WO2021251103A1 - ガラス繊維強化樹脂成形品、電子機器筐体、モビリティ製品用内装部品、及び、モビリティ製品用外装部品 - Google Patents
ガラス繊維強化樹脂成形品、電子機器筐体、モビリティ製品用内装部品、及び、モビリティ製品用外装部品 Download PDFInfo
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- WO2021251103A1 WO2021251103A1 PCT/JP2021/019312 JP2021019312W WO2021251103A1 WO 2021251103 A1 WO2021251103 A1 WO 2021251103A1 JP 2021019312 W JP2021019312 W JP 2021019312W WO 2021251103 A1 WO2021251103 A1 WO 2021251103A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D13/00—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft
- D03D13/008—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft characterised by weave density or surface weight
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/1095—Coating to obtain coated fabrics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
- B29C70/22—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two dimensional structure
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/04—Fibre optics, e.g. core and clad fibre compositions
- C03C13/045—Silica-containing oxide glass compositions
- C03C13/046—Multicomponent glass compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/242—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
- D03D15/267—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2201/00—Chemical constitution of the fibres, threads or yarns
- D06N2201/08—Inorganic fibres
- D06N2201/082—Glass fibres
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
- D10B2101/06—Glass
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/02—Reinforcing materials; Prepregs
Definitions
- the present invention relates to glass fiber reinforced resin molded products, electronic device housings, interior parts for mobility products, and exterior parts for mobility products.
- glass fiber woven fabric has been widely used to impart strength, rigidity, insulation, nonflammability, etc. to a sheet-shaped resin material.
- the woven pattern of the glass fiber woven fabric has a unique aesthetic appearance
- the present inventors cannot visually recognize the texture of the glass fiber woven fabric in the transparent composite sheet, and the original design of the glass fiber woven fabric is obtained. I found that there is an inconvenience that is impaired.
- the present inventors have a problem that the transparent resin does not sufficiently impregnate the glass fiber fabric during the production of the transparent composite sheet, the glass fiber fabric is not sufficiently impregnated with the transparent resin. Although the texture can be observed, it has been found that the inconvenience that the reinforcing effect of the glass fiber reinforced resin molded body by the glass fiber woven material is lost occurs.
- the present invention has been made in view of the above circumstances, and the texture of the glass fiber woven fabric can be visually recognized, the design of the glass fiber woven fabric is exhibited, and the glass fiber woven fabric exhibits a sufficient reinforcing effect. It is an object of the present invention to provide a glass fiber reinforced resin molded product.
- the glass fiber reinforced resin molded product of the present invention is a glass fiber reinforced resin molded product containing a glass fiber woven fabric and a transparent resin, and the glass fiber woven fabric is not impregnated with a resin near the filament.
- the ratio is in the range of more than 2.0% and 50.0% or less, and the thread width Bt of the warp and the thread width By of the weft of the glass fiber woven fabric are in the range of 0.50 mm to 8.50 mm, respectively.
- the weaving density Wt of the warp and the weft density Wy of the glass fiber woven fabric are in the range of 3.0 / 25 mm to 50.0 / 25 mm, respectively, and the Bt / of the glass fiber woven fabric.
- the warp widening degree Et calculated at (25 / Wt) and the weft widening degree Ey calculated at By / (25 / Wy) are each in the range of 0.70 to 1.10. do.
- the filament-near resin unimpregnated rate of the glass fiber woven fabric is in the range of more than 2.0% and 50.0% or less, and the Bt, By, Wt, and the like.
- Wy, Et and Ey are in the above-mentioned range, the texture of the glass fiber woven fabric can be visually recognized, the design of the glass fiber woven fabric is exhibited, and the glass fiber woven fabric exhibits a sufficient reinforcing effect.
- the fact that the glass fiber woven fabric exerts a sufficient reinforcing effect means that the flexural modulus of the glass fiber reinforced resin molded product is 10 GPa or more.
- the resin non-impregnation rate in the vicinity of the average filament of the glass fiber woven fabric can be measured by the following method.
- a glass fiber reinforced resin molded product is cut using a diamond cutter, a jigsaw, or the like, and the cut surface is mechanically polished to prepare a measurement sample.
- the polished surface of the measurement sample was photographed at a magnification of 2500 times using a digital microscope (manufactured by Hirox Co., Ltd., model name: KH-8700), and the obtained image was taken.
- image processing software WinRooF2013 binarization processing is performed so that the glass filament 1 becomes black.
- a measurement region 2 is set in which 5 to 20 glass filaments 1 are included.
- the white portion in the measurement region is specified as the void portion 3, and the area of each void portion 3 is obtained.
- at least five measurement regions 2 having different numbers of glass filaments contained and not overlapping each other are set, and in each measurement region 2, the filament-neighboring resin non-impregnation rate is measured and the average is taken to obtain an average filament. Obtain the neighborhood resin non-impregnation rate.
- the flexural modulus of the glass fiber reinforced resin molded product is measured in accordance with JIS K 7017: 1999 using a precision universal testing machine (manufactured by Shimadzu Corporation, model name: AG-X Plus 50KN). be able to.
- the filament-near resin unimpregnated rate of the glass fiber woven fabric is in the range of 2.1% or more and 28.0% or less.
- the glass fiber woven fabric is excellently reinforced when the filament-near resin unimpregnated rate of the glass fiber woven fabric is in the range of 2.1% or more and 28.0% or less. It is effective.
- the fact that the glass fiber woven fabric exerts an excellent reinforcing effect means that the flexural modulus of the glass fiber reinforced resin molded product is 15 GPa or more.
- the filament-near resin unimpregnated rate of the glass fiber woven fabric is in the range of 2.5% or more and 10.0% or less.
- the glass fiber woven fabric is more excellent because the filament-near resin unimpregnated rate of the glass fiber woven fabric is in the range of 2.5% or more and 10.0% or less. Demonstrates a reinforcing effect.
- the fact that the glass fiber woven fabric exerts a more excellent reinforcing effect means that the flexural modulus of the glass fiber reinforced resin molded product is 18 GPa or more.
- the filament-near resin unimpregnated rate of the glass fiber woven fabric is in the range of 3.1% or more and 5.0% or less.
- the glass fiber woven fabric is further excellent because the filament-near resin unimpregnated rate of the glass fiber woven fabric is in the range of 3.1% or more and 5.0% or less. Demonstrates a reinforcing effect.
- the fact that the glass fiber woven fabric exerts a more excellent reinforcing effect means that the flexural modulus of the glass fiber reinforced resin molded product is 20 GPa or more.
- the mass of the warp (mass per unit length) and the mass of the warp (mass per unit length) of the glass fiber woven fabric are 210 tex to 850 tex, respectively. It is preferable that it is in the range of. In addition, 1tex corresponds to 1g / 1000m.
- the mass of the warp and the mass of the weft of the glass fiber woven fabric are in the range of 210 tex to 850 tex, respectively, so that the design of the glass fiber woven fabric is improved. It is more exhibited, and the smoothness of the glass fiber reinforced resin molded product becomes excellent.
- the fact that the glass fiber reinforced resin molded product has excellent smoothness means that the central average roughness Ra of the surface of the glass fiber reinforced resin molded product is 1 ⁇ m or less.
- the central average roughness Ra of the surface of the glass fiber reinforced resin molded product conforms to JIS B 0601: 2013 using a surface roughness measuring machine (manufactured by Mitutoyo Co., Ltd., model name: J? 47-2 to 0130). Can be measured.
- the glass fiber reinforced resin molded product of the present invention preferably has a dielectric constant of 5.5 or less at a measurement frequency of 1 GHz for the glass fibers constituting the warp and weft of the glass fiber woven fabric.
- the glass fiber reinforced resin molded product of the present invention has a dielectric constant of 5.5 or less at a measurement frequency of 1 GHz of the glass fibers constituting the warp and weft of the glass fiber woven fabric. It has excellent radio wave transmission.
- the glass composition of the glass fibers constituting the warp and weft of the glass fiber woven fabric is 60.0% by mass to 70.0% by mass with respect to the total amount of the glass fibers. and SiO 2 range of the Al 2 O 3 of 20.0 wt% to 30.0 wt%, it is preferable that the glass composition containing MgO in the range of 5.0 wt% to 15.0 wt% ..
- the glass composition of the glass fibers constituting the warp and weft of the glass fiber woven fabric has the above-mentioned glass composition, so that the glass fiber woven fabric has a particularly excellent reinforcing effect. Demonstrate.
- the fact that the glass fiber woven fabric exerts a particularly excellent reinforcing effect means that the flexural modulus of the glass fiber reinforced resin molded product is 24 GPa or more.
- the electronic device housing of the present invention includes the glass fiber reinforced resin molded product of the present invention.
- the electronic device housing of the present invention by including the glass fiber reinforced resin molded product of the present invention, sufficient rigidity and excellent designability are provided.
- the interior parts for mobility products of the present invention include the glass fiber reinforced resin molded product of the present invention.
- the interior parts for mobility products of the present invention by including the glass fiber reinforced resin molded product of the present invention, sufficient rigidity and excellent designability are provided.
- the exterior parts for mobility products of the present invention include the glass fiber reinforced resin molded products of the present invention.
- the exterior parts for mobility products of the present invention by including the glass fiber reinforced resin molded product of the present invention, sufficient rigidity and excellent designability are provided.
- the glass fiber reinforced resin molded product of the present embodiment is a glass fiber reinforced resin molded product containing a glass fiber woven fabric and a transparent resin, and the average filament-near resin non-impregnation rate of the glass fiber woven fabric is 2.0.
- the warp yarn width Bt and the weft yarn width By of the glass fiber woven fabric are in the range of 0.50 mm to 8.50 mm, respectively, and the glass fiber woven fabric is in the range of more than 50.0%.
- the weaving density Wt of the warp and the weaving density Wy of the weft are in the range of 3.0 / 25 mm to 50.0 / 25 mm, respectively, at Bt / (25 / Wt) of the glass fiber woven fabric.
- the warp widening degree Et calculated and the weft widening degree Ey calculated by By / (25 / Wy) are each in the range of 0.70 to 1.10.
- the average filament non-impregnated rate of the glass fiber woven fabric is in the range of more than 2.0% and 50.0% or less, and the Bt, By, and so on.
- Wt, Wy, Et and Ey are in the above-mentioned range, the texture of the glass fiber woven fabric can be visually recognized, the design of the glass fiber woven fabric is exhibited, and the glass fiber woven fabric exhibits a sufficient reinforcing effect. ..
- the fact that the glass fiber woven fabric exerts a sufficient reinforcing effect means that the flexural modulus of the glass fiber reinforced resin molded product is 10 GPa or more.
- the glass fiber reinforced resin molded product of the present embodiment when the resin non-impregnation rate in the vicinity of the average filament of the glass fiber woven product is 2.0% or less, the texture of the glass fiber woven fabric in the state of the glass fiber reinforced resin molded product. Is not visible, and therefore the design of the glass fiber woven fabric is not exhibited. On the other hand, if the resin non-impregnation rate in the vicinity of the average filament of the glass fiber woven fabric is more than 50.0%, the reinforcing effect of the glass fiber woven fabric is not sufficiently exhibited.
- the average filament non-impregnated rate of the glass fiber woven fabric is 2.1% or more and 28.0%. It is preferably in the following range. Further, since the glass fiber woven fabric exerts a more excellent reinforcing effect, the average filament non-impregnated rate of the glass fiber woven fabric is more preferably in the range of 2.5% or more and 10.0% or less. Further, since the glass fiber woven fabric exerts a more excellent reinforcing effect, the average filament non-impregnated rate of the glass fiber woven fabric is more preferably in the range of 3.1% or more and 5.0% or less.
- the resin non-impregnation rate in the vicinity of the average filament of the glass fiber woven fabric may be in the range of 3.1% or more and 4.0% or less. Particularly preferably, it is particularly preferably in the range of 3.1% or more and 3.9% or less, particularly preferably in the range of 3.1% or more and 3.7% or less, and 3.1% or more and 3.4. Most preferably, it is in the range of% or less.
- the unimpregnated rate of the resin near the filament of the glass fiber woven fabric can be controlled by the amount of the silane coupling agent and the dye or pigment other than the silane coupling agent adhering to the surface of the glass fiber woven fabric.
- the resin non-impregnation rate near the average filament of the glass fiber woven fabric can be obtained. Can be reduced.
- the amount of the silane coupling agent adhered to the surface of the glass fiber woven fabric may be, for example, 0.03% by mass or less, and the amount of the dye or pigment adhered may be. , 1.0% by mass or less.
- the yarn width Bt of the warp and the yarn width By of the weft of the glass fiber woven fabric are less than 0.50 mm or more than 8.50 mm, respectively, the glass.
- the design of the fiber woven fabric becomes insufficient.
- the yarn width Bt of the warp and the yarn width By of the weft of the glass fiber woven fabric are set to 0. It is preferably in the range of 80 mm to 4.80 mm, more preferably in the range of 1.60 mm to 3.30 mm, and even more preferably in the range of 1.70 mm to 2.30 mm.
- the thread widths Bt and By can be obtained by the following method. First, the surface of the glass fiber reinforced resin molded product is photographed with a digital microscope (manufactured by Hirox Co., Ltd., model name: KH-8700) at a magnification of 35 to 100 times. Next, for the obtained image, at least five warp threads are selected from one image or a plurality of images using the image processing software WinRooF2013, and one warp (weft) thread is selected for each warp (weft) thread. The warp (weft) thread width is measured at least 5 points from the region where the weft (warp) thread exists under the warp (weft) thread from the image of the above or a plurality of images. Bt (By) can be obtained by calculating the average of the warp (weft) yarn widths measured from one image.
- the thread widths Bt and By of the glass fiber fabric are, for example, whether or not the warp and the weft are rewound and the conditions, the tension condition applied to the warp during weaving the glass fiber fabric, and the conditions. Adjusted the weft driving conditions, the conditions for opening the fiberglass fabric using high-pressure water flow or ultrasonic waves that may be performed after weaving the glass fiber fabric, and the press conditions for producing the glass fiber reinforced resin molded product. It can be controlled by doing. For example, when the fiber opening treatment is performed with a high-pressure water flow, Bt and By can be increased by setting the water flow pressure in the range of 0.1 MPa to 4.0 MPa.
- the ratio of By to Bt (By / Bt) is, for example, in the range of 0.90 to 1.30 and in the range of 1.00 to 1.20. It is preferable, and it is more preferable that it is in the range of 1.00 to 1.05.
- the weaving density Wt of the warp and the weaving density Wy of the weft of the glass fiber woven fabric are each less than 3.0 / 25 mm or 50.0 / 25 mm, respectively. If it is super, the design of the glass fiber woven fabric becomes insufficient.
- the weaving density Wt of the warp and the weaving density Wy of the weft of the glass fiber fabric are set to 5. It is preferably in the range of 0/25 mm to 25.0 / 25 mm, more preferably in the range of 7.0 / 25 mm to 19.0 / 25 mm, and 7.5 / 25 mm to 17. It is more preferably in the range of 0/25 mm, particularly preferably in the range of 8.0 / 25 mm to 16.0 / 25 mm, and particularly preferably in the range of 11.0 / 25 mm to 14.0 / 25 mm. It is particularly preferable to be in.
- the Wt and Wy can be obtained by the following method. First, observe the surface of the glass fiber reinforced resin molded product using a scale loupe 6 times, ⁇ 30 (manufactured by KOKUYO Co., Ltd.), set at least 5 points of 25 mm in the weft (warp) yarn direction, and set at least 5 points in each area. Visually measure the number of warp (weft) threads that exist. Next, the Wt (Wy) can be obtained by averaging the number of warp (weft) yarns visually measured.
- the ratio of Wy to Wt is, for example, in the range of 0.85 to 1.20 and in the range of 0.95 to 1.15. It is preferably in the range of 1.00 to 1.10, more preferably in the range of 1.00 to 1.05, and particularly preferably in the range of 1.00 to 1.05.
- the glass fiber reinforced resin molded product of the present embodiment is calculated by the warp widening degree Et and By (25 / Wy) calculated by Bt / (25 / Wt) based on the Bt, By, Wt and Wy.
- Et and By 25 / Wy
- Bt / (25 / Wt) based on the Bt, By, Wt and Wy.
- Et and Ey are more than 1.10, respectively, the unevenness caused by the texture of the glass fiber woven fabric is reduced due to the overlap of the warp threads and the weft threads in the glass fiber woven fabric, and the unevenness is reduced.
- the texture of the glass fiber woven fabric is not regularly arranged, so that the glass fiber woven fabric cannot sufficiently exhibit the design in the glass fiber reinforced resin molded product.
- the Et is preferably in the range of 0.75 to 1.08, preferably 0.90 to 1.08, in order to more reliably exhibit the design of the glass fiber woven fabric. It is more preferably in the range of 1.07, further preferably in the range of 0.93 to 1.06, and particularly preferably in the range of 0.95 to 1.05. Further, the Ey is preferably in the range of 0.85 to 1.08, more preferably in the range of 0.90 to 1.07, and more preferably in the range of 0.95 to 1.06. It is more preferably in the range of 1.00 to 1.05, and particularly preferably in the range of 1.00 to 1.05.
- the Et and Ey can be controlled by adjusting Bt and By by the method described above.
- the glass composition of the glass fibers constituting the warp and weft of the glass fiber woven fabric is not particularly limited.
- the glass composition that the glass fiber can take the most general-purpose E glass composition (SiO 2 in the range of 52.0% by mass to 56.0% by mass in terms of oxide with respect to the total amount of the glass fiber, and 12 and 2.0% to 16.0% by mass of Al 2 O 3 in the range, and MgO and CaO in the range of 20.0% to 25.0 wt% in total, 5.0% to 10.0 mass Composition containing B 2 O 3 in the range of% ), high-strength, high-elasticity glass composition (SiO 2 in the range of 60.0% by mass to 70.0% by mass with respect to the total amount of glass fibers, and 20.0% by mass.
- MgO in the range of weight percent
- CaO in the range of 10.0% to 13.0 wt%
- B 2 O 3 in the range of 0.5 wt% to 1.5 wt%
- SiO 2 in the range of 0% by mass
- B 2 O 3 in the range of 17.0% by mass to 26.0% by mass
- Al 2 O 3 in the range of 9.0% by mass to 18.0% by mass.
- a composition containing F 2 and Cl 2 in the range of 0% by mass and P 2 O 5 in the range of 0% by mass to 6.0% by mass) can be mentioned.
- the glass composition of the glass fibers constituting the warp and weft of the glass fiber woven fabric has high strength and high elasticity. and SiO 2 in the range of 60.0% to 70.0% by mass with respect to the glass composition (glass fiber based on the total amount of the Al 2 O 3 in the range of 20.0% to 30.0 wt%, 5.0 It is preferable that the composition contains MgO in the range of% by mass to 15.0% by mass).
- the content of each component described above is measured by using an ICP emission spectrophotometer for Li, which is a light element, and wavelength dispersive for other elements. This can be done using a type fluorescent X-ray analyzer.
- the glass fiber reinforced resin molded product is heated in a muffle furnace at 300 ° C. to 650 ° C. for about 2 hours to 24 hours to remove the transparent resin, and the glass fiber woven fabric is taken out. , The removed glass fiber woven fabric is crushed.
- the obtained pulverized product is placed in a platinum crucible, kept at a temperature of 1550 ° C. for 6 hours in an electric furnace, and melted while stirring to obtain a homogeneous molten glass.
- the obtained molten glass is poured onto a carbon plate to produce a glass cullet, which is then pulverized and pulverized.
- Li which is a light element, is quantitatively analyzed using an ICP emission spectrophotometer after heat-decomposing the glass powder with an acid. Other elements are quantitatively analyzed using a wavelength dispersive fluorescent X-ray analyzer after the glass powder is formed into a disk shape by a press machine. The content and total amount of each component can be calculated by converting these quantitative analysis results into oxides, and the content (mass%) of each component described above can be obtained from these numerical values.
- the glass fibers constituting the warp and weft of the glass fiber woven fabric have a unique dielectric constant depending on the glass composition. Since the glass fiber reinforced resin molded product has excellent radio wave transmission, the glass fibers constituting the warp and weft of the glass fiber woven fabric have a dielectric constant of 5.5 or less at a measurement frequency of 1 GHz. It is preferably 5.0 or less, and more preferably 5.0 or less.
- the dielectric constant of the glass fiber constituting the warp and weft of the glass fiber woven fabric at a measurement frequency of 1 GHz can be obtained by the following method. First, at least 20 g of the glass fiber reinforced resin molded product is heated in a muffle furnace at 300 ° C. to 650 ° C. for about 2 hours to 24 hours to remove the transparent resin, and the glass fiber woven fabric is taken out and taken out. Crush the glass fiber woven fabric. Next, the obtained pulverized product is placed in a platinum crucible, kept at a temperature of 1550 ° C. for 6 hours in an electric furnace, and melted while stirring to obtain a homogeneous molten glass.
- the obtained molten glass is poured onto a carbon plate and polished to obtain a disc-shaped glass having a diameter of 40 mm and a thickness of 1 mm to 1.5 mm.
- the measurement frequency was set to 1 GHz, and the test method was based on ASTM test method D150 "Standard test method for AC loss characteristics and electric medium constant (dielectric constant) of solid electrical insulating material".
- ASTM test method D150 Standard test method for AC loss characteristics and electric medium constant (dielectric constant) of solid electrical insulating material.
- the warp and weft of the glass fiber woven fabric are manufactured as follows. First, the glass raw material (glass batch) prepared to have the above-mentioned composition is melted based on the components contained in the ore used as the glass raw material, the content of each component, and the volatilization amount of each component in the melting process. It is supplied to a furnace and melts at a temperature in the range of 1450 ° C to 1550 ° C, for example. Next, the molten glass batch (molten glass) is pulled out from 50 to 8000 nozzle tips of a bushing controlled to a predetermined temperature and rapidly cooled to form a glass filament.
- a sizing agent or a binder is applied to the formed glass filaments using an applicator, which is a coating device, and a sizing shoe is used to squeeze 50 to 8000 glass filaments while using a winder.
- Warp or weft can be obtained by winding on a tube at high speed.
- the molten glass is pulled out from 50 to 8000 nozzle tips of the bushing and rapidly cooled to form a glass filament, and a sizing agent or a binder is applied to the glass filament to squeeze 50 to 8000 glass filaments.
- a glass fiber strand is obtained by winding it around a tube, and the warp or weft can also be obtained by arranging 2 to 20 of the glass fiber strands while unwinding from the tube.
- the filament diameter of the glass filament constituting the warp and weft of the glass fiber woven fabric is, for example, in the range of 3.0 ⁇ m to 30.0 ⁇ m, preferably 6.5 ⁇ m. It is in the range of ⁇ 18.0 ⁇ m.
- the number of glass filaments constituting the warp and weft of the glass fiber woven fabric is, for example, in the range of 200 to 4000, preferably 800 to 2000. It is in the range.
- the filament diameter of the warp or weft is such that the glass fiber reinforced resin molded product is heated in a muffle furnace at 300 ° C. to 650 ° C. for about 2 hours to 24 hours.
- the transparent resin is removed, and the glass fiber woven fabric is taken out.
- a scanning electron microscope manufactured by Hitachi High-Technologies Co., Ltd.
- S-3400N magnification: 3000 times
- the number of glass filaments constituting the warp or weft is a scanning electron microscope (manufactured by Hitachi High-Technologies Co., Ltd., trade name: S-3400N, magnification: 500 times) for each 50 cross sections of the warp or weft. ) Is the average value of the measured values when the number of the warp or the glass filament constituting the weft is measured.
- the mass of the warp and weft of the glass fiber woven fabric is, for example, in the range of 120 tex to 1200 tex, the design of the glass fiber woven fabric is more exhibited, and the glass fiber is further exhibited.
- the smoothness of the reinforced resin molded product is excellent, it is preferably in the range of 210 tex to 850 tex, more preferably in the range of 220 tex to 750 tex, and further preferably in the range of 230 tex to 700 tex. , 240 tex to 650 tex, particularly preferably 250 tex to 500 tex, particularly preferably 260 tex to 440 tex, and most preferably 270 tex to 390 tex.
- the mass of the warp and weft of the glass fiber woven fabric is such that the glass fiber reinforced resin molded product is used in a muffle furnace at 300 ° C. to 650 ° C. for 2 hours to 24 hours.
- the transparent resin is removed by heating to some extent, the glass fiber woven fabric is taken out, and the taken out glass fiber woven fabric can be used for measurement in accordance with JIS R 3420: 2013.
- the warp and weft of the glass fiber woven fabric may be twisted in the range of 0.01 times / 25 mm to 4.0 times / 25 mm.
- the number of twists of the warp or weft is determined by removing the transparent resin by heating the glass fiber reinforced resin molded product in a muffle furnace at 300 ° C. to 650 ° C. for about 2 hours to 24 hours.
- the fiberglass fabric is taken out, the glass fiberglass fabric taken out is used, and a twisting device is used in accordance with JIS R3912, under the number of turns required for untwisting the test piece and the standard tension before untwisting the test piece. It can be calculated from the length in.
- the above-mentioned warp and weft are woven by a known loom such as a rapier loom under known conditions so as to have the above-mentioned weaving density. Can be manufactured.
- the glass fiber woven fabric can adjust the Bt and By by rewinding the warp and weft using a rewinding device before weaving. Further, in order to set the Bt and By to desired values, the glass fiber woven fabric after weaving has, for example, a fiber-spreading treatment by water flow pressure, a fiber-spreading treatment by high-frequency vibration using a liquid as a medium, and a surface pressure. It is possible to perform the fiber-spreading process by the pressure of the fluid and the fiber-spreading process by the pressurization by the roll.
- the woven glass fiber woven fabric in order to adjust the resin non-impregnation rate in the vicinity of the average filament of the glass fiber woven fabric, the woven glass fiber woven fabric is subjected to a temperature range of 200 ° C. to 650 ° C. and a temperature range of 200 ° C. to 650 ° C.
- the heating temperature and heating time in the range of 2 hours to 24 hours and heating, the sizing agent adhering to the warp and weft or the silane coupling agent contained in the binder is incinerated to incinerate the glass fiber woven fabric.
- the amount of the silane coupling agent adhering to the surface can be reduced to a desired amount.
- the glass fiber woven fabric after the silane coupling agent contained in the sizing agent or the binder adhering to the warp and the weft is incinerated is subjected to the silane coupling agent solution by adjusting the silane coupling agent concentration and the immersion time.
- the amount of the silane coupling agent adhering to the surface of the glass fiber woven fabric can be controlled to a desired value.
- the glass fiber woven fabric can be colored by being immersed in a solution containing a dye or a pigment.
- the weaving structure of the glass fiber woven fabric is not particularly limited, and plain weave, twill weave, satin weave and the like can be used. From the viewpoint of suppressing the occurrence of misalignment of the glass fiber woven fabric during the production of the glass fiber reinforced resin molded product, the woven structure of the glass fiber woven fabric is preferably plain weave.
- the mass per unit area of the glass fiber woven fabric is, for example, in the range of 150 g / m 2 to 800 g / m 2 , preferably 210 g / m 2 to 650 g / m. It is in the range of m 2 , more preferably in the range of 240 g / m 2 to 500 g / m 2 , still more preferably in the range of 260 g / m 2 to 390 g / m 2 , and particularly preferably in the range of 265 to 340 g. It is in the range of / m 2.
- the mass per unit area of the glass fiber woven fabric is 2 hours to 24 hours in a glass fiber reinforced resin molded product, for example, in a muffle furnace at 300 ° C to 650 ° C.
- the transparent resin is removed by heating to some extent, and the glass fiber woven fabric is taken out.
- a glass cloth cut into a size of 200 mm ⁇ 200 mm with a JIS R 3420 compliant scale. It is the average value of the values obtained by measuring the mass of 3 points and converting each into the mass per 1 m 2.
- the thickness of the glass fiber woven fabric is, for example, in the range of 150 ⁇ m to 900 ⁇ m, preferably in the range of 250 ⁇ m to 700 ⁇ m, and more preferably in the range of 350 ⁇ m to 500 ⁇ m. It is in the range.
- the thickness of the glass fiber woven fabric is such that the glass fiber reinforced resin molded product is heated in a muffle furnace at 300 ° C. to 650 ° C. for about 2 hours to 24 hours. Then, the transparent resin was removed, the glass fiber woven fabric was taken out, and the thickness of the taken out glass fiber woven fabric was measured with a micrometer at 15 points in the glass cloth in accordance with JIS R 3420. It is the average value of the measured values at the time.
- the amount of the silane coupling agent attached to the surface of the glass fiber woven fabric is, for example, based on the mass of the glass fiber woven fabric to which no organic matter or the like adheres to the surface. It is 0.03% by mass or less, preferably 0.02% by mass or less.
- silane coupling agent examples include aminosilane, vinylsilane, epoxysilane, methacrylsilane, cationicsilane, acrylicsilane, phenylsilane, halogenosilane, ureidosilane, mercaptosilane, sulfidesilane, isocyanatesilane, isocyanuratesilane, and styryl. Silane can be mentioned.
- the silane coupling agents may be used alone or in combination of two or more.
- aminosilane examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, ureidopropyltrimethoxysilane, ureidopropyltriethoxysilane, and N-.
- Examples thereof include 2- (aminoethyl) -3-aminopropyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane.
- vinyl silane examples include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl acetoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropylmethyldimethoxy.
- examples thereof include silane, 3-methacryloxypropylmethyldiethoxysilane, and 3-acryloxypropyltrimethoxysilane.
- epoxysilane examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-. (3,4-Epylcyclohexyl) ethyltrimethoxysilane can be mentioned.
- methacrylsilane examples include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
- Examples of the cationic silane include N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane hydrochloride, and the like.
- acrylic silane examples include 3-acryloxypropyltrimethoxysilane.
- phenylsilane examples include trimethoxyphenylsilane and triethoxyphenylsilane.
- halogenosilane examples include (3-chloropropyl) trimethoxysilane and (3-chloropropyl) triethoxysilane.
- ureidosilane examples include 3-ureidopropyltriethoxysilane.
- Examples of the mercaptosilane include ⁇ -mercaptopropyltrimethoxysilane.
- sulfide silane examples include bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide.
- isocyanate silane examples include 3-isocyanate propyltriethoxysilane.
- isocyanate silane examples include tris (trimethoxysilylpropyl) isocyanate.
- styrylsilane examples include styryltrimethoxysilane.
- the glass fiber woven fabric is usually white, but may be colored black, gold, silver, blue, or red with a dye or pigment.
- the amount of the dye or pigment adhering to the surface of the glass fiber woven fabric is, for example, 1.0% by mass or less based on the weight of the glass fiber woven fabric.
- Examples of the dye or pigment include carbon black, titanium oxide, zinc oxide, iron oxide, chromium oxide, synthetic silica, fired pigment, zinc sulfide and the like.
- the glass fiber reinforced resin molded product of the present embodiment it is possible to print a pattern, a pattern, an image, letters, numbers, etc. on the surface of the glass fiber woven fabric, but the aesthetic appearance of the woven pattern of the glass fiber woven fabric can be obtained. In order to maximize the effect, it is preferable that the surface of the glass fiber woven fabric is not printed with a pattern, a pattern, an image, letters, numbers or the like.
- the transparent resin means a resin having a total light transmittance of 85% or more measured in accordance with JIS K 7375: 2008.
- the transparent resin include curable resins such as epoxy resin, unsaturated polyester resin, vinyl ester resin, polyisocyanate resin, and polyimide resin, polystyrene resin, acrylonitrile / butadiene / styrene (ABS) resin, and (meth).
- Thermoplastic resins such as acrylic resin, polyacetal resin, polyethylene terephthalate (PET) resin, polycarbonate resin, and polyarylate (PAR) resin can be mentioned.
- the glass fiber reinforced resin molded product of the present embodiment uses a press molding method, a hand lay-up molding method, a continuous panel molding method, an infusion molding method, an RTM molding method, or the like. It can be obtained by impregnating the glass fiber woven fabric with a curable resin and curing or semi-curing the curable resin by thermosetting or photocuring. Further, it is also possible to obtain a glass fiber reinforced resin molded product by using a press molding method for a glass fiber reinforced resin molded product (prepreg) in a state where the curable resin is semi-cured.
- preg glass fiber reinforced resin molded product
- the transparent resin is a thermoplastic resin
- a press molding method or a double belt type is used for a laminated product of the thermoplastic resin film and the glass fiber woven fabric. It can be obtained by using the continuous press molding method or the like.
- the glass fiber woven fabric may be used alone or may be used by laminating 2 to 5 sheets. Further, one or more of the glass fiber woven fabrics may be arranged on the surface layer portion, and a reinforcing fiber woven fabric other than the glass fiber woven fabric may be laminated on the lower layer portion of the glass fiber woven fabric.
- the ratio of the glass fiber woven fabric (the total amount when a plurality of glass fiber woven fabrics are contained) to the total amount may be referred to as glass content).
- glass content the ratio of the glass fiber woven fabric (the total amount when a plurality of glass fiber woven fabrics are contained) to the total amount (hereinafter, may be referred to as glass content).
- glass content is in the range of 55% by mass to 80% by mass, preferably in the range of 60% by mass to 78% by mass, and more preferably in the range of 65% by mass to 75% by mass.
- the glass content can be calculated in accordance with JIS K7052: 1999.
- the transparent resin may be a transparent resin composition containing the transparent resin and an additive.
- the additive include reinforcing fibers (for example, glass fiber, carbon fiber, metal fiber, etc.), fillers (for example, glass powder, talc, mica, etc.), curing agents, polymerization initiators, flame retardants, ultraviolet absorbers, and the like. Examples thereof include heat stabilizers, antioxidants, antistatic agents, fluidity improvers, antiblocking agents, lubricants, nucleating agents, antibacterial agents, pigments and the like.
- these additives may be contained in the range of 0.1 to 50.0% by mass with respect to the total amount of the resin composition.
- the glass fiber reinforced resin molded product of the present invention has sufficient rigidity and excellent designability, it can be suitably used for electronic device housings, interior parts for mobility products, exterior parts for mobility products, and the like. ..
- Examples of the electronic device housing include a smartphone housing, a mobile personal computer housing, a notebook computer housing, a tablet housing, a WiFi router housing, a smart speaker housing, a television housing, a monitor housing, and a smart home appliance housing. And so on.
- Examples of the interior parts for mobility products include automobile interior parts, aircraft interior parts, and railroad vehicle interior parts.
- Examples of the automobile interior parts include a dash panel, a console box, an air conditioner louver, and the like.
- aircraft interior parts examples include wall materials, trays, remote control housings, screen housings, and the like.
- Examples of the interior parts for railway vehicles include wall materials, window frames, ceiling materials, and the like.
- Examples of the exterior parts for mobility products include automobile exterior parts and railroad vehicle exterior parts.
- Examples of the automobile exterior parts include fenders, doors, roofs, hoods, spoilers, and the like.
- Examples of the exterior parts for railway vehicles include vehicle body outer panels and the like.
- Example 1 The glass fiber yarns shown in Table 1 having a glass composition A and having a mass of 285 tex were used as warps and wefts.
- the warp weft density Wt was 12.5 wefts / 25 mm
- the weft weft density Wy was 12.5 wefts / 25 mm
- weaving was performed into a plain weave using a rapier loom to obtain a glass fiber woven fabric of 275 g / m 2.
- the glass fiber woven fabric was subjected to a fiber opening treatment by a water flow pressure set to 1.0 MPa. Next, after heating this glass fiber woven fabric at 600 ° C.
- silane using 3-aminopropyltriethoxysilane as a silane coupling agent so that the amount of the silane coupling agent adhered is 0.02% by mass.
- Immersed in an aqueous solution of the coupling agent Immersed in an aqueous solution of the coupling agent.
- an unsaturated polyester resin composition (denoted as "polyester” in Table 2) was applied to the glass fiber woven fabric as a transparent resin and pressed at 100 ° C. and 20 MPa to reinforce the glass fiber of Example 1.
- a molded product was obtained.
- the unsaturated polyester resin composition contains 100 parts by mass of an unsaturated polyester resin (manufactured by Japan Composite Co., Ltd., trade name: Polyhope 6339) and 2 parts by mass of a curing agent (manufactured by Tokyo Kasei Kogyo Co., Ltd., trade name: BPO). , The total light transmittance of the resin composition is 94%.
- the average filament near resin unimpregnated rate, the warp thread width Bt, the weft thread width By, and the glass content were measured by the above-mentioned method, and the warp widening degree Et and the weft were measured.
- the widening degree Eye was calculated. The results are shown in Table 2.
- the flexural modulus was measured by the above-mentioned method, and the texture visibility, design (texture unevenness), surface smoothness and surface smoothness were measured by the methods shown below.
- the radio wave permeability was evaluated. The results are shown in Table 2.
- the center average roughness Ra of the surface of the glass fiber reinforced resin molded product is measured according to JIS B 0601: 2013 using a surface roughness measuring machine (manufactured by Mitutoyo Co., Ltd., model name: J? 47-2 to 0130). The measurement was performed and evaluated as "A” when the central average roughness Ra was 1 ⁇ m or less, “B” when it was more than 1 ⁇ m and 10 ⁇ m or less, and “C” when it was more than 10 ⁇ m.
- Example 2 The same as in Example 1 was carried out except that the glass fiber yarn having the glass composition B and the mass of 275 tex shown in Table 1 was used as the warp and the weft to obtain a glass fiber woven fabric of 270 g / m 2.
- the glass fiber reinforced resin molded product of Example 2 was obtained.
- the average filament near resin unimpregnated rate, the warp thread width Bt, the weft thread width By, and the glass content were measured by the above-mentioned method, and the warp widening degree Et and the weft were measured.
- the widening degree Eye was calculated. The results are shown in Table 2.
- the flexural modulus was measured by the above-mentioned method, and the texture visibility, designability (texture unevenness), surface smoothness and radio wave transmission were evaluated. .. The results are shown in Table 2.
- Example 3 The same as in Example 1 was carried out except that the glass fiber yarn having the glass composition C and the mass of 295tex shown in Table 1 was used as the warp and the weft to obtain a glass fiber fabric of 280 g / m 2.
- the glass fiber reinforced resin molded product of Example 3 was obtained.
- the average filament near resin unimpregnated rate, the warp thread width Bt, the weft thread width By, and the glass content were measured by the above-mentioned method, and the warp widening degree Et and the weft were measured.
- the widening degree Eye was calculated. The results are shown in Table 2.
- the flexural modulus was measured by the above-mentioned method, and the texture visibility, designability (texture unevenness), surface smoothness and radio wave transmission were evaluated. .. The results are shown in Table 2.
- Example 4 The glass fiber yarns having a glass composition C and having a mass of 600 tex shown in Table 1 are used as warp and weft, and the warp weaving density Wt is 9.0 / 25 mm and the weft density Wy is 8.0 / 25 mm. , A glass fiber reinforced resin molded product of Example 4 was obtained in exactly the same manner as in Example 1 except that a glass fiber woven fabric of 420 g / m 2 was obtained.
- the average filament near resin unimpregnated rate, the warp thread width Bt, the weft thread width By, and the glass content were measured by the above-mentioned method, and the warp widening degree Et and the weft were measured.
- the widening degree Eye was calculated. The results are shown in Table 2.
- the flexural modulus was measured by the above-mentioned method, and the texture visibility, designability (texture unevenness), surface smoothness and radio wave transmission were evaluated. .. The results are shown in Table 2.
- Example 5 The glass fiber yarns having a glass composition C and a mass of 1150 tex shown in Table 1 are used as warp and weft, and the warp weaving density Wt is 7.0 / 25 mm and the weft weaving density Wy is 6.5 / 25 mm. , A glass fiber reinforced resin molded product of Example 5 was obtained in exactly the same manner as in Example 1 except that a glass fiber woven fabric of 630 g / m 2 was obtained.
- the average filament near resin unimpregnated rate, the warp thread width Bt, the weft thread width By, and the glass content were measured by the above-mentioned method, and the warp widening degree Et and the weft were measured.
- the widening degree Eye was calculated. The results are shown in Table 2.
- the flexural modulus was measured by the above-mentioned method, and the texture visibility, designability (texture unevenness), surface smoothness and radio wave transmission were evaluated. .. The results are shown in Table 2.
- Example 6 The glass fiber yarns having a glass composition C and having a mass of 135 tex shown in Table 1 are used as warp yarns and weft yarns, and the warp weaving density Wt is 20.0 yarns / 25 mm and the weft weaving density Wy is 20.0 yarns / 25 mm.
- a glass fiber reinforced resin molded product of Example 6 was obtained in exactly the same manner as in Example 1 except that a glass fiber woven fabric of 215 g / m 2 was obtained.
- the average filament near resin unimpregnated rate, the warp thread width Bt, the weft thread width By, and the glass content were measured by the above-mentioned method, and the warp widening degree Et and the weft were measured.
- the widening degree Eye was calculated. The results are shown in Table 3.
- the flexural modulus was measured by the above-mentioned method, and the texture visibility, designability (texture unevenness), surface smoothness and radio wave transmission were evaluated. .. The results are shown in Table 3.
- Example 7 The glass fiber reinforced resin molded product of Example 7 was obtained in exactly the same manner as in Example 5 except that it was immersed in the silane coupling agent aqueous solution so that the amount of the silane coupling agent adhered was 0.01% by mass.
- the average filament near resin unimpregnated rate, the warp thread width Bt, the weft thread width By, and the glass content were measured by the above-mentioned method, and the warp widening degree Et and the weft were measured.
- the widening degree Eye was calculated. The results are shown in Table 3.
- the flexural modulus was measured by the above-mentioned method, and the texture visibility, design (texture unevenness), surface smoothness and radio wave transmission were evaluated. .. The results are shown in Table 3.
- Example 8 The glass fiber reinforced resin molded product of Example 8 was obtained in exactly the same manner as in Example 5 except that it was immersed in the silane coupling agent aqueous solution so that the amount of the silane coupling agent adhered was 0.005% by mass.
- the average filament near resin unimpregnated rate, the warp thread width Bt, the weft thread width By, and the glass content were measured by the above-mentioned method, and the warp widening degree Et and the weft were measured.
- the widening degree Eye was calculated. The results are shown in Table 3.
- the flexural modulus was measured by the above-mentioned method, and the texture visibility, design (texture unevenness), surface smoothness and radio wave transmission were evaluated. .. The results are shown in Table 3.
- Example 9 A glass fiber reinforced resin molded product of Example 9 was obtained in exactly the same manner as in Example 3 except that an acrylic resin composition (denoted as “acrylic” in Table 3) was used as the transparent resin.
- the acrylic resin composition includes an acrylic resin (manufactured by Osaka Organic Chemical Co., Ltd., trade name: Viscoat # 155), a photopolymerization initiator (manufactured by BASF, trade name: Irgacure 184, (1-hydroxy-cyclohexyl-phenyl-ketone)).
- a solvent diethylene glycol monoethyl ether acetate manufactured by Shinko Organic Chemical Industry Co., Ltd.
- the total light transmittance of the resin composition is 98%.
- the average filament near resin unimpregnated rate, the warp thread width Bt, the weft thread width By, and the glass content were measured by the above-mentioned method, and the warp widening degree Et and the weft were measured.
- the widening degree Eye was calculated. The results are shown in Table 3.
- the flexural modulus was measured by the above-mentioned method, and the texture visibility, designability (texture unevenness), surface smoothness and radio wave transmission were evaluated. .. The results are shown in Table 3.
- Comparative Example 1 A glass fiber reinforced resin molded product of Comparative Example 1 was obtained in exactly the same manner as in Example 3 except that it was immersed in an aqueous solution of a silane coupling agent so that the amount of the silane coupling agent adhered was 0.04% by mass.
- the flexural modulus was measured by the above-mentioned method, and the texture visibility, designability (texture unevenness), surface smoothness and radio wave transmission were evaluated. .. The results are shown in Table 4.
- Comparative Example 2 A glass fiber reinforced resin molded product of Comparative Example 2 was obtained in exactly the same manner as in Example 5 except that it was immersed in an aqueous solution of a silane coupling agent so that the amount of the silane coupling agent adhered was 0.04% by mass.
- the flexural modulus was measured by the above-mentioned method, and the texture visibility, design (texture unevenness), surface smoothness and radio wave transmission were evaluated. .. The results are shown in Table 4.
- Example 3 After immersing the glass fiber woven fabric in the silane coupling agent aqueous solution, the glass fiber woven fabric was immersed in a black dye (manufactured by DIC Corporation, trade name: Ryudai W Black B) solution so that the amount of the dye adhered was 2.0% by mass. Except for the above, the same as in Example 5 was used to obtain a glass fiber reinforced resin molded product of Comparative Example 3.
- a black dye manufactured by DIC Corporation, trade name: Ryudai W Black B
- the flexural modulus was measured by the above-mentioned method, and the texture visibility, designability (texture unevenness), surface smoothness and radio wave transmission were evaluated. .. The results are shown in Table 4.
- Comparative Example 4 The glass fiber reinforced resin molded product of Comparative Example 4 was obtained in exactly the same manner as in Example 5 except that the fiber opening treatment was performed by the water flow pressure set to 0.1 MPa.
- Comparative Example 5 A glass fiber reinforced resin molded product of Comparative Example 5 was obtained in exactly the same manner as in Example 5 except that the fiber opening treatment was performed by the water flow pressure set to 3.5 MPa.
- the resin unimpregnated rate in the vicinity of the average filament of the glass fiber woven fabric is more than 2.0% and 50.0% or less, and the yarn width Bt of the warp of the glass fiber woven fabric and the yarn width Bt.
- the thread width By of the weft is in the range of 0.50 to 8.50 mm, respectively, and the weaving density Wt of the warp of the glass fiber woven fabric and the weaving density Wy of the weft are 3.0 lines / 25 mm or more, respectively.
- the warp widening degree Et calculated by Bt / (25 / Wt) and the weft widening degree Ey calculated by By / (25 / Wy) of the glass fiber woven fabric in the range of 50 threads / 25 mm.
- the texture of the glass fiber woven fabric can be visually recognized, the design of the glass fiber woven fabric is exhibited, and the design is exhibited. , The glass fiber woven fabric exerts a sufficient reinforcing effect.
- the glass fiber reinforced resin molded products of Comparative Examples 1 to 3 in which the unimpregnated rate of the resin near the average filament is outside the range of more than 2.0% and 50.0% or less The texture of the glass fiber fabric is not visible, or the glass fiber fabric does not exert a sufficient reinforcing effect.
- the glass fiber reinforced resin molded products of Comparative Examples 4 and 5 in which the warp widening degree Et and the weft widening degree Ey are outside the range of 0.70 to 1.10 have sufficient designability of the glass fiber woven fabric. Not demonstrated in.
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Abstract
Description
表1に示す、ガラス組成Aを備える、285texの質量を備えるガラス繊維糸を経糸及び緯糸として用いた。経糸織密度Wtを12.5本/25mm、緯糸織密度Wyを12.5本/25mmとし、レピア織機を用いて、平織に製織して、275g/m2のガラス繊維織物を得た。このガラス繊維織物に対して、水流圧力を1.0MPaに設定した水流圧力による開繊処理を行った。次いで、このガラス繊維織物を、600℃で、2時間加熱した後に、3-アミノプロピルトリエトキシシランをシランカップリング剤として、シランカップリング剤の付着量が0.02質量%となるようにシランカップリング剤水溶液に浸漬した。
10cm×10cmのサイズのガラス繊維強化樹脂成形品を目視で観察し、ガラス繊維強化樹脂成形品中に含まれるガラス繊維糸全本数に対して、ガラス繊維糸に光が反射して、その存在を確認できるガラス繊維糸の数が50%以上である場合を「可」、50%未満である場合を「不可」と評価した。
ガラス繊維強化樹脂成形品を目視で観察し、視野を上下(経糸方向)、又は、左右(緯糸方向)に移動した際に、それぞれの場合において、視野の動きと垂直に配置されているガラス繊維織物の織目に沿っては、視野の動きに追随した、反射光の移動が起きず、織目における反射光による美観が損なわれない場合に「A」、視野の動きと垂直に配置されているガラス繊維織物の織目の一部に沿って、視野の動きに追随した反射光の移動が生じ、織目における反射光による美観がわずかに損なわれる場合に「B」、視野の動きと垂直に配置されているガラス繊維織物の織目に沿って、視野の動きに追随した反射光の移動が生じ、織目における反射光による美観が損なわれる場合に「C」と評価した。
ガラス繊維強化樹脂成形品表面の中心平均粗さRaを、表面粗さ測定機(株式会社ミツトヨ製、型式名:J?47?2?0130)を用いて、JIS B 0601:2013に準拠して測定し、中心平均粗さRaが1μm以下の場合に「A」、1μm超10μm以下の場合に「B」、10μm超の場合に「C」と評価した。
ガラス繊維強化樹脂成形品を、1.5mm×80mm以上のサイズに切断した測定試料について、ネットワークアナライザ(アジレント・テクノロジー株式会社製、商品名:PNA-LネットワークアナライザN5230A)、及び、空洞共振器(株式会社関東電子応用開発製、型式名:CP431)を用いて、JIS C 2138:2007に準拠して、測定周波数1GHzの誘電率を測定し、誘電率が5.0未満の場合を「A」、誘電率が5.0以上の場合を「B」と評価した。
表1に示す、ガラス組成Bを備える、275texの質量を備えるガラス繊維糸を経糸及び緯糸として用い、270g/m2のガラス繊維織物を得た以外は、実施例1と全く同一にして、実施例2のガラス繊維強化樹脂成形品を得た。
表1に示す、ガラス組成Cを備える、295texの質量を備えるガラス繊維糸を経糸及び緯糸として用い、280g/m2のガラス繊維織物を得た以外は、実施例1と全く同一にして、実施例3のガラス繊維強化樹脂成形品を得た。
表1に示す、ガラス組成Cを備える、600texの質量を備えるガラス繊維糸を経糸及び緯糸として用い、経糸織密度Wtを9.0本/25mm、緯糸織密度Wyを8.0本/25mmとし、420g/m2のガラス繊維織物を得た以外は、実施例1と全く同一にして、実施例4のガラス繊維強化樹脂成形品を得た。
表1に示す、ガラス組成Cを備える、1150texの質量を備えるガラス繊維糸を経糸及び緯糸として用い、経糸織密度Wtを7.0本/25mm、緯糸織密度Wyを6.5本/25mmとし、630g/m2のガラス繊維織物を得た以外は、実施例1と全く同一にして、実施例5のガラス繊維強化樹脂成形品を得た。
表1に示す、ガラス組成Cを備える、135texの質量を備えるガラス繊維糸を経糸及び緯糸として用い、経糸織密度Wtを20.0本/25mm、緯糸織密度Wyを20.0本/25mmとし、215g/m2のガラス繊維織物を得た以外は、実施例1と全く同一にして、実施例6のガラス繊維強化樹脂成形品を得た。
シランカップリング剤付着量が0.01質量%となるようにシランカップリング剤水溶液に浸漬した以外は、実施例5と全く同一にして、実施例7のガラス繊維強化樹脂成形品を得た。
シランカップリング剤付着量が0.005質量%となるようにシランカップリング剤水溶液に浸漬した以外は、実施例5と全く同一にして、実施例8のガラス繊維強化樹脂成形品を得た。
透明樹脂として、アクリル樹脂組成物(表3中「アクリル」と表記する)を用いた以外は、実施例3と全く同一にして、実施例9のガラス繊維強化樹脂成形品を得た。前記アクリル樹脂組成物は、アクリル樹脂(大阪有機化学株式製、商品名:ビスコート#155)、光重合開始剤(BASF社製、商品名:イルガキュア184、(1-ヒドロキシ-シクロヘキシル-フェニル-ケトン)、溶媒(神港有機化学工業株式会社製ジエチレングリコールモノエチルエーテルアセテート)を含み、樹脂組成物の全光線透過率が98%である。
シランカップリング剤付着量が0.04質量%となるようにシランカップリング剤水溶液に浸漬した以外は、実施例3と全く同一にして、比較例1のガラス繊維強化樹脂成形品を得た。
シランカップリング剤付着量が0.04質量%となるようにシランカップリング剤水溶液に浸漬した以外は、実施例5と全く同一にして、比較例2のガラス繊維強化樹脂成形品を得た。
ガラス繊維織物を、シランカップリング剤水溶液に浸漬した後に、染料の付着量が2.0質量%となるように、黒色染料(DIC株式会社製、商品名:リューダイWブラックB)溶液に浸漬した以外は、実施例5と全く同一にして、比較例3のガラス繊維強化樹脂成形品を得た。
水流圧力を0.1MPaに設定した水流圧力による開繊処理を行った以外は、実施例5と全く同一にして、比較例4のガラス繊維強化樹脂成形品を得た。
水流圧力を3.5MPaに設定した水流圧力による開繊処理を行った以外は、実施例5と全く同一にして、比較例5のガラス繊維強化樹脂成形品を得た。
Claims (10)
- ガラス繊維織物と、透明樹脂とを含む、ガラス繊維強化樹脂成形品であって、
前記ガラス繊維織物の平均フィラメント近傍樹脂未含浸率が、2.0%超50.0%以下であり、
前記ガラス繊維織物の経糸の糸幅Bt、及び、緯糸の糸幅Byが、それぞれ、0.50~8.50mmの範囲にあり、
前記ガラス繊維織物の経糸の織密度Wt、及び、緯糸の織密度Wyが、それぞれ、3.0本/25mm~50本/25mmの範囲にあり、
前記ガラス繊維織物の、Bt/(25/Wt)で計算される経糸拡幅度Et、及び、By/(25/Wy)で計算される緯糸拡幅度Eyが、それぞれ、0.70~1.10の範囲にあることを特徴とする、ガラス繊維強化樹脂成形品。 - 請求項1に記載のガラス繊維強化樹脂成形品において、前記ガラス繊維織物の平均フィラメント近傍樹脂未含浸率が、2.1%以上28.0%以下であることを特徴とすることを特徴とする、ガラス繊維強化樹脂成形品。
- 請求項1に記載のガラス繊維強化樹脂成形品において、前記ガラス繊維織物のフィラメント平均近傍樹脂未含浸率が、2.5%以上10.0%以下であることを特徴とすることを特徴とする、ガラス繊維強化樹脂成形品。
- 請求項1に記載のガラス繊維強化樹脂成形品において、前記ガラス繊維織物のフィラメント近傍樹脂未含浸率が、平均3.1%以上5.0%以下であることを特徴とすることを特徴とする、ガラス繊維強化樹脂成形品。
- 請求項1~4のいずれか1項に記載のガラス繊維強化樹脂成形品において、前記ガラス繊維織物の経糸の重量、及び、緯糸の重量が、それぞれ、210tex~850texの範囲にあることを特徴とする、ガラス繊維強化樹脂成形品。
- 請求項1~5のいずれか1項に記載のガラス繊維強化樹脂成形品において、前記ガラス繊維織物の経糸及び緯糸を構成するガラス繊維の測定周波数1GHzにおける誘電率が5.5以下であることを特徴とする、ガラス繊維強化樹脂成形品。
- 請求項1~6のいずれか1項に記載のガラス繊維強化樹脂成形品において、前記ガラス繊維織物の経糸及び緯糸を構成するガラス繊維のガラス組成が、ガラス繊維の全量に対して、60.0質量%~70.0質量%の範囲のSiO2と、20.0質量%~30.0質量%のAl2O3と、5.0質量%~15.0質量%の範囲のMgOとを含むガラス組成であることを特徴とする、ガラス繊維強化樹脂成形品。
- 請求項1~7のいずれか1項に記載のガラス繊維強化樹脂成形品を含むことを特徴とする、電子機器筐体。
- 請求項1~7のいずれか1項に記載のガラス繊維強化樹脂成形品を含むことを特徴とする、モビリティ製品用内装部品。
- 請求項1~7のいずれか1項に記載のガラス繊維強化樹脂成形品を含むことを特徴とする、モビリティ製品用外装部品。
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KR102459984B1 (ko) | 2022-10-27 |
KR20220047390A (ko) | 2022-04-15 |
CN114729134A (zh) | 2022-07-08 |
JPWO2021251103A1 (ja) | 2021-12-16 |
EP4023700B1 (en) | 2023-10-18 |
TW202204503A (zh) | 2022-02-01 |
TWI768943B (zh) | 2022-06-21 |
EP4023700A1 (en) | 2022-07-06 |
EP4023700A4 (en) | 2022-12-14 |
US11591723B2 (en) | 2023-02-28 |
JP7014346B1 (ja) | 2022-02-01 |
US20220356609A1 (en) | 2022-11-10 |
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