JPS61162347A - Heat-resistant sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a heat-resistant sheet, and more specifically, to a fiber sheet with excellent heat resistance, sewing properties, and bending resistance. .

Conventionally, thermoplastic resins, such as polyvinyl chloride (
pvc) (heat-resistant temperature 66-79°C), polyurethane (heat-resistant temperature 90-120°C), acrylic resin (heat-resistant temperature 60°C)
~88℃),? Liethylene (heat-resistant temperature 80-120℃)
, -lyso-a-pyrene (heat-resistant temperature 120-160°C), polyamide (heat-resistant temperature 80-150°C) or polyester (
A sheet material obtained by coating with a heat resistance temperature of about 120° C. is known. In this case, since the melting point of the fibrous base fabric is relatively low, the coating material that covers it must be one that can be coated at a processing temperature that the fibrous base fabric can withstand. As mentioned above, the coating material also uses a resin having relatively low heat resistance. However, in recent years, ljl, male sheet materials, e.g.
It is increasingly being used in firefighter's clothing, heat-resistant clothing, building materials, etc., to maintain safety from fires, burns, and other thermal disasters.
Demand for non-combustibility and flame retardancy is increasing. Therefore, the development of heat-resistant sheet materials is strongly desired.

In response to the above-mentioned request, JP-A-58-120.67
No. 7 and No. 58-127,757 proposes a high-temperature insulation paint and a fire-resistant insulation film containing an alkali titanate and a silicone resin, and Japanese Patent Application Laid-Open No. 58-1989
-130,183, 58-199,791° and 5
No. 9-35,938 discloses a fire-resistant sheet obtained by forming a coating layer containing a silicone resin and an alkali titanate on the surface of an inorganic core material such as a glass base fabric or asbestos paper. There is.

Also, JP-A-59-26,987 and JP-A-59-36,1
In issue 57? A heat-resistant composition in which a silicone resin, an alkyl luciligate, or the like is mixed with a lyolkanophosphonitrile compound, and coating an inorganic core material with this heat-resistant composition are disclosed.

Heat-resistant sheets using these inorganic fiber base fabrics had excellent fire-resistance, heat-insulating properties, stain resistance, and weather resistance, but their large weight (fabric weight) made them inconvenient to use and handle. Moreover, since it is difficult to sew and has low bending resistance, it is easy to break during use and easily tear from perforations.

It has satisfactory heat resistance and is easy to sew.
To provide a heat-resistant fiber sheet that has good bending resistance and is less likely to be cut at perforations.

The heat-resistant sheet of the present invention includes a base fabric made of heat-resistant fibers,
It is characterized by having a heat-resistant coating layer formed on at least one surface thereof and containing a fluorine-containing resin and an alkali titanate.

The heat-resistant fibers constituting the base fabric used in the present invention can be selected from inorganic fibers such as asbestos fibers, ceramic fibers, silica fibers, glass fibers, Kagen fibers, and metal fibers. Moreover, the heat-resistant fiber may be an organic fiber having a melting point of 300° C. or higher or a thermal decomposition point.

Polymers that form such high melting point or high decomposition point fibers include those shown in Table 1.

The heat resistance shown in Table 1 in the margin below, ? At IJ Mama, especially I-rimeta-phenylene-in-phthalamide 1 and poly-para-phenylene terephthalamide 0 are commonly used, and other para-aramid fibers other than those mentioned above include r HM manufactured by Kaneni Co., Ltd.
-50J etc. can also be used.

Aromatic polyamides useful in such fibers also have at least 50 moles of formulas (1) and 01), tA r
; -CO2") I + (1) Ar 1
-Co-Ar2-FJTICO) [In the above formula, Ar
t and A r 2 represent a divalent aromatic group, and these may be the same or different.] At least one type of unit selected from the following is used as the main repeating unit. It is preferable that the In the above formulas (1) and (II), the divalent aromatic group represented by Ar and Ar2 is represented by the following formula, [wherein A is -o-, -s-, -5o- , -5o2-
, -co-.

-CH2- or -(CH3)2-] is preferably selected from the group of aromatic residues represented by -CH2- or -(CH3)2-. These aromatic residues may contain inert substituents such as halodane, alkyl groups, nido a groups, and the like.

Generally, as aromatic polyamides, those having repeating units represented by the following formula as a main component are more preferable.

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

Fibers having lower melting or decomposition points may also be incorporated into the base fabric to enhance adhesion and other properties with the heat-resistant coating layer. However, it is preferable that the base fabric contains 50% by weight or more of heat-resistant organic fibers, and more preferably 60% by weight or more.

These heat-resistant fibers include short fiber spun yarn, long fiber yarn,
The base fabric may be in any form such as split yarn or tape yarn, and the base fabric may be a woven fabric, a knitted fabric, a nonwoven fabric, or a composite fabric thereof. However, in consideration of the strength of the sewn portion and the bending resistance, woven or knitted fabrics are preferable as the base fabric, and woven fabrics are more preferable. The fibers are preferably in the form of long fibers (filaments) that have little elongation under stress, and are preferably in the form of a plain woven fabric. However, there are no particular limitations on the weaving structure or its form. The multi-fiber base fabric is useful for maintaining the mechanical strength of the resulting heat-resistant sheet at a high level.

In the heat-resistant sheet of the present invention, the heat-resistant coating layer contains a fluorine-containing resin and an alkali titanate.

The fluorine-containing resin used in the present invention is polytetrafluoroethylene, tetrafluoroethylene-fluoroolefin copolymer (e.g., tetrafluoroethylene-fluoroolefin copolymer),
hexafluoropropylene copolymer), tetrafluoroethylene-/#-fluoro(alkyl vinyl ether)
copolymer, tetrafluoroethylene-/ψ-fluoroalkylvinyl s-fl copolymer, tetrafluoroethylene-perfluoroalkylethylene copolymer, ? It is preferable that the material contains at least one selected from dichlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, chlorotrifluoroethylene-ethylene copolymer, and the like.

Among the above-mentioned fluorine-containing resins, blends of those having a melting point of 300° C. or lower and alkali titanates are particularly preferred for forming the heat-resistant coating layer of the present invention. This formulation shows particularly good effects when applied to a base fabric made of heat-resistant organic fibers.

Although these fluorine-containing resins have extremely good weather resistance, ultraviolet absorbers may be blended into these resins for the purpose of protecting the base fabric. It goes without saying that colorants and other performance-imparting agents may also be added. The coating layer made of these resins may be microporous,
Alternatively, it may be one having continuous or discontinuous cells.

The alkali titanate used in the present invention has the general formula M
20-nTiC)2・mH2O (where M is Li, Na,
represents an alkali metal such as, n represents a positive real number of 8 or less, and m represents O or a positive real number of 4 or less. ), more specifically, L14
Ti04Li 2Tio5<O<n<1. m=0)
Alkali titanate, Na2T, has a salt-type structure represented by
I7015, K2Ti6O13- to 2Ti804. (n
<6. m=o), etc., and an alkali titanate having a tunnel structure. Among these, 20,6T in the general formula
Large potassium titanate and its hydrate represented by 10□mH20 (in the formula, m is the same as above) are suitable in that they greatly improve the fire resistance and heat insulation properties of the final object.

Not only potassium hexatitanate but also alkali titanates are generally made of powder or fibrous microcrystals, and among these, those with a fiber length of 5 μm or more and an aspect ratio of 20 or more, particularly 100 or more, are suitable for use in the heat-resistant sheet of the present invention. Provides favorable results in improving strength. In addition, fibrous potassium titanate has a high specific heat and excellent heat insulation performance, and is particularly preferable for realizing the performance of the heat-resistant sheet of the present invention.

Furthermore, the coating layer of the present invention may contain a high refractive index inorganic compound or a heat-absorbing inorganic compound.

High refractive index inorganic compounds have excellent shielding performance against radiant heat, and endothermic inorganic compounds, when in direct contact with slag during welding or fusing, are heated at this contact surface and an endothermic reaction occurs during decomposition, causing the temperature of the slag to rise. decrease. Therefore, the above-mentioned inorganic compound can suppress the collapse and penetration failure of the coating layer of the present invention, and can further protect the sheet base material.

The high refractive index inorganic compound useful in the present invention may have a refractive index of 1.5 or more, but those with a specific gravity of 2.8 or more are particularly suitable. Examples thereof include the following: be.

1) Dolomite (dolomite, specific gravity 2.8-2.9, refractive index 1.50-1
．． 68) Magnesite (Rhiochite 〃3.0~3.1 1 1.51~1.
72) Aragonite (72,9~3.0 #1.53~1.68) Apatite (Apatite 〃3.1~3.2 #1.53~
1.54) Spinel (Spinel 〃3.5~3.6 1 1.72~1.
73) Corundum (〃3.9-4.0 N 1.76-1.77) Zircon (s 3.90-4.10 1 1.79-1.81
) Silicon carbide (#3.17~3.19 1 2.65~2.69)
Powder of crushed natural or synthetic minerals such as

2) Fine powders, granules, fibrous materials, foams, etc. of 7 liters or high refractive index glass or dissolved phosphorus fertilizer obtained as a solid solution of phosphate rock and serpentine or other similar solid solutions.

In addition, endothermic inorganic compounds include calcined gypsum, alum, calcium carbonate, aluminum hydroxide, silicate aluminum, crystal water release type, carbon dioxide release type, decomposition endothermic type, and phase conversion type. Examples include endothermic inorganic compounds such as.

By mixing and dispersing a fibrous alkali titanate and, if necessary, a high refractive index inorganic compound and/or an endothermic inorganic compound in a silicone resin, a coating mixture for sheet production according to the invention is obtained. All known means can be used to prepare the mixed dispersion. In addition, the above coating mixture contains dispersants and defoamers to homogeneously disperse each component, colorants to fully adjust color, mechanical strength, etc., resin powder, flame retardants, metal powder, and others. Various fillers can be freely mixed. Incidentally, the mixing of metal powder such as copper powder, nickel powder, brass powder, aluminum powder, etc. is preferable from the viewpoint of improving surface heat, reflection effect, and penetration suppressing effect, and a method of coating the surface of the base fabric with the above-mentioned coating layer. Methods include applying the coating mixture to the surface of the base fabric by spray painting, brush coating, roll coating, etc., or attaching a film formed from the coating mixture to the surface of the base fabric. There is a method of impregnating the material by immersing it in a coating mixture.

The heat-resistant sheet of the present invention is manufactured, for example, as follows. That is, after adding appropriate curing accelerators and additives to a mixture of a fluorine-containing resin, an alkali titanate, and, if necessary, a high refractive index inorganic compound and/or an endothermic inorganic compound,
Furthermore, if necessary, add an organic solvent such as toluene, xylene, trichlene, etc. to make a dispersion with an appropriate concentration, and use this dispersion by dipping or spraying.

rollco) i,! j Apply to one or both sides of the base fabric by a conventionally well-known coating method such as bath roll coat 1 or knife coat method, and apply at room temperature or under heating, preferably at 150%
It is integrally fixed to the above-mentioned base material by heat treatment within the range of ~500°C for 1 to 30 minutes. The blending ratio of the fluorine-containing resin, alkali titanate, high refractive index inorganic compound, and/or endothermic inorganic compound, etc. varies depending on the type and particle size of the fluorine-containing resin and inorganic compound used.
In general, if the amount of fluorine-containing resin is too low, the strength of the covering layer will be insufficient, resulting in defects such as cracks in the covering layer or peeling of the covering layer from the base fabric when used as a fireproof heat insulating sheet. On the other hand, if there is too much fluorine-containing resin, the heat resistance will decrease, and in severe cases, flaming combustion may occur.

Therefore, in the present invention, the amount of the alkali titanate blended with respect to 100 parts by weight (hereinafter referred to as "parts") of the fluorine-containing resin is 1 to 200 parts, preferably 30 to 100 parts, Furthermore, if a high refractive index inorganic compound and/or an endothermic inorganic compound, etc. are added to these, the amount should be limited to 400 parts.
Although it can be blended in place of the alkali titanate that is present in the same amount up to 1/4 of the weight, it is usually preferably in the range of 10 to 300 parts. Incidentally, part or all of these high refractive index inorganic compounds and endothermic inorganic compounds can be replaced with commonly used inorganic pigments, inorganic bulking fillers, inorganic powders that impart flame retardancy, etc. The amount of the user is preferably 400 parts or less, preferably 300 parts or less, per 100 parts of the fluorine-containing resin.

The thickness of the heat-resistant sheet of the present invention is 0. It is preferably O2nm or more, and O,OS~2. More preferably, it is within the range of Oart.

In order to improve the adhesion and durability between the base fabric and the coating layer,
An adhesive substance may be interposed between the two.

In this case, as long as the adhesive force is to be improved, it is not necessary to interpose K particularly thickly. Adhesive substances are not used for film formation; therefore substances known as adhesives can be used. For example, acrylates containing amino groups, imino groups, ethyleneimine residues, diamide/residues in alkali, acrylates containing aziridinyl groups, amino ester-modified vinyl polymer-aromatic adhesives, methacrylate polymers containing amine nitrogen. , and other adhesives may be used in combination. Further, a resin having the same quality as the resin constituting the fiber base fabric, such as polyamideimide or polyimide, or an RFL modified substance, etc. can be arbitrarily selected.

In the heat-resistant sheet of the present invention, the heat-resistant coating layer may be formed only on one side, but may be formed on both sides to compensate for the low weather resistance of the base fabric, and depending on the usage situation, the heat-resistant coating layer may be formed on both sides. may be a necessary condition. 9. On the other side, depending on the performance required for the sheet, natural rubber, neoprene rubber, chloroprene rubber, silicone rubber, Hypalon and other synthetic rubbers, NPVC resin, ethylene-vinyl acetate copolymer (EVA) resin, acrylic resin, etc. Resin, silicone resin, urethane resin, polyester resin and other synthetic resins can also be used. In this case, it is more preferable that these resins are flame retardant.

The thickness of the coating layer is 5-2000I+r+s, 10-1%
Preferably, it is 500 μm.

Examples The heat-resistant sheet of the present invention will be explained in more detail with reference to Examples.

Example 1 A glass fiber fabric having the following structure was used as the base fabric.

Fabric weight 290 g/m'' To prepare the coating composition, the following composition: 50% aqueous dispersion of tetrafluoroethylene-hexafluoropropylene copolymer (FEP) 100% water-soluble acrylic resin (circulating viscosity: j) 0. A mixture of 65 potassium titanate (Katsutismo 01 manufactured by Otsuka Chemical Co., Ltd.) was prepared.The viscosity of this mixture was about 900 centipoise.

The base fabric was dipped in the composition and wrung out for 25 minutes.
Gradually raise the temperature to 0 to 300°C, then dry at 350°C.
It was fired at a temperature of The thickness of the heat-resistant coating layer obtained was approximately 150 μm on both surfaces.

For comparison, the same operation as above was repeated. However, potassium titanate was not used.

The obtained sheet was subjected to a fire resistance and insulation test as described in Japanese Patent Application Laid-Open No. 58-130, 1834. The evaluation criteria for fire resistance and heat insulation properties at this time were as follows.

Afll: When cutting a 9" thick spark-generating steel plate, there shall be no through-holes that are harmful to the sparks generated and harmful to fire prevention.

Class B: When cutting a 4.5-thick steel plate for spark generation, there shall be no through-holes that are harmful to the sparks generated and harmful to fire prevention.

Class 0: There are no through-holes that are harmful to flames and fire prevention from the sparks generated when cutting the spark-generating steel plate of 3.2-thick silk.

Class D: When cutting a 3.2-thick spark-generating steel plate, a through-hole is created that is harmful to fire prevention.

Class E: Flames occur when cutting a spark-generating steel plate with a thickness of 3.2 mm.

The fire resistance and insulation properties of the heat resistant sheet of Example 1 were Class A, but those of the comparative sheet were Class 0, and commercially available asbestos paper (3
It was classified as E class.

That is, the heat-resistant sheet of the present invention exhibited extremely excellent fire-resistant and heat-insulating properties.

Example 2 Aromatic 41J amide II! with the following structure was used as the base fabric. ,
#a (trademark, Conex, Kinsho M) spun yarn fabric was used.

Fabric weight: 90 fl/m" Tensile strength (average in both weft and weft directions): 66 kv As a composition for three-stripe application, a 50% aqueous dispersion of FEP (tetrafluoroethylene-hexafluoropropylene copolymer) 10
0 parts by weight of potassium titanate were mixed with 60 fi parts of potassium titanate, and a small amount of water-soluble acrylic resin (thickener) was added thereto to prepare a coating liquid having a viscosity of 1200 cp. Using this liquid,
A heat-resistant sheet was manufactured by the same process as in Example 1. The fire resistance and heat insulation properties of the obtained sheet were evaluated as Class B.

For comparison, the same operation as above was performed. However, calcium titanate was not used. The fire resistance and heat insulation properties of the comparison sheet obtained were Class D.

In addition, the heat-resistant sheet of this example was JIS P 8115
(1976), ``Method for testing the folding strength of paper and paperboard using an MIT-type tester'', the folding strength of paper and paperboard was tested.
.

It did not break even after repeated use, and showed almost infinite bending strength.

Example 3 The same operation as in Example 2 was performed. However, the spun yarn used for the base fabric was a blended yarn (30'') of 50% by weight Conex fiber and 50% by weight noriethylene terephthalate fiber.

The obtained heat-resistant sheet had a fire resistance and heat insulation property of 0 types, and its folding strength was such that it could withstand bending more than 10,000 times. By using an alkali titanate in combination with the resin, it has extremely superior fire resistance and heat insulation properties than when a fluorine-containing resin is used alone. In addition, by using a heat-resistant organic fiber fabric as the base fabric, it is possible to create a heat-resistant sheet 2s that is suitable for applications that are subject to repeated bending, violent vibrations, and flapping (for example, fire-resistant clothing, opening/closing curtains) at the back temperature. .

Claims (1)

[Scope of Claims] 1. A heat-resistant sheet comprising a base fabric made of heat-resistant fibers and a heat-resistant coating layer formed on at least one surface thereof and containing a fluorine-containing resin and an alkali titanate. 2. The fiber according to claim 1, wherein the heat-resistant fiber is an inorganic fiber selected from asbestos fiber, ceramic fiber, silica fiber, glass fiber, carbon fiber, and metal fiber. 3. The heat-resistant sheet according to claim 1, wherein the heat-resistant fiber is an organic synthetic fiber having a melting point of 300° C. or higher or a thermal decomposition point. 4. The fluorine-containing resin is polytetrafluoroethylene, tetrafluoroethylene-perfluoroolefin copolymer, tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, Comprising at least one selected from tetoffluoroethylene-perfluoroalkylethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, and chlorotrifluoroethylene-ethylene copolymer, Claim 1
Heat-resistant sheet as described in section. 5. The fluorine-containing resin has a melting point of 300°C or less,
A heat-resistant sheet according to claim 1. 6. The heat-resistant sheet according to claim 1, which is the alkali titanate, potassium hexatitanate, or a hydrate thereof. 7. The heat-resistant sheet according to claim 1, wherein the heat-resistant coating layer contains 1 to 200 parts by weight of alkali titanate based on 100 parts by weight of the fluorine-containing resin.