WO2023153127A1 - 繊維強化樹脂シート - Google Patents

繊維強化樹脂シート Download PDF

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Publication number
WO2023153127A1
WO2023153127A1 PCT/JP2023/000666 JP2023000666W WO2023153127A1 WO 2023153127 A1 WO2023153127 A1 WO 2023153127A1 JP 2023000666 W JP2023000666 W JP 2023000666W WO 2023153127 A1 WO2023153127 A1 WO 2023153127A1
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WIPO (PCT)
Prior art keywords
plasticizer
mass
glass fiber
fiber fabric
resin sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/000666
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English (en)
French (fr)
Japanese (ja)
Inventor
哲也 足立
哲也 石田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Boseki Co Ltd
Original Assignee
Nitto Boseki Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Boseki Co Ltd filed Critical Nitto Boseki Co Ltd
Priority to KR1020247029410A priority Critical patent/KR20240144321A/ko
Priority to EP23752596.9A priority patent/EP4450537A4/en
Priority to CN202380020621.3A priority patent/CN118696080A/zh
Priority to US18/835,240 priority patent/US20250135746A1/en
Priority to JP2023580118A priority patent/JPWO2023153127A1/ja
Publication of WO2023153127A1 publication Critical patent/WO2023153127A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • 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
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    • 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
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    • 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
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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
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    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/285—Acrylic resins
    • 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
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    • C03C25/40—Organo-silicon compounds
    • 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
    • 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
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    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with 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
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    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/52—Phosphorus bound to oxygen only
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    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K7/04—Fibres or whiskers inorganic
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Definitions

  • the present invention relates to fiber reinforced resin sheets.
  • Patent Document 1 discloses a fiber-reinforced resin sheet obtained by impregnating a glass fiber fabric with a resin composition containing a vinyl chloride-based resin as a transparent partition sheet used for partitioning compartments in a factory or the like.
  • the content of the glass fiber fabric is 10 to 50% by mass with respect to the total mass of the fiber-reinforced resin sheet, and the glass constituting the glass fiber fabric has a basic composition of at least one of CaO and MgO and SiO 2
  • the contents of SiO 2 , CaO and MgO with respect to the total mass of the glass are respectively X, Y and Z (% by mass)
  • the value of X ⁇ (Y+Z) is 40 to 60% by mass.
  • a fiber-reinforced resin sheet having a haze of 40% or less is disclosed.
  • the fiber-reinforced resin sheet as described in Patent Document 1 does not have sufficient mechanical strength, and thus cannot be used as a material that requires mechanical strength in addition to transparency, such as a base material for a tent membrane. I didn't.
  • the mass per unit length of the glass fiber is increased, although the mechanical strength of the fiber-reinforced resin sheet increases, there is a problem that the transparency deteriorates.
  • An object of the present invention is to provide a fiber-reinforced resin sheet having high tensile strength, transparency, and excellent impregnability and handleability (tackiness) during production.
  • the present invention provides the following [1] to [6].
  • [1] A glass fiber fabric having warp and weft yarns and a resin composition impregnated in the glass fiber fabric, wherein the amount of glass constituting the glass fiber fabric is 60.0 to 70 with respect to the total amount of the glass fiber fabric. 0% by weight of SiO 2 , 20.0-30.0% by weight of Al 2 O 3 and 5.0-15.0% by weight of MgO, wherein the glass fiber fabric The weight per 1000 m of the warp and the weft that constitute the The amount is 30.0 to 63.0% by mass with respect to the total amount of the resin composition, and the plasticizer is a plasticizer A that is an aromatic phosphate plasticizer, a diol, and a carboxylic acid.
  • the present invention it is possible to provide a fiber-reinforced resin sheet having high tensile strength, transparency, and excellent impregnability and handleability (tackiness) during production.
  • FIG. 1 is a perspective view of a fiber-reinforced resin sheet according to an embodiment
  • the numerical range indicated using “ ⁇ ” means the range including the numerical values before and after “ ⁇ ” as the minimum and maximum values, respectively. Unless otherwise specified, the units of numerical values before and after "-" are the same.
  • the upper limit value or lower limit value of the numerical range at one step may be replaced with the upper limit value or lower limit value of the numerical range at another step.
  • the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples. The upper and lower limits described individually can be combined arbitrarily.
  • FIG. 1 is a cross-sectional view showing one embodiment of the fiber-reinforced resin sheet of the present invention.
  • the fiber-reinforced resin sheet 1 is obtained by impregnating a glass fiber fabric 10 having warp yarns 12 and weft yarns 14 with a resin composition 15 . That is, the fiber-reinforced resin sheet 1 contains the glass fiber fabric 10 and the resin composition 15 . In the fiber-reinforced resin sheet 1 , the resin composition 15 is arranged around the glass fiber fabric 10 so as to enter the interstices of the glass fiber fabric 10 . Each component of the fiber-reinforced resin sheet 1 will be described in detail below.
  • the glass fiber fabric 10 is made by weaving warp yarns 12 and weft yarns 14, and is a material that serves as a base fabric for the fiber-reinforced resin sheet 1. As shown in FIG. Both the warp yarns 12 and the weft yarns 14 are made of glass fiber bundles, and the glass fiber bundles are made up of a plurality of glass fiber monofilaments.
  • the glass constituting the glass fiber fabric 10 contains SiO 2 in the range of 60.0 to 70.0% by mass and Al 2 O in the range of 20.0 to 30.0% by mass with respect to the total amount of the glass fiber fabric. 3 and MgO in the range of 5.0 to 15.0% by weight. If the contents of SiO 2 , Al 2 O 3 and MgO in the glass constituting the glass fiber fabric 10 are not within the above ranges, the tensile strength or transparency will deteriorate.
  • the content of SiO 2 is 60.5 to 68.0 mass%, 61.0 to 67.0 mass%, 63.0 to 63.0 mass%, based on the total amount of the glass fiber fabric. 66.5% by mass, or 64.0 to 66.0% by mass.
  • the content of Al 2 O 3 is 20.5 to 27.5% by mass, 21.0 to 27.0% by mass, 23.0% by mass, and 23.0% by mass. It may be 0 to 26.5% by mass, or 24.0 to 26.0% by mass.
  • the content of MgO is 6.0 to 14.0% by mass, 7.0 to 13.0% by mass, 8.0 to 12%, based on the total amount of the glass fiber fabric. .5% by weight, or 9.0 to 11.0% by weight.
  • the glass constituting the glass fiber fabric 10 may or may not contain components other than SiO 2 , Al 2 O 3 and MgO.
  • Components other than SiO 2 , Al 2 O 3 and MgO include, for example, CaO, Fe 2 O 3 , Li 2 O, K 2 O, Na 2 O, ZrO 2 , B 2 O 3 , F 2 , Cl 2 , TiO2 , CoO, NiO, CuO, ZnO , MnO2 , MoO3 , WO3 , GeO2 , P2O5 , V2O5 , BeO , BaO, SnO2 , CeO2 , Y2O3 , La2 O 3 , Bi 2 O 3 , Gd 2 O 3 , Pr 2 O 3 , Sc 2 O 3 , Yb 2 O 3 and Cr 2 O 3 and the like.
  • the content of components other than SiO 2 , Al 2 O 3 and MgO is 15.0% by mass or less, 10.0% by mass or less, relative to the total amount of the glass fiber fabric. It may be 5.0% by mass or less, or 1.0% by mass or less.
  • the contents of components other than SiO 2 , Al 2 O 3 and MgO are each independently less than 0.5% by mass, 0.4% by mass or less, and 0.1% by mass with respect to the total amount of the glass fiber fabric. less than or less than 0.05 mass %.
  • An example of the glass constituting the glass fiber fabric 10 is 65.0% by mass of SiO 2 , 25.0% by mass of Al 2 O 3 and 10% by mass of MgO with respect to the total amount of the glass fiber fabric. glass containing.
  • the content of each component with respect to the total amount of the glass fiber fabric can be measured using a wavelength dispersive X-ray fluorescence spectrometer.
  • a glass fiber fabric is placed in a platinum crucible.
  • organic matter is attached to the surface of the glass fiber fabric, or when the glass fiber fabric is contained in the resin, for example, it is heated in a muffle furnace at 300 to 650° C. for 0.5 to 24 hours. Use after removing the organic matter by heating to a certain degree.
  • the glass fiber fabric in the platinum crucible is held at a temperature of 1650° C. for 6 hours in an electric furnace and melted with stirring to obtain homogeneous molten glass.
  • the obtained molten glass is poured onto a carbon plate to produce glass cullet, which is then pulverized into powder to obtain glass powder.
  • a wavelength dispersive X-ray fluorescence spectrometer After molding the glass powder into a disc shape with a press, quantitative analysis is performed using a wavelength dispersive X-ray fluorescence spectrometer. Specifically, quantitative analysis using a wavelength dispersive X-ray fluorescence spectrometer can be performed by preparing a calibration curve sample based on the results measured by the fundamental parameter method and analyzing by the calibration curve method. The content of each component in the calibration curve sample can be quantitatively analyzed by an ICP emission spectrometer. These quantitative analysis results are converted into oxides to calculate the content and total amount of each component, and from these numerical values, the content of each component described above can be determined.
  • the mass per 1000m of the warp and weft that constitute the glass fiber fabric 10 is 45.0 to 335.0g/1000m, respectively. Sufficient strength cannot be maintained if the mass per 1000 m of the warp and weft is less than 45.0 g/1000 m. If the weight per 1,000 m of the warp and weft exceeds 335.0 g/1,000 m, the transparency deteriorates.
  • the mass per 1000 m of the warp and weft is 45.0 to 170.0 g/1000 m, 50.0 to 140.0 g/1000 m, 55.0 to 110.0 g/1000 m, respectively, because the transparency is further improved. 60.0 to 80.0 g/1000 m, or preferably 65.0 to 70.0 g/1000 m.
  • the mass per 1000 m of the warp and weft is 170.0 to 335.0 g/1000 m, 190.0 to 320.0 g/1000 m, 210.0 to 310.0 g/1000 m, respectively, because the tensile strength is further improved. It is preferably 230.0 to 300.0 g/1000 m, 250.0 to 290.0 g/1000 m, or 260.0 to 280.0 g/1000 m.
  • the mass per 1000m of warp and weft can be measured according to JIS R 3420:2013.
  • the fiber diameter of the glass filaments constituting the warp and weft measured by the method described later, the number of bundles of the glass filaments, and the warp and weft
  • the mass of the warp and weft can be calculated by calculation.
  • the specific gravity of the glass constituting the warp and weft is obtained by determining the composition of the glass constituting the glass fiber fabric by the method described above, blending the glass batch so as to have the same composition, melting and cooling the glass batch to obtain the glass bulk. can be obtained by preparing and measuring the specific gravity of the glass bulk.
  • the fiber diameter of the glass filaments can be determined, for example, by first polishing the cross section of the fiber reinforced resin sheet, then using an electron microscope to observe the cross section of the fiber reinforced resin sheet, and 100 glass filaments exposed in the observed cross section. The above can be obtained by measuring the length of the diameter of the glass filament and calculating the average value of these values.
  • the number of glass filaments bundled can be obtained by measuring the number of filaments constituting the warp and weft exposed in the observed cross section.
  • the specific gravity of the glass forming the warp and weft can be measured by the following method.
  • the fiber-reinforced resin sheet is heated, for example, in a muffle furnace at 300-650° C. for about 0.5-24 hours to decompose organic substances.
  • the remaining glass fibers are placed in a platinum crucible, held at a temperature of 1650° C. for 6 hours in an electric furnace, and melted with stirring to obtain homogeneous molten glass.
  • the platinum crucible containing the molten glass is taken out from the electric furnace, and the molten glass is cooled.
  • the mass per unit area of the glass fiber fabric 10 is preferably 130 g/m 2 or more to increase tensile strength, and is preferably 565 g/m 2 or less to increase impregnability and transparency. .
  • the mass per unit area of the glass fiber fabric 10 is in the range of 130 to 330 g/m 2 , 140 to 280 g/m 2 , or 150 to 230 g/m 2 in order to further improve the transparency.
  • the range may be, for example, 210 to 565 g/m 2 , 330 to 565 g/m 2 , 410 to 535 g/m 2 , or 450 to 510 g/m 2 .
  • the mass per unit area of the glass fiber fabric 10 is measured by measuring the mass of the glass fiber fabric cut to a size of 200 mm ⁇ 200 mm at three points with a scale conforming to JIS R 3420, and converting each to the mass per 1 m 2 . It is the average value of the values obtained.
  • the glass fiber fabric 10 is produced by plain weaving the warp yarns 12 and the weft yarns 14 .
  • the weaving method of the glass fiber fabric 10 is not limited to plain weaving, and various weaving methods such as twill weave, satin weave, basket weave, and ridge weave can be employed.
  • the weaving density of the warp yarns 12 is preferably 22/25 mm or more, and preferably 51/25 mm or less.
  • the weaving density of the warp yarns 12 is more preferably 33 to 51/25 mm because the thickness of the glass fiber fabric can be reduced to further improve the transparency.
  • the weaving density of the warp yarns 12 is more preferably 22 to 33/25 mm because the thickness of the glass fiber fabric can be increased to further improve the tensile strength.
  • the weaving density of the weft 14 is preferably 19 threads/25 mm or more, and preferably 51 threads/25 mm or less.
  • the weaving density of the weft yarns 14 is more preferably 26 to 51 threads/25 mm because the thickness of the glass fiber fabric can be reduced to further improve the transparency.
  • the weaving density of the weft yarns 14 is more preferably 19 to 26 threads/25 mm because the thickness of the glass fiber fabric can be increased to further improve the tensile strength.
  • the weave density can be obtained by measuring the number of warp or weft threads per 25 mm width of the glass cloth using a fabric disassembling mirror in accordance with JIS R 3420:2013.
  • the air permeability of the glass fiber fabric may be, for example, 0.5-50.0 cm 3 /cm 2 /s, or 0.8-20.0 cm 3 /cm 2 /s.
  • the thickness of the glass fiber fabric is preferably 124 ⁇ m or more, and may be 140 ⁇ m or more, because the tensile strength is improved. There may be.
  • the thickness of the glass fiber fabric is more preferably 124 to 307 ⁇ m in order to further improve transparency.
  • the thickness of the glass fiber fabric is more preferably 307 to 485 ⁇ m in order to further improve the tensile strength.
  • the thickness of the glass fiber fabric is the average value of the measured values when measuring the thickness at 15 points in the glass fiber fabric with a micrometer in accordance with JIS R 3420.
  • the filament diameter of the glass filaments constituting the warp and weft constituting the glass fiber fabric is, for example, in the range of 2.5 to 21.0 ⁇ m, preferably in the range of 3.0 to 13.0 ⁇ m, more preferably. is in the range of 3.0 to 9.0 ⁇ m.
  • the glass fiber fabric 10 may be woven from one type of glass fiber bundle, or may be woven from two or more types of glass fiber bundles.
  • warp yarns 12 and weft yarns 14 may be composed of glasses of different compositions.
  • the mass of the glass fiber bundles per 1000 m and the diameter of the glass fiber monofilaments constituting the glass fiber bundles may be the same or different. good.
  • the glass composition of the glass fiber bundles may be the same, but the count of the glass fiber bundles and the diameter of the glass fiber monofilaments may be different.
  • the fiber bundle constituting the glass fiber fabric 10 may be a plied yarn, a twisted yarn, or a plied and twisted yarn.
  • the fiber bundles constituting the glass fiber fabric 10 are preferably plied yarns from the viewpoint of enhancing the strength of the glass fiber bundles.
  • the fiber bundles constituting the glass fiber woven fabric 10 are preferably doubling yarns from the viewpoint of being easily impregnated with the resin.
  • the thread gap can be narrowed by the fiber opening process.
  • the fiber opening treatment By the fiber opening treatment, the warp yarns 12 and the weft yarns 14 constituting the glass fiber fabric 10 are spread apart, and the entire glass fiber fabric 10 can be made flatter. In this way, the fiber opening process makes it possible to change the volume and area range occupied by the glass fiber bundles.
  • the glass fiber fabric 10 may be surface-treated in advance to attach an adhesive substance.
  • a silane coupling agent can be used as the adhesive substance. This improves the interfacial adhesion between the glass fiber fabric 10 and the resin composition 15 .
  • Examples of silane coupling agents include methacryloxypropyltrimethoxysilane.
  • the resin composition 15 contains a vinyl chloride resin and a plasticizer.
  • a vinyl chloride resin refers to a resin having a molecular chain composed of a copolymer containing vinyl chloride as a monomer unit in addition to polyvinyl chloride.
  • Monomers copolymerizable with vinyl chloride include vinylidene chloride, vinyl acetate, ethylene, propylene, acrylonitrile, maleic acid or its ester, acrylic acid or its ester, and methacrylic acid or its ester.
  • the content of the vinyl chloride resin may be 37-70% by mass, 35-60% by mass, 40-55% by mass, or 45-55% by mass based on the total amount of the resin composition.
  • the plasticizer includes plasticizer A, which is an aromatic phosphate plasticizer, and plasticizer B, which is an ester compound of diol and carboxylic acid.
  • Plasticizer A includes triarylisopropyl phosphate (TIPP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyldiphenyl phosphate (CDP), monophosphate Isopropyldiphenyl (IPP), diisopropylmonophenyl phosphate (BIPP), 2-ethylhexyl (diphenyl phosphate) (EHDP), (4-tert-butylphenyl)diphenyl phosphate (t-BDP), phenyl bis(4 -tert-butylphenyl) (BBDP), tris(2,4-di-tert-butylphenyl) phosphite (TBDP), resorcinol bis(diphenyl phosphate) (RDP), resorcinol bis(dixylenyl phosphate) (RDX) , bis
  • Plasticizer A is preferably a plasticizer represented by the following formula (1).
  • R 1 , R 2 and R 3 each independently represent an alkyl group having 1 to 6 carbon atoms.
  • n1, n2 and n3 each independently represent an integer of 0 to 5; n1, n2 and n3 may each independently be 0, 1-5, 1-4, 1-3, 1-2 or 1;
  • alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group and isopropyl group.
  • Plasticizer A is more preferably a plasticizer represented by the following formula (2).
  • iPr represents an isopropyl group.
  • n represents an integer of 0-5. n may be 0, 1-5, 1-4, 1-3, 1-2 or 1. Multiple n may be the same or different.
  • Plasticizer A is preferably triphenyl phosphate in which all n are 0 in formula (2), or triaryl isopropyl phosphate in which at least one n is 1 or more in formula (2).
  • Plasticizer A is preferably a mixture of two or more aromatic phosphate plasticizers, preferably a mixture of triarylisopropyl phosphate and triphenyl phosphate.
  • the mass ratio of triarylisopropyl phosphate to triphenyl phosphate may be from 2/1 to 4/1.
  • the content of the plasticizer A is preferably 5.5% by mass or more, more preferably 13.0% by mass or more, in order to increase transparency, based on the total amount of the resin composition. It is more preferably 0% by mass or more, particularly preferably 22.5% by mass or more, and preferably 40.0% by mass or less for excellent transparency and tackiness. , is more preferably 34.8% by mass or less, still more preferably 30.0% by mass or less, and particularly preferably 28.5% by mass or less.
  • Plasticizer B is an ester compound of diol and carboxylic acid.
  • the plasticizer B is an aliphatic dibasic acid ester plasticizer or a phthalate ester plasticizer, which is an ester compound of a non-diol alcohol and a carboxylic acid, transparency and tackiness is better.
  • diols examples include 2,2,4-trimethyl-1,3-pentanediol, 1,2-ethanediol, triethylene glycol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, and the like. mentioned.
  • Carboxylic acids include, for example, monocarboxylic acids and dicarboxylic acids (excluding phthalic acid).
  • monocarboxylic acids include isobutanoic acid, acetic acid, 2-ethylhexanoic acid, methacrylic acid, acrylic acid and the like.
  • dicarboxylic acids include maleic acid and 1,2-cyclohexanedicarboxylic acid.
  • the carboxylic acid is preferably a monocarboxylic acid.
  • the ester compound may be a monoester in which one hydroxy group in the diol is esterified, or a diester in which two hydroxy groups in the diol are esterified.
  • the ester compound is preferably a diester in which two hydroxy groups in a diol are esterified.
  • Plasticizer B includes 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, 1,2-ethanediol diacetate, and 2,2,4-trimethyl-1,3-pentanediol isobutyrate. (texanol), 2,2′-(ethylenebisoxy)bisethanolbis(2-ethylhexanoate), neopentyl glycol dimethacrylate, 1,6-bis(acryloyloxy)hexane, 1,9-nonanediol diacrylate and the like.
  • the molecular weight of the plasticizer B may be 100-500, preferably 200-350. By setting the molecular weight of the plasticizer B to 200 to 350, the transparency can be further enhanced.
  • the content of the plasticizer B is preferably 14.0% by mass or more, and 19.0% by mass, based on the total amount of the resin composition, because it provides excellent transparency and tackiness. More preferably, it is more preferably 22.0% by mass or more, and for excellent transparency, it is preferably 45.0% by mass or less, and 37.0% by mass or less. It is more preferably 30.0% by mass or less, and particularly preferably 28.0% by mass or less.
  • the content of the plasticizer is 30.0-63.0% by mass with respect to the total amount of the resin composition. If the content of the plasticizer exceeds 63.0% by mass relative to the total amount of the resin composition, the tackiness deteriorates and handling during production becomes difficult. If the content of the plasticizer is less than 30.0% by mass relative to the total amount of the resin composition, the impregnability and transparency will deteriorate.
  • the content of the plasticizer may be 35.0 to 60.0% by mass, 40.0 to 55.0% by mass, or 45.0 to 53.0% by mass with respect to the total amount of the resin composition.
  • the total content of the plasticizer A and the plasticizer B may be within the range described above as the content of the plasticizer with respect to the total amount of the resin composition.
  • the mass ratio of plasticizer B to plasticizer A (mass of plasticizer B/mass of plasticizer A) is 0.13 to 3.50.
  • mass ratio of the plasticizer B to the plasticizer A is within the above numerical range, transparency, tackiness, impregnation and tensile strength are all improved.
  • the lower limit of the mass ratio of plasticizer B to plasticizer A may be 0.18 or more. It is preferably 50 or more, more preferably 0.60 or more, 0.70 or more, 0.78 or more, 0.85 or more, 0.90 or more, or 0.95 or more.
  • the upper limit of the mass ratio of the plasticizer B to the plasticizer A is 2.99 or less, 2.48 or less, 1.97 or less, 1.68 or less, 1.39 or less from the viewpoint of further improving transparency and tackiness. , or 1.10 or less.
  • the mass ratio of plasticizer B to plasticizer A may be 0.38 to 1.97 from the viewpoint of further improving transparency, and from the viewpoint of further improving transparency and tackiness, it is 0.78 to 1. .39.
  • the component, component amount, and composition ratio of the plasticizer in the fiber-reinforced resin sheet of this embodiment can be analyzed by GC-MS.
  • the resin is scraped down to a 20 ⁇ m portion near the glass fiber fabric using a grinder, a fine processing machine, a microtome, or the like, By analyzing the remaining resin by GC-MS, it is possible to obtain the component amounts and composition ratios.
  • the resin composition 15 may further contain additives such as flame retardants, ultraviolet absorbers, fillers, and antistatic agents.
  • the glass fiber fabric contained in the fiber-reinforced resin sheet of the present embodiment may be one sheet or a laminate of a plurality of sheets.
  • the number of glass fiber fabrics contained in the fiber-reinforced resin sheet is preferably one.
  • the fiber-reinforced resin sheet preferably has a configuration in which a reinforcing fiber layer obtained by impregnating a glass fiber fabric with a resin composition is sandwiched between resin layers made of the resin composition described above or a resin different from this. That is, it is preferable that resin layers are formed on both sides of the glass fiber fabric impregnated with the resin composition.
  • the resin constituting the resin layer may be, for example, soft vinyl chloride.
  • a flame retardant, a plasticizer, an antistatic agent, an ultraviolet absorber, a stabilizer, and the like may be added to the resin constituting the resin layer.
  • the mass of the fiber-reinforced resin sheet may be 200 g/m 2 or more, 360 g/m 2 , or 550 g/m 2 or more because it facilitates maintaining the rigidity of the fiber-reinforced resin sheet. Since the fiber-reinforced resin sheet does not easily sag under its own weight when used, it may be 3700 g/m 2 or less, 2500 g/m 2 or less, or 1500 g/m 2 or less.
  • the total content of the resin composition and the resin layers sandwiching the glass fiber fabric impregnated with the resin composition is 150 g/m 2 or more, 260 g/m 2 or more, or It may be 660 g/m 2 or more, and from the viewpoint of making the fiber reinforced resin sheet more difficult to burn, it may be 3000 g/m 2 or less, 2000 g/m 2 or less, or 1500 g/m 2 or less.
  • the content of the glass fiber fabric is 3.0% by mass or more, 8.0% by mass or more, 11.0% by mass or more, or It may be 16.0% by mass or more, and from the viewpoint of further improving the impregnating property, it is 60.0% by mass or less, 50.0% by mass or less, 28.0% by mass with respect to the total mass of the fiber reinforced resin sheet. % or less, or 24.0% by mass or less.
  • the content of the glass fiber fabric can be measured according to JIS K7052:1999.
  • the total content of the resin composition and the resin layers sandwiching the glass fiber fabric impregnated with the resin composition can be determined as the difference in mass of the test piece before and after firing according to JIS K7052:1999.
  • the total light transmittance of the fiber-reinforced resin sheet 1 is preferably 85% or more, more preferably 90% or more.
  • the total light transmittance of the fiber-reinforced resin sheet 1 is measured by the method described in Examples below.
  • the haze of the fiber-reinforced resin sheet 1 is preferably less than 20%, less than 10%, or less than 6%.
  • the haze of the fiber-reinforced resin sheet 1 is measured by the method described in Examples below.
  • the tensile strength of the fiber-reinforced resin sheet 1 may be 1000 N/25 mm or more, 1500 N/25 mm or more, or 2000 N/25 mm or more. Although the upper limit of the tensile strength of the fiber-reinforced resin sheet 1 is not particularly limited, it may be, for example, 10000 N/cm or less. The tensile strength of the fiber-reinforced resin sheet 1 is measured by the method described in Examples below.
  • the method of manufacturing the fiber-reinforced resin sheet 1 includes an impregnation step of impregnating the glass fiber fabric 10 with a solution containing the resin composition 15 and an organic solvent, and a volatilization step of volatilizing the organic solvent.
  • the resin composition 15 is dissolved in an organic solvent to prepare a solution.
  • the organic solvent used here is not particularly limited as long as it can dissolve the vinyl chloride resin contained in the resin composition 15 .
  • examples of organic solvents include methyl ethyl ketone, methyl cellosolve, and acetone.
  • An organic solvent may be used individually by 1 type or in mixture of 2 or more types. The operation and conditions for dissolving the resin composition 15 in the organic solvent may be appropriately determined according to the type of the organic solvent used, the type of the resin composition 15, and the like. If necessary, insoluble components may be removed by filtration or the like.
  • the glass fiber fabric 10 is impregnated with the solution containing the resin composition 15 and the organic solvent as it is or after being appropriately concentrated or diluted.
  • the method for impregnating the glass fiber fabric 10 with the solution containing the resin composition 15 and the organic solvent include a method of immersing the glass fiber fabric 10 in the solution, and a method of applying the solution to the glass fiber fabric 10. etc.
  • a solution containing the resin composition 15 and the organic solvent coats the glass fiber fabric 10 and penetrates into yarn gaps between the warp yarns 12 and between the weft yarns 14 .
  • the organic solvent is volatilized, and a glass fiber fabric in which the resin composition 15 has entered the interstices between the glass fiber bundles is obtained.
  • a reinforced resin sheet 1 is obtained.
  • a method for producing a fiber-reinforced resin sheet having a configuration in which a reinforcing fiber layer in which a resin composition is impregnated in a glass fiber fabric is sandwiched between resin layers includes, in addition to the above steps, a glass fiber fabric impregnated with a resin composition. It has a forming step of forming a resin layer on both sides.
  • the resin layer is formed by attaching a sheet containing a resin (preferably soft vinyl chloride) that constitutes the resin layer to a glass fiber fabric impregnated with a resin composition.
  • a sheet containing a resin constituting the resin layer is attached to both sides of the glass fiber fabric impregnated with the resin composition obtained in the above step, and attached by heating and pressurizing, so that the reinforcing fiber layer is a resin layer. It is possible to obtain a fiber reinforced resin sheet having a structure sandwiched by.
  • the method of forming the resin layer is not limited to the above method, and for example, a method of applying an uncured resin to a glass fiber fabric impregnated with a resin composition and curing the resin composition may be used.
  • the fiber-reinforced resin sheet according to the present embodiment can be used, for example, as membrane ceilings, tent warehouses, and roofs of fireproof buildings.
  • IPPP/TPP A mixture of triarylisopropyl phosphate and triphenyl phosphate at a mass ratio of 3:1 (manufactured by Ajinomoto Fine-Techno Co., Inc., trade name: Leophos 65)
  • TXIB 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (molecular weight 286)
  • Neopentyl glycol dimethacrylate molecular weight 240
  • 1,2-ethanediol diacetate molecular weight 146)
  • Example 1 [Production of glass fiber fabric] 67.5 g / 1000 m with a composition (referred to as composition A) with a SiO2 content of 65.0 wt.%, an Al2O3 content of 25.0 wt.% and an MgO content of 10.0 wt.%
  • composition A a composition with a SiO2 content of 65.0 wt.%, an Al2O3 content of 25.0 wt.% and an MgO content of 10.0 wt.%
  • the glass fiber bundles as warp and weft, plain weave so that the warp weave density is 42 / 25 mm and the weft weave density is 32 / 25 mm, then heat deoiling and methacryloxypropyltrimethoxysilane.
  • a surface treatment and an opening treatment were applied to produce a glass fiber fabric.
  • the resulting glass fiber fabric had a mass of 210 g/m 2 , a thickness of 163 ⁇ m, and an air permeability of 1.5 cm 3
  • the above glass fiber fabric was impregnated with this resin composition and dried at 130°C to volatilize methyl ethyl ketone to obtain a glass fiber fabric impregnated with the resin composition.
  • the content of the glass fiber fabric was 52 mass % of the glass fiber fabric impregnated with the resin composition.
  • a 300 ⁇ m thick transparent soft vinyl chloride sheet manufactured by Achilles Co., Ltd., trade name: Achilles Fuller
  • the surface is heated with a hot press at 150 ° C. Press lamination was carried out to obtain a fiber reinforced resin sheet.
  • the mass of the obtained fiber-reinforced resin sheet was 910 g/m 2 .
  • the resin composition (including the soft vinyl chloride sheet) impregnated into the glass fiber fabric was 700 g/m 2 , and the content of the glass fiber fabric was 23% by mass with respect to the total mass of the fiber-reinforced resin sheet. .
  • Example 2 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that the amount of plasticizer A was changed to 20 parts by mass and the amount of plasticizer B was changed to 20 parts by mass to prepare a sol.
  • Example 3 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that neopentyl glycol dimethacrylate was used as the plasticizer B instead of 2,2,4-trimethyl-1,3-pentadiol isobutyrate. Ta.
  • Example 4 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that tricresyl phosphate was used as plasticizer A instead of a mixture of triarylisopropyl phosphate and triphenyl phosphate at a mass ratio of 3:1.
  • Example 5 A fiber-reinforced resin sheet was produced in the same manner as in Example 1, except that 1,2-ethanediol acetate was used as the plasticizer B instead of 2,2,4-trimethyl-1,3-pentadiol isobutyrate. Obtained.
  • Example 6 Using a glass twisted yarn having a weight per unit length of warp and a weight per unit length of weft of 270 g/1000 m, the weaving density of the warp is 24.5 / 25 mm, and the weaving density of the weft is 19.5 fibers/25 mm, the mass of the glass fiber fabric was 500 g/m 2 , the thickness was 450 ⁇ m, and the air permeability was 10.9 cm 3 /cm 2 /s.
  • a fiber-reinforced resin sheet was obtained in the same manner as in Example 1.
  • Example 7 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that the amount of plasticizer A was changed to 18 parts by mass and the amount of plasticizer B was changed to 32 parts by mass to prepare a sol.
  • Example 8 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that the amount of plasticizer A was changed to 32 parts by mass and the amount of plasticizer B to 18 parts by mass.
  • Example 9 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1 except that the amount of plasticizer A was changed to 8 parts by mass and the amount of plasticizer B was changed to 42 parts by mass to prepare a sol.
  • Comparative Example 1 A glass fiber fabric of Comparative Example 1 was produced in the same manner as in Example 1, except that Composition A was changed to Composition B shown below. Then, in the same manner as in Example 1, a fiber-reinforced resin sheet was obtained.
  • Composition B SiO2 : 55.0% by mass, Al2O3 : 14.0% by mass, CaO: 23.0 % by mass, MgO: 1.0% by mass, Li2O + Na2O + K2O : 0.6 mass%, B2O3 : 6.0 mass%, TiO2 : 0.4 mass %
  • Comparative Example 2 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that instead of using the plasticizer A, the amount of the plasticizer B was changed to 50 parts by mass and the sol was prepared.
  • Comparative Example 3 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that the amount of plasticizer A was changed to 42 parts by mass and the amount of plasticizer B to 8 parts by mass.
  • Comparative Example 4 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that the amount of plasticizer A was changed to 3 parts by mass and the amount of plasticizer B was changed to 47 parts by mass to prepare a sol.
  • Comparative Example 5 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that instead of using the plasticizer B, the amount of the plasticizer A was changed to 50 parts by mass and the sol was prepared.
  • Comparative Example 6 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that the amount of plasticizer A was changed to 10 parts by mass and the amount of plasticizer B was changed to 10 parts by mass to prepare a sol.
  • Comparative Example 7 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1 except that the amount of plasticizer A was changed to 37.5 parts by mass and the amount of plasticizer B was changed to 37.5 parts by mass to prepare a sol.
  • Comparative Example 8 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that di-2-ethylhexyl phthalate was used as the plasticizer B to prepare the sol.
  • Comparative Example 9 A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that dibutyl adipate was used as the plasticizer B to prepare the sol.
  • Comparative Example 10 A fiber-reinforced resin sheet was obtained in the same manner as in Comparative Example 1 except that the amount of plasticizer A was changed to 8 parts by mass and the amount of plasticizer B was changed to 42 parts by mass to prepare a sol.
  • Comparative Example 11 A fiber-reinforced resin sheet was obtained in the same manner as in Comparative Example 1, except that the amount of plasticizer A was changed to 42 parts by mass and the amount of plasticizer B to 8 parts by mass.
  • Comparative Example 12 The warp mass per unit length and the weft mass per unit length are both 405g/1000m, the warp weaving density is 18.5/25mm, and the weft weaving density is 18.5/25mm.
  • the glass fiber fabric was produced in the same manner as in Example 1, except that the glass fiber fabric had a mass of 630 g/m 2 , a thickness of 520 ⁇ m, and an air permeability of 13.5 cm 3 /cm 2 /s. , to obtain a fiber-reinforced resin sheet of Comparative Example 12.
  • Comparative Example 13 The mass per unit length of the warp and the mass per unit length of the weft are both 22.4 g/1000 m, the weaving density of the warp is 60.0/25 mm, and the weaving density of the weft is 58.0/ 25 mm, the mass of the glass fiber fabric is 100 g/m 2 , the thickness is 85 ⁇ m, and the air permeability is 6.0 cm 3 /cm 2 /s. Then, a fiber-reinforced resin sheet of Comparative Example 13 was obtained.
  • test piece was prepared by cutting a glass fiber fabric into a width of 25 mm and a length of 150 mm in both the vertical and horizontal directions, and evaluated by a tensile test in accordance with JIS L 1096: 2010. /25 mm or more, A is less than 1000 N/25 mm, B is less than 1000 N/25 mm, and C is less than 1000 N/25 mm.
  • Tables 1 and 2 show the evaluation results of transparency, tackiness, impregnation and tensile strength.
  • the fiber-reinforced resin sheets of Examples had high tensile strength, had transparency, and were excellent in impregnability and handleability (tackiness) during production.
  • SYMBOLS 1 Fiber reinforced resin sheet, 10... Glass fiber fabric, 12... Warp, 14... Weft, 15... Resin composition.

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CN202380020621.3A CN118696080A (zh) 2022-02-08 2023-01-12 纤维增强树脂片材
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0455481A (ja) * 1990-06-22 1992-02-24 Kyowa Yuka Kk 塗装材
WO2009063809A1 (ja) 2007-11-13 2009-05-22 Nitto Boseki Co., Ltd. 不燃性及び透明性を有する繊維強化樹脂シート及びその製造方法
CN101812206A (zh) * 2009-02-23 2010-08-25 E.I.内穆尔杜邦公司 聚氯乙烯塑溶胶组合物和由其制得的制品
JP2015155156A (ja) * 2014-02-20 2015-08-27 ユニチカ株式会社 透明不燃性シート
WO2021251103A1 (ja) * 2020-06-10 2021-12-16 日東紡績株式会社 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

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Publication number Priority date Publication date Assignee Title
JP5115931B2 (ja) * 2008-08-29 2013-01-09 平岡織染株式会社 透明性複合シート
JP2015077756A (ja) * 2013-10-18 2015-04-23 ユニチカ株式会社 透明不燃性シート及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0455481A (ja) * 1990-06-22 1992-02-24 Kyowa Yuka Kk 塗装材
WO2009063809A1 (ja) 2007-11-13 2009-05-22 Nitto Boseki Co., Ltd. 不燃性及び透明性を有する繊維強化樹脂シート及びその製造方法
CN101812206A (zh) * 2009-02-23 2010-08-25 E.I.内穆尔杜邦公司 聚氯乙烯塑溶胶组合物和由其制得的制品
JP2015155156A (ja) * 2014-02-20 2015-08-27 ユニチカ株式会社 透明不燃性シート
WO2021251103A1 (ja) * 2020-06-10 2021-12-16 日東紡績株式会社 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

Non-Patent Citations (1)

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Title
See also references of EP4450537A4

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