JPWO2019035447A1 - Fluororesin-containing glass fiber cloth and a dust collecting filter containing the fluororesin-containing glass fiber cloth - Google Patents

Abstract

An object of the present invention is to provide a fluororesin-containing glass fiber cloth capable of having excellent folding resistance even after heat exposure at an atmospheric temperature exceeding 250 ° C. A fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound on the glass fiber can have excellent folding resistance even after heat exposure at an atmospheric temperature exceeding 250 ° C.

Description

The present invention relates to a fluororesin-containing glass fiber cloth. More specifically, the present invention relates to a fluororesin-containing glass fiber cloth useful as a dust collecting filter that is required to have folding resistance such as a bag filter. The present invention also relates to a dust collecting filter containing the fluororesin-containing glass fiber cloth.

A cloth mainly made of glass fiber as a filter material used in a dust collector for capturing dust (fly ash) in exhaust gas generated in municipal waste incinerators, industrial waste incinerators, coal-fired boilers, metal melting furnaces, etc. Is used.

Generally, a bag filter method is adopted for filtering exhaust gas from an incinerator of municipal waste. Specifically, in the bag filter method, a cloth formed of glass fiber is used to sew a bug (for example, a cylindrical shape having a diameter of 120 to 170 mm and a length of 4 to 7 m), and a large number of the bugs are collected in a dust collector. This is installed. Then, dust-containing exhaust gas (usually, the gas temperature is 130 to 280 ° C.) flows in from the outer surface of the bug, dust in the gas is collected on the outer surface of the bug, and only the exhaust gas flows out from the inner surface of the bug. To go. In this case, the pressure loss of the bug increases with the lapse of the operating time of the incinerator, which adversely affects the filtration performance. Therefore, it is necessary to wipe off the dust accumulated on the outer surface of the bug at any time. As a method of removing dust, a vibration type, a backwash type, and a pulse type are generally used. For example, in the case of the pulse type, compressed air is instantaneously (for example, about 0.1 to 0.3 seconds) injected into the inside of the bug from the nozzle at the top of the bug to wipe off the dust on the outer surface of the bug. The injection air pressure in this case is as high as 5 to 7 kg / square cm, for example, and is injected every fixed time (for example, 1 to 3 min). During the removal of these dusts, the cloth made of glass fibers constituting the bag filter is repeatedly bent. Therefore, the cloth is required to have resistance to repeated bending, that is, folding resistance.

As the bag filter cloth, a glass fiber woven fabric made of a glass fiber bundle of acid resistant glass and a resin coating layer for coating the glass fiber woven fabric are provided. 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) are contained as components, and each component when the total mass of the acid-resistant glass is 100% by mass. The contents are 55 to 60% by mass of SiO ₂ , 10 to 14% by mass of Al ₂ O ₃ , 20 to 28% by mass of CaO and MgO in total, 1% by mass or less of B ₂ O ₃ and R ₂ O. Is 1% by mass or less, and a glass fiber woven fabric for a bag filter is known in which the resin coating layer is formed by coating with a resin composition containing an ethylene tetrafluoride resin, graphite and a silicone resin. (See, for example, Patent Document 1). According to the woven fabric, a glass fiber woven fabric for a bag filter, which is excellent in acid resistance and heat resistance and whose tensile strength and folding resistance are not easily deteriorated even in a high temperature (250 ° C. in the example) and acidic environment, is provided. Is said to be possible.

Japanese Unexamined Patent Publication No. 2009-233481

The glass fiber woven fabric of Patent Document 1 uses a specific acid-resistant glass as the glass material constituting the glass fiber, and has excellent folding resistance to some extent in a high temperature environment of about 250 ° C. However, as examined by the present inventor, when the glass fiber woven fabric is heat-exposed to an atmospheric temperature exceeding 250 ° C., for example, 350 ° C., the fold resistance possessed before the heat exposure is significantly impaired. I learned that there is a problem of getting rid of it. It has also been found that the problem becomes particularly remarkable when 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 or the like.

Therefore, an object of the present invention is to provide a fluororesin-containing glass fiber cloth capable of solving the above-mentioned problems and having excellent folding resistance even after heat exposure at an atmospheric temperature exceeding 250 ° C.

In Patent Document 1 described above, it is stated that folding resistance in a high temperature environment can be imparted by forming a resin coating layer containing a silicone resin. Specifically, in Patent Document 1, it is shown that in Comparative Example 2 in which a resin coating layer containing no silicone resin is adopted, the folding resistance in a high temperature environment is inferior to that in other Examples. However, Patent Document 1 does not assume heat exposure at an ambient temperature exceeding 250 ° C. under a high temperature environment. Then, when the glass fiber woven fabric disclosed in Patent Document 1 is exposed to an atmospheric temperature exceeding 250 ° C., the present inventors denature the silicone resin by combustion, oxidation, or the like, resulting in heat. It was speculated that the folding resistance that had been possessed before the exposure would be significantly impaired.

As a result of repeated studies to solve the above problems, the present inventors have found that the treatment agent for glass fiber cloth is not a silicone resin, which is said to contribute to folding resistance in a high temperature environment in Patent Document 1. It has been found that by using a fluororesin and an organic titanium compound as essential components, it is possible to provide excellent folding resistance even after heat exposure at an atmospheric temperature exceeding 250 ° C. The present invention is an invention completed by further studying based on these findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. A fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound on the glass fiber.
Item 2. Item 2. The fluororesin-containing glass fiber cloth according to Item 1, further comprising a silane coupling agent and / or a reaction product thereof on the glass fiber.
Item 3. Item 2. 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 2. The fluororesin-containing glass fiber cloth according to Item 2 or 3, wherein the silane coupling agent and / or a reaction product thereof is present in the fluororesin.
Item 5. Item 4. The fluororesin-containing glass fiber cloth according to any one of Items 1 to 4, further comprising graphite and / or silicone resin.
Item 6. Item 2. The fluororesin-containing glass fiber cloth according to any one of Items 1 to 5, which is used for a dust collection filter.
Item 7. A dust collecting filter comprising the fluororesin-containing glass fiber cloth according to any one of Items 1 to 5.

According to the fluororesin-containing glass fiber cloth of the present invention, by including the fluororesin and the organic titanium compound on the glass fiber, excellent folding resistance can be provided even after heat exposure at an atmospheric temperature exceeding 250 ° C. Therefore, the fluororesin-containing glass fiber cloth of the present invention is suitable for use as a dust collecting filter that is required to have folding resistance in a high temperature environment such as a bag filter.

1. 1. Fluororesin-containing glass fiber cloth The fluororesin-containing glass fiber cloth of the present invention is characterized by containing a fluororesin and an organic titanium compound on the glass fiber. Hereinafter, the present invention will be described in detail.

(Glass fiber cloth)
The glass material constituting the glass fiber is not particularly limited, and a known glass material can be used. Specific examples of the glass material include non-alkali glass (E glass), acid-resistant alkali-containing glass (C glass), high-strength and high-elasticity glass (S glass, T glass, etc.), and alkali-resistant glass (AR glass). ) Etc. can be mentioned. Among these glass materials, the glass composition constituting the glass fiber is made of SiO ₂ from the viewpoint of providing excellent folding resistance and excellent tensile strength after heat exposure at an atmospheric temperature exceeding 250 ° C. The content is 64.0 to 66.0% by mass, the content of Al ₂ O ₃ is 24.0 to 26.0% by mass, the content of MgO is 9.0 to 11.0%, and the content of other components. Is more preferably 3% by mass or less (including 0% by mass). Further, in the present invention, the glass composition constituting the glass fiber has, for example, a SiO ₂ content of 60.0 to 66.0 mass% and an Al ₂ O ₃ content of 18.0 to 26.0 mass. A glass composition containing 8.0 to 20.0% of MgO can be obtained. Further, in the present invention, the glass composition constituting the glass fiber has a SiO ₂ content of 60.0 to 66.0 mass% and an Al ₂ O ₃ content of 18.0 to 26.0 mass%. the content of MgO is a glass composition comprising from 8.0 to 20.0% (the content of SiO ₂ is 64.0 to 66.0 wt%, the content of Al ₂ O ₃ is from 24.0 to 26.0 Glass compositions having a mass%, MgO content of 9.0 to 11.0%, and other component content of 3% by mass or less (including 0% by mass) can also be used. Further, the glass composition constituting the glass fiber has a SiO ₂ content of 60.0 to 64 from the viewpoint of making it easier to provide excellent folding resistance even after heat exposure at an atmospheric temperature exceeding 250 ° C. 0.0% by mass, Al ₂ O ₃ content 18.0 to 22.0 mass%, Mg O content 14 to 18 mass%, SiO ₂ content, Al ₂ O ₃ content A glass composition having a total content of MgO and MgO of 94% by mass or more can be obtained. From the same viewpoint, 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%. , MgO content 14-18% by mass, Fe ₂ O ₃ content 0.05-0.5% by mass, CaO content 0.05-0.5% 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 composition can be obtained, and in this case, the total content of SiO ₂ , Al ₂ O ₃ and Mg O is preferably 94% by mass or more. On the other hand, since the fluororesin-containing glass fiber cloth of the present invention contains a fluororesin and an organic titanium compound on the glass fiber, even when the glass material is general-purpose E glass, the atmospheric temperature exceeds 250 ° C. Even after heat exposure in the glass, it becomes possible to provide excellent folding resistance. Specifically, the composition of the 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, and B ₂ Examples thereof include glass compositions in which O ₃ is 5 to 13% by mass and Na ₂ O ₃ and K ₂ O ₃ are 0 to 1% by mass.

In the present invention, the glass fiber may be either a long fiber or a short fiber. Long fibers are preferable from the viewpoint of further improving mechanical properties such as tensile strength of the cloth. Examples of the long fibers include a monofilament yarn composed of one continuous single fiber and a multifilament yarn composed of a plurality of continuous single fibers, and are resistant to breakage when exposed to heat under conditions of an atmospheric temperature exceeding 250 ° C. A multifilament yarn is preferable from the viewpoint of making the property more excellent.

In the case of the above-mentioned long fibers, the form of the cloth of the present invention may be a woven fabric, a knitted fabric, a non-woven fabric (including felt), or a combination thereof. In the case of a woven fabric, it is preferable that the warp is a yarn which is a multifilament yarn and the weft is a bulky processed yarn (bulky processed yarn) which is a multifilament yarn from the viewpoint of further enhancing the mechanical properties and the dust collecting property. Examples of the yarn include single yarn and twisted yarn. From the viewpoint of further improving the folding resistance after heat exposure at an atmospheric temperature exceeding 250 ° C., a twisted yarn is preferable as the yarn. The structure of the combined twisted yarn is not particularly limited, but for example, from the viewpoint of further improving the folding resistance after heat exposure at an atmospheric temperature exceeding 250 ° C., the single yarn yarn 2 twisted in the S direction or the Z direction. It is mentioned that ~ 8 yarns (preferably 2-4 yarns) are twisted yarns twisted in the direction opposite to the twisting direction of the yarn. In the case of a combined twisted yarn, the number of twists (number of upper twists) of the combined twisted yarn is preferably 2 to 5 times / 25 mm, more preferably 3.0 to 4.5 times / 25 mm.

When the warp yarn is a yarn and the weft yarn is a bulky processed yarn, the filament diameter (single fiber diameter) of the yarn is, for example, 4 to 9 μm. From the viewpoint of further improving the folding resistance after heat exposure at an atmospheric temperature exceeding 250 ° C., the filament diameter of the yarn is more preferably 4 to 7 μm, particularly preferably 5 to 7 μm. On the other hand, in the above case, the filament diameter (single fiber diameter) of the bulky processed yarn is, for example, 4 to 9 μm. From the viewpoint of further improving the folding resistance after heat exposure at an atmospheric temperature exceeding 250 ° C., the filament diameter of the bulky processed yarn is more preferably 4 to 7 μm, particularly preferably 5 to 7 μm.

In the present invention, when the glass fiber cloth is a woven fabric in which warp yarns are yarns and weft yarns are bulky processed yarns, the yarn count includes, for example, 30 to 600 tex, and has mechanical properties and dust collection properties. From the viewpoint of further enhancing, 50 to 450 tex is more preferable. From the viewpoint of further improving the breakage resistance before and after heat exposure while further improving the mechanical properties and dust collection property, 100 to 200 tex is more preferable as the yarn count. On the other hand, in the above case, the count of the bulky processed yarn is, for example, 30 to 600 tex, and 50 to 500 tex is more preferable from the viewpoint of further enhancing the mechanical properties and the dust collecting property. From the viewpoint of further improving the breakage resistance before and after heat exposure while further improving the mechanical properties and dust collecting property, 200 to 400 tex is more preferable as the count of the bulky processed yarn. Further, when the cloth is a woven fabric in which the warp yarn is yarn and the weft yarn is bulky processed yarn, the ratio of the warp yarn to the weft yarn count (warp yarn count / weft yarn count) has even better folding resistance. From the viewpoint of further improving the effect of reducing the decrease in folding resistance after heat exposure at an atmospheric temperature exceeding 250 ° C., 1/4 to 1/1 is preferable, and 2/5 to 1/2. Is more preferable.

In the present invention, when the glass fiber cloth is a woven fabric in which the warp yarn is a yarn and the weft yarn is a bulky processed yarn or a hybrid twisted yarn of the bulky processed yarn and the yarn, the weaving structure is not limited, and for example, plain weave and satin weave. , Twill weave, satin weave, ridge weave, double weave (warp double weave, weft double weave, warp and weft double weave) and the like. A double woven structure is preferable, and a weft double woven is more preferable, from the viewpoint of further improving the dust collecting property while further improving the folding resistance before and after heat exposure. In the glass fiber cloth used in the present invention, the weaving density is not particularly limited. For example, when the glass fiber cloth is a woven fabric in which the warp yarn is a yarn and the weft yarn is a bulky processed yarn, the warp yarn (yarn) is 20. ~ 80/25 mm is preferable, and 40 to 60 is more preferable. The weft (bulky yarn or) is preferably 20 to 80 yarns / 25 mm, more preferably 30 to 60 yarns.

(Excluding components other than the glass fiber (fluorine resin).) Fiberglass cloth used in the present invention as mass (g / m ²⁾ of, but not particularly limited, for example, include 500-1500 g / m ² , 700 to 1100 g / m ² is preferable.

Further, in the present invention, the thickness (mm) of the glass fiber cloth (excluding components other than glass fiber (fluororesin, etc.)) is not particularly limited, and examples thereof include 0.3 to 1.5 mm. , 0.6 to 1.2 mm is preferable.

(Fluororesin)
The fluororesin-containing glass fiber cloth of the present invention contains a fluororesin on the glass fiber. The fluororesin plays a role of improving the flexibility of the fluororesin-containing glass fiber cloth of the present invention and providing the cloth with excellent folding resistance even after heat exposure at an atmospheric temperature exceeding 250 ° C.

In the present invention, the fluororesin is a polymer (homogeneous polymer or copolymer) having a repeating unit derived from at least one fluorine-containing monomer. Examples of the fluororesin include polyvinylidene fluoride (PVDF), vinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), and tetrafluoroethylene / perfluoroalkyl ether copolymer (PFA). ), Tetrafluoroethylene / hexafluoropropylene copolymer (FEP), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoroethylene / hexafluoropropylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer. Combined, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / pentafluoropropylene copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), vinylidene fluoride / pentafluoropropylene / Examples thereof include tetrafluoroethylene copolymer, vinylidene fluoride / perfluoroalkyl vinyl ether / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE), vinylidene fluoride / chlorotrifluoroethylene copolymer. .. These fluororesins may be used alone or in combination of two or more.

Among these fluororesins, when the fluororesin-containing glass fiber cloth of the present invention is used as a bug, the viewpoint of making it easier to sew by further reducing the coefficient of dynamic friction with the needle and further improving the needle passability. Therefore, a fluororesin having no side chain or branch in the molecular structure is preferable, and PTFE is a preferable example.

In the fluororesin-containing glass fiber cloth of the present invention, the ratio of the fluororesin to the total amount of the non-volatile components adhered to the glass fiber is, for example, the fluororesin per 100 parts by mass of the total amount of the non-volatile components adhered to the glass fiber. Examples thereof include 30 to 98 parts by mass, preferably 50 to 98 parts by mass. In the present specification, the "nonvolatile component" refers to an absolute dry component when a constant amount is reached by heat-treating at 120 ° C. under normal pressure to remove a solvent or the like. Fluororesin, organic titanium compounds described later, silane coupling agents and their reactants,
Silicone resin, graphite, etc. correspond to non-volatile components.

(Organic titanium compound)
The fluororesin-containing glass fiber cloth of the present invention contains an organic titanium compound on the glass fiber. The organic titanium compound functions as the above-mentioned fluororesin modifier, and has excellent folding resistance to the fluororesin-containing glass fiber cloth of the present invention even after heat exposure at an atmospheric temperature exceeding 250 ° C. Play a role in

In the present invention, 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 via an oxygen atom or a nitrogen atom. Examples of the organic titanium compound include an alkoxide-based organic titanium compound, a chelate-based organic titanium compound, and an acylate-based organic titanium compound, and a chelate-based organic titanium compound is preferable.

The chelate-based organic titanium compound is a chelate compound in which a chelate ligand coordinates with a titanium atom to form a chelate ring. Examples of the chelating ligand constituting the chelate-based organic titanium compound include hydroxycarboxylic acids having at least one hydroxyl group and at least one carboxyl group in the molecule (for example, citric acid, lactic acid, malic acid, tartrate). Or glycolic acid, etc.), β-diketones (eg, acetylacetone, 3-phenylacetylacetone, etc.), alkanolamines (eg, triethanolamine, etc.) and the like. Among the chelate-based organic titanium compounds, an alkoxy group, preferably a C1 to 6 alkoxy group (for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group and the like) is contained as a chelate ligand. Those are more preferably mentioned.

In the present invention, specific examples of the organic titanium compound include titanium tetraisopropoxide (Ti (O-i-C ₃ H ₇ ) ₄ ) and titanium tetranormal butoxide (Ti (On-C ₄ H _9). ) ₄ ), Titanium Butoxide Dimer ((n-C ₄ H ₉ O) ₃ Ti-O-Ti (On-C ₄ H ₉ ) ₃ ), Titanium Tetra-2-ethylhexoxide (Ti (OC ₈₎ H ₁₇ ) ₄ , Titanium Diisopropoxybis (Acetyl Acetate) (Ti (O-i-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 (Ethylacetacetate) (Ti (O-i-C ₃ H ₇ ) ₂ (C ₆ H ₉ O ₃ ) ₂ ), Titanium Diisopropoxybis (Triethanol Aminoate) (Ti (O-i-C _{3) H 7) 2 (C 6 H} 14 O 3 N) 2), titanium lactate ammonium salt _{(Ti (OH) 2 [OCH} (CH 3) COO -)] 2 (NH 4 +) 2), titanium lactate ((Ti _{(OH) 2 [OCH (CH} 3) COO -)] 2), polyhydroxy titanium stearate _{(i-C 3 H 7 O} [Ti (OH) (OCOC 17 H 35) O] n-i-C 3 H ₇ ), Titanium-i-propoxyoctylene glycolate, di-i-propoxybis (acetylacetonato) titanium (Ti [OCH (CH ₃ ) ₂ ] ₂ ] ₂ [OC (CH ₃ ) CHCOCH ₃ ] ₂ ), propane Dioxytitanium bis (ethylacetate acetate), i-C ₃ H ₇ O [Ti (O-i-C ₃ H ₇ ) ₂ O] _N- i-C ₃ H ₇ polymer, i-C ₄ H ₉ O [Ti (O-i-C ₄ H ₉ ) ₂ O] Polymer represented by _n- i-C ₄ H ₉ , tri-n-butoxytitanium monostearate, di-i-propoxytitanium disstearate , Titanium stearate, di-i-propoxytitanium diisostearate, (2-n-butoxycarbonylbenzo) Iloxy) Tributoxy Titanium, Di-n-Butoxy Bis (Triethanol Aminato) Titanium (Ti (On-C ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH) ₂ ] ₂ , Examples thereof include titanium lactate monoammonium salts, hydrolysates thereof, and dehydration condensates of the hydrolysates.

These organic titanium compounds may be used alone or in combination of two or more.

Among these organic titanium compounds, preferably di-i-propoxybis (acetylacetonato) titanium (Ti [OCH (CH ₃ ) ₂ ] ₂ [OC (CH ₃ ) CHCOCH ₃ ] ₂ ), its hydrolysis. Examples thereof include a product and a dehydrated condensate of the hydrolyzate.

In general, it is known that an organic titanium compound exhibits hydrolyzability, and in the present invention, the organic titanium compound may exist as a hydrolyzate on glass fibers. Further, in the present invention, the organic titanium compound may exist as a reaction product that has reacted with a fluororesin or other components on the glass fiber.

As the above-mentioned organic titanium compound, a commercially available product can be used. Commercially available products include, for example, Organics TA-10, TA-22, TA-25, TA-30, TC-100, TC-401, TC-200, TC-750, TC-400, TC-300, TC. -310, TC-315, TPHS (all manufactured by Matsumoto Fine Chemical Co., Ltd., product name), and A-1, B-1, TOT, TOG, T-50, T-60, A-10, B-2. , B-4, B-7, B-10, TBSTA, DPSTA-25, S-151, S-152, S-181, TAT, TLA-A-50 (all manufactured by Nippon Soda Co., Ltd., product name) Can be mentioned.

In the present invention, by containing the fluororesin and the organic titanium compound on the glass fiber, as an action mechanism capable of providing excellent folding resistance even after heat exposure at an atmospheric temperature exceeding 250 ° C. Is not always clear, but can be inferred as follows.

As a result of studies by the present inventors, it was found that the organic titanium compound has a function of improving the wettability of the fluororesin with respect to the glass fiber. Therefore, it is considered that the fluororesin-containing glass fiber cloth of the present invention contains an organic titanium compound in addition to the fluororesin to improve the impregnation property of the fluororesin into the glass fiber. Further, when the present inventors heat-heated a fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound on the glass fiber at 350 ° C., the fluororesin is three-dimensionally formed on the glass fiber. It was observed that it became a mesh and remained so as to bridge the glass fibers. From these, the result is that the fluororesin 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 fluororesin is also present along the skeleton. It is presumed that the fluororesin and the organic titanium compound exist in a three-dimensional network on the glass fiber. The flexible fluororesin exists in a three-dimensional network while showing good impregnation between the glass fibers, thereby imparting more excellent flexibility to the glass fiber cloth, and the fluororesin can be used. As a result of further improving the heat resistance of the fluororesin by being present along the skeleton of the organic titanium compound having excellent heat resistance, it is possible to have excellent folding resistance even after heat exposure at an atmospheric temperature exceeding 250 ° C. Guess.

In the fluororesin-containing glass fiber cloth of the present invention, the organic titanium compound is present in the fluororesin from the viewpoint of facilitating the modification of the fluororesin (that is, it covers at least a part of the surface of the glass fiber). It is preferable that the fluororesin film is provided, and the fluororesin film contains an organic titanium compound and / or a reaction product of the organic titanium compound). To do so, a treatment liquid in which a fluororesin and an organic titanium compound are mixed in advance may be prepared, the glass fiber cloth may be impregnated with the treatment liquid, and then dried.

In the fluororesin-containing glass fiber cloth of the present invention, the ratio of the fluororesin to the organic titanium compound to be adhered to the glass fiber is not particularly limited, but for example, 1 to 1 to 100 parts by mass of the fluororesin. Examples thereof include 50 parts by mass, preferably 2 to 40 parts by mass.

(Silane coupling agent)
The fluororesin-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 fluororesin and the organic titanium compound. When the glass fiber contains a silane coupling agent and / or a reaction product thereof, it is possible to further improve the folding resistance after heat exposure at an atmospheric temperature exceeding 250 ° C.

In the present invention, the silane coupling agent is, for example, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-glycidoxyethoxytrimethoxysilane, 2-. Glycydoxyethyl triethoxysilane, 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 -Aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- Acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanuppropyltriethoxysilane, N- [2- (vinylbenzylamino) ethyl ] -3-Aminopropyltrimethoxysilane, hydrochloride, and the like.

These silane coupling agents may be used alone or in combination of two or more.

Among these silane coupling agents, aminosilane coupling agents having an amino group are preferable, and 3-aminopropyltriethoxysilane and N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane hydrochloride are preferable. Is more preferable, and N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane hydrochloride is particularly preferable.

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. When a silane coupling agent is allowed to coexist on the glass fiber together with the fluororesin and the organic titanium compound, the silane coupling agent is hydrolyzed and exists as a hydrolyzate, or exists as a dehydration condensate of the hydrolyzate. I have something to do. When a silane coupling agent is allowed to coexist on the glass fiber together with the fluororesin and the organic titanium compound, the functional group of the silane coupling agent may exist in a state of being bonded to the glass fiber, the organic titanium compound or the like.

In the fluororesin-containing glass fiber cloth of the present invention, the silane coupling agent and / or its reactant is present in the fluororesin from the viewpoint of facilitating the modification of the fluororesin (that is, the surface of the glass fiber). It is preferable to have a fluororesin film covering at least a part of the above, and the fluororesin film contains a silane coupling agent and / or a reaction product of the silane coupling agent). In order to do so, a treatment liquid in which the fluororesin and the silane coupling agent and / or its reaction product are mixed in advance may be prepared, the glass fiber cloth may be impregnated with the treatment liquid, and then dried.

In the case of adhering a silane coupling agent and / or its reactant on the glass fiber in the fluororesin-containing glass fiber cloth of the present invention, the ratio of the fluororesin to the silane coupling agent and / or its reactant is particularly high. Although not limited, for example, 1 to 20 parts by mass of the silane coupling agent and / or its reaction product may be mentioned with respect to 100 parts by mass of the fluororesin.

(Other ingredients)
The fluororesin-containing glass fiber cloth of the present invention can further contain a component other than the above-mentioned components on the glass fiber.

An example of the above other components is a silicone resin. In the fluororesin-containing glass fiber cloth of the present invention, the needle-through property is more likely to be improved by containing the silicone resin on the glass fiber. Further, when the silicone resin is contained in the glass fiber, the slipperiness between the glass fibers (between the filaments) is further improved, and the folding resistance after heat exposure at an atmospheric temperature exceeding 250 ° C. is further improved. You can also do it.

In the fluororesin-containing glass fiber cloth of the present invention, when the silicone resin is adhered onto the glass fiber, the ratio of the fluororesin to the silicone resin is not particularly limited, but for example, the silicone resin is based on 100 parts by mass of the fluororesin. Is 1 to 20 parts by mass, preferably 1 to 10 parts by mass.

On the other hand, the fluororesin-containing glass fiber cloth of the present invention may be substantially free of silicone resin. As will be described later, the fluororesin-containing glass fiber cloth of the present invention can further contain a catalyst for decomposing gaseous dioxins, NOx and the like to purify the gas. When the fluororesin-containing glass fiber cloth of the present invention contains the catalyst, as a method for supporting the catalyst, an aqueous slurry in which the catalyst is dispersed is impregnated with the fluororesin-containing glass fiber cloth, and the catalyst is made of fluororesin-containing glass. Examples thereof include a method of supporting the material on a fiberglass cloth. In this method, when the fluororesin-containing glass fiber cloth of the present invention does not contain a silicone resin, the water-wetting property of the fluororesin-containing glass fiber cloth of the present invention is further improved, and the water-based slurry wettability in which the catalyst is dispersed is improved. As a result, it becomes easy to carry the catalyst. Therefore, the fluororesin-containing glass fiber cloth of the present invention may be substantially free of silicone resin. Here, "substantially free of silicone resin" means a content of the fluororesin-containing glass fiber cloth to the extent that the water wettability does not decrease. For example, the silicone resin is 0 with respect to 100 parts by mass of the fluororesin. ~ 0.5 parts by mass is mentioned, 0 to 0.3 parts by mass is preferably mentioned, and 0 parts by mass is more preferably mentioned. In the present invention, the silicone resin also includes those obtained by drying silicone oil and silicone emulsion.

Further, as one of the examples of the above other components, graphite can be mentioned. By further containing graphite on the glass fiber, the fluororesin-containing glass fiber cloth of the present invention makes it easier to maintain the dust-removing property when continuously used as a bag filter at an atmospheric temperature exceeding 250 ° C. Become.

In the fluororesin-containing glass fiber cloth of the present invention, when graphite is adhered onto the glass fiber, the ratio of the fluororesin to the graphite is not particularly limited, but for example, graphite is 1 to 100 parts by mass of the fluororesin. Examples thereof include 30 parts by mass, preferably 1 to 25 parts by mass.

Further, the fluororesin-containing glass fiber cloth of the present invention may not contain graphite.

Further, as one of the examples of the above other components, it is possible to include a catalyst for decomposing gaseous dioxins, NOx and the like to purify the gas. Examples of the catalyst include known ones, and examples thereof include vanadium pentoxide and the like. Further, a known carrier for supporting the catalyst can also be used.

In addition, as an example of the above other components, other resins other than the wet penetrant, the surfactant, and the fluorine (for example, no side chains and branches in the molecular structure) that further improve the impregnation property of the fluororesin are not used. Thermoplastic resins such as vinyl chloride resin, polyphenylene sulfide resin, nylon 6 resin, polyacetal resin, polyethylene resin, and polytetrafluoroethylene are preferable), pigments such as carbon black, mica, and carboxymethyl cellulose. it can.

(Ignition loss)
The ignition loss (%) 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 ignition loss in the fluororesin-containing glass fiber cloth of the present invention roughly matches the total amount of organic components such as fluororesin adhering to the glass fiber. In the present specification, "Ignition weight loss" is a muffle set at 625 ° C. according to the method specified in "7.3.2 Ignition weight loss" of "JIS R 3420: 2013 Glass Fiber General Test Method". It is a value obtained by heating the furnace for 30 minutes and calculating the weight loss rate.

(mass)
The mass of the fluororesin-containing glass fiber fabrics of the present invention is not particularly limited, for example, 500-1500 g / m ² can be mentioned, 700~1100g / m ² may be preferably mentioned. In the present specification, the "mass of fluororesin-containing glass fiber cloth" is the method specified in "7.2 Mass of cloth and mat (mass)" of "JIS R 3420: 2013 General Test Method for Glass Fiber". It is a value measured and calculated according to the above.

(thickness)
The thickness (mm) of the fluororesin-containing glass fiber cloth of the present invention is not particularly limited, and examples thereof include 0.3 to 1.5 mm, preferably 0.6 to 1.2 mm. In the present specification, the "thickness of the fluororesin-containing glass fiber cloth" is in accordance with the method A specified in "7.10 cloth thickness" of the "JIS R 3420: 2013 general glass fiber test method". It is a value obtained by measuring up to a digit of 0.001 mm (1 μm) using a micrometer and calculating the average value of the thicknesses at five locations.

(Air volume)
The amount of 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 when used as a bag filter. Preferred are 5 to 15 cm ³ · cm ⁻² · s ^-1 . In the present specification, the "ventilation amount of the fluororesin-containing glass fiber cloth" is a Frazier type test according to the method specified in "7.13 Breathability" of "JIS R 3420: 2013 Glass Fiber General Test Method". It is a value measured and calculated using a machine.

(Fold resistance)
By containing the fluororesin and the organic titanium compound on the glass fiber, the fluororesin-containing glass fiber cloth of the present invention can have excellent folding resistance even after heat exposure at an atmospheric temperature exceeding 250 ° C. .. As a preferable example of the folding resistance of the fluororesin-containing glass fiber cloth of the present invention, the retention rate of the number of folding resistances after heat exposure at 350 ° C., which is obtained by the following method, is preferably 50% or more in the warp direction. Is 100 to 400%, and the weft direction is 20% or more, preferably 40 to 200%.

Further, as a preferable example of the folding resistance of the fluororesin-containing glass fiber cloth of the present invention, the number of folding resistances after heat exposure at 350 ° C., which is obtained by the following method, is 20,000 times or more in the warp direction, preferably 80,000 times. The number of times or more is mentioned, and the weft direction is 8000 times or more, preferably 10000 times or more.

Further, as a preferable example of the folding resistance of the fluororesin-containing glass fiber cloth of the present invention, the number of folding resistances before heat exposure required by the following method is 20,000 times or more in the warp direction, preferably 40,000 times or more. The weft direction is 5000 times or more, preferably 20000 times or more.

<Method of measuring and calculating the number of folds before heat exposure, the number of folds after heat exposure at 350 ° C, and the retention rate of the number of folds after heat exposure at 350 ° C>
The length of the fluororesin-containing glass fiber cloth in the measurement direction (that is, the warp direction when measuring the folding resistance in the warp direction) is 32 cm, and the length in a direction different from the measurement direction (that is, the folding resistance in the warp direction). When measuring, cut out to a size of 23 cm (in the weft direction) and use it as a sample. The sample is heat-treated at a temperature of 350 ° C. for 24 hours to prepare a sample after heat exposure. Measure the number of folding resistances of the sample not exposed to heat (sample before heat exposure) and the sample after heat exposure. The number of fold resistance is based on the method specified in "7.14 Cloth Fold Resistance" of "JIS R 3420: 2013 Glass Fiber General Test Method", and a MIT fold resistance tester is used. Set the radius of curvature of the bent surface to 0.38 mm and the tension to 9.8 N, bend at a speed of 175 ± 10 per minute, and measure the number of folding resistances (number of reciprocating bends) until the sample is cut. For the number of folding resistances, four samples are prepared for one fluororesin-containing glass fiber cloth, and the average value thereof 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 formulas.
Retention rate of the number of folds in the warp direction (%) = {Average value of the number of folds in the warp of the sample after heat exposure (times) / Average value of the number of folds in the warp of the sample before heat exposure (times) )} × 100
Retention rate of fold resistance in the weft direction (%) = {Average value of fold resistance in the weft direction of the sample after heat exposure (times) / Average value of fold resistance in the weft direction of the sample before heat exposure (times) )} × 100

A preferred embodiment of the fluororesin-containing glass fiber cloth of the present invention is that it has excellent tensile strength even after heat exposure at an atmospheric temperature exceeding 250 ° C. As a preferable example of the tensile strength of the fluororesin-containing glass fiber cloth of the present invention, the retention rate of the tensile strength after heat exposure at 350 ° C. obtained by the following method is preferably 30% or more in the warp direction. Is 40% or more, and the weft direction is 50% or more, preferably 60% or more.

Further, as a preferable example of the tensile strength of the fluororesin-containing glass fiber cloth of the present invention, the tensile strength after heat exposure at 350 ° C. obtained by the following method is 900 (N / 25 mm) or more in the warp direction. , 1000 (N / 25 mm) or more is preferable, and the weft direction is 1000 (N / 25 mm) or more, preferably 1500 (N / 25 mm) or more.

Further, as a preferable example of the tensile strength of the fluororesin-containing glass fiber cloth of the present invention, the tensile strength before heat exposure obtained by the following method is 2000 (N / 25 mm) or more in the warp direction, preferably 3000. (N / 25 mm) or more, and the weft direction is 2000 (N / 25 mm) or more, preferably 2500 (N / 25 mm) or more.

<Measurement / calculation method of tensile strength before heat exposure, tensile strength after heat exposure at 350 ° C, and retention rate of tensile strength after heat exposure at 350 ° C>
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 heat exposure) and a sample after heat exposure. The tensile strength is 250 mm in length by the constant velocity load type tensile test method according to the method specified in "7.4 Tensile Strength" of "JIS R 3420: 2013 General Glass Fiber Test Method". The width is 25 mm, the grip interval is 150 mm, and the speed is 200 mm / min. For the tensile strength, 5 samples are prepared for one fluororesin-containing glass fiber cloth, and the average value thereof is calculated. The retention rate of tensile strength after heat exposure is calculated by the following formula.
Retention rate of tensile strength in the warp direction (%) = {Average value of tensile strength in the warp direction of the sample after heat exposure (N / 25 mm) / Average value of tensile strength in the warp direction of the sample before heat exposure (N / 25mm)} x 100
Retention rate of tensile strength in the weft direction (%) = {Average value of tensile strength in the weft direction of the sample after heat exposure (N / 25 mm) / Average value of tensile strength in the weft direction of the sample before heat exposure (N / 25mm)} x 100

(Production method)
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, a treatment liquid containing a fluororesin, an organic titanium compound, and other components used as necessary is prepared, and the treatment liquid is applied to the glass fiber cloth by a known method such as a spray method or a dip method. The fluororesin-containing glass fiber cloth of the present invention can be obtained by impregnating the constituent glass fibers, drying them, and removing the solvent.

Since the composition of the non-volatile component contained in the treatment liquid impregnated in the glass fiber cloth becomes the composition of the non-volatile component directly adhered on the glass fiber, the composition of the treatment liquid is the composition of the non-volatile component adhered on the glass fiber. It may be set appropriately according to.

Further, the step of impregnating the treatment liquid may be performed once or may be performed a plurality of times.

When the step of impregnating the above treatment liquid is performed a plurality of times, the treatment liquid having the same composition may be used in the multiple impregnation steps, or the treatment liquid having a different composition may be used for each impregnation step. .. For example, when the fluororesin, the organic titanium compound, the silane coupling agent and / or its reactant are adhered to the glass fiber by the two impregnation steps, the fluororesin and the organic titanium compound are contained in the first impregnation step. An impregnating solution can be used, and an impregnating solution containing a fluororesin and a silane coupling agent and / or a reaction product thereof can be used in the second impregnation step. When the step of impregnating the treatment liquid is performed a plurality of times, it is preferable to use a treatment liquid containing at least a fluororesin and an organic titanium compound in the first impregnation step.

The glass fiber cloth impregnated with the treatment liquid can be adjusted to a desired range by adjusting the drawing pressure with a roll press device to squeeze the glass fiber cloth.

(Use)
The fluororesin-containing glass fiber cloth of the present invention is used as a dust collector for capturing dust (fly ash) in exhaust gas generated in municipal waste incinerators, industrial waste incinerators, coal-fired boilers, metal melting furnaces, etc. It is preferably used as a filter material (dust collection filter material), and particularly preferably as a bag filter material. Since the fluororesin-containing glass fiber cloth of the present invention is excellent in folding resistance even when exposed to heat under conditions of an atmospheric temperature exceeding 250 ° C., for example, an atmospheric temperature of 350 ° C., the fluororesin-containing glass fiber cloth of the present invention is contained. If the glass fiber cloth is impregnated with a catalyst for purifying the above-mentioned gas and used in a temperature range of about 300 to 400 ° C or 300 to 350 ° C, which is a preferable temperature range for denitration, it is usually after the bag filter. It is not necessary to reheat the exhaust gas in the catalytic denitration process performed in the above process, and it is possible to greatly contribute to CO ₂ reduction.

2. 2. Glass Fiber Treatment Agent The present invention also provides a glass fiber treatment agent containing a fluororesin and an organic titanium compound. The glass fiber treatment agent can be used as a treatment liquid used in the production of the fluororesin-containing glass fiber cloth.

In addition to the fluororesin and the organic titanium compound, the glass fiber treatment agent may contain a silane coupling agent and / or a reaction product thereof, a silicone resin, graphite, and other components, if necessary. ..

The types, ratios, etc. of the components to be blended in the glass fiber treatment agent are as described in the column of "1. Fluororesin-containing glass fiber cloth".

3. 3. Resin Composition Further, the present invention provides a resin composition containing a fluororesin and an organic titanium compound. The resin composition is a film composition used as a film for coating at least a part of the glass fiber cloth in the fluororesin-containing glass fiber cloth.

In addition to the fluororesin and the organic titanium compound, the resin composition may contain a silane coupling agent and / or a reaction product thereof, a silicone resin, graphite, and other components, if necessary.

The types, ratios, etc. of the components contained in the resin composition are as described in the column of "1. Fluororesin-containing glass fiber cloth".

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

1. 1. Evaluation Method Each Example and Comparative Example were evaluated by the following methods.

(1) Composition and mass ratio (mass%) of the glass composition constituting the glass fiber
Alkaline melting-measured by ICP emission spectroscopy and atomic absorption spectroscopic method.

(2) Single fiber diameter (μm) of glass fiber
It was measured and calculated according to the A method (contour method) specified in "7.6 Single fiber diameter" of "JIS R 3420: 2013 General glass fiber test method".

(3) Count (tex) of glass yarn (yarn, bulky processed yarn, and twisted yarn of yarn and bulky processed yarn)
The measurement and calculation were performed according to the method specified in "7.1th" of "JIS R 3420: 2013 General Glass Fiber Test Method".

(4) Number of twists of yarn and synthetic twisted yarn (times / 25 mm)
The measurement and calculation were performed according to the method specified in "Number from 7.5" of "JIS R 3420: 2013 General Test Method for Glass Fiber".

(5) Weaving density of fluororesin-containing glass fiber cloth (book / 25 mm)
The weaving densities of the warp and weft in the fluororesin-containing glass fiber cloth were measured and calculated according to "7.9 density (weaving density)" of "JIS R 3420: 2013 General Test Method for Glass Fiber".

(6) Thickness of glass fiber cloth and fluororesin-containing glass fiber cloth (mm)
According to the method A specified in "7.10 cloth thickness" of "JIS R 3420: 2013 general glass fiber test method", measurements were made up to a digit of 0.001 mm (1 μm) using a micrometer. The measurement was performed at 5 points, and the average value of the 5 points was rounded according to JIS Z 8401 Rule B and calculated to the digit of 0.001 mm (1 μm).

(7) Mass of glass fiber cloth and fluororesin-containing glass fiber cloth (g / m ² )
Measurement and calculation were performed according to the method specified in "7.2 Mass of cloth and mat (mass)" of "JIS R 3420: 2013 General Test Method for Glass Fiber".

(8) Composition ratio of components adhering to glass fiber (parts by mass)
Since each composition ratio of the components adhering to the glass fiber is the same as the composition ratio of the non-volatile component in the treatment liquid used, it was determined from the ratio of the non-volatile component concentration in the treatment liquid used, and the fluororesin was set to 100. The mass part of the time was calculated. When the number of baths of the treatment liquid was 2, it was calculated as the ratio of the total concentration of each non-volatile component in the first bath and the second bath.

(9) Ignition loss (mass%)
Measured and calculated under the condition of heating in a muffle furnace set at 625 ° C. for 30 minutes according to the method specified in "7.3.2 Ignition loss" of "JIS R 3420: 2013 Glass Fiber General Test Method". ..

(10) Aeration amount of fluororesin-containing glass fiber cloth (cm ³・ cm ^-2・ s ^-1 )
Measurement and calculation were performed according to the method specified in "7.13 Breathability" of "JIS R 3420: 2013 General Test Method for Glass Fiber". As a measuring machine, a Frazier type tester (Frazier Permiyameter manufactured by Toyo Seiki Seisakusho Co., Ltd. (Frazier type air permeability tester model number: FP-2)) was used.

(11) Folding resistance of fluororesin-containing glass fiber cloth The length of the fluororesin-containing glass fiber cloth in the measurement direction (that is, the warp direction when measuring the folding resistance in the warp direction) is 32 cm, which is different from the measurement direction. A sample was cut out to a size of 23 cm in length in the direction (that is, in the weft direction when measuring the folding resistance in the warp direction). The sample was heat-treated in a high temp oven (trade name HP80 manufactured by Asahi Kagaku Co., Ltd.) at a temperature of 350 ° C. for 24 hours to prepare a sample after heat exposure. The number of folding resistances of the sample not exposed to heat (the sample before heat exposure) and the sample after heat exposure was determined. The number of fold resistance is based on the method specified in "7.14 Cloth Fold Resistance" of "JIS R 3420: 2013 Glass Fiber General Test Method", and the MIT fold resistance tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) The radius of curvature of the bending surface of the bending device is set to 0.38 mm and the tension is set to 9.8 N, and the product is bent at a speed of 175 ± 10 per minute to withstand the number of times the sample is cut. (Number of reciprocating bends) was measured. For the number of folding resistances, four samples were prepared for one fluororesin-containing glass fiber cloth, and the average value thereof was calculated. The retention rate of the number of folding resistances after heat exposure was calculated according to the above formula.

(12) Tensile strength of fluororesin-containing glass fiber cloth The fluororesin-containing glass fiber cloth is heat-treated in a high-temp oven (trade name HP80 manufactured by Asahi Kagaku Co., Ltd.) at a temperature of 350 ° C. for 24 hours, and a sample after heat exposure. Was prepared. The tensile strength (N / 25 mm) of the sample not exposed to heat (the sample before heat exposure) and the sample after heat exposure was determined. The tensile strength is 250 mm in length by the constant velocity load type tensile test method according to the method specified in "7.4 Tensile Strength" of "JIS R 3420: 2013 General Glass Fiber Test Method". The width was 25 mm, and the tensile tester was RTC-1310A manufactured by Orient Tech Co., Ltd., and the measurement and calculation were performed under the conditions of a grip interval of 150 mm and a speed of 200 mm / min. The retention rate of tensile strength after heat exposure was calculated according to the above formula.

2. 2. Fluororesin-containing glass fiber cloth production and evaluation results-1
(Example 1)
As warp yarns, DE75 1 / 2.8S manufactured by Unitika Co., Ltd. (two single yarns DE75 1/0 0.7Z twisted in the Z direction are additionally twisted in the Z direction, and the number of upper twists is 3 in the S direction. .8 times / 25 mm twisted yarn, filament diameter 6 μm, count 135 tex), as weft, Unitika Co., Ltd. trade name TDE300 (bulky processed yarn, filament diameter 6.0 μm, count 302.0 tex) Was used. The glass material constituting the glass fiber for both the warp and the weft was E glass.

Using the above warp and weft, weaving with a weft double weave structure (warp density 48/25 mm, weft density 48/25 mm), caramelizing (temperature 680 ° C, time 20 seconds), glass fiber woven fabric Got The mass of the glass fiber woven fabric was 841 g / m ² .

Next, the treatment liquid for the first bath was prepared. The treatment liquid contains 220 g / L of a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui DuPont Fluorochemical Co., Ltd., concentration of non-volatile component of PTFE is 60% by mass) as a fluororesin, and di-i-propoxy as an organic titanium compound. I-propanol solution of bis (acetylacetonato) titanium (Ti [OCH (CH ₃ ) ₂ ] ₂ [OCH (CH ₃ ) CHCOCH ₃ ] ₂ ) (trade name T-50 manufactured by Nippon Soda Co., Ltd., purity 74.1) It was obtained by mixing 14.3 g / L (mass%), 6 g / L of acetic acid (pure content 90%), and the balance of pure water.

The caramelized glass fiber woven fabric was impregnated in the treatment liquid of the first bath, squeezed with a nip roll at a nip pressure of 1.1 kgf / cm ² , and dried at a temperature of 250 ° C. for 5 minutes. ..

Next, the treatment liquid for the second bath was prepared. The treatment liquid contains 220 g / L of a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui-Dupont Fluorochemical Co., Ltd., 60% by mass of non-volatile component concentration of PTFE) as a fluororesin, and a silane coupling agent (product manufactured by JNC Co., Ltd.). Name Sila Ace S350, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane / hydrochloride 40% by mass) 10 g / L, acetic acid (pure 90%) 1.8 g / L , Obtained by mixing so that the balance becomes pure water.

The glass fiber woven fabric obtained by impregnating and drying the treatment liquid of the first bath is impregnated into the treatment liquid of the second bath, squeezed with a nip roll to a nip pressure of 1.1 kgf / cm ² , and the temperature is 250 ° C. The glass fiber cloth containing a fluororesin and an organic titanium compound was obtained on the glass fiber by drying under the condition of 5 minutes. The fluororesin-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 mass%, and an air permeability of 10.0 cc / cm ² / s.

(Comparative Example 1)
In Example 1, the treatment liquid of the first bath was a fluororesin, a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui / DuPont Fluorochemical Co., Ltd., acetic acid (pure content 90%) 6 g / L, and the balance of 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 in such a manner (that is, a treatment liquid containing no organic titanium compound was used). The thickness of the cloth was 0.872 mm, the mass was 931.9 g / m ² , the strong heat loss was 8.7 mass%, and the air permeability was 11.3 cc / cm ² / s.

(Example 2)
As warp yarns, DE75 1 / 2.8S manufactured by Unitika Co., Ltd. (two single yarns DE75 1/0 0.7Z twisted in the Z direction are additionally twisted in the Z direction, and the number of upper twists is 3 in the S direction. .8 times / 25 mm twisted yarn, filament diameter 6 μm, count 135 tex), as weft, Unitika Co., Ltd. trade name TDE300 (bulky processed yarn, filament diameter 6.0 μm, count 302.0 tex) Was used. The glass material constituting the glass fiber for both the warp and the weft was E glass.

Using the above warp and weft, weaving with a weft double weave structure (warp density 48/25 mm, weft density 48/25 mm), caramelizing (temperature 680 ° C, time 20 seconds), glass fiber woven fabric Got The mass of the glass fiber woven fabric was 841 g / m ² .

Next, the treatment liquid was prepared. The treatment liquid contains 50 g / L of a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 60% by mass of non-volatile component concentration of PTFE) as a fluororesin, and di-i-propoxy as an organic titanium compound. I-propanol solution of bis (acetylacetonato) titanium (Ti [OCH (CH ₃ ) ₂ ] ₂ [OCH (CH ₃ ) CHCOCH ₃ ] ₂ ) (trade name T-50 manufactured by Nippon Soda Co., Ltd., purity 74.1) 14 g / L (mass%), graphite dispersion (aqueous dispersion containing 22.5 mass% graphite solids, carboxymethyl cellulose (hereinafter, may be abbreviated as "CMC") 7.5 mass% solids) 28 g / L, silane coupling agent (trade name Sila Ace (registered trademark) S330 manufactured by JNC Co., Ltd., 3-aminopropyltriethoxysilane, non-volatile content 100% by mass) 5 g / L, and the balance is pure water. Obtained by that.

The caramelized glass fiber woven fabric is impregnated in the treatment liquid, 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 then placed on the glass fiber. A fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound was obtained. The fluororesin-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 mass%, and an air permeability of 11.8 cc / cm ² / s.

(Comparative Example 2)
In Example 2, the treatment liquid was a fluororesin, and 50 g / L of a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui-DuPont Fluorochemical Co., Ltd., 60% by mass of non-volatile component concentration of PTFE) and a graphite dispersion (graphite solid). 28 g / L (aqueous dispersion containing 22.5% by mass of CMC and 7.5% by mass of CMC solid), silane coupling agent (JNC Co., Ltd. trade name Sila Ace (registered trademark) S330, 3-aminopropyltriethoxy) Under the same conditions as in Example 2 except that the mixture was obtained by mixing so that silane, non-volatile content (100% by mass), and the balance were pure water (that is, a treatment solution containing no organic titanium compound was used). A fluororesin-containing glass fiber cloth was obtained. The fluororesin-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 mass%, and an air permeability of 12.3 cc / cm ² / s.

(Example 3)
As warp yarns, DE75 1 / 2.8S manufactured by Unitika Co., Ltd. (two single yarns DE75 1/0 0.7Z twisted in the Z direction are additionally twisted in the Z direction, and the number of upper twists is 3 in the S direction. .8 times / 25 mm twisted yarn, filament diameter 6 μm, count 135 tex), as weft, Unitika Co., Ltd. trade name TDE300 (bulky processed yarn, filament diameter 6.0 μm, count 302.0 tex) Was used. The glass material constituting the glass fiber for both the warp and the weft was E glass.

Using the above warp and weft, weaving was performed with a weft double weave structure (warp density 48 lines / 25 mm, weft density 48 lines / 25 mm) to obtain a glass fiber woven fabric (caramelization treatment was not performed). The mass of the glass fiber woven fabric was 850 g / m ² .

Next, the treatment liquid was prepared. The treatment liquid contains 269.1 g / L of a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui-Dupont Fluorochemical Co., Ltd., 60% by mass of non-volatile component concentration of PTFE) as a fluororesin, and di-i- as an organic titanium compound. I-propanol solution of propoxy-bis (acetylacetonato) titanium (Ti [OCH (CH ₃ ) ₂ ] ₂ [OCH (CH ₃ ) CHCOCH ₃ ] ₂ ) (trade name T-50, purity 74, manufactured by Nippon Soda Co., Ltd.) .1% by mass) 18.59g / L, wet penetrant (Kao Co., Ltd. trade name Perex (registered trademark) OT-P (70% by mass of sodium dialkyl sulfosuccinate)) 1.95 g / L, carbon black (Dainichisei) It was obtained by mixing so that the trade name Black FLTR Conk, manufactured by Kagyo Kogyo Co., Ltd., 100%) 39 g / L, and the balance was pure water.

The woven glass fiber woven fabric is impregnated in the treatment liquid, squeezed with a nip roll to a nip pressure of 1.1 kgf / cm2, dried at a temperature of 250 ° C. for 10 minutes, and fluororesin is placed on the glass fiber. A fluororesin-containing glass fiber cloth containing the organic titanium compound and / or the reaction product of the organic titanium compound was obtained. The fluororesin-containing glass fiber cloth had a thickness of 1.018 mm, a mass of 948.2 g / m ² , a loss on ignition of 9.1 mass%, and an air permeability of 9.1 cc / cm ² / s.

(Comparative Example 3)
In Example 3, the treatment liquid was a fluororesin, and a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui-Dupont Fluorochemical Co., Ltd., non-volatile component concentration 60% by mass of PTFE) was 269.1 g / L, and a wet penetrant (wet penetrant). Kao Co., Ltd. Product name Perex (registered trademark) OT-P (70% by mass of sodium dialkyl sulfosuccinate) 1.95 g / L, Carbon black (Product name Black FLTR Compound, 100% manufactured by Dainichi Seika Kogyo Co., Ltd.) 39 g / A fluororesin-containing glass fiber cloth was obtained under the same conditions as in Example 3 except that it was obtained by mixing L so that the balance was pure water (that is, a treatment liquid containing no organic titanium compound was used). The fluororesin-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 mass%, and an air permeability of 14.3 cc / cm ² / s.

The performance and the like of the fluororesin-containing glass fiber cloths of Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated. The results are shown in Table 1.

As is clear from the comparison between Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, and Example 3 and Comparative Example 3, a fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound on the glass fiber. It was clarified that (Examples 1 to 3) can maintain excellent folding resistance even when exposed to heat at an atmospheric temperature exceeding 250 ° C. Further, in the fluororesin-containing glass fiber cloths of Examples 1 to 3, it was observed that the fluororesin was present on the glass fiber in a three-dimensional network after heat exposure.

3. 3. Fluororesin-containing glass fiber cloth production and evaluation results-2
(Example 4)
The second bath treatment solution was a fluororesin containing 220 g / L of PTFE solution (trade name PTFE 31-JR manufactured by Mitsui-Dupont Fluorochemical Co., Ltd., non-volatile component concentration 60% by mass of PTFE), acetic acid (pure content 90%). On the glass fiber under the same conditions as in Example 1 except that it was obtained by mixing 1.8 g / L so that the balance was pure water (that is, a treatment liquid containing no silane coupling agent was used). A fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound was obtained. The fluororesin-containing glass fiber cloth had a thickness of 0.885 mm, a mass of 936.2 g / m ² , a loss on ignition of 9.8 mass%, and an air permeability of 11.0 cc / cm ² / s.

(Example 5)
The treatment solution of the first bath was 220 g / L of a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui-Dupont Fluorochemical Co., Ltd., 60% by mass of non-volatile component concentration of PTFE) as a fluororesin, and di-i as an organic titanium compound. -I-Propanol solution of propoxy-bis (acetylacetonato) titanium (Ti [OCH (CH ₃ ) ₂ ] ₂ [OCH (CH ₃ ) CHCOCH ₃ ] ₂ ) (trade name T-50 manufactured by Nippon Soda Co., Ltd., purity) It was obtained by mixing 74.1% by mass) to 28.6 g / L, acetic acid (90% pure content) to 6 g / L, and the balance of pure water (that is, doubling the amount of the organic titanium compound). A fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound on the glass fiber was obtained under the same conditions as in Example 1 except that the treatment liquid was increased to the above. The fluororesin-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)
The second bath treatment solution is a fluororesin containing 220 g / L of a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui-Dupont Fluorochemical Co., Ltd., 60% by mass of non-volatile component concentration of PTFE), and a silane coupling agent (JNC stock). Company brand name Sila Ace S350, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane / hydrochloride 40% by mass) 10 g / L, acetic acid (pure 90%) 1. Obtained by mixing 8 g / L, silicone oil (trade name KM-9739 manufactured by Shin-Etsu Chemical Co., Ltd. (nonvolatile content: 30% by mass)) so as to be 50 g / L and the balance of pure water (that is, silicone resin). A fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound was obtained on the glass fiber under the same conditions as in Example 1 except for (). The fluororesin-containing glass fiber cloth had a thickness of 0.886 mm, a mass of 937.4 g / m ² , a loss on ignition of 10.1 mass%, and an air permeability of 11.6 cc / cm ² / s.

(Example 7)
The second bath treatment solution was a fluororesin containing 220 g / L of a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui-Dupont Fluorochemical Co., Ltd., 60% by mass of non-volatile component concentration of PTFE), and a silane coupling agent (JNC stock). Company-manufactured product name Sila Ace S350, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane / hydrochloride 40% by mass) 10 g / L, acetic acid (pure 90%) 1. It was obtained by mixing 8 g / L of a graphite dispersion (an aqueous dispersion containing 20% by mass of a graphite solid content and 10% by mass of a CMC solid content) so as to have a balance of pure water at 50 g / L (that is,). A fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound on the glass fiber was obtained under the same conditions as in Example 1 except that the treatment solution further added graphite and CMC was used. The fluororesin-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 mass%, and an air permeability of 9.9 cc / cm ² / s.

Each performance of the fluororesin-containing glass fiber cloth of Examples 4 to 7 was evaluated. The results are shown in Table 2. The results of Example 1 are also shown again in Table 2 for comparison.

In Example 1, the folding resistance and the retention rate of tensile strength after heat exposure at an atmospheric temperature exceeding 250 ° C. were higher than those in Example 4. That is, the glass fiber contains, in addition to the fluororesin and the organic titanium compound, one or more compounds selected from the group consisting of a silane coupling agent, a hydrolyzate thereof, and a dehydration condensate of the hydrolyzate. As a result, it was clarified that the folding resistance and the holding performance of tensile strength after heat exposure were further improved.

In Example 5, the retention performance of folding resistance after heat exposure at an atmospheric temperature exceeding 250 ° C. was excellent as in Example 1. Therefore, even if the amount of the organic titanium compound is relatively large, It was confirmed that the folding resistance could be sufficiently maintained even after heat exposure.

Example 6 was superior to Example 1 in the ability to retain folding resistance after heat exposure at an atmospheric temperature exceeding 250 ° C. That is, it was found that by further containing the silicone resin, the slipperiness between the glass fibers (between the filaments) was further improved, and as a result, the holding performance of the folding resistance after heat exposure could be further improved.

Compared with Example 7, Example 1 was slightly superior in holding performance of folding resistance after heat exposure at an atmospheric temperature exceeding 250 ° C. On the other hand, in Example 7, since graphite was present even after heat exposure, it is easier to maintain the dust-removing property in combination with the excellent folding resistance holding performance. there were.

4. Fluororesin-containing glass fiber cloth production and evaluation results-3
(Example 8)
As the warp, 3 single yarn yarns (filament diameter 5.0 μm, number of filaments 400, number of twists once in the Z direction / 25 mm) using the glass material constituting the glass fiber as the glass material having the following glass composition X are used. This, the twisted yarns were collected while additional twisting so that the number of twists was 1 time / 25 mm in the Z direction, and the two lower twisted yarns were twisted 3.8 times / 25 mm in the S direction. A single yarn yarn (filament diameter 5.0 μm, number of filaments 400) in which the glass material constituting the glass fiber is the following glass composition X is used as the weft yarn (a count of 135.7 tex is used). Three yarns are additionally twisted so that the number of lower twists is 4 times / 25 mm to obtain a lower twist yarn, and the four lower twist yarns are twisted into a combined yarn having an upper twist number of 3.8 times / 25 mm in the S direction. As the raw material yarn, a bulky processed yarn (filament diameter 5.0 μm, count 287.5 tex) obtained by Taslan processing the raw material yarn was used.

(Glass composition X)
SiO ₂ : 62.32% by mass
Al ₂ O ₃ : 19.31% by mass
MgO: 15.15% by mass
Fe ₂ O ₃ : 0.19% by mass
CaO: 0.13% by mass
Na ₂ O ₃ : 1.23% by mass
K ₂ O: 0.10% by mass
B ₂ O ₃ : 1.57% by mass

Using the above warp and weft, weaving with a weft double weave structure (warp density 48/25 mm, weft density 48/25 mm), caramelizing (temperature 680 ° C, time 20 seconds), glass fiber woven fabric Got The mass of the glass fiber woven fabric was 807 g / m ² .

Next, the treatment liquid for the first bath was prepared. The treatment liquid contains 220 g / L of a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui DuPont Fluorochemical Co., Ltd., concentration of non-volatile component of PTFE is 60% by mass) as a fluororesin, and di-i-propoxy as an organic titanium compound. I-propanol solution of bis (acetylacetonato) titanium (Ti [OCH (CH ₃ ) ₂ ] ₂ [OCH (CH ₃ ) CHCOCH ₃ ] ₂ ) (trade name T-50 manufactured by Nippon Soda Co., Ltd., purity 74.1) It was obtained by mixing 14.3 g / L (mass%), 6 g / L of acetic acid (pure content 90%), and the balance of pure water.

The caramelized glass fiber woven fabric was impregnated in the treatment liquid of the first bath, squeezed with a nip roll at a nip pressure of 1.1 kgf / cm ² , and dried at a temperature of 250 ° C. for 5 minutes. ..

Next, the treatment liquid for the second bath was prepared. The treatment liquid contains 220 g / L of a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui-Dupont Fluorochemical Co., Ltd., 60% by mass of non-volatile component concentration of PTFE) as a fluororesin, and a silane coupling agent (product manufactured by JNC Co., Ltd.). Name Sila Ace S350, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane / hydrochloride 40% by mass) 10 g / L, acetic acid (pure 90%) 1.8 g / L , Obtained by mixing so that the balance becomes pure water.

The glass fiber woven fabric obtained by impregnating and drying the treatment liquid of the first bath is impregnated into the treatment liquid of the second bath, squeezed with a nip roll to a nip pressure of 1.1 kgf / cm ² , and the temperature is 250 ° C. The glass fiber cloth containing a fluororesin and an organic titanium compound was obtained on the glass fiber by drying under the condition of 5 minutes. The fluororesin-containing glass fiber cloth had a thickness of 0.839 mm, a mass of 899.1 g / m ² , a loss on ignition of 10.2 mass%, and an air permeability of 7.0 cc / cm ² / s.

(Example 9)
As the warp, 3 single yarn yarns (filament diameter 5.0 μm, number of filaments 400, number of twists once in the Z direction / 25 mm) in which the glass material constituting the glass fiber is the glass material having the glass composition X. This, the twisted yarns were collected while additional twisting so that the number of twists was 1 time / 25 mm in the Z direction, and the two lower twisted yarns were twisted 3.8 times / 25 mm in the S direction. A single yarn yarn (filament diameter 5.0 μm, number of filaments 400) is used as a twisted yarn (a count of 135.7 tex is used. As a weft, a glass material having the following glass composition X as a glass material constituting the glass fiber) is used. Three yarns are additionally twisted so that the number of lower twists is 4 times / 25 mm to obtain a lower twist yarn, and the four lower twist yarns are twisted into a combined yarn having an upper twist number of 3.8 times / 25 mm in the S direction. As the raw material yarn, a bulky processed yarn (filament diameter 5.0 μm, count 287.5 tex) obtained by Taslan processing the raw material yarn was used.

Using the above warp and weft, weaving with a weft double weave structure (warp density 48/25 mm, weft density 48/25 mm), caramelizing (temperature 680 ° C, time 20 seconds), glass fiber woven fabric Got The mass of the glass fiber woven fabric was 813 g / m ² .

Next, the treatment liquid was prepared. The treatment liquid is a fluororesin containing 50 g / L of a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui DuPont Fluorochemical Co., Ltd., concentration of non-volatile components of PTFE is 60% by mass), and di-i-propoxy as an organic titanium compound. I-propanol solution of bis (acetylacetonato) titanium (Ti [OCH (CH ₃ ) ₂ ] ₂ [OCH (CH ₃ ) CHCOCH ₃ ] ₂ ) (trade name T-50 manufactured by Nippon Soda Co., Ltd., purity 74.1) 14 g / L (mass%), 28 g / L graphite dispersion (aqueous dispersion containing 22.5 mass% graphite solids and 7.5 mass% CMC solids), silane coupling agent (JNC Co., Ltd. product) It was obtained by mixing so that the name Sila Ace (registered trademark) S330, 3-aminopropyltriethoxysilane, non-volatile content 100% by mass) was 5 g / L, and the balance was pure water.

The caramelized glass fiber woven fabric is impregnated in the treatment liquid, 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 then placed on the glass fiber. A fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound was obtained. The fluororesin-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 mass%, and an air permeability of 7.8 cc / cm ² / s.

The performance and the like of the fluororesin-containing glass fiber cloths of Examples 8 and 9 were evaluated. The results are shown in Table 3. Table 3 also shows the results of Examples 1 and 2 for comparison.

In Example 8, the retention rate of folding resistance after heat exposure at an atmospheric temperature exceeding 250 ° C. was higher than that in Example 1. In Example 9, the retention rate of folding resistance after heat exposure at an atmospheric temperature exceeding 250 ° C. was higher than that in Example 2. That is, the glass material constituting the glass fiber has a SiO ₂ content of 60.0 to 64.0 mass%, an Al ₂ O ₃ content of 18.0 to 22.0 mass%, and an Mg O content of 18.0 to 22.0 mass%. Atmospheric temperature exceeding 250 ° C. by making the glass composition having 14 to 18% by mass and having a total of the content of SiO ₂ , the content of Al ₂ O _{3 and} the content of Mg O of 94% by mass or more. It was clarified that it is possible to more easily provide excellent folding resistance even after heat exposure in.

Claims (7)

A fluororesin-containing glass fiber cloth containing a fluororesin and an organic titanium compound on the glass fiber. The fluororesin-containing glass fiber cloth according to claim 1, further comprising a silane coupling agent and / or a reaction product thereof on the glass fiber. The fluororesin-containing glass fiber cloth according to claim 1 or 2, wherein the organic titanium compound is present in the fluororesin. The fluororesin-containing glass fiber cloth according to claim 2 or 3, wherein the silane coupling agent and / or a reaction product thereof is present in the fluororesin. The fluororesin-containing glass fiber cloth according to any one of claims 1 to 4, further comprising graphite and / or silicone resin. The fluororesin-containing glass fiber cloth according to any one of claims 1 to 5, which is used for a dust collecting filter. A dust collecting filter comprising the fluororesin-containing glass fiber cloth according to any one of claims 1 to 5.