibers whose surfaces were modified with hydroxyl groups were fed to the impregnation device, thereby thoroughly impregnating the long glass fibers with the mixed plastic melt. The long glass fibers impregnated with the mixed plastic melt were molded, cooled, and granulated to obtain a polyamide long glass fiber reinforced composite material.

[0077] The differences between Comparative Examples 1 to 3 and the above-mentioned Examples are that the raw materials in Comparative Examples 1 to 3 contained only polyamide, antioxidant, lubricant, and colorant, and did not contain the toughening agent, compatibilizer, and flow modifier in Examples 1 to 7.

[0078] Next, the polyamide glass long fiber reinforced composite materials manufactured in the above examples and comparative examples were measured for tensile strength, elongation, flexural strength, impact strength, heat distortion temperature, gloss, water absorption, etc. Here, the tensile strength and elongation were measured based on the ISO 527 standard. The flexural strength was measured based on the ISO 178 standard. The impact strength CHARPY was measured based on the ISO 179 standard. The heat distortion temperature (HDT) was measured based on the ISO 75 standard. The gloss was measured on the surface of the sample using a gloss measurement device with VG-7000. The moisture absorption conditions for water absorption were a temperature of 23°C and a relative humidity of 50%. The measurement results are shown in Table 1B.

[0079] [Table 1A] TIFF0007637717000001.tif237135[Table 1B] TIFF0007637717000002.tif193121

[0080] [Results and Discussion] According to the above experimental results, in the physical property measurement results, Examples 1 to 7 had better elongation (2.5 to 3.6% in the examples and 1.9 to 2.3% in the comparative examples) and impact strength (i.e., toughness) than Comparative Examples 1 to 3. In particular, the impact strength at low temperature (CHARPY KJ / m 2 (23°C), the examples are 37.6 to 54.5 KJ / m 2 The comparative example is 12.2 to 16.1 KJ / m 2 and CHARPY KJ / m 2 (-40℃) Example: 32.1~53.7KJ / m 2 The comparative example is 2.1 to 3.5 KJ / m 2 ), and this embodiment is superior.

[0081] In addition, in the manufacturing process, the impregnation effect of the melt-mixed raw materials on the glass fibers is superior in Examples 1 to 7 compared to Comparative Examples 1 to 3, and therefore the problem of poor impregnation effect in the prior art was improved.

[0082] [Advantageous Effects of the Embodiments] The advantageous effects of the present invention are that the long glass fiber reinforced polyamide composite material and its manufacturing method according to the present invention have the following technical features: "the toughener is an elastomer made of a first polyolefin material and modified with maleic anhydride, the compatibilizer is a resin material made of a second polyolefin material and modified with maleic anhydride, and the first melt index of the toughener is lower than the second melt index of the compatibilizer" and "the long glass fiber material is sufficiently impregnated and covered with an impregnation material, and the surface of the long glass fiber material is modified with hydroxyl groups and / or carboxyl groups". This improves the toughness of polyamide (nylon plastic) and solves the problem of poor impregnation effect in the process.

[0083] In further detail, the polyamide long glass fiber reinforced composite material according to the present invention has excellent heat resistance, rigidity, mechanical strength, chemical resistance, and surface glossiness, and also has relatively low water absorption and good dimensional stability. The polyamide long glass fiber reinforced composite material according to the embodiment of the present invention can be widely applied in fields such as electronic equipment, automobiles, military industry, and other fields.

[0084] The above disclosure is merely a preferred embodiment of the present invention, and the scope of the claims of the present invention is not limited thereto. Therefore, all equivalent technical modifications made by utilizing the specification and drawings of the present invention are included in the scope of the claims of the present invention. [Explanation of symbols]

[0085] 1...Extruder 2. Impregnation equipment 3…Bobbin device 4...Spreading device 5…Forming equipment 6. Guide device 7...Pelletizer RM…Raw materials GF: Long glass fiber P...Product

Claims

1. feeding raw materials into an extruder for mixing and melting to form a mixed plastic melt; an impregnation step in which the mixed plastic melt is supplied to an impregnation device, and continuous long glass fibers are supplied to the impregnation device, thereby sufficiently impregnating the long glass fibers with the mixed plastic melt, and the surfaces of the long glass fibers are modified with hydroxyl groups and / or carboxyl groups; a molding step of molding, cooling and granulating the long glass fibers impregnated with the mixed plastic melt to obtain a polyamide long glass fiber reinforced composite material, The raw materials include a polyamide resin, a toughening agent, and a compatibilizer; The toughening agent is an elastomer modified with maleic anhydride, which is composed of a first polyolefin material, and the first polyolefin material is at least one selected from the group consisting of ethylene propylene diene rubber (EPDM), thermoplastic polyolefin (TPO), polyolefin elastomer (POE), and ethylene-methyl acrylate-glycidyl methacrylate terpolymer (E-MA-GMA), the graft ratio of the first maleic anhydride of the toughening agent is 0.3% to 1.5%, and the first melt index of the toughening agent is 1 g / 10 min to 20 g / 10 min; A method for producing a long polyamide glass fiber reinforced composite material, characterized in that the compatibilizer is a resin material formed of a second polyolefin material and modified with maleic anhydride, the second polyolefin material being at least one selected from the group consisting of polyethylene (PE), polypropylene (PP), and an ethylene-propylene copolymer, the graft ratio of the second maleic anhydride of the compatibilizer being 0.3% to 1.5%, and the second melt index of the compatibilizer being 100 g / 10 min to 600 g / 10 min.

2. 2. The method for producing a polyamide long glass fiber reinforced composite material according to claim 1, wherein the extruder is a twin screw extruder, the processing temperature of the extruder is 250°C to 400°C, and the screw speed is 200 rpm to 300 rpm.

3. 2. The method for producing a long polyamide glass fiber reinforced composite material according to claim 1, wherein, when the toughening agent and the compatibilizer are mixed and melted with the polyamide resin in the extruder, an active acid anhydride group of the maleic anhydride modified by the toughening agent and / or the compatibilizer reacts with an amino group at an end of a polymer chain of the polyamide resin to form an amide bond first, and then a ring-closing reaction is carried out to form an imide bond, thereby forming a graft copolymer.

4. 2. The method for producing a long polyamide glass fiber reinforced composite material according to claim 1, wherein the raw material further comprises a flow modifier which is a polyolefin hyperdispersant having a number average molecular weight of 1000 g / mol to 10,000 g / mol.

5. 2. The method for producing a polyamide long glass fiber reinforced composite material according to claim 1, wherein in the impregnation step, the long glass fibers are supplied to a stretching device via a bobbin device, and after undergoing a preheating operation and a stretching operation, are introduced into the impregnation device, so that the long glass fibers are impregnated with the mixed plastic melt in a preheated and stretched state.

6. 6. The method for producing a polyamide long glass fiber reinforced composite material according to claim 5, wherein the long glass fibers impregnated with the mixed plastic melt are bundled and covered by a die head of the impregnation device, are led out of the impregnation device, are then shaped and cooled at a cooling temperature of 15°C to 35°C through a molding device, are guided through a guide device to a granulator and granulated, and the long glass fibers are glass fibers having a length of 5 mm to 30 mm.

7. An impregnated material which is a graft copolymer in which a toughening agent and a compatibilizer are grafted to a polyamide resin; a glass fiber material impregnated with and covered by said impregnation material; The toughening agent is an elastomer modified with maleic anhydride, which is composed of a first polyolefin material, and the first polyolefin material is at least one selected from the group consisting of ethylene propylene diene rubber (EPDM), thermoplastic polyolefin (TPO), polyolefin elastomer (POE), and ethylene-methyl acrylate-glycidyl methacrylate terpolymer (E-MA-GMA), the graft ratio of the first maleic anhydride of the toughening agent is 0.3% to 1.5%, and the first melt index of the toughening agent is 1 g / 10 min to 20 g / 10 min; The compatibilizer is a resin material composed of a second polyolefin material and modified with maleic anhydride, the second polyolefin material of the compatibilizer is at least one selected from the group consisting of polyethylene (PE), polypropylene (PP), and an ethylene-propylene copolymer, the graft ratio of the second maleic anhydride of the compatibilizer is 0.3% to 1.5%, and the second melt index of the compatibilizer is 100 g / 10 min to 600 g / 10 min; A polyamide long glass fiber reinforced composite material, characterized in that the glass fiber material contains long glass fibers whose surfaces are modified with hydroxyl groups and / or carboxyl groups.

8. 8. The long polyamide glass fiber reinforced composite material according to claim 7, wherein the impregnating material further comprises a flow modifier which is a polyolefin hyperdispersant having a number average molecular weight of 1000 g / mol to 10,000 g / mol.

9. 9. The polyamide long glass fiber reinforced composite material according to claim 8, wherein the content of the polyamide resin is 50 to 97 parts by weight, the content of the toughening agent is 0.1 to 20 parts by weight, the content of the compatibilizer is 0.1 to 20 parts by weight, and the content of the flowability modifier is 10 parts by weight or less, based on 100 parts by weight of the total weight of the impregnation material.

10. 10. The polyamide long glass fiber reinforced composite material according to claim 9, wherein the weight ratio of the glass fiber material to the impregnating material (glass fiber material: impregnating material) is 5:95 to 65:35.

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