JP2022100338A - Graphite-adhered glass fiber fabric and dust collection filter using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass fiber fabric which exhibits excellent folding resistance even in an atmosphere having a temperature in excess of 250°C, and which can be advantageously used as a dust collection filter.

SOLUTION: The graphite-adhered glass fiber fabric has a glass fiber fabric and a graphite-containing coating film. The coating film covers at least a part of the surface of glass fibers that constitute the glass fiber fabric, and a glass composition that constitutes the glass fibers contains 60.0-66.0 mass% of SiO₂, 18.0-26.0 mass% of Al₂O₃ and 8.0-20.0 mass% of MgO.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a graphite-attached glass fiber fabric which has excellent folding resistance at an atmospheric temperature exceeding 250 ° C. and is suitably used as a dust collecting filter. The present invention also relates to a dust collecting filter using the graphite-adhered glass fiber fabric.

Glass fiber fabric is used as a filter material used in dust collectors for capturing dust (flying ash) in exhaust gas generated in urban waste incinerators, industrial waste incinerators, coal incinerators, metal melting furnaces, etc. There is.

Generally, a bag filter method is adopted for filtering the exhaust gas from an incinerator of municipal waste. Specifically, in the bag filter method, a glass fiber fabric is used, a bag (for example, a cylindrical shape having a diameter of 120 to 170 mm and a length of 4 to 7 m) is sewn, and a large number of the bags are installed in a dust collector. .. 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. 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 momentarily (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 glass fiber fabrics that make up the bag filter are repeatedly bent. Therefore, the glass fiber fabric is required to have resistance to bending, that is, folding resistance.

Conventionally, as a cloth for a back filter, for example, a double woven cloth having a tyrogue structure on both the front and back sides composed of a flat yarn made of glass fiber as a warp and a bulky yarn made of glass fiber as a warp, and a bulky rate KB of 30% or more on both sides. A bag filter cloth having a bulky ratio KB of at least one side of 85% or less is known (see, for example, Patent Document 1). According to the cloth, it is possible to improve the dust releasability while maintaining the dust collection efficiency.

Japanese Unexamined Patent Publication No. 4-327237

In Patent Document 1, specifically, in Examples, it is disclosed that E glass is used as a glass material constituting a glass fiber and that it is impregnated with a water emulsion of a polytetrafluoroethylene resin. ..

However, as examined by the present inventor, the cloth disclosed in Patent Document 1 has a problem that its folding resistance may be significantly reduced when it is heat-exposed to an atmospheric temperature exceeding 250 ° C., for example, 400 ° C. I knew that there was.

Therefore, an object of the present invention is to solve the above-mentioned problems and to provide a glass fiber fabric which is excellent in folding resistance even at an atmospheric temperature exceeding 250 ° C. and can be suitably used as a dust collecting filter.

As a result of repeated studies to solve the above problems, the present inventor has not considered that it is contained as an antistatic agent, for example, and directly contributes to the improvement of folding resistance for the purpose of improving folding resistance. , Focused on graphite. Then, by adopting a glass fiber having a specific glass composition as the glass fiber constituting the glass fiber fabric and covering at least a part of the surface of the glass fiber constituting the glass fiber fabric with a film containing graphite. It has been found that the folding resistance at an atmospheric temperature exceeding 250 ° C. is dramatically improved. The present invention is an invention completed by further studies based on these findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. With fiberglass fabric,
With a film containing graphite,
The film covers at least a part of the surface of the glass fiber constituting the glass fiber fabric.
The glass composition constituting the glass fiber contains 60.0 to 66.0% by mass of SiO ₂ , 18.0 to 26.0% by mass of Al ₂ O ₃ , and 8.0 to 20.0% by mass of MgO. %contains,
Graphite-attached fiberglass fabric.
Item 2. The glass composition constituting the glass fiber contains 44.0 to 66.0% by mass of SiO ₂ , 24.0 to 26.0% by mass of Al ₂ O ₃ , and 9.0 to 11.0% of MgO. Item 2. The graphite-attached glass fiber fabric according to Item 1, which contains 3% by mass or less (including 0% by mass) of other components.
Item 3. Item 2. The graphite-attached glass fiber fabric according to Item 1 or 2, wherein the film contains a thermoplastic resin and / or a silicone oil having no side chains and branches in the molecular structure.
Item 4. Item 2. The graphite-attached glass fiber fabric according to any one of Items 1 to 3, wherein the film contains carboxymethyl cellulose.
Item 5. The glass fiber fabric is a woven fabric and
The warp and weft constituting the woven fabric is a combined twisted yarn of a bulky processed yarn made of a multifilament yarn and a yarn made of a multifilament yarn.
Item 4. The graphite-attached glass fiber fabric according to any one of Items 1 to 4.
Item 6. Item 2. The graphite-attached glass fiber fabric according to any one of Items 1 to 5, wherein the graphite is contained in an amount of 30 parts by mass or more per 100 parts by mass of the film.
Item 7. A dust collecting filter containing the graphite-attached glass fiber fabric according to any one of Items 1 to 6.
Item 8. Item 6. The dust collecting filter according to Item 7, which is a bag filter.
Item 9. Use of the graphite-attached glass fiber fabric according to any one of Items 1 to 6 as a dust collection filter.

The graphite-attached glass fiber fabric of the present invention has dramatically improved folding resistance at an atmospheric temperature exceeding 250 ° C., and is used in urban waste incinerators, industrial waste incinerators, coal-fired boilers, metal melting furnaces, etc. It is possible to satisfy the required performance as a dust collecting filter for capturing dust in the generated exhaust gas.

It is an image which observed the surface of an example of the graphite-attached glass fiber fabric of this invention with a scanning electron microscope.

The graphite-attached glass fiber fabric of the present invention has a glass fiber fabric and a film containing graphite, and the film covers at least a part of the surface of the glass fiber constituting the glass fiber fabric. The glass composition constituting the glass fiber contains 60.0 to 66.0% by mass of SiO ₂ , 18.0 to 26.0% by mass of Al ₂ O ₃ , and 8.0 to 20.0% by mass of MgO. It is characterized by containing. Hereinafter, the graphite-attached glass fiber fabric of the present invention will be described in detail.

[Glass fiber fabric]
In the present invention, the "glass fiber fabric" is a fabric in which the constituent fibers are made of glass fibers.

In the present invention, the glass composition constituting the glass fiber used for the glass fiber fabric has a SiO ₂ content of 60.0 to 66.0% by mass and an Al ₂ O ₃ content of 18.0 to 26. The content of MgO is 8.0 to 20.0% by mass (preferably 8 to 16% by mass). By adopting a glass fiber made of such a glass composition having a specific composition and coating the glass fiber with a specific film described later, it is possible to have excellent folding resistance even at an atmospheric temperature exceeding 250 ° C. It will be possible.

As a suitable example of the glass composition constituting the glass fiber, the content of SiO ₂ is 64.0 to 66.0% by mass, the content of Al ₂ O ₃ is 24.0 to 26.0% by mass, and MgO. Examples thereof include those having a content of 9.0 to 11.0% by mass and a content of other components of 3% by mass or less (including 0% by mass).

Further, as one aspect of the glass composition constituting the glass fiber, 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 so on. Examples thereof include those having an MgO content of 14 to 18% by mass and a total of the SiO ₂ content, the Al ₂ O ₃ content and the MgO content of 94% by mass or more.

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 glass fiber fabric. Examples of the long fiber include a monofilament yarn composed of one continuous single fiber and a multifilament yarn composed of a plurality of continuous single fibers. Among these long fibers, a multifilament yarn is preferable from the viewpoint of making the folding resistance more excellent when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C.

When the long fibers are used as the glass fibers constituting the glass fiber fabric, the form of the glass fiber fabric may be a woven fabric, a knitted fabric, a non-woven fabric (including felt), or a combination thereof. A woven fabric is a preferred form of the glass fiber fabric from the viewpoint of making it more excellent in folding resistance when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C.

When the glass fiber fabric is in the form of a woven fabric, the physical properties of the warp and weft used are not particularly limited, but the folding resistance is further improved when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C. From the viewpoint of making the warp and weft, it is preferable to use a bulky processed yarn made of a multifilament yarn and a yarn made of a multifilament yarn (hereinafter, also referred to as "twisted yarn A"). ..

The number of twists of the combined twisted yarn A is not particularly limited, but for example, from the viewpoint of further excellent folding resistance when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C., upper twisting is performed. 2 to 5 times / 25 mm, preferably 3.0 to 4.5 times / 25 mm.

The count of the entire combined twisted yarn A is not particularly limited, and examples thereof include 30 to 600 tex. From the viewpoint of further enhancing mechanical properties and dust collecting property, 50 to 500 tex is more preferable and mechanical. 200 to 400 tex is more preferable from the viewpoint of further improving the folding resistance when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C. while further improving the characteristics and the dust collecting property.

Further, in the above-mentioned combined twisted yarn A, the mass ratio of the bulky processed yarn and the yarn per unit length (mass per unit length of the bulky processed yarn (tex) / mass per unit length of yarn (tex)). Is not particularly limited, but from the viewpoint of further improving the mechanical properties and dust collecting property, and further improving the folding resistance when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C. 3 to 20 is preferable, 5 to 15 is more preferable, and 8 to 12 is particularly preferable.

When the glass fiber fabric is in the form of a woven fabric, a yarn that is a multifilament yarn is used as a warp and a multifilament yarn is used as a weft as a preferable aspect from the viewpoint of further enhancing mechanical properties and dust collection. Examples thereof include woven fabrics using bulky processed yarns (bulky processed yarns) made of (hereinafter, may be referred to as "aspect X").

Further, when the glass fiber fabric is in the form of a woven fabric, the mechanical properties and the dust collecting property are further enhanced, and the folding resistance in the weft direction is improved when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C. From the viewpoint of making it even more excellent, as another preferred embodiment, a woven fabric using yarn which is a multifilament yarn as a warp and the above-mentioned twisted yarn A as a weft (hereinafter referred to as "aspect Y"). It may be written).

Examples of the yarn used as the warp in the woven fabrics of the above embodiments X and Y include single yarn and twisted yarn, which have better folding resistance when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C. Combined twisted yarn is preferable from the viewpoint of making the yarn. The composition of the combined twisted yarn is not particularly limited, but for example, 4 to 8 single yarn yarns are used from the viewpoint of further improving the folding resistance when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C. It is preferable to use 2 to 4 yarns which are twisted down in the S direction or the Z direction to form one yarn, and which are twisted up in the direction opposite to the bottom twist.

In the woven fabrics of the above aspects X and Y, the number of twists of the yarn used as the warp is not particularly limited, but for example, when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C., the folding resistance is further further improved. From the viewpoint of making it excellent, the top twist is preferably 2 to 5 times / 25 mm, more preferably 3.0 to 4.5 times / 25 mm.

In the woven fabrics of the above aspects X and Y, the filament diameter (single fiber diameter) of the yarn used as the warp is not particularly limited, and examples thereof include 4 to 9 μm under the condition of an atmospheric temperature exceeding 250 ° C. From the viewpoint of making the folding resistance more excellent when exposed to heat, 4 to 7 μm is more preferable, and 4.5 to 5.5 μm is particularly preferable.

In the woven fabrics of the above aspects X and Y, the yarn count used as the warp is not particularly limited, and examples thereof include 30 to 600 tex. From the viewpoint of further enhancing the mechanical properties and the dust collecting property, 50 ~ 450tex is more preferable, and from the viewpoint of further improving the mechanical properties and the dust collecting property, and further improving the folding resistance when exposed to heat under the condition of the atmospheric temperature exceeding 250 ° C. More preferably 100 to 200 tex.

In the woven fabric of the above aspect X, the filament diameter (single fiber diameter) of the bulky processed yarn used as the warp is not particularly limited, and examples thereof include 4 to 9 μm, which are heat-exposed under the condition of an atmospheric temperature exceeding 250 ° C. In some cases, 4 to 7 μm is more preferable, and 4.5 to 5.5 μm is particularly preferable, from the viewpoint of making the folding resistance more excellent.

In the woven fabric of the above aspect X, the count of the bulky processed yarn used as the weft is not particularly limited, and examples thereof include 30 to 600 tex. From the viewpoint of further enhancing the mechanical properties and the dust collecting property, 50 ~ 500tex is more preferable, and from the viewpoint of further improving the mechanical properties and the dust collecting property, and further improving the folding resistance when exposed to heat under the condition of the atmospheric temperature exceeding 250 ° C. 200-400 tex is more preferable.

The combined twisted yarn A used as the warp and weft in the woven fabric of the above aspect Y is as described above.

In the case of the woven fabric of the above aspect X, the ratio of the counts (warp / weft) of the warp to the weft is not particularly limited, but the folding resistance is further improved when exposed to heat under the condition of the atmospheric temperature exceeding 250 ° C. From the viewpoint of making it excellent, 1/4 to 1/1 is preferable, and 2/5 to 1/2 is more preferable.

Further, in the case of the woven fabric of the above aspect Y, the ratio of the counts of the warp and the weft (warp / weft) is not particularly limited, but the folding resistance is obtained when exposed to heat under the condition of the atmospheric temperature exceeding 250 ° C. Is preferably 1/5 to 1/1, and more preferably 1/4 to 1/2, from the viewpoint of making the above-mentioned more excellent.

When the glass fiber fabric is a woven fabric, the weaving structure thereof is not particularly limited, and for example, plain weave, satin weave, twill weave, diagonal weave, ridge weave, and double weave (warp double weave, weft double weave, etc.) Weave double weave, etc.). From the viewpoint of making the folding resistance more excellent when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C., the double woven structure is preferable, and the folding resistance and the dust collecting property are more compatible. From the viewpoint, the weft double weave is more preferable.

When the glass fiber fabric is a woven fabric, the weaving density is not particularly limited, but for example, in the case of the woven fabric of the above aspect X, the warp (yarn) is preferably 20 to 80 threads / 25 mm, and 40 to 60. A book is more preferable; the weft (bulky yarn) is preferably 20 to 80 yarns / 25 mm, and more preferably 30 to 60 yarns / 25 mm. Further, in the case of the woven fabric of the above aspect Y, the warp yarn (yarn) is preferably 20 to 80 yarns / 25 mm, more preferably 40 to 60 yarns; and the warp and weft (combined twisted yarn) is preferably 20 to 80 yarns / 25 mm. , 30 to 60 lines / 25 mm is more preferable.

In the present invention, the mass (g / m ² ) of the glass fiber fabric (excluding the weight of the film) is not particularly limited, and examples thereof include 500 to 1500 g / m ² and 700 to 1100 g / m ² . preferable.

Further, in the present invention, the thickness (mm) of the glass fiber fabric itself (excluding the weight of the film) is not particularly limited, and examples thereof include 0.3 to 1.5 mm and 0.6 to 1 .2 mm is preferable.

[Film]
In the present invention, at least a part of the surface of the glass fiber constituting the glass fiber fabric is covered with a film containing graphite. The glass composition constituting the glass fiber has the above-mentioned specific composition, and at least a part of the surface of the glass fiber is coated with a film containing graphite, so that the temperature at an atmosphere exceeding 250 ° C. It is possible to dramatically improve the folding resistance.

The form and size of graphite contained in the film are not particularly limited. Examples of the form of graphite include scale-like and earth-like forms. As for the size of graphite, for example, the integrated value in the particle size distribution of graphite measured using a laser diffraction / scattering type particle size distribution measuring device (for example, trade name LA-920 manufactured by HORIBA, Ltd.) is 50. The particle size (d50) to be% is 0.1 to 100 μm, preferably 1 to 50 μm.

The content of graphite in the film may be appropriately set according to the coating amount of the film in the glass fiber fabric, but it is even more resistant to folding when exposed to heat under conditions of an ambient temperature exceeding 250 ° C. For example, 30 parts by mass or more, preferably 30 to 50 parts by mass, and more preferably 30 to 45 parts by mass of graphite is mentioned per 100 parts by mass of the total amount of the film.

The graphite content in the graphite-attached glass fiber fabric of the present invention is determined by the graphite content in the film, the coating amount of the film, etc., but when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C. In addition, from the viewpoint of further improving the folding resistance, for example, the amount of graphite is 0.1 to 3 per the total amount of the graphite-attached glass fiber fabric of the present invention (total amount of the glass fiber fabric and the film). By mass, preferably 0.5 to 2.5% by mass, more preferably 1.0 to 2.0% by mass.

Further, it is preferable that the film contains a thermoplastic resin as a component that retains graphite and forms the film. The type of thermoplastic resin is not particularly limited as long as it can form a film on the surface of glass fibers while retaining graphite, but it has a folding resistance when exposed to heat under conditions of an ambient temperature exceeding 250 ° C. When the graphite-attached glass fiber fabric of the present invention is used as a bug filter while being superior, side chains are preferably included in the molecular structure from the viewpoint of facilitating sewing when the glass fiber fabric is used as a bug. And thermoplastic resins without branching. That is, by containing the above-mentioned thermoplastic resin and / or silicone oil in the film, the needle-passability at the time of sewing is further improved, and the folding resistance when exposed to heat under the condition of the atmospheric temperature exceeding 250 ° C. Can be made better.

Examples of the thermoplastic resin having no side chains and branches in the molecular structure include vinyl chloride resin, polyphenylene sulfide resin, nylon 6 resin, polyacetal resin, polyethylene resin, polytetrafluoroethylene and the like. Among these, nylon 6 resin, polyacetal resin, polyethylene resin, and polytetrafluoroethylene are more preferable, and polytetrafluoroethylene is particularly preferable. These thermoplastic resins may be used alone or in combination of two or more.

When the film contains the thermoplastic resin, the mass ratio of the thermoplastic resin to graphite is not particularly limited, but for example, 100 to 1500 parts by mass, preferably 100 parts by mass of the thermoplastic resin per 100 parts by mass of graphite. It is about 500 parts by mass, more preferably 100 to 200 parts by mass.

When the film contains the thermoplastic resin, the content of the thermoplastic resin in the film may be appropriately set according to the coating amount of the film in the glass fiber fabric, the content of graphite in the film, and the like. However, for example, from the viewpoint of further improving the folding resistance when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C., while providing good needle-passability during sewing. The amount of the thermoplastic resin is 30 to 95 parts by mass, preferably 30 to 70 parts by mass, and more preferably 45 to 70 parts by mass per 100 parts by mass of the total amount of the film.

Further, the film may contain silicone oil. When the film contains silicone oil, the coefficient of dynamic friction with the needle during sewing can be further reduced, and the needle threadability can be further improved.

Specific examples of the silicone oil include dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, methyl phenyl silicone oil, dimethyl silicone oil, and dimethyl silicone oil. These silicone oils may be used alone or in combination of two or more.

When the film contains silicone oil, the mass ratio of silicone oil to graphite is not particularly limited, and examples thereof include 10 to 500 parts by mass, preferably 10 to 100 parts by mass of silicone oil per 100 parts by mass of graphite. Be done.

When the film contains silicone oil, the content of the silicone oil in the film may be appropriately set according to the coating amount of the film in the glass fiber fabric, the content of graphite in the film, and the like. The total amount of the film is 100 from the viewpoint of further improving the folding resistance when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C. while providing good needle-passability during sewing. The amount of silicone oil is 1 to 15 parts by mass, preferably 3 to 12 parts by mass, and more preferably 5 to 10 parts by mass per part by mass.

Further, the carboxymethyl cellulose is provided on the film from the viewpoint of further improving the fixability to the glass fiber and further improving the folding resistance when exposed to heat under the condition of the atmospheric temperature exceeding 250 ° C. Is preferably contained.

When the film contains carboxymethyl cellulose, the mass ratio of carboxymethyl cellulose to graphite is not particularly limited, and examples thereof include 10 to 60 parts by mass, preferably 15 to 55 parts by mass of carboxymethyl cellulose per 100 parts by mass of graphite. Be done.

When the film contains carboxymethyl cellulose, the content of carboxymethyl cellulose in the film may be appropriately set according to the coating amount of the film in the glass fiber fabric, the content of graphite in the film, and the like. Carboxymethyl cellulose per 100 parts by mass of the total amount of the film from the viewpoint of further improving the fixability to the glass fiber and having better folding resistance when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C. Is 1 to 25 parts by mass, preferably 2 to 20 parts by mass, and more preferably 3 to 18 parts by mass.

Further, the film may contain an acrylic resin, if necessary, in order to further improve the fixability to the glass fiber.

When the film contains an acrylic resin, the mass ratio of the acrylic resin to the graphite is not particularly limited, and for example, 20 to 40 parts by mass, preferably 25 to 35 parts by mass of the acrylic resin per 100 parts by mass of graphite. Be done.

When the film contains an acrylic resin, the content of the acrylic resin in the film may be appropriately set according to the coating amount of the film in the glass fiber fabric, the content of graphite in the film, and the like. Acrylic resin per 100 parts by mass of the total amount of the film from the viewpoint of further improving the fixability to the glass fiber and having better folding resistance when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C. Is 1 to 8 parts by mass, preferably 2 to 6 parts by mass, and more preferably 3 to 5 parts by mass.

The film may contain a silicone resin, if necessary.

When the film contains a silicone resin, the mass ratio of the silicone resin to graphite is not particularly limited, but for example, the silicone resin is 0.3 to 3 parts by mass, preferably 1 to 2 parts by mass per 100 parts by mass of graphite. Can be mentioned.

When the film contains a silicone resin, the content of the silicone resin in the film is appropriately set according to the coating amount of the film in the glass fiber fabric, the content of graphite in the film, and the like. However, for example, 0.1 to 1 part by mass, preferably 0.1 to 0.5 part by mass of the silicone resin may be mentioned per 100 parts by mass of the total amount of the film.

Further, the film is, if necessary, one or more compounds selected from the group consisting of a silane coupling agent, a hydrolyzate thereof, and a dehydrated condensate of the hydrolyzate (hereinafter referred to as "silane compound"). Can be included). In a film containing a silane compound, the silane compound is present not only on the surface of the film but also inside the film, so that the physical characteristics of the entire film can be improved. At that time, it becomes possible to further improve the folding resistance.

The type of silane coupling agent used in the present invention is not particularly limited, and is, for example, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-. Glycydoxyethoxytrimethoxysilane, 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-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, vinyltrimethoxysilane, vinyltriethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isoxapropyltriethoxysilane, etc. Can be mentioned. These silane coupling agents may be used alone or in combination of two or more.

When the film contains a silane compound, the mass ratio of the silane compound to graphite is not particularly limited, and examples thereof include 10 to 200 parts by mass, preferably 50 to 100 parts by mass of the silane compound per 100 parts by mass of graphite. Be done.

When a silane compound is contained in the film, the content of the silane compound in the film depends on the coating amount of the film in the glass fiber fabric, the content of graphite in the film, and the like. It may be set appropriately, but for example, from the viewpoint of having better folding resistance when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C., 3 to 15 silane compounds are contained per 100 parts by mass of the total amount of the film. By mass, preferably 5 to 12 parts by mass, more preferably 8 to 12 parts by mass.

Further, the film may contain diethylene glycol, if necessary.

When the film contains diethylene glycol, the mass ratio of diethylene glycol to graphite is not particularly limited, and examples thereof include 20 to 40 parts by mass, preferably 25 to 35 parts by mass of diethylene glycol per 100 parts by mass of graphite.

When the film contains diethylene glycol, the content of diethylene glycol in the film may be appropriately set according to the coating amount of the film in the glass fiber fabric, the content of graphite in the film, and the like. 6 to 20 parts by mass, preferably 7.5 to 16 parts by mass of diethylene glycol is mentioned per 100 parts by mass of the total amount.

In the present invention, the content of the constituent components of the film other than graphite is determined depending on the content of graphite in the film, the coating amount of the film, etc., but when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C. From the viewpoint of further improving the folding resistance, for example, the constituent components of the film other than graphite per total amount of the graphite-attached glass fiber fabric of the present invention (total amount of the glass fiber fabric and the film). The total amount is 0.1 to 5.0% by mass, preferably 0.5 to 4.0% by mass, and more preferably 1.0 to 3.0% by mass.

In the present invention, the coating amount of the film on the glass fiber fabric is not particularly limited, but for example, the film is 1.0 to 1.0 per the total amount of the graphite-attached glass fiber fabric of the present invention (total weight of the glass fiber fabric and the film). 10% by mass, preferably 1.0 to 7.0% by mass, and more preferably 1.0 to 5.0% by mass.

In the present invention, the film may cover at least a part of the surface of the glass fiber constituting the glass fiber fabric, but it is more resistant to breakage when exposed to heat under the condition of an atmospheric temperature exceeding 250 ° C. From the viewpoint of further excellent properties, it is preferable that the film covers the entire surface of the glass fiber constituting the glass fiber fabric. FIG. 1 shows an example of the results of observing the surface shape of the graphite-attached glass fiber fabric of the present invention with a scanning electron microscope. In the graphite-attached glass fiber fabric shown in FIG. 1, the entire surface of the glass fiber constituting the glass fiber fabric is covered with a film containing graphite. Further, in the graphite-attached glass fiber fabric shown in FIG. 1, a film containing graphite covers the glass fibers existing on the surface and inside of the glass fiber fabric.

[Catalyst support]
If necessary, the graphite-attached glass fiber fabric of the present invention may carry a catalyst for decomposing gaseous dioxins, NOx and the like to purify the gas. Examples of the catalyst include vanadium pentoxide and the like. Further, a known carrier that supports the catalyst can also be used. As a method for supporting the catalyst on the graphite-attached glass fiber fabric of the present invention, a known method can be adopted.

[Physical characteristics and identification]
The mass (g / m ² ) per unit area of the graphite-attached glass fiber fabric of the present invention is not particularly limited, and examples thereof include 500 to 1500 g / m ² , preferably 700 to 1100 g / m ² .

The thickness (mm) of the graphite-attached glass fiber fabric 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.

The air permeability of the graphite-attached glass fiber fabric of the present invention may be within an acceptable range as a dust collecting filter, but from the viewpoint of achieving both gas permeability and dust collecting property when used as a dust collecting filter. For example, 3 to 20 (cc / cm ² / s), preferably 5 to 15 (cc / cm ² / s) can be mentioned. In the present invention, the "air permeability" is a value measured using a Frazier type tester, and specifically, 7.13 "Cross" of Japanese Industrial Standards JIS R 3420: 2013 "Glass Fiber General Test Method". It is a value measured according to the method specified in "Breathability".

The tensile strength of the graphite-attached glass fiber fabric of the present invention may be within an acceptable range as a dust collection filter. For example, when the glass fiber fabric is a woven fabric, the tensile strength in the direction parallel to the warp is high. 1300N / 25mm or more and the tensile strength in the direction parallel to the weft is 800N / 25mm or more; preferably, the tensile strength in the direction parallel to the warp is 2000 to 6000N / 25mm and the tensile strength in the direction parallel to the weft is 2000 to 6000N. / 25 mm can be mentioned. In the present invention, the "tensile strength" is determined by using a tensile tester with a graphite-adhered glass fiber fabric to be measured as a test piece having a length of 250 mm and a width of 25 mm, a gripping interval of 15 mm, and a tensile speed of 200 mm / min. It is a value obtained by performing a fast-load type tensile test with the value set to and determining the tensile strength at break. The tensile strength is measured in accordance with the method specified in 7.4 "Tensile strength" of Japanese Industrial Standards JIS R 3420: 2013 "Glass fiber general test method".

The graphite-attached glass fiber fabric of the present invention has excellent folding resistance when exposed to heat under conditions of an atmospheric temperature exceeding 250 ° C., for example, an atmospheric temperature of 400 ° C. In the graphite-attached glass fiber fabric of the present invention, when the glass fiber fabric is a fabric, the folding resistance is specifically such that the number of reciprocating bends measured by the evaluation method 1 shown below is in the direction parallel to the warp and weft. 20,000 times or more, 20,000 times or more in the direction parallel to the warp; preferably 20,000 times or more in the direction parallel to the warp, 30,000 times or more in the direction parallel to the weft; more preferably 20,000 times or more in the direction parallel to the warp, with the weft. More than 40,000 times in the parallel direction.

(Evaluation method 1)
(1) The length of the graphite-attached glass fiber fabric to be measured in the measurement direction (that is, in the direction parallel to the warp when measuring the folding resistance in the direction parallel to the warp) is 32 cm, in a direction different from the measurement direction. Cut out to a size of 23 cm in length (that is, when measuring the folding resistance in the direction parallel to the warp), and use this as a test piece. Prepare 10 pieces of the test piece.
(2) With 10 test pieces stacked, they are placed in a muffle furnace, exposed to heat at 400 ° C. for 24 hours, and then naturally cooled.
(3) After natural cooling, take out the 5th piece from the top of the 10 stacked test pieces, and use a MIT folding resistance tester to load 9.8N, the radius of curvature of the bending surface of the bending device is 0.38mm, and the bending speed. Set to 175 ± 10 times / minute and measure the number of reciprocating bends until the test piece is cut. The number of reciprocating bends can be measured in accordance with the method specified in 7.14 “Cross folding resistance” of Japanese Industrial Standards JIS R 3420: 2013 “Glass fiber general test method”.

Further, in the graphite-attached glass fiber fabric of the present invention, when the glass fiber fabric is a woven fabric, as another suitable example of the folding resistance, the number of reciprocating bends measured by the evaluation method 2 shown below is the warp and weft. 300 times or more in the parallel direction, 300 times or more in the direction parallel to the warp; preferably 350 times or more in the direction parallel to the warp, 400 times or more in the direction parallel to the weft; more preferably 400 times or more in the direction parallel to the warp. More than 500 times in the direction parallel to the weft.

(Evaluation method 2)
(1) The length of the graphite-attached glass fiber fabric to be measured in the measurement direction (that is, in the direction parallel to the warp when measuring the folding resistance in the direction parallel to the warp) is 32 cm, in a direction different from the measurement direction. Cut out to a size of 23 cm in length (that is, when measuring the folding resistance in the direction parallel to the warp), and use this as a test piece.
(2) One test piece is placed in a hot air circulation type high temperature furnace, exposed to heat at 400 ° C. for 24 hours, and then naturally cooled.
(3) For the test piece after natural cooling, set the load to 9.8 N, the radius of curvature of the bending surface of the bending device to 0.38 mm, and the bending speed to 175 ± 10 times / minute using a MIT folding resistance tester. Measure the number of reciprocating bends until the test piece is cut. The number of reciprocating bends can be measured in accordance with the method specified in 7.14 “Cross folding resistance” of Japanese Industrial Standards JIS R 3420: 2013 “Glass fiber general test method”.

[Use]
The use of the graphite-attached glass fiber fabric of the present invention is not particularly limited, but is suitably used as a dust collecting filter. In particular, the graphite-attached glass fiber fabric of the present invention has excellent folding resistance even when exposed to heat under conditions of an atmospheric temperature exceeding 250 ° C., for example, an atmospheric temperature of 400 ° C., and therefore contains high-temperature dust. It is particularly preferably used as a dust collecting filter used in a dust collector for collecting dust from exhaust gas. As a dust collector for collecting dust from high-temperature dust-containing exhaust gas, for example, in order to capture dust in exhaust gas generated in an urban waste incinerator, an industrial waste incinerator, a coal-only combustion boiler, a metal melting furnace, etc. The dust collector to be installed can be mentioned.

Further, when the graphite-attached glass fiber fabric of the present invention is used as a dust collection filter, it can be sewn into a bag (for example, a cylindrical shape having a diameter of 120 to 170 mm and a length of 4 to 7 m) and used as a bag filter. ..

Further, when the graphite-attached glass fiber fabric of the present invention carries a catalyst for decomposing gaseous dioxin, NOx, etc., the temperature range is 300 ° C. or higher and 400 ° C. or lower, which is a preferable temperature range for denitration. If it is used as a dust collecting filter for dust-containing exhaust gas, it is not necessary to reheat the exhaust gas in the catalytic denitration step after dust collection, and it is possible to greatly contribute to CO ₂ reduction.

[Production method]
The method for producing the graphite-attached glass fiber fabric of the present invention is not particularly limited. For example, first, a glass fiber fabric is prepared. Separately, a film-forming liquid in which the components contained in the film are dispersed or dissolved in a solvent such as water or an organic solvent is prepared. The solid content (total amount of components contained in the film) in the film-forming liquid may be set to, for example, about 20 to 60% by mass, preferably about 30 to 55% by mass. Then, the film-forming liquid is attached to the glass fiber fabric prepared above by a known method such as a spray method or a dip method. Then, it is dried and the solvent derived from the film-forming liquid is removed to obtain the graphite-attached glass fiber fabric of the present invention.

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 spectrophotometer.

(2) Glass fiber filament diameter (μm)
The measurement was performed in accordance with the A method specified in 7.6 "Single fiber diameter" of Japanese Industrial Standard JIS R 3420: 2013 "Glass fiber general test method".

(3) Count (tex) of glass yarn (yarn, bulky processed yarn, and twisted yarn of yarn and bulky processed yarn)
The measurement was performed in accordance with the method specified in 7.1 "Count" of Japanese Industrial Standards JIS R 3420: 2013 "Glass Fiber General Test Method". Regarding the mass ratio of the bulky processed yarn constituting the combined twisted yarn of the yarn and the bulky processed yarn and the yarn per unit length, 1 m of the combined twisted yarn is collected and the collected combined twisted yarn is untwisted to bulky. Separated into processed yarn and yarn, and the mass of the separated bulky processed yarn and yarn conforms to the method specified in 7.1 "Count" of the Japanese Industrial Standard JIS R 3420: 2013 "Glass Fiber General Test Method". The mass ratio was determined from each of the obtained values.

(4) Number of twists of yarn and combined twisted yarn of yarn and bulky processed yarn (times / 25 mm)
The measurement was performed in accordance with the method specified in 7.5 "Twisting number" of Japanese Industrial Standard JIS R 3420: 2013 "Glass fiber general test method".

(5) Weaving density of glass fiber woven fabric (book / 25 mm)
The obtained glass fiber woven fabric is woven of warp and weft in accordance with the method specified in 7.9 "Density (weaving density)" of the Japanese Industrial Standard JIS R 3420: 2013 "Glass Fiber General Test Method". The density was measured.

(6) Thickness of glass fiber woven fabric (μm)
0.001 mm (1 μm) using a micrometer in accordance with Method A specified in 7.10.1 “Cross thickness” of Japanese Industrial Standards JIS R 3420: 2013 “Glass fiber general test method”. Measured up to the digit of. This is done for 5 locations, and the average value of the 5 locations is rounded to 0.001 mm (1 μm) according to Rule B specified in Japanese Industrial Standards JIS Z 8401: 1999 "How to round the numerical value". Calculated up to the digit of.

(7) Mass of glass fiber woven fabric (g / m ² )
The measurement was performed in accordance with the method specified in 7.2 "Mass (mass) of cloth and mat" of Japanese Industrial Standard JIS R 3420: 2013 "General test method for glass fiber".

(8) Adhesion amount of film (mass%), each composition ratio (mass part)
The composition ratio of each film covering the glass fiber was determined from the solid content concentration of each component in the film-forming liquid described later. Regarding the coating amount of the film, first, regarding the film covering the glass fiber, the amount of components other than graphite is determined by Japanese Industrial Standards JIS R 3420: 2013 "Glass Fiber General Test Method" 7.3. 2 Calculated according to the method specified in "Strong heat loss". Then, the amount of coating of the film covering the glass fiber and the amount of graphite were calculated from the amount of the obtained components other than graphite and the composition ratios obtained above.

(9) Air permeability of graphite-attached glass fiber woven fabric (cc / cm ² / s)
Using a Frazier type tester (Frazier Permiyameter (Frazier type air permeability tester model number: FP-2) manufactured by Toyo Seiki Seisakusho Co., Ltd.), Japanese Industrial Standards JIS R 3420: 2013 "Glass fiber general test method" The air permeability of the graphite-attached glass fiber fabric was measured according to the method specified in 7.13 “Cloth Breathability”.

(10) Folding resistance of graphite-attached glass fiber woven fabric or glass fiber woven fabric I (times)
The number of reciprocating bends was measured according to the evaluation method 1 (heat treatment test I) described above. In this measurement, the muffle furnace used was (KL-600) manufactured by (ADVANTEC), and the MIT folding resistance tester used was (D type) manufactured by (Toyo Seiki Seisakusho Co., Ltd.).

(11) Folding resistance II (times) of graphite-attached glass fiber woven fabric or glass fiber woven fabric
The number of reciprocating bends was measured according to the evaluation method 2 (heat treatment test II) described above. In this measurement, the hot air circulation type high temperature furnace uses a high temp oven (trade name HP80 manufactured by Asahi Kagaku Co., Ltd.), and the MIT folding resistance tester is (D type) manufactured by (Toyo Seiki Seisakusho Co., Ltd.). )It was used.

(12) Tension strength of graphite-attached glass fiber woven fabric or glass fiber woven fabric (N / 25 mm)
A test piece having a length of 250 mm and a width of 25 mm was prepared from the graphite-attached glass fiber woven fabric or the glass fiber woven fabric to be measured. The test piece is subjected to a graphite-adhered glass fiber woven fabric or glass by a constant-velocity load type tensile test method specified in 7.4 "Tensile strength" of Japanese Industrial Standard JIS R 3420: 2013 "Glass fiber general test method". The tensile strength of the fiberglass fabric was measured. In this measurement, a tensile tester manufactured by Orientec Co., Ltd. under the trade name RTC-1310A was used, and the gripping interval was set to 150 mm and the tensile speed was set to 200 mm / min. The tensile strength was measured for the graphite-attached glass fiber woven fabric or the glass fiber woven fabric before and after heat exposure in the evaluations (10) and (11) above.

2. 2. Glass Composition Consisting of Used Glass Fiber When the glass composition constituting the used glass fiber was measured by the above method, it was confirmed that the composition was as follows. The glass composition C is E glass, and the following composition regarding the glass composition C shows a general composition of E glass.
(1) Glass composition A: Glass composition in which SiO ₂ is 65.0% by mass, Al ₂ O ₃ is 25.0% by mass, and MgO is 10.0% by mass. (2) Glass composition B: SiO ₂ Is 61.9% by mass, Al ₂ O ₃ is 19.4% by mass, MgO is 15.3% by mass, and the balance is N ₂ O, K ₂ O, Fe ₂ O ₃ , Ca O and B ₂ O ₃ glass. Composition (3) Glass composition C: E glass composition (SiO ₂ is 52 to 56% by mass, Al ₂ O ₃ is 12 to 16% by mass, CaO is 15 to 25% by mass, MgO is 0 to 6% by mass. , B ₂ O ₃ is 5 to 13% by mass, and the balance is Na ₂ O ₃ and K ₂ O ₃ )

3. 3. Production of Graphite-Adhered Glass Fiber Woven Fabric and Glass Fiber Woven Fabric without Film (Example 1)
As warp and weft, trade name D450 6/2 3.8S manufactured by Unitika Co., Ltd. (D450 1/0 1Z 6 lower twisted, 2 upper twisted combined twisted yarn, upper twist number 3.8 times / 25 mm, filament diameter 5.0 μm, count 134.4 tex), and as the weft, a trade name STD410 (bulky processed yarn, filament diameter 5.0 μm, count 410.0 tex) manufactured by Unitika Co., Ltd. was used. Both the warp and weft are the above-mentioned glass composition A as the glass composition constituting the glass fiber.

Using the above warp and weft, weaving with a double weft structure (warp density 48/25 mm, weft density 38/25 mm), caramelizing treatment is performed under the conditions of temperature 680 ° C and time 30 seconds, and glass fiber. Obtained a woven fabric.

Next, a film-forming liquid was prepared. The film-forming liquid is 100 parts by mass of a graphite dispersion (an aqueous dispersion containing 22.5% by mass of graphite and 7.5% by mass of carboxymethyl cellulose (hereinafter, may be abbreviated as "CMC")) and poly. Mix 50 parts by mass of a tetrafluoroethylene (hereinafter, abbreviated as "PTFE") solution (trade name: PTFE 31-JR, manufactured by Mitsui-Dupont Fluorochemical Co., Ltd., concentration 60% by mass of PTFE). I got it.

The obtained glass fiber woven fabric is impregnated in the film-forming liquid, squeezed with a nip roll to a nip pressure of 1 kgf / cm ² , and dried in two stages (first stage: temperature 210 ° C., time 15 minutes, second stage). The eyes were dried at a temperature of 250 ° C. and a time of 15 minutes) to obtain a graphite-attached glass fiber woven fabric. When the obtained graphite-attached glass fiber woven fabric was observed with a scanning electron microscope, as shown in FIG. 1, the film containing graphite was present on at least a part of the glass fibers in a state of covering the glass fibers. Was. Further, the film containing graphite covered the glass fiber on the surface and the inside of the glass fiber woven fabric. Graphite was contained in an amount of 37.5 parts by mass per 100 parts by mass of the film covering the glass fiber.

(Example 2)
The film-forming liquid is 100 parts by mass of a graphite dispersion (water dispersion containing 20% by mass of graphite solid content and 10% by mass of CMC solid content) and a PTFE solution (trade name manufactured by Mitsui Dupont Fluorochemical Co., Ltd.). A graphite-attached glass fiber woven fabric was obtained under the same conditions as in Example 1 except that it was obtained by mixing PTFE 31-JR and 50 parts by mass of PTFE with a solid content concentration of 60% by mass). When the obtained graphite-attached glass fiber woven fabric was observed with a scanning electron microscope, as in FIG. 1, the film containing graphite was present on at least a part of the glass fibers in a state of covering the glass fibers. Was there. Further, the film containing graphite was contained on the surface and the inner glass fiber of the glass fiber woven fabric. Graphite was contained in 33.4 parts by mass per 100 parts by mass of the film covering the glass fiber.

(Example 3)
The film-forming liquid is 100 parts by mass of a graphite dispersion (water dispersion containing 25% by mass of graphite and 5% by mass of CMC) and a PTFE solution (trade name PTFE 31-JR manufactured by Mitsui / DuPont Fluorochemical Co., Ltd.). , PTFE concentration 60% by mass) 50 parts by mass, and the same conditions as in Example 1 were obtained to obtain a graphite-attached glass fiber woven fabric. When the obtained graphite-attached glass fiber woven fabric was observed with a scanning electron microscope, as in FIG. 1, the film containing graphite was present on at least a part of the glass fibers in a state of covering the glass fibers. Was there. Further, the film containing graphite was contained on the surface and the inner glass fiber of the glass fiber woven fabric. 41.7 parts by mass of graphite was contained in 100 parts by mass of the film covering the glass fiber.

(Example 4)
As the warp and weft, trade name D450 6/2 3.8S manufactured by Unitika Co., Ltd. (D450 1/0 1Z 6 lower twisted, 2 upper twisted combined yarn, upper twist number 3.8 times / 25 mm, filament diameter 5.0 μm, count 134.4 tex), as a weft, one STD300 (bulky processed yarn, filament diameter 5.0 μm, count 302.0 tex) manufactured by Unitika Co., Ltd. and trade name D450 3/0 manufactured by Unitica Co., Ltd. (Filament diameter 5.0 μm, count 33.6 tex) A yarn obtained by combining and twisting one yarn (twist number 2.0 S, count 335.6 tex) was used. Both the warp and weft are the above-mentioned glass composition A as the glass composition constituting the glass fiber.

Using the above warp and weft, weaving with a double weft structure (warp density 48 lines / 25 mm, weft density 47 lines / 25 mm), caramelizing treatment is performed under the conditions of temperature 680 ° C. and time 30 seconds, and glass fiber woven fabric. Got

Next, a film-forming liquid was prepared. The film-forming liquid is 100 parts by mass of a graphite dispersion (water dispersion containing 22.5% by mass of graphite and 7.5% by mass of CMC) and a PTFE solution (trade name PTFE 31-manufactured by Mitsui DuPont Fluorochemical Co., Ltd.). JR, PTFE concentration 60% by mass) 50 parts by mass and was obtained by mixing.

The obtained glass fiber woven fabric is impregnated in the film-forming liquid, squeezed with a nip roll to a nip pressure of 1 kgf / cm ² , and dried in two stages (first stage: temperature 210 ° C., time 15 minutes, second stage). The eyes were dried at a temperature of 250 ° C. and a time of 15 minutes) to obtain a graphite-attached glass fiber woven fabric. When the obtained graphite-attached glass fiber woven fabric was observed with a scanning electron microscope, as in FIG. 1, the film containing graphite was present on at least a part of the glass fibers in a state of covering the glass fibers. Was there. Further, the film containing graphite was contained on the surface and the inner glass fiber of the glass fiber woven fabric. Graphite was contained in an amount of 37.5 parts by mass per 100 parts by mass of the film covering the glass fiber.

(Example 5)
As warp and weft, trade name D450 6/2 3.8S manufactured by Unitika Co., Ltd. (D450 1/0 1Z 6 lower twisted, 2 upper twisted combined twisted yarn, upper twist number 3.8 times / 25 mm, filament diameter 5.0 μm, count 134.4 tex), and as the weft, a trade name STD410 (bulky processed yarn, filament diameter 5.0 μm, count 410.0 tex) manufactured by Unitika Co., Ltd. was used. Both the warp and weft are the above-mentioned glass composition A as the glass composition constituting the glass fiber.

Using the above warp and weft, weaving with a double weft structure (warp density 48 lines / 25 mm, weft density 38 lines / 25 mm), caramelizing treatment is performed under the conditions of temperature 680 ° C. and time 30 seconds, and glass fiber woven fabric. Got

Next, a film-forming liquid was prepared. The film-forming liquid is 25 parts by mass of a graphite dispersion (water dispersion containing 22.5% by mass of graphite and 7.5% by mass of CMC) and a PTFE solution (trade name PTFE 31-manufactured by Mitsui / DuPont Fluorochemical Co., Ltd.). JR, PTFE concentration 60% by mass) 50 parts by mass and was obtained by mixing.

The obtained glass fiber woven fabric is impregnated in the film-forming liquid, squeezed with a nip roll to a nip pressure of 1 kgf / cm ² , and dried in two stages (first stage: temperature 210 ° C., time 15 minutes, second stage). The eyes were dried at a temperature of 250 ° C. and a time of 15 minutes) to obtain a graphite-attached glass fiber woven fabric. When the obtained graphite-attached glass fiber woven fabric was observed with a scanning electron microscope, as in FIG. 1, the film containing graphite was present on at least a part of the glass fibers in a state of covering the glass fibers. Was there. Further, the film containing graphite was contained on the surface and the inner glass fiber of the glass fiber woven fabric. Graphite was contained in an amount of 15.0 parts by mass per 100 parts by mass of the film covering the glass fiber.

(Example 6)
As warp and weft, trade name D450 6/2 3.8S manufactured by Unitika Co., Ltd. (D450 1/0 1Z 6 lower twisted, 2 upper twisted combined twisted yarn, upper twist number 3.8 times / 25 mm, filament diameter 5.0 μm, count 134.4 tex), and as the weft, a trade name STD410 (bulky processed yarn, filament diameter 5.0 μm, count 410.0 tex) manufactured by Unitika Co., Ltd. was used. Both the warp and weft are the above-mentioned glass composition A as the glass composition constituting the glass fiber.

Using the above warp and weft, weaving with a double weft structure (warp density 48 lines / 25 mm, weft density 38 lines / 25 mm), caramelizing treatment is performed under the conditions of temperature 680 ° C. and time 30 seconds, and glass fiber woven fabric. Got

Next, a film-forming liquid was prepared. The film-forming liquid is 10 parts by mass of a graphite dispersion (water dispersion containing 22.5% by mass of graphite and 7.5% by mass of CMC) and a PTFE solution (trade name PTFE 31-manufactured by Mitsui / DuPont Fluorochemical Co., Ltd.). JR, PTFE concentration 60% by mass) 50 parts by mass and was obtained by mixing.

The obtained glass fiber woven fabric is impregnated in the film-forming liquid, squeezed with a nip roll to a nip pressure of 1 kgf / cm ² , and dried in two stages (first stage: temperature 210 ° C., time 15 minutes, second stage). The eyes were dried at a temperature of 250 ° C. and a time of 15 minutes) to obtain a graphite-attached glass fiber woven fabric. When the obtained graphite-attached glass fiber woven fabric was observed with a scanning electron microscope, as in FIG. 1, the film containing graphite was present on at least a part of the glass fibers in a state of covering the glass fibers. Was there. Further, the film containing graphite was contained on the surface and the inner glass fiber of the glass fiber woven fabric. 6.8 parts by mass of graphite was contained per 100 parts by mass of the film covering the glass fiber.

(Example 7)
As warp and weft, trade name D450 6/2 3.8S manufactured by Unitika Co., Ltd. (D450 1/0 1Z 6 lower twisted, 2 upper twisted combined twisted yarn, upper twist number 3.8 times / 25 mm, filament diameter 5.0 μm, count 134.4 tex), and as the weft, a trade name STD410 (bulky processed yarn, filament diameter 5.0 μm, count 410.0 tex) manufactured by Unitika Co., Ltd. was used. Both the warp and weft are the above-mentioned glass composition A as the glass composition constituting the glass fiber.

Using the above warp and weft, weaving with a double weft structure (warp density 48 lines / 25 mm, weft density 38 lines / 25 mm), caramelizing treatment is performed under the conditions of temperature 680 ° C. and time 30 seconds, and glass fiber woven fabric. Got

Next, a film-forming liquid was prepared. The film-forming liquid is 50 parts by mass of a graphite dispersion (water dispersion containing 22.5% by mass of graphite and 7.5% by mass of CMC) and a silane coupling agent (trade name Syrah Ace manufactured by JNC Co., Ltd.). Registered trademark) S330, non-volatile content 0%) 5 parts by mass, 25% ammonia aqueous solution 0.2 parts by mass, silicone oil (trade name KM-9739 manufactured by Shin-Etsu Chemical Industry Co., Ltd. (non-volatile content 30% by mass)) 12 0.6 parts by mass, silicone resin (DIC Kita Nihon Polyma Co., Ltd. trade name Dick Silicon Softener 500 (nonvolatile content 15% by mass) 0.6 parts by mass, acrylic resin (DIC Co., Ltd. trade name DICNAL® E-8410WH) (Non-volatile content 40% by mass)) Obtained by mixing 5 parts by mass and 1.5 parts by mass of a wet penetrant (Kao Co., Ltd. trade name Perex (registered trademark) OT-P (70% by mass of active ingredient)). rice field.

The obtained glass fiber woven fabric is impregnated in the film-forming liquid, squeezed with a nip roll to a nip pressure of 1 kgf / cm ² , and dried in two stages (first stage: temperature 210 ° C., time 15 minutes, second stage). The eyes were dried at a temperature of 250 ° C. and a time of 15 minutes) to obtain a graphite-attached glass fiber woven fabric. When the obtained graphite-attached glass fiber woven fabric was observed with a scanning electron microscope, as in FIG. 1, the film containing graphite was present on at least a part of the glass fibers in a state of covering the glass fibers. Was there. Further, the film containing graphite was contained on the surface and the inner glass fiber of the glass fiber woven fabric. Graphite was contained in an amount of 12.6 parts by mass per 100 parts by mass of the film covering the glass fiber.

(Example 8)
As warp and weft, trade name D450 6/2 3.8S manufactured by Unitika Co., Ltd. (D450 1/0 1Z 6 lower twisted, 2 upper twisted combined twisted yarn, upper twist number 3.8 times / 25 mm, filament diameter 5.0 μm, count 134.4 tex), and as the weft, a trade name STD410 (bulky processed yarn, filament diameter 5.0 μm, count 410.0 tex) manufactured by Unitika Co., Ltd. was used. Both the warp and weft are the above-mentioned glass composition A as the glass composition constituting the glass fiber.

Using the above warp and weft, weaving with a double weft structure (warp density 48 lines / 25 mm, weft density 38 lines / 25 mm), caramelizing treatment is performed under the conditions of temperature 680 ° C. and time 30 seconds, and glass fiber woven fabric. Got

Next, a film-forming liquid was prepared. The film-forming liquid includes 50 parts by mass of a graphite dispersion (an aqueous dispersion containing a graphite concentration of 22.5% by mass and a CMC concentration of 7.5% by mass), 0.2 parts by mass of a 25% aqueous ammonia solution, and silicone. 12 parts by mass of oil (trade name KM-9739 manufactured by Shin-Etsu Chemical Industry Co., Ltd. (nonvolatile content 30% by mass)) and silicone resin (trade name DIC Silicon Softener 500 manufactured by DIC Kita Nihon Polyma Co., Ltd. (nonvolatile content 15% by mass)) 0. 6 parts by mass, acrylic resin (trade name DICNAL (registered trademark) E-8410WH (nonvolatile content 40% by mass) manufactured by DIC Co., Ltd.), 5 parts by mass, and wet penetrant (trade name Perex (registered trademark) OT of Kao Co., Ltd.) Obtained by mixing with 1.5 parts by mass of −P (active ingredient 70% by mass)).

The obtained glass fiber woven fabric is impregnated in the film-forming liquid, squeezed with a nip roll to a nip pressure of 1 kgf / cm ² , and dried in two stages (first stage: temperature 210 ° C., time 15 minutes, second stage). The eyes were dried at a temperature of 250 ° C. and a time of 15 minutes) to obtain a graphite-attached glass fiber woven fabric. When the obtained graphite-attached glass fiber woven fabric was observed with a scanning electron microscope, as in FIG. 1, the film containing graphite was present on at least a part of the glass fibers in a state of covering the glass fibers. Was there. Further, the film containing graphite was contained on the surface and the inner glass fiber of the glass fiber woven fabric. Graphite was contained in an amount of 13.9 parts by mass per 100 parts by mass of the film covering the glass fiber.

(Example 9)
As warp and weft, trade name D450 6/2 3.8S manufactured by Unitika Co., Ltd. (D450 1/0 1Z 6 lower twisted, 2 upper twisted combined twisted yarn, upper twist number 3.8 times / 25 mm, filament diameter 5.0 μm, count 134.4 tex), and as the weft, UTD410 (bulky processed yarn, filament diameter 5.0 μm, count 410.0 tex) manufactured by Unitika Co., Ltd. was used. Both the warp and weft are the above-mentioned glass composition B as the glass composition constituting the glass fiber.

Using the above warp and weft, weaving with a double weft structure (warp density 48 lines / 25 mm, weft density 38 lines / 25 mm), caramelizing treatment is performed under the conditions of temperature 680 ° C. and time 30 seconds, and glass fiber woven fabric. Got

Next, a film-forming liquid was prepared. The film-forming liquid is 100 parts by mass of a graphite dispersion (water dispersion containing 22.5% by mass of graphite solid content and 7.5% by mass of CMC solid content) and a PTFE solution (a product manufactured by Mitsui Dupont Fluorochemical Co., Ltd.). Name PTFE 31-JR, solid content concentration of PTFE 60% by mass) 50 parts by mass, and obtained by mixing.

The obtained glass fiber woven fabric is impregnated in the film-forming liquid, squeezed with a nip roll to a nip pressure of 1 kgf / cm ² , and dried in two stages (first stage: temperature 210 ° C., time 15 minutes, second stage). The eyes were dried at a temperature of 250 ° C. and a time of 15 minutes) to obtain a graphite-attached glass fiber woven fabric. When the obtained graphite-attached glass fiber woven fabric was observed with a scanning electron microscope, as in FIG. 1, the film containing graphite was present on at least a part of the glass fibers in a state of covering the glass fibers. Was there. Further, the film containing graphite was contained on the surface and the inner glass fiber of the glass fiber woven fabric. Graphite was contained in an amount of 37.5 parts by mass per 100 parts by mass of the film covering the glass fiber.

(Comparative Example 1)
As warp and weft, trade name D450 6/2 3.8S manufactured by Unitika Co., Ltd. (D450 1/0 1Z 6 lower twisted, 2 upper twisted combined twisted yarn, upper twist number 3.8 times / 25 mm, filament diameter 5.0 μm, count 134.4 tex), and as the weft, a trade name STD410 (bulky processed yarn, filament diameter 5.0 μm, count 410.0 tex) manufactured by Unitika Co., Ltd. was used. Both the warp and weft are the above-mentioned glass composition A as the glass composition constituting the glass fiber.

Using the above warp and weft, weaving with a double weft structure (warp density 48 lines / 25 mm, weft density 38 lines / 25 mm), caramelizing treatment is performed under the conditions of temperature 680 ° C. and time 30 seconds, and glass fiber woven fabric. Got The mass of the glass fiber woven fabric was 876.5 g / m ² .

(Comparative Example 2)
As the warp and weft, trade name D450 6/2 3.8S manufactured by Unitika Co., Ltd. (D450 1/0 1Z 6 lower twisted, 2 upper twisted combined yarn, upper twist number 3.8 times / 25 mm, filament diameter 5.0 μm, count 134.4 tex), as a weft, one STD300 (bulky processed yarn, filament diameter 5.0 μm, count 302.0 tex) manufactured by Unitika Co., Ltd. and trade name D450 3/0 manufactured by Unitica Co., Ltd. (Filament diameter 5.0 μm, count 33.6 tex) A yarn obtained by combining and twisting one yarn (twist number 2.0 S, count 335.6 tex) was used. Both the warp and weft are the above-mentioned glass composition A as the glass composition constituting the glass fiber.

Using the above warp and weft, weaving with a double weft structure (warp density 48 lines / 25 mm, weft density 47 lines / 25 mm), caramelizing treatment is performed under the conditions of temperature 680 ° C. and time 30 seconds, and glass fiber woven fabric. Got The mass of the glass fiber woven fabric was 839 g / m ² .

(Comparative Example 3)
As warp and weft, trade name D450 6/2 3.8S manufactured by Unitika Co., Ltd. (D450 1/0 1Z 6 lower twisted, 2 upper twisted combined twisted yarn, upper twist number 3.8 times / 25 mm, filament diameter 5.0 μm, count 134.4 tex), and as the weft, a trade name STD300 (bulky processed yarn, filament diameter 5.0 μm, count 302.0 tex) manufactured by Unitika Co., Ltd. was used. Both the warp and weft are the above-mentioned glass composition B as the glass composition constituting the glass fiber.

Using the above warp and weft, weaving with a double weft structure (warp density 48/25 mm, weft density 47/25 mm), caramelizing treatment is performed under the conditions of temperature 680 ° C and time 30 seconds, and glass fiber. Obtained a woven fabric. The mass of the glass fiber woven fabric was 815.9 g / m ² .

(Comparative Example 4)
As warp and weft, trade name D450 6/2 3.8S manufactured by Unitika Co., Ltd. (D450 1/0 1Z 6 lower twisted, 2 upper twisted combined twisted yarn, upper twist number 3.8 times / 25 mm, filament diameter 5.0 μm, count 134.4 tex), and as the weft, TDE300 (bulky processed yarn, filament diameter 6.0 μm, count 302.0 tex) manufactured by Unitika Co., Ltd. was used. Both the warp and weft are the above-mentioned glass composition C as the glass composition constituting the glass fiber.

Using the above warp and weft, weaving was performed with a double weft structure (warp density 48/25 mm, warp density 38/25 mm) to obtain a glass fiber woven fabric.

Next, a film-forming liquid was prepared. The film-forming liquid was 28 parts by mass of a graphite dispersion (an aqueous dispersion containing a graphite concentration of 22.5% by mass and a CMC concentration of 7.5% by mass) and a silane coupling agent (trade name: Sila Ace manufactured by JNC Co., Ltd.). Registered trademark) S330, non-volatile content 0%) 5 parts by mass, 25% ammonia aqueous solution 0.2 parts by mass, silicone oil (trade name KM-9739 (non-volatile content 30% by mass) manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 12 0.6 parts by mass, silicone resin (DIC Kita Nihon Polyma Co., Ltd. trade name Dick Silicon Softener 500 (nonvolatile content 15% by mass) 0.6 parts by mass, acrylic resin (DIC Co., Ltd. trade name DICNAL® E-8410WH) (Non-volatile content 40% by mass)) Obtained by mixing 5 parts by mass and a wet penetrant (Kao Co., Ltd. trade name Perex (registered trademark) OT-P (active ingredient 70% by mass)).

The obtained glass fiber woven fabric is impregnated in the film-forming liquid, squeezed with a nip roll to a nip pressure of 1 kgf / cm ² , and dried in two stages (first stage: temperature 210 ° C., time 15 minutes, second stage). The eyes were dried at a temperature of 250 ° C. and a time of 15 minutes) to obtain a graphite-attached glass fiber woven fabric. When the obtained graphite-attached glass fiber woven fabric was observed with a scanning electron microscope, as in FIG. 1, the film containing graphite was present on at least a part of the glass fibers in a state of covering the glass fibers. Was there. Further, the film containing graphite was contained on the surface and the inner glass fiber of the glass fiber woven fabric. Graphite was contained in an amount of 31.2 parts by mass per 100 parts by mass of the film covering the glass fiber.

(Comparative Example 5)
As warp and weft, trade name D450 6/2 3.8S manufactured by Unitika Co., Ltd. (D450 1/0 1Z 6 lower twisted, 2 upper twisted combined twisted yarn, upper twist number 3.8 times / 25 mm, filament diameter 5.0 μm, count 134.4 tex), and as the weft, TDE300 (bulky processed yarn, filament diameter 6.0 μm, count 302.0 tex) manufactured by Unitika Co., Ltd. was used. Both the warp and weft are the above-mentioned glass composition C as the glass composition constituting the glass fiber.

Using the above warp and weft, weaving was performed with a double weft structure (warp density 48/25 mm, warp density 38/25 mm) to obtain a glass fiber woven fabric.

Next, the treatment liquid was prepared. The treatment liquid is 50 parts by mass of a graphite dispersion (water dispersion containing 20% by mass of graphite solid content and 10% by mass of CMC solid content) and a silane coupling agent (trade name Sila Ace (registered trademark) manufactured by JNC Co., Ltd.). ) S330, non-volatile content 0%) 5 parts by mass, 25% ammonia aqueous solution 0.2 parts by mass, silicone oil (trade name KM-9739 manufactured by Shin-Etsu Chemical Industry Co., Ltd. (non-volatile content 30% by mass)) 12 parts by mass And silicone resin (DIC Kita Nihon Polyma Co., Ltd. trade name Dick Silicon Softener 500 (non-volatile content 15% by mass) 0.6 parts by mass, and acrylic resin (DIC Co., Ltd. trade name DICNAL® E-8410WH (non-volatile content) (40% by mass))) 5 parts by mass and a wet penetrant (Kao Co., Ltd. trade name Perex (registered trademark) OT-P (70% by mass of active ingredient)) were mixed.

The obtained glass fiber woven fabric is impregnated in the film-forming liquid, squeezed with a nip roll to a nip pressure of 1 kgf / cm ² , and dried in two stages (first stage: temperature 210 ° C., time 15 minutes, second stage). The eyes were dried at a temperature of 250 ° C. and a time of 15 minutes) to obtain a graphite-attached glass fiber woven fabric. When the obtained graphite-attached glass fiber woven fabric was observed with a scanning electron microscope, as in FIG. 1, the film containing graphite was present on at least a part of the glass fibers in a state of covering the glass fibers. Was there. Further, the film containing graphite was contained on the surface and the inner glass fiber of the glass fiber woven fabric. Graphite was contained in an amount of 42.0 parts by mass per 100 parts by mass of the film covering the glass fiber.

4. Evaluation Results Table 1 shows the evaluation results of the obtained graphite-attached glass fiber woven fabric.

The composition of the glass fiber constituting the glass fiber woven fabric is 60.0 to 66.0% by mass for SiO ₂ , 18.0 to 26.0% by mass for Al ₂ O ₃ , and 8.0 to 20.0% for MgO. When at least a part of the surface of the glass fiber was covered with a film containing graphite, excellent folding resistance could be maintained even when exposed to heat of 400 ° C. (Example). 1-9). In particular, when a combined twisted yarn of bulky processed yarn made of multifilament yarn and yarn made of multifilament yarn is used as the weft constituting the glass fiber woven fabric, the folding resistance in the weft direction is further excellent. There was (Example 4). Further, in Examples 1 to 9, in the film containing graphite, PTFE resin, which is a thermoplastic resin having no side chain or branch in the molecular structure, is used as a binder component, so that needle-passability during sewing is improved. It was particularly good. Further, in Examples 1 to 9, the dust collecting property when used as a dust collecting filter was also good.

On the other hand, the glass fiber woven fabric in which the glass fiber was not coated with the film containing graphite had insufficient folding resistance after heat exposure at 400 ° C. (Comparative Examples 1 to 3). Further, Comparative Examples 1 to 3 were inferior in needle threadability at the time of sewing. Further, even when the glass fiber was coated with a film containing graphite, even when the glass fiber was formed of E glass, the folding resistance after heat exposure at 400 ° C. was insufficient.

Claims (9)

With fiberglass fabric,
With a film containing graphite,
The film covers at least a part of the surface of the glass fiber constituting the glass fiber fabric.
The glass composition constituting the glass fiber contains 60.0 to 66.0% by mass of SiO ₂ , 18.0 to 26.0% by mass of Al ₂ O ₃ , and 8.0 to 20.0% by mass of MgO. %contains,
Graphite-attached fiberglass fabric. The glass composition constituting the glass fiber has SiO ₂ of 64.0 to 66.0% by mass, Al ₂ O ₃ of 24.0 to 26.0% by mass, and MgO of 9.0 to 11.0%. The graphite-attached glass fiber fabric according to claim 1, which contains 3% by mass or less (including 0% by mass) of other components. The graphite-attached glass fiber fabric according to claim 1 or 2, wherein the film comprises a thermoplastic resin and / or a silicone oil having no side chains and branches in its molecular structure. The graphite-attached glass fiber fabric according to any one of claims 1 to 3, wherein the film contains carboxymethyl cellulose. The glass fiber fabric is a woven fabric and
The warp and weft constituting the woven fabric is a combined twisted yarn of a bulky processed yarn made of a multifilament yarn and a yarn made of a multifilament yarn.
The graphite-attached glass fiber fabric according to any one of claims 1 to 4. The graphite-attached glass fiber fabric according to any one of claims 1 to 5, wherein 30 parts by mass or more of the graphite is contained in 100 parts by mass of the film. A dust collecting filter comprising the graphite-adhered glass fiber fabric according to any one of claims 1 to 6. The dust collection filter according to claim 7, which is a bag filter. Use of the graphite-attached glass fiber fabric according to any one of claims 1 to 6 as a dust collection filter.

Images