Fiber-reinforced resin film, use thereof and process for its production as well as laminate and its use

Abstract

Fiber-reinforced resin film comprising: a matrix resin containing at least 50% by mass of a fluorinated resin, and a textile glass fibre fabric having an open area of no more than 20% and embedded in the matrix resin, wherein the fiber-reinforced resin film has a total light transmittance of at least 70%; wherein (a) the fluorinated resin is a cured product of a curable fluorinated copolymer comprising units derived from a fluoroolefin and units derived from a monomer other than the fluoroolefin, the monomer being copolymerizable with the fluoroolefin, or (b) the matrix resin is a mixed resin containing polyvinylidene fluoride and polymethyl methacrylate.

Description

TECHNICAL FIELD

[0001] The present invention relates to a fiber-reinforced resin film comprising a matrix resin and a glass fiber textile fabric embedded in the matrix resin, the use of the same, a method for producing the same, and a laminate comprising a layer of the fiber-reinforced resin film and a layer of a fluorinated resin, and the use thereof. STATE OF THE ART

[0002] A fiber-reinforced resin film is used as a membrane material (such as a roofing material or an exterior wall material) for membrane structures (such as sports facilities, large greenhouses, and atriums or courtyards). The fiber-reinforced resin film as a membrane material for membrane structures must, for example, exhibit flame-retardant properties, weather resistance, and transparency.

[0003] For example, the following film was proposed as a fiber-reinforced resin film having flame retardant properties. (1) A non-flammable sheet material having a resin layer made of a vinyl chloride resin (hereinafter referred to as "PVC") provided on at least one surface of a glass fiber cloth (Patent Document 1).

[0004] For example, the following films have been proposed as fiber-reinforced resin films using a fluorinated resin that has good weather resistance. (2) A fluororesin laminate obtained by impregnating a glass fiber textile fabric with a dispersion of polytetrafluoroethylene (hereinafter referred to as "PTFE") and heat-sintering the dispersion of PTFE (Patent Document 2). (3) A laminate film obtained by sandwiching a glass fiber textile fabric with a pair of ethylene / tetrafluoroethylene copolymer (hereinafter referred to as "ETFE") films and heating them to laminate them (Patent Document 3).

[0005] Patent Document 4 describes a composite body comprising a substrate and photosensitive resin layers formed on the substrate. The substrate comprises a fabric; and layers formed on the fabric comprising tetrafluoroethylene resin and silicon dioxide.

[0006] Patent Document 5 describes the production of a film material in which a PTFE dispersion can be used. PRIOR ART DOCUMENTS PATENT DOCUMENTS Patent document 1: JP 4 186 488 B2 Patent document 2: JP 2 577 389 B2 Patent document 3: WO 2008 / 105298 A1 Patent document 4: EP 2 915 667 A1 Patent document 5: JP H06 - 55 688 A DISCLOSURE OF THE INVENTION TECHNICAL PROBLEM

[0007] However, the flame retardant film material of the above (1) has insufficient weather resistance because the resin layer is made of PVC.

[0008] The fluororesin laminate of the above (2) has a plurality of air gaps between PTFE particles because a matrix resin is obtained by heat-sintering the dispersion of PTFE. Therefore, due to the difference in refractive index between PTFE or the glass fiber and air, light is scattered by air gaps, thereby deteriorating transparency.

[0009] In the case of the laminate film of the above (3) in which fluorinated resin films and a glass fiber textile fabric are simply laminated, a fluorinated resin is less likely to permeate glass fibers of the glass fiber textile fabric, and a plurality of air gaps remain in the glass fibers. Therefore, due to the difference in refractive index between the glass fiber or the fluorinated resin and air, light is scattered from air gaps, thereby deteriorating transparency. Accordingly, in the laminate film of the above (3), the glass fiber textile fabric is formed to have an open area ratio of at least 30%, so that transparency is improved. However, the glass fiber textile fabric having such a high open ratio may be damaged by a fire, for example,in an external fire exposure test, they are simply burned out and the flame retardant properties are therefore inadequate.

[0010] It is an object of the present invention to provide a fiber-reinforced resin film having flame retardant properties and excellent weather resistance and transparency, and to provide a method for producing the same. SOLUTION TO THE PROBLEM

[0011] The present invention provides a fiber-reinforced resin film, the use thereof, a manufacturing method thereof and a laminate and its use as defined in the appended claims. ADVANTAGEOUS EFFECTS OF THE INVENTION

[0012] The fiber-reinforced resin film of the present invention and the laminate of the present invention have flame retardant properties and excellent weather resistance and transparency.

[0013] According to the method for producing a fiber-reinforced resin film of the present invention, a fiber-reinforced resin film with flame retardant properties and excellent weather resistance and transparency can be produced. The laminate of the present invention can be produced, for example, by a method of laminating a film or sheet of a second fluorinated resin onto the produced fiber-reinforced resin film. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an embodiment of the fiber-reinforced resin sheet of the present invention. DESCRIPTION OF EMBODIMENTS

[0014] The following definitions of terms apply throughout the specification and claims.

[0015] “Fiber-reinforced resin film” means a film material that has a textile fiberglass fabric embedded in a matrix resin.

[0016] “Fluorinated resin” means a polymer compound (hereinafter referred to as “a fluorinated polymer”) having fluorine atoms in its molecule, and also means a curable fluorinated copolymer or a cured product thereof.

[0017] “Solvent-soluble fluorinated resin” means a fluorinated resin that is soluble in some solvents to form a solution.

[0018] “Matrix resin” refers to a resin in which a textile glass fiber fabric is to be embedded in a fiber-reinforced resin film.

[0019] “Textile glass fiber fabric” means a fabric or nonwoven made of glass fibers.

[0020] “Membrane structure” means a structure in which, for example, a roof or an external wall is completely or partially formed from a membrane material.

[0021] Units in a polymer derived from a monomer are also called monomer units. For example, units derived from an olefin are also called olefin units. [Fiber-reinforced resin film]

[0022] The Fig. Figure 1 is a cross-sectional view showing one embodiment of the fiber-reinforced resin sheet of the present invention. The fiber-reinforced resin sheet 10 includes a matrix resin 12 and a glass fiber textile fabric 14 embedded in the matrix resin 12. (matrix resin)

[0023] A matrix resin contains at least 50% by mass of a fluorinated resin and may optionally contain other resins or an additive.

[0024] The content of the fluorinated resin is at least 50 mass%, preferably at least 60 mass%, more preferably at least 75 mass%, based on the matrix resin (100 mass%). When the content of the fluorinated resin is at least the above-mentioned lower limit, the fiber-reinforced resin film exhibits excellent flame retardancy and weather resistance. The upper limit of the content of the fluorinated resin is 100 mass%. <Fluoriertes Harz>

[0025] The fluorinated resin may be, for example, a fluoroolefin polymer or a copolymer of a fluoroolefin and a monomer copolymerizable with the fluoroolefin. The monomer (hereinafter referred to as monomer (a)) copolymerizable with the fluoroolefin is a monomer other than the fluoroolefin. The copolymer of the fluoroolefin and the monomer (a) is hereinafter referred to as copolymer (A).

[0026] The fluoroolefin can be, for example, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, pentafluoropropylene or hexafluoropropylene.

[0027] The fluoroolefin polymer is polyvinylidene fluoride (hereinafter referred to as PVDF).

[0028] The fluorinated resin in the matrix is preferably a fluorinated resin soluble in a solvent or a cured product of a curable fluorinated copolymer soluble in an uncured state in view of the method for producing a fiber-reinforced resin film described below.

[0029] In the case of a fluorinated resin such as PVDF or polyvinyl fluoride (hereinafter referred to as PVF; not according to the invention) which is soluble in a solvent, a glass fiber fabric is impregnated with a solution of the fluorinated resin, and a solvent is then removed, thereby forming a matrix resin. The solvent-soluble fluorinated resin may be a copolymer (A). Further, the matrix resin may be a mixed resin of a solvent-soluble resin other than a fluorinated resin and a solvent-soluble fluorinated resin. According to the invention, PVDF is mixed with an acrylic resin which is PMMA. The acrylic resin may be, for example, polymethyl methacrylate (hereinafter referred to as PMMA), and is PMMA in the case of PVDF.

[0030] The curable fluorinated copolymer is a copolymer classified as copolymer (A). The curable fluorinated copolymer is a fluorinated copolymer that is soluble in a solvent and further has a reactive group. For example, a glass fiber textile fabric is impregnated with a solution containing a curable fluorinated copolymer having hydroxy groups as reactive groups and a curing agent having functional groups reactive with the hydroxy groups. Subsequently, a solvent is removed, and thereafter, the curable fluorinated copolymer and the curing agent are reacted, for example, by heating, to form a cured product of the curable fluorinated copolymer. This cured product is a fluorinated resin in the matrix resin.

[0031] The copolymer (A) is the curable fluorinated copolymer in view of excellent adhesion to a glass fiber textile fabric and the formation of a matrix resin having high mechanical strength after curing when cured in combination with a curing agent. This curable fluorinated copolymer has fluoroolefin units and units derived from a monomer having a reactive functional group as units derived from the monomer (a). Further, such a curable fluorinated copolymer may have units derived from a monomer (hereinafter referred to as "monomer (a2)") that is neither a fluoroolefin nor the monomer having a reactive functional group. The reactive functional group may be, for example, a hydroxy group, a carboxyl group, or an amino group.

[0032] The curable fluorinated copolymer is preferably a hydroxy group-containing fluorinated copolymer comprising fluoroolefin units, units derived from a monomer (hereinafter referred to as "monomer (a1)") having a hydroxy group, and monomer (a2) units. It is preferable that the monomer (a2) units can impart properties (e.g., solvent solubility, transparency, gloss, hardness, flexibility, and pigment dispersibility) to a curable fluoropolymer or a cured product thereof other than curability.

[0033] The curable fluorinated copolymer having hydroxy groups is preferably a copolymer obtainable by copolymerizing a fluoroolefin, the monomer (a1) and the monomer (a2).

[0034] The fluoroolefin for obtaining the curable fluorinated copolymer can be used alone or in combination with two or more of them. The fluoroolefin is preferably chlorotrifluoroethylene or tetrafluoroethylene.

[0035] The monomer (a1) may be, for example, an allyl alcohol, a hydroxyalkyl vinyl ether (such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, or cyclohexanediol monovinyl ether), a hydroxyalkyl allyl ether (such as 2-hydroxyethyl allyl ether), a vinyl hydroxyalkanoate (such as vinyl hydroxypropionate), a hydroxyalkyl acrylate (such as hydroxyethyl acrylate), or a hydroxyalkyl methacrylate (such as hydroxyethyl methacrylate). The monomer (a1) having a hydroxy group may be used alone or in a combination of two or more thereof.

[0036] The monomer (a2) is preferably a vinyl monomer, which is a compound having a carbon-carbon double bond. The vinyl monomer, which exhibits excellent alternating polymerizability with a fluoroolefin, can increase the polymerization yield. Furthermore, even if it remains unreacted, its influence on the matrix resin is minimal and it can be easily removed in one manufacturing step.

[0037] The vinyl monomer can be, for example, a vinyl ether, an allyl ether, a vinyl carboxylate, an allyl carboxylate or an olefin which does not have any reactive functional groups.

[0038] The vinyl ether which does not have reactive functional groups can be, for example, a cycloalkyl vinyl ether (such as cyclohexyl vinyl ether) or an alkyl vinyl ether (such as nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether or t-butyl vinyl ether).

[0039] The allyl ether which does not have reactive functional groups can be, for example, an alkyl allyl ether (such as ethyl allyl ether or hexyl allyl ether).

[0040] The carboxylic acid vinyl ester that does not have reactive functional groups can be, for example, a vinyl ester of a carboxylic acid (such as acetic acid, butyric acid, pivalic acid, benzoic acid, or propionic acid). Furthermore, as the carboxylic acid vinyl ester that has a branched alkyl group, commercially available products such as Veova 9 or Veova 10 (trade name, manufactured by Shell Kagaku KK) can be used.

[0041] The carboxylic acid allyl ester which does not have reactive functional groups can be, for example, an allyl ester of a carboxylic acid (such as acetic acid, butyric acid, pivalic acid, benzoic acid or propionic acid).

[0042] The olefin can be, for example, ethylene, propylene or isobutylene.

[0043] The monomer (a2) is preferably a monomer having a linear or branched alkyl group having at least three carbon atoms in view of excellent flexibility of the matrix resin and good conformability of the matrix resin to the glass fiber fabric when forming the fiber-reinforced resin film.

[0044] The monomer (a2) may be used alone or in a combination of two or more thereof.

[0045] The combination of monomers for forming a curable fluorinated copolymer having hydroxy groups is preferably the following combination (1), more preferably the following combination (2) or (3) thereof, in view of flame retardancy, weather resistance, adhesion, and flexibility. Combination (1)

[0046] Fluoroolefin: tetrafluoroethylene or chlorotrifluoroethylene, Monomer (a1): hydroxyalkyl vinyl ether, Monomer (a2): At least one selected from cycloalkyl vinyl ether, alkyl vinyl ether and carboxylic acid vinyl ester. Combination (2)

[0047] Fluorolefin: tetrafluoroethylene, Monomer (a1): hydroxyalkyl vinyl ether, Monomer (a2): t-butyl vinyl ether and vinyl carboxylate. Combination (3)

[0048] Fluorolefin: chlorotrifluoroethylene, Monomer (a1): hydroxyalkyl vinyl ether, Monomer (a2): t-butyl vinyl ether and vinyl carboxylate.

[0049] The proportion of fluoroolefin units in the curable fluorinated copolymer containing hydroxy groups is preferably from 30 to 70 mol%, more preferably from 40 to 60 mol%, in all units (100 mol%) of the copolymer. When the proportion of fluoroolefin units is at least the lower limit, the fiber-reinforced resin film exhibits superior flame retardancy and weather resistance. When the proportion of fluoroolefin units is at most the upper limit, the matrix resin exhibits excellent adhesion to the glass fiber textile fabric.

[0050] The proportion of the monomer units (a1) is preferably from 0.5 to 20 mol%, more preferably from 1 to 15 mol%, in all units (100 mol%) of the copolymer. When the proportion of the monomer units (a1) is at least the lower limit, the matrix resin exhibits excellent adhesion to the glass fiber textile fabric. When the proportion of the monomer units (a1) is at most the upper limit, the fiber-reinforced resin film exhibits excellent flexibility.

[0051] The proportion of the monomer units (a2) is preferably from 20 to 60 mol%, more preferably from 30 to 50 mol%, in all units (100 mol%) of the copolymer. When the proportion of the monomer units (a2) is at least the lower limit, the fiber-reinforced resin film has excellent flexibility. When the proportion of the monomer units (a2) is at most the above-mentioned upper limit, the matrix resin has excellent adhesion to the glass fiber textile fabric. The monomer (a2) is particularly preferably a monomer having a linear or branched alkyl group having at least three carbon atoms.

[0052] The number-average molecular weight of the curable fluorinated copolymer is preferably from 3,000 to 50,000, more preferably from 5,000 to 30,000. When the number-average molecular weight of the curable fluorinated copolymer is at least the lower limit, the heat resistance is excellent. When the number-average molecular weight of the curable fluorinated copolymer is at most the upper limit, it is easily soluble in the solvent.

[0053] Commercially available products of the thermosetting fluorinated copolymer having hydroxy groups may include, for example, the LUMIFLON (registered trademark) series (such as LF200, LF100 or LF710) (manufactured by Asahi Glass Company, Limited), the ZEFFLE (registered trademark) GK series (such as GK-500, GK-510, GK-550, GK-570 or GK-580) (manufactured by Daikin Industries, Ltd.), the FLUONATE (registered trademark) series (such as K-700, K-702, K-703, K-704, K-705 or K-707) (manufactured by DIC Corporation) or the ETERFLON series (such as 4101, 41011, 4102, 41021, 4261A, 4262A, 42631, 4102A, 41041, 41111 or 4261A) (manufactured by Eternal Chemical Co., Ltd.).

[0054] The curable fluorinated copolymer is cured by a curing agent, thereby forming a fluorinated resin as the matrix resin. The curing agent for the curable fluorinated copolymer having hydroxy groups can be an isocyanate-type curing agent or a melamine-type curing agent such as methylolmelamine. <Andere Harze>

[0055] The matrix resin may be a mixed resin according to claim 1 containing a resin other than the fluorinated resin.

[0056] Such other resins are preferably PMMA, polycarbonate, polyarylate, polycycloolefin in view of compatibility with the fluorinated resin and solubility in a solvent.

[0057] The combination of the fluorinated resin and such other resins is, according to the invention, a combination of PVDF and PMMA in view of flame retardancy, weather resistance and solubility in a solvent.

[0058] The proportion of such other resins in the mixed resin is preferably at most 50 mass% in view of flame retardancy and weather resistance, more preferably at most 40 mass% in the mixed resin (100 mass%). In the case of the combination of PVDF and PMMA according to the invention, the proportion of such other resins is preferably at least 10 mass%, more preferably at least 20 mass%, in view of solubility in a solvent. In the case other than the combination of PVDF and PMMA, the proportion of such other resins is more than 0 mass%. <additive>

[0059] The matrix resin may optionally contain a known additive. In a case where the matrix resin is a cured product of the curable fluorinated copolymer, it is preferable that an additive is blended into the curable fluorinated copolymer to perform curing, thereby forming a cured product containing the additive.

[0060] The additive may be, for example, an ultraviolet absorbent, a light stabilizer, an antioxidant, an infrared absorbent, a flame retardant, a flame retardant filler, an organic pigment, an inorganic pigment or a dye.

[0061] The matrix resin preferably contains an ultraviolet absorbent to enable outdoor use for a longer period of time.

[0062] The proportion of the ultraviolet absorbent is preferably from 0.5 to 20 parts by mass, more preferably from 1.0 to 10 parts by mass per 100 parts by mass of the matrix resin.

[0063] The ultraviolet absorbent may be, for example, an organic type ultraviolet absorbent or an inorganic type ultraviolet absorbent.

[0064] The organic type ultraviolet absorbent, which is a compound having a π-conjugated molecular structure, is an organic compound that has ultraviolet shielding ability by absorbing ultraviolet light and emitting it as a changed secondary energy.

[0065] The organic type ultraviolet absorbent may be, for example, a benzotriazole type ultraviolet absorbent, a benzophenone type ultraviolet absorbent, a salicylate type ultraviolet absorbent, a cyanoacrylate type ultraviolet absorbent, a nickel type ultraviolet absorbent or a triazine type ultraviolet absorbent.

[0066] The inorganic type ultraviolet absorbent is predominantly one that has two types of performance of an ultraviolet absorption performance inherent in an inorganic compound and a scattering performance (referred to as Mie scattering or Rayleigh scattering) in an ultraviolet ray wavelength range obtained by adjusting the particle size.

[0067] The inorganic type ultraviolet absorbent may be, for example, titanium oxide, zinc oxide, cerium oxide or iron oxide.

[0068] The light stabilizer can be, for example, a hindered amine type light stabilizer.

[0069] Antioxidants are classified as chain-interrupting agents, peroxide decomposing agents, or metal deactivators according to their mechanism of action. For example, antioxidants can be phenol-type antioxidants, phosphorus-type antioxidants, sulfur-type antioxidants, or amine-type antioxidants.

[0070] The flame retardant may be, for example, a phosphorus type flame retardant or a bromine type flame retardant.

[0071] The flame retardant filler can be, for example, aluminum hydroxide or magnesium hydroxide. (Textile glass fiber fabric)

[0072] A glass fiber textile fabric is a woven or nonwoven fabric made of glass fibers. The glass fiber textile fabric can be one that has been previously bonded between the glass fibers using a binder. <glasfasern>

[0073] The glass fibers may be, for example, glass fibers made from alkali-free glass (E-glass) containing SiO2, Al2O3, and CaO as their main components, glass fibers made from low-dielectric-constant glass (D-glass) containing SiO2 and B2O3 as their main components, and glass fibers made from quartz glass, which is mostly just SiO2. The glass fibers made from quartz glass are preferably glass fibers containing at least 80 mass% SiO2, more preferably glass fibers containing at least 90 mass% SiO2, particularly preferably glass fibers containing at least 93 mass% SiO2.

[0074] The difference (absolute value) between the refractive index of the glass fibers and the refractive index of the matrix is preferably at most 0.20 with a view to increasing the total light transmittance, and particularly preferably at most 0.10 with a view to reducing haze.

[0075] The refractive index is a refractive index for light with a wavelength of 589 nm, which is a numerical value measured according to JIS Z8402-1. <gewebe>

[0076] The fabric is preferably a fabric obtained by weaving a yarn made of a plurality of individual glass fibers in view of the flexibility and high strength of a fabric obtained.

[0077] The thickness of the individual glass fibers is preferably from 0.018 to 1 tex (g / 1000 m), more preferably from 0.07 to 0.46 tex. When the thickness of the individual glass fibers is at least the above-mentioned lower limit, the individual glass fibers are unlikely to break during the production of a fiber-reinforced resin film. When the thickness of the individual glass fibers is at most the above-mentioned upper limit, the resulting fabric has excellent flexibility and strength. The thickness of the individual glass fibers is measured according to JIS L0101.

[0078] The number of individual glass fibers constituting a yarn is preferably from 5 to 1000, more preferably from 10 to 300. When the number of individual glass fibers is at least the lower limit, handling during yarn production can be facilitated. When the number of individual glass fibers is at most the upper limit, a yarn can be produced stably.

[0079] The number of threads (longitudinal and transverse) is preferably from 10 to 200 mesh (number / inch), more preferably from 20 to 150 mesh. When the number of threads is at least the lower limit, the weaving speed during fabric production can be increased, thereby reducing costs. When the number of threads is at most the upper limit, a fabric with a low open area ratio can be obtained.

[0080] The weave of the fabric can be, for example, a plain weave, a twill weave, a leno weave or a knit.

[0081] The fabric may be a fabric made from one type or at least two types of individual glass fibers. Furthermore, the warp and weft of the fabric may have a different number of individual glass fibers to form a yarn. <vlies>

[0082] The nonwoven fabric is preferably a nonwoven fabric obtained by accumulating a plurality of glass fibers and fixing a space between glass fibers by a binder in view of ease of handling.

[0083] The basis weight of the fleece is preferably from 15 to 500 g / m 2 , particularly preferably from 30 to 300 g / m 2 . When the basis weight of the nonwoven fabric is at least the lower limit, the strength is excellent. When the basis weight of the nonwoven fabric is at most the upper limit, the matrix resin easily penetrates into the air gaps between the glass fibers.

[0084] The thickness of the nonwoven fabric is preferably from 80 to 600 µm, more preferably from 120 to 400 µm. When the thickness of the nonwoven fabric is at least the lower limit, the strength is excellent. When the thickness of the nonwoven fabric is at most the upper limit, the matrix resin can easily penetrate into the air gaps between the glass fibers.

[0085] The density of the fleece is preferably from 0.067 to 0.5 g / cm 3 , particularly preferably from 0.15 to 0.4 g / cm 3 If the density of the nonwoven fabric is at least the lower limit, the strength is excellent. If the density of the nonwoven fabric is at most the upper limit, the matrix resin can easily penetrate into the air gaps between the glass fibers.

[0086] The binder can be, for example, polyvinyl alcohol, polyvinyl acetate, an acrylic resin, an epoxy resin, an unsaturated polyester resin or a melamine resin.

[0087] The nonwoven fabric may be a nonwoven fabric made from one type or at least two types of individual glass fibers. <Anteil der offenen Fläche>

[0088] The open area ratio of the glass fiber textile fabric is at most 20%, preferably at most 15%, more preferably at most 12%, particularly preferably at most 9%. When the open area ratio of the glass fiber textile fabric is at most the upper limit, the fiber-reinforced resin film exhibits excellent flame retardancy. The open area ratio of the glass fiber textile fabric is preferably at least 1%, more preferably at least 2%, particularly preferably at least 3%, considering that a solvent-soluble fluorinated resin solution or a curable fluorinated copolymer solution can easily penetrate into air gaps between the glass fibers.

[0089] The proportion of the open area of the textile glass fiber fabric is determined using the following formula (1). Percentage of open area = (distance between glass fibers in the longitudinal direction of the glass fiber textile fabric × distance between glass fibers in the transverse direction of the glass fiber textile fabric) / (distance between centers of glass fibers in the longitudinal direction of the glass fiber textile fabric × distance between centers of glass fibers in the transverse direction of the glass fiber textile fabric) × 100

[0090] The proportion of the open area can be adjusted by changing, for example, the thickness of the glass fibers and the number of twisted glass fibers. (Fiber-reinforced resin film)

[0091] The thickness (at an intersection of glass fibers) of the fiber-reinforced resin film is preferably at most 1000 µm, more preferably at most 400 µm, in view of, for example, excellent transparency and processability. The thickness of the fiber-reinforced resin film is preferably at least 24 µm, more preferably at least 50 µm, in view of, for example, excellent strength.

[0092] The total light transmittance of the fiber-reinforced resin film is at least 70%, preferably at least 80%, more preferably at least 83%, particularly preferably at least 86%.

[0093] The total light transmittance of the fiber-reinforced resin film is measured with light source D according to JIS K7361-1: 1997.

[0094] The total light transmittance of the fiber-reinforced resin film can be increased by reducing air gaps in the fiber-reinforced resin film. For example, according to the method for producing a fiber-reinforced resin film of the present invention as described below, the air gaps in the fiber-reinforced resin film can be reduced. Therefore, light scattering due to the difference in refractive index between the glass fibers or the matrix resins and air in the air gaps can be suppressed, whereby the total light transmittance of the fiber-reinforced resin film can be at least 80%. (Function and effect)

[0095] The fiber-reinforced resin sheet of the present invention as described above, which comprises a matrix resin containing at least 50% by mass of a fluorinated resin and a glass fiber fabric having an open area ratio of at most 20% embedded in the matrix resin, exhibits flame retardancy and excellent weather resistance. Furthermore, the fiber-reinforced resin sheet is obtained by the production method of the present invention described below, whereby the air gaps in the fiber-reinforced resin sheet are reduced, the total light transmittance is at least 70%, and the transparency is excellent. [Method for producing a fiber-reinforced resin film]

[0096] Furthermore, the present invention relates to a method for producing a fiber-reinforced resin film.

[0097] In a case where the matrix resin is a cured product of a curable fluorinated copolymer, a curable resin material containing a curable fluorinated copolymer is dissolved in a solvent to obtain a solution, the above-mentioned glass fiber textile fabric is impregnated with the solution, the solvent is removed, and then the above-mentioned curable resin material is cured to form the above-mentioned matrix resin, thereby producing the fiber-reinforced resin sheet.

[0098] In a case where the matrix resin is a solvent-soluble fluorinated resin, the matrix resin is dissolved in a solvent to obtain a solution, and then the glass fiber textile fabric is impregnated with the solution, after which the solvent is removed, thereby producing the fiber-reinforced resin film.

[0099] In particular, a production method comprising the following steps (I) to (III) is preferable in a case where the matrix resin is a cured product of a curable fluorinated copolymer, and a production method comprising the following steps (I) and (II) is preferable in a case where the matrix resin is a solvent-soluble fluorinated resin.

[0100] Here, the following "resin material" means a solvent-soluble fluorinated resin itself as a matrix resin or a resin formed into a matrix resin by, for example, curing. A curable resin material containing a curable fluorinated copolymer means a material containing at least one component for curing the curable fluorinated copolymer, such as a curing agent, and a curable fluorinated copolymer. The resin material may also contain, for example, the above-mentioned additives.

[0101] As a method for producing a fiber-reinforced resin film of the present invention, a production method comprising the following steps (I) to (III) is preferable in a case where the matrix resin is a cured product of a curable fluorinated copolymer, and a production method comprising the following steps (I) and (II) is preferable in a case where the matrix resin is a solvent-soluble fluorinated resin. (I) A step of impregnating a glass fiber textile fabric with a solution comprising a resin material for forming a matrix resin dissolved in a solvent. (II) A step of removing the solvent after the above-mentioned step (I), thereby forming a resin material containing no solvent (in a case where the resin material is a fluorinated resin soluble in a solvent, a matrix resin is formed). (III) A step of forming a matrix resin by curing the resin material simultaneously with the above-mentioned step (II) or after the above-mentioned step (II) in the case of a resin material containing a curable fluorinated copolymer. (Step (I))

[0102] The resin material may be, for example, a solvent-soluble fluorinated resin for a matrix resin, a combination of a curable fluorinated copolymer and a curing agent, or a combination thereof with other resins as mentioned above.

[0103] The solvent can be, for example, toluene, xylene, butyl acetate, methyl ethyl ketone, or methylene chloride. The proportion of the resin material in the solution (100 mass%) is preferably from 30 to 85 mass%, particularly preferably from 40 to 75 mass%.

[0104] The solution may contain the following additives for adjusting the properties of the solution, which are different from the above-mentioned additives for the matrix resin.

[0105] A surface adjuster, an emulsifier, a film-forming aid (a high boiling point organic solvent), a thickener, a preservative, a silane coupling agent, an antifoam, and the like.

[0106] The method for impregnating a textile glass fiber fabric with a solution may, for example, be a method comprising the following steps 1 to 5. Step 1: A textile fiberglass fabric is provided on an underlying film. Step 2: A predetermined amount of a solution of a resin material is added to the textile glass fiber fabric. Step 3: A covering film is placed on the textile fiberglass fabric impregnated with the above-mentioned solution. Step 4: A hand roller is moved back and forth on the cover film to remove bubbles from the solvent-impregnated glass fiber textile fabric. Step 5: The cover film is removed and passed to step (II). (Step (II))

[0107] The removal of the solvent is usually carried out by heating.

[0108] The heating temperature may be at least a temperature at which the solvent evaporates and lower than a temperature at which a resin material and additives are decomposed, or lower than a temperature at which an underlying film deforms.

[0109] The heating time can be a time during which a solvent is completely evaporated and removed.

[0110] If the resin material is non-curable, a fiber-reinforced resin film can be obtained through this step (II). If the resin material is a curable resin material, such as a combination of a curable fluorinated copolymer and a curing agent, the resin material is cured in the following step (III). (Step (III))

[0111] Curing of the resin material is usually done by heating.

[0112] When the resin material is a curable resin material such as the combination of a curable fluorinated copolymer and a curing agent, step (III) is performed after step (II). Steps (III) and (II) may be a continuous step. For example, heating may be continued even after the solvent is removed by heating in step (II), so that a curable resin material is cured. After the solvent is evaporated, the heating temperature may be raised to perform curing. Alternatively, the heating temperature may be gradually raised during solvent removal, so that curing is performed while continuously raising the temperature after solvent removal.

[0113] For example, the heating temperature may be at least a temperature at which the curing agent is reacted with hydroxy groups in the curable fluorinated copolymer and lower than a temperature at which a resin material and additives are decomposed, or lower than a temperature at which an underlying film is deformed.

[0114] The heating time can be adjusted in an appropriate manner depending on the degree of curing of the resin material. (Function and effect)

[0115] According to the method for producing a fiber-reinforced resin sheet of the present invention as described above, since the glass fiber fabric is impregnated with the solution containing the resin material dissolved in the solvent, the resin material can easily penetrate into air gaps between the glass fibers. As a result, air gaps in the obtainable fiber-reinforced resin sheet can be reduced, and therefore, light scattering due to the difference in indexes between the glass fibers or the matrix resin and air in the air gaps can be suppressed, whereby the total light transmittance of the fiber-reinforced resin sheet can be at least 70%. (laminate)

[0116] Furthermore, the present invention relates to a laminate comprising a layer of the above-described fiber-reinforced resin film and a layer of a second fluorinated resin provided on one or each side of the fiber-reinforced resin film, the laminate having a total light transmittance of at least 70%. The total light transmittance of the laminate is preferably at least 80%.

[0117] The laminate of the present invention has flame retardant properties and excellent weather resistance and transparency, as is the case with the fiber-reinforced resin film described above.

[0118] The second fluorinated resin may be of the same type as the fluorinated resin (hereinafter also referred to as a first fluorinated resin) in the above-described matrix resin, or a different type from the first fluorinated resin. The same type of fluorinated resin means a fluorinated resin used as the above-described matrix resin, which is referred to as the above-described first fluorinated resin. The different type of fluorinated resin means a fluorinated resin that cannot substantially be used as the above-described first fluorinated resin, which is a curable fluorinated copolymer or a fluorinated copolymer that is substantially insoluble in a solvent.

[0119] In a case where the second fluorinated resin is of the same type as the first fluorinated resin, the second fluorinated resin in the laminate may be the same as or different from the first fluorinated resin. In the laminate, a case where the second fluorinated resin is different from the first fluorinated resin may be, for example, a case where the first fluorinated resin is a cured product of a hydroxy group-containing fluorinated copolymer and the second fluorinated resin is a thermoplastic fluorinated resin.

[0120] The second fluorinated resin is preferably a thermoplastic fluorinated resin. The thermoplastic fluorinated resin may be, for example, a homopolymer of a fluoroolefin, a copolymer of at least two types of fluoroolefins, a copolymer of a fluoroolefin and another fluorinated monomer, such as a perfluoroalkyl vinyl ether, or a copolymer of a fluoroolefin and an olefin.

[0121] The thermoplastic fluorinated resin may be a fluorinated resin that is substantially insoluble in a solvent.

[0122] Since the thermoplastic fluorinated resin can be subjected to melt molding such as extrusion molding or injection molding, the resulting molded product can be used to form a layer of the laminate of the present invention. It is preferable that a film or sheet obtained, particularly by extrusion molding, be used to produce the laminate of the present invention.

[0123] The thickness of a film or sheet of the second fluorinated resin is preferably from 25 to 300 µm, more preferably from 50 to 200 µm, in view of an ultraviolet shielding effect and heat-bonding strength.

[0124] A specific thermoplastic fluorinated resin can be, for example, ETFE, a tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer [PFA], a tetrafluoroethylene / perfluoro(methyl vinyl ether) / perfluoro(propyl vinyl ether) copolymer [MFA], a tetrafluoroethylene / hexafluoropropylene copolymer [FEP], PVDF, PVF, a tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer [THV], polychlorotrifluoroethylene [PCTFE], an ethylene / chlorotrifluoroethylene copolymer [ECTFE] or a tetrafluoroethylene / 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole copolymer.

[0125] A second fluorinated resin layer may optionally also contain, for example, a resin other than a fluorinated resin or an additive. The second fluorinated resin layer preferably contains an ultraviolet absorbent as an additive in view of the weather resistance of the fiber-reinforced resin film.

[0126] Examples and preferred types of the ultraviolet absorbent in the second fluorinated resin layer are the same as those of the ultraviolet absorbent that may be contained in the matrix resin. Furthermore, the proportion of the ultraviolet absorbent is preferably from 0.1 to 20 parts by mass, more preferably from 0.2 to 10 parts by mass, per 100 parts by mass of the second fluorinated resin.

[0127] The fiber-reinforced resin film layer and the second fluorinated resin layer can be directly bonded, for example, by melting, or they can be bonded through an adhesive layer. In a case where the second fluorinated resin is, for example, a cured product of a curable fluorinated copolymer, the curable fluorinated copolymer can be cured on the surface of the fiber-reinforced resin film, thereby making it possible to form the second fluorinated resin layer directly bonded to the fiber-reinforced resin film.

[0128] In a case where the second fluorinated resin layer is formed by laminating a film or sheet of the thermoplastic fluorinated resin as mentioned below, it is preferable to adhere the film to the fiber-reinforced resin sheet using an adhesive, for example. The adhesive is preferably a thermosetting adhesive or a hot-melt adhesive. A specific adhesive may be, for example, a polyester adhesive, an epoxy adhesive, an acrylate adhesive, or a urethane adhesive.

[0129] The laminate can be, for example, the following.

[0130] ETFE layer (containing an ultraviolet absorbent) / adhesive layer / fiber-reinforced resin film layer / adhesive layer / ETFE layer (containing an ultraviolet absorbent).

[0131] ETFE layer (containing an ultraviolet absorbent) / adhesive layer (containing an ultraviolet absorbent) / fiber-reinforced resin film layer / adhesive layer (containing an ultraviolet absorbent) / ETFE layer (containing an ultraviolet absorbent).

[0132] ETFE layer (containing an ultraviolet absorbent) / adhesive layer (containing an ultraviolet absorbent) / fiber-reinforced resin film layer / adhesive layer / ETFE layer (containing an ultraviolet absorbent).

[0133] ETFE layer (containing an ultraviolet absorbent) / adhesive layer / fiber-reinforced resin film layer / ETFE layer (containing an ultraviolet absorbent).

[0134] ETFE layer (containing an ultraviolet absorbent) / fiber-reinforced resin film layer / ETFE layer (containing an ultraviolet absorbent).

[0135] Fiber-reinforced resin film layer / adhesive layer / ETFE layer (containing an ultraviolet absorbent).

[0136] Fiber-reinforced resin film layer / adhesive layer (containing an ultraviolet absorbent) / ETFE layer (containing an ultraviolet absorbent).

[0137] Fiber-reinforced resin film layer / ETFE layer (containing an ultraviolet absorbent).

[0138] A method for producing a laminate is preferably a method of hot-pressing the fiber-reinforced resin sheet and a film or sheet of the second fluorinated resin, or a method of adhering the fiber-reinforced resin sheet and a film or sheet of the second fluorinated resin using an adhesive. In the case where, for example, a thermosetting adhesive or a hot-melt adhesive is used as the adhesive, a method in which an adhesive layer is formed on the surface of the fiber-reinforced resin sheet and a film or sheet of the second fluorinated resin is laminated to perform hot-pressing, or a method in which an adhesive layer is formed on one side of a film or sheet of the second fluorinated resin and then the fiber-reinforced resin sheet is laminated to perform hot-pressing is preferable.

[0139] In addition, a method of applying a solution or dispersion of the second fluorinated resin to the surface of the fiber-reinforced resin sheet and removing a solvent to solidify the second fluorinated resin, or a method of forming a layer of the second fluorinated resin by applying a solution of the curable polymer to the surface of the fiber-reinforced resin sheet, removing the solvent, and curing the curable polymer, for example, by heating, may be used. EXAMPLES

[0140] Hereinafter, the present invention will be described in more detail with reference to examples, but it should be noted that the present invention is by no means limited thereto.

[0141] Examples 1 and 5 to 8 are examples of the invention and Examples 2 to 4 are comparative examples. [Evaluation method](Total light transmittance and haze)

[0142] Using a haze meter (NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance and haze of a fiber-reinforced resin film were measured with a D-light source according to JIS K7361-1: 1997. (Accelerated Weather Resistance Test)

[0143] An accelerated weatherability test was conducted using an accelerated weatherability tester (Eye Super UV Tester, manufactured by Suga Test Instruments Co., Ltd.). The total light transmittance and haze of a fiber-reinforced resin film after exposure for 225 hours were measured. (Flame retardant property rating 1)

[0144] A test specimen (30 cm × 30 cm) of fiber-reinforced resin film was fixed so that the surface of the specimen was inclined at 45° to the horizontal direction. The test specimen was exposed to a flame (length: 2.5 cm) of a spirit lamp from below the test specimen, and the time until the test specimen ignited was measured, and an evaluation was conducted based on the following standards. O (Good): The time to ignition was at least 30 seconds. Δ (Permissible): The time to ignition was at least 10 seconds and less than 30 seconds. × (Poor): The time to ignition was less than 10 seconds. (Flame retardant property rating 2)

[0145] A test specimen (30 cm × 30 cm) made of fiber-reinforced resin film was fixed so that the surface of the specimen was horizontal. A cotton pad was placed below the test specimen. After igniting a piece of wood (2 cm × 2 cm × 2 cm), the wood pad was placed on the test specimen, and the time until the cotton pad ignited was measured, with evaluation based on the following standards. O (Good): The time to ignition was at least 5 minutes. Δ (Permissible): The time to ignition was at least 1 minute and less than 5 minutes. × (Poor): The time to ignition was less than 1 minute. [Example 1]

[0146] A glass fiber fabric (using a glass fiber made of E-glass, refractive index of the glass: 1.55, thickness of a single glass fiber: 0.162 Tex, number of individual glass fibers forming a yarn: 130, number of twists (longitudinal and transverse directions): 60 mesh, basis weight of the fabric: 100 g / m 2 , Thickness of the fabric at a point of intersection of the yarn: 93 µm, ratio of the open area of the fabric: 3%, total light transmittance of the fabric: 50%), which was obtained by weaving a glass fiber yarn in a plain weave, was manufactured.

[0147] To a xylene solution (solid content: 60 mass%) of a fluoroolefin / vinyl ether copolymer (trade name: LUMIFLON (registered trademark) LF200, manufactured by Asahi Glass Company, Limited; this hydroxyl group-containing copolymer is hereinafter referred to as "LF200"), 48.2 parts by mass of a hexamethylene diisocyanate (Duranate (registered trademark) E402-90T, manufactured by Asahi Kasei Chemicals Corporation) and 2 parts by mass of a benzophenone-type ultraviolet absorbent (CYASORBUV531, manufactured by CYTEC Industries Inc.) were added per 100 parts by mass of LF200, so that a resin solution was prepared.

[0148] The above-mentioned glass fiber cloth was spread on a polyethylene terephthalate (hereinafter referred to as "PET") film with a thickness of 50 µm. The resin solution was supplied to the center of the glass fiber cloth, and the PET film with a thickness of 50 µm was placed on the glass fiber cloth. A hand roller was reciprocated on the PET film to remove bubbles from the glass fiber cloth impregnated with the resin solution.

[0149] The PET film deposited on the glass fiber fabric was peeled off, and the glass fiber textile fabric impregnated with the resin solution was placed in a constant-temperature hot-air oven. The constant-temperature hot-air oven was heated at 80°C for 1 hour to remove the solvent, and LF200 was simultaneously cured with hexamethylene diisocyanate to produce a fiber-reinforced resin film. In Example 1, each impregnation and drying step was performed once. The thickness (at an intersection of glass fibers) of the fiber-reinforced resin film was 136 µm. The evaluation result of the fiber-reinforced resin film is shown in Table 1. [Example 2] (not according to the invention)

[0150] A tetrahydrofuran solution (solid content: 20 mass%) of PVC (TH-640, manufactured by Taiyo Vinyl Corporation) was prepared.

[0151] In the same manner as in Example 1, a glass fiber fabric was impregnated with the PVC solution and then dried. To achieve the thickness of the matrix resin, the same step was repeated three times to produce a fiber-reinforced resin sheet. The thickness (at an intersection of glass fibers) of the fiber-reinforced resin sheet was 143 µm. The evaluation result of the fiber-reinforced resin sheet is shown in Table 1. [Example 3] (not according to the invention)

[0152] A dispersion (Fluon (registered trademark) PTFE AD912L manufactured by Asahi Glass Company, Limited, PTFE concentration: 50 mass%, containing a non-ionic stabilizer) of PTFE was prepared.

[0153] In the same manner as in Example 1, a glass fiber fabric was impregnated with a PTFE dispersion, followed by sintering at 380 °C for five minutes. The same step was repeated twice to produce a fiber-reinforced resin film. The thickness (at an intersection of glass fibers) of the fiber-reinforced resin film was 130 µm. The evaluation result of the fiber-reinforced resin film is shown in Table 1. [Example 4] (not according to the invention)

[0154] A fiber-reinforced resin sheet was prepared in the same manner as in Example 1, except that the glass fiber woven fabric was changed to a glass fiber woven fabric with an open area ratio of 30%. The thickness (at an intersection of glass fibers) of the fiber-reinforced resin sheet was 152 µm. The evaluation result of the fiber-reinforced resin sheet is shown in Table 1. [Example 5]

[0155] A fiber-reinforced resin film was prepared in the same manner as in Example 1, except that LF200 was changed to a mixture of PVDF and PMMA (an N-methylpyrrolidone solution (solid content concentration: 38 mass%) comprising PVDF manufactured by Arkemas and PMMA manufactured by Kuraray Co., Ltd. blended in a ratio of PVDF:PMMA = 60:40 (mass ratio)). The thickness (at an intersection point of glass fibers) of the fiber-reinforced resin film was 128 µm. The evaluation result of the fiber-reinforced resin film is shown in Table 1. [Example 6]

[0156] A 100 µm-thick ETFE film containing 0.5 mass% cerium oxide as an ultraviolet absorbent was laminated to at least one side of the fiber-reinforced sheet in Example 1 via an adhesive layer (Product No. BLS-PC27, manufactured by Toyo Ink Manufacturing Co., Ltd., 8 µm dry thickness) to form a laminate. The thickness (at an intersection of glass fibers) of the laminate was 242 µm. The evaluation result of the laminate is shown in Table 2. Furthermore, the weatherability test was conducted with the ETFE laminate surface directed toward a UV lamp of the tester. [Example 7]

[0157] The ETFE film containing an ultraviolet absorbent prepared in Example 6 was laminated to each side of the fiber-reinforced sheet described in Example 1 with the same adhesive layer as in Example 6, thereby obtaining a laminate. The thickness (at an intersection of glass fibers) of the laminate was 256 µm. The evaluation result of the laminate is shown in Table 2. [Example 8]

[0158] A fabric (refractive index of the glass: 1.45, thickness of a single glass fiber: 0.148 Tex, number of individual glass fibers forming a yarn: 150, number of twists (length and width): 60 mesh, basis weight of the fabric: 105 g / m 2 , Thickness of the fabric at a yarn intersection: 99 µm, open area ratio of the fabric: 2%, total light transmittance of the fabric: 48%) from glass fibers made of a high silica glass containing 96 mass% SiO2 was prepared. The fiber-reinforced resin sheet was manufactured in the same manner as in Example 1, except that the glass fiber fabric was used. The thickness (at a glass fiber intersection) of the fiber-reinforced resin sheet was 144 µm. The evaluation result of the fiber-reinforced resin sheet is shown in Table 1. TABLE 1 e.g. 1 2 3 4 5 8 Matrix resin Cured product of LF200 PVC PTFE Cured product of LF200 PVDF + PMMA Cured product of LF200 Percentage of open area of the textile glass fiber fabric (%) 3 3 3 30 3 2 Before the accelerated weather resistance test Total light transmittance (%) 89 91 32,6 91 85 90 Turbidity (%) 94 33 - 81 98 8 After the accelerated weather resistance test Total light transmittance (%) 88 65 34,5 90 85 88 Turbidity (%) 95 42 - 80 97 10 Flame retardant property rating 1 ◯ × - ◯ ◯ ◯ Flame retardant property rating 2 ◯ × to Δ - × ◯ ◯ TABLE 2 e.g. 6 7 Matrix resin Cured product of LF200 Cured product of LF200 Percentage of open area of the textile glass fiber fabric (%) 3 3 Laminate structure ETFE layer / adhesive layer / fiber-reinforced resin film in Example 1 ETFE layer / adhesive layer / fiber-reinforced resin film in Example 1 / adhesive layer / ETFE layer Before the accelerated weather resistance test Total light transmittance (%) 86 84 Turbidity (%) 96 97 After the accelerated weather resistance test Total light transmittance (%) 86 84 Turbidity (%) 95 96 Flame retardant property rating 1 ◯ ◯ Flame retardant property rating 2 ◯ ◯

[0159] The fiber-reinforced resin film in each of Examples 1, 5, and 8 and the laminate in each of Examples 6 and 7 exhibited excellent overall light transmittance, weather resistance, and excellent flame retardancy.

[0160] The fiber-reinforced resin film in Example 2, in which the matrix resin was PVC, exhibited insufficient weather resistance and flame-retardant properties. The fiber-reinforced resin film in Example 3, in which the matrix resin was a sintered product of a PTFE dispersion, exhibited low total light transmittance. The fiber-reinforced resin film in Example 4, in which the glass fiber fabric had a high open area ratio, exhibited insufficient flame-retardant properties. Examples 2-4 are also not in accordance with the invention.

[0161] The laminate in each of Examples 6 and 7 had an ETFE film on one side or both sides of the laminate, whereby the fiber-reinforced resin film is protected by the ETFE film. INDUSTRIAL APPLICABILITY

[0162] The fiber-reinforced resin film of the present invention and the laminate of the present invention, which have flame retardant properties and excellent weather resistance and transparency, are suitable as a membrane material (such as a roofing material, a ceiling material, an exterior wall material, or an interior wall material) for membrane structural buildings (such as sports facilities, large greenhouses, and yards) or as a covering material for agricultural greenhouses. Furthermore, when bonding the fiber-reinforced resin film or the laminate of the present invention to other members by heat sealing, a conventional heat sealing device can be used under conventional conditions.

[0163] The fiber-reinforced resin film of the present invention and the laminate of the present invention can be used for various applications, not only for membrane materials for membrane structural buildings or cover materials for agricultural greenhouses, but also for materials made of a fiber-reinforced resin. As further applications, the fiber-reinforced resin film and the laminate are, for example, a panel material for outdoor use (e.g., a soundproof wall, a windbreak fence, a wave barrier fence, a cover for garages, a shopping arcade, a wall for a passageway, or a ceiling material), an anti-shatter film for glass, a heat-resistant / water-resistant film, a building material (such asa tent material for tent camps, a membrane material for sun visors, a partial roof material for a skylight, a window material as an alternative to glass, a partition membrane material for flame retardant properties, a curtain, an exterior wall reinforcement material, a water-resistant membrane, a smoke-resistant membrane, an incombustible transparent partition, a road reinforcement material, an interior material (such as a lighting fixture, a wall surface, a blind) or an exterior material (such as a tent or a signboard), recreational items (such as a fishing rod, a bat, a golf club, and a screen), a material for motor vehicles (such as a hood, a damping material, or a car body), a material for aircraft, a material for ships, an exterior material for household electrical appliances, a tank, a container inner wall, a filter, a membrane material for construction work, an electronic material (such asa printed circuit board material, a wiring board material, an insulating film or a separating film), a surface material for a solar cell module, a mirror protective material for a solar thermal power generation device or a solar water heating device. REFERENCE SYMBOL 10 Fiber-reinforced resin film 12 Matrix resin 14 Textile glass fiber fabric< / vlies> < / gewebe> < / glasfasern> < / additive>

Claims

[1] Fiber-reinforced resin film comprising: a matrix resin containing at least 50% by mass of a fluorinated resin, and a textile glass fibre fabric having an open area of no more than 20% and embedded in the matrix resin, wherein the fiber-reinforced resin film has a total light transmittance of at least 70%; wherein (a) the fluorinated resin is a cured product of a curable fluorinated copolymer comprising units derived from a fluoroolefin and units derived from a monomer other than the fluoroolefin, the monomer being copolymerizable with the fluoroolefin, or (b) the matrix resin is a mixed resin containing polyvinylidene fluoride and polymethyl methacrylate. [2] The fiber-reinforced resin film according to claim 1, wherein the total light transmittance is at least 80%. [3] The fiber-reinforced resin film according to claim 1 or 2, wherein the matrix resin is made of the fluorinated resin. [4] The fiber-reinforced resin film according to any one of claims 1 to 3, wherein the fluorinated resin is the cured product of the curable fluorinated copolymer. [5] The fiber-reinforced resin film according to claim 4, wherein the units derived from a monomer other than the fluoroolefin are units derived from a monomer having a hydroxy group. [6] The fiber-reinforced resin film according to any one of claims 1 to 3, wherein the matrix resin is the mixed resin containing polyvinylidene fluoride and polymethyl methacrylate. [7] A fiber-reinforced resin film according to any one of claims 1 to 6, wherein the matrix resin further contains an ultraviolet absorbent. [8] Use of the fiber-reinforced resin film according to any one of claims 1 to 7 as a membrane material for membrane structural constructions. [9] A process for producing the fiber-reinforced resin film as defined in claim 4 or 5, comprising: Impregnating the textile glass fiber fabric with a solution comprising a curable resin material containing the curable fluorinated copolymer dissolved in a solvent, Remove the solvent and then Curing the curable resin material to form the matrix resin. [10] A process for producing the fiber-reinforced resin film as defined in claim 6, comprising: Impregnating the textile glass fiber fabric with a solution in which the matrix resin is dissolved in a solvent, and then Removing the solvent. [11] Laminate comprising: a layer of the fiber-reinforced resin film as defined in any one of claims 1 to 7, and a layer of a second fluorinated resin provided on one side or each side of the fiber-reinforced resin film, wherein the laminate has a total light transmittance of at least 70%. [12] The laminate according to claim 11, wherein the second fluorinated resin layer is a layer formed from a film or sheet of the second fluorinated resin. [13] A laminate according to claim 11 or 12, wherein the second fluorinated resin layer contains an ultraviolet absorber. [14] Use of the laminate according to any one of claims 11 to 13 as a membrane material for membrane structural constructions.

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