WO2019035447A1 - Toile de fibres de verre comprenant une résine fluorée, et filtre de captage de poussière contenant celle-ci - Google Patents

Toile de fibres de verre comprenant une résine fluorée, et filtre de captage de poussière contenant celle-ci Download PDF

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Publication number
WO2019035447A1
WO2019035447A1 PCT/JP2018/030219 JP2018030219W WO2019035447A1 WO 2019035447 A1 WO2019035447 A1 WO 2019035447A1 JP 2018030219 W JP2018030219 W JP 2018030219W WO 2019035447 A1 WO2019035447 A1 WO 2019035447A1
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WIPO (PCT)
Prior art keywords
glass fiber
fiber cloth
mass
fluororesin
containing glass
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PCT/JP2018/030219
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English (en)
Japanese (ja)
Inventor
信貴 武内
裕樹 堀越
俊憲 横尾
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ユニチカ株式会社
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Priority to JP2019536775A priority Critical patent/JP6838758B2/ja
Publication of WO2019035447A1 publication Critical patent/WO2019035447A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

  • the present invention relates to a fluororesin-containing glass fiber cloth. More particularly, the present invention relates to a fluororesin-containing glass fiber cloth useful as a dust collection filter for which bag folding resistance is required. In addition, the present invention relates to a dust collection filter including the fluororesin-containing glass fiber cloth.
  • Cloth consisting mainly of glass fiber as a filter material used for dust collectors to capture dust (fly ash) in exhaust gas generated in municipal waste incinerators, industrial waste incinerators, coal-only boilers, metal melting furnaces, etc. Is used.
  • a bag filter system is adopted for the filtration of the exhaust gas of the municipal waste incinerator.
  • the bag filter method uses a cloth made of glass fiber to sew a bug (for example, a cylindrical shape with a diameter of 120 to 170 mm and a length of 4 to 7 m), and a large number of such bugs in a dust collection device Install this.
  • dust-containing exhaust gas usually, the gas temperature is 130 to 280 ° C.
  • dust in the gas is collected on the outer surface of the bag, and only the exhaust gas flows out from the inner surface of the bag.
  • the pressure loss of the bug increases with the operation time of the incinerator, which adversely affects the filtration performance, and therefore it is necessary to remove dust accumulated on the outer surface of the bug as needed.
  • vibration type, backwashing type and pulse type are generally used.
  • compressed air is jetted momentarily (for example, about 0.1 to 0.3 seconds) from the nozzle at the top of the bug into the interior of the bug to remove dust on the outer surface of the bug.
  • the injection air pressure in this case is as high as, for example, 5 to 7 kg / square cm, and is injected every fixed time (for example, 1 to 3 minutes).
  • the cloth formed of glass fibers constituting the bag filter is repeatedly bent. Therefore, the fabric is required to have resistance to repeated bending, ie, folding resistance.
  • a glass fiber fabric for bag filters comprising a glass fiber fabric made of glass fiber bundles of acid resistant glass and a resin coating layer for covering the glass fiber fabric as a bag filter cloth, wherein the acid resistant glass is SiO 2 , Al 2 O 3 , CaO, MgO, B 2 O 3 , and R 2 O (R is Na or K) as a component, and the total mass of the acid resistant glass is 100% by mass.
  • the acid resistant glass is SiO 2 , Al 2 O 3 , CaO, MgO, B 2 O 3 , and R 2 O (R is Na or K) as a component, and the total mass of the acid resistant glass is 100% by mass.
  • the content is 55 to 60% by mass of SiO 2 , 10 to 14% by mass of Al 2 O 3 , 20 to 28% by mass in total of CaO and MgO, 1% by mass or less of B 2 O 3 and R 2 O
  • a glass fiber woven fabric for bag filter wherein the resin coating layer is formed by coating with a resin composition containing tetrafluoroethylene resin, graphite and a silicone resin.
  • Patent Document 1 Japanese Patent Document 1
  • According to the woven fabric it is possible to provide a glass fiber fabric for bag filter which is excellent in acid resistance and heat resistance, and in which tensile strength and folding resistance are not easily deteriorated even under high temperature (250 ° C. in the example) and acidic environment. Will be possible.
  • the glass fiber woven fabric of Patent Document 1 uses a specific acid resistant glass as a glass material constituting the glass fiber, and is excellent in bending resistance to some extent in a high temperature environment of about 250 ° C.
  • the glass fiber woven fabric greatly loses the folding endurance that it had before heat exposure when it is exposed to heat at an ambient temperature exceeding 250 ° C., for example, 350 ° C.
  • the glass material constituting the glass fiber is a glass material other than the above-mentioned specific acid-resistant glass, for example, general-purpose E glass.
  • this invention solves the said problem, and makes it a subject to provide the fluorine resin containing glass fiber cloth which can be equipped with the outstanding folding resistance even after the heat exposure in the atmospheric temperature exceeding 250 degreeC.
  • the bending resistance in high temperature environment can be provided by forming the resin coating layer containing a silicone resin.
  • Comparative Example 2 in which a resin coating layer containing no silicone resin is adopted in Patent Document 1, it is shown that the bending resistance under a high temperature environment is inferior as compared with the other examples.
  • heat exposure at an ambient temperature exceeding 250 ° C. is not assumed as a high temperature environment.
  • the silicone resin is modified by combustion, oxidation, etc. It was estimated that the folding resistance which had been had before exposure was greatly impaired.
  • Item 1 A fluorine resin-containing glass fiber cloth comprising a fluorine resin and an organic titanium compound on glass fiber.
  • Item 2. The fluororesin-containing glass fiber cloth according to Item 1, further comprising a silane coupling agent and / or a reactant thereof on the glass fiber.
  • Item 3. The fluororesin-containing glass fiber cloth according to Item 1 or 2, wherein the organic titanium compound is present in the fluororesin.
  • Item 4. Item 4. The fluororesin-containing glass fiber cloth according to Item 2 or 3, wherein the silane coupling agent and / or a reactant thereof is present in the fluororesin.
  • Item 6 The fluororesin-containing glass fiber cloth according to any one of Items 1 to 5, which is for a dust collection filter.
  • Item 7. A dust collection filter comprising the fluororesin-containing glass fiber cloth according to any one of Items 1 to 5.
  • the fluorine resin-containing glass fiber cloth of the present invention by containing the fluorine resin and the organic titanium compound on the glass fiber, excellent bending resistance can be provided even after heat exposure at an atmosphere temperature exceeding 250 ° C. Accordingly, the fluorocarbon resin-containing glass fiber cloth of the present invention is suitable for use as a dust collection filter which is required to have resistance to bending under a high temperature environment such as a bag filter.
  • the fluorocarbon resin-containing glass fiber cloth according to the present invention is characterized in that it contains a fluorocarbon resin and an organic titanium compound on glass fiber.
  • the present invention will be described in detail.
  • Glass fiber cloth It does not restrict
  • the glass composition constituting the glass fiber is SiO 2 from the viewpoint of providing excellent tensile strength together with excellent folding resistance after heat exposure at an ambient temperature exceeding 250 ° C.
  • the glass composition constituting the glass fiber has, for example, a content of 60.0 to 66.0% by mass of SiO 2 and a content of 18.0 to 26.0 mass of Al 2 O 3 %, And the content of MgO may be 8.0 to 20.0%.
  • the glass composition constituting the glass fiber has a content of 60.0 to 66.0% by mass of SiO 2, a content of 18.0 to 26.0% by mass of Al 2 O 3 , A glass composition containing 8.0 to 20.0% of MgO (a content of 64.0 to 66.0% by mass of SiO 2 and a content of 24.0 to 26.0 of Al 2 O 3 ) It is also possible to use a glass composition with a mass%, a content of MgO of 9.0 to 11.0%, and a content of other components of 3 mass% or less (including 0 mass%).
  • the glass composition constituting the glass fiber has a content of SiO 2 of 60.0 to 64, from the viewpoint of more easily providing excellent bending resistance even after heat exposure at an ambient temperature exceeding 250 ° C. .0 mass%, the content of Al 2 O 3 is 18.0 to 22.0 mass%, the content of MgO is 14 to 18 mass%, the content of SiO 2 , the content of Al 2 O 3 And it can be set as the glass composition whose sum total of content of MgO is 94 mass% or more. From the same point of view, the glass composition constituting the glass fiber has a SiO 2 content of 60.0 to 64.0 mass% and an Al 2 O 3 content of 18.0 to 22.0 mass%.
  • the content of MgO is 14 to 18% by mass
  • the content of Fe 2 O 3 is 0.05 to 0.5% by mass
  • the content of CaO is 0.05 to 0.5% by mass
  • Na 2 O 3 Glass with a content of 0.5 to 3.0% by mass
  • a content of K 2 O of 0.05 to 0.5% by mass and a content of B 2 O 3 of 0.5 to 3.0% by mass
  • the total of the content of SiO 2 , the content of Al 2 O 3 and the content of MgO is preferably 94% by mass or more.
  • the fluorocarbon resin-containing glass fiber cloth of the present invention contains a fluorocarbon resin and an organic titanium compound on glass fiber, the atmosphere temperature exceeds 250 ° C.
  • the glass material is made of general-purpose E glass. It is possible to provide excellent folding resistance even after heat exposure at.
  • the composition of E glass is 52 to 56% by mass of SiO 2 , 12 to 16% by mass of Al 2 O 3 , 15 to 25% by mass of CaO, 0 to 6% by mass of MgO, B 2 O 3 is 5-13 wt%, the glass composition can be mentioned Na 2 O 3 and K 2 O 3 is 0-1 wt%.
  • the glass fibers may be either long fibers or short fibers. From the viewpoint of further improving the mechanical properties such as tensile strength of the cloth, long fibers are preferred.
  • Long fibers include monofilament yarns consisting of one continuous single fiber, multifilament yarns consisting of a plurality of continuous single fibers, and when exposed to heat at an ambient temperature exceeding 250 ° C.
  • a multifilament yarn is preferred from the viewpoint of making the properties more excellent.
  • a woven fabric When it is set as the said long fiber, as a form of the cloth of this invention, a woven fabric, a knitted fabric, a nonwoven fabric (including a felt), or those combining these can be used.
  • a woven fabric it is preferable to use a yarn as a multifilament yarn and a bulky processed yarn (bulk processed yarn) made of a multifilament yarn from the viewpoint of enhancing mechanical properties and dust collection properties.
  • the yarn include single yarns and yarns. From the viewpoint of further improving the folding resistance after heat exposure at an ambient temperature of more than 250 ° C., a combined twisting yarn is preferable as the above yarn.
  • the configuration of the composite yarn is not particularly limited.
  • a single yarn yarn 2 twisted in the S direction or Z direction It can be mentioned that ⁇ 8 yarns (preferably 2 to 4 yarns) are mixed and twisted in the direction opposite to the twisting direction of the yarn.
  • the twisting number (upper twisting number) of the combined twisting yarn is preferably 2 to 5 times / 25 mm, and more preferably 3.0 to 4.5 times / 25 mm.
  • the filament diameter (single fiber diameter) of the yarn is, for example, 4 to 9 ⁇ m.
  • the filament diameter of the above yarn is more preferably 4 to 7 ⁇ m, particularly preferably 5 to 7 ⁇ m, from the viewpoint of further improving the folding resistance after heat exposure at an ambient temperature exceeding 250 ° C.
  • examples of the filament diameter (single fiber diameter) of the bulky processed yarn include 4 to 9 ⁇ m.
  • the filament diameter of the above-mentioned bulky processed yarn is more preferably 4 to 7 ⁇ m, particularly preferably 5 to 7 ⁇ m.
  • examples of yarn counts include 30 to 600 tex. In order to further enhance the hardness, 50 to 450 tex is more preferable. A yarn count of 100 to 200 tex is more preferable from the viewpoint of further improving the bending resistance before and after heat exposure while further improving the mechanical properties and the dust collection properties.
  • examples of the bulkiness yarn count include 30 to 600 tex, and more preferably 50 to 500 tex from the viewpoint of further improving the mechanical characteristics and the dust collecting property.
  • 200 to 400 tex is more preferable as the count of the bulky textured yarn.
  • the fabric is a woven fabric in which warp yarns are used as yarns and weft yarns are processed as bulky yarns, the ratio of counts of warp yarns to weft yarns (warp count / weft count) has even more excellent folding resistance.
  • the effect of reducing the bending resistance decrease after heat exposure at an ambient temperature exceeding 250.degree. C., and preferably 2/5 to 1/2. Is more preferred.
  • the glass fiber cloth when the glass fiber cloth is a woven fabric which is woven as a warp yarn as yarn, a weft yarn as bulky yarn or a combination yarn of bulky yarn and yarn and yarn, it is not limited as a woven structure, for example, plain weave, satin weave And twill weaves, hosiery weaves, twill weaves, double weaves (transwoven double weave, weft double weave, warp double weave) and the like.
  • a double weave structure is preferable, and a weft double weave is more preferable, from the viewpoint of further improving the dust collection property while further improving the folding resistance before and after heat exposure.
  • the weave density is not particularly limited.
  • the glass fiber cloth is a woven fabric in which a warp is a yarn and a weft is a balky yarn
  • 20 yarns are used. It is preferably 80 to 25 mm, more preferably 40 to 60.
  • the weft (bulky yarn or) is preferably 20 to 80/25 mm, and more preferably 30 to 60.
  • the mass (g / m 2 ) of the glass fiber cloth (excluding components other than glass fiber (such as fluorine resin)) used in the present invention is not particularly limited, and for example, 500 to 1500 g / m 2 may be mentioned. And 700 to 1100 g / m 2 are preferable.
  • the thickness (mm) of the glass fiber cloth (excluding components other than glass fiber (such as fluorocarbon resin)) is not particularly limited, and for example, 0.3 to 1.5 mm may be mentioned. And 0.6 to 1.2 mm are preferable.
  • the fluororesin-containing glass fiber cloth of the present invention contains a fluororesin on glass fibers.
  • the fluorine resin improves the flexibility of the fluorine resin-containing glass fiber cloth of the present invention, and plays a role of providing the cloth with excellent bending resistance even after heat exposure at an atmospheric temperature exceeding 250 ° C.
  • the fluorine resin is a polymer (homopolymer or copolymer) having a repeating unit derived from at least one fluorine-containing monomer.
  • a fluorine resin for example, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / perfluoroalkyl ether copolymer (PFA) ), Tetrafluoroethylene / hexafluoropropylene copolymer (FEP), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoroethylene / hexafluoropropylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer Combination, vinylidene fluoride / tetrafluoroethylene copolymer Combin
  • fluorine resins when using the fluorine resin-containing glass fiber cloth of the present invention as a bag, it is possible to further reduce the coefficient of dynamic friction with the needle and further improve the needle penetration to make sewing easier. From the above, a fluorine resin having no side chain and no branching in the molecular structure is preferable, and PTFE is a preferable example.
  • the ratio of the fluorocarbon resin to the total amount of non-volatile components deposited on the glass fibers is, for example, fluorocarbon resin per 100 parts by mass of the total non-volatile components deposited on glass fibers.
  • the amount is 30 to 98 parts by mass, preferably 50 to 98 parts by mass.
  • a "nonvolatile component” means the bone dry component when heat processing is carried out at 120 degreeC under normal pressure, a solvent etc. is removed, and constant weight is reached.
  • Fluoro resin, organic titanium compound to be described later, silane coupling agent and reaction product thereof, Silicone resin, graphite and the like correspond to non-volatile components.
  • the fluororesin-containing glass fiber cloth of the present invention contains an organic titanium compound on glass fiber.
  • the organic titanium compound functions as a fluorine resin modifier as described above, and has excellent folding resistance even after heat exposure at an ambient temperature exceeding 250 ° C. to the fluorine resin-containing glass fiber cloth of the present invention Play a role.
  • the organic titanium compound is a compound in which an organic group is directly bonded to a titanium atom, or a compound in which a titanium atom is bonded to an organic group through an oxygen atom or a nitrogen atom.
  • an organic titanium compound an alkoxide type organic titanium compound, a chelate type organic titanium compound, an acylate type organic titanium compound is mentioned, for example, A chelate type organic titanium compound is preferable.
  • the chelate organic titanium compound is a chelate compound in which a chelate ligand is coordinated to a titanium atom to form a chelate ring.
  • the chelating ligand constituting the chelating organic titanium compound is, for example, hydroxycarboxylic acids having at least one hydroxyl group and at least one carboxyl group in the molecule (eg, citric acid, lactic acid, malic acid, tartaric acid) Or glycolic acid etc., ⁇ -diketones (eg acetylacetone, 3-phenylacetylacetone etc.), alkanolamines (eg triethanolamine etc.) and the like.
  • an alkoxy group preferably a C1-6 alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group etc. may be mentioned) is included as a chelate ligand.
  • a C1-6 alkoxy group for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group etc. may be mentioned
  • a chelate ligand are more preferably mentioned.
  • organic titanium compound examples include titanium tetraisopropoxide (Ti (Oi-C 3 H 7 ) 4 ) and titanium tetranormal butoxide (Ti (O n C 4 H 9). 4 ), titanium butoxide dimer ((nC 4 H 9 O) 3 Ti-O-Ti (O n c 4 H 9 ) 3 ), titanium tetra-2-ethylhexoxide (Ti (OC 8) H 17 ) 4 , titanium diisopropoxy bis (acetyl acetate) (Ti (Oi-C 3 H 7 ) 2 (C 5 H 7 O 2 ) 2 ), titanium tetraacetyl acetate (Ti (C 5 H 7 O) 2 ) 4 ), titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide) (Ti (OC 8 H 17 ) 2 (C 8 H 17 O 2 ) 2 ), titanium diisopropoxy Bis
  • organic titanium compounds may be used singly or in combination of two or more.
  • organic titanium compounds preferably di -i- propoxy bis (acetylacetonato) titanium (Ti [OCH (CH 3) 2] 2 [OC (CH 3) CHCOCH 3] 2), a hydrolyzate And dehydrated condensates of the hydrolyzate.
  • organic titanium compounds are known to exhibit hydrolyzability, and in the present invention, the organic titanium compounds may be present as a hydrolyzate on glass fibers. Further, in the present invention, the organic titanium compound may be present as a reaction product which is reacted with a fluorine resin or other components on a glass fiber.
  • a commercial item can be used for the organic titanium compound mentioned above.
  • the inventors of the present invention have found that the organic titanium compound has the function of improving the wettability of the fluorocarbon resin to the glass fiber. Therefore, the fluorine resin-containing glass fiber cloth of the present invention is considered to be improved in the impregnating property of the fluorine resin to the glass fiber by containing the organic titanium compound in addition to the fluorine resin.
  • the present inventors heat-treated a fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound on glass fibers at 350 ° C., the fluororesin was three-dimensional on the glass fibers. It was observed that it was reticulated and remained so as to bridge the glass fibers.
  • the fluorocarbon resin and the organic titanium compound are well impregnated between the glass fibers, the impregnated organic titanium compound forms a skeleton in a three-dimensional network, and the fluorocarbon resin also exists along the skeleton It is surmised that the fluorocarbon resin and the organic titanium compound are present in a three-dimensional network on the glass fiber.
  • a flexible fluorocarbon resin is present in a three-dimensional network, thereby imparting more excellent flexibility to the glass fiber cloth, and the fluorocarbon resin is By being present along the skeleton of the organotitanium compound excellent in heat resistance, the heat resistance of the fluorocarbon resin is further improved, so that excellent bending resistance can be provided even after heat exposure at an atmosphere temperature exceeding 250 ° C. It is guessed.
  • the organic titanium compound is present in the fluororesin from the viewpoint of facilitating modification of the fluororesin (that is, it covers at least a part of the surface of the glass fiber). It is preferable to have a fluorocarbon resin film, and to contain a reaction product of an organic titanium compound and / or an organic titanium compound in the fluorocarbon resin film. In order to do this, a treatment liquid in which a fluorocarbon resin and an organic titanium compound are mixed in advance may be prepared, and the glass fiber cloth may be impregnated with the treatment liquid and then dried.
  • the ratio of the fluorocarbon resin to the organic titanium compound to be deposited on the glass fiber is not particularly limited. There are 50 parts by mass, preferably 2 to 40 parts by mass.
  • the fluorine resin-containing glass fiber cloth of the present invention may further contain a silane coupling agent and / or a reaction product thereof on the glass fiber in addition to the fluorine resin and the organic titanium compound.
  • a silane coupling agent and / or a reactant thereof is contained on the glass fiber, it becomes possible to further improve the folding resistance after heat exposure at an ambient temperature exceeding 250 ° C.
  • the silane coupling agent is, for example, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-glycidoxyethoxytrimethoxysilane, 2- Glycidoxyethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3 -Aminopropyltri
  • silane coupling agents may be used alone or in combination of two or more.
  • aminosilane coupling agents having an amino group are preferable, and 3-aminopropyltriethoxysilane, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane hydrochloride Is more preferred, and N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane hydrochloride is particularly preferred.
  • Examples of the reaction product of the silane coupling agent include a hydrolyzate of the silane coupling agent, a dehydrated condensate of the hydrolyzate, and the like.
  • a silane coupling agent When a silane coupling agent is coexistent with a fluorocarbon resin and an organic titanium compound on glass fiber, the silane coupling agent is hydrolyzed to be present as a hydrolyzate or as a dehydrating condensate of the hydrolyzate. There is something to do.
  • the functional group of the silane coupling agent may be present in a state of being bonded to the glass fiber, the organic titanium compound and the like.
  • the silane coupling agent and / or the reactant thereof is present in the fluororesin from the viewpoint of facilitating modification of the fluororesin (that is, the surface of the glass fiber
  • the reaction product of a silane coupling agent and / or a silane coupling agent is preferably contained in the fluororesin film.
  • a treatment liquid in which a fluorocarbon resin and a silane coupling agent and / or a reactant thereof are mixed beforehand may be prepared, and the glass fiber cloth may be impregnated with the treatment liquid and then dried.
  • the ratio of the fluorocarbon resin to the silane coupling agent and / or the reactant is particularly Although not limited thereto, for example, 1 to 20 parts by mass of the silane coupling agent and / or the reaction product thereof can be mentioned with respect to 100 parts by mass of the fluorocarbon resin.
  • the fluororesin-containing glass fiber cloth of the present invention may further contain other components other than the components described above on the glass fiber.
  • a silicone resin is mentioned as one of the examples of the said other component.
  • the inclusion of the silicone resin on the glass fiber makes it easier to improve the needle penetration.
  • the slipperiness between glass fibers (between filaments) is further improved, and the bending resistance after heat exposure at an ambient temperature exceeding 250 ° C. is further improved. It can also be done.
  • the ratio of the fluorocarbon resin and the silicone resin is not particularly limited, but for example, silicone resin with respect to 100 parts by mass of fluorocarbon resin. There are 1 to 20 parts by weight, preferably 1 to 10 parts by weight.
  • the fluororesin-containing glass fiber cloth of the present invention may be substantially free of silicone resin.
  • the fluorocarbon resin-containing glass fiber cloth of the present invention may further include a catalyst for decomposing gaseous dioxins and NOx and purifying gas.
  • the fluororesin-containing glass fiber cloth of the present invention contains the catalyst, the aqueous resin slurry in which the catalyst is dispersed is impregnated with the fluororesin-containing glass fiber cloth as a method for supporting the catalyst, and the catalyst is a fluororesin-containing glass A method of supporting on fiber cloth is mentioned.
  • the fluorocarbon resin-containing glass fiber cloth of the present invention may be substantially free of silicone resin.
  • "does not substantially contain a silicone resin” means a content that does not reduce the water wettability of the fluororesin-containing glass fiber cloth, and for example, the silicone resin is 0 based on 100 parts by mass of the fluororesin. The amount is from 0.5 to 0.5 parts by mass, preferably from 0 to 0.3 parts by mass, and more preferably 0 parts by mass.
  • silicone resins include silicone oils and those obtained by drying silicone emulsions.
  • the fluorocarbon resin-containing glass fiber cloth of the present invention further facilitates the maintenance of the dust removal property when continuously used as a bag filter at an atmosphere temperature exceeding 250 ° C. by further containing graphite on glass fiber Become.
  • the ratio of fluorine resin to graphite is not particularly limited.
  • 1 to 100 of graphite is used per 100 parts by mass of fluorine resin.
  • the amount is 30 parts by mass, preferably 1 to 25 parts by mass.
  • the fluorocarbon resin-containing glass fiber cloth of the present invention can also be made free of graphite.
  • a catalyst for decomposing gaseous dioxins, NOx, and the like and purifying gas can be included.
  • the catalyst include known ones, and examples thereof include vanadium pentoxide and the like.
  • the carrier supporting the above-mentioned catalyst known ones can be used.
  • a wet penetrant for further improving the impregnatability of the fluorocarbon resin, a surfactant, and other resins other than fluorine (for example, having no side chain and branching in the molecular structure)
  • Thermoplastic resins such as vinyl chloride resin, polyphenylene sulfide resin, nylon 6 resin, polyacetal resin, polyethylene resin, polytetrafluoroethylene are preferably mentioned), pigments such as carbon black, mica, carboxymethyl cellulose etc. it can.
  • the loss on ignition (%) of the fluororesin-containing glass fiber cloth of the present invention is 0.5 to 20% by mass, preferably 0.5 to 15% by mass.
  • the loss on ignition in the fluorocarbon resin-containing glass fiber cloth of the present invention approximately corresponds to the total amount of organic components such as fluorocarbon resin adhering to the glass fiber.
  • a loss on ignition is a muffle set at 625 ° C. according to the method prescribed in “7.3.2 loss on ignition” in “JIS R 3420: 2013 Glass fiber general test method”. It is a value calculated
  • the mass of the fluororesin-containing glass fiber cloth of the present invention is not particularly limited, but, for example, 500 to 1500 g / m 2 may be mentioned, and 700 to 1100 g / m 2 may preferably be mentioned.
  • the "mass of fluorocarbon resin-containing glass fiber cloth” is defined by the method defined in "7.2 Mass (mass) of cloth and mat” of "JIS R 3420: 2013 glass fiber general test method”. It is a value measured and calculated according to the same.
  • the thickness (mm) of the fluorocarbon resin-containing glass fiber cloth of the present invention is not particularly limited, but may be, for example, 0.3 to 1.5 mm, preferably 0.6 to 1.2 mm.
  • “the thickness of the fluororesin-containing glass fiber cloth” is in accordance with the method A specified in “7.10 cross thickness” in “JIS R 3420: 2013 glass fiber general test method”, It is a value obtained by measuring to the order of 0.001 mm (1 ⁇ m) using a micrometer and calculating an average value of five thicknesses.
  • the air permeability of the fluororesin-containing glass fiber cloth of the present invention is, for example, 3 to 20 cm 3 ⁇ cm -2 ⁇ s -1 , from the viewpoint of achieving both gas permeability and dust collection properties when used as a bag filter. Preferably, 5 to 15 cm 3 ⁇ cm -2 ⁇ s -1 can be mentioned.
  • “aerated amount of fluorocarbon resin-containing glass fiber cloth” is a flailed type test according to the method defined in “7.13 air permeability” of “JIS R 3420: 2013 glass fiber general test method”. It is a value measured and calculated using a machine.
  • the fluorine resin-containing glass fiber cloth of the present invention can be provided with excellent bending resistance even after heat exposure at an atmosphere temperature exceeding 250 ° C. by containing a fluorine resin and an organic titanium compound on glass fiber .
  • the folding resistance of the fluororesin-containing glass fiber cloth of the present invention is preferably 50% or more in the warp direction Is 100 to 400%, and the latitudinal direction is 20% or more, preferably 40 to 200%.
  • the number of foldings after heat exposure at 350 ° C. determined by the following method is 20000 or more, preferably 80,000 in the warp direction.
  • the direction of the latitudinal direction is 8000 times or more, preferably 10000 times or more.
  • the number of foldings before heat exposure determined by the following method is 20000 or more, preferably 40000 or more in the warp direction.
  • the latitudinal direction is 5000 times or more, preferably 20000 times or more.
  • the length in the measurement direction of the fluorocarbon resin-containing glass fiber cloth (that is, the warp direction when measuring the bending resistance in the warp direction) is 32 cm, and the length in the direction different from the measurement direction (that is, the bending resistance in the warp direction)
  • the sample is heat treated at a temperature of 350 ° C. for 24 hours to prepare a sample after thermal exposure.
  • the number of folding is determined using the MIT folding resistance tester according to the method specified in “7.14 Cross Folding resistance” of “JIS R 3420: 2013 Glass fiber general test method”, and the bending device The radius of curvature of the bending surface is set to 0.38 mm, the tension is set to 9.8 N, and bending is performed at a speed of 175 ⁇ 10 per minute to measure the number of folding resistances until the sample breaks (reciprocal bending number). For the number of times of folding, four samples are prepared for one fluorocarbon resin-containing glass fiber cloth, and their average value is calculated.
  • the retention rate of the number of folds in the warp direction and the retention rate of the number of folds in the weft direction are calculated by the following equations.
  • Retention rate of warp number of folds (%) ⁇ average value of fold number of warps of sample after heat exposure (times) / average value of fold number of warps of sample before heat exposure (times) ) ⁇ ⁇ 100
  • Holding rate of the number of folds in the latitudinal direction (%) ⁇ average value of the number of folds in the latitudinal direction of the sample after thermal exposure (times) / average value of the number of folds in the lateral direction of the sample before thermal exposure (times) ) ⁇ ⁇ 100
  • a preferred embodiment of the fluorocarbon resin-containing glass fiber cloth of the present invention is to have excellent tensile strength even after heat exposure at an ambient temperature exceeding 250 ° C.
  • the retention of tensile strength after heat exposure at 350 ° C. determined by the following method is preferably 30% or more in the warp direction Is 40% or more, and 50% or more, preferably 60% or more in the latitudinal direction.
  • the tensile strength after heat exposure at 350 ° C. determined by the following method is 900 (N / 25 mm) or more in the warp direction Preferably, it is 1000 (N / 25 mm) or more, and the latitudinal direction is 1000 (N / 25 mm) or more, preferably 1500 (N / 25 mm) or more.
  • the tensile strength before heat exposure determined by the following method is 2000 (N / 25 mm) or more, preferably 3000 in the warp direction. (N / 25 mm) or more may be mentioned, and the latitudinal direction may be 2000 (N / 25 mm) or more, preferably 2500 (N / 25 mm) or more.
  • the fluororesin-containing glass fiber cloth is heat treated at 350 ° C. for 24 hours to prepare a sample after heat exposure.
  • the tensile strength (N / 25 mm) is measured using a sample not exposed to heat (a sample before exposure to heat) and a sample after exposure to heat.
  • the tensile strength is 250 mm in length according to the constant speed load type tensile test method.
  • Retention rate of tensile strength in the transverse direction (%) ⁇ average value of tensile strength in the longitudinal direction of the sample after thermal exposure (N / 25 mm) / average value of tensile strength in the transverse direction of the sample before thermal exposure (N / 25 mm) ⁇ ⁇ 100
  • Retention of tensile strength in the latitudinal direction (%) ⁇ average value of tensile strength in the latitudinal direction of the sample after thermal exposure (N / 25 mm) / average value of tensile strength in the lateral direction of the sample before thermal exposure (N / 25 mm) ⁇ ⁇ 100
  • the method for producing the fluororesin-containing glass fiber cloth of the present invention is not particularly limited. For example, first, a glass fiber cloth is prepared. Then, prepare a treatment solution in which a fluorine resin, an organic titanium compound, and other components used as needed are mixed, and use the treatment solution with the glass fiber cloth by a known method such as a spray method or dip method.
  • the fluororesin-containing glass fiber cloth of the present invention can be obtained by impregnating the glass fiber to be constituted, drying and removing the solvent.
  • the composition of the non-volatile component contained in the treatment liquid to be impregnated into the glass fiber cloth becomes the composition of the non-volatile component to be deposited on the glass fiber as it is, the composition of the treatment liquid is the composition of the non-volatile component deposited on the glass fiber It may be set appropriately according to
  • the step of impregnating the treatment liquid may be performed once or plural times.
  • the treatment liquid having the same composition may be used in the plurality of impregnation steps, or the treatment liquid having a different composition may be used for each impregnation step.
  • the fluorocarbon resin, the organic titanium compound and the silane coupling agent and / or the reaction product thereof are deposited on the glass fiber by two impregnation steps, the fluorocarbon resin and the organic titanium compound are contained in the first impregnation step
  • An impregnation liquid can be used, and an impregnation liquid containing a fluorocarbon resin and a silane coupling agent and / or a reaction product thereof can be used in the second impregnation step.
  • the glass fiber cloth impregnated with the treatment liquid can be adjusted in a desired range by impregnating the treatment liquid by adjusting the squeezing pressure with a roll press and squeezing.
  • the fluorocarbon resin-containing glass fiber cloth of the present invention is used in a dust collector for capturing dust (fly ash) in exhaust gas generated in municipal waste incinerators, industrial waste incinerators, coal-only boilers, metal melting furnaces, etc.
  • a filter material dust collection filter material
  • bag filter material particularly preferably used as a bag filter material.
  • the fluororesin-containing glass fiber cloth of the present invention is excellent in bending resistance even when exposed to heat at an atmosphere temperature exceeding 250 ° C., for example, an atmosphere temperature of 350 ° C.
  • the fluorine resin-containing glass fiber cloth of the present invention If a glass fiber cloth is added with a catalyst for purifying the above-mentioned gas and it is used within a temperature range of about 300 to 400 ° C. or 300 to 350 ° C. which is a preferable temperature range for denitrification, It becomes unnecessary to reheat the exhaust gas in the catalyst denitration step carried out in the above, and it is possible to greatly contribute to CO 2 reduction.
  • Glass fiber treating agent also provides a glass fiber treating agent containing a fluorocarbon resin and an organic titanium compound.
  • the said glass fiber processing agent can be used as a process liquid used for manufacture of the said fluororesin containing glass fiber cloth.
  • the said glass fiber processing agent may contain a silane coupling agent and / or its reaction product, a silicone resin, a graphite, and other components as needed other than a fluorine resin and an organic titanium compound. .
  • the present invention provides a resin composition comprising a fluorine resin and an organic titanium compound.
  • the said resin composition is a composition for film
  • the resin composition may contain, in addition to the fluorine resin and the organic titanium compound, a silane coupling agent and / or a reactant thereof, a silicone resin, graphite, and other components, as necessary.
  • composition and mass ratio (mass%) of glass composition constituting glass fiber It was measured by alkaline melting-ICP emission spectrometry and atomic absorption spectrophotometry.
  • Thickness of glass fiber cloth and glass fiber cloth containing fluorocarbon resin (mm) According to the method A specified in "7.10 thickness of cloth” of "JIS R 3420: 2013 glass fiber general test method", it measured to the digit of 0.001 mm (1 micrometer) using the micrometer. The measurement was performed at five places, and the average value of the five places was rounded to a numerical value according to JIS Z 8401 rule B, and calculated to a digit of 0.001 mm (1 ⁇ m).
  • Mass of glass fiber cloth and glass fiber cloth containing fluorocarbon resin (g / m 2 ) It measured and computed according to the method prescribed
  • composition ratio of components adhering to glass fiber (parts by mass)
  • Each composition ratio of the components adhering to the glass fiber is the same as the composition ratio of the non-volatile components in the treatment liquid used, so the fluorine resin was determined to be 100 from the ratio of the non-volatile component concentration in the treatment liquid used.
  • the mass part of time was calculated.
  • the number of baths of a process liquid is 2, it computed as a ratio of the total density
  • Ignition weight loss (mass%) Measured and calculated under the conditions of heating in a muffle furnace set at 625 ° C for 30 minutes according to the method prescribed in "7.3.2 Loss on ignition” in "JIS R 3420: 2013 Glass fiber general test method” .
  • the length in the measuring direction (that is, when measuring bending resistance in the longitudinal direction, the length is in the measuring direction) is 32 cm, which is different from the measuring direction
  • the length of the direction i.e., the latitudinal direction when measuring the bending resistance in the warp direction
  • the sample was heat-treated at a temperature of 350 ° C. for 24 hours in a high-temp oven (trade name: HP80 manufactured by Asahi Scientific Co., Ltd.) to prepare a sample after heat exposure.
  • the number of folds was determined for samples not exposed to heat (samples before exposure to heat) and samples after exposure to heat.
  • the number of times of folding is the MIT folding endurance tester (made by Toyo Seiki Seisakusho Co., Ltd.) in accordance with the method prescribed in “7.14 cross folding resistance” in “JIS R 3420: 2013 Glass fiber general test method”. D type), the curvature radius of the bending surface of the bending device is set to 0.38 mm, tension is set to 9.8 N, bending is performed at a speed of 175 ⁇ 10 per minute, and the number of folding resistances until the sample breaks The number of reciprocative bending was measured. As for the number of times of folding, four samples were prepared per one fluorocarbon resin-containing glass fiber cloth, and their average value was calculated. The retention of the number of times of folding after heat exposure was calculated according to the equation described above.
  • the width was 25 mm, and measurement and calculation were performed under the conditions of a grip interval of 150 mm and a speed of 200 mm / min using RTC-1310A manufactured by ORIENTEC CO., LTD. As a tensile tester. The retention of tensile strength after heat exposure was calculated according to the equation described above.
  • glass fiber fabric I got The mass of the glass fiber woven fabric was 841 g / m 2 .
  • the processing solution contains 220 g / L of a PTFE solution (Mitsubishi DuPont Fluorochemicals Co., Ltd., trade name PTFE 31-JR, non-volatile component concentration of 60 mass% of PTFE) as a fluorocarbon resin, and an organic titanium compound of di-i-propoxy.
  • An i-propanol solution of bis (acetylacetonato) titanium Ti [OCH (CH 3 ) 2 ] 2 [OCH (CH 3 ) CHCOCH 3 ] 2
  • T-50 purity 74.1
  • the above-mentioned characterized glass fiber fabric was impregnated in the first bath treatment solution, and the nip pressure was squeezed by a nip roll to 1.1 kgf / cm 2 and dried at 250 ° C. for 5 minutes. .
  • the treatment liquid is 220 g / L of a PTFE solution (Mitsubishi DuPont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of 60 mass% of PTFE) as a fluorine resin, a silane coupling agent (a product manufactured by JNC Co., Ltd.) Name: Silaace S 350, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane ⁇ Hydrochloride 40% by mass) 10 g / L, Acetic acid (90% pure) 1.8 g / L The remaining portion was obtained by mixing so as to be pure water.
  • a PTFE solution Mitsubishi DuPont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of 60 mass% of PTFE
  • silane coupling agent a product manufactured by JNC Co., Ltd.
  • a glass fiber fabric obtained by impregnating and drying the first bath treatment solution is impregnated into the second bath treatment solution, and the nip pressure is squeezed at 1.1 kgf / cm 2 with a nip roll, and the temperature is 250 ° C.
  • a fluorocarbon resin-containing glass fiber cloth containing a fluorocarbon resin and an organic titanium compound on glass fiber was obtained.
  • the fluorine resin-containing glass fiber cloth had a thickness of 0.831 mm, a mass of 941.3 g / m 2 , a loss on ignition of 10.6% by mass, and an air permeability of 10.0 cc / cm 2 / s.
  • Example 1 In Example 1, the first bath processing solution was replaced with a PTFE solution (PTFE 31-JR manufactured by DuPont Fluorochemicals Co., Ltd., trade name: PTFE 31-JR, pure acetic acid (90% pure) 6 g / L, balance pure water) as a fluorine resin.
  • PTFE 31-JR manufactured by DuPont Fluorochemicals Co., Ltd., trade name: PTFE 31-JR, pure acetic acid (90% pure) 6 g / L, balance pure water
  • a fluororesin-containing glass fiber cloth was obtained under the same conditions as in Example 1 except that it was obtained by mixing as described above (that is, using a treatment liquid not containing an organic titanium compound).
  • the cloth had a thickness of 0.872 mm, a weight of 931.9 g / m 2 , a loss on ignition of 8.7% by mass, and an air permeability of 11.3 cc / cm 2 / s.
  • Example 2 As warp, DE 75 1/2 3.8S (single yarn yarn DE 75 1/0 0.7Z2 two strands twisted in the Z direction are additionally twisted in the Z direction as a warp yarn, and the number of upper twists is 3 in the S direction .8 times / 25mm of plied yarn, filament diameter 6 ⁇ m, count 135tex), as weft, trade name TDE 300 (Valky-processed yarn, filament diameter 6.0 ⁇ m, count 302.0tex) manufactured by UNITIKA CO., LTD. Was used.
  • the glass material which comprises glass fiber with both warp yarns and wefts was E glass.
  • glass fiber fabric I got The mass of the glass fiber woven fabric was 841 g / m 2 .
  • the processing solution contains 50 g / L of a PTFE solution (Mitsubishi DuPont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of 60 mass% of PTFE) as a fluorine resin, and di-i-propoxy.
  • a PTFE solution Mitsubishi DuPont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of 60 mass% of PTFE
  • An i-propanol solution of bis (acetylacetonato) titanium Ti [OCH (CH 3 ) 2 ] 2 [OCH (CH 3 ) CHCOCH 3 ] 2
  • T-50 purity 74.1.
  • CMC carboxymethyl cellulose
  • Silane coupling agent trade name: SILAACE (registered trademark) S330, manufactured by JNC Co., Ltd., 3-aminopropyltriethoxysilane, non-volatile matter 100% by mass
  • the above-mentioned characterized glass fiber fabric is impregnated in the above processing solution, squeezed with a nip roll at a nip pressure of 1.1 kgf / cm 2 , dried at a temperature of 250 ° C. for 10 minutes, and on glass fiber.
  • a fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound was obtained.
  • the fluorine resin-containing glass fiber cloth had a thickness of 0.864 mm, a mass of 858.9 g / m 2 , a loss on ignition of 1.3% by mass, and an air permeability of 11.8 cc / cm 2 / s.
  • Example 2 In Example 2, 50 g / L of a PTFE solution (trade name PTFE 31-JR, manufactured by DuPont Fluorochemicals Co., Ltd .; non-volatile component concentration of 60 mass% of PTFE) as a fluorocarbon resin, and a graphite dispersion (graphite solid) 28 g / L of an aqueous dispersion containing 22.5% by mass of CMC solid content of 7.5% by mass, a silane coupling agent (trade name: SYRAACE (registered trademark) S330, manufactured by JNC Corporation, 3-aminopropyltriethoxy) Under the same conditions as in Example 2 except that silane, nonvolatile content 100% by mass) 5 g / L, balance obtained by mixing so as to be pure water (that is, using a treatment liquid not containing an organic titanium compound) A fluororesin-containing glass fiber cloth was obtained.
  • a silane coupling agent trade name: SYRAACE (registered trademark) S330
  • the fluorine resin-containing glass fiber cloth had a thickness of 0.895 mm, a mass of 858.5 g / m 2 , a loss on ignition of 1.2% by mass, and an air permeability of 12.3 cc / cm 2 / s.
  • Example 3 As warp, DE 75 1/2 3.8S (single yarn yarn DE 75 1/0 0.7Z2 two strands twisted in the Z direction are additionally twisted in the Z direction as a warp yarn, and the number of upper twists is 3 in the S direction .8 times / 25mm of plied yarn, filament diameter 6 ⁇ m, count 135tex), as weft, trade name TDE 300 (Valky-processed yarn, filament diameter 6.0 ⁇ m, count 302.0tex) manufactured by UNITIKA CO., LTD. Was used.
  • the glass material which comprises glass fiber with both warp yarns and wefts was E glass.
  • weft weaving (warp density 48/25 mm, weft density 48/25 mm) was performed with a weft double weave structure to obtain a glass fiber fabric (without characterization).
  • the mass of the glass fiber woven fabric was 850 g / m 2 .
  • the treatment liquid contains 269.1 g / L of a PTFE solution (Mitsubishi / Dupont Fluorochemicals Co., Ltd., trade name PTFE 31-JR, non-volatile component concentration of PTFE 60 mass%) as a fluorocarbon resin, and an organic titanium compound of di-i- A solution of propoxy bis (acetylacetonato) titanium (Ti [OCH (CH 3 ) 2 ] 2 [OCH (CH 3 ) CHCOCH 3 ] 2 ) in i-propanol (Nippon Soda Co., Ltd.
  • a PTFE solution Mitsubishi / Dupont Fluorochemicals Co., Ltd., trade name PTFE 31-JR, non-volatile component concentration of PTFE 60 mass
  • an organic titanium compound of di-i- A solution of propoxy bis (acetylacetonato) titanium Ti [OCH (CH 3 ) 2 ] 2 [OCH (CH 3 ) CHCOCH 3
  • the above woven glass fiber fabric is impregnated in the above processing solution, squeezed with a nip roll to a nip pressure of 1.1 kgf / cm 2, dried at a temperature of 250 ° C. for 10 minutes, and on the glass fiber
  • a fluororesin-containing glass fiber cloth comprising the organic titanium compound and / or the reaction product of the organic titanium compound is obtained.
  • the fluorine resin-containing glass fiber cloth had a thickness of 1.018 mm, a weight of 948.2 g / m 2 , a loss on ignition of 9.1% by mass, and an air permeability of 9.1 cc / cm 2 / s.
  • Example 3 In Example 3, 269.1 g / L of a treatment solution containing 269.1 g / L of a PTFE solution (trade name PTFE 31-JR manufactured by Dupont Fluorochemicals Co., Ltd., non-volatile component concentration of PTFE 60% by mass) as a fluorine resin Kao Co., Ltd.
  • a PTFE solution trade name PTFE 31-JR manufactured by Dupont Fluorochemicals Co., Ltd., non-volatile component concentration of PTFE 60% by mass
  • the fluorine resin-containing glass fiber cloth had a thickness of 1.044 mm, a mass of 935.4 g / m 2 , a loss on ignition of 7.3% by mass, and an air permeability of 14.3 cc / cm 2 / s.
  • Example 1 and Comparative Example 1 As apparent from the comparison of Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, and Example 3 and Comparative Example 3, a fluorocarbon resin-containing glass fiber cloth comprising a fluorocarbon resin and an organic titanium compound on glass fiber It was revealed that (Examples 1 to 3) can maintain excellent bending resistance even when thermally exposed to an ambient temperature exceeding 250 ° C. In addition, it was observed that in the fluorocarbon resin-containing glass fiber cloths of Examples 1 to 3, the fluorocarbon resin became a three-dimensional network and was present on the glass fiber after the thermal exposure.
  • the second bath treatment solution is a fluoroplastic, a PTFE solution (Mitsubishi / Dupont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of PTFE 60% by mass) 220 g / L, acetic acid (90% pure)
  • a glass fiber under the same conditions as in Example 1 except that it was obtained by mixing it so as to be 1.8 g / L and the remainder pure water (that is, using a treatment liquid not containing a silane coupling agent).
  • a fluorocarbon resin-containing glass fiber cloth containing the fluorocarbon resin and the organic titanium compound was obtained.
  • the fluorine resin-containing glass fiber cloth had a thickness of 0.885 mm, a mass of 936.2 g / m 2 , an ignition loss of 9.8 mass%, and an air permeability of 11.0 cc / cm 2 / s.
  • Example 5 220 g / L of a 1st bath processing solution containing a PTFE solution (Mitsubishi / Dupont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of PTFE 60 mass%) as a fluorine resin, and an organic titanium compound as di-i -Propoxy-bis (acetylacetonato) titanium (Ti [OCH (CH 3 ) 2 ] 2 [OCH (CH 3 ) CHCOCH 3 ] 2 ) in i-propanol solution (Nippon Soda Co., Ltd.
  • a PTFE solution Mitsubishi / Dupont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of PTFE 60 mass
  • an organic titanium compound as di-i -Propoxy-bis (acetylacetonato) titanium (Ti [OCH (CH 3 ) 2 ] 2 [OCH (CH 3
  • the fluororesin fiberglass cloth containing the fluororesin and the organic titanium compound on the glass fiber was obtained.
  • the fluorine resin-containing glass fiber cloth had a thickness of 0.885 mm, a mass of 934.4 g / m 2 , a loss on ignition of 10.0 mass%, and an air permeability of 10.6 cc / cm 2 / s.
  • Example 6 220 g / L of a 2nd bath processing solution, a PTFE solution (Mitsubishi / Dupont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of PTFE 60 mass%) as a fluorine resin, silane coupling agent (JNC stock 10 g / L of N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane / hydrochloride 40% by weight, acetic acid (90% pure), 1.
  • a PTFE solution Mitsubishi / Dupont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of PTFE 60 mass
  • silane coupling agent JNC stock 10 g / L of N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane / hydrochloride 40%
  • Example 7 220 g / L of a 2nd bath processing solution, a PTFE solution (Mitsubishi / Dupont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of PTFE 60 mass%) as a fluorine resin, silane coupling agent (JNC stock 10 g / L of N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane / hydrochloride 40% by weight, acetic acid (90% pure), 1.
  • a PTFE solution Mitsubishi / Dupont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of PTFE 60 mass
  • silane coupling agent JNC stock 10 g / L of N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane / hydrochloride 40%
  • the fluorine resin-containing glass fiber cloth had a thickness of 0.885 mm, a mass of 929.5 g / m 2 , a loss on ignition of 9.4% by mass, and an air permeability of 9.9 cc / cm 2 / s.
  • Example 1 compared with Example 4, the retention of folding endurance and tensile strength after heat exposure at an ambient temperature exceeding 250 ° C. was higher. That is, in addition to the fluorocarbon resin and the organic titanium compound, the glass fiber further includes one or more compounds selected from the group consisting of a silane coupling agent, a hydrolyzate thereof, and a dehydrated condensate of the hydrolyzate. It has been revealed that by this, the folding endurance and the tensile strength retention performance after heat exposure are further improved.
  • Example 5 since the retention of folding endurance after heat exposure at an ambient temperature exceeding 250 ° C. was excellent as in Example 1, even when the amount of the organotitanium compound was relatively large, It was confirmed that the folding endurance can be sufficiently maintained even after heat exposure.
  • Example 6 was superior to Example 1 in the retention of folding endurance after heat exposure at an ambient temperature of more than 250 ° C. That is, it was found that by further containing a silicone resin, the slipperiness between glass fibers (between filaments) was further improved, and as a result, the retention of folding endurance after heat exposure could be further improved.
  • Example 1 was somewhat superior to Example 7 in the retention of the folding endurance after heat exposure at an ambient temperature exceeding 250 ° C. On the other hand, in Example 7, since graphite was present even after heat exposure, it is easier to maintain maintenance of the dust removability in combination with the excellent retention of folding endurance. there were.
  • a double-twisted yarn comprising three additional twists so that the number of first twists is 4 times / 25 mm to make lower twist yarns and making the number of upper twists 3.8 times / 25 mm in the S direction
  • a bulky textured yarn (filament diameter 5.0 ⁇ m, count 287.5 tex) obtained by subjecting the raw material yarn to Taslan processing was used.
  • glass fiber fabric I got The mass of the glass fiber woven fabric was 807 g / m 2 .
  • the processing solution contains 220 g / L of a PTFE solution (Mitsubishi DuPont Fluorochemicals Co., Ltd., trade name PTFE 31-JR, non-volatile component concentration of 60 mass% of PTFE) as a fluorocarbon resin, and an organic titanium compound of di-i-propoxy.
  • An i-propanol solution of bis (acetylacetonato) titanium Ti [OCH (CH 3 ) 2 ] 2 [OCH (CH 3 ) CHCOCH 3 ] 2
  • T-50 purity 74.1
  • the above-mentioned characterized glass fiber fabric was impregnated in the first bath treatment solution, and the nip pressure was squeezed by a nip roll to 1.1 kgf / cm 2 and dried at 250 ° C. for 5 minutes. .
  • the treatment liquid is 220 g / L of a PTFE solution (Mitsubishi DuPont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of 60 mass% of PTFE) as a fluorine resin, a silane coupling agent (a product manufactured by JNC Co., Ltd.) Name: Silaace S 350, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane ⁇ Hydrochloride 40% by mass) 10 g / L, Acetic acid (90% pure) 1.8 g / L The remaining portion was obtained by mixing so as to be pure water.
  • a PTFE solution Mitsubishi DuPont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of 60 mass% of PTFE
  • silane coupling agent a product manufactured by JNC Co., Ltd.
  • a glass fiber fabric obtained by impregnating and drying the first bath treatment solution is impregnated into the second bath treatment solution, and the nip pressure is squeezed at 1.1 kgf / cm 2 with a nip roll, and the temperature is 250 ° C.
  • a fluorocarbon resin-containing glass fiber cloth containing a fluorocarbon resin and an organic titanium compound on glass fiber was obtained.
  • the fluorine resin-containing glass fiber cloth had a thickness of 0.839 mm, a weight of 899.1 g / m 2 , a loss on ignition of 10.2% by mass, and an air permeability of 7.0 cc / cm 2 / s.
  • a single yarn yarn (a filament diameter of 5.0 ⁇ m, a number of filaments of 400 with a twist number of once in the Z direction / 25 mm) of 3 glass materials whose glass composition is glass composition X described above is 3
  • the second twist was collected while twisting to make the number of twists once / 25 mm in the Z direction to make two lower twist yarns so that the number of upper twists was 3.8 times / 25 mm in the S direction.
  • Single twist yarn (filament diameter: 5.0 ⁇ m, number of filaments: 400) whose glass material constituting the glass fiber is the glass composition X below as a weft.
  • a double-twisted yarn comprising three additional twists so that the number of first twists is 4 times / 25 mm to make lower twist yarns and making the number of upper twists 3.8 times / 25 mm in the S direction
  • a bulky textured yarn (filament diameter 5.0 ⁇ m, count 287.5 tex) obtained by subjecting the raw material yarn to Taslan processing was used.
  • glass fiber fabric I got The mass of the glass fiber fabric was 813 g / m 2 .
  • the processing solution contains 50 g / L of a PTFE solution (Mitsubishi DuPont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of 60 mass% of PTFE) as a fluorine resin, and di-i-propoxy.
  • a PTFE solution Mitsubishi DuPont Fluorochemicals Co., Ltd. trade name PTFE 31-JR, non-volatile component concentration of 60 mass% of PTFE
  • An i-propanol solution of bis (acetylacetonato) titanium Ti [OCH (CH 3 ) 2 ] 2 [OCH (CH 3 ) CHCOCH 3 ] 2
  • T-50 purity 74.1.
  • the above-mentioned characterized glass fiber fabric is impregnated in the above processing solution, squeezed with a nip roll at a nip pressure of 1.1 kgf / cm 2 , dried at a temperature of 250 ° C. for 10 minutes, and on glass fiber.
  • a fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound was obtained.
  • the fluorine resin-containing glass fiber cloth had a thickness of 0.844 mm, a mass of 825.3 g / m 2 , a loss on ignition of 1.4% by mass, and an air permeability of 7.8 cc / cm 2 / s.
  • Example 8 compared with Example 1, the retention of the folding endurance after heat exposure at an ambient temperature exceeding 250 ° C. was higher.
  • Example 9 the retention of folding endurance after heat exposure at an ambient temperature exceeding 250 ° C. was higher. That is, the content of SiO 2 is 60.0 to 64.0% by mass, the content of Al 2 O 3 is 18.0 to 22.0% by mass, and the content of MgO is 14 to 18 mass%, and the total of the content of SiO 2 , the content of Al 2 O 3 and the content of MgO is 94 mass% or more, so that the atmosphere temperature exceeds 250 ° C. It has become clear that even after heat exposure in the above, it is possible to more easily provide excellent folding endurance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Filtering Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Woven Fabrics (AREA)

Abstract

L'invention a pour objet de fournir une toile de fibres de verre comprenant une résine fluorée qui peut présenter une excellente résistance au pliage, y compris après exposition à la chaleur à une température ambiante dépassant 250°C. Plus précisément, l'invention concerne une toile de fibres de verre comprenant une résine fluorée qui contient une résine fluorée et un composé titane organique sur des fibres de verre, et qui peut présenter une excellente résistance au pliage, y compris après exposition à la chaleur à une température ambiante dépassant 250°C.
PCT/JP2018/030219 2017-08-15 2018-08-13 Toile de fibres de verre comprenant une résine fluorée, et filtre de captage de poussière contenant celle-ci WO2019035447A1 (fr)

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JPS5210332A (en) * 1975-07-15 1977-01-26 Daikin Ind Ltd Fluoro-resin coating composition
JP2011202034A (ja) * 2010-03-25 2011-10-13 Nippon Futsuso Kogyo Kk 塗料組成物、該塗料組成物を用いた被膜製造方法および被膜体
CN104436861A (zh) * 2014-11-17 2015-03-25 营口海硕环保滤材有限公司 高精度涂层滤料的制作方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114575165A (zh) * 2022-03-08 2022-06-03 江苏博诚新科技材料有限公司 一种高柔性耐折叠聚四氟乙烯玻璃纤维材料的制备方法

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