WO2014069547A1 - 複合体 - Google Patents

複合体 Download PDF

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Publication number
WO2014069547A1
WO2014069547A1 PCT/JP2013/079469 JP2013079469W WO2014069547A1 WO 2014069547 A1 WO2014069547 A1 WO 2014069547A1 JP 2013079469 W JP2013079469 W JP 2013079469W WO 2014069547 A1 WO2014069547 A1 WO 2014069547A1
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WO
WIPO (PCT)
Prior art keywords
resin
composite
silicon dioxide
tetrafluoroethylene
woven fabric
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/JP2013/079469
Other languages
English (en)
French (fr)
Inventor
成教 田村
雄斗 山口
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.)
Chukoh Chemical Industries Ltd
Original Assignee
Chukoh Chemical Industries 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 Chukoh Chemical Industries Ltd filed Critical Chukoh Chemical Industries Ltd
Priority to BR112015009580A priority Critical patent/BR112015009580A2/pt
Priority to SG11201503361SA priority patent/SG11201503361SA/en
Priority to EP17198703.5A priority patent/EP3312005B1/en
Priority to CN201380057121.3A priority patent/CN104812578B/zh
Priority to EP13850786.8A priority patent/EP2915667B1/en
Publication of WO2014069547A1 publication Critical patent/WO2014069547A1/ja
Priority to US14/701,215 priority patent/US11162213B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B32B5/024—Woven fabric
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
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    • 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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    • B32B17/10009—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
    • B32B17/10027—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet the glass sheet not being an outer layer
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    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
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    • C03C25/47—Coatings containing composite materials containing particles, fibres or flakes, e.g. in a continuous phase
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0006—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0022—Glass fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/047—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with fluoropolymers
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    • D06N2211/00—Specially adapted uses
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    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer

Definitions

  • the present invention relates to a composite.
  • a sheet in which a resin film is laminated on a woven fabric or a non-woven fabric is used in many fields. Fibers made of glass or the like are used for woven fabrics and nonwoven fabrics, and various sealing treatments are applied to maintain the shape. For this treatment, a thermoplastic resin is widely used. Moreover, in the laminated sheet used for a building use, the fluororesin film which is excellent in a weather resistance, contamination resistance, water resistance, etc. is widely used as a resin film.
  • Patent Document 1 discloses a laminated sheet in which a woven or nonwoven fabric made of glass fibers fixed with a binder and a fluororesin film are laminated, and a so-called melting type fluororesin is used for the binder.
  • a woven or nonwoven fabric made of glass fibers fixed with a binder and a fluororesin film are laminated, and a so-called melting type fluororesin is used for the binder.
  • the problem to be solved by the present invention is to provide a composite excellent in strength against bending stress, adhesion between resin layers, and handling.
  • the composite according to the present invention is a composite comprising a substrate and a light-transmitting resin layer formed on the substrate,
  • the base material includes a woven fabric and a composition layer formed on the woven fabric and including a tetrafluoroethylene resin and silicon dioxide.
  • the composite includes a base material and a light-transmitting resin layer formed on the base material.
  • the base material includes a woven fabric and a composition layer formed on the woven fabric and including a tetrafluoroethylene resin and silicon dioxide.
  • the flexibility of the substrate can be improved. For this reason, even when a bending process with a small radius of curvature is performed, the occurrence of cracks due to kink (buckling) in the composition layer can be reduced. As a result, stress concentration on the fibers constituting the woven fabric can be alleviated, so that the strength reduction of the single fibers can be delayed when repeated bending stress is applied. Therefore, according to the composite according to the embodiment, the strength against bending stress can be improved.
  • the silicon dioxide contained in the composition layer can improve the adhesion between the composition layer and the light-transmitting resin layer.
  • the composite in addition to improving the strength against bending stress and the adhesion between the resin layers, the composite also has improved flexibility. Therefore, the composite is easy to handle, carry and enforce, and has excellent handling properties.
  • the woven fabric constituting the base material is formed from, for example, a yarn composed of a single fiber bundle.
  • the material of the single fiber include at least one selected from the group consisting of glass, aromatic polyamide, carbon, and alumina.
  • the kind of fiber to be used can be 1 type or 2 types or more. Preference is given to glass fibers.
  • the wire diameter of the single fiber is desirably in the range of 3 ⁇ m to 9 ⁇ m. Moreover, it is desirable that the yarn constituted by the single fiber bundle is in the range of 10 tex or more and 300 tex or less. By these, the softness
  • the weaving structure of the woven fabric can be plain weave, twill weave, satin weave, tangle weave, or silk weave.
  • the opening ratio of the woven fabric of the woven fabric is measured by the following method. Using a woven fabric with a dimension of 100 mm in length and 100 mm in width (woven fabric covered with ethylene tetrafluoride resin) as a sample, the area of the opening of the sample is a microscope (model VHX-1000 made by Keyence Corporation) Or have the same performance) and calculate from the following formula.
  • X (S 1 / S 2 ) ⁇ 100
  • X is a woven fabric opening ratio (%)
  • S 1 is a woven fabric opening partial area (mm 2 )
  • S 2 is a woven fabric area (mm 2 ).
  • the opening ratio of the woven fabric is desirably in the range of 10% to 30%. By setting it in this range, a composite having a desired light transmittance can be obtained.
  • the light transmittance is measured by a method according to JIS R 3106.
  • the light transmittance of the composite is preferably 30% or more and 95% or less. Thereby, desired composite strength and optimal brightness for the space can be obtained. A more preferable range is 50% or more and 90% or less.
  • the composition layer formed on the woven fabric contains a tetrafluoroethylene resin and silicon dioxide.
  • the particles of the ethylene tetrafluoride resin can be dispersed throughout a part or the whole of the composition layer, but it is desirable to coat the woven fabric for the strength against the bending stress of the composite.
  • the silicon dioxide particles can be dispersed over a part or the whole of the composition layer. However, for adhesion between the resin layers, the silicon dioxide particles are exposed on the surface of the composition layer and are in contact with the light-transmitting resin layer. Is desirable.
  • a melt-flowable fluororesin can be added to the composition layer as necessary.
  • the melt-flowable fluororesin can further improve the fusibility between the composition layer and the light-transmitting resin layer.
  • the particles of the melt flowable fluororesin can be dispersed throughout a part or the whole of the composition layer. Specifically, the melt-flowable fluororesin particles can be held on a woven fabric or can be present on the surface of the composition layer.
  • the tetrafluoroethylene resin is present as a sintered body of tetrafluoroethylene resin particles in the composition layer.
  • the tetrafluoroethylene resin particles preferably have an average primary particle diameter in the range of 0.02 ⁇ m to 0.5 ⁇ m. A more preferable range is 0.1 ⁇ m or more and 0.3 ⁇ m or less.
  • the tetrafluoroethylene resin weight percent in the substrate weight is in the range of 5 wt% to 40 wt%. This is due to the following reason.
  • the tetrafluoroethylene resin weight% is set to 5% by weight or more, it becomes possible to suppress deformation of the woven fabric constituting the base material due to external stress at the time of enforcement.
  • the amount of the tetrafluoroethylene resin is increased, sufficient fusion with the light-transmitting resin layer cannot be ensured and the product cost itself is increased. The problem of decrease in fusibility is likely to occur when a composite is produced by the method described later.
  • an ethylene tetrafluoride resin layer is formed on a woven fabric, and then the woven fabric is impregnated with a dispersion obtained by mixing silicon dioxide particles with an aqueous dispersion of melt flowable fluororesin particles.
  • a dispersion obtained by mixing silicon dioxide particles with an aqueous dispersion of melt flowable fluororesin particles.
  • Silicon dioxide is preferably amorphous silica.
  • the amorphous silica is more preferably hydrophilic amorphous silica.
  • the silicon dioxide particles preferably have a specific surface area of 10 m 2 / g or more according to the adsorption isotherm of Brunauer, Emmett, Teller (BET).
  • BET Brunauer, Emmett, Teller
  • a more preferable range is 50 m 2 / g or more and 400 m 2 / g or less.
  • the silicon dioxide particles preferably have an average primary particle diameter in the range of 5 nm to 80 nm. A more preferable range is 7 nm or more and 40 nm or less.
  • the average primary particle diameter of the tetrafluoroethylene resin particles and the silicon dioxide particles can be measured with a transmission electron microscope.
  • the silicon dioxide weight% in the composition layer weight is preferably in the range of 0.5 wt% to 30 wt%.
  • the silicon dioxide weight% By adjusting the silicon dioxide weight% to 0.5 weight% or more, the adhesion between the light transmissive resin layer and the composition layer can be improved.
  • the amount of silicon dioxide is larger, the adhesion between the light-transmitting resin layer and the composition layer becomes higher, but the flexibility of the substrate may be lowered.
  • By setting the silicon dioxide weight% to 30 weight% or less excellent flexibility in the substrate can be obtained.
  • a more preferable range is 5% by weight or more and 20% by weight or less.
  • melt flowable fluororesins examples include tetrafluoroethylene-ethylene copolymer resin (ETFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer. Resin (FEP) is included.
  • the kind of resin to be used can be 1 type or 2 types or more.
  • the light-transmitting resin layer preferably contains a melt-flowable fluororesin.
  • melt flowable fluororesins include tetrafluoroethylene-ethylene copolymer resin (ETFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer.
  • FEP tetrafluoroethylene-ethylene copolymer resin
  • PFA tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin
  • PVDF vinylidene fluoride resin
  • the kind of resin to be used can be 1 type or 2 types or more.
  • the composite has a tensile breaking strength of 300 N / 15 mm or more and a tensile breaking elongation of 35% or less.
  • the tensile breaking strength and the tensile breaking elongation are measured by a method (cut strip, tensile speed: 200 mm / min, specimen width: 30 mm) based on the strip method of JIS L1096.
  • the composite is produced, for example, by the following method.
  • the woven fabric was coated by impregnating with an aqueous dispersion of tetrafluoroethylene resin particles (hereinafter referred to as a first dispersion), dried at 100 ° C. or more and 200 ° C. or less, and then the ambient temperature was 330 ° C. or more and 400 Bake at a temperature below °C. By repeating a series of steps of coating, drying and baking a plurality of times, an ethylene tetrafluoride resin layer is formed on the woven fabric.
  • a first dispersion aqueous dispersion of tetrafluoroethylene resin particles
  • a dispersion liquid (hereinafter referred to as a second dispersion liquid) in which silicon dioxide particles were mixed with an aqueous dispersion liquid of melt flowable fluororesin particles was prepared, and an ethylene tetrafluoride resin layer was formed from this dispersion liquid. It is applied by impregnating the woven fabric, dried at 100 ° C. or higher and 200 ° C. or lower, and then fired at an ambient temperature of 330 ° C. or higher and 400 ° C. or lower.
  • a composition layer containing a tetrafluoroethylene resin, a melt flowable fluororesin and silicon dioxide is formed on the woven fabric to obtain a substrate.
  • melt-flowable fluororesin particles may be added to the first dispersion.
  • a series of steps of coating, drying and firing the first dispersion was performed, and then a sequence of steps of coating, drying and firing of the second dispersion was performed.
  • a series of steps of applying, drying and baking the dispersion and a series of steps of applying, drying and baking the second dispersion may be alternately repeated.
  • the tetrafluoroethylene resin particles in the first dispersion liquid can be made highly dispersible.
  • the dispersibility of the silicon dioxide particle in a 2nd dispersion liquid can be made high by making the average primary particle diameter of a silicon dioxide particle into the range of 5 nm or more and 80 nm or less. Therefore, the composition layer is obtained by repeating the steps of applying a dispersion of uniformly dispersed ethylene tetrafluoride resin particles and a dispersion of uniformly dispersed silicon dioxide particles to a woven fabric, drying, and firing. Therefore, it is possible to realize a composition layer in which the dispersibility of the tetrafluoroethylene resin particles and the silicon dioxide particles in the dispersion is maintained almost as it is.
  • FIG. 1 shows a schematic cross section of an example of the composite.
  • the composite 1 includes a base 2 and a light-transmitting resin layer 3 formed on both surfaces of the base 2.
  • the base material 2 has a woven fabric 4 and a composition layer 5 formed on both surfaces of the woven fabric 4.
  • the composition layer 5 contains a tetrafluoroethylene resin and silicon dioxide.
  • an interface 6 is provided between the woven fabric 4, the composition layer 5, and the light transmissive resin layer 3 for convenience. 1. Since the composition layer is obtained by repeating the steps of applying, drying and firing the second dispersion, there is no clear interface in the composition layer or between the composition layer and the woven fabric. Sometimes.
  • the composite includes a layer other than the base material and the light-transmitting resin layer (for example, a light diffusion layer and an antifouling layer).
  • Applications of the composite include, for example, membrane structures such as roofing materials such as large-scale greenhouses and atriums, outer walls of sports facilities, roofing materials, medium and large tents, and agricultural greenhouse coatings.
  • the oven was baked for 5 minutes in a sealed oven adjusted to an atmospheric temperature of 360 ° C.
  • the series of steps of impregnation, drying and firing was repeated a plurality of times to obtain a 50 ⁇ m thick ethylene tetrafluoride resin layer.
  • the opening ratio of the woven fabric covered with the ethylene tetrafluoride resin layer was 60%.
  • hydrophilic amorphous silica particles manufactured by Nippon Aerosil Co., Ltd., Brunauer, Emmett, 1 kg of ethylene tetrafluoride-hexafluoropropylene copolymer resin (FEP) particle aqueous dispersion (manufactured by Mitsui DuPont Fluorochemical) are used.
  • FEP ethylene tetrafluoride-hexafluoropropylene copolymer resin
  • FEP ethylene tetrafluoride-hexafluoropropylene copolymer resin
  • 0.1 kg of Teller (BET) adsorption isotherm with a specific surface area of 50 m 2 / g and an average primary particle size of 30 nm) is mixed and stirred to prepare an ethylene tetrafluoride-hexafluoropropylene copolymer resin particle aqueous dispersion. It was adjusted.
  • the glass fiber fabric formed with an ethylene tetrafluoride resin layer was coated by impregnating this dispersion, dried for 5 minutes in a sealed oven with the atmospheric temperature adjusted to 100 ° C. Was fired in a sealed furnace adjusted to 360 ° C. for 5 minutes.
  • an ethylene tetrafluoride-hexafluoropropylene copolymer resin layer having a thickness of 20 ⁇ m is formed on the tetratetrafluoroethylene resin layer, and the amount of PTFE resin was 85 g / m 2 , and the amount of FEP resin was 30 g / m 2 .
  • a 100 ⁇ m ETFE film was thermocompression bonded for 3 minutes at a temperature of 300 ° C. and a pressure of 3.4 kgf / cm 2 on both sides of the substrate prepared as described above. Subsequently, the ETFE film was fused to the substrate by performing a cooling press for 20 seconds at a temperature of about 25 ° C. and a pressure of 1 kgf / cm 2 , thereby obtaining a composite of the example.
  • ethylene tetrafluoride-hexafluoropropylene copolymer particles are 60% by weight of ethylene tetrafluoride-hexafluoropropylene copolymer resin particles.
  • drying and firing steps a plurality of times, a 50 ⁇ m thick ethylene tetrafluoride-hexafluoropropylene copolymer resin layer was obtained.
  • a 100 ⁇ m ETFE film was laminated on both sides of the obtained fiber base fabric, and the ETFE film was fused to the base material by thermocompression bonding and cooling press under the same conditions as in the example to obtain a composite of the comparative example.
  • the tensile strength at break after 100, 200, 500, and 1000 bends was expressed as 100% of the tensile break strength of the test piece before bending (number of bends), which was defined as the breaking strength retention rate.
  • Table 1 shows the tensile rupture strength and rupture strength retention ratio after bending at 0, 100, 200, 500, and 1000 times, and bending at 0, 100, 200, 500, and 1000 times.
  • FIG. 2 shows the breaking strength retention after the heating.
  • the tensile rupture strength retention rate of each of the folding times 100, 200, 500, and 1000 is comparative example.
  • the composites of the examples are excellent in tensile strength at break as compared with the composites of the comparative examples, and thus are excellent in strength against bending stress, adhesion between resin layers, and handling.
  • SYMBOLS 1 Composite body, 2 ... Base material, 3 ... Light-transmitting resin layer, 4 ... Woven cloth, 5 ... Composition layer, 6 ... Interface.

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Abstract

複合体１は、基材２と、基材２に形成される光透過性樹脂層３とを含む。基材２は、織布４と、織布４に形成され、四ふっ化エチレン樹脂及び二酸化ケイ素を含む組成物層５とを含む。

Description

複合体
　本発明は、複合体に関する。
　高い光透過性を有する複合材料として、織布または不織布に樹脂フィルムを積層したシートが多くの分野で用いられている。織布や不織布には、ガラス等からなる繊維が用いられており、形状を保持させるために各種の目止め処理が施されている。この処理には、熱可塑性樹脂が広く用いられている。また、建築用途に使用される積層シートでは、樹脂フィルムとして、耐候性、耐汚染性、耐水性等に優れるフッ素樹脂フィルムが広く用いられている。
　例えば、特許文献１には、バインダーで固着されたガラス繊維からなる織布または不織布と、含フッ素樹脂フィルムとが積層された積層シートであって、バインダーにいわゆる溶融タイプのフッ素樹脂を用いることが記載されている。
　しかしながら、これまでの積層シートは、折り曲げ応力に対する強度、樹脂層間の接着性、ハンドリングに課題がある。
ＷＯ２００８／１０５２９８Ａ１国際公開公報
　本発明が解決しようとする課題は、折り曲げ応力に対する強度、樹脂層間の接着性、ハンドリングに優れた複合体を提供することである。
　本発明に係る複合体は、基材と、前記基材に形成される光透過性樹脂層とを含む複合体であって、
　前記基材は、織布と、前記織布に形成され、四ふっ化エチレン樹脂及び二酸化ケイ素を含む組成物層とを含むことを特徴とする。
　本発明によれば、折り曲げ応力に対する強度、樹脂層間の接着性、ハンドリングに優れた複合体を提供することができる。
実施形態に係る複合体を示す断面図である。 実施例及び比較例の複合体についての屈曲回数と引張破断強度保持率との関係を示す図である。
　以下、本発明の実施の形態について、詳細に説明する。
　複合体は、基材と、基材に形成される光透過性樹脂層とを含む。基材は、織布と、織布に形成され、四ふっ化エチレン樹脂及び二酸化ケイ素を含む組成物層とを含む。このような複合体によると、基材の柔軟性を向上することができる。このため、曲率半径が小さい折り曲げ加工を行なった場合においても、組成物層にキンク（座屈）によるクラックが発生するのを少なくすることができる。その結果、織布を構成する繊維への応力集中を緩和することができるため、繰り返しの曲げ応力を加えた場合の単繊維の強度低下を遅らせることができる。従って、実施形態に係る複合体によると、折り曲げ応力に対する強度を向上することができる。
　また、組成物層に含まれる二酸化ケイ素は、組成物層と光透過性樹脂層との接着性を向上することができる。
　さらに、複合体は、折り曲げ応力に対する強度及び樹脂層間の接着性の向上に加え、柔軟性も改善される。よって、複合体は、取り扱い、持ち運び、施行がしやすく、ハンドリング性にも優れている。
　これに対し、四ふっ化エチレン樹脂及び二酸化ケイ素を含む組成物層の代りに溶融タイプのフッ素樹脂層を織布に形成すると、基材が剛直になる。このため、曲率半径が小さい折り曲げ加工を行なったり、繰り返しの曲げ応力を加えた場合には、溶融タイプフッ素樹脂層がキンクすることによって樹脂層自体にクラックが発生する。また、織布を構成する単繊維にも応力が集中することによって、単繊維の強度低下や破断が発生する。
　以下、実施形態の複合体の基材及び光透過性樹脂層について説明する。
　基材を構成する織布は、例えば、単繊維束によって構成される糸から形成される。単繊維の材質には、例えば、ガラス、芳香族ポリアミド、カーボン及びアルミナよりなる群から選択される少なくとも１種類を挙げることができる。使用する繊維の種類は、１種または２種以上にすることができる。好ましいのは、ガラス繊維を含むものである。
　単繊維の線径は、３μｍ以上９μｍ以下の範囲にすることが望ましい。また、単繊維束によって構成される糸は、１０テックス以上３００テックス以下の範囲にすることが望ましい。これらにより、織布の柔軟性と強度をより向上することができる。
　織布の織組織は、平織、綾織、朱子織、からみ織、または摸紗織にすることができる。
　織布の織組織の開口率は、以下の方法で測定される。縦が１００ｍｍ、横が１００ｍｍの寸法の織布（四ふっ化エチレン樹脂で被覆された状態の織布）をサンプルとし、サンプルの開口部分の面積をマイクロスコープ（型式VHX-1000の株式会社キーエンス製のものか、これと同等の性能を有するもの）にて測定し、次の計算式から算出する。
　　Ｘ＝（Ｓ1／Ｓ2）×１００
　但し、Ｘは織布開口率（％）、Ｓ1は織布開口部分面積（ｍｍ2）、Ｓ2は織布面積（ｍｍ2）である。
　織布開口率は１０％以上３０％以下の範囲にすることが望ましい。この範囲にすることによって、所望の光透過率を有する複合体を得ることができる。光透過率は、ＪＩＳ　Ｒ　３１０６に準拠する方法で測定される。
　複合体の光透過率は、３０％以上、９５％以下にすることが望ましい。これにより、所望の複合体強度と、空間に最適な明るさとを得ることができる。さらに好ましい範囲は、５０％以上、９０％以下である。
　織布に形成される組成物層は、四ふっ化エチレン樹脂及び二酸化ケイ素を含む。四ふっ化エチレン樹脂の粒子は、組成物層の一部あるいは全体に亘って分散させることができるが、複合体の折り曲げ応力に対する強度のために、織布を被覆していることが望ましい。一方、二酸化ケイ素の粒子は、組成物層の一部あるいは全体に亘って分散させることができるが、樹脂層間の接着のため、組成物層の表面に露出して光透過性樹脂層と接することが望ましい。
　組成物層には、必要に応じて、溶融流動性フッ素樹脂を添加することができる。溶融流動性フッ素樹脂は、組成物層と光透過性樹脂層との融着性をより高めることができる。溶融流動性フッ素樹脂の粒子は、組成物層の一部あるいは全体に亘って分散させることができる。具体的には、溶融流動性フッ素樹脂の粒子は、織布に保持させたり、あるいは組成物層の表面に存在させることができる。
　四ふっ化エチレン樹脂は、組成物層において、四ふっ化エチレン樹脂粒子の焼結体として存在する。四ふっ化エチレン樹脂粒子は、平均一次粒子径が０．０２μｍ以上０．５μｍ以下の範囲であることが望ましい。より好ましい範囲は、０．１μｍ以上０．３μｍ以下である。
　基材重量中の四フッ化エチレン樹脂重量％は、５重量％以上４０重量％以下の範囲であることが望ましい。これは、以下の理由によるものである。四フッ化エチレン樹脂重量％を５重量％以上にすることにより、施行時の外部応力等によって基材を構成する織布の変形を抑制することが可能となる。しかし、四フッ化エチレン樹脂量が多くなると、光透過性樹脂層との十分な融着性が確保できなくなると共に、製品コスト自体が高くなる。融着性の低下の問題は、後述する方法で複合体を作製した場合に生じやすい。後述する方法では、織布に四ふっ化エチレン樹脂層を形成した後、溶融流動性フッ素樹脂粒子の水系分散液に二酸化ケイ素粒子を混合させた分散液を、この織布に含浸させる。四フッ化エチレン樹脂量が多くなると、当該分散液からなる層が四フッ化エチレン樹脂表面に形成され難くなるため、光透過性樹脂層との十分な融着性が確保できなくなる。また、四フッ化エチレン樹脂量が多くなると、製品重量が大きくなるので、建築物を高強度にする必要があるため、建築コストが高くなる。よって、四フッ化エチレン樹脂重量％を４０重量％以下にすることが望ましい。より好ましい範囲は、１０重量％以上２５重量％以下である。
　二酸化ケイ素（ＳｉＯ2）は、非晶質シリカであることが好ましい。非晶質シリカは、親水性非晶質シリカであることがより好ましい。
　二酸化ケイ素の粒子は、Brunauer, Emmett, Teller（ＢＥＴ）の吸着等温式による比表面積が１０ｍ2／ｇ以上であることが好ましい。比表面積を１０ｍ2／ｇ以上にすることにより、光透過性樹脂層と組成物層との密着性を向上することができる。より好ましい範囲は、５０ｍ2／ｇ以上４００ｍ2／ｇ以下である。
　二酸化ケイ素の粒子は、平均一次粒子径が５ｎｍ以上８０ｎｍ以下の範囲であることが好ましい。より好ましい範囲は、７ｎｍ以上４０ｎｍ以下である。
　四ふっ化エチレン樹脂粒子、二酸化ケイ素粒子の平均一次粒子径は、透過型電子顕微鏡によって測定可能である。
　組成物層重量中の二酸化ケイ素重量％は、０．５重量％以上３０重量％以下の範囲であることが好ましい。二酸化ケイ素重量％を０．５重量％以上にすることにより、光透過性樹脂層と組成物層との密着性を向上することができる。二酸化ケイ素量が多い方が光透過性樹脂層と組成物層との密着性が高くなるものの、基材の柔軟性が低くなる恐れがある。二酸化ケイ素重量％を３０重量％以下にすることにより、基材において優れた柔軟性を得ることができる。より好ましい範囲は、５重量％以上２０重量％以下である。
　溶融流動性フッ素樹脂の例には、四ふっ化エチレン－エチレン共重合樹脂（ＥＴＦＥ）、四ふっ化エチレンパーフルオロアルキルビニルエーテル共重合樹脂（ＰＦＡ）、及び四ふっ化エチレン－六ふっ化プロピレン共重合樹脂（ＦＥＰ）が含まれる。使用する樹脂の種類は、１種または２種以上にすることができる。
　光透過性樹脂層は、溶融流動性フッ素樹脂を含むものが望ましい。溶融流動性フッ素樹脂の例には、四ふっ化エチレン－エチレン共重合樹脂（ＥＴＦＥ）、四ふっ化エチレンパーフルオロアルキルビニルエーテル共重合樹脂（ＰＦＡ）、及び四ふっ化エチレン－六ふっ化プロピレン共重合樹脂（ＦＥＰ）、ふっ化ビニリデン樹脂（ＰＶＤＦ）が含まれる。使用する樹脂の種類は、１種または２種以上にすることができる。
　複合体は、引張破断強度が３００Ｎ／１５ｍｍ以上で、引張破断伸びは３５％以下であることが望ましい。引張破断強度及び引張破断伸びは、ＪＩＳ　Ｌ１０９６のストリップ法に準拠する方法（カットストリップ、引張速度；２００ｍｍ／ｍｉｎ、試験片幅；３０ｍｍ）で測定される。
　複合体は、例えば、以下の方法で作製される。
　織布に、四ふっ化エチレン樹脂粒子の水系分散液（以下、第１の分散液）を含浸させることによって塗布し、１００℃以上２００℃以下で乾燥させた後、雰囲気温度が３３０℃以上４００℃以下で焼成する。塗布、乾燥及び焼成の一連の工程を複数回繰り返すことによって、織布に四ふっ化エチレン樹脂層を形成する。次いで、溶融流動性フッ素樹脂粒子の水系分散液に二酸化ケイ素粒子を混合させた分散液（以下、第２の分散液）を用意し、この分散液を、四ふっ化エチレン樹脂層が形成された織布に含浸させることによって塗布し、１００℃以上２００℃以下で乾燥させた後、雰囲気温度が３３０℃以上４００℃以下で焼成する。塗布、乾燥及び焼成の一連の工程を複数回繰り返すことによって、織布に四ふっ化エチレン樹脂、溶融流動性フッ素樹脂及び二酸化ケイ素を含む組成物層を形成し、基材を得る。基材の両面に、光透過性樹脂フィルムを配置した後、加熱加圧プレスによって熱圧着した後、冷却加圧プレスによって冷却を施し、複合体を得る。
　なお、第１の分散液に、溶融流動性フッ素樹脂粒子を添加しても良い。また、前述した方法では、第１の分散液の塗布、乾燥及び焼成の一連の工程を行った後、第２の分散液の塗布、乾燥及び焼成の一連の工程を行ったが、第１の分散液の塗布、乾燥及び焼成の一連の工程と、第２の分散液の塗布、乾燥及び焼成の一連の工程とを交互に繰り返しても良い。
　上記これらの方法で作成する場合に、四ふっ化エチレン樹脂粒子の平均一次粒子径を０．０２μｍ以上０．５μｍ以下の範囲にすることによって、第１の分散液中の四ふっ化エチレン樹脂粒子の分散性を高くすることができる。また、二酸化ケイ素粒子の平均一次粒子径を５ｎｍ以上８０ｎｍ以下の範囲にすることによって、第２の分散液中の二酸化ケイ素粒子の分散性を高くすることができる。従って、四ふっ化エチレン樹脂粒子が均一に分散された分散液、二酸化ケイ素粒子が均一に分散された分散液それぞれについて、織布に塗布し、乾燥し、焼成する工程を繰り返すことにより組成物層が得られるため、分散液中の四ふっ化エチレン樹脂粒子や二酸化ケイ素粒子の分散性をほぼそのまま維持した組成物層を実現することができる。
　複合体の一例の略断面を図１に示す。図１に例示されるように、複合体１は、基材２と、基材２の両面に形成される光透過性樹脂層３とを有する。基材２は、織布４と、織布４の両面に形成された組成物層５を有する。組成物層５は、四ふっ化エチレン樹脂及び二酸化ケイ素を含む。図１では、各層がどのように積層されているかを説明するため、織布４と組成物層５と光透過性樹脂層３間に便宜上、界面６を設けたが、上記製造方法では、第１、第２の分散液の塗布、乾燥及び焼成の工程を繰り返すことにより組成物層を得るため、組成物層中にも、組成物層と織布との間にも明確な界面が存在しないことがある。
　複合体には、基材、光透過性樹脂層以外の層（例えば、光拡散層、防汚層）を含むことを許容する。
　複合体の用途には、例えば、大規模温室やアトリウムなどの屋根材、運動施設の外壁、屋根材、中大型テント、農業用温室の被覆材等の膜構造物が挙げられる。
　以下、実施例を説明する。
（実施例）
　耐熱性織布として厚さが５８０μｍ、３７０ｇ／ｍ2メッシュ、織組織が絡み織のガラス繊維織物（日東紡績製）に対して、平均一次粒子径が０．２μｍの四ふっ化エチレン樹脂（ＰＴＦＥ）粒子分が６０重量％、非イオン界面活性剤が６重量％及び水が３４重量％からなる四ふっ化エチレン樹脂微粒子水系分散液（ダイキン工業製）を含浸することによって塗布し、雰囲気温度を１００℃に調整した密封炉で５分乾燥させ、水分を飛ばしたのち、雰囲気温度を３６０℃に調整した密封炉にて５分焼成した。この含浸、乾燥及び焼成の一連の工程を複数回繰り返すことによって厚さ５０μｍの四ふっ化エチレン樹脂層を得た。四ふっ化エチレン樹脂層で被覆された織布の開口率は６０％であった。
　次に、四ふっ化エチレン－六ふっ化プロピレン共重合体樹脂（ＦＥＰ）粒子水系分散液（三井デュポンフロロケミカル製）１ｋｇに対して親水性非晶質シリカ粒子（日本アエロジル製、Brunauer, Emmett, Teller（ＢＥＴ）の吸着等温式による比表面積が５０ｍ2／ｇ、平均一次粒子径が３０ｎｍ）を０．１ｋｇ混合撹拌して四ふっ化エチレン－六ふっ化プロピレン共重合体樹脂粒子水系分散液を調整した。四ふっ化エチレン樹脂層が形成されたガラス繊維織物に、この分散液を含浸することによって塗布し、雰囲気温度を１００℃に調整した密封炉で５分乾燥させ、水分を飛ばしたのち、雰囲気温度を３６０℃に調整した密封炉にて５分焼成した。この含浸、乾燥及び焼成の一連の工程を複数回繰り返すことによって、四ふっ化エチレン樹脂層上に厚さ２０μｍの四ふっ化エチレン－六ふっ化プロピレン共重合体樹脂層を形成し、ＰＴＦＥ樹脂量が８５ｇ／ｍ2、ＦＥＰ樹脂量が３０ｇ／ｍ2の組成物層を得た。
　上述のようにして作製した基材の両面に１００μｍのＥＴＦＥフィルムをそれぞれ温度３００℃、圧力３．４ｋｇｆ／ｃｍ2で３分間熱圧着した。次いで、温度約２５℃、圧力１ｋｇｆ／ｃｍ2で２０秒間の冷却プレスを行うことにより、ＥＴＦＥフィルムを基材に融着させ、実施例の複合体を得た。
　実施例の複合体では、基材重量中の四フッ化エチレン樹脂重量％が１７．５重量％、組成物層重量中の親水性非晶質シリカ重量％が３．９重量％、基材重量中の四ふっ化エチレン－六ふっ化プロピレン共重合体重量％が６．２重量％であった。
（比較例）
　実施例と同様なガラス繊維織物（日東紡績製）に対して、四ふっ化エチレン－六ふっ化プロピレン共重合体粒子分が６０重量％の四ふっ化エチレン－六ふっ化プロピレン共重合体樹脂粒子水系分散液（三井デュポンフロロケミカル製）を含浸することによって塗布し、雰囲気温度を１００℃に調整した密封炉で５分乾燥させ、水分を飛ばしたのち、雰囲気温度を３６０℃に調整した密封炉にて５分焼成した。この含浸、乾燥及び焼成の一連の工程を複数回繰り返すことによって、厚さ５０μｍの四ふっ化エチレン－六ふっ化プロピレン共重合体樹脂層を得た。
　得られた繊維基布の両面に１００μｍのＥＴＦＥフィルムを積層し、実施例と同様な条件の熱圧着及び冷却プレスにより、ＥＴＦＥフィルムを基材に融着させ、比較例の複合体を得た。
　実施例及び比較例の複合体に対し、以下の試験方法で屈曲回数と引張破断強度との関係を測定し、その結果を下記の表１に示す。
　試験は、（社）日本膜構造協会試験法標準の膜材料の品質及び性能試験方法（ＭＳＡＪ／Ｍ－０３－２００３）に準拠した方法で行った。すなわち、ＭＩＴ試験機を使用し、荷重１ｋｇ／１．５ｃｍ、屈曲角１７５°、Ｒ＝１及びＲ＝３の条件で試験片を規定回数繰り返し折り曲げた際の引張破断強度を求めた。屈曲回数は、１００、２００、５００、１０００回と変化させた。引張破断強度は、ＪＩＳ　Ｌ１０９６のストリップ法に準拠する方法（カットストリップ、引張速度；２００ｍｍ／ｍｉｎ、試験片幅；３０ｍｍ）で測定した。また、１００、２００、５００、１０００回屈曲を行った後の引張破断強度を、屈曲を行う前の試験片（屈曲回数）の引張破断強度を１００％として表した値を破断強度保持率とした。０、１００、２００、５００、１０００回それぞれの回数で屈曲を行った後の引張破断強度及び破断強度保持率を表１に、０、１００、２００、５００、１０００回それぞれの回数で屈曲を行った後の破断強度保持率を図２に示す。
Figure JPOXMLDOC01-appb-T000001
　表１及び図２から明らかなように、実施例の複合体は、Ｒ＝３の条件で試験片を繰り返し折り曲げた際の引張破断強度保持率が、折り曲げ回数１００、２００、５００、１０００回のいずれにおいても、比較例に比して高く、また、折り曲げ条件がＲ＝３よりも過酷なＲ＝１においても、折り曲げ回数１００、２００、５００、１０００回それぞれの引張破断強度保持率が比較例に比して高い。よって、実施例の複合体は、比較例の複合体に比して引張破断強度に優れているため、折り曲げ応力に対する強度、樹脂層間の接着性、ハンドリングに優れた複合体である。
　１…複合体、２…基材、３…光透過性樹脂層、４…織布、５…組成物層、６…界面。

Claims (8)

  1. 　基材と、前記基材に形成される光透過性樹脂層とを含む複合体であって、
    　前記基材は、織布と、前記織布に形成され、四ふっ化エチレン樹脂及び二酸化ケイ素を含む組成物層とを含むことを特徴とする複合体。
  2. 　前記四ふっ化エチレン樹脂は、平均一次粒子径が０．０２μｍ以上０．５μｍ以下の範囲であることを特徴とする請求項１記載の複合体。
  3. 　前記二酸化ケイ素は、親水性非晶質シリカであることを特徴とする請求項１または２記載の複合体。
  4. 　前記二酸化ケイ素は、Brunauer, Emmett, Teller（ＢＥＴ）の吸着等温式による比表面積が１０ｍ2／ｇ以上であることを特徴とする請求項１～３いずれか１項記載の複合体。
  5. 　前記二酸化ケイ素は、平均一次粒子径が５ｎｍ以上８０ｎｍ以下の範囲であることを特徴とする請求項１～４いずれか１項記載の複合体。
  6. 　前記基材の重量中の前記四フッ化エチレン樹脂の重量％は、５重量％以上４０重量％以下の範囲であることを特徴とする請求項１～５いずれか１項記載の複合体。
  7. 　前記組成物の重量中の前記二酸化ケイ素の重量％は、０．５重量％以上３０重量％以下の範囲であることを特徴とする請求項１～６いずれか１項記載の複合体。
  8. 　前記光透過性樹脂層は、四ふっ化エチレン－エチレン共重合樹脂、四ふっ化エチレンパーフルオロアルキルビニルエーテル共重合樹脂、四ふっ化エチレン－六ふっ化プロピレン共重合樹脂及びふっ化ビニリデン樹脂よりなる群から選択される少なくとも一種を含むことを特徴とする請求項１～７いずれか１項記載の複合体。
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