Glass fiber composite material and thermoplastic continuous fiber reinforced textile comprising same

Abstract

The glass fiber composite material of the present invention comprises: about 100 parts by weight of glass fibers; about 35 parts by weight to about 72 parts by weight of a polypropylene resin; about 12 parts by weight to about 35 parts by weight of piperazine pyrophosphate; about 1 part by weight to about 20 parts by weight of a phosphazene compound; and about 1 to about 20 parts by weight of zeolite. The glass fiber composite material is excellent in lightweight property, flame retardance, impact resistance and rigidity.

Description

Technical Field

[0001] The present invention relates to a glass fiber composite material and a thermoplastic continuous fiber reinforced textile including the same. More specifically, the present invention relates to a glass fiber composite material having excellent properties in terms of lightness, flame retardancy, impact resistance, and rigidity, a thermoplastic continuous fiber reinforced textile manufactured using the same, and a molded article including the same. Background Art

[0002] In order to meet the increasingly stringent demands for weight reduction and environmental friendliness in the automotive industry, there is a strong trend toward lightweight vehicle parts and the adoption of thermoplastic resins, particularly polypropylene (PP), in vehicle parts instead of environmentally harmful materials and thermosetting resins. In particular, with regard to the development of technologies for lightweight electric vehicle parts, there is a need for improvements in the materials used for battery pack covers that support electric vehicle batteries.

[0003] However, the use of thermoplastic resins as materials for battery pack covers and the like for the purpose of weight reduction causes problems such as deterioration in flame retardancy, impact resistance, rigidity, and the like compared to metals or thermosetting resins.

[0004] Therefore, despite the use of thermoplastic resins, there is a need to develop glass fiber composite materials and thermoplastic continuous fiber reinforced textiles produced using the same that have excellent characteristics in terms of lightness, flame retardancy, impact resistance, and rigidity.

[0005] Background art of the present invention is disclosed in Korean Patent Laid-Open Publication No. 10-2020-0033783 and the like. Summary of the Invention

[0006]

Technical Issues

[0007] An object of the present invention is to provide a glass fiber composite material having excellent characteristics in terms of lightness, flame retardancy, impact resistance, and rigidity.

[0008] Another object of the present invention is to provide a thermoplastic continuous fiber reinforced textile fabric manufactured using glass fiber composite materials.

[0009] It is a further object of the present invention to provide a molded article comprising the glass fiber composite material.

[0010] The above and other objects of the present invention can be achieved by the embodiments of the present invention described below.

[0011]

Technical solution

[0012] 1. One aspect of the present invention relates to a glass fiber composite material. The glass fiber composite material includes: about 100 parts by weight of glass fiber; about 35 to about 72 parts by weight of a polypropylene resin; about 12 to about 35 parts by weight of piperazine pyrophosphate; about 1 to about 20 parts by weight of a phosphazene compound; and about 1 to about 20 parts by weight of a zeolite.

[0013] 2. In embodiment 1, the polypropylene resin may include at least one of a homopolypropylene resin, a block polypropylene resin, and a random polypropylene resin.

[0014] 3. In embodiment 2, the weight ratio of piperazine pyrophosphate to the phosphazene compound may be in the range of about 1:0.1 to about 1:0.4.

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

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

[0017] 6. In embodiments 1 to 5, the glass fiber composite material may have a hardness of about 1.40 g / cm2 as measured in accordance with ISO 1183-1. 3 to about 1.55g / cm 3 density.

[0018] 7. In embodiments 1 to 6, the glass fiber composite material may have a flame retardancy of V-1 or higher measured on a 2 mm thick sample by the UL-94 vertical flammability test method.

[0019] 8. In embodiments 1 to 7, the fiberglass composite material may have a peak force of about 3.5 kN to about 6.0 kN, a total displacement of about 20 mm to about 35 mm, and an energy absorption of about 30 J to about 50 J at a displacement of 15 mm, measured in accordance with ISO 6603-2 using a 20 kg drop weight at a speed of 4.4 m / s and an impact energy of 198 J on a 60 mm × 60 mm × 2 mm sample.

[0020] 9. In embodiments 1 to 8, the glass fiber composite material may have a tensile strength of about 180 MPa to about 270 MPa measured on a 3 mm thick sample according to ISO 527.

[0021] 10. In embodiments 1 to 9, the glass fiber composite material may have a flexural strength of about 190 MPa to about 280 MPa measured on a 3 mm thick sample according to ISO 14125.

[0022] 11. In embodiments 1 to 10, the glass fiber composite material can self-extinguish without burning in a long-term flame retardancy test conducted by directly heating a 330 mm x 330 mm x 2 mm sample with a blue flame from a blowtorch at a distance of 7 cm for 2 minutes and 10 seconds and then removing the flame.

[0023] 12. Another aspect of the present invention relates to a thermoplastic continuous fiber reinforced textile fabric, which is manufactured using the glass fiber composite material according to any one of Embodiments 1 to 11 as warp and weft yarns.

[0024] 13. In embodiment 12, the thermoplastic continuous fiber reinforced textile may have a gap having a size of about 5 mm x about 5 mm or less between each pair of adjacent warp yarns and between each pair of adjacent weft yarns.

[0025] 14. A further aspect of the present invention relates to a molded article comprising a thermoplastic continuous fiber reinforced textile.

[0026] 15. In embodiment 14, the molded article may be a battery pack cover.

[0027] Beneficial effects

[0028] The present invention provides a glass fiber composite material having excellent characteristics in terms of lightness, flame retardancy, impact resistance, rigidity, etc., a thermoplastic continuous fiber reinforced textile produced using the same, and a molded product including the same. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 FIG. 4 is a plan view of a thermoplastic continuous fiber reinforced textile according to one embodiment of the present invention. DETAILED DESCRIPTION

[0030] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it should be understood that the following specific embodiments are provided to ensure that those skilled in the art have a thorough understanding of the present invention and that the following specific embodiments may be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.

[0031] In the accompanying drawings, the dimensions of the components, such as width or thickness, may be exaggerated for clarity. In addition, for ease of explanation, although only a portion of a particular component is shown in the accompanying drawings, those skilled in the art will be able to easily understand the remaining portions of the component. In addition, it will be apparent to those skilled in the art that the technical features of the present invention may be implemented in various other forms without departing from the spirit of the present invention. In this document, the description of the accompanying drawings is based on the observer's perspective, and the terms "top", "bottom", "left", "right", "front" and "rear" are defined relative to the directions of the accompanying drawings. In addition, it will be apparent to those skilled in the art that the technical features of the present invention may be implemented in various other forms without departing from the spirit of the present invention. Throughout the specification, the same components will be represented by the same figure numerals.

[0032] As used herein, the singular forms, "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. Moreover, when used in this specification, the terms "comprises," "comprising," "includes," and / or "including" indicate the presence of recited features, integers, steps, operations, elements, components, and / or combinations thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or combinations thereof.

[0033] The glass fiber composite material according to the present invention includes: (A) glass fiber; (B) polypropylene resin; (C) piperazine pyrophosphate; (D) a phosphazene compound; and (E) zeolite.

[0034] As used herein, when expressing a specific numerical range, "a to b" is defined as "≥a and ≤b".

[0035] (A) Glass fiber

[0036] The glass fiber according to one embodiment of the present invention, when impregnated with polypropylene resin, piperazine pyrophosphate, a phosphazene compound, and zeolite, can form a tape-shaped glass fiber composite material having excellent characteristics in terms of lightness, flame retardancy, impact resistance, and rigidity.

[0037] In some embodiments, the glass fiber may be provided in a fiber form and may have various cross-sectional shapes, such as round, oval, and rectangular, etc. For example, fibrous glass fibers having a circular cross-section and / or a rectangular cross-section as the glass fiber may be advantageous in terms of mechanical properties.

[0038] In some embodiments, when the glass fiber has a circular cross-section, the glass fiber may have a diameter of about 5 μm to about 20 μm, for example, about 7 μm to about 15 μm, measured using a scanning electron microscope (manufacturer: JEOL Co., Ltd., device name: JSM-6390A). When the glass fiber has a rectangular cross-section, the glass fiber may have an aspect ratio (major cross-sectional axis / minor cross-sectional axis) of about 1.5 to about 10, for example, about 2 to about 8, and a cross-sectional minor axis of about 2 μm to about 10 μm, for example, about 4 μm to about 8 μm, measured using a scanning electron microscope (manufacturer: JEOL Co., Ltd., device name: JSM-6390A). The glass fiber may have a pre-processed length of about 1 mm to about 30 mm, for example, about 2 mm to about 16 mm. Within these ranges, the glass fiber composite material may have good properties in terms of productivity and impregnation performance.

[0039] In some embodiments, the glass fiber may be treated with a typical surface treatment agent, which may include, but is not limited to, silane compounds, urethane compounds, and epoxy compounds.

[0040] (B) Polypropylene resin

[0041] The polypropylene resin according to one embodiment of the present invention, when impregnated onto glass fibers together with piperazine pyrophosphate, a phosphazene compound, and a zeolite, can form a tape-shaped glass fiber composite material having excellent characteristics in terms of lightness, flame retardancy, impact resistance, and rigidity, and can include a polypropylene resin used in a typical thermoplastic resin composition.

[0042] In some embodiments, the polypropylene resin may include at least one of a homopolymer polypropylene resin, a block polypropylene resin, and a random polypropylene resin. Here, the block polypropylene resin may include a block polypropylene resin comprising a homopolymer polypropylene block and an ethylene-propylene copolymer block and / or a homopolymer polyethylene block, and the random polypropylene resin may include a propylene-ethylene random copolymer.

[0043] In some embodiments, the polypropylene resin may have a melt flow index (MI) of about 1 g / 10 min to about 1,600 g / 10 min, for example, about 5 g / 10 min to about 1,400 g / 10 min, as measured under a load of 2.16 kg at a temperature of 230° C. according to ASTM D1238. Within this range, the glass fiber composite material may be excellent in mechanical properties, molding processability, and the like.

[0044] In some embodiments, the polypropylene resin may be present in an amount of about 35 parts by weight to about 72 parts by weight, for example, about 36 parts by weight to about 70 parts by weight, relative to about 100 parts by weight of the glass fiber. If the content of the polypropylene resin relative to about 100 parts by weight of the glass fiber is less than about 35 parts by weight, the glass fiber may break, making it impossible to manufacture a glass fiber composite material or the glass fiber composite material may suffer from deterioration in lightness, impregnation performance, and plasticity, etc., while if the content of the polypropylene resin relative to about 100 parts by weight of the glass fiber exceeds about 72 parts by weight, the glass fiber composite material may suffer from deterioration in flame retardancy, impact resistance, and rigidity, etc.

[0045] (C) Piperazine pyrophosphate

[0046] According to one embodiment of the present invention, piperazine pyrophosphate, when impregnated onto glass fiber together with a polypropylene resin, a phosphazene compound, and a zeolite, can form a tape-shaped glass fiber composite material having excellent characteristics in terms of lightness, flame retardancy, impact resistance, and rigidity, and can include piperazine pyrophosphate used as a phosphorus-nitrogen flame retardant.

[0047] In some embodiments, piperazine pyrophosphate may be present in an amount of about 12 parts by weight to about 35 parts by weight, for example, about 15 parts by weight to about 33 parts by weight, relative to about 100 parts by weight of the glass fiber. If the content of piperazine pyrophosphate relative to about 100 parts by weight of the glass fiber is less than about 12 parts by weight, the glass fiber composite material may suffer from deterioration in flame retardancy, etc., and if the content of piperazine pyrophosphate relative to about 100 parts by weight of the glass fiber exceeds about 35 parts by weight, the glass fiber composite material may suffer from deterioration in impact resistance, rigidity, and plasticity, etc.

[0048] In some embodiments, the weight ratio of the polypropylene resin to the piperazine pyrophosphate (polypropylene resin:piperazine pyrophosphate) may be in the range of about 1:0.2 to about 1:1, for example, about 1:0.25 to about 1:0.90. Within this range, the glass fiber composite material may have further improved properties in terms of flame retardancy, impact resistance, rigidity, and impregnation performance.

[0049] (D) Phosphazene compounds

[0050] The phosphazene compound according to one embodiment of the present invention, when impregnated onto glass fibers together with a polypropylene resin, piperazine pyrophosphate, and zeolite, can form a tape-shaped glass fiber composite material having excellent characteristics in terms of lightness, flame retardancy, impact resistance, and rigidity, and can include the phosphazene compound used in typical flame-retardant thermoplastic resin compositions.

[0051] In some embodiments, the phosphazene compound may include a phosphazene compound represented by Formula 1.

[0052] [Formula 1]

[0053]

[0054] In Formula 1, R1, R2, R3, R4, R5 and R6 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C 20 Alkyl, substituted or unsubstituted C2 to C7 alkenyl, substituted or unsubstituted C3 to C 20 Cycloalkyl, substituted or unsubstituted C2 to C 20 Heterocycloalkyl, C1 to C 20 Alkoxy, C6 to C 20 Aryl or aryloxy, C5 to C 20 Heteroaryl, substituted or unsubstituted C3 to C 20 Alkoxycarbonylalkyl, substituted or unsubstituted C2 to C 10 carbonylalkyl, amino or hydroxy.

[0055] In this context, "substituted" means that the hydrogen atoms in the corresponding functional groups are replaced by C1 to C 10 Alkyl, halogen, nitro, cyano, hydroxyl, amino, C6 to C 10 Aryl, C3 to C 10 Cycloalkyl, C3 to C 10 Heterocycloalkyl, C4 to C 10 The heteroaryl group is substituted with a substituent or combinations thereof.

[0056] In addition, "alkyl", "alkoxy" and other substitution products containing "alkyl" moieties include both straight-chain and branched forms, "alkenyl" includes both straight-chain and branched forms having 2 to 8 carbon atoms and containing at least one double bond, and "cycloalkyl" includes both saturated monocyclic ring structures and saturated bicyclic ring structures having 3 to 20 carbon atoms. In addition, "aryl" refers to a cyclic organic radical derived from an aromatic hydrocarbon by removing one hydrogen atom, and includes a monocyclic or fused ring system, wherein each ring appropriately contains 4 to 7, preferably 5 or 6 backbone atoms. Specific examples of "aryl" may include phenyl, naphthyl, biphenyl and tolyl, etc.

[0057] In addition, the "heterocycloalkyl group" refers to a cycloalkyl group containing 1 to 3 heteroatoms selected from N, O and S as backbone atoms of a saturated cyclic hydrocarbon structure and containing carbon as other backbone atoms of a saturated monocyclic ring structure or a saturated bicyclic ring structure, and may include, for example, pyrrolidinyl, azetidinyl, pyrazolidinyl, oxazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, tetrahydrothiazolyl, hydantoinyl, valerolactamyl, oxetanyl, oxetanyl, dioxolanyl, dioxanyl, oxathiolanyl, oxathianyl, dithianyl, dihydrofuranyl, tetrahydrofuranyl, dihydropyranyl, tetrahydropyranyl, tetrahydropyridinyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, diazepanyl and azepanyl and the like.

[0058] In addition, "heteroaryl" refers to an aryl group containing 1 to 3 heteroatoms selected from N, O and S as backbone atoms of the aromatic ring structure and containing carbon as other backbone atoms of the aromatic ring structure. Heteroaryl includes divalent aryl groups in which the heteroatoms in the ring structure are oxidized or quaternized to form, for example, N-oxides or quaternary salts. Specific examples of "heteroaryl" may include furyl, thienyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl.

[0059] In some embodiments, the phosphazene compound may be present in an amount of about 1 part by weight to about 20 parts by weight, for example, about 2 parts by weight to about 15 parts by weight, relative to about 100 parts by weight of the glass fiber. If the content of the phosphazene compound relative to about 100 parts by weight of the glass fiber is less than about 1 part by weight, the glass fiber composite material may suffer from deterioration in flame retardancy, etc., and if the content of the phosphazene compound relative to about 100 parts by weight of the glass fiber exceeds about 20 parts by weight, the glass fiber composite material may suffer from deterioration in productivity, impact resistance, rigidity, etc.

[0060] In some embodiments, the weight ratio of piperazine pyrophosphate to the phosphazene compound (piperazine pyrophosphate:phosphazene compound) may be in the range of about 1:0.1 to about 1:0.4, for example, about 1:0.13 to about 1:0.35. Within this range, the glass fiber composite material may have further improved properties in terms of flame retardancy, productivity, impregnation performance, etc.

[0061] (E) Zeolite

[0062] The zeolite according to one embodiment of the present invention, when impregnated onto glass fibers together with a polypropylene resin, piperazine pyrophosphate, and a phosphazene compound, can form a tape-shaped glass fiber composite material having excellent characteristics in terms of lightness, flame retardancy, impact resistance, and rigidity, and can include the zeolite used in typical thermoplastic resin compositions.

[0063] In some embodiments, the zeolite may include porous particles having a pore size of about 2 nm to about 8 nm, for example, about 3 nm to about 6 nm, and an average particle size of about 1 μm to about 7 μm, for example, about 3 μm to about 5 μm. Within these ranges, the glass fiber composite material may have good characteristics in terms of productivity and impregnation performance. Here, the average particle size of the zeolite is defined as the particle size at the 50% cumulative value obtained from the particle size distribution measured by the laser diffraction / scattering method.

[0064] In some embodiments, the zeolite may be present in an amount of about 1 part by weight to about 20 parts by weight, for example, about 2 parts by weight to about 15 parts by weight, relative to about 100 parts by weight of the glass fiber. If the zeolite content is less than about 1 part by weight relative to about 100 parts by weight of the glass fiber, the glass fiber composite material may suffer from deterioration in impact resistance and rigidity, etc., and if the zeolite content exceeds about 20 parts by weight relative to about 100 parts by weight of the glass fiber, the glass fiber composite material may suffer from deterioration in productivity and impregnation performance, etc.

[0065] In some embodiments, the weight ratio of the polypropylene resin to the zeolite (polypropylene resin:zeolite) may be in the range of about 1:0.05 to about 1:0.40, for example, about 1:0.06 to about 1:0.30. Within this range, the glass fiber composite material may have further improved properties in terms of impregnation performance, impact resistance, and rigidity.

[0066] The glass fiber composite material according to one embodiment of the present invention can be provided in a tape form, wherein the glass fiber is impregnated with a polypropylene resin, piperazine pyrophosphate, a phosphazene compound, and a zeolite, and can have a thickness of about 0.2 mm to about 1.5 mm, for example, about 0.3 mm to about 1.1 mm, and a width of about 5 mm to about 25 mm, for example, about 7 mm to about 20 mm. Within these ranges, the glass fiber composite material can have good properties in terms of flame retardancy, impact resistance, and rigidity.

[0067] In some embodiments, the glass fiber composite material can be manufactured by any suitable method known in the art. For example, the glass fiber composite material can be manufactured using the manufacturing equipment disclosed in Korean Patent Laid-Open Publication No. 10-2018-0035064.

[0068] In some embodiments, the glass fiber composite material may have a hardness of about 1.40 g / cm² as measured in accordance with ISO 1183-1. 3 to about 1.55g / cm 3 , for example, about 1.41 g / cm 3 to about 1.54g / cm 3 density.

[0069] In some embodiments, the fiberglass composite material may have a flame retardancy of V-1 or higher as measured by the UL-94 vertical flammability test method on a 2 mm thick specimen.

[0070] In some embodiments, the fiberglass composite material can have a peak force of about 3.5 kN to about 6.0 kN, e.g., about 3.6 kN to about 5.0 kN, measured in accordance with ISO 6603-2 on a 60 mm x 60 mm x 2 mm sample at a velocity of 4.4 m / s using a 20 kg drop weight at an impact energy of 198 J, a total displacement of about 20 mm to about 35 mm, e.g., about 22 mm to about 35 mm, and an energy absorption of about 30 J to about 50 J, e.g., about 30 J to about 45 J at a displacement of 15 mm.

[0071] In some embodiments, the fiberglass composite material can have a tensile strength of about 180 MPa to about 270 MPa, for example, about 181 MPa to about 260 MPa, as measured according to ISO 527 on a 3 mm thick sample.

[0072] In some embodiments, the fiberglass composite material can have a flexural strength of about 190 MPa to about 280 MPa, eg, 191 MPa to 270 MPa, as measured according to ISO 14125 on a 3 mm thick sample.

[0073] In some embodiments, the fiberglass composite can self-extinguish without burning in an extended flame retardancy test conducted by directly heating a 330 mm x 330 mm x 2 mm sample with a blue flame from a blowtorch at a distance of 7 cm for 2 minutes and 10 seconds, followed by removal of the flame.

[0074] Figure 1 FIG1 is a plan view of a thermoplastic continuous fiber reinforced textile according to one embodiment of the present invention. Figure 1 The thermoplastic continuous fiber reinforced textile 100 according to an embodiment of the present invention is a textile manufactured using a tape-shaped glass fiber composite material as the warp yarn 110 and the weft yarn 120. Such a textile can be manufactured by any appropriate method known in the art.

[0075] In some embodiments, the thermoplastic continuous fiber reinforced textile may have a gap 130 having a size of about 5 mm x about 5 mm or less between each pair of adjacent warp yarns 110 and between each pair of adjacent weft yarns 120. Within this gap size range, the gaps (pores) can be minimized during the manufacture of the molded article and the thermoplastic continuous fiber reinforced textile can be ensured to have good properties in terms of moldability, flame retardancy, impact resistance, rigidity, etc.

[0076] The molded article according to the present invention includes a thermoplastic continuous fiber reinforced textile and can be formed by a thermoplastic continuous fiber reinforced textile. The thermoplastic continuous fiber reinforced textile can be made into various molded articles by subjecting the thermoplastic continuous fiber reinforced textile to a temperature suitable for molding, (hot) pressing to minimize the gaps (pores) and compression molding. This molding method is well known to those skilled in the art to which the present invention belongs. The molded article has good properties in terms of lightness, flame retardancy, impact resistance, rigidity and the balance of properties therebetween, and therefore can be used as an internal material / external material for electronic devices, an internal material / external material for vehicles and a structural material for vehicles, in particular as a battery pack cover for electric vehicles.

[0077] [Invention Method]

[0078] Next, the present invention will be described in more detail with reference to some examples. It should be understood that these examples are provided for illustration only and are not to be construed as limiting the present invention in any way.

[0079] Example

[0080] Details of the components used in Examples and Comparative Examples are as follows.

[0081] (A) Glass fiber

[0082] Glass fiber having a circular cross section (manufacturer: Owens Corning, product name: SE4121 HP) was used.

[0083] (B) Polypropylene resin

[0084] Homopolymer polypropylene resin (manufacturer: LG Chem, product name: H7914A) was used.

[0085] (C) Phosphorus and nitrogen compounds

[0086] (C1) Piperazine pyrophosphate (manufacturer: Chempia, product name: FR220N) was used.

[0087] (C2) Melamine pyrophosphate (manufacturer: Chempia, product name: MPP-D) was used.

[0088] (D) Phosphorus compounds

[0089] (D1) A phosphazene compound (manufacturer: Chempia, product name: FRPPZ) was used.

[0090] (D2) Bisphenol A diphosphate (manufacturer: Jiangsu Yoke Technology, product name: YokeBDP) was used.

[0091] (E) Zeolite

[0092] Zeolite (manufacturer: Huin Chemical, product name: APS 30) was used.

[0093] Examples 1 to 5 and Comparative Examples 1 to 6

[0094] Glass fibers were impregnated with a polypropylene resin, a phosphorus-nitrogen compound (piperazine pyrophosphate or melamine pyrophosphate), a phosphorus compound (phosphazene compound or bisphenol A diphosphate), and zeolite in the amounts listed in Tables 1 and 2. A tape-shaped glass fiber composite (continuous fiber thermoplastic (CFT)) having a thickness of approximately 0.4 mm and a width of approximately 11 mm was then prepared using a method well known in the art. The resulting glass fiber composite was then woven as weft and warp yarns, forming a gap of 2 mm x 2 mm or less between each pair of adjacent weft yarns and between each pair of adjacent warp yarns to produce a thermoplastic continuous fiber-reinforced textile. Several layers of the thermoplastic continuous fiber-reinforced textile were then stacked to a predetermined thickness and then formed into flat sheet samples using hot and cold pressing. The flat sheet samples were then cut into predetermined sizes using a numerically controlled machine (NC machine) to prepare samples for property evaluation. The following properties of the prepared samples were evaluated, and the results are shown in Tables 1 and 2.

[0095] Characteristic evaluation

[0096] (1) Lightweight: Density is measured according to ISO 1183-1 (unit: g / cm 3 ).

[0097] (2) Flame retardancy: The flame retardancy of a 2 mm thick sample was measured by the UL-94 vertical flammability test method (unit: flammability grade).

[0098] (3) Impact resistance: The flat impact strength was evaluated by measuring the peak force (unit: kN), total displacement (unit: mm), and energy absorption at a displacement of 15 mm (unit: J) of a 60 mm × 60 mm × 2 mm sample at an impact energy of 198 J using a 20 kg drop hammer weight at a speed of 4.4 m / s in accordance with ISO 6603-2.

[0099] (4) Rigidity: The tensile strength of a 3 mm thick sample was measured according to ISO 527 (unit: MPa).

[0100] (5) Rigidity: The flexural strength of a 3 mm thick sample was measured in accordance with ISO 14125 (unit: MPa).

[0101] (6) Long-term flame retardancy: A long-term flame retardancy test was conducted by directly heating a 330 mm × 330 mm × 2 mm sample with a blue flame from a blowtorch at a distance of 7 cm for 2 minutes and 10 seconds, and then removing the flame. When the sample extinguished itself without burning after the flame was removed, the corresponding textile was evaluated as "passed" and, when the sample ignited after the flame was removed, the corresponding textile was evaluated as "failed".

[0102] Table 1

[0103]

[0104] Table 2

[0105]

[0106]

[0107] From the above results, it can be seen that the glass fiber composite materials, thermoplastic continuous fiber reinforced textiles and molded products according to the present invention exhibit good characteristics in terms of lightness (density), flame retardancy, impact resistance (peak force, total displacement, energy absorption at a displacement of 15 mm), rigidity (tensile strength, flexural strength) and balance of characteristics therebetween.

[0108] On the contrary, it can be seen that the glass fiber composite material of Comparative Example 1, which was manufactured using an insufficient amount of polypropylene resin, could not be manufactured into a tape form due to breakage of the glass fibers caused by increased friction between the nozzle and the glass fibers. The glass fiber composite material of Comparative Example 2, which was manufactured using an excessive amount of polypropylene resin, suffered from deterioration in flame retardancy, impact resistance, and rigidity. And the glass fiber composite material of Comparative Example 3, which was manufactured using an excessive amount of piperazine pyrophosphate, suffered from deterioration in impact resistance and rigidity. In addition, it can be seen that the glass fiber composite materials of Comparative Examples 4 and 5, which were manufactured using melamine pyrophosphate (C2) and bisphenol A diphosphate (D2) instead of piperazine pyrophosphate and the phosphazene compound according to the present invention, respectively, could not be manufactured into a tape form due to increased viscosity and reduced wettability. In addition, it can be seen that the glass fiber composite material of Comparative Example 6, which was manufactured without using zeolite, suffered from deterioration in impact resistance and rigidity.

[0109] Although some embodiments have been described herein, it will be understood by those skilled in the art that various modifications, changes and variations may be made without departing from the spirit and scope of the present invention. Therefore, it should be understood that these embodiments are provided for illustration only and are not to be construed as limiting the present invention in any way. The scope of the present invention is to be defined by the claims, rather than by the foregoing description, and the claims and their equivalents are intended to cover such modifications and the like that would fall within the scope of the present invention.

Claims

1. A glass fiber composite material comprising: about 100 parts by weight of glass fiber; about 35 parts by weight to about 72 parts by weight of a polypropylene resin; from about 12 parts by weight to about 35 parts by weight of piperazine pyrophosphate; about 1 part by weight to about 20 parts by weight of a phosphazene compound; and About 1 part by weight to about 20 parts by weight of zeolite. 2 . The glass fiber composite material according to claim 1 , wherein the polypropylene resin comprises at least one of a homopolypropylene resin, a block polypropylene resin, and a random polypropylene resin.

3. The fiberglass composite material according to claim 1 or claim 2, wherein the weight ratio of the piperazine pyrophosphate to the phosphazene compound is in the range of about 1:0.1 to about 1:0.

4.

4. The glass fiber composite material according to any one of claims 1 to 3, wherein the glass fiber composite material is provided in a tape form, wherein the glass fibers are impregnated with the polypropylene resin, the piperazine pyrophosphate, the phosphazene compound, and the zeolite.

5. The glass fiber composite material according to any one of claims 1 to 4, wherein the glass fiber composite material is provided in the form of a tape having a thickness of about 0.2 mm to about 1.5 mm and a width of about 5 mm to about 25 mm.

6. The glass fiber composite material according to any one of claims 1 to 5, wherein the glass fiber composite material has a density of about 1.40 g / cm3 as measured according to ISO 1183-1. 3 to about 1.55g / cm 3 density.

7. The glass fiber composite material according to any one of claims 1 to 6, wherein the glass fiber composite material has a flame retardancy of V-1 or higher measured on a 2 mm thick specimen by the UL-94 vertical flammability test method.

8. The glass fiber composite material according to any one of claims 1 to 7, wherein the glass fiber composite material has a peak force of about 3.5 kN to about 6.0 kN, a total displacement of about 20 mm to about 35 mm, and an energy absorption of about 30 J to about 50 J at a displacement of 15 mm, measured in accordance with ISO 6603-2 using a 20 kg drop weight at a velocity of 4.4 m / s at an impact energy of 198 J on a 60 mm x 60 mm x 2 mm sample.

9. The glass fiber composite material according to any one of claims 1 to 8, wherein the glass fiber composite material has a tensile strength of about 180 MPa to about 270 MPa measured according to ISO 527 on a 3 mm thick sample.

10. The glass fiber composite material according to any one of claims 1 to 9, wherein the glass fiber composite material has a flexural strength of about 190 MPa to about 280 MPa measured according to ISO 14125 on a 3 mm thick sample.

11. The glass fiber composite material according to any one of claims 1 to 10, wherein the glass fiber composite material self-extinguishes without burning in a long-term flame retardancy test conducted by directly heating a 330 mm x 330 mm x 2 mm sample with a blue flame from a blowtorch at a distance of 7 cm for 2 minutes and 10 seconds and then removing the flame.

12. A thermoplastic continuous fiber reinforced textile fabric, manufactured using the glass fiber composite material according to any one of claims 1 to 11 as warp yarns and weft yarns.

13. The thermoplastic continuous fiber reinforced textile according to claim 12, wherein the thermoplastic continuous fiber reinforced textile has a gap having a size of about 5 mm x about 5 mm or less between each pair of adjacent warp yarns and between each pair of adjacent weft yarns.

14. A molded product comprising the thermoplastic continuous fiber reinforced textile fabric according to claim 12. The molded article according to claim 14 , wherein the molded article is a battery pack cover.

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