Molded article comprising thermoplastic continuous fiber reinforced woven composite and method for preparing the same

Abstract

The molded article of the present invention comprises: a woven sheet in which two or more thermoplastic continuous fiber reinforced woven bodies are laminated; and a nonwoven fabric laminated by heating and pressing on at least one side of the woven sheet; wherein the thermoplastic continuous fiber reinforced woven body is characterized by being woven using a glass fiber composite material comprising 100 parts by weight of glass fiber; 35 to 72 parts by weight of polypropylene resin; 12 to 35 parts by weight of piperazine pyrophosphate; 1 to 20 parts by weight of phosphazene compound; and 1 to 20 parts by weight of zeolite as warp and weft threads. The glass fiber composite material has excellent lightness, flame retardancy, impact resistance, rigidity, appearance characteristics, etc.

Description

Technology Field

[0001] The present invention relates to a molded article comprising a thermoplastic continuous fiber reinforced woven body and a method for manufacturing the same. More specifically, the present invention relates to a molded article comprising a thermoplastic continuous fiber reinforced woven body having excellent lightness, flame retardancy, impact resistance, rigidity, appearance characteristics, etc., and a method for manufacturing the same. Background Technology

[0003] To meet the continuously strengthening demands for lightweighting and eco-friendliness in the automotive industry, there is a strong trend toward making automotive parts lighter by applying plastic materials instead of metals, and by introducing thermoplastic resins, particularly polypropylene (PP), to avoid environmentally harmful substances and thermosetting resins. In particular, regarding the technological development for lightweighting electric vehicle (EV) components, there is a need to change the materials used for components such as the underbody protection plates of EV battery modules.

[0004] However, when thermoplastic resins are applied to materials (such as continuous fiber-reinforced woven fabrics) of molded products (such as lower protection plates for electric vehicle battery modules) for purposes such as weight reduction, there is a problem in that flame retardancy, impact resistance, and rigidity are reduced compared to metals or thermosetting resins. Furthermore, when these materials are applied alone, there is a problem in that the appearance characteristics are poor, such as the reinforcing fibers protruding after molding.

[0005] Therefore, there is a need to develop molded products containing thermoplastic continuous fiber reinforced woven materials that exhibit excellent properties such as lightness, flame retardancy, impact resistance, rigidity, and appearance characteristics, even when using thermoplastic resins.

[0006] The background technology of the present invention is disclosed in Korean Patent Publication No. 10-2020-0033783, etc. The problem to be solved

[0008] The objective of the present invention is to provide a molded article comprising a thermoplastic continuous fiber reinforced woven body having excellent lightness, flame retardancy, impact resistance, rigidity, and appearance characteristics.

[0009] Another objective of the present invention is to provide a method for manufacturing the molded article.

[0010] The above and other objectives of the present invention can all be achieved by the present invention described below. means of solving the problem

[0012] 1. One aspect of the present invention relates to a molded article. The molded article comprises a woven sheet in which two or more thermoplastic continuous fiber reinforced woven bodies are laminated; and a nonwoven fabric laminated by heating and pressing on at least one side of the woven sheet; wherein the thermoplastic continuous fiber reinforced woven body is characterized by being woven using a glass fiber composite material comprising 100 parts by weight of glass fiber; 35 to 72 parts by weight of polypropylene resin; 12 to 35 parts by weight of piperazine pyrophosphate; 1 to 20 parts by weight of phosphazene compound; and 1 to 20 parts by weight of zeolite as warp and weft threads.

[0013] 2. In the above 1 embodiment, the polypropylene resin may include one or more of homopolypropylene resin, block polypropylene resin, and random polypropylene resin.

[0014] 3. In the above 2 embodiments, the weight ratio of the piperazine pyrophosphate and the phosphazene compound may be 1:0.1 to 1:0.4.

[0015] 4. In the above 2 or 3 embodiments, the glass fiber composite material may be in the form of a tape in which the glass fiber is impregnated with the polypropylene resin, the piperazine pyrophosphate, the phosphazene compound, and the zeolite.

[0016] 5. In the above 1 to 4 embodiments, the glass fiber composite material may be in the form of a tape having a thickness of 0.2 to 1.5 mm and a width of 5 to 25 mm.

[0017] 6. In the above 1 to 5 embodiments, the thermoplastic continuous fiber reinforced woven body may have empty spaces of 5 mm × 5 mm or less formed between the warp threads and between the weft threads.

[0018] 7. In the above 1 to 6 embodiments, the nonwoven fabric may be a polyethylene terephthalate nonwoven fabric having a thickness of 0.2 to 1.5 mm.

[0019] 8. In the above embodiments 1 to 7, the molded article has a density of 1.40 to 1.55 g / cm³ as measured in accordance with ISO 1183-1. 3 It could be.

[0020] 9. In the above 1 to 8 embodiments, the molded article may have a flame retardancy of V-1 or higher for a 2 mm thick specimen measured by the UL-94 vertical test method.

[0021] 10. In the above 1 to 9 embodiments, the molded article may have a peak force of 3.5 to 6.0 kN for a specimen of size 60 mm × 60 mm × 2 mm measured at a speed of 4.4 m / s and a weight of 20 kg with an impact energy value of 198 J according to ISO 6603-2, a total displacement of 20 to 35 mm, and an energy absorption of 30 to 50 J at a displacement of 15 mm.

[0022] 11. In the above 1 to 10 embodiments, the molded article may have a tensile strength of 180 to 270 MPa of a 3 mm thick specimen measured according to ISO 527, and a flexural strength of 190 to 280 MPa of a 3 mm thick specimen measured according to ISO 14125.

[0023] 12. In the above 1 to 11 embodiments, the molded article may be naturally extinguished without catching fire in a long-term flame retardancy test in which a specimen of size 330 mm × 330 mm × 2 mm is heated directly with a blue flame at a distance of 7 cm for 2 minutes and 10 seconds using a torch, and then the flame is removed.

[0024] 13. In the above 1 to 12 embodiments, the molded product may be a lower protective plate for a battery module for an electric vehicle.

[0025] 14. Another aspect of the present invention relates to a method for manufacturing a molded article. The manufacturing method comprises the steps of: stacking two or more thermoplastic continuous fiber reinforced woven bodies and heating and pressing to produce a woven sheet; and then stacking a nonwoven fabric on at least one side of the woven sheet and then heating and pressing; wherein the thermoplastic continuous fiber reinforced woven body is characterized by being woven using a glass fiber composite material comprising 100 parts by weight of glass fiber; 35 to 72 parts by weight of polypropylene resin; 12 to 35 parts by weight of piperazine pyrophosphate; 1 to 20 parts by weight of a phosphazene compound; and 1 to 20 parts by weight of zeolite as warp and weft. Effects of the invention

[0027] The present invention has the effect of providing a molded article comprising a thermoplastic continuous fiber reinforced woven body having excellent lightness, flame retardancy, impact resistance, rigidity, and appearance characteristics, and a method for manufacturing the same. Brief explanation of the drawing

[0029] FIG. 1 is a plan view of a thermoplastic continuous fiber reinforced woven body according to one embodiment of the present invention. Specific details for implementing the invention

[0030] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings. However, the following embodiments are provided to enable those skilled in the art to fully understand the present invention and may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

[0031] In order to clearly represent the components in the drawings, the dimensions, such as the width or thickness of the components, have been shown slightly enlarged. Additionally, for the convenience of explanation, only parts of the components have been illustrated, but those skilled in the art will be able to easily understand the remaining parts of the components. Furthermore, those with ordinary knowledge in the relevant field may implement the concept of the present invention in various other forms within the scope of the technical concept of the present invention without departing from it. Overall, the drawings have been described from the observer's perspective, and the references for "top," "bottom," "left," "right," "front," and "back" are based on the drawings. Moreover, those with ordinary knowledge in the relevant field may implement the concept of the present invention in various other forms within the scope of the technical concept of the present invention without departing from it. Furthermore, in multiple drawings, the same reference numerals refer to substantially identical elements.

[0032] Furthermore, singular expressions should be understood to include plural expressions unless the context clearly indicates otherwise, and terms such as "include" and "have" are intended to specify the existence of the described features, numbers, steps, actions, components, parts, or combinations thereof, and should not be understood as precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0034] The molded article according to the present invention comprises (A) a woven sheet; and (B) a nonwoven fabric.

[0035] In this specification, "a to b" indicating a numerical range is defined as "≥a and ≤b".

[0037] (A) Woven sheet

[0038] A woven sheet according to one embodiment of the present invention is capable of improving the lightness, flame retardancy, impact resistance, and rigidity of a molded article even when a thermoplastic resin is applied, and is in the form of two or more layers of thermoplastic continuous fiber reinforced woven sheets laminated together.

[0039] FIG. 1 is a plan view of a thermoplastic continuous fiber reinforced woven body according to one embodiment of the present invention. As shown in FIG. 1, the thermoplastic continuous fiber reinforced woven body (100) according to one embodiment of the present invention is a woven body woven using a tape-shaped glass fiber composite material as warp (110) and weft (120). Such a woven body can be manufactured by a known manufacturing method.

[0040] In a specific example, the thermoplastic continuous fiber reinforced woven body may have empty spaces (130) of 5 mm × 5 mm or less formed between the warp threads (110) and the warp threads (110) and between the weft threads (120). Within this range, the empty spaces (voids) can be minimized when manufacturing a molded product, and the moldability, flame retardancy, impact resistance, and rigidity of the thermoplastic continuous fiber reinforced woven body may be excellent.

[0041] In a specific example, the glass fiber composite material is a tape-type glass fiber composite material that has excellent lightness, flame retardancy, impact resistance, and stiffness even when a thermoplastic resin is applied, and can improve the lightness, flame retardancy, impact resistance, and stiffness of a thermoplastic continuous fiber reinforced woven body woven with warp and weft threads, a woven sheet manufactured by laminating two or more of the same, and a molded article containing the same. The glass fiber composite material comprises (a) glass fiber; (b) polypropylene resin; (c) piperazine pyrophosphate; (d) phosphazene compound; and (e) zeolite.

[0042] (a) glass fiber

[0043] Glass fibers according to one embodiment of the present invention are impregnated with polypropylene resin, piperazine pyrophosphate, a phosphazene compound, and zeolite, thereby forming a tape-shaped glass fiber composite material having excellent lightness, flame retardancy, impact resistance, and rigidity.

[0044] In a specific embodiment, the glass fiber may be in the form of a fiber and may have a cross-section of various shapes, such as circular, elliptical, or rectangular. For example, using a fiber-shaped glass fiber with a circular and / or rectangular cross-section may be preferable in terms of mechanical properties.

[0045] In a specific example, when the glass fiber has a circular cross-section, the diameter measured by a scanning electron microscope (manufacturer: JEOL, device name: JSM-6390A) may be 5 to 20 μm, for example, 7 to 15 μm; when the glass fiber has a rectangular cross-section, the aspect ratio (major axis of the cross-section / minor axis of the cross-section) may be 1.5 to 10, for example, 2 to 8; and the minor axis of the rectangular cross-section may be 2 to 10 μm, for example, 4 to 8 μm. The length of the glass fiber before processing may be 1 to 30 mm, for example, 2 to 16 mm. Within the above range, the productivity and impregnation properties of the glass fiber composite material may be excellent.

[0046] In a specific example, the glass fiber may be treated with a conventional surface treatment agent. The surface treatment agent may include, but is not limited to, silane compounds, urethane compounds, epoxy compounds, etc.

[0047] (b) Polypropylene resin

[0048] A polypropylene resin according to one embodiment of the present invention is impregnated with piperazine pyrophosphate, a phosphazene compound, and a zeolite to form a tape-shaped glass fiber composite material having excellent lightness, flame retardancy, impact resistance, and rigidity, and a polypropylene resin applied to a conventional thermoplastic resin composition can be used.

[0049] In a specific example, the polypropylene resin may include one or more of homopolypropylene resin, block polypropylene resin, and random polypropylene resin. Here, the block polypropylene resin may be a block polypropylene resin composed of a homopolypropylene block, an ethylene-propylene copolymer block and / or a homopolyethylene block, and the random polypropylene resin may be a propylene-ethylene random copolymer.

[0050] In a specific example, the polypropylene resin may have a Melt-flow Index (MI) of 1 to 1,600 g / 10 min, for example, 5 to 1,400 g / 10 min, measured according to ASTM D1238 under conditions of 230°C and a 2.16 kg load. Within this range, the mechanical properties and moldability of the glass fiber composite material may be excellent.

[0051] In a specific example, the polypropylene resin may be included in an amount of 35 to 72 parts by weight, for example, 36 to 70 parts by weight, relative to 100 parts by weight of the glass fiber. If the content of the polypropylene resin is less than 35 parts by weight relative to 100 parts by weight of the glass fiber, manufacturing may be impossible due to the single fiber of the glass fiber, or there is a risk that the lightness, impregnation, moldability, etc. of the glass fiber composite material may be reduced, and if it exceeds 72 parts by weight, there is a risk that the flame retardancy, impact resistance, rigidity, etc. of the glass fiber composite material may be reduced.

[0052] (c) Piperazine pyrophosphate

[0053] Piperazine pyrophosphate according to one embodiment of the present invention can be used to form a tape-shaped glass fiber composite material with excellent lightness, flame retardancy, impact resistance, and rigidity by impregnating the glass fiber together with the polypropylene resin, phosphazene compound, and zeolite.

[0054] In a specific example, the piperazine pyrophosphate may be included in an amount of 12 to 35 parts by weight, for example, 15 to 33 parts by weight, per 100 parts by weight of the glass fiber. If the content of the piperazine pyrophosphate is less than 12 parts by weight per 100 parts by weight of the glass fiber, there is a risk that the flame retardancy of the glass fiber composite material will be reduced, and if it exceeds 35 parts by weight, there is a risk that the impact resistance, stiffness, moldability, etc. of the glass fiber composite material will be reduced.

[0055] In a specific example, the weight ratio of the polypropylene resin and the piperazine pyrophosphate (polypropylene resin:piperazine pyrophosphate) may be 1:0.2 to 1:1, for example, 1:0.25 to 1:0.90. Within this range, the flame retardancy, impact resistance, rigidity, impregnation properties, etc. of the glass fiber composite material may be superior.

[0056] (d) Phosphazene compound

[0057] A phosphazene compound according to one embodiment of the present invention can be impregnated with the polypropylene resin, piperazine pyrophosphate, and zeolite together with the glass fiber to form a tape-shaped glass fiber composite material having excellent lightness, flame retardancy, impact resistance, and rigidity, and can use a phosphazene compound used in a conventional flame-retardant thermoplastic resin composition.

[0058] In a specific example, the phosphazene compound may include a phosphazene compound represented by the following chemical formula 1.

[0059] [Chemical Formula 1]

[0060]

[0061] In the above chemical formula 1, R1, R2, R3, R4, R5, and R6 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 7 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group or aryloxy group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbonylalkyl group having 2 to 10 carbon atoms, an amino group, or a hydroxyl group.

[0062] Here, the term "substitution" means that a hydrogen atom is substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 3 to 10 carbon atoms, a heteroaryl group having 4 to 10 carbon atoms, or a combination thereof.

[0063] In addition, the substituents comprising the "alkyl," "alkoxy," and other "alkyl" portions include both straight-chain and broken-chain forms, the "alkenyl" includes both straight-chain and broken-chain forms having 2 to 8 carbon atoms and containing one or more double bonds, and the "cycloalkyl" includes both saturated monocyclic or saturated bicyclic ring structures having 3 to 20 carbon atoms. The "aryl" is a ring-structured organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom, comprising a single or fused ring system having, suitably, 4 to 7, preferably 5 or 6, ring backbone atoms in each ring. Specifically, examples may include phenyl, naphthyl, biphenyl, tolyl, etc.

[0064] The above "heterocycloalkyl" refers to a cycloalkyl group comprising 1 to 3 heteroatoms selected from N, O, and S as saturated cyclic hydrocarbon backbone atoms, wherein the remaining saturated monocyclic or bicyclic ring backbone atoms are carbon, and includes pyrrolidinyl, azetidinyl, pyrazolidinyl, oxazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomophorinyl, thiazolidinyl, hydantoinyl, valerolactamil, oxiranil, oxetanil, dioxolanil, dioxanil, oxathionil, oxatianil, dithianil, dihydrofuranil, tetrahydrofuranil, dihydropyranil, tetrahydropyranil, tetrahydropyridinyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiopyranil, diazepanil, azepanil, etc. Can be an example.

[0065] The above "heteroaryl" refers to an aryl group comprising one to three heteroatoms selected from N, O, and S as aromatic ring backbone atoms, and the remaining aromatic ring backbone atoms being carbon. The heteroaryl group includes a divalent aryl group in which the heteroatoms within the ring are oxidized or quaternized to form, for example, N-oxide or a quaternary salt. Specifically, examples may include furyl, thienyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc.

[0066] In a specific example, the phosphazene compound may be included in an amount of 1 to 20 parts by weight, for example, 2 to 15 parts by weight, per 100 parts by weight of the glass fiber. If the content of the phosphazene compound is less than 1 part by weight per 100 parts by weight of the glass fiber, there is a risk that the flame retardancy of the glass fiber composite material will decrease, and if it exceeds 20 parts by weight, there is a risk that the productivity, impact resistance, and stiffness of the glass fiber composite material will decrease.

[0067] In a specific example, the weight ratio of the piperazine pyrophosphate and the phosphazene compound (piperazine pyrophosphate:phosphazene compound) may be 1:0.1 to 1:0.4, for example, 1:0.13 to 1:0.35. Within this range, the flame retardancy, productivity, impregnation properties, etc. of the glass fiber composite material may be superior.

[0068] (e) Zeolite

[0069] A zeolite according to one embodiment of the present invention is impregnated with the polypropylene resin, the piperazine pyrophosphate, and the phosphazene compound together with the glass fiber to form a tape-shaped glass fiber composite material having excellent lightness, flame retardancy, impact resistance, and rigidity, and a zeolite used in a conventional thermoplastic resin composition may be used.

[0070] In a specific example, the zeolite may be a porous particle having a pore size of 2 to 8 nm, for example, 3 to 6 nm, and an average particle size of 1 to 7 μm, for example, 3 to 5 μm. Within this range, the productivity and impregnation properties of the glass fiber composite material may be excellent. Here, the average particle size of the zeolite was determined by obtaining the particle size distribution using laser diffraction scattering and taking the particle diameter at 50% of the cumulative value as the average particle size.

[0071] In a specific example, the zeolite may be included in an amount of 1 to 20 parts by weight, for example, 2 to 15 parts by weight, per 100 parts by weight of the glass fiber. If the content of the zeolite is less than 1 part by weight per 100 parts by weight of the glass fiber, there is a risk that the impact resistance, stiffness, etc. of the glass fiber composite material will decrease, and if it exceeds 20 parts by weight, there is a risk that the productivity, impregnation, etc. of the glass fiber composite material will decrease.

[0072] In a specific example, the weight ratio of the polypropylene resin and the zeolite (polypropylene resin : zeolite) may be 1 : 0.05 to 1 : 0.40, for example, 1 : 0.06 to 1 : 0.30. Within this range, the impregnation, impact resistance, and rigidity of the glass fiber composite material may be superior.

[0073] A glass fiber composite material according to one embodiment of the present invention may be in the form of a tape in which the polypropylene resin, the piperazine pyrophosphate, the phosphazene compound, and the zeolite are impregnated into the glass fiber, and may have a thickness of 0.2 to 1.5 mm, for example, 0.3 to 1.1 mm, and a width of 5 to 25 mm, for example, 7 to 20 mm. Within the above range, the flame retardancy, impact resistance, rigidity, etc. of the glass fiber composite material may be excellent.

[0074] In a specific example, the glass fiber composite material may be manufactured by a known manufacturing method, for example, using a manufacturing apparatus disclosed in Korean Patent Publication No. 10-2018-0035064.

[0076] (B) Non-woven fabric

[0077] A nonwoven fabric according to one embodiment of the present invention is applied together with the woven sheet to improve the appearance characteristics of a molded product.

[0078] In a specific example, the nonwoven fabric may have a thickness of 0.2 to 1.5 mm, for example, 0.5 to 1.0 mm. Within this range, delamination does not occur in the final product due to interfacial bonding issues with the woven sheet, and the appearance characteristics may be excellent.

[0079] In a specific example, the nonwoven fabric may be a polyethylene terephthalate nonwoven fabric. When a polyethylene terephthalate nonwoven fabric is used as the nonwoven fabric, its melting point is higher than that of the polypropylene resin, which is the base resin of the woven sheet, so the shape of the nonwoven fabric can be maintained even during molding. Furthermore, when manufacturing a molded product, the polypropylene resin of the woven sheet, which is melted during the heating and pressing process, permeates into the nonwoven fabric, thereby improving the bonding performance between the nonwoven fabric and the woven sheet. In addition, by allowing the flame retardant system of the woven sheet (such as piperazine pyrophosphate and phosphazene compounds) to permeate into the nonwoven fabric along with the polypropylene resin, the flame retardancy of the woven sheet can also be shared. That is, flame retardant performance can be maintained even when using a non-flame-retardant general nonwoven fabric instead of a flame-retardant nonwoven fabric.

[0080] In a specific example, the nonwoven fabric may be a conventional flame-retardant nonwoven fabric, for example, a polyethylene terephthalate nonwoven fabric endowed with flame retardancy. In this case, the flame retardancy of the molded article may be superior.

[0082] A molded article according to one embodiment of the present invention may be manufactured by stacking two or more of the thermoplastic continuous fiber reinforced woven bodies and heating and pressing to produce the woven body sheet; and then stacking the nonwoven fabric on at least one side of the woven body sheet and heating and pressing. Such a molding method is well known to those skilled in the art to which the present invention belongs.

[0083] In a specific example, when manufacturing the woven sheet, heating and pressing are performed by pressing with a pressing roller at 180 to 260°C, and for example, by pressing using a pressing roller at 230 to 260°C. In the above temperature range, the peel resistance and mechanical properties of the woven sheet may be excellent.

[0084] In a specific example, the heating and pressing after laminating the nonwoven fabric may be performed using a press molding machine at 230 to 260°C. In the above temperature range, the bonding performance of the woven sheet and the nonwoven fabric may be excellent, the woven sheet and the nonwoven fabric may share flame retardant performance, and the appearance characteristics of the molded product may be excellent. The press molding machine may be a 2,000 to 3,000-ton class press molding machine, but is not limited thereto.

[0085] In a specific example, the molded article has a density of 1.40 to 1.55 g / cm³ as measured in accordance with ISO 1183-1. 3 , for example, 1.41 to 1.54 g / cm³ 3 It could be.

[0086] In a specific example, the molded article may have a flame retardancy of V-1 or higher for a 2 mm thick specimen measured by the UL-94 vertical test method.

[0087] In a specific example, the molded article may have a peak force of 3.5 to 6.0 kN, for example 3.6 to 5.0 kN, measured in accordance with ISO 6603-2 at a speed of 4.4 m / s and an impact energy value of 198 J based on a weight of 20 kg, a total displacement of 20 to 35 mm, for example 22 to 35 mm, and an energy absorption amount at a displacement of 15 mm of 30 to 50 J, for example 30 to 45 J.

[0088] In a specific example, the molded article may have a tensile strength of 180 to 270 MPa, for example, 181 to 260 MPa, of a 3 mm thick specimen measured according to ISO 527.

[0089] In a specific example, the molded article may have a flexural strength of 190 to 280 MPa, for example, 191 to 270 MPa, of a 3 mm thick specimen measured according to ISO 14125.

[0090] In a specific example, the molded product may be naturally extinguished without catching fire in a long-term flame retardancy test in which a specimen of size 330 mm × 330 mm × 2 mm is heated directly with a blue flame from a distance of 7 cm using a torch for 2 minutes and 10 seconds, and then the flame is removed.

[0091] In a specific example, the molded product has excellent lightness, flame retardancy, impact resistance, rigidity, appearance characteristics, and a balance of these physical properties, so it is useful as an interior and exterior material for electronic devices, an interior and exterior material for automobiles, a structural material, and in particular, is useful as a lower protection plate for a battery module for an electric vehicle.

[0093] The present invention is to be explained more specifically through the following examples, but these examples are for illustrative purposes only and should not be interpreted as limiting the invention.

[0095] Examples

[0096] The specifications of each component used in the examples and comparative examples below are as follows.

[0097] (A) Glass fiber

[0098] Circular cross-section glass fiber (Manufacturer: Owens Corning, Product Name: SE4121 HP) was used.

[0099] (B) Polypropylene resin

[0100] Homopolypropylene resin (Manufacturer: LG Chem, Product Name: H7914A) was used.

[0101] (C) Phosphate compounds

[0102] (C1) Piperazine pyrophosphate (Manufacturer: Kempia, Product name: FR220N) was used.

[0103] (C2) Melamine pyrophosphate (Manufacturer: Kempia, Product name: MPP-D) was used.

[0104] (D) Phosphorus compounds

[0105] (D1) A phosphazene compound (Manufacturer: Kempia, Product name: FRPPZ) was used.

[0106] (D2) Bisphenol-A diphosphate (Manufacturer: Jiangsu Yoke Technology, Product name: Yoke BDP) was used.

[0107] (E) Zeolite

[0108] Zeolite (Manufacturer: Huin Chemical, Product Name: APS 30) was used.

[0110] Examples 1 to 3 and Comparative Examples 1 to 6

[0111] By using each of the above components in the amounts listed in Tables 1 and 2 below, a polypropylene resin, a phosphate-nitrogen compound (piperazine pyrophosphate or melamine pyrophosphate), a phosphorus-based compound (phosphazene compound or bisphenol-A diphosphate), and a zeolite were impregnated into glass fibers to produce a tape-shaped glass fiber composite material (continuous fiber reinforced composite material (CFT)) with a thickness of about 0.4 mm and a width of about 11 mm by a known method, and the produced glass fiber composite material was woven using the warp and weft threads to produce a thermoplastic continuous fiber reinforced woven body such that empty spaces of 2 mm × 2 mm or less were formed between the glass fiber composite materials.

[0112] Next, several sheets of the above thermoplastic continuous fiber reinforced woven fabric were laminated to match the thickness of the specimen. Then, depending on whether a nonwoven fabric was applied as shown in Tables 1 and 2 below, a polyethylene terephthalate nonwoven fabric (manufacturer: Hoan, product name: Chemical Nonwoven Fabric) was laminated on one side (the side visible to the outside after molding) of the laminated woven fabric sheets. After preheating before molding, a flat molded product was manufactured by compression molding using a hot press and a cooling press, and a specimen for measuring physical properties was produced by cutting it to the required specifications using a numerically controlled machine tool (NC machine). The physical properties of the produced specimens for measuring physical properties were evaluated by the following method, and the results are shown in Tables 1 and 2 below.

[0114] Methods for measuring physical properties

[0115] (1) Lightweight: Density according to ISO 1183-1 (Unit: g / cm³) 3 ) was measured.

[0116] (2) Flame retardancy: The flame retardancy (unit: grade) of a 2 mm thick specimen was measured using the UL-94 vertical test method.

[0117] (3) Impact resistance: According to ISO 6603-2, the impact strength was measured by measuring the peak force (unit: kN), total displacement (unit: mm), and energy absorption (unit: J) at a displacement of 15 mm for a specimen of size 60 mm × 60 mm × 2 mm, with an impact energy value of 198 J based on a speed of 4.4 m / s and a weight of 20 kg.

[0118] (4) Stiffness: The tensile strength (unit: MPa) of a 3 mm thick specimen was measured according to ISO 527.

[0119] (5) Stiffness: The flexural strength (unit: MPa) of a 3 mm thick specimen was measured according to ISO 14125.

[0120] (6) Long-term flame retardancy: A long-term flame retardancy test was performed by directly heating a specimen with a blue flame from a distance of 7 cm using a torch for 2 minutes and 10 seconds, and then removing the flame. If the specimen did not catch fire and extinguished naturally after removing the flame, it was evaluated as Pass, and if the specimen caught fire, it was evaluated as Fail.

[0121] (7) Appearance characteristics: Visual evaluation of the appearance of the molded product was performed to check for glass fiber protrusion, non-woven fabric tearing, exposure of the woven laminated sheet, and cracks / breakage.

[0123] Examples 1 2 3 (A) (weight part) 100 100 100 (B) (weight part) 45.5 54.5 50 (C1) (weight part) 25.5 18.2 30 (C2) (weight part) - - - (D1) (weight part) 3.6 5.5 10 (D2) (weight part) - - - (E) (parts by weight) 7.3 3.6 10 Whether non-woven fabric is applied apply apply apply Density (g / cm³) 3 ) 1.51 1.47 1.45 Flame retardancy (grade) V-0 V-1 V-1 Peak force (kN) 4.4 4.2 3.7 Total variation (mm) 26 28 32 Energy absorption @ 15 mm (J) 42 39 32 Tensile strength (MPa) 245 205 185 Flexural strength (MPa) 274 220 215 Long-term flame retardancy Pass Pass Pass External characteristics Pass Pass Pass

[0125] Comparative example 1 2 3 4 5 6 (A) (weight part) 100 100 100 100 100 100 (B) (weight part) 31.7 73.3 66.7 45.5 54.5 41.8 (C1) (weight part) 25 31.1 37.8 - - 30.9 (C2) (weight part) - - - 7.3 5.5 - (D1) (weight part) 5 8.9 8.9 - - 9.1 (D2) (weight part) - - - 21.8 18.2 - (E) (parts by weight) 5 8.9 8.9 7.3 3.6 - Whether non-woven fabric is applied Not applied Not applied Not applied Not applied Not applied Not applied Density (g / cm³) 3 ) Unmanufacturable 1.41 1.43 Unmanufacturable Unmanufacturable 1.52 Flame retardancy (grade) Fail V-1 V-1 Peak force (kN) 3.3 2.8 3.3 Total variation (mm) 38 37 36 Energy absorption @ 15 mm (J) 27 28 29 Tensile strength (MPa) 165 170 171 Flexural strength (MPa) 173 171 166 Long-term flame retardancy Fail Pass Pass Appearance evaluation Fail Fail Fail

[0127] From the above results, it can be seen that the glass fiber composite material, thermoplastic continuous fiber reinforced woven body, and molded article of the present invention all have excellent lightness (density), flame retardancy, impact resistance (peak force, total displacement, energy absorption at a displacement of 15 mm), stiffness (tensile strength, flexural strength), appearance characteristics, and the balance of these physical properties.

[0128] On the other hand, in Comparative Example 1, in which a small amount of polypropylene resin was applied, the production of a tape-type glass fiber composite material was impossible due to the occurrence of single glass fibers caused by increased friction between the nozzle and the glass fiber; in Comparative Example 2, in which an excessive amount of polypropylene resin was applied, it was found that flame retardancy, impact resistance, and stiffness were reduced; and in Comparative Example 3, in which an excessive amount of piperazine pyrophosphate was applied, it was found that impact resistance and stiffness were reduced. In Comparative Examples 4 and 5, in which melamine pyrophosphate (C2) and bisphenol-A diphosphate (D2), respectively, were applied instead of the piperazine pyrophosphate and phosphazene compounds of the present invention, it was impossible to produce a tape-type glass fiber composite material due to increased viscosity and reduced wetting properties. In Comparative Example 6, in which zeolite was not applied, it was found that impact resistance and stiffness were reduced. In addition, Comparative Examples 2, 3, and 6 did not apply a nonwoven fabric, so the woven sheet was exposed, and accordingly, it can be seen that the appearance characteristics were degraded, such as glass fibers protruding from the surface of the molded product specimen for measuring physical properties.

[0130] The present invention has been described above with reference to embodiments. Those skilled in the art will understand that the present invention may be embodied in modified forms without departing from the essential characteristics of the invention. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the invention is defined by the claims, not by the foregoing description, and all variations within the scope of equivalents should be interpreted as being included in the invention.

Claims

Claim 1 A molded article comprising: a woven sheet having two or more layers of thermoplastic continuous fiber reinforced woven bodies laminated together; and a nonwoven fabric laminated by heating and pressing on at least one side of the woven sheet; wherein the thermoplastic continuous fiber reinforced woven bodies are woven using a glass fiber composite material comprising 100 parts by weight of glass fiber; 35 to 72 parts by weight of polypropylene resin; 12 to 35 parts by weight of piperazine pyrophosphate; 1 to 20 parts by weight of a phosphazene compound; and 1 to 20 parts by weight of zeolite as warp and weft threads, and wherein the glass fiber composite material is in the form of a tape in which the polypropylene resin, the piperazine pyrophosphate, the phosphazene compound, and the zeolite are impregnated into the glass fiber. Claim 2 A molded article according to claim 1, characterized in that the polypropylene resin comprises one or more of homopolypropylene resin, block polypropylene resin, and random polypropylene resin. Claim 3 A molded article according to claim 1, characterized in that the weight ratio of the piperazine pyrophosphate and the phosphazene compound is 1:0.1 to 1:0.

4. Claim 4 delete Claim 5 A molded article according to claim 1, characterized in that the glass fiber composite material is in the form of a tape having a thickness of 0.2 to 1.5 mm and a width of 5 to 25 mm. Claim 6 A molded article according to claim 1, characterized in that the thermoplastic continuous fiber reinforced woven body has empty spaces of 5 mm × 5 mm or less formed between warp and warp and between weft and weft. Claim 7 A molded article according to claim 1, characterized in that the nonwoven fabric is a polyethylene terephthalate nonwoven fabric having a thickness of 0.2 to 1.5 mm. Claim 8 In claim 1, the molded article has a density of 1.40 to 1.55 g / cm³ as measured in accordance with ISO 1183-1. 3 A molded product characterized by being. Claim 9 The molded article according to claim 1 is characterized in that the flame retardancy of a 2 mm thick specimen measured by the UL-94 vertical test method is V-1 or higher. Claim 10 The molded article according to claim 1 is characterized in that, in accordance with ISO 6603-2, the peak force of a specimen of size 60 mm × 60 mm × 2 mm is 3.5 to 6.0 kN, the total displacement is 20 to 35 mm, and the energy absorption at a displacement value of 15 mm is 30 to 50 J. Claim 11 The molded article according to claim 1, characterized in that the tensile strength of a 3 mm thick specimen measured according to ISO 527 is 180 to 270 MPa, and the flexural strength of a 3 mm thick specimen measured according to ISO 14125 is 190 to 280 MPa. Claim 12 The molded product according to claim 1 is characterized in that, in a long-term flame retardancy test in which a specimen of size 330 mm × 330 mm × 2 mm is directly heated with a blue flame at a distance of 7 cm for 2 minutes and 10 seconds using a torch, and then the flame is removed, the specimen does not catch fire and naturally extinguishes. Claim 13 A molded product according to claim 1, characterized in that the molded product is a lower protective plate for a battery module for an electric vehicle. Claim 14 A method for manufacturing a molded article comprising the steps of: laminating two or more thermoplastic continuous fiber reinforced woven bodies and heating and pressing to produce a woven sheet; and laminating a nonwoven fabric on at least one side of the woven sheet and then heating and pressing; wherein the thermoplastic continuous fiber reinforced woven body is woven using a glass fiber composite material comprising 100 parts by weight of glass fiber; 35 to 72 parts by weight of polypropylene resin; 12 to 35 parts by weight of piperazine pyrophosphate; 1 to 20 parts by weight of phosphazene compound; and 1 to 20 parts by weight of zeolite as warp and weft threads, and wherein the glass fiber composite material is in the form of a tape in which the polypropylene resin, the piperazine pyrophosphate, the phosphazene compound, and the zeolite are impregnated into the glass fiber.

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