TW202402895A - Glass-fiber-reinforced sheet - Google Patents

Abstract

The present invention provides a glass-fiber-reinforced sheet which has high transparency and sufficient strength, and for which a reduction in bending strength after exposure to flames is suppressed. This present invention is a glass-fiber-reinforced sheet that contains a chlorinated vinyl chloride resin and glass fibers, that has a void content as determined according to JIS K7075 of 10 vol% or less, and that has a fiber volume content (Vf) as determined according to JIS K7075 of 10 to 65 vol%.

Description

Glass fiber reinforced sheet

The invention relates to a glass fiber reinforced sheet.

Various batteries, such as lithium-ion batteries, are at risk of thermal runaway due to internal short circuits, etc., resulting in fires. Especially in vehicle batteries, there is a risk that the battery may undergo thermal runaway and catch fire due to impact such as a vehicle accident, resulting in a vehicle fire. Therefore, the cover covering the battery must not easily transmit the heat of the abnormally high temperature battery due to thermal runaway to the surroundings, or the flame or heat generated by the battery fire to the outside.

As a material for this type of battery case, fiberglass sheets are used because they do not easily generate heat in high-temperature environments such as flames. As such a glass fiber sheet, for example, Patent Document 1 describes a transparent non-combustible sheet in which a thermoplastic resin film is laminated on the surface of glass cloth, and an adhesive layer containing polyvinyl chloride and a plasticizer is disclosed. its composition. Furthermore, for example, Patent Document 2 discloses a waterproof sheet having a surface of a polyvinyl chloride sheet covered with glass cloth. [Prior technical literature] [Patent Document]

Patent Document 1: Japanese Patent Application Publication No. 2019-162831 Patent Document 2: Japanese Patent Application Publication No. 2011-36355

[Problem to be solved by the invention]

In addition, in the past, the casing of lithium-ion batteries for electric vehicles was fastened and sealed with bolts. Therefore, when an abnormality occurs or during inspection, the fastening part must be opened. This may make the operation time-consuming and laborious, or the lithium-ion battery may become abnormal after opening. Risk of endangering workers due to fever. For example, when the sheets described in Patent Documents 1 and 2 are used as covers for lithium ion batteries, although the transparency is high, there is a problem that the bending strength is significantly reduced by heating.

An object of the present invention is to provide a glass fiber reinforced sheet that has high transparency and sufficient strength and can suppress the decrease in bending strength after contact with flame. [Technical means to solve the problem]

The present invention (1) is a glass fiber reinforced sheet, which contains chlorinated vinyl chloride resin and glass fiber. The porosity measured according to JIS K7075 is less than 10% by volume, and the fiber volume occupation measured according to JIS K7075 The rate (Vf) is 10 volume% or more and 65 volume% or less. The present invention (2) is a glass fiber reinforced sheet as in the present invention (1), wherein the ratio of the refractive index of the chlorinated vinyl chloride resin to the refractive index of the glass fiber (refractive index of the chlorinated vinyl chloride resin/glass fiber Refractive index) is 0.8 or more and 1.2 or less. (3) of the present invention is a glass fiber reinforced sheet as in (1) or (2) of the present invention, and its total light transmittance is more than 50%. The invention (4) is a glass fiber reinforced sheet arbitrarily combined with any one of the inventions (1) to (3), and its bending strength reduction rate before and after being exposed to the burner flame for 30 seconds is 50% or less. The present invention (5) is a glass fiber reinforced sheet arbitrarily combined with any one of the present inventions (1) to (4), and its heating weight loss rate after removing the glass fiber component after heating at 500°C for 5 hours is 10 mass% or more. . The present invention (6) is a glass fiber reinforced sheet arbitrarily combined with any one of the present inventions (1) to (5), which is a cover material for lithium ion batteries. The present invention will be described in detail below.

The present inventors conducted intensive research and found that a glass fiber-reinforced sheet containing a chlorinated vinyl chloride resin and glass fiber with a porosity of 10 volume % or less has high transparency and sufficient strength, and can The present invention was completed by suppressing the decrease in bending strength after contact with flame.

The above-mentioned glass fiber reinforced sheet contains chlorinated vinyl chloride resin. By containing chlorinated vinyl chloride resin, both flame retardancy and transparency can be achieved.

The chlorine content of the above-mentioned chlorinated vinyl chloride-based resin is preferably 57 mass% or more, more preferably 60 mass% or more, and more preferably 75 mass% or less, more preferably 73 mass% or less. If the chlorine content is within the above range, the heat resistance and formability of the glass fiber reinforced sheet can be improved. The above-mentioned chlorine content can be measured by a method based on JIS K 7229, for example.

The average degree of polymerization of the above-mentioned chlorinated vinyl chloride-based resin is preferably 400 or more, more preferably 600 or more, and is preferably 3,000 or less, more preferably 2,000 or less. If the average degree of polymerization is within the above range, the thermal decomposition products are less likely to scatter during combustion, and the flame retardant performance can be maintained at a high level. The above-mentioned average degree of polymerization can be measured by a method based on JIS K 6720-2:1999, for example.

The above-mentioned chlorinated vinyl chloride resin generally has the following structural units (a) to (c). The ratio of the structural unit (a) in the chlorinated vinyl chloride resin to the total molar number of the structural units (a), (b) and (c) is preferably 5.2 mol% or more, more preferably 30.1 Mol% or more, more preferably 35.1 Mol% or more, more preferably 89.8 Mol% or less, more preferably 59.8 Mol% or less. Furthermore, the ratio of the structural unit (b) in the chlorinated vinyl chloride resin to the total molar number of the structural units (a), (b) and (c) is preferably 5.1 mol% or more, more preferably It is 15.2 mol% or more, and preferably 39.8 mol% or less, more preferably 30.0 mol% or less, and still more preferably 24.9 mol% or less. Furthermore, the ratio of the structural unit (c) in the chlorinated vinyl chloride resin to the total molar number of the structural units (a), (b) and (c) is preferably 5.3 mol% or more, more preferably It is 25.2 mol% or more, preferably 54.8 mol% or less, more preferably 39.9 mol% or less.

[Chemical 1]

The molar ratios of the above structural units (a), (b) and (c) can be measured by molecular structure analysis using NMR. NMR analysis can be performed according to the method described in R. A. Komoroski, R. G. Parker, J. P. Shocker, Macromolecules, 1985, 18, 1257-1265.

The oxygen index of the above-mentioned chlorinated vinyl chloride-based resin is preferably 20 or more, more preferably 22 or more, and is preferably 90 or less, more preferably 70 or less. If the oxygen index is within the above range, excellent flame retardant properties can be exhibited. The above-mentioned oxygen index is the minimum oxygen concentration (volume %) required for continuous combustion of the material, and can be determined according to JIS K7201-2:2007, for example.

The glass transition temperature of the above-mentioned chlorinated vinyl chloride-based resin is preferably 0°C or higher, more preferably 20°C or higher, further preferably 40°C or higher, and preferably 300°C or lower, more preferably 250°C or lower, and further preferably The best temperature is below 200℃. The above-mentioned glass transition temperature can be measured by a method based on JIS K 7121, for example.

The refractive index of the chlorinated vinyl chloride resin is preferably 1.2 or more, more preferably 1.3 or more, further preferably 1.4 or more, and preferably 1.9 or less, more preferably 1.8 or less, further preferably 1.7 or less. By setting it to the above range, sufficient transparency can be ensured. The refractive index of the above-mentioned chlorinated vinyl chloride resin can be measured by methods based on JIS K 7142 (A method) and ASTM D542. Furthermore, the refractive index can be adjusted by the chlorination degree (chlorine content) and weight average molecular weight of the chlorinated vinyl chloride resin.

Moreover, regarding the above-mentioned glass fiber reinforced sheet, the refractive index of a molded article obtained by drying and pressurizing the filtrate obtained by extraction with tetrahydrofuran (hereinafter also referred to as "refractive index of the molded article") is preferably 1.2 or more, more preferably It is 1.3 or more, more preferably 1.4 or more, more preferably 1.9 or less, more preferably 1.8 or less, still more preferably 1.7 or less. By setting it to the above range, sufficient transparency can be ensured. The above refractive index can be measured by methods based on JIS K 7142 (A method) and ASTM D542. More specifically, the following method can be used: dissolve 500 g of the above-mentioned glass fiber reinforced sheet in 3 L of tetrahydrofuran, filter out the insoluble matter, dry the filtrate to remove the solvent component, and pressurize the resin composition thus obtained. It was molded into a flat plate with a thickness of 0.5 mm to produce a molded product, and the refractive index of the obtained molded product was measured by the above method.

The weight average molecular weight of the above-mentioned chlorinated vinyl chloride-based resin is preferably 1,000 or more, more preferably 3,000 or more, and preferably 1,000,000 or less, more preferably 950,000 or less. The above-mentioned weight average molecular weight (Mw) can be measured, for example, by a method according to ASTM D2503.

The above-mentioned chlorinated vinyl chloride resin is a resin obtained by chlorinating vinyl chloride resin (PVC). As the above-mentioned vinyl chloride resin, a vinyl chloride homopolymer, a copolymer of a monomer having an unsaturated bond copolymerizable with a vinyl chloride monomer, and a vinyl chloride monomer can be used, and a vinyl chloride monomer graft-copolymerized on the polymer can be used. Graft copolymers, etc. These polymers may be used individually or in combination of 2 or more types.

Examples of the monomer having an unsaturated bond copolymerizable with a vinyl chloride monomer include α-olefins, vinyl esters, vinyl ethers, (meth)acrylates, aromatic vinyls, and vinyl halides. , N-substituted maleimides, etc., one or more of these may be used. Examples of the α-olefins include ethylene, propylene, butene, and the like. Examples of the vinyl esters include vinyl acetate, vinyl propionate, and the like. Examples of the vinyl ethers include butyl vinyl ether, cetyl vinyl ether, and the like. Examples of the (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl acrylate, and phenyl methacrylate. Examples of the aromatic vinyl compounds include styrene, α-methylstyrene, and the like. Examples of the vinyl halides include vinylidene chloride, vinylidene fluoride, and the like. Examples of the N-substituted maleimines include N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

The polymer used to graft-copolymerize vinyl chloride is not particularly limited as long as it is graft-polymerized vinyl chloride. Examples thereof include ethylene copolymer, acrylonitrile-butadiene copolymer, polyurethane, chlorinated polyethylene, chlorinated polypropylene, and the like. These may be used individually, or 2 or more types may be used together. Examples of the ethylene copolymer include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate-carbon monoxide copolymer, and ethylene-methacrylic acid Methyl ester copolymer, ethylene-propylene copolymer, etc.

The average degree of polymerization of the above-mentioned PVC is not particularly limited, but is preferably generally 400 to 3000, more preferably 600 to 2000. The average degree of polymerization can be measured by the method described in JIS K 6720-2:1999. The polymerization method of the above-mentioned PVC is not particularly limited, and conventionally known water suspension polymerization, block polymerization, solution polymerization, emulsion polymerization, etc. can be used.

The content of the above-mentioned chlorinated vinyl chloride resin in the above-mentioned glass fiber reinforced sheet is preferably 10 mass% or more, more preferably 20 mass% or more, further preferably 25 mass% or more, and preferably 80 mass% or less. More preferably, it is 70 mass % or less, and still more preferably, it is 60 mass % or less. By setting it within the above range, both transparency and flame retardancy can be achieved.

The content of the above-mentioned chlorinated vinyl chloride resin in the above-mentioned glass fiber reinforced sheet is preferably 20 volume % or more, more preferably 30 volume % or more, further preferably 35 volume % or more, and preferably 80 volume % or less. More preferably, it is 70 volume% or less, and still more preferably, it is 65 volume% or less.

The glass fiber reinforced sheet may contain thermoplastic resin other than chlorinated vinyl chloride resin, synthetic resin such as thermosetting resin, elastomer, etc.

Examples of the thermoplastic resin include vinyl chloride resin (PVC), polyolefins such as polyethylene and polypropylene, polystyrene (PS), acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene. -Styrene copolymer (ABS resin), polymethyl methacrylate and other acrylic resins, polyamide, polycarbonate, polystyrene (PSU resin), polyphenyl styrene (PPSU), polyether styrene (PES resin) , polyetherimide (PEI resin), polyphenylene sulfide (PPS resin), polyethylene terephthalate and polybutylene terephthalate and other polyester resins, polyacetal, polyimide, polyphenylene Ether, polyetheretherketone, liquid crystal polymer, etc.

Examples of the thermosetting resin include polyurethane, phenol resin, epoxy resin, urea resin, melamine resin, polysiloxy resin, unsaturated polyester resin, alkyd resin, thermosetting polyimide, and the like.

Examples of the elastomer include thermoplastic elastomers such as olefin elastomers, styrene elastomers, ester elastomers, amide elastomers, and vinyl chloride elastomers.

The above-mentioned glass fiber reinforced sheet contains glass fiber. By containing glass fiber, the strength after burning can be improved. Examples of the glass fiber include E glass, C glass, S glass, T glass, and the like.

The refractive index of the glass fiber is preferably 1.2 or more, more preferably 1.3 or more, further preferably 1.4 or more, and more preferably 1.9 or less, more preferably 1.8 or less, still more preferably 1.7 or less. By setting it to the above range, sufficient transparency can be ensured. The refractive index of the above-mentioned glass fiber can be measured according to the method of STM C1648 or ASTM E1967-19.

Furthermore, the ratio of the refractive index of the chlorinated vinyl chloride resin to the refractive index of the glass fiber (refractive index of the chlorinated vinyl chloride resin/refractive index of the glass fiber) is preferably 0.8 or more, more preferably 0.9 or more. And it is preferably 1.2 or less, more preferably 1.1 or less. By setting it within the above range, scattering and refraction of incident light can be suppressed and transparency can be ensured.

The ratio of the refractive index of the molded article to the refractive index of the glass fiber (refractive index of the molded article/refractive index of the glass fiber) is preferably 0.8 or more, more preferably 0.9 or more, and preferably 1.2 or less, more preferably 1.1 or less.

The average fiber diameter of the above-mentioned glass fiber is preferably 2 μm or more, more preferably 3 μm or more, and preferably 30 μm or less, more preferably 26 μm or less.

The above-mentioned glass fiber may be a discontinuous fiber in which the fiber is intermittently divided, or may be an undivided continuous fiber. When the above-mentioned glass fibers are discontinuous fibers, the average fiber length of the above-mentioned glass fibers is preferably 2 mm or more, more preferably 4 mm or more, and preferably 100 mm or less, more preferably 80 mm or less.

The specific gravity of the glass fiber is preferably 1.5 or more, more preferably 1.7 or more, further preferably 2.0 or more, and preferably 3.0 or less, more preferably 2.7 or less, further preferably 2.6 or less. The specific gravity can be measured using, for example, an electronic hydrometer.

The form of the glass fiber is not particularly limited, and examples thereof include fiber, woven fabric, knitted fabric, nonwoven sheet, and the like. When the above-mentioned glass fiber is in sheet form, the weight per unit area of the above-mentioned glass fiber is preferably 100 g/m ² or more, more preferably 350 g/m ² or more, and preferably 1000 g/m ² or less, and more preferably The best value is less than 650 g/ ^m2 . By setting it within the above range, both transparency and physical properties can be achieved.

The content of the above-mentioned glass fiber in the above-mentioned glass fiber reinforced sheet is preferably 10 mass% or more, more preferably 20 mass% or more, further preferably 25 mass% or more, and preferably 80 mass% or less, more preferably 70 mass% or less, and more preferably 60 mass% or less. If it is within the above range, the mechanical strength of the glass fiber reinforced sheet can be sufficiently improved.

The content of the above-mentioned glass fiber in the above-mentioned glass fiber reinforced sheet is preferably 20 volume % or more, more preferably 30 volume % or more, further preferably 35 volume % or more, and preferably 80 volume % or less, more preferably 70 Volume % or less, more preferably 65 volume % or less.

The above-mentioned glass fiber reinforced sheet may, in addition to the above-mentioned chlorinated vinyl chloride resin and glass fiber, optionally contain reinforcing fibers such as carbon fiber, metal fiber, organic fiber, and inorganic fiber. Examples of the carbon fiber include PAN-based carbon fiber, pitch-based carbon fiber, cellulose-based carbon fiber, and vapor-grown carbon fiber. Examples of the metal fibers include fibers made of metals such as iron, gold, silver, copper, aluminum, brass, and stainless steel. Examples of the above-mentioned organic fibers include polyarylamine, polybenzo Fibers composed of organic materials such as azole (PBO), polyphenylene sulfide, polyester, polyamide, polyethylene, etc. Examples of the inorganic fibers include fibers made of inorganic materials such as basalt, silicon carbide, and silicon nitride.

The fiber volume occupancy (Vf) of the above-mentioned glass fiber reinforced sheet measured in accordance with JIS K7075 is 10 volume % or more, preferably 15 volume % or more, more preferably 20 volume % or more, and further preferably 30 volume % or more. Furthermore, it is more preferably 35 volume % or more, and more preferably 65 volume % or less, preferably 60 volume % or less, more preferably 55 volume % or less, and still more preferably 50 volume % or less. By setting it within the above range, both transparency and physical properties can be achieved.

The above-mentioned glass fiber reinforced sheet preferably contains a heat stabilizer. Examples of the heat stabilizer include organic tin-based heat stabilizers, lead-based heat stabilizers, calcium-zinc heat stabilizers, barium-zinc heat stabilizers, and cadmium-barium heat stabilizers. Examples of the organic tin-based heat stabilizer include alkyl tins such as methyl tin, butyl tin, and octyl tin. Preferably, salts of aliphatic monocarboxylic acids such as dialkyl tin lauric acid or cis Salts of dicarboxylic acids such as butenedioic acid and phthalic acid. Specific examples include dibutyltin dilaurate, dioctyltin laurate, dibutyltin maleate, dibutyltin phthalate, dimethyltin bis(2-ethylhexyl thioglycolate), and sulfide. Dibutyltin alcohol, dimethyltin mercaptide, alkyltin mercaptide, etc. Examples of the lead-based heat stabilizer include lead stearate, dibasic lead phosphite, tribasic lead sulfate, and the like. Only one type of the above-mentioned heat stabilizer may be used, or two or more types may be used in combination.

The content of the heat stabilizer in the glass fiber reinforced sheet is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and preferably 30.0 mass% or less, more preferably 10.0 mass% or less. Furthermore, the content of the heat stabilizer in the glass fiber reinforced sheet is preferably 0.1 parts by mass or more, more preferably 0.8 parts by mass or more, and preferably 30.0 parts by mass, based on 100 parts by weight of the chlorinated vinyl chloride resin. parts or less, more preferably 15.0 parts by mass or less.

The above-mentioned glass fiber reinforced sheet may further contain additives such as lubricants, impact modifiers, inorganic fillers, pigments, flame retardants, antioxidants, processing aids, ultraviolet absorbers, and light stabilizers.

The above-mentioned glass fiber reinforced sheet preferably has a porosity of 10% by volume or less as measured in accordance with JIS K7075. By setting it within the above range, the decrease in bending strength after contact with flame can be suppressed. The above-mentioned porosity is preferably 0.1 volume % or more, more preferably 0.2 volume % or more, further preferably 0.3 volume % or more, and more preferably 10.0 volume % or less, more preferably 9.0 volume % or less, and still more preferably 8.0% by volume or less. The above-mentioned porosity refers to the ratio of the volume of pores (voids) in the glass fiber reinforced sheet. It can be determined by the pressure forming time, pressure forming temperature, the amount of solvent used during molding, and the addition of plasticizer. Adjust the amount, etc.

Moreover, the volume ratio (Vr) of the resin composition in the above-mentioned glass fiber reinforced sheet is preferably 25 volume % or more, more preferably 30 volume % or more, further preferably 35 volume % or more, still more preferably 40 volume % or more. , and it is preferably 80 volume % or less, more preferably 75 volume % or less, still more preferably 70 volume % or less, still more preferably 65 volume % or less. In addition, the above-mentioned resin composition volume ratio (Vr) is obtained by removing the above-mentioned fiber volume occupation ratio (Vf) and porosity from the volume of the entire glass fiber reinforced sheet, and can be calculated by the following formula. Resin composition volume ratio (Vr) = 100 - Vf - porosity

The heating weight loss rate of the above-mentioned glass fiber reinforced sheet after removing the glass fiber component after heating at 500°C for 5 hours is preferably 10 mass% or more. By setting it to the above range, transparency can be ensured and rigidity can be ensured. The heating weight loss rate is more preferably 10 mass% or more, further preferably 15 mass% or more, and is preferably 95 mass% or less, more preferably 85 mass% or less.

The total light transmittance of the above-mentioned glass fiber reinforced sheet is preferably above 50%. By setting it to the above range, transparency can be ensured. The above-mentioned total light transmittance is more preferably 50% or more, more preferably 60% or more, more preferably 100% or less, more preferably 99% or less, and still more preferably 98% or less. The above total light transmittance can be measured by the method according to JIS K7361-1.

The bending strength of the above-mentioned glass fiber reinforced sheet is preferably 100 MPa or more, more preferably 110 MPa or more, and preferably 300 MPa or less, more preferably 280 MPa or less. The above-mentioned bending strength can be measured by the method according to JIS K7171.

The bending strength of the above-mentioned glass fiber reinforced sheet before and after being exposed to the burner flame for 30 seconds is preferably 80 MPa or more, more preferably 90 MPa or more, and preferably 300 MPa or less, more preferably 280 MPa or less. Regarding the above-mentioned bending strength, specifically, the glass fiber reinforced sheet can be fixed to a fixture so that the thickness direction is vertical, the distance between the glass fiber reinforced sheet and the burner is set to 20 mm, and the glass fiber reinforced sheet is heated from below at 800°C. After heating for 30 seconds, the flexural strength of the heated glass fiber reinforced sheet was measured according to the method of JIS K7171.

The bending strength reduction rate of the above-mentioned glass fiber reinforced sheet before and after being exposed to the burner flame for 30 seconds is preferably less than 50%. By setting it to the above range, sufficient strength can be ensured after contact with the flame. The bending strength reduction rate is preferably 5% or more, more preferably 7% or more, further preferably 10% or more, and more preferably 75% or less, further preferably 60% or less.

The tensile strength of the above-mentioned glass fiber reinforced sheet is preferably 100 MPa or more, more preferably 120 MPa or more, and preferably 300 MPa or less, more preferably 280 MPa or less. The above tensile strength can be measured by a method according to ASTM D638.

The thickness of the above-mentioned glass fiber reinforced sheet is preferably 0.2 mm or more, more preferably 0.4 mm or more, and preferably 10 mm or less, more preferably 7 mm or less.

An example of a method for producing the above-mentioned glass fiber reinforced sheet is the following method: the above-mentioned chlorinated vinyl chloride resin and other additives are dissolved in a solvent to prepare a resin solution, and then the sheet-shaped glass fibers are impregnated with the resin solution and dried. The machine dries the solvent into shape. Examples of the molding method include manual coating molding, injection molding, resin transfer molding, pressure molding, bag molding, injection molding, extrusion molding, and press molding. .

Particularly when a press molding method is used, the pressing temperature is preferably 130°C or higher and 140°C or lower. Moreover, the pressurization time is preferably 10 seconds or more and 30 minutes or less. Furthermore, the pressurizing pressure is preferably 0.1 MPa or more and 30.0 MPa or less.

The above-mentioned glass fiber reinforced sheet has high transparency and can suppress the decrease in bending strength after being exposed to flame, so it can be suitably used as components for transportation machines, components for battery devices, and building materials. In addition, it can be suitably used as drone parts such as casings for small cameras mounted on drones.

Examples of the transport aircraft include automobiles such as gasoline vehicles, gasoline-electric hybrid vehicles, electric vehicles, and fuel cell vehicles; motorcycles such as gasoline locomotives, gasoline-electric hybrid locomotives, and electric locomotives; bicycles such as electric-assisted bicycles; rail vehicles; ships; and aircraft. . Moreover, examples of the above-mentioned transport vehicle members include structural members, interior members, exterior members, window glass, lampshades, and the like. Examples of the above-mentioned mechanical components include a cooling duct, an air bag cover, a ventilation duct, a heater unit, and the like. Examples of the interior components include ceilings, instrument panels, console boxes, armrests, seat belt buckles, switches, door trims, and the like. Examples of the exterior components include emblems, license plate casings, bumper cores, bottom covers, and the like.

Examples of the battery device include primary batteries such as nickel-manganese batteries, lithium batteries, and zinc-air batteries, secondary batteries such as nickel-metal hydride batteries, lithium-ion batteries, and lead-acid batteries, silicon-based solar cells, dye-sensitized solar cells, and calcium titanium batteries. Solar cells such as mine-type solar cells, solid polymer fuel cells, alkaline fuel cells, phosphoric acid fuel cells, solid oxide fuel cells and other fuel cells. Examples of the battery device components include battery covers, battery cooling water jackets, hydrogen tank cases, connectors, insulating sheets, and the like. In particular, the above-mentioned glass fiber reinforced sheet can be suitably used as a cover material for lithium-ion batteries. Furthermore, it can be suitably used as a vehicle-mounted battery in that it has high transparency and can suppress a decrease in bending strength after exposure to flame. Use cover material.

Examples of the above-mentioned building materials include lighting panels for entrances, dome roofs, etc., ceiling materials for garages, bicycle parking lots, bus stops, sunrooms, etc., translucent sound insulation panels and corrugated panels for roads, tracks, factory surroundings, etc. Industrial boards, etc. [Effects of the invention]

According to the present invention, it is possible to provide a glass fiber reinforced sheet that has high transparency and sufficient strength and can suppress a decrease in bending strength after exposure to flame.

The following examples are given to illustrate the present invention in more detail. The present invention is not limited to the following examples.

The following materials were used in Examples and Comparative Examples. <Chlorinated vinyl chloride resin> HA-05K: manufactured by Tokuyama Sekisui Industrial Co., Ltd., average degree of polymerization 500, chlorine content 67.3% by mass, refractive index 1.54 HA-28K: manufactured by Tokuyama Sekisui Industrial Co., Ltd., average degree of polymerization 700, chlorine Content 67.3% by mass, refractive index 1.54 HA-58K: manufactured by Tokuyama Sekisui Industrial Co., Ltd., average degree of polymerization 1000, chlorine content 67.3% by mass, refractive index 1.58 HA-27F: manufactured by Tokuyama Sekisui Industrial Co., Ltd., average degree of polymerization 700, chlorine Content 64.8% by mass, refractive index 1.48 HA-31N: manufactured by Tokuyama Sekisui Industrial Co., Ltd., average degree of polymerization 800, chlorine content 70% by mass, refractive index 1.62 <Other resins> Vinyl chloride resin TS-1000R: manufactured by Tokuyama Sekisui Industrial Co., Ltd. , average degree of polymerization 1000, refractive index 1.48 Polycarbonate Iupizeta PCZ-200: manufactured by Mitsubishi Gas Chemical Co., Ltd., viscosity average molecular weight 21,500, refractive index 1.58 <solvent> THF: tetrahydrofuran <glass fiber> Strand felt: manufactured by Nittobo Co., Ltd. "MC450A-104SS", refractive index 1.52, average fiber diameter 7 μm, unit area weight 450 g/m ² continuous filament mat: manufactured by Owens Corning Company, refractive index 1.52, average fiber diameter 10 μm, unit area weight 450 g/ m ² In addition, the refractive index of chlorinated vinyl chloride resin, vinyl chloride resin, and polycarbonate is measured by a method based on JIS K 7142 (A method). In addition, the refractive index of glass fiber is measured according to ASTM C1648. The viscosity average molecular weight [Mv] is calculated by using methylene chloride as the solvent and using an Ubbelohde viscometer to determine the ultimate viscosity [η] (unit dl/g) at 20°C. According to Schnell's viscosity formula, η = 1.23 × 10 ^{- 4} ×Mv ^0.83 is calculated. In addition, the limiting viscosity [eta] is a value calculated from the following formula by measuring the specific viscosity [eta _sp ] at each solution concentration [C] (g/dl). [Number 1]

(Example 1) A resin solution was prepared by mixing 90 parts by mass of chlorinated vinyl chloride-based resin, 10 parts by mass of a heat stabilizer (organotin-based heat stabilizer "TVS#1380" manufactured by Nitto Kasei Co., Ltd.) and 400 parts by mass of a solvent. Next, the sheet-shaped glass fiber is impregnated with the resin solution using a manual coating method. Repeat the above steps 7 times to build up 7 layers of glass fiber. Thereafter, the solvent is evaporated and dried using a dryer, and the glass is heated and pressurized (pressure molding time: 2 minutes, pressure molding temperature: 200°C, pressure molding pressure: 10 MPa) to obtain glass with a thickness of 2 mm. Fiber reinforced sheet. Furthermore, 500 g of the obtained glass fiber reinforced sheet was dissolved in 3 L of tetrahydrofuran, and the filtrate obtained by filtering out the insoluble matter was dried to remove the solvent component, thereby obtaining a resin composition. The obtained resin composition was pressed to produce a flat-shaped molded product with a thickness of 0.5 mm. The refractive index of the obtained molded article was measured by the method according to JIS K 7142 (A method).

(Example 2) 90 parts by mass of chlorinated vinyl chloride resin and 10 parts by mass of a heat stabilizer (organotin heat stabilizer "TVS#1380" manufactured by Nitto Kasei Co., Ltd.) were rolled and kneaded, and the resulting kneaded product was press-molded. Obtain a resin film. Use the glass fibers shown in Table 1 in the order of glass fiber/resin film/glass fiber/resin film/glass fiber/resin film/glass fiber/resin film/glass fiber/resin film/glass fiber/resin film/glass fiber The layers are laminated and heated and pressurized (pressure forming time: 5 minutes, press forming temperature: 210°C, press forming pressure: 20 MPa) to obtain a glass fiber reinforced sheet with a thickness of 2 mm.

(Examples 3 to 8) A glass fiber reinforced sheet was obtained in the same manner as in Example 1, except that the types and contents of the chlorinated vinyl chloride resin and glass fiber were set as shown in Table 1.

(Comparative example 1) Without using glass fiber, the resin solution is dried and then heated and pressed to obtain a resin sheet with a thickness of 2 mm.

(Comparative example 2) A glass fiber reinforced sheet was obtained in the same manner as in Example 1, except that the types and contents of the chlorinated vinyl chloride resin and glass fiber were set as shown in Table 1.

(Comparative example 3) Use the resin components in Table 1 instead of chlorinated vinyl chloride resin. Set the resin component content, heat stabilizer content, glass fiber type and content as shown in Table 1, and set the pressure molding temperature to 280°C, except that Except for this, a glass fiber reinforced sheet was obtained in the same manner as in Example 1.

(Comparative example 4) The resin component in Table 1 was used instead of the chlorinated vinyl chloride resin. The content of the resin component, the content of the heat stabilizer, and the type and content of the glass fiber were set as in Table 1. Except for this, glass was obtained in the same manner as in Example 1. Fiber reinforced sheet.

(evaluation) The laminates obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1.

(1) Fiber volume occupancy (Vf) For the obtained sheet, the fiber volume occupancy (Vf) was measured by a method based on JIS K7075 (combustion method). Specifically, it was measured under the following conditions. Test piece shape: length 10.0 mm × width 10.0 mm × thickness 2 mm

(2) Porosity The porosity of the obtained sheet was measured by a method based on JIS K7075 (combustion method). Specifically, it was measured under the following conditions. Test piece shape: length 10.0 mm × width 10.0 mm × thickness 2 mm

(3) Resin composition volume ratio (Vr) The volume ratio of the resin composition in the sheet based on Vf and porosity was calculated by the following formula. Vr＝100－Vf－porosity

(4) Total light transmittance For the obtained sheet, a hazemeter (Hazemeter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the total light transmittance under the following conditions. Sample size: 100 mm×100 mm×thickness 2 mm Light source: Halogen lamp 5 V, 2 A

(5) Bending strength For the obtained sheet, "Tensilon" manufactured by ORIENTEC was used and the bending strength was measured under the following conditions in accordance with JIS K7171. Test piece shape: length 80 mm × width 10 mm × thickness 2 mm Distance between fulcrums: 16×(test piece thickness) Temperature: 23℃ Test speed: 10 mm/min Sample cutting method: Composite material cutting machine (AC-300CF) manufactured by Maruto Manufacturing Co., Ltd. Condition adjustment: After cutting the sample with the above-mentioned cutting machine, dry it at 100°C for 3 hours, and then leave it to stand at 23°C for more than 24 hours before performing the measurement.

Furthermore, the obtained sheet was fixed to a jig so that the thickness direction was vertical, and the distance between the sheet and the burner was set to 20 mm, and the sheet was heated from below at 800° C. for 30 seconds. For the heated sheet, the flexural strength was measured in the same way. Furthermore, based on the bending strength before and after contact with the flame, the bending strength reduction rate was calculated.

(6) Tensile strength For the obtained sheet, "Tensilon" manufactured by ORIENTEC was used, and the tensile strength was measured under the following conditions according to the method of ASTM D638. Sample production method: Cutting using a water jet cutting machine Test speed: 5 mm/min Condition adjustment: After cutting the sample with the above-mentioned cutting machine, dry it at 100°C for 3 hours, and then leave it to stand at 23°C for more than 24 hours before performing the measurement.

(7) Heating loss rate Regarding Examples and Comparative Examples, sheets were produced without using glass fibers. For the obtained sheet, the heating weight loss rate after heating at 500° C. for 5 hours was measured using a thermogravimetric measuring device (TG/DTA6200 manufactured by Seiko Instruments) under the following conditions. Measuring temperature: 50～500℃ Heating rate: 10℃/min Measuring gas environment: nitrogen environment

[Table 1] Example Comparative example 1 2 3 4 5 6 7 8 1 2 3 4 Resin (parts by mass) CPVC HA-05K 90 90 90 - - 90 - - 90 90 - - HA-28K - - - 90 - - - - - - - - HA-58K - - - - 90 - - - - - - - HA-27F - - - - - - - 90 - - - - HA-31N - - - - - - 90 - - - - - PVC TS-1000R - - - - - - - - - - - 90 PC Iupizeta PCZ-200 - - - - - - - - - - 100 - Heat stabilizer (parts by mass) Organotin heat stabilizer 10 10 10 10 10 10 10 10 10 10 - 10 Solvent (parts by mass) THF 400 - 400 400 400 400 400 400 400 400 400 400 Glass fiber (mass parts) Strand felt 25 12 - 28 26 99 28 25 0 15 25 twenty four continuous filament felt - - 25 - - - - - - - - - Refractive index of resin 1.54 1.54 1.54 1.54 1.58 1.54 1.62 1.48 1.54 1.54 1.58 1.48 Refractive index of molded products 1.51 1.51 1.51 1.51 1.51 1.51 1.56 1.50 1.54 1.53 1.54 1.51 The refractive index of glass fiber 1.52 1.52 1.52 1.52 1.52 1.52 1.49 1.52 - 1.52 1.52 1.52 Refractive index of resin/refractive index of glass fiber 1.01 1.01 1.01 1.01 1.04 1.01 1.09 0.97 - 1.01 1.04 0.97 Refractive index of molded product/refractive index of glass fiber 0.99 0.99 0.99 0.99 0.99 0.99 1.05 0.99 - 1.01 1.01 0.99 f % 28 15 28 30 29 60 30 28 0 18 28 28 Porosity % 3 9.5 3 5 4 3 5 3 0 11 3 3 Vr % 69 76 69 65 67 37 65 69 100 71 69 69 Total light transmittance % 75 62 70 69 55 55 57 60 80 48 66 75 Bending strength before flame contact MPa 172 161 150 179 168 240 190 162 25 143 150 147 Bending strength after contact with flame MPa 121 118 115 123 112 160 138 102 10 98 twenty one 70 Bending strength reduction rate % 30 27 twenty three 31 33 33 27 37 60 31 86 52 tensile strength MPa 153 148 149 149 167 242 191 155 54 110 150 151 Heating loss rate mass % 99 99 99 99 99 99 99 99 100 99 99 99 [Industrial availability]

According to the present invention, it is possible to provide a glass fiber reinforced sheet that has high transparency and sufficient strength and can suppress a decrease in bending strength after exposure to flame.

without

without

Claims (6)

A glass fiber reinforced sheet, which contains chlorinated vinyl chloride resin and glass fiber, The porosity measured according to JIS K7075 is less than 10% by volume. The fiber volume occupancy (Vf) measured in accordance with JIS K7075 is 10 volume % or more and 65 volume % or less. The glass fiber reinforced sheet of Claim 1, wherein the ratio of the refractive index of the chlorinated vinyl chloride resin to the refractive index of the glass fiber (refractive index of the chlorinated vinyl chloride resin/refractive index of the glass fiber) is 0.8 or more and 1.2 the following. For example, the glass fiber reinforced sheet required in item 1 or 2 must have a total light transmittance of more than 50%. For example, for the glass fiber reinforced sheet in any one of claims 1 to 3, the bending strength reduction rate before and after being exposed to the burner flame for 30 seconds is less than 50%. For example, the glass fiber reinforced sheet according to any one of claims 1 to 4 has a heating weight loss rate of 10 mass% or more after removing the glass fiber component after heating at 500°C for 5 hours. The glass fiber reinforced sheet according to any one of claims 1 to 5 is a cover material for lithium ion batteries.