JPH07216747A - Heat resistant sheet - Google Patents

Abstract

PURPOSE:To obtain a heat resistant sheet excellent in heat resistance, flexing resistance and sewing properties. CONSTITUTION:This heat resistant sheet is obtained by forming a heat-resistant coated layer containing a fluorine-containing resin having a melting point of 300 deg.C or below and a heat-resistant inorganic material at a weight ratio of (20/100)-(80/0) in a base fabric containing an inorganic fiber and a heat-resistant organic synthetic fiber having >=300 deg.C melting point or heat decomposition point at a weight ratio of (50/50) to (90/10) by impregnation or coating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant sheet, and more specifically to a soft and flexible fiber sheet which has excellent heat resistance, sewability and bending resistance.

[0002]

2. Description of the Related Art Conventionally, polyester fibers (having a melting point of 255 to
260 ° C.), polyamide fiber (melting point 215 to 260 ° C.)
A fibrous base fabric made of, for example, a thermoplastic resin such as polyvinyl chloride (PVC, heat resistant temperature 66 to 79 ° C), polyurethane (heat resistant temperature 90 to 120 ° C), acrylic resin (heat resistant temperature 60 to 88 ° C), Polyethylene (heat resistant temperature 80 ~
120 ° C, polypropylene (heat resistant temperature 120 to 160)
C.), polyamide (heat resistant temperature of 80 to 150.degree. C.) or polyester (heat resistant temperature of about 120.degree. C.) is known, and a sheet material obtained is known. In this case, since the fibrous base cloth has a relatively low melting point, as a coating material for covering the fibrous base cloth,
The fibrous base fabric must be capable of being coated at a processing temperature that the fibrous base fabric can withstand. Therefore, as the coating material, a resin having relatively low heat resistance is used as described above. However, recently, the fiber sheet material is often used in, for example, fire clothes, heat-resistant garments, film-like building materials, etc., and in order to maintain safety from flames, burns, and other thermal disasters,・ Demand for flame retardancy is increasing. Therefore, development of heat resistant sheet material is strongly desired.

In response to the above demands, Japanese Patent Laid-Open No. 58-58
120677 and JP-A-58-127757 propose high-temperature heat-insulating paints and fire-resistant heat-insulating films containing alkali titanate and silicone resin, and JP-A-58-130183 and 58- 1
No. 99791 and JP-A-59-35938 disclose fire resistance obtained by forming a coating layer containing a silicone resin and an alkali titanate on the surface of an inorganic core material such as glass fiber base cloth or asbestos paper. A sheet is disclosed.

Further, JP-A-59-26987 and JP-A-59-36157 disclose heat-resistant compositions obtained by mixing a polyorganophosphonitrile compound with a silicone resin or an alkyl silicate, and the heat-resistant compositions. It is disclosed to coat an inorganic core material. Heat-resistant sheets using these inorganic fiber base fabrics have excellent fire and heat insulating properties, antifouling properties, weather resistance, etc., but their weight (weight) is large and they are inconvenient to use and handle. Also, it is difficult to sew, and its bending resistance is low, so it is easy to break during use, especially if it is used for vibration or fluttering, or for applications with severe bending, and it is easy to tear from perforations. However, there has been a strong demand for solving this problem.

[0005]

SUMMARY OF THE INVENTION According to the present invention, a flexible and heat-resistant sheet is improved in its bending resistance so that it can withstand vibration, fluttering, or repeated bending, and is sewn. It is easy to do and makes it difficult for tears to occur from the perforations.

[0006]

The heat-resistant sheet of the present invention comprises inorganic fibers and heat-resistant organic synthetic fibers having a melting point of 300 ° C. or higher or a thermal decomposition point of 50:50 to 90:
A base fabric made of a knitted fabric containing 10 to 10 by weight, 20 to 100% by weight of a fluorine-containing resin impregnated or applied to the base fabric and having a melting point of 300 ° C. or less, and 80 to
And a heat resistant coating layer containing 0 wt% of a heat resistant inorganic material.

[0007]

The heat-resistant sheet of the present invention has a base fabric made of a knitted fabric containing inorganic fibers and heat-resistant organic synthetic fibers, and a heat-resistant coating layer containing a fluorine-containing resin.

The inorganic fibers constituting the base cloth used in the present invention can be selected from asbestos fibers, ceramic fibers, silica fibers, glass fibers, carbon fibers, metal fibers and the like.

The organic fiber used as the base fabric in the present invention is a heat-resistant organic synthetic fiber having a melting point of 300 ° C. or higher or a thermal decomposition temperature, and if necessary, contains an organic fiber different from that. Good. Such heterogeneous organic fibers include natural fibers such as cotton and hemp, regenerated fibers such as viscose rayon, cupra and the like, semi-synthetic fibers such as di- and tri-acetate fibers, and synthetic fibers such as. , Polyamide (nylon 6,
Nylon 66 etc.) fiber, polyester (polyethylene terephthalate etc.) fiber, acrylic fiber, etc. can be selected.

The polymers forming the heat-resistant organic synthetic fiber having the high melting point or the high thermal decomposition point are shown in Tables 1 and 2.

[0011]

[Table 1]

[0012]

[Table 2]

Among the heat-resistant polymers shown in Tables 1 and 2, polymetaphenylene isophthalamide and polyparaphenylene terephthalamide are common, and other para-type aramid fibers manufactured by Teijin Ltd. "HM-50" of No. can also be used.

Aromatic polyamides useful in such fibers are:
In addition, at least 50 mol% of the following formulas (I) and (I
I),-(Ar ₁ -CONH)-(I)-(Ar ₁ -CONH-Ar ₂ -NHCO)-(II) [wherein Ar ₁ and Ar ₂ represent a divalent aromatic group, These may be the same as or different from each other.] It is preferable to have at least one kind selected from the units shown as the main repeating unit. In the above formulas (I) and (II), the divalent aromatic group represented by Ar ₁ and Ar ₂ has the following formula:

[Chemical 1] [In the above formula, A is -O-, -S-, -SO-, -SO
_{2 -, - CO -, -} CH 2 - or -C (CH _{3) 2} - to be selected from aromatic residue group preferably represented by the representative]. These aromatic residues may contain an inert substituent such as a halogen, an alkyl group or a nitro group.

Generally, the aromatic polyamide has the following formula:

[Chemical 2] Those having a repeating unit represented by as a main component are more preferable.

As the heat-resistant organic synthetic fiber, in addition to the above, fluorine-based fibers and other fibers can be used as long as they have a melting point or a thermal decomposition point of 300 ° C. or higher.

When the heat-resistant organic synthetic fiber is used, the weight ratio of the heat-resistant organic synthetic fiber to the inorganic fiber in the base fabric is in the range of 50:50 to 90:10, and 50:50 to 50.
It is preferably within the range of 80:20. Further, in order to promote adhesion with the heat resistant coating layer and other performances, a fiber having a melting point or a thermal decomposition point lower than 300 ° C., for example, an organic fiber different from the heat resistant organic synthetic fiber is used as a base fabric. Can also be mixed. However, it is preferable that the heat resistant fiber (the total amount of the inorganic fiber and the heat resistant organic synthetic fiber) is contained in the base fabric in an amount of 50% by weight or more, and 60
It is more preferable that the content is at least wt%.

The inorganic and heat resistant organic synthetic fibers and heterogeneous organic fibers in the base fabric may be in any shape such as short fiber spun yarn, long fiber yarn, split yarn, tape yarn, etc. May be woven or knitted. However, considering the strength and bending resistance of the sewn portion, the base fabric is preferably a woven fabric. In addition, as the form of the fiber, a form of long fiber (filament) having a small elongation against stress is preferable, and a plain woven fabric is preferably formed. However, the weaving structure of the base fabric and its form are not particularly limited. The heat resistant organic synthetic fiber is useful for maintaining the mechanical strength of the obtained heat resistant sheet at a high level.

In the base cloth, the inorganic fibers and the heat-resistant organic synthetic fibers may be mixed in any manner. For example, any of mixed yarn, mixed knitted fabric, mixed twisted yarn, aligned yarn, and the like may be used. However, the heat-resistant organic synthetic fiber is 1
It is contained in an amount of 0 to 50% by weight, preferably 20 to 50% by weight. In addition, the inorganic fiber is 50 to 90 in the base cloth.
% By weight, preferably 50 to 80% by weight. When the content ratio of the inorganic fibers is less than 50% in the mixing ratio of the inorganic fibers and the heat resistant organic synthetic fibers, the heat resistance of the resulting heat resistant sheet may not reach the desired level, and the heat resistant organic synthetic fibers may be used. When the content of the heat-resistant sheet is less than 10%, the folding resistance and sewability of the resulting heat-resistant sheet may not reach desired levels, and when the content of the expensive heat-resistant organic synthetic fiber exceeds 50% by weight. However, the cost of the heat resistant sheet becomes high and it becomes unpractical.

When glass fibers are used as the inorganic fibers, the type and fineness thereof are not particularly limited, but those generally called beta yarn having a thickness of about 2 to 10 μm, especially about 3 μm, are used. It is used.

In the heat resistant sheet of the present invention, the heat resistant coating layer contains 20 to 100% by weight of a fluorine-containing resin having a melting point of 300 ° C. or lower and 80 to 0% by weight of a heat resistant inorganic material.

The fluorine-containing resin used in the present invention is 30
A polymer having a melting point of 0 ° C. or less, a tetrafluoroethylene-perfluoroolefin copolymer (for example, tetrafluoroethylene-hexafluoropropylene copolymer), a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-perfluoroalkylethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, chlorotrifluoroethylene-ethylene copolymer, etc. It is preferable that at least one selected from the above is included.

The heat-resistant coating layer of the present invention contains 2% fluorine-containing resin.
The heat resistant inorganic material is contained at a content of 0 to 100% by weight, and the heat resistant inorganic material is contained at a content of 80 to 0% by weight. If the content of the fluorine-containing resin is less than 20% by weight, the resulting heat-resistant coating layer will have insufficient flexibility and bending resistance, and the sewability and adhesiveness to the base cloth will be unsatisfactory. The compounding ratio of the fluorine-containing resin and the heat resistant inorganic material is 20:80 to 8
It is preferably 0:20. Although the above-mentioned fluorine-containing resins have extremely good weather resistance, an ultraviolet absorber may be incorporated into these resins for the purpose of protecting the base cloth. Further, it goes without saying that a colorant or other performance-imparting agent may be added. The coating layer made of these resins may be microporous, or may have open or discontinuous cells. As the heat-resistant inorganic material contained in the heat-resistant coating layer of the present invention, a fluorine-containing resin 10
It is preferable to use 1 to 200 parts by weight of alkali titanate with respect to 0 parts by weight.

Alkali titanate is preferably used as the heat resistant inorganic material contained in the heat resistant coating layer of the present invention. The alkali titanate used in the present invention has the general formula M ₂ O.nTiO ₂ .mH ₂ O (where M is Li, N
a represents an alkali metal such as K, n represents a positive real number of 8 or less, and m represents 0 or a positive real number of 4 or less. )
Is a well-known compound represented by
i ₄ TiO ₄ Li ₂ TiO ₃ (0 <n <1, m = 0), an alkali titanate having a salt structure, Na ₂ Ti
₇ O ₁₅・ K ₂ Ti ₆ O ₁₅・ K ₂ Ti ₈ O ₁₇ (0 <6, m
= 0), including a tunnel structure alkali titanate and the like. Of these, the general formula K ₂ O · 6TiO ₂
The potassium hexatitanate represented by mH ₂ O (m in the formula is the same as described above) and its hydrate are preferable in that the fire resistance and heat insulating properties of the final target product are further improved. Alkali titanate is not limited to potassium hexatitanate, and is generally a powder or fibrous fine crystal. Of these, the fiber length is 5 μm.
Those having m or more and an aspect ratio of 20 or more, particularly 100 or more bring about preferable results for improving the strength of the heat resistant sheet of the present invention. Further, in particular, fibrous potassium titanate has a high specific heat and is excellent in heat insulation performance, and is particularly effective for further improving the heat resistance and heat insulation performance of the heat resistant sheet of the present invention.

Further, the heat resistant coating layer of the present invention may contain a high refractive index inorganic compound or a heat absorbing inorganic compound within a range in which the content of the fluorine-containing resin can be maintained at 20% or more. High-refractive-index inorganic compounds have excellent shielding performance against radiant heat, and endothermic inorganic compounds are heated at this contact surface when they come into direct contact with slag during welding or fusing, and an endothermic reaction occurs during their decomposition, resulting in a slag temperature. Lower. Therefore, the above-mentioned inorganic compound can prevent the heat-resistant coating layer of the present invention from collapsing or break through heat and can further protect the heat-resistant sheet substrate.

The high-refractive-index inorganic compound useful in the present invention may have a refractive index of 1.5 or more, and particularly preferably has a specific gravity of 2.8 or more. Examples thereof are as follows. There is something. 1) Dolomite (dolomite: specific gravity 2.8 to 2.9, refractive index 1.50 to 1.
68) Magnesite (rhodochrosite: specific gravity 3.0 to 3.1, refractive index 1.51 to
1.72) Aragonite (specific gravity 2.9 to 3.0, refractive index 1.53 to 1.68) Abatite (apatite: specific gravity 3.1 to 3.2, refractive index 1.53 to 1.68).
54) Spinel (Spinel, specific gravity 3.5-3.6, refractive index 1.72-1.
73) Corundum (specific gravity 3.9 to 4.0, refractive index 1.76 to 1.77) Zircon (specific gravity 3.90 to 4.10, refractive index 1.79 to 1.8)
1) Silicon carbide (specific gravity 3.17 to 3.19, refractive index 2.65 to 2.6)
9) Powder of crushed products of natural or synthetic minerals such as. 2) Fine powder or granules, fibrous substances or foams of frit or high refraction glass or fused phosphorus fertilizer or other similar solid solution obtained as a solid solution of phosphate rock and serpentine.

As the endothermic inorganic compound, calcined gypsum,
Alum, calcium carbonate, aluminum hydroxide, hydrosalcite type aluminum silicate, etc.
Examples thereof include endothermic inorganic compounds such as carbon dioxide releasing type, decomposition endothermic type and phase inversion type. Alkali titanate,
And, if necessary, a high refractive index inorganic compound and / or an endothermic inorganic compound are mixed and dispersed in a fluorine-containing resin to obtain a mixture for a heat resistant coating layer for producing a heat resistant sheet according to the present invention. As a method for preparing the mixed dispersion, any known means can be used. In addition, in the mixture for the heat-resistant coating layer, a dispersant or a defoaming agent for uniformly dispersing each component, a colorant for adjusting the color or mechanical strength, a resin powder, a flame retardant, a metal powder. , And other various fillers can be mixed freely. In addition, mixing of metal powder such as copper powder, nickel powder, titanium powder, silicon powder, brass powder, aluminum powder, and iron powder is preferable from the viewpoint of improving the surface heat reflection effect and the heat penetration suppressing effect.

As a method for coating the surface of the base cloth with the heat resistant coating layer, a method for coating the surface of the base cloth with a mixture for heat resistant coating such as spray coating, brush coating, and roll coating,
Alternatively, there is a method in which a film obtained by molding the heat-resistant coating mixture is attached to the surface of the base cloth, or a method in which the base cloth is dipped in the heat-resistant coating mixture and impregnated.

The heat resistant sheet of the present invention is manufactured, for example, as follows. That is, after appropriately adding a reaction accelerator and an additive to a mixture of a fluorine-containing resin, an alkali titanate and optionally a high refractive index inorganic compound, and / or an endothermic inorganic compound, toluene, xylene, trichlene are further added if necessary. An organic solvent such as the above is added to prepare a dispersion having an appropriate concentration. This dispersion is a dipping method, a spraying method, a roll coating method,
The base cloth is impregnated by a conventionally well-known impregnation such as a reverse roll coating method or a knife coating method, or a coating means, or one or both surfaces thereof are coated.

Impregnation of the dispersion liquid is carried out by the dipping method, and coating is carried out by a spraying method, a roll coating method, a reverse roll coating method, a knife coating method or the like. Which of the impregnation method and the coating method is used may be appropriately set depending on the structure, thickness, and type of the base fabric, the intended use of the heat-resistant sheet, the desired performance, the feel, and the like.

Next, the base cloth impregnated or coated with the fluorine-containing resin-containing dispersion as described above is 400 ° C. or lower, preferably 150 to 370 ° C., more preferably 150.
The heat-resistant coating layer is integrally fixed to the above-mentioned base cloth by heat treatment in the range of ˜350 ° C. for 1-30 minutes. The mixing ratio of the fluorine-containing resin, alkali titanate, high-refractive-index inorganic compound, and / or endothermic inorganic compound varies depending on the type and particle size of the fluorine-containing resin and heat-resistant inorganic compound used. If the ratio is less than 20% by weight, the strength of the heat-resistant coating layer is insufficient, and as a result, when the heat-resistant sheet obtained is used for fire insulation, the heat-resistant coating layer may crack or the heat-resistant coating layer may become a base material. It causes defects such as peeling from the cloth.

In the present invention, the amount of alkali titanate blended with 100 parts by weight of the fluorine-containing resin is preferably 1 to 200 parts by weight, more preferably 30 to 100 parts by weight.
Parts by weight. When the heat-resistant coating layer of the present invention contains a fluorine-containing resin and an alkali titanate, when the content of the alkali titanate is less than 1 part by weight per 100 parts by weight of the fluorine-containing resin, the heat shielding property by the addition of the alkali titanate is obtained. The improvement effect becomes insufficient. Moreover, even if it exceeds 200 parts by weight, the effect is saturated, which is economically disadvantageous.

When a heat-resistant inorganic material such as a high-refractive-index inorganic compound and / or an endothermic inorganic compound is added to the heat-resistant coating layer, its content should be 400 parts by weight or less relative to 100 parts by weight of the fluorine-containing resin. In this case, it is preferable to use the same amount as the alkali titanate and a weight of 1/4 to that of the alkali titanate. Ordinary fluorine-containing resin 1
It is preferably used in the range of 10 to 300 parts by weight with respect to 00 parts by weight. It should be noted that these alkali titanates, high-refractive-index inorganic compounds, part or the whole amount of the endothermic inorganic compounds are generally replaced with commonly used inorganic pigments, inorganic fillers for increasing the amount, inorganic powder for imparting flame retardancy, etc. However, the amount of these heat-resistant inorganic materials used is 10
400 parts by weight or less with respect to 0 parts by weight, preferably 3
It is not more than 00 parts by weight.

The heat resistant sheet of the present invention has a thickness of 0.02 mm.
It is preferably above, and more preferably within the range of 0.05 to 2.0 mm.

An adhesive substance may be interposed between the base cloth and the heat-resistant coating layer for the purpose of improving the adhesion and durability. In this case, it is not necessary to intervene particularly thickly in order to improve the adhesive strength. The adhesive substance is not used for forming a film, and therefore a substance known as an adhesive can be used. For example, amino groups, imino groups, ethyleneimine residues, acrylates containing alkylenediamine residues, acrylates containing aziridinyl groups, aminoester-modified vinyl polymers, aromatic epoxy adhesives,
Amino nitrogen-containing methacrylate polymer and other adhesives may be used together. Further, it is also possible to arbitrarily select a resin having the same quality as the resin constituting the fiber base cloth such as polyamide-imide or polyimide, or an RFL-modified substance.

In the heat-resistant sheet of the present invention, the heat-resistant coating layer may be formed on only one side, but it may be formed on both sides to compensate for the low weather resistance of the base fabric, etc. In some cases, double-sided formation may be an essential condition.
On the other side, depending on the performance required for the heat resistant sheet, natural rubber, neoprene rubber, chloroprene rubber,
It is also possible to use silicone rubber, chlorosulfonated polyethylene (hypalon) or other synthetic rubber, or PVC resin, ethylene-vinyl acetate copolymer (EVA) resin, acrylic resin, silicone resin, urethane resin, polyester resin or other synthetic resin. In this case, it is more preferable that these resins are flame-retarded.

The thickness of the heat-resistant coating layer is preferably 5 to 2000 μm, particularly 10 to 1500 μm. The heat-resistant sheet of the present invention can also be used in combination with other materials such as foam or mat. The heat-resistant sheet of the present invention may be formed into a tape shape or a strip shape, or a sheet-like material may be cut into a tape shape or a strip shape. Such a tape-shaped heat-resistant sheet can be used by being coated or wound in applications requiring heat resistance and flame retardancy such as electric wires and cables. It may also be used in combination with other materials such as foams, nets, mats and the like.

[0038]

EXAMPLES The heat resistant sheet of the present invention will be described in more detail with reference to examples. Comparative Example 1 As the base fabric, a glass fiber fabric having the following structure was used. A basis weight of 290 g / m ^{2 An} acrylic adhesive (SC462, manufactured by Sony Chemical Co., Ltd.) was applied to both surfaces of the above base cloth at a coating amount of 30 g / m ² and dried.

Separately, a fluorine-containing resin composition having the following composition was prepared. Following composition: INGREDIENT AMOUNT (parts by weight) tetrafluoroethylene - hexafluoropropylene 100 copolymer (FEP, mp275 ℃) 50% aqueous dispersion a water-soluble acrylic resin (thickener) Potassium 0.65 titanate (trademark of : Tismo D, Otsuka Chemical Co., Ltd.) 60 The viscosity of this composition was about 900 centipoise.

The above base cloth was dipped in the above composition and squeezed, and it was gradually heated to a temperature of 250 to 300 ° C. and dried, and then a coating film was formed at a temperature of 350 ° C. The thickness of the obtained heat resistant coating layer was about 150 μm on both surfaces.

The obtained sheet was used in Japanese Patent Application Laid-Open No. 58-13018.
It was subjected to the fireproof heat insulation test described in No. 3. At this time, the evaluation criteria of the fire resistance and heat insulation were as follows. Type A: When melting a 9 mm-thick steel plate for spark generation, there should be no through-holes that are harmful to the sparks generated and fire prevention. Class B: When a 4.5 mm-thick steel plate for spark generation is melt-cut, there should be no through holes that are harmful to the spark generated and to prevent fire. Class C: When a 3.2 mm thick steel plate for spark generation is melt-cut, there should be no through-holes that are harmful to the spark generated and fire prevention. Class D: When melting 3.2 mm thick steel plate for spark generation, through holes harmful for fire prevention are generated. Class E: Flame was generated when a 3.2 mm thick steel plate for spark generation was blown.

The fire resistance of the sheet of Comparative Example 1 was Class A. For the sheet of Comparative Example 1, JIS P8115
(1976) "Folding strength test method of MIT type tester for paper and paperboard" was performed, and the sheet was broken at 3000 times of bending. That is, the sheet of Comparative Example 1 had a low durability against vibration, fluttering, or bending because it used the base fabric made of only glass fibers.

Further, for the sheet of Comparative Example 1, a 112W-115 industrial sewing machine (two needles, lock stitch thread feed, for tent) manufactured by Singer was used, and Nomex multifilament thread (500d) was used as a stitch thread. Lockstitch, straight line, 2
When the stitches were sewn with 50 stitches / 10 cm by the lock stitch, the sewn portion (perforation) was torn during the sewing.

[0044] In tissues of the base fabric used in Example 1 Comparative Example 1, one glass fiber yarns to, aromatic polyamide fiber yarns (Kevlar, 1
95 denier / 130 f) A base cloth was prepared by using the warp and weft in a ratio of 2 pieces. The weight mixing ratio of the inorganic fiber and the heat-resistant organic synthetic fiber in this base cloth was 60.5: 39.5. The above base cloth was subjected to the same adhesive treatment and heat resistant coating treatment as in Comparative Example 1 to produce a heat resistant sheet.

The heat resistance of this heat resistant sheet was Class B, and in its folding endurance test, it did not break even after 10,000 times of bending, and showed almost infinite folding endurance. Also,
The same sewing as in Comparative Example 1 was carried out, but the sewing part (perforation)
I could sew smoothly without tearing.

Example 2 The same operation as in Example 1 was performed. However, in the base cloth,
Carbon fiber threads were used instead of the glass fiber threads. The weight mixing ratio of the inorganic fiber and the heat-resistant organic synthetic fiber in this base cloth was 52.0: 48.0. The obtained heat-resistant sheet has a fire insulation property of Class B and a folding strength of 1
It was over 10,000 times. Further, as in the case of Example 1, sufficient sewability was obtained.

Example 3 The same operation as in Example 1 was performed. However, in the warp and weft of the base fabric, one glass fiber yarn and one Kevlar fiber yarn and one polyethylene terephthalate multifilament yarn were used by being interwoven. The weight mixing ratio of the inorganic fiber and the heat resistant organic synthetic fiber in this base cloth is 65.4:
It was 34.5. The maximum heat treatment temperature was 280 ° C. The resulting heat-resistant sheet had Class C fire resistance and heat resistance, exhibited a folding strength of 10,000 times or more, and exhibited the same good sewing property as in Example 1.

Example 4 The same operation as in Example 1 was performed. However, sodium titanate was not used. The heat-resistant sheet obtained had a fire resistance of Class C and a folding endurance of 10,000 times or more. Also, a good sutured portion was obtained as in Example 1.

Example 5 The same operation as in Example 1 was performed. However, the fluorine-containing resin composition was applied to both sides of the base fabric using a roll coater to form a heat resistant coating layer having a thickness of about 150 μm on each side.
The performance and sewability of the obtained heat resistant sheet were almost the same as in Example 1.

Comparative Example 2 The same operation as in Example 1 was performed. However, in the preparation of the fluorine-containing resin composition, instead of the tetrafluoroethylene-hexafluoropropylene copolymer 50% aqueous dispersion, a flame retardant treatment liquid having the following composition was used. Component Parts by weight flame retardant silicone resin KR2038 100 (trademark, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%) Flame-retardant silicone crosslinker D2038 2 (trademark, manufactured by Shin-Etsu Chemical Co.) 40 solution viscosity in toluene (B-type No. 6, 20 rpm) 35 Poise [Note: (*) ₁ ... vinyl group-containing organosiloxane] A base cloth is dipped in the above treatment solution, squeezed and dried at 100 ° C for 2 minutes, and at 200 ° C for 1 minute. Heat treated. The folding endurance of the obtained heat resistant sheet was 10,000 times, but the surface of the silicone resin coating the surface was soft,
It showed a slight tackiness and was brittle, and due to this, when the state after the folding endurance test was observed on the surface, peeling of the resin was clearly observed. In addition, its fire resistance and heat insulation is Class C, and its sewability is unsatisfactory in terms of workability because the sheet is soft and sticky at the time of sewing, and the sheet is not fed well at the time of sewing It was something.

Comparative Example 3 A heat resistant sheet was prepared in the same manner as in Example 1. However,
In preparing the fluorine-containing resin composition, polytetrafluoroethylene (PTF) was used instead of the tetrafluoroethylene-hexafluoropropylene copolymer 50% aqueous dispersion.
E) Using an aqueous dispersion (solid content: 60%), the film formation temperature was set to 480 ° C. The obtained heat-resistant sheet became coarse and brittle because the organic fibers contained therein deteriorated and hardened, and its folding endurance was less than 3,000 times, which was not practical. In addition, the film formation temperature,
When the temperature was set to 350 ° C., the film formation and adhesion were insufficient, and the film was easily peeled off from the base fabric and could not be put to practical use.

[0052]

EFFECTS OF THE INVENTION The heat-resistant sheet of the present invention has a required amount of heat-resistant organic synthetic fibers mixed with the inorganic fibers, and therefore has a desired flexibility and excellent bending resistance while maintaining desired heat resistance. In addition, it has excellent sewability, and thus can be widely used for applications where it is repeatedly bent at high temperatures, or undergoes violent vibration or fluttering (for example, fireproof clothing, opening / closing curtains and architectural film materials).

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[Procedure amendment]

[Submission date] November 21, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 3

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

[0011]

[Table 1]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

In the base cloth, the inorganic fibers and the heat-resistant organic synthetic fibers may be mixed in any manner. For example, any of mixed yarn, mixed knitted fabric, mixed twisted yarn, aligned yarn, and the like may be used. However, the heat-resistant organic synthetic fiber is 1
It is contained in an amount of 0 to 50% by weight, preferably 20 to 50% by weight. In addition, the inorganic fiber is 50 to 90 in the base cloth.
% By weight, preferably 50 to 80% by weight. When the content ratio of the inorganic fibers is less than 50% by weight in the mixing ratio of the inorganic fibers and the heat-resistant organic synthetic fibers, the heat resistance of the resulting heat-resistant sheet may not reach the desired level. If the fiber content is less than 10% by weight, the resulting heat-resistant sheet may not reach desired levels in folding strength and sewing property, and the expensive heat-resistant organic synthetic fiber content may be 50% by weight. If it exceeds%, the cost of the heat resistant sheet becomes high and it becomes impractical.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

Further, the heat resistant coating layer of the present invention may contain a high refractive index inorganic compound or a heat absorbing inorganic compound within a range in which the content of the fluorine-containing resin can be maintained at 20% by weight or more. High-refractive-index inorganic compounds have excellent shielding performance against radiant heat, and endothermic inorganic compounds are heated at this contact surface when they come into direct contact with slag during welding or fusing, and an endothermic reaction occurs during their decomposition, resulting in a slag temperature. Lower. Therefore, the above-mentioned inorganic compound can prevent the heat-resistant coating layer of the present invention from collapsing or break through heat and can further protect the heat-resistant sheet substrate.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

Next, the base fabric impregnated or coated with the fluorine-containing resin-containing dispersion as described above is 400 ° C. or lower, preferably 150 to 370 ° C., more preferably 15 ° C.
The heat-resistant coating layer is integrally fixed to the above-mentioned base fabric by heat treatment in the range of 0-350 ° C for 1-30 minutes.
The mixing ratio of the fluorine-containing resin, alkali titanate, high-refractive-index inorganic compound, and / or endothermic inorganic compound varies depending on the type and particle size of the fluorine-containing resin and heat-resistant inorganic compound used. Rate is 20
If the content is less than 10% by weight, the strength of the heat-resistant coating layer becomes insufficient, and as a result, when the obtained heat-resistant sheet is used for fire insulation, the heat-resistant coating layer may crack or peel off from the base fabric. There are drawbacks such as damage.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

Comparative Example 2 The same operation as in Example 1 was performed. However, in the preparation of the fluorine-containing resin composition, instead of the tetrafluoroethylene-hexafluoropropylene copolymer 50% aqueous dispersion, a flame retardant treatment liquid having the following composition was used. Component Parts by weight flame retardant silicone resin KR2038 (*) ₁ 100 (trademark, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%) Flame-retardant silicone crosslinker D2038 2 (trademark, manufactured by Shin-Etsu Chemical Co., Ltd.) Toluene 40 Liquid viscosity (B-type No. 6, 20 rpm) 35 poise [Note: (*) ₁ ... Vinyl group-containing organosiloxane] Dip a base cloth in the above treatment solution, squeeze, and at 2 ° C at 100 ° C.
It was dried for 1 minute and heat-treated at 200 ° C. for 1 minute. The folding endurance of the obtained heat resistant sheet was 10,000 times, but the surface of the silicone resin coating the surface was soft,
It showed a slight tackiness and was brittle, and due to this, when the state after the folding endurance test was observed on the surface, peeling of the resin was clearly observed. In addition, its fireproof heat insulation is Class C, and its sewability is that the sheet is soft and sticky, so the sheet is not fed well at the time of sewing, and the needle passage is not rubbed strongly and is not smooth. Was also unsatisfactory.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

Comparative Example 3 A heat resistant sheet was prepared in the same manner as in Example 1. However,
In preparing the fluorine-containing resin composition, polytetrafluoroethylene (PTF) was used instead of the tetrafluoroethylene-hexafluoropropylene copolymer 50% aqueous dispersion.
E, mp 327 ° C.) An aqueous dispersion (solid content: 60%) was used and the film formation temperature was set to 480 ° C. The obtained heat-resistant sheet became coarse and brittle because the organic fibers contained therein deteriorated and hardened, and its folding endurance was less than 3,000 times, which was not practical. Further, when the film forming temperature was set to 350 ° C., the film was not sufficiently formed and adhered, and the film was easily peeled off from the base fabric and could not be put to practical use.

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Claims (6)

[Claims] 1. An inorganic fiber, and a melting point of 300 ° C. or higher,
Alternatively, a heat-resistant organic synthetic fiber having a heat decomposition point is set to 50: 5.
A base fabric made of a knitted woven fabric containing a weight ratio of 0 to 90:10, 20 to 100% by weight of a fluorine-containing resin impregnated or applied to the base fabric and having a melting point of 300 ° C. or less, and 80 to A heat-resistant sheet having a heat-resistant coating layer containing 0 wt% of a heat-resistant inorganic material. 2. The heat resistant sheet according to claim 1, wherein the inorganic fibers are selected from asbestos fibers, ceramic fibers, silica fibers, glass fibers, carbon fibers, and metal fibers. 3. The fluorine-containing resin has a melting point of 300 ° C. or lower, a tetrafluoroethylene-perfluoroolefin copolymer, a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, a tetrafluoroethylene-perfluoroalkyl copolymer. Vinyl ether copolymer, tetrafluoroethylene-perfluoroalkylethylene copolymer, polychlorotrifluoroethylene,
The heat resistant sheet according to claim 1, comprising at least one selected from polyvinyl denfluoride, polyvinyl fluoride, and chlorotrifluoroethylene-ethylene copolymer. 4. The heat resistant sheet according to claim 1, wherein the base fabric further includes an organic fiber different from the heat resistant organic synthetic fiber. 5. The heat resistant sheet according to claim 1, wherein the heat resistant inorganic material is an alkali titanate. 6. The heat resistant sheet according to claim 5, wherein the alkali titanate is potassium hexatitanate or a hydrate thereof.