TW201927542A - Non-combustible sheet and smoke barrier having the same capable of reducing dust adhesion when being used as a smoke barrier for a long period of time - Google Patents

Abstract

An object of the present invention is to provide a non-combustible sheet and a smoke barrier having the non-combustible sheet, which can reduce dust adhesion when being used as a smoke barrier for a long period of time. A non-combustible sheet comprises glass fiber cloth and a resin layer contained in the glass fiber cloth in an impregnated state, wherein the non-combustible sheet has a surface resistivity of 1×10<SP>11</SP> [Omega] or less before and after a specific heat cycle test. The non-combustible sheet is preferably an antistatic layer containing a metal or a metal oxide. The antistatic layer becomes a surface layer when the non-combustible sheet is in use.

Description

Non-combustible sheet and anti-smoke wall containing the incombustible sheet

FIELD OF THE INVENTION The present invention relates to a non-combustible sheet, and more particularly to a non-combustible sheet suitable for use in a smoke-proof wall or the like, and a smoke-proof wall using the same.

BACKGROUND OF THE INVENTION In Japan and other countries' decrees (for example, in Japan, the Building Standards Act and the Building Standards Act), in order to prevent the flow of smoke and toxic gases generated during building fires, firefighting activities can be carried out smoothly. To set up a smoke evacuation device. Therefore, in a building such as an office building or a commercial facility, a smoke prevention wall or the like is usually provided as a smoke evacuation device and a smoke shielding device.

The smoke-proof vertical wall is generally installed on the ceiling of a building, and the purpose thereof is to temporarily prevent the smoke, toxic gas, and the like from flowing to the corridor or the upper floor when the fire occurs, and to ensure the time required for evacuation. Therefore, in order not to block the visual field by the smoke prevention wall or to impair the appearance, a flat glass, a resin composite of glass fiber and resin, or the like is used as the smoke prevention wall. The resin composite of glass fiber and resin has an advantage of being less susceptible to cracking than flat glass. For example, Patent Document 1 discloses a transparent non-combustible sheet comprising a glass fiber woven fabric and a cured resin layer.

Further, for example, Patent Document 2 discloses a transparent non-combustible sheet having a base material layer comprising a glass fiber cloth and a transparent hardened resin layer impregnated into the glass fiber cloth, wherein at least one side of the base material layer A reinforcing layer is formed on the whole.

Further, for example, Patent Document 3 discloses a transparent non-combustible sheet which is obtained by using an adhesive impregnated coated glass cloth as a substrate, and a non-combustible laminated body in which a transparent layer of a soft vinyl chloride resin is provided on both surfaces of the substrate, wherein The adhesive-impregnated coated glass cloth is obtained by impregnating and coating a glass cloth treated with a decane coupling agent with an adhesive component containing a triisocyanate compound and a binder resin in a mass ratio of 1:5 to 1:35. a composite intermediate, wherein the triisocyanate compound is at least selected from the group consisting of isocyanurate-modified triisocyanate, biuret-modified triisocyanate, and trimethylolalkyl-modified triisocyanate. More than one type.
Advanced technical literature patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2005-319746 (JP2005-319746 A)
Patent Document 2: Japanese Laid-Open Patent Publication No. 2011-213093 (JP2011-213093 A)
Patent Document 3: Japanese Laid-Open Patent Publication No. 2014-76563 (JP2014-76563 A)

Disclosure of the Invention The inventors of the present invention have found that the incombustible sheets described in Patent Documents 1 to 3 have the following problems, for example, when used as a smoke preventing wall for a long period of time, Dust in the air in the building in which the smoke prevention wall is installed may adhere to the surface of the incombustible sheet to cause a poor appearance. In this case, an object of the present invention is to provide a non-combustible sheet and a smoke-proof wall comprising the non-combustible sheet, and the non-combustible sheet containing the glass cloth and the resin is, for example, reduced in smoke prevention. The dust on the vertical wall is attached when it is used for a long time.
Means to solve the problem

As a result of reviewing the above problems, the present inventors have found that the non-combustible sheets disclosed in Patent Documents 1 to 3 have a surface resistivity of about 1 × 10 ¹⁵ Ω, and thus cannot be sufficiently prevented from being present in the air. The situation where dust is attached. Therefore, the inventors of the present invention have conducted an effort to review and found that the adhesion of the dust can be reduced by setting the surface resistivity to 1 × 10 ¹¹ Ω or less before and after the specific heat cycle test. The present invention is based on this knowledge and is accomplished through further continuous review.

That is, the present invention provides an invention disclosed in the following aspects.
Item 1: A non-combustible sheet comprising: a glass fiber cloth and a resin layer contained in the glass fiber cloth in an impregnated state, the non-combustible sheet having a surface resistivity of 1×10 before and after the heat cycle test described below. ¹¹ Ω or less;
<Thermal cycle test conditions>
A sample of 100 mm × 100 mm was cut out from the non-combustible sheet as a sample, and the sample was placed in a thermo-hygrostat which was previously set to a temperature of 23 ° C and a relative humidity of 50% RH, and the following (1) to (5) ) as a cycle, a total of 10 cycles;
(1) setting the migration time to 14 minutes, moving from temperature 23 ° C, relative humidity 50% RH to temperature 60 ° C, relative humidity 50% RH;
(2) maintained at the above temperature of 60 ° C, relative humidity of 50% RH for 8 hours;
(3) setting the migration time to 45 minutes, and migrating from the above temperature of 60 ° C, relative humidity of 50% RH to a temperature of 20 ° C and a relative humidity of 50% RH;
(4) maintained at the above temperature of 20 ° C, relative humidity of 50% RH for 8 hours;
(5) The migration time was set to 1 minute, and the temperature was shifted from the above temperature of 20 ° C and the relative humidity of 50% RH to a temperature of 23 ° C and a relative humidity of 50% RH.
Item 2: The non-combustible sheet according to Item 1, which comprises an antistatic layer containing a metal or a metal oxide, and the antistatic layer serves as a surface layer when the nonflammable sheet is used.
Item 3: The non-combustible sheet according to Item 1, wherein the non-combustible sheet is used as a layer containing a surfactant in the surface layer; the quality of the surfactant in the non-combustible sheet ( g/m ² ) is from 0.5 to 1.5 g/m ² .
Item 4: The non-combustible sheet according to Item 1 or Item 2, which has a total light transmittance of 90% or more and a haze of 20% or less.
Item 5: A smoke-proof vertical wall comprising the non-combustible sheet according to any one of items 1 to 4.
Effect of the invention

According to the nonflammable sheet of the present invention, by setting the surface resistivity to 1 × 10 ¹¹ Ω or less before and after the specific heat cycle test, it is possible to reduce the adhesion of dust, for example, when used as a smoke preventing wall for a long period of time.

The non-combustible sheet of the present invention comprises a glass fiber cloth and a resin layer contained in the glass fiber cloth in an impregnated state, characterized in that the non-combustible sheet has a surface resistivity of 1 × before and after the heat cycle test described below. 10 ¹¹ Ω or less;
<Thermal cycle test conditions>
A sample of 100 mm × 100 mm was cut out from the non-combustible sheet as a sample, and the sample was placed in a thermo-hygrostat which was previously set to a temperature of 23 ° C and a relative humidity of 50% RH, and the following steps (1) to ( 5) As a cycle, a total of 10 cycles;
(1) setting the migration time to 14 minutes, moving from temperature 23 ° C, relative humidity 50% RH to temperature 60 ° C, relative humidity 50% RH;
(2) maintained at the above temperature of 60 ° C, relative humidity of 50% RH for 8 hours;
(3) setting the migration time to 45 minutes, and migrating from the above temperature of 60 ° C, relative humidity of 50% RH to a temperature of 20 ° C and a relative humidity of 50% RH;
(4) maintained at the above temperature of 20 ° C, relative humidity of 50% RH for 8 hours;
(5) The migration time was set to 1 minute, and the temperature was shifted from the above temperature of 20 ° C and the relative humidity of 50% RH to a temperature of 23 ° C and a relative humidity of 50% RH.

For example, as shown in FIGS. 1 to 4, the incombustible sheet 1 of the present invention has a laminated structure including a glass cloth 2 and a resin layer 3 impregnated into the glass cloth 2. In the non-combustible sheet 1, at least one layer of the glass cloth 2 may be included, or a plurality of layers may be included.

Further, as shown in FIGS. 2 to 4, the incombustible sheet 1 of the present invention may also comprise a laminated structure comprising: a glass cloth 2; a resin layer 3 impregnated into the glass cloth 2; and a film layer 4 On at least one side of the resin layer 3, and preferably on both sides. Further, as shown in FIGS. 3 and 4, the incombustible sheet 1 of the present invention may further comprise a peelable protective film 5 which is on at least one side of the resin layer 3 or the film layer 4, preferably On both sides, and as, for example, a smoke-proof wall and peelable when in use.

In FIGS. 1 to 4, the resin layer 3 fills the voids of the plurality of glass fibers constituting the glass fiber cloth 2, and the surface side portion 31 on one side of the resin layer 3 and the surface side portion 32 on the other side pass through the space. The gap portions are in communication with each other. Further, in the nonflammable sheet 1 of the present invention, from the viewpoint of improving transparency, for example, as shown in Figs. 1 to 4, it is preferable to form the resin layer 3 on at least one side of the 2 layers of the glass cloth. It is preferable to form the resin layer 3 on both surfaces of the two layers of the glass fiber cloth.

For example, as shown in FIG. 4, in the case where the film layer 4 is not laminated, an antistatic layer 6 containing a metal or a metal compound may be provided on the surface side (31, 32 side in FIG. 1) of the resin layer 3, or In the case of the laminated film layer 4, an antistatic layer 6 containing a metal or a metal compound may be provided on the surface side (the sides 41 and 42 in Figs. 2 and 3) of the film layer 4. Thereby, the surface resistivity can be further made lower before and after the specific heat cycle test, while further changing the surface resistivity before and after the specific heat cycle test, and obtaining more excellent transparency. The antistatic layer 6 containing a metal or a metal compound is preferably disposed so as to become a surface layer when the nonflammable sheet 1 is used. Further, in the case where the antistatic layer 6 is not provided, it will become a layer of the surface layer at the time of use (the resin layer 3 in the case where the film layer 4 is not laminated, and the resin layer in the case where the film layer 4 is laminated) Layer 3) is preferably included as a surfactant. Thereby, the surface resistivity can be satisfied to be 1 × 10 ¹¹ Ω or less before and after the specific heat cycle test.

Hereinafter, the composition of each layer constituting the incombustible sheet 1 of the present invention will be described in detail.

(glass fiber cloth 2)
In the incombustible sheet 1 of the present invention, the glass cloth 2 is composed of a plurality of glass fibers. In the glass cloth 2, a plurality of glass fibers are entangled with each other to form a cloth. The glass fiber cloth 2 is, for example, a glass fiber woven fabric (glass cloth) composed of a plurality of warp threads and a plurality of weft yarns. The woven structure of the glass fiber woven fabric is not particularly limited, and examples thereof include a plain weave structure, a satin weave structure, a square weave structure, and a musage structure.

The glass material constituting the glass fiber of the glass fiber cloth 2 is not particularly limited, and for example, a known glass material can be used. Examples of the glass material include alkali-free glass (E-glass fiber), acid-resistant medium alkali glass (C-glass fiber), high-strength/high-modulus glass (S-glass fiber, T-glass fiber, etc.). As the alkali-resistant glass (AR glass fiber), etc., it is preferable to mention the alkali-free glass (E-glass fiber) with high versatility. The glass fiber constituting the glass fiber cloth 2 may be made of one type of glass material, or may be a combination of two or more kinds of glass fibers made of different glass materials. Further, from the viewpoint of improving transparency, it is preferred to select a glass material which is close to the refractive index of the resin layer 3 to be described later.

As the glass fiber constituting the glass fiber cloth 2, a glass fiber yarn obtained by twisting a single fiber of a plurality of glass long fibers is preferable. The number of the single fibers in the glass yarn is preferably from about 30 to 400, preferably from about 40 to 120. Further, from the viewpoint of suppressing bleeding of the incombustible sheet 1, the diameter of the single fibers in the glass yarn is preferably from about 3.0 to 6.0 μm, more preferably from about 3.0 to 5.0 μm. The glass yarn has a fineness of from 3 to 30 tex, preferably from 1 to 12 tex, more preferably from 1 to 6 tex, even more preferably from 1.5 to 5 tex, from the viewpoint of suppressing bleeding. Further, as another aspect of the glass yarn count, 3 to 12 tex is preferable, and 3 to 5 tex is preferable. Further, the unit tex of the glass yarn count corresponds to the number of grams per 1000 m. Although the detailed mechanism for suppressing the bleeding of the incombustible sheet 1 is not known, it can be considered that the condition that the single fiber diameter and the glass yarn count in the glass yarn constituting the glass fiber cloth 2 are within the above range can be satisfied. The shrinkage at the interface between the glass yarn and the resin layer 3 is effectively suppressed, and as a result, the bleeding of the incombustible sheet 1 is suppressed. The glass fiber cloth 2 may be composed of one type of glass yarn, or may be composed of two or more kinds of glass yarns having a single fiber number, a diameter, and a number of branches.

In the non-combustible sheet 1, the ratio (% by mass) of the glass cloth 2 is preferably 20 to 50% by mass in the total amount of the glass cloth 2 and the resin layer 3 to be described later. It is preferable that it is 20 to 40% by mass, and preferably 20 to 30% by mass. Further, the mass (g/m ² ) of a piece of the glass cloth 2 is preferably 10 to 120 (g/m ² ), preferably 10 to 60 (g/m ² ), preferably 10 to 40 (g/m). ² ) For better.

The difference in refractive index between the glass fiber cloth 2 and the resin layer 3 to be described later is preferably 0.05 or less, more preferably 0.02 or less, and still more preferably 0.01 or less. The refractive index of the glass cloth 2 is preferably from about 1.45 to 1.65, more preferably from about 1.50 to 1.60.

In addition, the measurement of the refractive index of the glass fiber cloth 2 is carried out according to "Method B" prescribed by the Japanese Industrial Standard "JIS K 7142:2008 Plastic Refractive Index Measurement Method". Specifically, first, the glass fibers constituting the glass fiber cloth were pulverized to the extent that the Beck line was observed when observed with an optical microscope at a magnification of 400 times. Then, using a halogen lamp provided with a D-line interference filter as a light source, observation and measurement were performed using an optical microscope at a magnification of 400 times and a temperature of 23 ° C, and the average value of the three tests was taken as the refractive index value. . In addition, the measurement of the refractive index of the resin layer 3 mentioned later is also performed according to the "method B" prescribed by the Japanese Industrial Standard "JIS K 7142:2008 Measuring Method of Plastic Refractive Index". Specifically, the resin layer 3 was pulverized to the extent that the Beck line was observed when observed with an optical microscope at a magnification of 400 times. Then, using a halogen lamp provided with a D-line interference filter as a light source, observation and measurement were performed using an optical microscope at a magnification of 400 times and a temperature of 23 ° C, and the average value of the three tests was taken as the refractive index value. .

The difference in the Abbe number between the glass cloth 2 and the resin layer 3 is preferably 30 or less, more preferably 28 or less, still more preferably 20 or less, and particularly preferably 10 or less. The Abbe number of the glass cloth 2 is preferably from 30 to 80, more preferably from 40 to 70, still more preferably from 50 to 65. Further, the Abbe number of the resin layer 3 and the glass cloth 2 was measured in the following manner.

(Abbe number of resin layer 3)
A resin sheet having the same thickness and containing no glass fiber cloth was produced under the same conditions as in the case of containing a glass fiber cloth, and the test piece was made to have a width of 8 mm and a length of 20 mm and carefully polished, according to Japanese Industrial Standard "JIS K 7142 Plastic Refraction". "Method A" specified in the "Measurement Method of Rate" uses an Abbe refractometer (for example, NAR-2T manufactured by ATAGO Co., Ltd.), and the contact liquid is diiodomethane, and the light source is a sodium D line having a wavelength of 589 nm. The refractive index at a wavelength of 589 nm was measured under the conditions of a temperature of 23 °C. Next, the natural light is used as a light source to measure, calculate the dispersion ratio, and calculate the Abbe number according to the following formula (I).
Abbe number = (refractive index-1 at a wavelength of 589 nm) / dispersion rate (I)

(Abbe number of fiberglass cloth)
A glass sheet having a width of 8 mm, a length of 20 mm, and a thickness of 5 mm was produced using a glass material constituting the glass fiber, and the surface was carefully polished, and the method was used according to "Method A" prescribed by Japanese Industrial Standard "JIS K 7142 Plastic Refractive Index Measurement Method". Abbe refractometer (for example, NAR-2T manufactured by ATAGO Co., Ltd.), measuring the refractive index at a wavelength of 589 nm under the condition that the contact liquid is diiodomethane, the light source is a sodium D line having a wavelength of 589 nm, and the measurement temperature is 23 ° C. . Next, the natural light is used as a light source to measure, calculate the dispersion ratio, and calculate the Abbe number according to the above formula (I).

The thickness of the glass cloth 2 is, for example, about 10 to 100 μm, preferably 10 to 55 μm, and preferably 10 to 35 μm from the viewpoint of suppressing bleeding. When the thickness of the glass cloth 2 is 10 to 35 μm, the glass fiber cloth 2 has a glass volume fraction calculated by the following formula (II) of 36% or more (especially 36 to 45%). The glass fiber cloth 2 having a thickness of 10 to 35 μm and a glass volume ratio of 36% or more can be obtained, for example, by subjecting the glass fibers to a fiber opening treatment.

Glass volume (%) = (A / (B × C)) × 100 (II)
A: mass of glass fiber cloth (g/m ² )
B: specific gravity (g/m ³ ) of the glass material constituting the glass fiber cloth
C: thickness of glass fiber cloth (m)

(resin layer 3)
In the nonflammable sheet 1 of the present invention, the resin layer 3 is formed by being impregnated into the glass cloth 2 and hardened or cured. Further, in the present invention, the resin layer 3 may be referred to as "resin composition layer 3" regardless of whether the layer contains a single component or two or more components.

Specifically, the resin layer 3 may be a cured resin layer made of a curable resin or a thermoplastic resin layer made of a thermoplastic resin. In the case where the resin layer 3 is a hardened resin layer, it can be obtained by applying energy such as light or heat to the curable resin to harden it into a cured product (photohardenable resin or heat-cured resin). When the resin layer 3 is a thermoplastic resin layer, it can be obtained by drying and solidifying a thermoplastic resin.

As the curable resin, from the viewpoint of further improving the transparency of the incombustible sheet 1 before and after the specific heat cycle test, it is preferred to use a resin having a refractive index close to that of the glass fiber cloth 2. A suitable curable resin is preferably a photocurable resin, and examples thereof include a vinyl ester resin, a polyurethane acrylate resin, an oxime acrylate resin, an unsaturated polyester resin, a curable acrylic resin, and an epoxy resin. In the case where the thin film layer 4 is provided, from the viewpoint of further improving the adhesion to the thin film layer 4, a curable acrylic resin is preferable, and a resin obtained by hardening a resin composition containing Acrysilap is particularly preferable. good. In the present invention, Acrysilap refers to a polymerizable liquid mixture in which a (meth) acrylate polymer such as polymethyl methacrylate (PMMA) is dissolved in an acrylic monomer such as methyl methacrylate. In the above Acrysilap, one selected from the group consisting of polymethyl methacrylate, methyl methacrylate/methyl acrylate copolymer, and methyl methacrylate/n-butyl acrylate copolymer. More than one type of acrylate polymer is dissolved in Acrysilap of a methyl methacrylate monomer. When the resin layer 3 is used as a cured resin layer obtained by curing the resin composition containing Acrysilap, in order to further improve the adhesion to the film layer 4, it is necessary to further improve the incombustible sheet 1 in the aforementioned specific The transparency before and after the heat cycle test is preferred.

As the thermoplastic resin, from the viewpoint of further improving the transparency of the incombustible sheet 1 before and after the specific heat cycle test, it is preferred to use a resin having a resin layer 3 and a refractive index close to the glass fiber cloth 2. Suitable thermoplastic resins include, for example, polyvinyl chloride resin, saturated polyester resin, polyolefin resin, thermoplastic acrylic resin, polycarbonate resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer, polyamide resin, poly An aryl ester resin or the like. For example, in the case where E-glass fiber is used as the glass material constituting the glass fiber of the glass fiber cloth 2, from the viewpoint of the refractive index, polyvinyl chloride resin, saturated polyester resin, thermoplastic acrylic resin is also used among these resins. It is better. The thermoplastic resin may be used singly or in combination of two or more kinds of resins having different refractive indices for the purpose of obtaining the refractive index of the glass fiber to be used. Further, in the non-combustible sheet 1 of the present invention, in the case where a thermoplastic resin layer is used as the resin layer 3, the portion impregnated into the glass fiber cloth 2 is such that a sol-like or thermoplastic resin composition dissolved in a solvent is Infiltration, curing (curing by heating, or curing by drying) is preferred. Further, the portion of the resin layer 3 that is not impregnated into the glass fiber cloth 2 may be such that the sol-like or thermoplastic resin composition dissolved in the solvent is impregnated and solidified (curing by heating, or solidification by drying). It can be formed of a film-like thermoplastic resin.

In the case where the non-combustible sheet is used, for example, when the non-combustible sheet is joined, for example, when the non-combustible sheet is joined, the end portion of the incombustible sheet is joined by the high-frequency welding treatment. When the resin layer 3 impregnated with the glass cloth 2 is a cured resin layer, it is preferable from the viewpoint that the end portion of the incombustible sheet subjected to the high-frequency welding treatment is more likely to maintain transparency before and after the welding process.

The resin forming the resin layer 3 may further contain an additive such as a curing accelerator, a flame retardant, an ultraviolet absorber, a filler, and a photoinitiator. Examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, trichloroethyl phosphate, triallyl phosphate, ammonium polyphosphate, and phosphate. Examples of the ultraviolet absorber include benzotriazole and the like. Examples of the filler include calcium carbonate, vermiculite, and talc. Examples of the photoinitiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, and 2-hydroxy-2-methyl. 1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2- Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6 - Trimethylbenzimidyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, and the like. In the case where a curable acrylic resin is used as the curable resin constituting the resin layer 3, 1-hydroxy-cyclohexyl-phenyl-ketone is preferred from the viewpoint of improving transparency. These additives may be used alone or in combination of two or more.

In the non-combustible sheet 1 of the present invention, for example, as shown in Fig. 1, in the case where the film layer 4 and the antistatic layer 6 are not laminated, and the resin layer 3 becomes a surface layer at the time of use, it is necessary to make a specific The surface resistivity before and after the heat cycle test satisfies the range of 1 × 10 ¹¹ Ω or less. For example, in order to reduce dust adhesion when used as a smoke preventing wall for a long period of time, the resin layer 3 must contain a surfactant. That is, in the case of the incombustible sheet 1 of the present invention, in the case where the resin layer 3 becomes a surface layer at the time of use, by including the surfactant in the resin layer 3, the surface before and after the specific heat cycle test can be made. The electrical resistivity satisfies the range of 1 × 10 ¹¹ Ω or less, and for example, dust adhesion when used as a smoke preventing vertical wall for a long period of time can be reduced.

In the present invention, examples of the surfactant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.

The cationic surfactant may, for example, be an alkylamine salt such as a monoalkylamine salt, a dialkylamine salt or a trialkylamine salt; an alkyltrimethylammonium hydroxide or a dialkyldimethylammonium hydroxide; Quaternary ammonium salts and the like. Further, the cationic surfactant may also be a reactive cationic interfacial activity having a reactive double bond. Further, the cationic surfactant may also be a fluorine-based cationic surfactant having a perfluoroalkyl group in the structure.

Examples of the anionic surfactant include a sulfate ester of a higher alcohol, a higher alkylsulfonic acid and a salt thereof, an alkylbenzenesulfonic acid and a salt thereof, a polyoxyalkylene sulfate salt, and a polyoxyethylene salt. An alkylphenyl ether sulfate salt, a vinyl sulfosuccinate, a polyoxyalkylene alkyl ether sulfate, and the like. In addition, the anionic surfactant may also be a sulfate salt of an alkyl propylene phenol polyethylene oxide adduct, a sulfate salt of an allyl alkyl phenol polyethylene oxide adduct, an allyl group A reactive anionic interfacial activity of a reactive double bond such as a sulfate salt of an alkylphenol polyethylene oxide adduct. Further, the anionic surfactant may also be a fluorine-based anionic surfactant having a perfluoroalkyl group in the structure.

Examples of the nonionic surfactant include polyoxyethylene ethyl ether, polyoxyethylene ethyl phenyl ether, polyethylene glycol fatty acid ester, and ethylene oxide-propylene oxide block copolymer. a polyoxyethylene fatty acid decylamine, an ethylene oxide-propylene oxide copolymer, or the like, or a sorbitan derivative such as a polyoxyethylene sorbitan fatty acid ester. In addition, the nonionic surfactant may also be an alkyl propenyl phenol polyethylene oxide adduct, an allyl alkyl phenol polyethylene oxide adduct, an allyl dialkyl phenol polyepoxy A reactive nonionic interfacial activity having a reactive double bond such as an alkane adduct. Further, the nonionic surfactant may also be a fluorine-based nonionic surfactant having a perfluoroalkyl group in the structure.

Examples of the amphoteric surfactant include lauryl betaine, lauryl dimethyl amine oxide, and the like. In addition, the amphoteric surfactant may also be a reactive cationic interfacial activity having a reactive double bond. Further, the amphoteric surfactant may also be a fluorine-based amphoteric surfactant having a perfluoroalkyl group in the structure.

From the viewpoint of further improving the transparency and antistatic property of the incombustible sheet 1, it is preferable to use an anionic surfactant among these surfactants, and to form a polyalkylene alkyl alkyl ether sulfate and a higher alcohol. Sulfate salts are preferred.

In the case of using the resin layer 3 containing a surfactant as the surface layer, the content of the surfactant in the resin layer 3 may be, for example, 0.5 to 3.0% by mass, in addition to the glass cloth 2 . On the other hand, in the incombustible sheet 1 of the present invention, if the resin layer 3 contains an excessive amount of the surfactant, the transparency of the incombustible sheet 1 may be impaired. This is because the compatibility of the surfactant with the resin is generally poor. Therefore, the surface resistivity before and after the specific heat cycle test is made to satisfy the range of 1 × 10 ¹¹ Ω or less, for example, from ensuring the function of dust adhesion as a smoke-proof wall for a long period of time, and at the same time, obtaining excellent transparency. From the viewpoint, in the case of using the resin layer 3 containing a surfactant as the surface layer, the content of the surfactant in the resin layer 3 is preferably 0.5 to 2.0% by mass, and 0.5 or less, in addition to the glass fiber cloth 2. It is preferably from 1.5% by mass to more preferably from 0.5 to 1.0% by mass, particularly preferably from 0.5 to 0.75% by mass.

Further, in the case where the resin layer 3 containing a surfactant is used as the surface layer, the quality of the surfactant contained in the resin layer 3 is, for example, 0.5 to 3.0 g/m ² in the incombustible sheet. In addition, the surface resistivity before and after the specific heat cycle test is made to satisfy the range of 1 × 10 ¹¹ Ω or less, for example, from ensuring the function of dust adhesion as a smoke-proof wall for a long period of time, and at the same time obtaining excellent transparency. From the viewpoint, the mass (g/m ² ) of the surfactant contained in the resin layer 3 which becomes the surface layer at the time of use is preferably 0.5 to 2.0 g/m ² in the incombustible sheet, and is 0.5 to 1.5. Preferably, g/m ² is more preferably 0.5 to 1.0 g/m ^{2 and particularly} preferably 0.5 to 0.75 g/m ² .

Further, in the case of the nonflammable sheet 1 of the present invention, when the resin layer 3 does not become a surface layer at the time of use, in order to improve the transparency of the incombustible sheet 1 of the present invention, the content of the surfactant is less. Or no surfactant is preferred. Specifically, in the non-combustible sheet 1 of the present invention, in the case where the antistatic layer 6 containing a metal or a metal compound is laminated on the surface side of the resin layer 3, the resin layer 3 is removed in addition to the glass cloth 2 The content of the surfactant is preferably 1% by mass or less, preferably 0.3% by mass or less, more preferably 0.1% by mass or less, particularly preferably 0.01% by mass or less, and particularly preferably 0% by mass. Further, in the non-combustible sheet 1 of the present invention, even in the case where the film layer 4 is provided as shown in FIGS. 2 and 3, in the case where the film layer 4 contains a surfactant, in addition to the glass cloth 2 The content of the surfactant in the resin layer 3 is preferably 1% by mass or less, preferably 0.3% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less, and 0% by mass. Especially good. Further, even in the case of the incombustible sheet 1 of the present invention, for example, the film layer 4 is provided as shown in FIG. 4, and the antistatic layer 6 is laminated on the surface side of the film layer 4, except for the glass cloth 2 The content of the surfactant in the resin layer 3 is preferably 1% by mass or less, preferably 0.3% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less, and 0% by mass. Especially good.

In the non-combustible sheet 1 of the present invention, the quality of the resin layer 3 is, for example, 20 to 400 g/m ² , and it is preferable from the viewpoint of further satisfying the transparency and incombustibility before and after the specific heat cycle test described above. From 20 to 250 g/m ² is preferred, and from 20 to 100 g/m ^{2 is} preferred. In addition, the thickness of the resin layer 3 is, for example, 20 to 500 μm, and is preferably 20 to 300 μm, and more preferably 30 to 150 μm, from the viewpoint of further improving the transparency and incombustibility before and after the specific heat cycle test.

In the non-combustible sheet 1 of the present invention, the weight ratio of the glass cloth 2 to the resin layer 3 is compared with the glass cloth 2 and the viewpoint of the transparency and non-combustibility before and after the specific heat cycle test. The total mass of the resin layer 3 and the mass ratio of the glass cloth 2 are preferably 5 to 50% by mass, preferably 10 to 35% by mass, and particularly preferably 10 to 30% by mass.

(film layer 4)
In the nonflammable sheet 1 of the present invention, if necessary, the film layer 4 is a layer composed of a film, and is laminated on the surface of at least one side of the resin layer 3 impregnated with the glass cloth 2, preferably laminated. On both sides, it further enhances the initial tear strength (the tear strength measured without the slit in the sample) while further improving the transparency of the incombustible sheet 1 before and after the aforementioned specific heat cycle test. The role of ).

The constituent material of the film layer 4 is not particularly limited, and it is preferably a thermoplastic resin other than the polyvinyl chloride resin. The thermoplastic resin other than the polyvinyl chloride resin may, for example, be a resin having a small amount of a plasticizer or a film, and a biaxially stretched film containing an amorphous thermoplastic resin other than a polyvinyl chloride resin is preferable. The thermoplastic resin other than the polyvinyl chloride resin may, for example, be a polyester resin, a polycarbonate resin, or a polyamide resin, and may contain at least one of these resins. Further, the film layer 4 may be composed of a film containing no polyvinyl chloride resin. From the viewpoint of making the initial tear strength of the incombustible sheet 1 more excellent, the film layer 4 is exemplified by the Tensile propagation resistance in the vertical (MD) direction and If the horizontal (TD) direction is 1 N/mm or more, it is preferable to give 3 to 20 N/mm, and it is preferable to cite 5 to 15 N/mm. Among them, the film layer 4 is formed of a film of a polyester resin from the viewpoint of further improving chemical resistance (including alkali detergent resistance when used as a smoke preventing vertical wall), and improving initial tear strength and transparency. good. The polyester resin may, for example, be polyethylene terephthalate (PET) or polyethylene naphthalate (PEN). In addition, Elmendorf's tear propagation resistance refers to the use of the Elmendorf tear tester (for example, the Elmendorf tear tester manufactured by Toyo Seiki Co., Ltd.), according to the "Japanese Industrial Specifications". JIS K7128-2:1998 Plastics - Test Methods for Tear Strength of Films and Sheets - Part 2: Elmendorf Tear Method, Measurement of Tear Strength (N) on Rectangular Test Pieces, and Measurements The tear propagation resistance (N/mm) obtained by dividing the film thickness. In addition, the tear strength is the average of the test results of the 20 samples in the vertical direction and the horizontal direction, respectively.

The film layer 4 may also contain a plasticizer. The content of the plasticizer in the film layer 4 is, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass. Below mass%. The plasticizer may be a known plasticizer for vinyl chloride resin, and examples thereof include di-n-butyl phthalate, di-n-octyl phthalate, and di(2-ethyl phthalate). Hexyl)ester, diisooctyl phthalate, dioctyldecyl phthalate, diisononyl phthalate, butyl benzyl phthalate, isophthalic acid Phthalate plasticizers such as 2-ethylhexyl) ester; (2-ethylhexyl) adipic acid, di(2-indenyl) adipate, dibutyl sebacate, hydrazine Fatty acid ester plasticizer such as diacid (2-ethylhexyl) ester; tributyl phosphate, tris(2-ethylhexyl) phosphate, (2-ethylhexyl) diphenyl phosphate, tricresyl phosphate Phosphate plasticizer; trimellitate plasticizer such as tris(2-ethylhexyl) trimellitate or trioctyl trimellitate; adipic acid polyester plasticizer, adjacent Polyester plasticizer such as phthalic acid polyester plasticizer; terephthalate plasticizer.

The surface of the film layer 4 on the side of the resin layer 3 (the surface in contact with the surface side portions 31 and 32 of the resin layer 3 in FIGS. 2 to 4) may contain calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, and oxidation. Magnesium, cerium oxide, sodium citrate, aluminum hydroxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, tin oxide, antimony trioxide, carbon black, molybdenum disulfide, acrylic cross-linked polymer, styrene Particles composed of inorganic particles or organic particles such as a copolymer, a fluorinated resin, a fluororesin, a benzoguanamine resin, a phenol resin, or a nylon resin. Thereby, the adhesion between the resin layer 3 and the film layer 4 can be improved. For example, the protective film 5 to be described later is provided. When the non-combustible sheet 1 is used and the protective film layer 5 is peeled off, the resin layer 3 and the film layer 4 are changed. It is difficult to peel off. This effect becomes more remarkable when the antistatic layer 6 containing the metal or metal compound fine particles described later is laminated on the surface side of the thin film layer 4. In other words, in the case where the antistatic layer 6 containing the metal or metal compound fine particles described later is laminated on the surface side of the thin film layer 4 so as to be in contact with the protective film 5, it may be difficult to make the protective film 5 from the antistatic layer 6 In the case of peeling, the above-mentioned inorganic particles or organic particles are contained on the surface of the film layer 4 on the side of the resin layer 3 as described above, and the anchoring effect by the inorganic particles or the organic particles acts to make the resin layer 3 and the film layer. The adhesion of 4 becomes good, and the protective film 5 becomes easy to peel. The film layer 4 may be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, etc., or may be provided with a coating that imparts various functions such as lubricity and easy adhesion; and a hard coating layer that improves wear resistance. And so on.

In the non-combustible sheet 1 of the present invention, for example, as shown in FIGS. 2 and 3, in the case where the film layer 4 is laminated and the antistatic layer 6 is not provided, when the film layer 4 is used as the surface layer in use, The surface resistivity before and after the specific heat cycle test must be made to be in the range of 1 × 10 ¹¹ Ω or less. For example, in order to reduce dust adhesion when used as a smoke preventing wall for a long period of time, the film layer 4 must contain a surfactant. That is, in the non-combustible sheet 1 of the present invention, in the case where the film layer 4 becomes a surface layer at the time of use, by providing the film layer 4 with a surfactant, the surface resistivity before and after the specific heat cycle test can be made. When the range of 1 × 10 ¹¹ Ω or less is satisfied, for example, dust adhesion when used as a smoke preventing wall for a long period of time can be reduced.

The type of the surfactant contained in the film layer 4 is the same as the case where the resin layer 3 contains a surfactant.

Further, in the case of using the film layer 4 containing a surfactant as the surface layer, the content of the surfactant in the film layer 4 may be, for example, 0.5 to 3.0% by mass. Further, when the film layer 4 contains an excessive amount of the surfactant, the compatibility between the surfactant and the resin may be inferior, and the transparency of the incombustible sheet 1 may be impaired. Therefore, the surface resistivity before and after the specific heat cycle test is made to satisfy the range of 1 × 10 ¹¹ Ω or less, for example, from ensuring the function of dust adhesion as a smoke-proof wall for a long period of time, and at the same time, obtaining excellent transparency. From the viewpoint, in the case where the film layer 4 containing a surfactant is used as the surface layer, the content of the surfactant in the film layer 4 is preferably 0.5 to 2.0% by mass, preferably 0.5 to 1.5% by mass. More preferably, it is 0.5 to 1.0% by mass, and particularly preferably 0.5 to 0.75% by mass.

Further, in the case where the film layer 4 containing a surfactant is used as the surface layer, the quality of the surfactant contained in the film layer 4 is, for example, 0.5 to 3.0 g/m ² in the incombustible sheet. In addition, the surface resistivity before and after the specific heat cycle test is made to satisfy the range of 1 × 10 ¹¹ Ω or less, for example, from ensuring the function of dust adhesion as a smoke-proof wall for a long period of time, and at the same time obtaining excellent transparency. From the viewpoint, the mass (g/m ² ) of the surfactant contained in the film layer 4 which becomes the surface layer is preferably 0.5 to 2.0 g/m ² in the nonflammable sheet, and is 0.5 to 1.5 g/m. ² is more preferable, more preferably 0.5 to 1.0 g/m ² , and particularly preferably 0.5 to 0.75 g/m ² .

Further, in the non-combustible sheet 1 of the present invention, the antistatic layer 6 is laminated on the surface side of the film layer 4 as shown in FIG. 4 (that is, the film layer 4 does not become the surface layer at the time of use). In order to improve the transparency of the incombustible sheet 1 of the present invention, it is preferred that the content of the surfactant is small or that no surfactant is contained. In the case where the antistatic layer 6 is laminated on the surface side of the film layer 4, the surface resistivity is further lowered before and after the specific heat cycle test, and the change in the surface resistivity before and after the specific heat cycle test is further reduced. Further, from the viewpoint of obtaining more excellent transparency, the content of the surfactant contained in the film layer 4 is preferably 1% by mass or less, preferably 0.3% by mass or less, and more preferably 0.1% by mass or less. It is particularly preferably 0.01% by mass or less, and particularly preferably 0% by mass.

In the incombustible sheet 1 of the present invention, the film layer 4 is preferably one having excellent transparency and smoothness. The transparency of the film layer 4 is preferably, for example, 90% or more in total light transmittance, and preferably 91% to 98%. Further, for example, the haze is preferably 1.5% or less, and preferably 0.3 to 1.0%. In addition, the total light transmittance and haze of the film layer 4 are used as test pieces for the film constituting the film layer 4, according to "Japanese Industrial Standard JIS K 7105:1981 Plastic - Total Light Transmittance and Total Light Reflectance Measurement Method" The value measured by the method described.

(antistatic layer 6)
The nonflammable sheet 1 of the present invention is required to have a surface resistivity of 1 × 10 ¹¹ Ω or less before and after the aforementioned specific heat cycle test. Then, from the above, the surface resistivity is made lower than 1 × 10 ¹⁰ Ω and the dust adhesion is further reduced when used as a smoke preventing wall for a long period of time, and the surface resistivity is further made before and after the specific heat cycle test. From the viewpoint of a decrease in the thickness and a more excellent transparency, it is preferable to include the antistatic layer 6 on the surface side portion (31, 32 in FIG. 1) of the resin layer 3 in the case where the film layer 4 is not laminated. Alternatively, in the case of the laminated film layer 4, it is preferable that the antistatic layer 6 is contained in the surface side portion (41 and 42 in FIGS. 2 and 3) of the film layer 4, and the antistatic layer 6 contains metal or metal oxide. Things.

In the antistatic layer 6 containing a metal or a metal compound, examples of the metal element contained include, for example, Ag, Ni, Cu, Sn, Sb, Al, In, Ti, etc., and may be exemplified as a metal monomer. The metal element whose standard electrode potential is lower than 0 eV. Examples of the metal compound include metal oxides (niobium pentoxide, tin oxide, zinc oxide, indium oxide, antimony-doped indium oxide, tin-doped indium oxide, and silver oxide). Further, in the antistatic layer 6, fine particles composed of barium sulfate, calcium carbonate, alumina, magnesium citrate, glass, or the like can be excluded.

The form of the metal or metal compound in the antistatic layer 6 may be, for example, a film of a metal or a metal compound caused by vapor deposition, sputtering, plating, or the like, or fine particles of a metal or a metal compound may be dispersed in the resin. Layer. The shape of the fine particles of the metal or metal compound may be in the form of a pellet, a sheet or a needle (fibrous). The average particle diameter of the fine particles of the metal or metal compound is determined, for example, by the BET method (from the specific surface area (m ² /g) measured by a nitrogen gas adsorption method, and the specific surface area of the average particle diameter is calculated by a conventional method. The diameter) is 100 nm or less below the wavelength of visible light, and it is preferable to make the transparency of the incombustible sheet 1 more easily by making it 1 to 100 nm, and it is preferable to make it 5 to 50 nm.

In the case where the antistatic layer 6 is a layer in which fine particles of a metal or a metal compound are dispersed in a resin (fixed resin), the type of the resin to be used is determined as a dispersible metal or metal compound fine particle and can be fixed to The resin layer 3 or the film layer 4 is not particularly limited, and examples thereof include a polyurethane resin, a polyester resin, an acrylic resin, a polyether resin, a cellulose resin, a polyvinyl alcohol resin, an epoxy resin, and a poly Examples of the vinylpyrrolidone, the polystyrene resin, the polyethylene glycol, and the pentaerythritol are preferably a polyurethane resin, a polyester resin, or an acrylic resin. As the acrylic resin, for example, a modified acrylic resin (amine ester modification, polyester modification, polycarbonate modification, fluorine modification, or the like) can be used.

In the case where the antistatic layer 6 is a layer in which fine particles of a metal or a metal compound are dispersed in the resin, the antistatic layer 6 is obtained from the viewpoint of further reducing the surface resistivity before and after the specific heat cycle test and improving the transparency. The mass ratio of the resin to the fine particles of the metal or metal compound (the mass of the fixed resin (g/m ² ): the mass of the metal or metal compound fine particles (g/m ² )) is preferably 10:1 to 1:1, 8:1 to 2:1 is preferred, and 4:1 to 2:1 is particularly preferred.

Further, the content of the metal and metal compound fine particles in the antistatic layer 6 is, for example, 50 to 10% by mass, preferably 30 to 20% by mass.

In the case where the antistatic layer 6 is a layer in which fine particles of a metal or a metal compound are dispersed in the resin, the antistatic layer 6 is obtained from the viewpoint of further reducing the surface resistivity before and after the specific heat cycle test and improving the transparency. The mass (the total mass of the fine particles of the metal or metal compound and the resin) is, for example, 0.1 to 10 g/m ² per layer, preferably 0.1 to 5 g/m ² , more preferably 0.1 to 3 g/m. ² , special should be given 0.1 to 1g / m ² .

In addition, when the thickness of the antistatic layer 6 is a layer in which fine particles of a metal or a metal compound are dispersed in the resin, for example, it is preferably 0.01 to 3 μm per layer, and preferably 0.05 to 1 μm. In the case of a film of a metal or a metal compound, it is 0.001 to 0.1 μm, preferably 0.01 to 0.05 μm.

Further, in the case where the antistatic layer 6 containing a metal or a metal compound is provided, the surface smoothness thereof is, for example, a surface roughness Ra of 1 to 200 nm.

Further, in the case where the antistatic layer 6 containing a metal or a metal compound is provided, the resin layer 3 or the film layer 4 in which the antistatic layer 6 is laminated suitably contains a small amount or no metal or metal compound, in the resin layer 3 or The content of the metal or the metal compound in the film layer 4 is, for example, 1% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and particularly preferably 0% by mass or less.

(protective film 5)
The non-combustible sheet 1 of the present invention may be further provided on the surface side of the resin layer 3 or the film layer 4 as necessary (in the case where the antistatic layer 6 is laminated on the surface side of the resin layer 3 or the film layer 4, the antistatic layer 6 is further provided). The surface side) is laminated to the peelable protective film 5 which is peeled off at the time of use. Thus, for example, when the incombustible sheet 1 of the present invention is used as a smoke preventing wall, it is easy to prevent the incombustible sheet 1 from being damaged during construction, and the transparency or the aesthetic feeling is deteriorated.

As the protective film 5, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyester film, or the like can be used. In the case where the light-transmitting protective film is used as the protective film 5, for example, when a photocurable cured resin is used as the resin forming the resin layer 3, even if it is used In the manufacturing step of curing the cured resin, the resin layer 3 or the film layer 4 is also protected by the protective film 5, and it is easy to prevent the resin layer 3 or the film layer 4 from being damaged, resulting in deterioration of transparency or aesthetics. The light transmissive property is not particularly limited as long as it can transmit light capable of curing the photocurable resin, and for example, light having a wavelength of 100 to 400 nm can be transmitted, and light having a wavelength of 250 to 400 nm can be transmitted. The light transmittance of the protective film 5 is measured by, for example, a UV transmittance measuring instrument (for example, trade name "UV3150" manufactured by Shimadzu Corporation), and the average light transmittance between 250 and 400 nm is 40% or more. Preferably, 50% or more is preferred, and 60% or more is preferred.

In addition, since the protective film 5 is peeled off when used as, for example, a smoke preventing wall or the like, transparency and smoothness are not particularly limited. For example, from the viewpoint of cost, the total light transmittance is about 80 to 95%, and the haze is about 2 to 10%. In addition, the total light transmittance and haze of the protective film 5 are a test piece of the film constituting the protective film 5, according to "Japanese Industrial Standard JIS K 7105:1981 Plastic - Total Light Transmittance and Total Light Reflectance Measurement Method" The value measured by the method described.

(physical properties and properties of non-combustible sheet 1)
The surface resistivity of the incombustible sheet before and after the heat cycle test described below must be 1 × 10 ¹¹ Ω or less.
<Thermal cycle test conditions>
The non-combustible sheet was cut into a size of 100 mm × 100 mm as a sample, and the sample was placed in a constant temperature and humidity device (for example, manufactured by Espec Co., Ltd.) which has been initially set to a temperature of 23 ° C and a relative humidity of 50% RH. In the case of the name PSL-2KPH), the following steps (1) to (5) are performed as one cycle, and a total of 10 cycles are performed.
(1) The migration time was set to 14 minutes, and the temperature was changed from a temperature of 23 ° C and a relative humidity of 50% RH to a temperature of 60 ° C and a relative humidity of 50% RH.
(2) The temperature was maintained at 60 ° C and a relative humidity of 50% RH for 8 hours.
(3) The migration time was set to 45 minutes, and the temperature was shifted from the above temperature of 60 ° C and the relative humidity of 50% RH to a temperature of 20 ° C and a relative humidity of 50% RH.
(4) The temperature was maintained at 20 ° C and a relative humidity of 50% RH for 8 hours.
(5) The migration time was set to 1 minute, and the temperature was shifted from the above temperature of 20 ° C and the relative humidity of 50% RH to a temperature of 23 ° C and a relative humidity of 50% RH.

As a result of the review by the inventors of the present invention, it has been found that, for example, the non-combustible sheets disclosed in Patent Documents 1 to 3 have a surface resistivity of about 1 × 10 ¹⁵ before and after the specific heat cycle test, and cannot be sufficiently prevented from being present. The dust in the air is attached. As a result of the intensive review, the inventors of the present invention found that the adhesion of the dust can be reduced by making the surface resistivity before and after the specific heat cycle test 1 × 10 ¹¹ Ω or less. As the surface resistivity, it is preferable that the surface resistivity of both before and after the above specific heat cycle test is 1.0 × 10 ¹⁰ Ω or less and 5.0 × 10 ⁹ Ω or less. The lower limit is not particularly limited, and is, for example, 1 × 10 ⁵ Ω or more, and from the viewpoint of further improving the transparency, 1.0 × 10 ⁷ Ω or more, and preferably 1.0 × 10 ⁸ Ω or more is mentioned. More preferably, it is 1.0 × 10 ⁹ Ω or more. More specifically, before and after the above specific heat cycle test, the surface resistivity is 1.0 × 10 ⁷ to 1 × 10 ¹¹ Ω, preferably 1.0 × 10 ⁸ to 1.0 × 10 ¹⁰ Ω, preferably 1.0 × 10 ⁹ to 5.0 × 10 ⁹ Ω.

In addition, the surface resistivity is based on the method described in "5.13.2 Laminates" of "5.13 Low Efficiency" of "Japanese Industrial Standard JIS K 6911 1995 Thermosetting Plastics General Test Method", and an insulation resistance measuring device is used (for example). , High Resistance Meter 4339B) manufactured by Agilent Technologies, Inc., measured under the conditions of an applied voltage of 100 V × 1 minute.

In addition, from the viewpoint of ensuring further reduction of the surface resistivity before and after the specific heat cycle test, the surface resistivity is different before and after the specific heat cycle test (= surface resistivity (Ω) after a specific heat cycle test - specific The surface resistivity (?) before the heat cycle test is preferably 1.0 × 10 ¹⁰ Ω or less, and more preferably 5.0 × 10 ⁹ Ω or less.

The thickness of the non-combustible sheet 1 of the present invention is, for example, the thickness of the non-combustible sheet 1 in the state in which the protective film 5 is removed (that is, the thickness of the peelable protective film 5 which is peeled off during use). Let it be 100 to 500 μm, preferably 150 to 300 μm. In addition, as the quality of the non-combustible sheet 1 of the present invention, for example, the mass in the state in which the protective film 5 is removed (that is, the mass of the peelable protective film 5 which is peeled off during use) is 100. Up to 500 g/m ^{2 is} preferably from 120 to 300 g/m ² , more preferably from 150 to 300 g/m ² . Further, in the non-combustible sheet 1 of the present invention, if the total mass of the resin layer 3 and the film layer 4 is 150 to 300 g/m ² , preferably 150 to 250 g/m ² , it is easier to further balance Non-combustible and tear strength are preferred.

In the nonflammable sheet 1 of the present invention, from the viewpoint of ensuring the transparency before and after the specific heat cycle test, the total light transmittance before and after the specific heat cycle test is preferably 85% or more. More than 90% should be cited. Further, the non-combustible sheet 1 of the present invention preferably has a haze of 20% or less before and after the specific heat cycle test, and is preferably 10% or less, more preferably 5% or less, and particularly preferably 3% or less. It is recommended to give 1% or less. In addition, the total light transmittance and the haze of the incombustible sheet 1 are values measured by the method described in "Japanese Industrial Standard JIS K 7105:1981 Plastic - Total Light Transmittance and Total Light Reflectance Measurement Method".

As described above, in order to ensure high transparency before and after a specific heat cycle test, for example, it can be carried out by the following method: (1) In the case where the layer of the surface layer is used as a surfactant, the interface activity is used. The content of the agent in the layer is adjusted to an appropriate range; (2) the antistatic layer 6 containing a metal or a metal compound is laminated without providing a layer containing a surfactant; (3) the metal or metal compound in the antistatic layer 6 The content is adjusted to an appropriate range; and/or (4) the thickness of the glass fiber cloth, the difference in refractive index between the glass fiber cloth 2 and the resin layer 3, the average diameter of the glass fiber, the number of filaments, and the glass cloth. The weaving density and the like are adjusted in an appropriate range; and the like.

In the non-combustible sheet 1 of the present invention, if the film layer 4 is provided, a high initial tear strength (tear strength measured without a slit in the sample) can be obtained. From the standpoint of ensuring a higher initial tear strength, the initial tear strength is preferably from 30 to 100 N, more preferably from 40 to 100 N, and particularly preferably from 50 to 100 N. In the present invention, the initial tear strength is measured and calculated in the following manner.
(experiment method)
According to the C method (trapezoidal method) of 7.16 of JIS R 3420:2013, a 75 mm × 150 mm test piece (without a slit) is taken from the non-combustible sheet in the vertical direction and the horizontal direction, and the tape for anti-slip is used (for example) The product name 600S manufactured by Sekisui Chemical Co., Ltd. is attached to both sides of the front and back of the trapezoidal part (corresponding to the trapezoidal part A shown in Fig. 5), and the slit is not cut. The constant speed load type tensile tester is used. (For example, trade name RTC-1310A manufactured by Orientec Co., Ltd.) was tested to measure the maximum load. The average value of the maximum load in the vertical direction and the maximum load in the horizontal direction (= (vertical maximum load (N) + horizontal maximum load (N)) / 2) is the initial tear strength (N).

Since the incombustible sheet 1 of the present invention contains the glass cloth 2, it can be provided with a property of being difficult to burn (nonflammability). In addition, the incombustibility of the non-combustible sheet 1 of the present invention is in the "fireproof and fire resistance performance test ‧ evaluation business method book" (change version on March 1, 26) 4.10.2 Heating test ‧ Evaluation method The heat generation test (the heat generation test of radiant heat of 50 kW/m ^{2 on} the surface of the sheet from the radiant electric heater) was carried out, and the maximum heat generation rate after the start of heating was continued. It is not more than 200 kW/m ^{2 for} 10 seconds or more, and the total calorific value is preferably 8 MJ/m ² or less. In order to further improve the incombustibility, for example, a behavior of adding a flame retardant or reducing the amount of an organic substance to the resin layer 3 and the film layer 4 can be performed.

(Production method)
The method for producing the incombustible sheet 1 of the present invention is not particularly limited. For example, when the resin layer 3 is formed using a curable resin, the following production method can be mentioned. First, a curable resin material (unhardened resin material) constituting the glass fiber cloth 2 and the resin layer 3 is prepared. The curable resin material is applied to a film (for example, a polyester film or the like) used as the film layer 4, and the glass fiber cloth 2 is placed on the curable resin material to impregnate the glass fiber 2 with the curable resin material. Further, another film for use as the film layer 4 is placed on the glass cloth 2, and pressure is applied from the surfaces of the two film layers 4, respectively, so that the curable resin material is further impregnated into the glass cloth 2. Next, the curable resin raw material is cured by heating or illuminating depending on the type of the curable resin raw material. Thereby, the incombustible sheet 1 in which the resin layer 3 is impregnated into the glass fiber cloth 2 and the film layer 4 is laminated to the resin layer 3 can be obtained (in accordance with the film layer 4/in the impregnation state, it is contained in the glass). The incombustible sheet 1) in which the resin layer 3/film layer 4 of the fiber cloth 2 is laminated in this order. In the case where the incombustible sheet 1 is a sheet containing no film layer 4, the protective film 5 may be peeled off by replacing the film layer 4 with a protective film 5 which is peeled off during use.

In the method for producing the incombustible sheet 1 of the present invention, when the resin layer 3 is formed using a thermoplastic resin, the following production method can be mentioned. First, a thermoplastic resin constituting the glass fiber cloth 2 and the resin layer 3 described above is prepared. Next, two sheets of the film for use as the film layer 4 are prepared, a thermoplastic resin is applied onto the film, and a glass fiber cloth 2 is placed on the thermoplastic resin to impregnate the glass fiber 2 to the glass fiber 2, and the other film is used. The film as the film layer 4 is placed on the glass cloth 2, and pressure is applied from the surfaces of the two film layers 4, respectively, so that the thermoplastic resin is further impregnated into the glass cloth 2. Next, the thermoplastic resin is dried and cured. Thereby, the incombustible sheet 1 in which the resin layer 3 is impregnated into the glass fiber cloth 2 and the film layer 4 is laminated to the resin layer 3 can be obtained (in accordance with the film layer 4/in the impregnation state, it is contained in the glass). The incombustible sheet 1) in which the resin layer 3/film layer 4 of the fiber cloth 2 is laminated in this order.

The antistatic layer 6 can be provided on the surface side portion of the incombustible sheet 1 obtained as described above. Further, in the case where the film layer 4 is contained, a film in which the antistatic layer 6 is provided in advance may be used. Known means can be used as means for providing the antistatic layer 6. Further, when the resin layer 3 is a surface layer at the time of use, the resin layer 3 may be formed by using a resin material mixed with a surfactant. Further, in the case where the film layer 4 is a surface layer at the time of use, a film in which a surfactant is formulated may be used as the film layer 4.

In addition, when the resin layer 3 is formed of a photocurable resin, the method for producing a non-combustible sheet of the present invention comprises a glass fiber cloth, a resin layer contained in the glass fiber cloth in an impregnated state, and a method for producing a non-combustible sheet which is laminated on the film layer of the resin layer, which may include a step A of preparing at least two laminated films having a light-transmitting protective film and a light-transmitting thermoplastic resin film; and The uncured photocurable resin material impregnated with the glass fiber cloth is used, and the two laminated films obtained in the above step A are irradiated with the uncured light in a state where the light-transmitting protective film is sandwiched outward. Step B of curing the resin raw material and hardening the aforementioned uncured photohardenable resin raw material.

(Use of the incombustible sheet of the present invention)
The use of the incombustible sheet 1 of the present invention includes a smoke preventing wall that is suspended from the ceiling of a building. The smoke prevention wall refers to a smoke evacuation device that is provided to temporarily prevent/guide the generation of smoke such as carbon monoxide or toxic gas generated in a fire to hang from the ceiling of the building. As the smoke prevention wall, a known smoke prevention wall using a non-combustible sheet made of a glass cloth and a resin may be used, and for example, a mounting rail provided on a ceiling surface of a building may be mentioned; a non-combustible sheet having a flexible upper end and suspended therefrom; an end mullion disposed on one of the pair of non-combustible sheets; wherein the non-combustible sheet and the end mullion are A smoke-proof wall that can be joined together in a freely separable manner. In the case of the non-combustible sheet of the present invention, when the layer which becomes the outermost layer when the smoke preventing wall is used is a layer made of a thermoplastic resin, since high-frequency welding processing is possible, it is preferable to use a tension type anti-smoke wall. In the present invention, the tension-type smoke-proof wall refers to a vertical wall in which a non-combustible sheet is stretched between two pairs of mullions, and for example, in the case of being suspended from a ceiling, incombustibility The lower side of the sheet does not have a smoke-proof wall of the beam.

Further, in the case where the transparency of the incombustible sheet 1 of the present invention is improved, since it can replace glass, it can also be applied to other uses using glass, such as a separator, a partition, a smoke-proof sheet, and a smoke-proof curtain. (for example, curtains used in factories and other places).

Further, in the case where the mass of the resin layer 3 is, for example, 20 to 100 g/m ² , more preferably 20 to 50 g/m ² , since the incombustible sheet 1 of the present invention becomes a sheet having more excellent flexibility, Therefore, it is easier to be made into a rolled product. The length in the longitudinal direction of the rolled product may be, for example, 5 to 300 m or the like.
[Examples]

The present invention will be described in detail below by way of examples and comparative examples. However, the invention is not limited to the embodiment.

1. Main raw materials used in the examples and comparative examples The main raw materials used in the following examples and comparative examples are as follows.
<Resin raw material constituting the resin layer 3>
Acrysilap [trade name "Acrysilap XD-8005" (refractive index: 1.550) and "Acrysilap XD-8006", which are made of the resin material constituting the resin layer 3, are used as the components of Table 1. (refractive index: 1.570) was obtained by mixing 1:1 by mass ratio, vinyl ester resin (manufactured by Japan UPICA Co., Ltd.), styrene monomer (manufactured by Japan UPICA Co., Ltd.), difunctional (meth) acrylate, A light initiator (manufactured by IGM, "Omnirad 184") or a surfactant as an antistatic agent ("Electrostripper ME-2" manufactured by Kao Co., Ltd., a solid content of 50% by mass). Further, as the difunctional (meth) acrylate which is a curing agent, NPGDA [new pentylene glycol diacrylate, molecular weight 212, (made by Japan UPICA Co., Ltd.)] shown in Table 1 is used. Further, the amount of the photoinitiator was 3 parts by mass based on 100 parts by mass of Acrysilap or 100 parts by mass based on the total of the vinyl ester resin and the styrene monomer and the difunctional (meth) acrylate.

<Materials constituting the film layer 4>
As the film layer 4, a biaxially stretched polyester film (manufactured by Toyobo Co., Ltd., trade name "Cosmoshine (registered trademark) A4300", thickness 50 μm, mass 70 g/m ² , total light transmittance (JIS K 7105: 1981) was used. 93%, haze (JIS K 7105: 1981) 0.9%) or a vinyl chloride resin film (manufactured by Okamoto Co., Ltd., generally PVC #320, thickness 100 μm, mass 120 g/m ² ).

<Materials constituting the protective film 5>
The peelable protective film 5 which is peelable at the time of use is coated with an acrylate-based adhesive which is peelably adhered to the film layer 4 on one side of a polypropylene film (thickness: 40 μm, mass: 36 g/m ² ). Adhesive PP film, or PET film (thickness 50μm, total light transmittance 93%, haze 4%).

2. Manufacture of incombustible sheet <Example 1>
(Manufacture of fiberglass cloth 2)
A glass yarn (trade name "ECC1200 1/0 1.0Z" manufactured by Unitika Glass Fiber Co., Ltd., an average filament diameter of 4.5 μm, an average number of filaments of 100, and a number of turns of 1.0 Z) was used as the warp and weft. The air jet loom was woven to obtain a plain fiberglass fabric having a warp density of 90/25 mm and a weft density of 90/25 mm. Then, the spinning sizing agent and the woven sizing agent attached to the obtained glass fiber woven fabric were removed by heating at 400 ° C for 30 hours. Thereafter, a decane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxydecane (hydrochloride) Chisso Co., Ltd.) as a surface treatment agent was adjusted to After the concentration of 15 g/L was pressed by a press roll, it was dried at 120 ° C for 1 minute and hardened. Then, the glass fiber fabric having a pressure of 1.5 MPa was subjected to a widening treatment while the tension of the glass fiber woven fabric was 100 N/m in the warp direction, whereby a glass fiber woven fabric used as the glass fiber cloth 2 was obtained. The obtained glass fiber woven fabric 2 had a warp density of 90 pieces/25 mm, a weft density of 90 pieces/25 mm, a thickness of 27 μm, a mass of 30 g/m ² , and a refractive index of 1.561.

(Lamination of the antistatic layer 6 to the thin film layer 4)
A biaxially stretched polyester film was used as the film layer 4. An antistatic layer 6 is laminated on one surface of the film layer 4 (biaxially stretched polyester film). The antistatic layer 6 is obtained by applying an antistatic agent to one surface of the film layer 4 (biaxially stretched polyester film) and drying it to obtain a layered body α of the antistatic layer 6 and the film layer 4, wherein antistatic layer In the agent, the tin oxide fine particles (average particle diameter: 20 nm) were mixed and dispersed in the polyester resin so that the mass ratio of the polyester resin to the tin oxide fine particles (polyester resin: tin oxide fine particles) was 75:25. The antistatic layer 6 was provided to have a mass of 0.5 g/m ² and a thickness of 0.4 μm.

(Protective film 5 resists lamination of electrostatic layer 6)
A coating adhesive PP film was used as the protective film 5. On the antistatic layer 6 of the layered product α obtained above, the protective film 5 (coating adhesive PP film) is laminated and dried so that the adhesive becomes the side of the antistatic layer 6 to obtain a laminated structure as a protective film 5 (polymerized) A laminate film A of the propylene film/acrylate adhesive)/antistatic layer 6/film layer 4. Two sheets of the laminate A were prepared.

(Manufacture of incombustible sheet)
The curable resin described in Table 1 for forming the resin layer 3 is applied to the side of the film layer 4 of the above-mentioned laminated body A (that is, the side opposite to the peelable protective film 5 which is peeled off at the time of use). raw material. Then, the glass fiber cloth 2 obtained above was placed on the curable resin material, and allowed to stand for 1 minute to allow the curable resin material to be impregnated into the voids of the glass cloth 2. Next, the other laminated body A of the two laminated bodies A prepared above is on the side of the thin film layer 4 of the laminated body A (that is, the side opposite to the peelable protective film 5 which is peeled off during use). It is placed in contact with the curable resin raw material, and is pressurized from the laminated body A by a roll so that the mass of the curable resin raw material becomes 90 g/m ² . After that, the protective film 5 is maintained in a laminated state, and is irradiated with a black fluorescent lamp (trade name: FL15BLB, manufactured by Toshiba Corporation) (irradiation condition: cumulative light amount: 200 mJ/cm ² ). The curable resin material is hardened by the curable resin material. The resin layer 3 is formed, and the laminated structure exemplified in FIG. 4 is obtained [protective film 5 (polypropylene film/acrylate adhesive)/antistatic layer 6/film layer 4/in the impregnation state is contained in the glass fiber cloth 2 Non-combustible sheet of resin layer 3 / film layer 4 / antistatic layer 6 / protective film 5 (polypropylene film / acrylate type adhesive). In the obtained nonflammable sheet, the resin layer 3 (curable resin) is impregnated into the voids between the glass fibers of the glass fiber cloth, and the resin layer 3 is formed on both surfaces of the glass fiber cloth layer.

<Example 2>
(Manufacture of fiberglass cloth 2)
Glass yarn (manufactured by Unitika Glass Fiber Co., Ltd., trade name "ECBC3000 1/0 0.5Z", average filament diameter 4 μm, average filament number 50, number of turns 0.5Z) was used as the warp and weft, and the jet was used. The loom was woven to obtain a plain weave fiberglass fabric having a warp density of 95/25 mm and a weft density of 95/25 mm. Then, the spinning sizing agent and the woven sizing agent attached to the obtained glass fiber woven fabric were removed by heating at 400 ° C for 30 hours. Thereafter, a decane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxydecane (hydrochloride) Chisso Co., Ltd.) as a surface treatment agent was adjusted to After the concentration of 15 g/L was pressed by a press roll, it was dried at 120 ° C for 1 minute and hardened. Then, the glass fiber fabric having a pressure of 1.5 MPa was subjected to two widening treatments while the tension of the glass fiber woven fabric was 100 N/m in the warp direction, thereby obtaining a glass fiber woven fabric used as the glass fiber cloth 2. The obtained glass fiber woven fabric 2 had a warp density of 95 pieces/25 mm, a weft density of 95 pieces/25 mm, a thickness of 13 μm, a mass of 12 g/m ² , and a refractive index of 1.561.

(Lamination of the antistatic layer 6 to the thin film layer 4)
A biaxially stretched polyester film was used as the film layer 4. An antistatic layer 6 is laminated on one surface of the film layer 4 (biaxially stretched polyester film). The antistatic layer 6 is obtained by applying an antistatic agent to one surface of the film layer 4 (biaxially stretched polyester film) and drying it to obtain a layered body α of the antistatic layer 6 and the film layer 4, wherein antistatic layer In the agent, the tin oxide fine particles (average particle diameter: 20 nm) were mixed and dispersed in the polyester resin so that the mass ratio of the polyester resin to the tin oxide fine particles (polyester resin: tin oxide fine particles) was 75:25. The antistatic layer 6 was provided to have a mass of 0.5 g/m ² and a thickness of 0.4 μm.

(Protective film 5 resists lamination of electrostatic layer 6)
A coating adhesive PP film was used as the protective film 5. On the antistatic layer 6 of the layered product α obtained above, the protective film 5 (coating adhesive PP film) is laminated and dried so that the adhesive becomes the side of the antistatic layer 6 to obtain a laminated structure as a protective film 5 (polymerized) A laminate film A of the propylene film/acrylate adhesive)/antistatic layer 6/film layer 4. Two sheets of the laminate A were prepared.

(Manufacture of incombustible sheet)
The curable resin described in Table 1 for forming the resin layer 3 is applied to the side of the film layer 4 of the above-mentioned laminated body A (that is, the side opposite to the peelable protective film 5 which is peeled off at the time of use). raw material. Then, the glass fiber cloth 2 obtained above was placed on the curable resin material, and allowed to stand for 1 minute to allow the curable resin material to be impregnated into the voids of the glass cloth 2. Next, the other laminated body A of the two laminated bodies A prepared above is on the side of the thin film layer 4 of the laminated body A (that is, the side opposite to the peelable protective film 5 which is peeled off during use). It is placed in contact with the curable resin raw material, and is pressurized from the laminated body A by a roll so that the mass of the curable resin raw material becomes 90 g/m ² . After that, the protective film 5 is maintained in a laminated state, and is irradiated with a black fluorescent lamp (trade name: FL15BLB, manufactured by Toshiba Corporation) (irradiation condition: cumulative light amount: 200 mJ/cm ² ). The curable resin material is hardened by the curable resin material. The resin layer 3 is formed, and the laminated structure exemplified in FIG. 4 is obtained [protective film 5 (polypropylene film/acrylate adhesive)/antistatic layer 6/film layer 4/in the impregnation state is contained in the glass fiber cloth 2 Non-combustible sheet of resin layer 3 / film layer 4 / antistatic layer 6 / protective film 5 (polypropylene film / acrylate type adhesive). In the obtained nonflammable sheet, the resin layer 3 (curable resin) is impregnated into the voids between the glass fibers of the glass fiber cloth, and the resin layer 3 is formed on both surfaces of the glass fiber cloth layer.

<Example 3>
(Manufacture of fiberglass cloth 2)
Glass yarn (manufactured by Unitika Glass Fiber Co., Ltd., trade name "ECBC3000 1/0 0.5Z", average filament diameter 4 μm, average filament number 50, number of turns 0.5Z) was used as the warp and weft, and the jet was used. The loom was woven to obtain a plain weave fiberglass fabric having a warp density of 95/25 mm and a weft density of 95/25 mm. Then, the spinning sizing agent and the woven sizing agent attached to the obtained glass fiber woven fabric were removed by heating at 400 ° C for 30 hours. Thereafter, a decane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxydecane (hydrochloride) Chisso Co., Ltd.) as a surface treatment agent was adjusted to After the concentration of 15 g/L was pressed by a press roll, it was dried at 120 ° C for 1 minute and hardened. Then, the glass fiber fabric having a pressure of 1.5 MPa was subjected to two widening treatments while the tension of the glass fiber woven fabric was 100 N/m in the warp direction, thereby obtaining a glass fiber woven fabric used as the glass fiber cloth 2. The obtained glass fiber woven fabric 2 had a warp density of 95 pieces/25 mm, a weft density of 95 pieces/25 mm, a thickness of 13 μm, a mass of 12 g/m ² , and a refractive index of 1.561.

(Lamination of the antistatic layer 6 to the thin film layer 4)
A biaxially stretched polyester film was used as the film layer 4. An antistatic layer 6 is laminated on one surface of the film layer 4 (biaxially stretched polyester film). The antistatic layer 6 is obtained by applying an antistatic agent to one surface of the film layer 4 (biaxially stretched polyester film) and drying it to obtain a layered body α of the antistatic layer 6 and the film layer 4, wherein antistatic layer In the agent, tin oxide fine particles (average particle diameter: 20 nm) were mixed and dispersed in a polyester resin as a fixing resin so that the mass ratio of the fixing resin to the tin oxide fine particles (fixed resin: tin oxide fine particles) was 75:25. The antistatic layer 6 was provided to have a mass of 0.5 g/m ² and a thickness of 0.4 μm.

(Protective film 5 resists lamination of electrostatic layer 6)
A coating adhesive PP film was used as the protective film 5. On the antistatic layer 6 of the layered product α obtained above, the protective film 5 (coating adhesive PP film) is laminated and dried so that the adhesive becomes the side of the antistatic layer 6 to obtain a laminated structure as a protective film 5 (polymerized) A laminate film A of the propylene film/acrylate adhesive)/antistatic layer 6/film layer 4. Two sheets of the laminate A were prepared.

(Manufacture of incombustible sheet)
The curable resin described in Table 1 for forming the resin layer 3 is applied to the side of the film layer 4 of the above-mentioned laminated body A (that is, the side opposite to the peelable protective film 5 which is peeled off at the time of use). raw material. Then, the glass fiber cloth 2 obtained above was placed on the curable resin material, and allowed to stand for 1 minute to allow the curable resin material to be impregnated into the voids of the glass cloth 2. Next, the other laminated body A of the two laminated bodies A prepared above is on the side of the thin film layer 4 of the laminated body A (that is, the side opposite to the peelable protective film 5 which is peeled off during use). It is placed in contact with the curable resin material, and is pressurized from the layered product A by a roll so that the mass of the curable resin material becomes 40 g/m ² . After that, the protective film 5 is maintained in a laminated state, and is irradiated with a black fluorescent lamp (trade name: FL15BLB, manufactured by Toshiba Corporation) (irradiation condition: cumulative light amount: 200 mJ/cm ² ). The curable resin material is hardened by the curable resin material. The resin layer 3 is formed, and the laminated structure exemplified in FIG. 4 is obtained [protective film 5 (polypropylene film/acrylate adhesive)/antistatic layer 6/film layer 4/in the impregnation state is contained in the glass fiber cloth 2 Non-combustible sheet of resin layer 3 / film layer 4 / antistatic layer 6 / protective film 5 (polypropylene film / acrylate type adhesive). In the obtained nonflammable sheet, the resin layer 3 (curable resin) is impregnated into the voids between the glass fibers of the glass fiber cloth, and the resin layer 3 is formed on both surfaces of the glass fiber cloth layer.

<Example 4>
(Manufacture of fiberglass cloth 2)
A glass yarn (trade name "ECC1200 1/0 1.0Z" manufactured by Unitika Glass Fiber Co., Ltd., an average filament diameter of 4.5 μm, an average number of filaments of 100, and a number of turns of 1.0 Z) was used as the warp and weft. The air jet loom was woven to obtain a plain fiberglass fabric having a warp density of 90/25 mm and a weft density of 90/25 mm. Then, the spinning sizing agent and the woven sizing agent attached to the obtained glass fiber woven fabric were removed by heating at 400 ° C for 30 hours. Thereafter, a decane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxydecane (hydrochloride) Chisso Co., Ltd.) as a surface treatment agent was adjusted to After the concentration of 15 g/L was pressed by a press roll, it was dried at 120 ° C for 1 minute and hardened. Then, the glass fiber fabric having a pressure of 1.5 MPa was subjected to a widening treatment while the tension of the glass fiber woven fabric was 100 N/m in the warp direction, whereby a glass fiber woven fabric used as the glass fiber cloth 2 was obtained. The obtained glass fiber woven fabric 2 had a warp density of 90 pieces/25 mm, a weft density of 90 pieces/25 mm, a thickness of 27 μm, a mass of 30 g/m ² , and a refractive index of 1.561.

(Manufacture of incombustible sheet)
Two PET films were used as the protective film 5. The curable resin raw material described in Table 1 for forming the resin layer 3 was applied to one surface of one protective film 5 (PET film). Then, the glass fiber cloth 2 obtained above was placed on the curable resin material, and allowed to stand for 1 minute to allow the curable resin material to be impregnated into the voids of the glass cloth 2. Then, another protective film 5 (PET film) was placed on the curable resin material impregnated into the glass fiber cloth 2, and the protective film was obtained so that the mass of the curable resin material became 90 g/m ² . 5 (PET film) was pressed with a roller. After that, the protective film 5 is maintained in a laminated state, and is irradiated with a black fluorescent lamp (trade name: FL15BLB, manufactured by Toshiba Corporation) (irradiation condition: cumulative light amount: 200 mJ/cm ² ). The curable resin material is hardened by the curable resin material. The resin layer 3 is formed, and a non-combustible sheet having a laminated structure [protective film 5 / resin layer 3 / protective film 5 contained in the glass fiber cloth 2 in an impregnated state] is obtained. In the obtained nonflammable sheet, the resin layer 3 (curable resin) is impregnated into the voids between the glass fibers of the glass fiber cloth, and the resin layer 3 is formed on both surfaces of the glass fiber cloth layer.

<Example 5>
(Manufacture of fiberglass cloth 2)
A glass yarn (trade name "ECC1200 1/0 1.0Z" manufactured by Unitika Glass Fiber Co., Ltd., an average filament diameter of 4.5 μm, an average number of filaments of 100, and a number of turns of 1.0 Z) was used as the warp and weft. The air jet loom was woven to obtain a plain fiberglass fabric having a warp density of 90/25 mm and a weft density of 90/25 mm. Then, the spinning sizing agent and the woven sizing agent attached to the obtained glass fiber woven fabric were removed by heating at 400 ° C for 30 hours. Thereafter, a decane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxydecane (hydrochloride) Chisso Co., Ltd.) as a surface treatment agent was adjusted to After the concentration of 15 g/L was pressed by a press roll, it was dried at 120 ° C for 1 minute and hardened. Then, the glass fiber fabric having a pressure of 1.5 MPa was subjected to a widening treatment while the tension of the glass fiber woven fabric was 100 N/m in the warp direction, whereby a glass fiber woven fabric used as the glass fiber cloth 2 was obtained. The obtained glass fiber woven fabric 2 had a warp density of 90 pieces/25 mm, a weft density of 90 pieces/25 mm, a thickness of 27 μm, a mass of 30 g/m ² , and a refractive index of 1.561.

(Manufacture of incombustible sheet)
Two PET films were used as the protective film 5. The curable resin raw material described in Table 1 for forming the resin layer 3 was applied to one surface of one protective film 5 (PET film). Then, the glass fiber cloth 2 obtained above was placed on the curable resin material, and allowed to stand for 1 minute to allow the curable resin material to be impregnated into the voids of the glass cloth 2. Then, another protective film 5 (PET film) was placed on the curable resin material impregnated into the glass fiber cloth 2, and the protective film was obtained so that the mass of the curable resin material became 90 g/m ² . 5 (PET film) was pressed with a roller. After that, the protective film 5 is maintained in a laminated state, and is irradiated with a black fluorescent lamp (trade name: FL15BLB, manufactured by Toshiba Corporation) (irradiation condition: cumulative light amount: 200 mJ/cm ² ). The curable resin material is hardened by the curable resin material. The resin layer 3 is formed, and a non-combustible sheet having a laminated structure [protective film 5 / resin layer 3 / protective film 5 contained in the glass fiber cloth 2 in an impregnated state] is obtained. In the obtained nonflammable sheet, the resin layer 3 (curable resin) is impregnated into the voids between the glass fibers of the glass fiber cloth, and the resin layer 3 is formed on both surfaces of the glass fiber cloth layer.

<Comparative Example 1>
The laminate structure was obtained in the same manner as in Example 1 except that the laminate of the antistatic layer 6 in Example 1 was not obtained. [Protective film 5 (polypropylene film/acrylate adhesive)/film layer 4/ A non-combustible sheet which is contained in the resin layer 3 / the film layer 4 / the protective film 5 (polypropylene film / acrylate type adhesive) of the glass fiber cloth 2 in an impregnation state.

<Comparative Example 2>
(Manufacture of fiberglass cloth 2)
A glass yarn (trade name "ECC1200 1/0 1.0Z" manufactured by Unitika Glass Fiber Co., Ltd., an average filament diameter of 4.5 μm, an average number of filaments of 100, and a number of turns of 1.0 Z) was used as the warp and weft. The air jet loom was woven to obtain a plain fiberglass fabric having a warp density of 90/25 mm and a weft density of 90/25 mm. Then, the spinning sizing agent and the woven sizing agent attached to the obtained glass fiber woven fabric were removed by heating at 400 ° C for 30 hours. Thereafter, a decane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxydecane (hydrochloride) Chisso Co., Ltd.) as a surface treatment agent was adjusted to After the concentration of 15 g/L was pressed by a press roll, it was dried at 120 ° C for 1 minute and hardened. Then, the glass fiber fabric having a pressure of 1.5 MPa was subjected to a widening treatment while the tension of the glass fiber woven fabric was 100 N/m in the warp direction, whereby a glass fiber woven fabric used as the glass fiber cloth 2 was obtained. The obtained glass fiber woven fabric 2 had a warp density of 90 pieces/25 mm, a weft density of 90 pieces/25 mm, a thickness of 27 μm, a mass of 30 g/m ² , and a refractive index of 1.561.

(Lamination of the protective film 5 to the film layer 4)
A biaxially stretched polyester film was used as the film layer 4, and a coating adhesive PP film was used as the protective film 5. On one surface of the film layer 4 (biaxially stretched polyester film), the protective film 5 is laminated and adhered so that the adhesive side contacts the film layer 4, and a laminated structure is obtained as a protective film 5 (polypropylene film/acrylate) Adhesive) / Laminate B of film layer 4. Two sheets of the layered body B were prepared.

(Manufacture of incombustible sheet)
The curable resin described in Table 1 for forming the resin layer 3 is applied to the side of the film layer 4 of the above-mentioned laminated body B (that is, the side opposite to the peelable protective film 5 which is peeled off at the time of use). raw material. Then, the glass fiber cloth 2 obtained above was placed on the curable resin material, and allowed to stand for 1 minute to allow the curable resin material to be impregnated into the voids of the glass cloth 2. Next, the other laminated body B among the two laminated bodies B prepared above is on the side of the thin film layer 4 of the laminated body B (that is, the side opposite to the peelable protective film 5 which is peeled off during use). It is placed in contact with the curable resin material, and is pressurized from the layered body B by a roll so that the mass of the curable resin material becomes 90 g/m ² . After that, the protective film 5 is maintained in a laminated state, and is irradiated with a black fluorescent lamp (trade name: FL15BLB, manufactured by Toshiba Corporation) (irradiation condition: cumulative light amount: 200 mJ/cm ² ). The curable resin material is hardened by the curable resin material. The resin layer 3 was formed, and the laminated structure was obtained as [protective film 5 (polypropylene film/acrylate type adhesive)/film layer 4/resin layer 3/film layer 4/containing in the impregnation state of the glass cloth 2/ Non-combustible sheet of protective film 5 (polypropylene film/acrylate adhesive). In the obtained nonflammable sheet, the resin layer 3 (curable resin) is impregnated into the voids between the glass fibers of the glass fiber cloth, and the resin layer 3 is formed on both surfaces of the glass fiber cloth layer.

<Comparative Example 3>
(Manufacture of fiberglass cloth 2)
Glass yarn (manufactured by Unitika Glass Fiber Co., Ltd., trade name "ECBC3000 1/0 0.5Z", average filament diameter 4 μm, average filament number 50, number of turns 0.5Z) was used as the warp and weft, and the jet was used. The loom was woven to obtain a plain weave fiberglass fabric having a warp density of 95/25 mm and a weft density of 95/25 mm. Then, the spinning sizing agent and the woven sizing agent attached to the obtained glass fiber woven fabric were removed by heating at 400 ° C for 30 hours. Thereafter, a decane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxydecane (hydrochloride) Chisso Co., Ltd.) as a surface treatment agent was adjusted to After the concentration of 15 g/L was pressed by a press roll, it was dried at 120 ° C for 1 minute and hardened. Then, the glass fiber fabric having a pressure of 1.5 MPa was subjected to two widening treatments while the tension of the glass fiber woven fabric was 100 N/m in the warp direction, thereby obtaining a glass fiber woven fabric used as the glass fiber cloth 2. The obtained glass fiber woven fabric 2 had a warp density of 95 pieces/25 mm, a weft density of 95 pieces/25 mm, a thickness of 13 μm, a mass of 12 g/m ² , and a refractive index of 1.561.

(Lamination of the protective film 5 to the film layer 4)
A vinyl chloride resin film was used as the film layer 4, and a coating adhesive PP film was used as the protective film 5. On one surface of the film layer 4 (vinyl chloride resin film), the protective film 5 is laminated and adhered so that the adhesive side contacts the film layer 4, and a laminated structure is obtained as a protective film 5 (polypropylene film/acrylate type adhesion) The layered body C of the film layer 4. Two sheets of the layered body C were prepared.

(Manufacture of incombustible sheet)
The curable resin described in Table 1 for forming the resin layer 3 is applied to the side of the film layer 4 of the above-mentioned laminated body C (that is, the side opposite to the peelable protective film 5 which is peeled off at the time of use). raw material. Then, the glass fiber cloth 2 obtained above was placed on the curable resin material, and allowed to stand for 1 minute to allow the curable resin material to be impregnated into the voids of the glass cloth 2. Next, the other laminated body C among the two laminated bodies C prepared above is on the side of the film layer of the laminated body C (that is, the side opposite to the peelable protective film 5 which is peeled off during use) It is placed in contact with the curable resin raw material, and is pressurized from the laminated body C by a roll so that the mass of the curable resin raw material becomes 40 g/m ² . After that, the protective film 5 is maintained in a laminated state, and is irradiated with a black fluorescent lamp (trade name: FL15BLB, manufactured by Toshiba Corporation) (irradiation condition: cumulative light amount: 200 mJ/cm ² ). The curable resin material is hardened by the curable resin material. The resin layer 3 was formed, and the laminated structure was obtained as [protective film 5 (polypropylene film/acrylate type adhesive)/film layer 4/resin layer 3/film layer 4/containing in the impregnation state of the glass cloth 2/ Non-combustible sheet of protective film 5 (polypropylene film/acrylate adhesive). In the obtained nonflammable sheet, the resin layer 3 (curable resin) is impregnated into the voids between the glass fibers of the glass fiber cloth, and the resin layer 3 is formed on both surfaces of the glass fiber cloth layer.

<Comparative Example 4>
(Manufacture of fiberglass cloth)
Glass yarn (manufactured by Unitika Glass Fiber Co., Ltd., trade name "ECBC3000 1/0 0.5Z", average filament diameter 4 μm, average filament number 50, number of turns 0.5Z) was used as the warp and weft, and the jet was used. The loom was woven to obtain a plain weave fiberglass fabric having a warp density of 95/25 mm and a weft density of 95/25 mm. Then, the spinning sizing agent and the woven sizing agent attached to the obtained glass fiber woven fabric were removed by heating at 400 ° C for 30 hours. Thereafter, a decane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxydecane (hydrochloride) Chisso Co., Ltd.) as a surface treatment agent was adjusted to After the concentration of 15 g/L was pressed by a press roll, it was dried at 120 ° C for 1 minute and hardened. Then, the glass fiber fabric having a pressure of 1.5 MPa was subjected to two widening treatments while the tension of the glass fiber woven fabric was 100 N/m in the warp direction, thereby obtaining a glass fiber woven fabric used as the glass fiber cloth 2. The obtained glass fiber woven fabric 2 had a warp density of 95 pieces/25 mm, a weft density of 95 pieces/25 mm, a thickness of 13 μm, a mass of 12 g/m ² , and a refractive index of 1.561.

(Manufacture of incombustible sheet)
Two PET films were used as the protective film 5. The curable resin raw material described in Table 1 for forming the resin layer 3 was applied to one surface of one protective film 5 (PET film). Then, the glass fiber cloth 2 obtained above was placed on the curable resin material, and allowed to stand for 1 minute to allow the curable resin material to be impregnated into the voids of the glass cloth 2. Then, another protective film 5 (PET film) was placed on the curable resin material impregnated into the glass fiber cloth 2, and the protective film was obtained so that the mass of the curable resin material became 90 g/m ² . 5 (PET film) was pressed with a roller. Then, the PET film which is the peelable protective film 5 which was peeled off at the time of use is maintained in a layered state, and is irradiated with a black fluorescent lamp (trade name: FL15BLB, manufactured by Toshiba Co., Ltd.) (irradiation condition: cumulative light amount is 200 mJ/cm) ² ) The curable resin material is cured to form the resin layer 3, and the incombustibility of the laminated structure [the protective film 5 / the resin layer 3 / the protective film 5 contained in the glass fiber cloth 2 in an impregnated state] is obtained. Sheet. In the obtained nonflammable sheet, the resin layer 3 (curable resin) is impregnated into the voids between the glass fibers of the glass fiber cloth, and the resin layer 3 is formed on both surfaces of the glass fiber cloth layer.

3. Measurement ‧ Evaluation method <Physical properties of glass fiber woven fabric and resin layer>
The weaving density of the glass fiber woven fabric is measured and calculated in accordance with the method specified in "7.9 Density (Wheel Density)" of "Japanese Industrial Standard JIS R 3420:2013 Glass Fiber General Test Method". In addition, the thickness of the glass fiber woven fabric is measured and calculated in accordance with the "A method" prescribed in "7.10 Cloth and Pad Thickness" of "Japanese Industrial Standard JIS R 3420:2013 Glass Fiber General Test Method". The quality of the glass fiber fabric is measured and calculated in accordance with the method specified in "Quality (Quality) of 7.2 Cloth Pads of the Japanese Industrial Standard JIS R 3420:2013 Glass Fiber Test Method".

The refractive indices of the resin layer 3 and the glass fiber woven fabric 2 were measured and calculated by the aforementioned methods. In addition, the measurement of the refractive index is performed using the apparatus exemplified above. The Abbe number of the resin layer 3 and the glass fiber fabric 2 was measured and calculated by the aforementioned method. In addition, the measurement of the Abbe number uses the NAR-2T manufactured by Atago Co., Ltd. as an Abbe refractometer.

<Physical properties of non-combustible sheets>
The various physical properties of the incombustible sheet were measured by the following methods. In addition, the measurement of various physical properties of the incombustible sheet shown below was performed after the incombustible sheet was produced and placed in the room for one week.

(Thermal cycle test and surface resistivity, total light transmittance and haze before and after the heat cycle test)
The thermal cycle test was carried out by the above method, and the surface resistivity, the total light transmittance, and the haze were measured by the aforementioned methods regarding the nonflammable sheet before and after the heat cycle test. Further, in the heat cycle test, a trade name of PSL-2KPH manufactured by Espec Co., Ltd. was used as a constant temperature humidifier, and in the measurement of the surface resistivity, High Resistance Meter 4339B manufactured by Agilent Technologies Co., Ltd. was used.

(Identify the degree of dust adhesion when used as a smoke prevention wall for a long time)
Regarding the obtained non-combustible sheet, the protective film 5 is peeled off (in the case where the peelable acrylate-based adhesive is contained together with the protective film 5, the adhesive is entirely peeled off), and the specific heat cycle test is performed, and the heat is applied. The incombustible sheet after the cycle test was cut into 20 cm square. In addition, 50 sheets of paper cut into 1 mm squares were spread on a test stand of 15 cm square. The non-combustible sheet (20 cm square) after the heat cycle test was statically placed on a test stand on which paper sheets were spread, and then the incombustible sheet was gently pulled up. At this time, the number of sheets of paper adsorbed on the incombustible sheet was measured. Further, the paper sheets used were obtained by cutting paper having a thickness of 0.1 mm and a mass of 70 g/m ² . Then, based on the following criteria, 3 or more points were passed.
3 points ‧ ‧ no adsorption to the paper
2 points ‧ ‧ 1 to 9 sheets of paper
1 minute, ‧ ‧ more than 10 sheets of paper

(initial tear strength)
The measurement of the initial tear strength (the tear strength measured without the slit in the sample) of the incombustible sheet was carried out by the aforementioned method. In the measurement of the initial tear strength, the tape used for slip resistance was used under the trade name 600S manufactured by Sekisui Chemical Co., Ltd., and the constant speed load type tensile tester was used under the trade name RTC-1310A manufactured by Orientec Co., Ltd.

(glass volume ratio)
The glass volume was calculated from the mass of the glass fiber woven fabric, the specific gravity of the glass material constituting the glass fiber woven fabric, and the thickness of the glass fiber woven fabric according to the above formula.

(non-combustibility evaluation)
The heat generation test (the heat generation test of radiant heat of 50 kW/m ^{2 on} the surface of the sheet from the radiant electric heater) was carried out according to the above-described method, and the judgment was made in accordance with the following criteria.
◎: The maximum heat generation rate after the start of heating is set to a condition of not exceeding 200 kW/m ² for 10 seconds or more and a total calorific value of 8 MJ/m ² or less.
x: The maximum heat generation rate after the start of heating is not satisfied, and the condition is such that the maximum heat generation rate is not more than 200 kW/m ² for 10 seconds or more and the total heat generation amount is 8 MJ/m ² or less.

4. Evaluation Results Each evaluation result is shown in Table 1.

[Table 1]

By making the non-combustible sheets of Examples 1 to 5 have a surface resistivity of 1 × 10 ¹¹ Ω or less before and after a specific heat cycle test, dust adhesion can be reduced, for example, when used as a smoke preventing wall for a long period of time. On the other hand, since the surface resistivity of the nonflammable sheet of Comparative Examples 1 to 4 exceeds 1 × 10 ¹¹ Ω, dust adhesion when used as a smoke preventing wall for a long period of time cannot be reduced.

Comparing Examples 4 and 5, in Example 4, since the mass (g/m ² ) of the surfactant contained in the incombustible sheet was from 1 to 1.5 g/m ² , it was ensured to be reduced as smoke prevention. The vertical wall is excellent in transparency while being attached to the dust for a long period of time. Further, since Examples 1 to 3 have the antistatic layer 6 containing a metal or a metal oxide which becomes a surface layer when used as a smoke preventing vertical wall, the surface resistivity is lower than 1 × 10 ¹⁰ Ω or less. Further, the adhesion of dust as a smoke-proof vertical wall for a long period of time is further reduced, and the change in surface resistivity before and after a specific heat cycle test is further reduced, and more excellent transparency is obtained. Further, after the specific heat cycle test, the incombustible sheets of Example 5 and Comparative Example 5 were confirmed to have a relatively high viscosity, and on the other hand, the incombustible sheets of Examples 1 to 3 were hardly confirmed to have a viscosity. Sex. Further, the nonflammable sheets of Examples 1 to 3 were confirmed to have a difference in surface resistivity before and after a specific heat cycle test (= surface resistivity (Ω) after a specific heat cycle test - surface before a specific heat cycle test The resistivity (Ω) is 5.0 × 10 ⁹ Ω or less and has stable antistatic properties. Further, since Examples 1 to 3 contain the film layer 4, the initial tear strength is also excellent.

1‧‧‧Incombustible sheet

2‧‧‧glass cloth

3‧‧‧ resin layer

31, 32‧‧‧ Surface side portion of the resin layer

4‧‧‧film layer

41, 42‧‧‧ Surface side part of the film layer

5‧‧‧Protective film

6‧‧‧Antistatic layer

Fig. 1 is a schematic cross-sectional view showing an example of a nonflammable sheet of the present invention.

Fig. 2 is a schematic cross-sectional view showing an example of the incombustible sheet of the present invention.

Fig. 3 is a schematic cross-sectional view showing an example of the incombustible sheet of the present invention.

Fig. 4 is a schematic cross-sectional view showing an example of the incombustible sheet of the present invention.

Fig. 5 is a schematic plan view showing a method of measuring the initial tear strength of the present invention.

Claims (5)

A non-combustible sheet comprising: a glass fiber cloth and a resin layer contained in the glass fiber cloth in an impregnated state, wherein the non-combustible sheet has a surface resistivity of 1×10 ¹¹ Ω or less before and after the heat cycle test described below; <Thermal cycle test conditions> A sample of 100 mm × 100 mm was cut out from the non-combustible sheet as a sample, and the sample was placed in a thermo-hygrostat which was previously set to a temperature of 23 ° C and a relative humidity of 50% RH. (1) to (5) A total of 10 cycles were performed as one cycle; (1) The migration time was set to 14 minutes, and the temperature was changed from a temperature of 23 ° C and a relative humidity of 50% RH to a temperature of 60 ° C and a relative humidity of 50% RH. (2) maintained at the above temperature of 60 ° C, relative humidity of 50% RH for 8 hours; (3) set the migration time to 45 minutes, from the above temperature of 60 ° C, relative humidity of 50% RH to 20 ° C, relative humidity of 50 (4) maintained at the above temperature of 20 ° C and relative humidity of 50% RH for 8 hours; (5) set the migration time to 1 minute, and migrated from the above temperature of 20 ° C, relative humidity of 50% RH to a temperature of 23 ° C, The relative humidity is 50% RH. The nonflammable sheet according to claim 1, which comprises an antistatic layer containing a metal or a metal oxide, and the antistatic layer becomes a surface layer when the nonflammable sheet is used. The non-combustible sheet according to claim 1, wherein the non-combustible sheet is used as a layer of a surface layer containing a surfactant, and the mass of the surfactant (g/m ² ) in the incombustible sheet It is from 0.5 to 1.5 g/m ² . The non-combustible sheet of claim 1 or 2 has a total light transmittance of 90% or more and a haze of 20% or less. A smoke-proof vertical wall comprising the non-combustible sheet according to any one of claims 1 to 4.