JP2024016062A - Noncombustible sheet, and smokeproof hanging wall including noncombustible sheet - Google Patents

Abstract

To provide a noncombustible sheet of a glass fabric and a resin, reducing adhesion of dust when used as a smokeproof hanging wall for a long time and the smokeproof hanging wall having the noncombustible sheet.SOLUTION: There is provided a noncombustible sheet containing a glass fiber fabric and a resin composition layer contained with a state to be impregnated into the glass fiber fabric, and having surface resistivity before and after a specific heat cycle test of the noncombustible sheet of 1×1011 Ω or less. Preferably it has an antistatic layer containing metal or metal oxide to be a surface layer when the noncombustible sheet is used.SELECTED DRAWING: Figure 1

Description

The present invention relates to a noncombustible sheet, and particularly to a noncombustible sheet suitable for smokeproof hanging walls, etc., and a smokeproof hanging wall using the same.

The Building Standards Act and the Building Standards Act Enforcement Order stipulate that smoke exhaust equipment must be installed to prevent the flow of smoke, toxic gas, etc. generated in the event of a building fire, and to facilitate evacuation and firefighting operations. There is. Therefore, in buildings such as office buildings and commercial facilities, smoke-proof hanging walls are often installed as smoke exhaust equipment and smoke-blocking equipment.

Smoke-proof hanging walls are usually installed in buildings for the purpose of temporarily blocking smoke, toxic gas, etc. from flowing into hallways and upper floors in the event of a fire, and securing the time necessary for evacuation. It is attached to the ceiling. For this reason, plate glass, a resin composite of glass fiber and resin, or the like is used as the smoke-proof hanging wall so that the field of view is not obstructed or the aesthetic appearance is not impaired by the smoke-proof hanging wall. A resin composite of glass fiber and resin has the advantage that it is less likely to break than plate glass. For example, Patent Document 1 discloses a transparent noncombustible sheet containing a glass fiber fabric and a cured resin layer.

Further, for example, Patent Document 2 has a base material layer including a glass fiber cloth and a transparent cured resin layer impregnated therein, and a reinforcing layer is integrally formed on at least one side of the base material layer. A transparent nonflammable sheet is disclosed.

Further, for example, Patent Document 3 discloses a nonflammable laminate including an adhesive-impregnated coated glass cloth as a base material and a soft vinyl chloride resin transparent layer provided on both sides of the adhesive-impregnated coated glass cloth. is a composite intermediate formed by impregnating and curing glass cloth treated with a silane 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 transparent noncombustible sheet is disclosed in which the triisocyanate compound is one or more selected from isocyanurate-modified triisocyanates, buret-modified triisocyanates, and trimethylolalkyl-modified triisocyanates.

Japanese Patent Application Publication No. 2005-319746 Japanese Patent Application Publication No. 2011-213093 Japanese Patent Application Publication No. 2014-76563

As a result of studies by the present inventors, the noncombustible sheets described in Patent Documents 1 to 3, for example, when used as smoke-proof hanging walls for a long period of time, It has been found that there is a problem in that the existing dust adheres to the surface of the nonflammable sheet, resulting in poor appearance. Under these circumstances, the present invention provides a noncombustible sheet made of glass cloth and resin that reduces the adhesion of dust when used for a long period of time, for example as a smokeproof hanging wall, and a preventive device comprising the noncombustible sheet. The purpose is to provide a chimney wall.

In order to solve the above problem, the present inventors investigated and found that the nonflammable sheets disclosed in Patent Documents 1 to 3, for example, have a surface resistivity of about 1×10 ¹⁵ Ω. It was found that the adhesion of dust present in the air could not be sufficiently prevented. Therefore, the inventors of the present invention conducted extensive studies and found that the above-mentioned dust adhesion can be reduced by setting the surface resistivity to 1×10 ¹¹ Ω or less before and after a specific heat cycle test. The present invention was completed through further studies based on these findings.

That is, the present invention provides inventions of the following aspects.
Item 1. A nonflammable sheet comprising a glass fiber cloth and a resin composition layer impregnated in the glass fiber cloth, the nonflammable sheet having a surface resistivity of 1× before and after the following heat cycle test. A noncombustible sheet with a resistance of 10 ¹¹ Ω or less.
<Heat cycle test conditions>
The non-combustible sheet was cut into a sample with a size of 100 mm x 100 mm, and the sample was placed in a constant temperature and humidity chamber (product name: PSL, manufactured by ESPEC Co., Ltd., which was initially set to a temperature of 23°C and a relative humidity of 50% RH). -2KPH), and carry out 10 cycles in total, with the following (1) to (5) being one cycle.
(1) Transition from a temperature of 23° C. and relative humidity of 50 RH to a temperature of 60° C. and relative humidity of 50% RH with a transition time of 14 minutes.
(2) Maintain at the above temperature of 60° C. and relative humidity of 50% RH for 8 hours.
(3) Transition from the above temperature of 60° C. and relative humidity of 50% RH to temperature of 20° C. and relative humidity of 50% RH with a transition time of 45 minutes.
(4) Maintain at the above temperature of 20° C. and relative humidity of 50% RH for 8 hours.
(5) Transition from the above temperature of 20° C. and relative humidity of 50% RH to temperature of 23° C. and relative humidity of 50% RH with a transition time of 1 minute.
Item 2. Item 2. The nonflammable sheet according to Item 1, further comprising an antistatic layer containing a metal or a metal oxide to serve as a surface layer when the nonflammable sheet is used.
Item 3. A layer that becomes a surface layer when the noncombustible sheet is used contains a surfactant, and the mass (g/m ² ) of the surfactant in the noncombustible sheet is 0.5 to 1.5 g/m ² , the nonflammable sheet according to item 1.
Item 4. Item 3. The nonflammable sheet according to any one of Items 1 to 3, which has a total light transmittance of 90% or more and a haze of 20% or less.
Item 5. The noncombustible sheet according to any one of items 1 to 4, which is used for smoke-proof hanging walls.
Item 6. A smoke-proof hanging wall comprising the noncombustible sheet according to any one of items 1 to 5.

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

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross-sectional view which shows an example of the noncombustible sheet of this invention. 1 is a schematic cross-sectional view showing an example of a noncombustible sheet of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross-sectional view which shows an example of the noncombustible sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross-sectional view which shows an example of the noncombustible sheet of this invention. FIG. 2 is a schematic plan view illustrating the method for measuring initial tear strength of the present invention.

The noncombustible sheet of the present invention includes a glass fiber cloth and a resin composition layer impregnated in the glass fiber cloth, the noncombustible sheet being tested before and after the following heat cycle test. The surface resistivity is 1×10 ¹¹ Ω or less.
<Heat cycle test conditions>
The non-combustible sheet was cut into a sample with a size of 100 mm x 100 mm, and the sample was placed in a constant temperature and humidity chamber (product name: PSL, manufactured by ESPEC Co., Ltd., which was initially set to a temperature of 23°C and a relative humidity of 50% RH). -2KPH), and carry out 10 cycles in total, with the following (1) to (5) being one cycle.
(1) Transition from a temperature of 23° C. and relative humidity of 50% RH to a temperature of 60° C. and relative humidity of 50% RH with a transition time of 14 minutes.
(2) Maintain at the above temperature of 60° C. and relative humidity of 50% RH for 8 hours.
(3) Transition from the above temperature of 60° C. and relative humidity of 50% RH to temperature of 20° C. and relative humidity of 50% RH with a transition time of 45 minutes.
(4) Maintain at the above temperature of 20° C. and relative humidity of 50% RH for 8 hours.
(5) Transition from the above temperature of 20° C. and relative humidity of 50% RH to temperature of 23° C. and relative humidity of 50% RH with a transition time of 1 minute.

For example, as shown in FIGS. 1 to 4, the noncombustible sheet 1 of the present invention has a laminated structure including a glass fiber cloth 2 and a resin composition layer 3 impregnated into the glass fiber cloth 2. The noncombustible sheet 1 only needs to include at least one layer of glass fiber cloth 2, and may include multiple layers.

Further, as shown in FIGS. 2 to 4, the nonflammable sheet 1 of the present invention includes a glass fiber cloth 2, a resin composition layer 3 impregnated into the glass fiber cloth 2, and at least one side of the resin composition layer 3. It can also be a laminated structure comprising a film layer 4 on top, preferably on both sides. Further, as shown in FIGS. 3 and 4, the noncombustible sheet 1 of the present invention can be used on at least one side, preferably both sides, of the resin composition layer 3 or the film layer 4, for example, as a smoke-proof hanging wall. It can include a peelable protective film 5 that is peeled off.

1 to 4, the resin composition layer 3 fills the gaps between the plurality of glass fibers constituting the glass fiber cloth 2, and the resin composition layer 3 has a surface side portion 31 on one side and a surface side portion 31 on the other side. The side portion and 32 communicate through the gap portion. In addition, in the noncombustible sheet 1 of the present invention, from the viewpoint of increasing transparency, the resin composition layer 3 is provided on at least one surface of the layer of glass fiber cloth 2, as shown in FIGS. 1 to 4, for example. It is preferable that the resin composition layer 3 be formed on both sides of the layer of the glass fiber cloth 2.

If the film layer 4 is not laminated as shown in FIG. 1, the surface side of the resin composition layer 3 (31 and 32 side in FIG. 1), or as shown in FIGS. As shown in FIG. 4, for example, an antistatic layer 6 containing a metal or a metal compound can be provided on the surface side of the film layer 4 (the 41 and 42 sides in FIGS. 2 and 3). This makes it possible to further reduce surface resistivity before and after a specific heat cycle test, further reduce changes in surface resistivity before and after a specific heat cycle test, and obtain better transparency. . It is more preferable that the antistatic layer 6 containing a metal or a metal compound is disposed as a surface layer when the noncombustible sheet 1 is used, for example, when used as a smoke-proof hanging wall. Hereinafter, the composition of each layer constituting the nonflammable sheet 1 of the present invention will be explained in detail.

(Glass fiber cloth 2)
In the noncombustible sheet 1 of the present invention, the glass fiber cloth 2 is composed of a plurality of glass fibers. In the glass fiber cloth 2, a plurality of glass fibers are intertwined with each other to form one cloth. Examples of the glass fiber cloth 2 include glass fiber fabric (glass cloth) composed of a plurality of warps and a plurality of wefts. The weave structure of the glass fiber fabric is not particularly limited, and examples thereof include plain weave, satin weave, twill weave, shank weave, and ribbed weave.

The glass material of the glass fibers constituting the glass fiber cloth 2 is not particularly limited, and for example, known glass materials can be used. Examples of glass materials include alkali-free glass (E glass), acid-resistant alkali-containing glass (C glass), high-strength/high-modulus glass (S glass, T glass, etc.), alkali-resistant glass (AR glass), etc. Preferably, highly versatile alkali-free glass (E glass) is used. The glass fibers constituting the glass fiber cloth 2 may be made of one type of glass material, or may be a combination of two or more types of glass fibers made of different glass materials. Moreover, from the viewpoint of improving transparency, it is preferable to select a glass material having a refractive index similar to that of the resin composition layer 3, which will be described later.

The count of the glass fibers constituting the glass fiber cloth 2 is not limited to a specific one as long as the glass fiber cloth 2 can be formed. From the viewpoint of improving transparency, the glass fiber count is preferably 20 tex or less, preferably 3 to 6 tex, and more preferably 3 to 5 tex. The number of glass fibers may be one type or a combination of two or more types. Note that the tex count of glass fiber corresponds to the number of grams per 1000 m.

The glass fibers constituting the glass fiber cloth 2 are preferably glass yarns in which a plurality of single fibers, which are long glass fibers, are twisted together. The number of single fibers in the glass yarn is preferably about 30 to 400, more preferably about 40 to 120. Further, the diameter of the single fibers in the glass yarn is preferably about 3.0 to 6.0 μm, more preferably about 3.0 to 5.0 μm, from the viewpoint of suppressing color bleeding of the nonflammable sheet 1. The count of the glass yarn is preferably 3 to 30 tex, more preferably 3 to 12 tex, and even more preferably 3 to 5 tex from the viewpoint of suppressing color bleeding. Although the details of the mechanism by which color bleeding of the noncombustible sheet 1 is suppressed by having the diameter of the single fibers and the count of the glass yarn in the glass yarn constituting the glass fiber cloth 2 within the above ranges are not clear, It is considered that by satisfying such conditions, shrinkage at the interface between the glass yarn and the resin composition layer 3 is more effectively suppressed, and as a result, color bleeding of the nonflammable sheet 1 is suppressed.

In the noncombustible sheet 1, from the viewpoint of suppressing color bleeding, the proportion (mass%) of the glass fiber cloth 2 is 20 to 50 mass% of the total amount of the glass fiber cloth 2 and the resin composition layer 3 described below. It is preferably 20 to 40% by weight, more preferably 20 to 30% by weight. The mass (g/m ² ) of one sheet of glass fiber cloth 2 is preferably 10 to 120 (g/m ² ), more preferably 10 to 60 (g/m ² ), and more preferably 10 to 40 (g/m 2 ). m ² ) is more preferred.

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

The refractive index of the glass fiber cloth 2 is measured according to method B of JIS K 7142:2008. Specifically, for the glass fibers constituting the glass fiber cloth 2, methylene iodide (n _D ²³ 1.747), butyl phthalate (n _D ²³ 1.491), and dimethyl carbonate (n _D ²³ 1) were used as the immersion liquid. .366), NAR-2T manufactured by Atago Co., Ltd. as an Abbe refractometer, and a sodium D line with a wavelength of 589 nm as a light source at a temperature of 23°C.The average value of 5 tests was calculated as the refraction Let be the value of the rate. Further, the refractive index of the resin composition 3 is measured according to method B of JIS K 7142:2008. Specifically, the cured or solidified resin composition is powdered, and methylene iodide (n _D ²³ 1.747), butyl phthalate (n _D ²³ 1.491), and dimethyl carbonate (n _D ²³ 1.366), a small measuring microscope STM5-311 (manufactured by Olympus, observation magnification: 400x), a sodium D line with a wavelength of 589 nm as a light source, and a temperature of 23°C. The average value of the five measurements is taken as the refractive index value.

The difference in Abbe number between the glass fiber cloth 2 and the cured resin composition layer 3 is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. The Abbe number of the glass fiber cloth 2 is preferably 30 to 80, more preferably 40 to 70, even more preferably 50 to 65. The Abbe number of the cured resin composition layer and glass fiber cloth is measured as follows.

(Abbe number of cured resin composition layer)
A sheet of a cured resin composition that does not contain glass fiber cloth is prepared under the same conditions as when it contains glass fiber cloth, and has the same thickness. A test piece is prepared with a width of 8 mm and a length of 20 mm, and the surface is well polished, and the JIS K According to the 7142A method, using NAR-2T manufactured by Atago Co., Ltd. as an Abbe refractometer, diiodomethane as a contact liquid, and sodium D line with a wavelength of 589 nm as a light source, the refractive index at a wavelength of 589 nm is measured at a measurement temperature of 23 ° C. . Subsequently, the dispersion value is measured and calculated using natural light as a light source, and the Abbe number is calculated according to the following formula (I).
Abbe number = (refractive index at wavelength 589 nm - 1) / dispersion value (I)

(Abbe number of glass fiber cloth)
A glass sheet with a width of 8 mm, a length of 20 mm, and a thickness of 5 mm was prepared using the glass material constituting the glass fibers, the surface was well polished, and an Abbe refractometer manufactured by Atago Co., Ltd. Using NAR-2T, diiodomethane as a contact liquid, and a sodium D line with a wavelength of 589 nm as a light source, the refractive index at a wavelength of 589 nm is measured at a measurement temperature of 23° C. Subsequently, the dispersion value is measured and calculated using natural light as a light source, and the Abbe number is calculated according to the above formula (I).

The thickness of the glass fiber cloth 2 is, for example, about 10 to 100 μm, preferably about 10 to 55 μm, and more preferably about 10 to 35 μm from the viewpoint of suppressing color bleeding. When the thickness of the glass fiber cloth 2 is 10 to 35 μm, it is particularly preferable that the glass fiber cloth 2 has a glass volume fraction of 38% or more as calculated by the following formula (II). The glass fiber cloth 2 having a thickness of 10 to 35 μm and a glass volume fraction of 38% or more can be obtained, for example, by subjecting glass fibers to an opening treatment.

Glass volume (%) = (A/(B x C)) x 100 (II)
A: Mass of glass fiber cloth (g/m ² )
B: Specific gravity of the glass material constituting the glass fiber cloth (g/m ³ )
C: Thickness of glass fiber cloth (m)

(Resin composition layer 3)
In the nonflammable sheet 1 of the present invention, the resin composition layer 3 is impregnated into the glass fiber cloth 2, and is formed by curing or solidifying a resin composition containing a resin. Specifically, the resin composition layer 3 can be a curable resin composition layer or a thermoplastic resin composition layer. In the case of a cured resin composition layer, a cured product obtained by applying energy such as light or heat to a resin composition containing a curable resin (a photocured resin composition or a thermocured resin composition) (resin composition). When setting it as a thermoplastic resin composition layer, it can be set as the hardened|cured material obtained by drying and solidifying a thermoplastic resin composition.

The curable resin is made to approximate the refractive index of the resin composition layer 3 and the glass fiber cloth 2 described above, from the viewpoint of further improving the transparency of the nonflammable sheet 1 before and after the aforementioned specific heat cycle test. Preferably one that can. Preferred curable resins include those whose cured resin compositions are photocurable, such as vinyl ester resins, urethane acrylate resins, fluorene acrylate resins, unsaturated polyester resins, curable acrylic resins, and epoxy resins. It will be done. Among these, in the case of providing the film layer 4, from the viewpoint of further improving the adhesiveness with the film layer 4, a curable acrylic resin is more preferable, and a cured resin composition containing acrylic syrup is particularly preferable. In the present invention, acrylic syrup refers to a polymerizable liquid mixture in which a (meth)acrylic acid ester polymer such as polymethyl methacrylate (PMMA) is dissolved in an acrylic monomer such as methyl methacrylate. Among the above acrylic syrups, one or more acrylic acid ester polymers selected from the group consisting of polymethyl methacrylate, methyl methacrylate/methyl acrylate copolymer, and methyl methacrylate/n-butyl acrylate copolymer are used as methacrylic syrups. Acrylic syrup dissolved in acid methyl monomer is particularly preferred. In this way, when the cured resin composition layer 3 is made of a cured resin composition containing acrylic syrup, the adhesion with the film layer 4 is further improved. This is preferable because the transparency before and after the cycle test is further improved.

As the thermoplastic resin, from the viewpoint of further improving the transparency of the nonflammable sheet 1 before and after the above-described specific heat cycle test, it is possible to approximate the refractive index of the resin composition layer 3 and the glass fiber cloth 2. Preferably something that can be done. Preferred thermoplastic resins include, for example, polyvinyl chloride resins, saturated polyester resins, polyolefin resins, thermoplastic acrylic resins, polycarbonate resins, polyvinyl alcohol resins, ethylene vinyl acetate copolymers, polyamide resins, polyarylate resins, and the like. For example, when E glass is used as the glass material for the glass fibers constituting the glass fiber cloth 2, polyvinyl chloride resin, saturated polyester resin, thermoplastic acrylic resin, etc. are preferred among these from the viewpoint of refractive index. One type of thermoplastic resin may be used alone, or two or more types having different refractive indexes may be used in combination for the purpose of approximating the refractive index of the glass fiber used. In addition, in the nonflammable sheet 1 of the present invention, when the resin composition layer 3 is a thermoplastic resin composition layer, the portion impregnated into the glass fiber cloth 2 is a thermoplastic resin composition in the form of a sol or dissolved in a solvent. It is preferable to impregnate and solidify (solidify by heating or solidifying by drying). In addition, the portion of the resin composition layer 3 that is not impregnated with the glass fiber cloth 2 is impregnated with a thermoplastic resin composition in sol form or dissolved in a solvent and solidified (solidified by heating or solidified by drying). or may be formed from a film-like thermoplastic resin composition.

In addition, in cases where it is necessary to join noncombustible sheets, such as when using noncombustible sheets as a tension-type smoke-proof hanging wall, which will be described later, and where the ends of the noncombustible sheets are joined by high-frequency welding. If the resin composition layer 3 impregnated with the glass fiber cloth 2 is a cured resin composition layer, the transparency before and after the welding process can be more easily maintained at the end of the noncombustible sheet where the high frequency welding process is performed. So, it's preferable.

The resin composition forming the resin composition layer 3 may further contain additives such as a curing accelerator, a flame retardant, an ultraviolet absorber, a filler, and a photopolymerization initiator. Examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, trichloroethyl phosphate, triallyl phosphate, ammonium polyphosphate, and phosphoric ester. Examples of the ultraviolet absorber include benzotriazole. Examples of fillers include calcium carbonate, silica, and talc. As a photopolymerization initiator, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy- 2-Methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2 -dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]- Examples include 1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Among these, when using a curable acrylic resin as the curable resin constituting the resin composition layer 3, 1-hydroxy-cyclohexyl-phenyl-ketone is preferable from the viewpoint of improving transparency. These additives may be used alone or in combination of two or more.

In the noncombustible sheet 1 of the present invention, when the film layer 4 is not laminated, as in the embodiment illustrated in FIG. The resin composition layer 3 can contain a surfactant. That is, when using a surfactant to achieve the effect of the present invention of reducing dust adhesion when used for a long period of time, for example, as a smoke-proof hanging wall, an interface layer is added to the layer that becomes the surface layer during use. It may contain an activator. In other words, when using a surfactant to achieve the effect of the present invention of reducing dust adhesion when used as a smoke-proof hanging wall for a long period of time, the surface active layer is It is necessary to contain a surfactant.

In the present invention, surfactants include cationic surfactants, anionic surfactants, nonionic (nonionic) surfactants, amphoteric surfactants, fluorinated surfactants, and reactive surfactants. Can be mentioned. For example, anionic surfactants include higher alcohol sulfate ester salts, higher alkyl sulfonic acids and their salts, alkylbenzene sulfonic acids and their salts, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, and vinyl sulfonate salts. Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, Examples of the surfactant include polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide copolymer, and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid ester. Examples of the amphoteric surfactant include lauryl betaine and lauryl dimethylamine oxide. Examples of reactive surfactants include alkylpropenylphenol polyethylene oxide adducts and their sulfuric ester salts, allylalkylphenol polyethylene oxide adducts and their sulfuric ester salts, allyldialkylphenol polyethylene oxide adducts and their sulfuric ester salts, etc. Examples include compounds having a reactive double bond. Among these, polyoxyalkylene alkyl ether sulfates are preferred from the viewpoint of further achieving both transparency and antistatic properties of the nonflammable sheet.

On the other hand, in the nonflammable sheet 1 of the present invention, if the resin composition layer 3 or the film layer 4 described below contains an excessive amount of surfactant, the transparency of the nonflammable sheet 1 may be impaired. This is because surfactants generally have poor compatibility with resins. Therefore, from the viewpoint of obtaining excellent transparency while ensuring the function of reducing dust adhesion when used for a long period of time, for example, as a smoke-proof hanging wall, the resin composition layer 3 or film layer that becomes the surface layer during use. The content of the surfactant in 4 is 0.5 to 2.0% by mass, preferably 0.5 to 1.5% by mass, more preferably 0.5 to 1.0% by mass, and More preferably .5 to 0.75% by mass. In addition, from the same viewpoint as above, the mass (g/m ² ) of the surfactant contained in the layer that becomes the surface layer during use is 0.5 to 2.0 g/m ² in the nonflammable sheet, It is preferably 0.5 to 1.5 g/m ² , more preferably 0.5 to 1.0 g/m ² , even more preferably 0.5 to 0.75 g/m ² .

As will be described later, in order to reduce the adhesion of dust when the noncombustible sheet of the present invention is used as a smoke-proof hanging wall for a long period of time, the surface resistivity is 1×10 ¹¹ before and after a specific heat cycle test. It is necessary that it is less than Ω. The surface resistivity can be achieved by, for example, by including only a surfactant in the resin composition layer 3 when the film layer 4 is not laminated, or by making the film layer 4 contain only a surfactant when the film layer 4 is laminated, as described above. becomes.

On the other hand, while further lowering the upper limit value of surface resistivity (1×10 ¹¹ Ω) before and after a specific heat cycle test, further reducing changes in surface resistivity before and after a specific heat cycle test, and From the viewpoint of obtaining better transparency, for example, rather than incorporating a surfactant in the resin composition layer 3 or film layer 4 that becomes the surface layer when used as a smoke-proof hanging wall, for example, 4, when the film layer 4 is not laminated, the surface side of the resin composition layer 3, or when the film layer 4 is laminated, the antistatic layer containing the metal or metal compound described below is applied to the surface side of the film layer 4. It is preferable to include a layer 6, and more preferably to include an antistatic layer 6 containing fine metal particles or fine metal compound particles. The reason for this is, according to the studies of the present inventors, that firstly, when the above-mentioned film layer 4 is not laminated, the resin composition layer 3, or when the film layer 4 is laminated, the surfactant is added to the film layer 4. In the case of containing only the above-mentioned material, it is possible to achieve both higher performance with a surface resistivity of 1×10 ¹⁰ Ω or less before and after a specific heat cycle test, and higher transparency with a total light transmittance of 90% or more and a haze of 20% or less. It turned out that it could not be done. On the other hand, in the case of an embodiment in which the antistatic layer 6 containing a metal or a metal compound is provided on the surface side of the resin composition layer 3 when the film layer 4 is not laminated, or on the surface side of the film layer 4 when the film layer 4 is laminated. It has been found that it is possible to achieve both of the above performances. Second, in the case of an embodiment in which only the surfactant is contained in the resin composition layer 3 when the above-mentioned film layer 4 is not laminated, or in the film layer 4 when the film layer 4 is laminated, a specific heat cycle test is performed. It has been found that the surfactant bleeds out, making it easy for the surface resistivity to change before and after a specific heat cycle test. On the other hand, in the case of an embodiment in which the antistatic layer 6 containing a metal or a metal compound is provided on the surface side of the resin composition layer 3 when the film layer 4 is not laminated, or on the surface side of the film layer 4 when the film layer 4 is laminated. Since there is no risk of bleed-out, it was found that the change in surface resistivity before and after a specific heat cycle test can be further reduced. In addition, thirdly, in the case of an embodiment in which only the surfactant is contained in the resin composition layer 3 when the above-mentioned film layer 4 is not laminated, or in the film layer 4 when the film layer 4 is laminated, especially the above-mentioned interface It has been found that due to bleed-out of the activator, the surface of the noncombustible sheet 1 may become sticky when used, for example, as a smoke-proof hanging wall. Once the stickiness occurs and dust adheres, it may not be easy to remove. On the other hand, when the antistatic layer 6 containing a metal or a metal compound is provided on the surface side of the resin composition layer 3 when the film layer 4 is not laminated, or on the surface side of the film layer 4 when the film layer 4 is laminated, The occurrence of stickiness can be further reduced.

Therefore, as shown in FIG. 1, for example, when the nonflammable sheet 1 of the present invention is not laminated with the film layer 4, the surface resistivity is lowered before and after the specific heat cycle test, and In order to further reduce the change in surface resistivity and obtain better transparency, it is preferable to provide an antistatic layer 6 containing a metal or a metal compound on the surface side of the resin composition layer 3. In this case, the resin composition layer 3 has a mass (g/m ² ) of the surfactant contained in the resin composition layer 3 with respect to the total mass (g/m 2 ) of the resin composition layer 3 excluding the glass fiber cloth ^2. ) is preferably 1% by mass or less, more preferably 0.3% by mass or less, even more preferably 0.1% by mass or less, particularly preferably 0.01% by mass or less, and even more preferably 0% by mass. Further, the nonflammable sheet 1 of the present invention can be used as a smoke-proof hanging wall for a long period of time when the film layer 4 shown in FIGS. 2 and 3 is provided, for example, and the film layer 4 contains a surfactant. Also when aiming to reduce the adhesion of dust, the mass of the surfactant contained in the resin composition layer (g/m 2 ) relative to the total mass (g/m ² ) of the resin composition layer 3 excluding the glass fiber cloth 2 /m ² ) is preferably 1% by mass or less, more preferably 0.3% by mass or less, even more preferably 0.1% by mass or less, particularly preferably 0.01% by mass or less, and even more preferably 0% by mass. preferable. Furthermore, the nonflammable sheet 1 of the present invention may be provided with the film layer 4 shown in FIG. The ratio of the mass (g/m ² ) of the surfactant contained in the resin composition layer 3 to the total mass (g/m ² ) of the resin composition layer 3 excluding the glass fiber cloth 2 is 1% by mass or less It is preferably 0.3% by mass or less, more preferably 0.1% by mass or less, particularly preferably 0.01% by mass or less, and even more preferably 0% by mass.

In the noncombustible sheet 1 of the present invention, the mass of the resin composition layer 3 is, for example, 20 to 400 g/m ² to achieve both transparency and noncombustibility before and after the specific heat cycle test described above. From this viewpoint, 20 to 250 g/m ² is preferred, and 20 to 100 g/m ² is more preferred. Further, the thickness of the resin composition layer 3 is, for example, 20 to 500 μm, and is preferably 20 to 300 μm from the viewpoint of achieving both transparency and nonflammability before and after the specific heat cycle test mentioned above. 30 to 150 μm is more preferred.

In the nonflammable sheet 1 of the present invention, the weight ratio of the glass fiber cloth 2 and the resin composition layer 3 is determined from the viewpoint of achieving both transparency and nonflammability before and after the specific heat cycle test described above. The ratio of the mass of the glass fiber cloth 2 to the total mass of the fiber cloth 2 and the resin composition layer 3 is preferably 5 to 50% by mass, more preferably 10 to 35% by mass, and particularly preferably 10 to 30% by mass. In addition, when the form layer 4 is provided, the total mass of the noncombustible sheet 1 after peeling off the removable protective film 5 of the glass fiber cloth 2 that is peeled off during use (i.e., the removable protective film that is peeled off during use) The ratio (=mass (g) of glass fiber cloth 2 / mass (g) excluding removable protective film 5 that is peeled off during use x 100 (%)) in the mass excluding film 5 is, for example, 3 -20% by weight, preferably 3-15% by weight, and more preferably 3-10% by weight.

(Film layer 4)
In the noncombustible sheet 1 of the present invention, the film layer 4 is laminated on the resin composition layer 3 impregnated into the glass fiber cloth 2 as necessary, and the noncombustible sheet 1 is subjected to the above-described specific heat cycle test. It plays the role of further improving initial tear strength while further improving transparency.

Although the film layer 4 is not particularly limited, it is preferable that the film layer 4 contains a thermoplastic resin other than polyvinyl chloride resin. Examples of thermoplastic resins other than polyvinyl chloride resins include those that can be formed into a film even with a small amount of plasticizer, and biaxially oriented thermoplastic resins containing amorphous thermoplastic resins other than polyvinyl chloride resins. Films are preferred. Examples of thermoplastic resins other than polyvinyl chloride resins include polyester resins, polycarbonate resins, and polyamide resins, and at least one type of these resins may be included. Furthermore, the film layer 4 may not contain polyvinyl chloride resin. From the viewpoint of further improving the initial tear strength of the noncombustible sheet 1, the film layer 4 may have an Elmendorff tear propagation resistance of 1 N/mm or more in both the longitudinal and lateral directions; 20 N/mm is preferred, and 5 to 15 N/mm is more preferred. Among these, from the viewpoint of further achieving both chemical resistance (including alkaline detergent resistance when used as a smoke-proof hanging wall), improvement of initial tear strength, and transparency, the film layer 4 should contain polyester resin. It is preferable that the Examples of the polyester resin include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). The Elmendorf tear propagation resistance was determined by measuring the tear strength (N) based on JIS K7128-2/1998 using an Elmendorf tearing machine manufactured by Toyo Seiki Seisakusho Co., Ltd., and dividing this measured value by the film thickness. Means tear propagation resistance (N/mm). Furthermore, the tear strength is the average value of the test results of 20 samples in each of the vertical and horizontal directions.

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, even more preferably 1% by mass or less, and 0.5% by mass. The following are particularly preferred. Examples of the plasticizer include those known as plasticizers for vinyl chloride resins, such as di-n-butyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, Phthalic acid plasticizers such as diothyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl isophthalate, 2-ethylhexyl adipate, di-2-decyl adipate, dibutyl sebatate, sebacic acid. Fatty acid ester plasticizers such as 2-ethylhexyl, tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyldiphenyl phosphate, phosphate ester plasticizers such as tricresyl phosphate, tri-2-ethylhexyl trimellitate , trimellitic acid ester plasticizers such as trioctyl trimellitate, polyester plasticizers such as adipic acid polyester plasticizers, phthalic acid polyester plasticizers, and terephthalic acid plasticizers.

The film layer 4 has calcium carbonate, magnesium carbonate, calcium oxide, calcium oxide, Zinc, magnesium oxide, silicon oxide, sodium silicate, aluminum hydroxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, tin oxide, antimony trioxide, carbon black, molybdenum disulfide, acrylic crosslinked polymer, styrene Particles made of inorganic or organic particles such as crosslinked polymers, silicone resins, fluororesins, benzoguanamine resins, phenol resins, and nylon resins can be included. This improves the adhesion between the resin composition layer 3 and the film layer 4, and for example, when the protective film 5 described below is peeled off when the nonflammable sheet 1 is used, the resin composition layer 3 and the film layer 4 are It becomes difficult to peel off. This effect becomes even more remarkable when an antistatic layer 6 containing metal or metal compound fine particles, which will be described later, is laminated on the surface side of the film layer 4. That is, when the antistatic layer 6 containing metal or metal compound fine particles described below is laminated on the surface side of the film layer 4 so as to be in contact with the protective film 5, the protective film 5 may peel off from the antistatic layer 6 to some extent. However, by incorporating the inorganic particles or organic particles into the surface of the film layer 4 facing the resin composition layer 3 as described above, the anchoring effect of the inorganic particles or organic particles works, and the resin Adhesion between the composition layer 3 and the film layer 4 is good, and the protective film 5 is easily peeled off. The film layer 4 can be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, etc. as necessary, and may also be coated with a coating layer that imparts various functions such as easy slippage and easy adhesion, and abrasion resistance. A hard coat layer or the like may be provided to improve properties.

For example, when the antistatic layer 6 containing a metal or a metal compound is provided on the surface side of the film layer 4 as shown in FIG. 4, the surface resistivity is further lowered before and after a specific heat cycle test, and From the viewpoint of further reducing the change in surface resistivity before and after and obtaining better transparency, the mass of the surfactant contained in the film layer 4 relative to the total mass (g/ ^m2 ) of the film layer 4 ( g/m ² ) is preferably 1% by mass or less, more preferably 0.3% by mass or less, further preferably 0.1% by mass or less, particularly preferably 0.01% by mass or less, and 0. Mass % is more preferred.

In the nonflammable sheet of the present invention, it is preferable that the film used as the film layer 4 has excellent transparency and smoothness. Regarding the transparency of the film used as the film layer 4, for example, the total light transmittance (JIS K 7105:1981) is preferably 90% or more, more preferably 91 to 98%. Further, for example, the haze (JIS K 7105:1981) is preferably 1.5% or less, more preferably 0.3 to 1.0%.

(Antistatic layer 6 containing metal or metal compound)
The nonflammable sheet 1 of the present invention needs to have a surface resistivity of 1×10 ¹¹ Ω or less before and after the above-described specific heat cycle test. As mentioned above, the surface resistivity is lower than 1×10 ¹⁰ Ω, which further reduces dust adhesion when used as a smoke-proof hanging wall for a long period of time, and furthermore, the surface resistivity is lower than 1×10 10 Ω. From the viewpoint of further reducing the change in ratio and obtaining better transparency, when the film layer 4 is not laminated, the surface side portion of the resin composition layer 3 (31, 32 in FIG. 1), or , when laminating the film layer 4 shown in FIGS. 2 and 3, an antistatic layer 6 containing metal or metal oxide is applied to the surface side portion of the film layer 4 (41, 42 in FIGS. 2 and 3). It is preferable to include.

In the antistatic layer 6 containing a metal or a metal compound, examples of the metal elements included include Ag, Ni, Cu, Sn, Sb, Al, In, Ti, etc., and the standard electrode potential when used as a single metal Examples include metal elements having a value of less than 0 eV. Examples of the metal compound include metal oxides (antimony pentoxide, tin oxide, zinc oxide, indium oxide, antimony-doped indium oxide, tin-doped indium oxide, silver oxide, etc.). Further, the antistatic layer 6 may not contain fine particles made of barium sulfate, calcium carbonate, aluminum oxide, magnesium silicate, glass, or the like. Examples of the form in which the metal or metal compound is contained include a metal or metal compound thin film formed by vapor deposition, sputtering, plating, etc., or a layer in which metal or metal compound fine particles are dispersed in a fixed resin. Examples of the shape of the metal or metal compound fine particles include granules, flakes, and needles (fibers). The average particle diameter of the metal or metal compound fine particles is, for example, the average particle diameter determined using the BET method (calculated as the average particle diameter by a conventional method from the specific surface area (m ² /g) measured by the nitrogen gas adsorption method). By setting the specific surface area (diameter) to 100 nm or less, which is the wavelength of visible light or less, preferably 1 to 100 nm, it becomes easier to maintain the transparency of the nonflammable sheet 1.

When the antistatic layer 6 containing metal or metal compound contains fine particles of metal or metal compound, it preferably contains a fixing resin that fixes the fine particles of metal or metal compound to the base material. That is, it is preferable that the antistatic layer 6 is a layer containing a fixed resin and metal or metal compound fine particles dispersed in the fixed resin. Examples of the fixing resin include polyurethane resin, polyester resin, acrylic resin, polyether resin, cellulose resin, polyvinyl alcohol resin, epoxy resin, polyvinylpyrrolidone, polystyrene resin, polyethylene glycol, and pentaerythritol. Among them, polyurethane resins, polyester resins, and acrylic resins are particularly preferred. The acrylic resin may be, for example, a modified acrylic resin (urethane modified, polyester modified, polycarbonate modified, fluorine modified, etc.). The mass of the antistatic layer 6 is, for example, 0.1 to 10 g/m ² per layer, from the viewpoint of achieving both surface resistivity and transparency before and after the specific heat cycle test mentioned above. Preferably, the amount is 0.1 to 5 g/m ² , more preferably 0.1 to 3 g/m ² , and particularly preferably 0.1 to 1 g/m ² . Further, the metal or metal compound can be present on the surface of the resin composition layer 3 or the film layer 4. The antistatic layer 6 containing a metal or a metal compound is provided within a range of 10% of the thickness of the resin composition layer 3 or film layer 4 from the center in the thickness direction of the layer (for example, the resin composition layer 3 or When the thickness of the film layer 4 is 100 μm, the content of the metal or metal compound is within the range of 40 to 60 μm from the one surface, centered at a distance of 50 μm from one surface in the thickness direction. For example, 1% by mass or less, 0.1% by mass or less, 0.01% by mass or less, based on the mass of the layer included in the range. Further, the thickness of the antistatic layer 6 is, for example, 0.01 to 3 μm per layer, preferably 0.05 to 1 μm. The mass ratio of the fixed resin to the metal or metal compound fine particles (mass of the fixed resin (g/m ² ):mass of the metal or metal compound fine particles (g/m ² )) in the antistatic layer 6 is as described above. From the viewpoint of achieving better compatibility between surface resistivity and transparency before and after the specific heat cycle test, 10:1 to 1:1 is preferable, 8:1 to 2:1 is more preferable, and 4:1 to 2:1 is preferable. Particularly preferred. Furthermore, the surface smoothness when the antistatic layer 6 containing a metal or a metal compound is provided includes, for example, a surface roughness Ra of 1 to 200 nm. Further, the ratio of the mass (g/m ² ) of the metal and metal compound fine particles to the total mass (g/m ² ) of the antistatic layer 6 is 50 to 10 mass%, and 30 to 20 mass%. Preferably.

(Peelable protective film 5 that is peeled off during use)
The nonflammable sheet 1 of the present invention may be provided on the surface side of the resin composition layer 3 or film layer 4 (if the antistatic layer 6 is provided on the surface side of the resin composition layer 3 or film layer 4, further A removable protective film 5 that is peeled off during use can be further laminated on the surface side of the antistatic layer 6. Thereby, for example, when the noncombustible sheet 1 of the present invention is used as a smoke-proof hanging wall, it becomes easier to prevent damage to the noncombustible sheet 1 from occurring during construction and deterioration of transparency and aesthetic appearance.

As the removable protective film 5 that is peeled off during use, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyester film, etc. can be used. Among them, if a light-transmissive protective film is used as the removable protective film 5 that is peeled off during use, for example, the resin composition forming the resin composition layer 3 described above may be a photocurable cured resin composition. In this case, it is preferable in that it becomes easier to prevent damage to the resin composition layer 3 and film layer 4 and deterioration of transparency and aesthetic appearance in the step of curing the cured resin composition. The above-mentioned light transmittance is not particularly limited as long as it transmits light that cures the photocurable resin, but for example, it transmits light with a wavelength of 100 to 400 nm, or transmits light with a wavelength of 250 to 400 nm. can be mentioned. The light transmittance of the protective film 5 is preferably 40% or more, with an average transmittance of 40% or more between measurement wavelengths of 250 to 400 nm, measured using a UV transmittance meter (product name: UV3150, manufactured by Shimadzu Corporation), for example. % or more is more preferable, and 60% or more is particularly preferable.

Note that the removable protective film 5 that is peeled off during use is not particularly limited in terms of transparency and smoothness, since it is peeled off during use, for example, as a smoke-proof hanging wall. For example, from the viewpoint of cost, the total light transmittance is about 80 to 95% (JIS K 7105:1981), and the haze is about 2 to 10% (JIS K 7105:1981).

(Physical properties and performance of nonflammable sheet 1)
It is necessary that the surface resistivity of the noncombustible sheet be 1×10 ¹¹ Ω or less before and after the following heat cycle test.
<Heat cycle test conditions>
The non-combustible sheet was cut into a sample with a size of 100 mm x 100 mm, and the sample was placed in a constant temperature and humidity chamber (product name: PSL, manufactured by ESPEC Co., Ltd., which was initially set to a temperature of 23°C and a relative humidity of 50% RH). -2KPH), and carry out 10 cycles in total, with the following (1) to (5) being one cycle.
(1) Transition from a temperature of 23° C. and relative humidity of 50% RH to a temperature of 60° C. and relative humidity of 50% RH with a transition time of 14 minutes.
(2) Maintain at the above temperature of 60° C. and relative humidity of 50% RH for 8 hours.
(3) Transition from the above temperature of 60° C. and relative humidity of 50% RH to temperature of 20° C. and relative humidity of 50% RH with a transition time of 45 minutes.
(4) Maintain at the above temperature of 20° C. and relative humidity of 50% RH for 8 hours.
(5) Transition from the above temperature of 20° C. and relative humidity of 50% RH to temperature of 23° C. and relative humidity of 50% RH with a transition time of 1 minute.

As a result of the studies conducted by the present inventors, the surface resistivity of nonflammable sheets such as those disclosed in Patent Documents 1 to 3 is approximately 1×10 ¹⁵ before and after the above-mentioned specific heat cycle test. It was found that the adhesion of dust present in the air could not be sufficiently prevented. Therefore, the inventors of the present invention conducted extensive studies and found that the adhesion of dust could be reduced by setting the surface resistivity to 1×10 ¹¹ Ω or less before and after the specific heat cycle test. More preferably, the surface resistivity is 1.0×10 ¹⁰ Ω or less and 5.0×10 ⁹ Ω or less before and after a specific heat cycle test. The lower limit is not particularly limited, but may be, for example, 1 x 10 ⁵ Ω or more, and from the viewpoint of further improving transparency, 1.0 x 10 ⁷ Ω or more, more preferably 1.0 x 10 ⁸ Ω or more. , more preferably 1.0×10 ⁹ Ω or more.

The above-mentioned surface resistivity is measured in accordance with JIS K 6911 1995 5.13.2 Resistivity using a high resistance meter 4339B manufactured by Agilent Technologies Co., Ltd. as a measuring device and applying an applied voltage of 100 V for 1 minute.

In addition, from the perspective of ensuring that the change in surface resistivity before and after a specific heat cycle test is further reduced, the difference in surface resistivity before and after a specific heat cycle test (= surface resistivity after a specific heat cycle test) (Ω) - surface resistivity (Ω) before a specific heat cycle test is preferably 1.0×10 ¹⁰ Ω or less, more preferably 5.0×10 ⁹ Ω or less.

The thickness of the noncombustible sheet 1 of the present invention is, for example, the thickness of the noncombustible sheet 1 after removing the removable protective film 5 that is peeled off during use (i.e., the removable protective film 5 that is peeled off during use). The thickness (excluding 5) is 100 to 500 μm, preferably 150 to 300 μm. In addition, as the mass of the noncombustible sheet 1 of the present invention, for example, the mass of the noncombustible sheet 1 after peeling off the removable protective film 5 that is peeled off during use (i.e., the removable protective film 5 that is peeled off during use) (excluding mass) is 100 to 500 g/m ² , preferably 150 to 300 g/m ² . Furthermore, in the nonflammable sheet 1 of the present invention, when the total mass of the resin composition layer and the film layer is 150 to 300 g/m ² , more preferably 150 to 250 g/m ² , nonflammability and tear strength are achieved. This is preferable because it makes it easier to achieve both.

In the nonflammable sheet 1 of the present invention, from the viewpoint of ensuring transparency before and after the specific heat cycle test described above, the total light transmittance before and after the specific heat cycle test described above is preferably 85% or more, More preferably 90% or more. Further, the haze of the nonflammable sheet 1 of the present invention before and after the above-mentioned specific heat cycle test is preferably 20% or less, more preferably 10% or less, still more preferably 5% or less, and 3% or less. Particularly preferred are the following, and more preferably 1% or less. The total light transmittance and haze of the noncombustible sheet 1 are values obtained by measurement according to JIS K7375 2008 "Plastics - How to determine total light transmittance and total light reflectance".

In order to ensure high transparency before and after the specific heat cycle test mentioned above, for example, when a surfactant is included in the surface layer when used as a smoke-proof hanging wall, it is necessary to In addition to making the content in the layer appropriate, or providing the antistatic layer 6 containing a metal or a metal compound, adjusting the content of the metal or metal compound in the antistatic layer 6, Examples include adjusting the thickness of the glass fiber cloth, the refractive index difference between the glass fiber cloth 2 and the resin composition layer 3, the average filament diameter of the glass fibers, the number of filaments, and the weaving density of the glass cloth.

In the noncombustible sheet 1 of the present invention, when the film layer 4 is provided, the initial tear strength can be made higher. From the viewpoint of ensuring higher initial tear strength, the initial tear strength is preferably 30 to 100 (N), more preferably 40 to 100 (N), and particularly preferably 50 to 100 (N). In the present invention, the initial tear strength is measured and calculated as follows.
(Test method)
According to JIS R 3420:2013 7.16 C method (trapezoid method), 75 mm x 150 mm test pieces were taken from the noncombustible sheet in the vertical and horizontal directions, and two trapezoidal parts including a right angle (Fig. Attach anti-slip tape (trade name: 600S, manufactured by Sekisui Chemical Co., Ltd.) to both the front and back sides of each (corresponding to the trapezoid A part shown in 5), and place it in a constant speed loading type tensile testing machine (Sekisui Chemical Co., Ltd., product name 600S) without making any cuts. The maximum load was measured using Orientec's product name RTC-1310A), and the average value of the maximum load in the vertical direction and the maximum load in the horizontal direction (= (maximum vertical load (N) + maximum horizontal load (N))/2) is the initial tear strength (N).

Since the noncombustible sheet 1 of the present invention includes the glass fiber cloth 2, it can have a property of being difficult to burn (noncombustibility). The noncombustibility of the noncombustible sheet 1 of the present invention is specified in 4.10.2 in the "Fireproof Performance Testing and Evaluation Business Methods" (revised version on March 1, 2014) of the Building Materials Testing Center, a general incorporated foundation. In a heat generation test in which radiant heat of 50kW/ ^m2 is irradiated onto the surface of the sheet from a radiant electric heater, the maximum heat generation rate after the start of heating is 200kW/m for 10 seconds or more, measured according to the heat generation test and evaluation method. ² and the total calorific value is preferably 8 MJ/m ² or less. In order to further improve the nonflammability, for example, a flame retardant may be added or the amount of organic matter may be reduced in the resin composition layer 3 and the film layer 4.

The method for manufacturing the noncombustible sheet 1 of the present invention is not particularly limited, and examples include the following manufacturing method. First, the above glass fiber cloth 2 and an uncured cured resin composition constituting the resin composition layer 3 are prepared. The cured resin composition is applied to a film (for example, a polyester film, etc.) serving as the film layer 4, a glass fiber cloth 2 is placed on top of the cured resin composition, and the glass fibers 2 are impregnated with the cured resin composition. , another film to be used as the film layer 4 is placed on the glass fiber cloth 2, and pressure is applied from the surface of each of the two film layers 4 to further impregnate the glass fiber cloth 2 with the cured resin composition. A non-flammable sheet 1 (film layer 4/ A noncombustible sheet 1) is obtained in which a resin composition layer 3/a film layer 4, which is impregnated into a glass fiber cloth 2, are laminated in this order. In addition, when the nonflammable sheet 1 does not contain the film layer 4, it is sufficient to replace the film layer 4 with a protective film 5 that is peeled off during use, and to peel off the protective film 5.

Moreover, as a manufacturing method of the noncombustible sheet 1 of this invention, the following manufacturing method is also mentioned. First, the above glass fiber cloth 2 and a thermoplastic resin composition constituting the resin composition layer 3 are prepared. Next, two films to be used as the film layer 4 are prepared, a thermoplastic resin composition is applied to the films, a glass fiber cloth 2 is placed on the thermoplastic resin composition, and the thermoplastic resin is applied to the glass fibers 2. After impregnating the composition, another film to be used as the film layer 4 is placed on the glass fiber cloth 2, pressure is applied from the surface of each of the two film layers 4, and the cured resin composition is further applied to the glass fiber cloth 2. The glass fiber cloth 2 is impregnated with a thermoplastic resin composition layer 3 by impregnation, and the thermoplastic resin composition is dried and solidified, and a film layer 4 is laminated on the thermoplastic resin composition layer 3. A nonflammable sheet 1 (a nonflammable sheet 1 in which film layer 4/resin composition layer 3 impregnated in glass fiber cloth 2/film layer 4 are laminated in this order) is obtained.

The antistatic layer 6 can be provided on the surface side portion of the nonflammable sheet 1 obtained above. Moreover, when the film layer 4 is included, a film provided with an antistatic layer 6 in advance can also be used. As a means for providing the antistatic layer 6, any known means may be used.

Further, the method for producing a noncombustible sheet of the present invention includes a glass fiber cloth, a photocurable resin composition layer impregnated in the glass fiber cloth, and a photocurable resin composition layer laminated on the photocurable resin composition layer. A method for producing a non-combustible sheet comprising a film layer, comprising: step A of preparing at least two light-transparent thermoplastic resin films laminated with a light-transparent protective film; and a step in which a glass fiber cloth is immersed. The uncured photocurable resin composition was sandwiched between the two thermoplastic resin films obtained in step A, with the light-transmissive protective film facing outward. The method may include a step B of irradiating the photocurable resin composition with light and curing the uncured photocurable resin composition.

(Applications of the nonflammable sheet of the present invention)
Applications of the noncombustible sheet of the present invention include use as a smoke-proof hanging wall that is hung from the ceiling of a building. Examples of smoke-proof hanging walls include known ones that use a noncombustible sheet of glass cloth and resin. a flexible noncombustible sheet that is suspended and a pair of end mullions arranged on both sides of the noncombustible sheet, the noncombustible sheet and the end mullions Examples include smoke-proof hanging walls that are joined together so that they can be separated. In particular, the noncombustible sheet of the present invention can be used for tension-type smoke-proof hanging walls because high-frequency welding is possible when the outermost layer is a layer made of thermoplastic resin when used in smoke-proof hanging walls. It can be suitably used for various purposes. In the present invention, a tension-type smoke-proof hanging wall is a hanging wall in which a noncombustible sheet is stretched between two pairs of mullions, and for example, a noncombustible sheet when installed hanging from the ceiling. An example of this is a smoke-proof hanging wall that does not have an opening on the lower side. In addition, if the transparency is increased, it can be used as a substitute for glass, so it can be used in other applications where glass is used, such as partitions, room partitions, smoke-proof sheets, and smoke-proof curtains (such as those used in factories). ), etc. Furthermore, the nonflammable sheet 1 of the present invention has even more flexibility when the mass of the curable resin composition layer 4 is, for example, 20 to 100 g/m ² , more preferably 20 to 50 g/m ² . This makes it easier to make roll products. The length of the roll product in the longitudinal direction is, for example, 5 to 300 m.

The present invention will be explained in detail below by showing Examples and Comparative Examples. However, the present invention is not limited to the examples.

The resin composition constituting the resin composition layer 3 to be impregnated into the glass fiber cloth 2 has the composition shown in Table 1. ” (refractive index 1.550) and “Acrysilap Monomer (manufactured by Nippon U-Pica Co., Ltd.), bifunctional (meth)acrylate, photopolymerization initiator (Omnirad 184, manufactured by IGM), or surfactant as an antistatic agent (“Electro Stripper ME-2”, manufactured by Kao Corporation, solid 50% by mass) was used. As the bifunctional (meth)acrylate that is the curing agent, NPGDA (neopentyl glycol diacrylate, molecular weight 212, manufactured by Nippon U-Pica Co., Ltd.) shown in Table 1 was used. The amount of the photopolymerization initiator was 3 parts by mass based on 100 parts by mass of acrylic syrup or 100 parts by mass of the vinyl ester resin, styrene monomer, and bifunctional (meth)acrylate. As the film layer 4, a commercially available 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%), commercially available vinyl chloride resin film (manufactured by Okamoto Co., Ltd., general purpose PVC #320, thickness 100%).
μm, mass 120 g/m ² ). Peelable protective film 5 that is peeled off during use
Examples include a polypropylene film (thickness: 40 μm, mass: 36 g/m ² ) coated with an acrylic ester adhesive that releasably adheres to the film layer 4 on one side, and a PET film (thickness: 50 μm, total light transmittance 93%, haze 4%).

<Example 1>
(Manufacture of glass fiber cloth 2)
Weaving was carried out using an air jet loom using Unitika Glass Fiber Co., Ltd.'s product name "ECC1200 1/0 1.0Z" (average filament diameter 4.5 μm, average number of filaments 100, number of twists 1.0Z) as the warp and weft threads. A plain weave glass fiber fabric having a warp density of 90 threads/25 mm and a weft thread density of 90 threads/25 mm was obtained. Then, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400° C. for 30 hours. After that, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g/L and squeezed with a padder roll. After that, it was dried and cured at 120°C for 1 minute. Then, the glass fiber fabric was widened once by water jet processing at a pressure of 1.5 MPa while setting the tension of the glass fiber fabric to 100 N/m in the warp direction to obtain a glass fiber fabric to be used as glass fiber fabric 2. The obtained glass fiber fabric 2 had a warp density of 90/25 mm, a weft density of 90/25 mm, a thickness of 27 μm, a mass of 30 g/m ² , and a refractive index of 1.561.

(Lamination of antistatic layer 6 on film layer 4)
An antistatic layer 6 was laminated on one surface of Cosmoshine (registered trademark) A4300 serving as the film layer 4. The antistatic layer 6 contains tin oxide fine particles (average particle diameter 20 nm) in a polyester resin as a binding resin, and the mass ratio of the binding resin to the tin oxide fine particles (fixing resin: tin oxide fine particles) is 75:25. The antistatic agent mixed and dispersed in the above manner was coated on one surface of Cosmoshine (registered trademark) A4300, which was to be the film layer 4, and dried. The provided antistatic layer 6 had a mass of 0.5 g/m ² and a thickness of 0.4 μm.

(Lamination of the removable protective film 5 that is peeled off during use on the film layer 4 (antistatic layer 6 side))
On the antistatic layer 6 of Cosmoshine (registered trademark) A4300, which is the film layer 4 and has the antistatic layer 6 provided on one side, there is a removable protective film 5 that is peeled off during use. A polypropylene film with an acrylic ester adhesive applied on one side is laminated so that the adhesive faces the antistatic layer 6 side, and is dried to form a peelable film that can be peeled off during use. A laminate A having a laminate structure of Cosmoshine (registered trademark) A4300 having a protective film 5/acrylic acid ester adhesive/antistatic layer 6/film layer 4 was obtained. Two pieces of the laminate A were prepared.

(Manufacture of nonflammable sheets)
A resin composition layer 3 is applied to the Cosmoshine (registered trademark) A4300 side of the laminate A obtained above (that is, the side opposite to the removable protective film 5 that is peeled off during use) as shown in Table 1. The cured resin composition described was applied. Next, the obtained glass fiber cloth 2 is placed on the cured resin composition, which is referred to as resin composition 3, and left to stand for 1 minute to impregnate the gap between the glass fiber cloth 2 with the cured resin composition. I let it happen. Next, the other side of the obtained laminate A is placed on the Cosmoshine (registered trademark) A4300 side of the laminate A (that is, the side opposite to the removable protective film 5 that is peeled off during use). was placed so that the cured resin composition layer 3 was on the cured resin composition 3 side, and pressure was applied from above the laminate A using a roller so that the mass of the cured resin composition layer 3 was 90 g/m ² . Thereafter, while the removable protective film 5 that is peeled off during use is still laminated, the cured resin composition forming the resin composition layer 3 is irradiated with light using a black light fluorescent lamp (product name: FL15BLB manufactured by Toshiba Corporation). Irradiation conditions: cumulative light amount of 200 mJ/cm ² ) to cure the cured resin composition to form a cured resin composition layer 3 with a laminated structure illustrated in FIG. 4 (a removable protective film 5 that is peeled off during use). / Acrylic ester adhesive that can be peeled off together with the protective film 5 / Antistatic layer 6 / Film layer 4 (Cosmoshine (registered trademark) A4300) / Resin composition layer 3 impregnated into glass fiber cloth 2 / Film layer 4 (Cosmoshine (registered trademark) A4300) / Antistatic layer 6 / Acrylic acid ester adhesive that can be peeled off together with the protective film 5 / Nonflammable sheet that is a peelable protective film 5) that is peeled off during use I got it. In the obtained noncombustible sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with a cured resin composition layer 3 (cured product of the resin composition), and on both sides of the glass fiber cloth layer A cured resin composition layer 3 was formed.

<Example 2>
(Manufacture of glass fiber cloth 2)
The product name "ECBC3000 1/0 0.5Z" manufactured by Unitika Glass Fiber Co., Ltd. (average filament diameter 4 μm, average number of filaments 50, number of twists 0.5Z) was used as the warp and weft, and the warp was woven using an air jet loom. A plain weave glass fiber fabric having a density of 95 threads/25 mm and a weft density of 95 threads/25 mm was obtained. Then, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400° C. for 30 hours. After that, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g/L and squeezed with a padder roll. After that, it was dried and cured at 120°C for 1 minute. Then, the glass fiber fabric was widened twice by water jet processing at a pressure of 1.5 MPa while setting the tension of the glass fiber fabric to 100 N/m in the warp direction to obtain a glass fiber fabric to be used as glass fiber fabric 2. The obtained glass fiber fabric 2 had a warp density of 95/25 mm, a weft density of 95/25 mm, a thickness of 13 μm, a mass of 12 g/m ² , and a refractive index of 1.561.

(Lamination of antistatic layer 6 on film layer 4)
An antistatic layer 6 was laminated on one surface of Cosmoshine (registered trademark) A4300 serving as the film layer 4. The antistatic layer 6 contains tin oxide fine particles (average particle diameter 20 nm) in a polyester resin as a binding resin, and the mass ratio of the binding resin to the tin oxide fine particles (fixing resin: tin oxide fine particles) is 75:25. The antistatic agent mixed and dispersed in the above manner was coated on one surface of Cosmoshine (registered trademark) A4300, which was to be the film layer 4, and dried. The provided antistatic layer 6 had a mass of 0.5 g/m ² and a thickness of 0.4 μm.

(Lamination of the removable protective film 5 that is peeled off during use on the film layer 4 (antistatic layer 6 side))
On the antistatic layer 6 of Cosmoshine (registered trademark) A4300, which is the film layer 4 and has the antistatic layer 6 provided on one side, there is a removable protective film 5 that is peeled off during use. A polypropylene film with an acrylic ester adhesive applied on one side is laminated so that the adhesive faces the antistatic layer 6 side, and is dried to form a peelable film that can be peeled off during use. A laminate A having a laminate structure of Cosmoshine (registered trademark) A4300 having a protective film 5/acrylic acid ester adhesive/antistatic layer 6/film layer 4 was obtained. Two pieces of the laminate A were prepared.

(Manufacture of nonflammable sheets)
A resin composition layer 3 is applied to the Cosmoshine (registered trademark) A4300 side of the laminate A obtained above (that is, the side opposite to the removable protective film 5 that is peeled off during use) as shown in Table 1. The cured resin composition described was applied. Next, the obtained glass fiber cloth 2 is placed on the cured resin composition, which is referred to as resin composition 3, and left to stand for 1 minute to impregnate the gap between the glass fiber cloth 2 with the cured resin composition. I let it happen. Next, the other side of the obtained laminate A is placed on the Cosmoshine (registered trademark) A4300 side of the laminate A (that is, the side opposite to the removable protective film 5 that is peeled off during use). was placed so that the cured resin composition layer 3 was on the cured resin composition 3 side, and pressure was applied from above the laminate A using a roller so that the mass of the cured resin composition layer 3 was 90 g/m ² . Thereafter, while the removable protective film 5 that is peeled off during use is still laminated, the cured resin composition forming the resin composition layer 3 is irradiated with light using a black light fluorescent lamp (product name: FL15BLB manufactured by Toshiba Corporation). Irradiation conditions: cumulative light amount of 200 mJ/cm ² ) to cure the cured resin composition to form a cured resin composition layer 3 with a laminated structure illustrated in FIG. 4 (a removable protective film 5 that is peeled off during use). / Acrylic ester adhesive that can be peeled off together with the protective film 5 / Antistatic layer 6 / Film layer 4 (Cosmoshine (registered trademark) A4300) / Resin composition layer 3 impregnated into glass fiber cloth 2 / Film layer 4 (Cosmoshine (registered trademark) A4300) / Antistatic layer 6 / Acrylic acid ester adhesive that can be peeled off together with the protective film 5 / Nonflammable sheet that is a peelable protective film 5) that is peeled off during use I got it. In the obtained noncombustible sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with a cured resin composition layer 3 (cured product of the resin composition), and on both sides of the glass fiber cloth layer A cured resin composition layer 3 was formed.

<Example 3>
(Manufacture of glass fiber cloth 2)
The product name "ECBC3000 1/0 0.5Z" manufactured by Unitika Glass Fiber Co., Ltd. (average filament diameter 4 μm, average number of filaments 50, number of twists 0.5Z) was used as the warp and weft, and the warp was woven using an air jet loom. A plain weave glass fiber fabric having a density of 95 threads/25 mm and a weft density of 95 threads/25 mm was obtained. Then, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400° C. for 30 hours. After that, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g/L and squeezed with a padder roll. After that, it was dried and cured at 120°C for 1 minute. Then, the glass fiber fabric was widened twice by water jet processing at a pressure of 1.5 MPa while setting the tension of the glass fiber fabric to 100 N/m in the warp direction to obtain a glass fiber fabric to be used as glass fiber fabric 2. The obtained glass fiber fabric 2 had a warp density of 95/25 mm, a weft density of 95/25 mm, a thickness of 13 μm, a mass of 12 g/m ² , and a refractive index of 1.561.

(Lamination of antistatic layer 6 on film layer 4)
An antistatic layer 6 was laminated on one surface of Cosmoshine (registered trademark) A4300 serving as the film layer 4. The antistatic layer 6 contains tin oxide fine particles (average particle diameter 20 nm) in a polyester resin as a binding resin, and the mass ratio of the binding resin to the tin oxide fine particles (fixing resin: tin oxide fine particles) is 75:25. The antistatic agent mixed and dispersed in the above manner was coated on one surface of Cosmoshine (registered trademark) A4300, which was to be the film layer 4, and dried. The provided antistatic layer 6 had a mass of 0.5 g/m ² and a thickness of 0.4 μm.

(Lamination of the removable protective film 5 that is peeled off during use on the film layer 4 (antistatic layer 6 side))
On the antistatic layer 6 of Cosmoshine (registered trademark) A4300, which is the film layer 4 and has the antistatic layer 6 provided on one side, there is a removable protective film 5 that is peeled off during use. A polypropylene film with an acrylic ester adhesive applied on one side is laminated so that the adhesive faces the antistatic layer 6 side, and is dried to form a peelable film that can be peeled off during use. A laminate A having a laminate structure of Cosmoshine (registered trademark) A4300 having a protective film 5/acrylic acid ester adhesive/antistatic layer 6/film layer 4 was obtained. Two pieces of the laminate A were prepared.

(Manufacture of nonflammable sheets)
A resin composition layer 3 is applied to the Cosmoshine (registered trademark) A4300 side of the laminate A obtained above (that is, the side opposite to the removable protective film 5 that is peeled off during use) as shown in Table 1. The cured resin composition described was applied. Next, the obtained glass fiber cloth 2 is placed on the cured resin composition, which is referred to as resin composition 3, and left to stand for 1 minute to impregnate the gap between the glass fiber cloth 2 with the cured resin composition. I let it happen. Next, the other side of the obtained laminate A is placed on the Cosmoshine (registered trademark) A4300 side of the laminate A (that is, the side opposite to the removable protective film 5 that is peeled off during use). was placed so that the cured resin composition layer 3 was on the cured resin composition 3 side, and pressure was applied from above the laminate A using a roller so that the mass of the cured resin composition layer 3 was 40 g/m ² . Thereafter, while the removable protective film 5 that is peeled off during use is still laminated, the cured resin composition forming the resin composition layer 3 is irradiated with light using a black light fluorescent lamp (product name: FL15BLB manufactured by Toshiba Corporation). Irradiation conditions: cumulative light amount of 200 mJ/cm ² ) to cure the cured resin composition to form a cured resin composition layer 3 with a laminated structure illustrated in FIG. 4 (a removable protective film 5 that is peeled off during use). / Acrylic ester adhesive that can be peeled off together with the protective film 5 / Antistatic layer 6 / Film layer 4 (Cosmoshine (registered trademark) A4300) / Resin composition layer 3 impregnated into glass fiber cloth 2 / Film layer 4 (Cosmoshine (registered trademark) A4300) / Antistatic layer 6 / Acrylic acid ester adhesive that can be peeled off together with the protective film 5 / Nonflammable sheet that is a peelable protective film 5) that is peeled off during use I got it. In the obtained noncombustible sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with a cured resin composition layer 3 (cured product of the resin composition), and on both sides of the glass fiber cloth layer A cured resin composition layer 3 was formed.

<Example 4>
(Manufacture of glass fiber cloth 2)
Weaving was carried out using an air jet loom using Unitika Glass Fiber Co., Ltd.'s product name "ECC1200 1/0 1.0Z" (average filament diameter 4.5 μm, average number of filaments 100, number of twists 1.0Z) as the warp and weft threads. A plain weave glass fiber fabric having a warp density of 90 threads/25 mm and a weft thread density of 90 threads/25 mm was obtained. Then, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400° C. for 30 hours. After that, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g/L and squeezed with a padder roll. After that, it was dried and cured at 120°C for 1 minute. Then, the glass fiber fabric was widened once by water jet processing at a pressure of 1.5 MPa while setting the tension of the glass fiber fabric to 100 N/m in the warp direction to obtain a glass fiber fabric to be used as glass fiber fabric 2. The obtained glass fiber fabric 2 had a warp density of 90/25 mm, a weft density of 90/25 mm, a thickness of 27 μm, a mass of 30 g/m ² , and a refractive index of 1.561.

(Manufacture of nonflammable sheets)
A cured resin composition as resin composition layer 3 shown in Table 1 was applied onto a 50 μm thick PET film as a removable protective film 5 that is peeled off during use. Next, the obtained glass fiber cloth 2 was placed on top of the resin composition and allowed to stand for 1 minute to impregnate the gap between the glass fiber cloth 2 with the cured resin composition. Next, another PET film of the same product as the PET film serving as the removable protective film 5 to be peeled off during use is placed on top, and the weight of the cured resin composition layer 3 is 90 g using a roller from above the PET film. / ^m2 . Thereafter, a black light fluorescent lamp (product name: FL15BLB manufactured by Toshiba Corporation) was used on the resin composition layer 3 while the PET film serving as the removable protective film 5, which is peeled off during use, was laminated. The resin composition is cured by light irradiation (light irradiation conditions: integrated light amount 200 mJ/cm ² ) to form a cured resin composition layer 3, and a removable protective film 5/glass fiber cloth 2 is peeled off at the time of use. A nonflammable sheet was obtained which had a laminated structure of a resin composition layer 3 impregnated with a removable protective film 5 that was peeled off during use. In the obtained noncombustible sheet, the gaps between the glass fibers of the glass fiber cloth 2 are impregnated with a cured resin composition layer 3 (cured product of the resin composition), and a cured resin composition layer 3 (cured product of the resin composition) is impregnated on both sides of the glass fiber cloth layer. A cured resin composition layer 3 was formed.

<Example 5>
(Manufacture of glass fiber cloth 2)
Weaving was carried out using an air jet loom using Unitika Glass Fiber Co., Ltd.'s product name "ECC1200 1/0 1.0Z" (average filament diameter 4.5 μm, average number of filaments 100, number of twists 1.0Z) as the warp and weft threads. A plain weave glass fiber fabric having a warp density of 90 threads/25 mm and a weft thread density of 90 threads/25 mm was obtained. Then, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400° C. for 30 hours. After that, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g/L and squeezed with a padder roll. After that, it was dried and cured at 120°C for 1 minute. Then, the glass fiber fabric was widened once by water jet processing at a pressure of 1.5 MPa while setting the tension of the glass fiber fabric to 100 N/m in the warp direction to obtain a glass fiber fabric to be used as glass fiber fabric 2. The obtained glass fiber fabric 2 had a warp density of 90/25 mm, a weft density of 90/25 mm, a thickness of 27 μm, a mass of 30 g/m ² , and a refractive index of 1.561.

(Manufacture of nonflammable sheets)
A cured resin composition as resin composition layer 3 shown in Table 1 was applied onto a 50 μm thick PET film as a removable protective film 5 that is peeled off during use. Next, the obtained glass fiber cloth 2 was placed on top of the resin composition and allowed to stand for 1 minute to impregnate the gap between the glass fiber cloth 2 with the cured resin composition. Next, another PET film of the same product as the PET film serving as the removable protective film 5 to be peeled off during use is placed on top, and the weight of the cured resin composition layer 3 is 90 g using a roller from above the PET film. / ^m2 . Thereafter, a black light fluorescent lamp (manufactured by Toshiba Corporation, product name FL15BLB) was used to coat the resin composition layer 3 while the PET film was laminated as the removable protective film 5 that was peeled off during use. The resin composition is cured by light irradiation (light irradiation conditions: cumulative light amount 200 mJ/cm ² ) to form a cured resin composition layer 3, and a removable protective film 5/glass fiber cloth 2 is peeled off at the time of use. A nonflammable sheet was obtained which had a laminated structure of a resin composition layer 3 impregnated with a removable protective film 5 that was peeled off during use. In the obtained noncombustible sheet, the gaps between the glass fibers of the glass fiber cloth 2 are impregnated with a cured resin composition layer 3 (cured product of the resin composition), and a cured resin composition layer 3 (cured product of the resin composition) is impregnated on both sides of the glass fiber cloth layer. A cured resin composition layer 3 was formed.

<Comparative example 1>
Example 1 was carried out in the same manner as in Example 1, except that the antistatic layer 6 was not laminated, and a removable protective film 5 that is peeled off during use/a removable acrylic ester adhesive along with the protective film 5 was used. agent / film layer 4 (Cosmoshine (registered trademark) A4300) / resin composition layer 3 contained in a state impregnated with glass fiber cloth 2 / film layer 4 (cosmoshine (registered trademark) A4300) / together with protective film 5 A nonflammable sheet of Comparative Example 1 was obtained, which had a laminated structure of a removable acrylic ester adhesive/a removable protective film 5 that is peeled off during use.

<Comparative example 2>
(Manufacture of glass fiber cloth 2)
Weaving was carried out using an air jet loom using Unitika Glass Fiber Co., Ltd.'s product name "ECC1200 1/0 1.0Z" (average filament diameter 4.5 μm, average number of filaments 100, number of twists 1.0Z) as the warp and weft threads. A plain weave glass fiber fabric having a warp density of 90 threads/25 mm and a weft thread density of 90 threads/25 mm was obtained. Then, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400° C. for 30 hours. After that, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g/L and squeezed with a padder roll. After that, it was dried and cured at 120°C for 1 minute. Then, the glass fiber fabric was widened once by water jet processing at a pressure of 1.5 MPa while setting the tension of the glass fiber fabric to 100 N/m in the warp direction to obtain a glass fiber fabric to be used as glass fiber fabric 2. The obtained glass fiber fabric 2 had a warp density of 90/25 mm, a weft density of 90/25 mm, a thickness of 27 μm, a mass of 30 g/m ² , and a refractive index of 1.561.

(Lamination of peelable protective film 5 that is peeled off when used on film layer 4)
Cosmoshine (registered trademark) A4300, which serves as the film layer 4, is coated with an acrylic ester adhesive on one side of a polypropylene film, which serves as the removable protective film 5, which is peeled off during use. are laminated so that the adhesive is on the Cosmoshine (registered trademark) A4300 side, and dried to form a removable protective film 5/acrylic ester adhesive/film layer 4 that is peeled off during use. A laminate B having a laminate structure of Shine (registered trademark) A4300 was obtained. Two sheets of the laminate B were prepared.

(Manufacture of nonflammable sheets)
A resin composition layer 3 is applied to the Cosmoshine (registered trademark) A4300 side (that is, the side opposite to the removable protective film 5 that is peeled off during use) of one laminate B obtained above. The cured resin composition described was applied. Next, the obtained glass fiber cloth 2 is placed on top of the cured resin composition which will become the resin composition layer 3, and the cured resin composition is applied to the gaps between the glass fiber cloths 2 after being left to stand for 1 minute. Impregnated. Next, the other side of the obtained laminate B is placed on the Cosmoshine (registered trademark) A4300 side of the laminate B (that is, the side opposite to the removable protective film 5 that is peeled off during use). was placed so that the cured resin composition layer 3 was on the cured resin composition 3 side, and pressure was applied from above the laminate B using a roller so that the mass of the cured resin composition layer 3 was 90 g/m ² . Thereafter, while the removable protective film 5 that is peeled off during use is still laminated, the cured resin composition forming the resin composition layer 3 is irradiated with light using a black light fluorescent lamp (product name: FL15BLB manufactured by Toshiba Corporation). Irradiation conditions: cumulative light amount of 200 mJ/ ^cm2 ) to cure the cured resin composition to form a cured resin composition layer 3, which is peelable together with the peelable protective film 5/protective film 5 that is peeled off during use. Acrylic ester adhesive/film layer 4 (Cosmoshine (registered trademark) A4300)/resin composition layer 3 impregnated in glass fiber cloth 2/film layer 4 (Cosmoshine (registered trademark) A4300) A noncombustible sheet of Comparative Example 2 was obtained, which had a laminated structure of /an acrylic ester pressure-sensitive adhesive that can be peeled off together with the protective film 5, and a peelable protective film 5 that can be peeled off during use. In the obtained noncombustible sheet, the gaps between the glass fibers of the glass fiber cloth 2 are impregnated with a cured resin composition layer 3 (cured product of the resin composition), and a cured resin composition layer 3 (cured product of the resin composition) is impregnated on both sides of the glass fiber cloth layer. A cured resin composition layer 3 was formed.

<Comparative example 3>
(Manufacture of glass fiber cloth 2)
The product name "ECBC3000 1/0 0.5Z" manufactured by Unitika Glass Fiber Co., Ltd. (average filament diameter 4 μm, average number of filaments 50, number of twists 0.5Z) was used as the warp and weft, and the warp was woven using an air jet loom. A plain weave glass fiber fabric having a density of 95 threads/25 mm and a weft density of 95 threads/25 mm was obtained. Then, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400° C. for 30 hours. After that, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g/L and squeezed with a padder roll. After that, it was dried and cured at 120°C for 1 minute. Then, the glass fiber fabric was widened twice by water jet processing at a pressure of 1.5 MPa while setting the tension of the glass fiber fabric to 100 N/m in the warp direction to obtain a glass fiber fabric to be used as glass fiber fabric 2. The obtained glass fiber fabric 2 had a warp density of 95/25 mm, a weft density of 95/25 mm, a thickness of 13 μm, a mass of 12 g/m ² , and a refractive index of 1.561.

(Lamination of peelable protective film 5 that is peeled off when used on film layer 4)
The above-mentioned vinyl chloride resin film (manufactured by Okamoto Co., Ltd., general purpose PVC #320, thickness 100 μm, mass 120 g/m ² ) serving as the film layer 4 is coated with the above-mentioned removable protective film 5 that is peeled off during use. An acrylic ester-based adhesive is applied to one side of a polypropylene film, which is then laminated so that the adhesive faces the vinyl chloride resin film, dried, and a peelable film that is peeled off during use is layered. A laminate C having a laminate structure of protective film 5/acrylic acid ester adhesive/vinyl chloride resin film serving as film layer 4 was obtained. Two laminates C were prepared.

(Manufacture of nonflammable sheets)
A resin composition layer 3 is formed on the vinyl chloride resin film side (that is, the side opposite to the removable protective film 5 that is peeled off during use) of the laminate C obtained above and cured according to Table 1. A resin composition was applied. Next, the obtained glass fiber cloth 2 is placed on top of the cured resin composition which will become the resin composition layer 3, and the cured resin composition is applied to the gaps between the glass fiber cloths 2 after being left to stand for 1 minute. Impregnated. Next, of the obtained laminate C, the other side of the laminate C is made of a cured resin so that the vinyl chloride resin film side of the laminate C (that is, the side opposite to the peelable protective film 5 that is peeled off at the time of use) It was placed so that the composition 3 side was placed, and pressure was applied from above the laminate C using a roller so that the mass of the cured resin composition layer 3 was 40 g/m ² . Thereafter, the cured resin composition is irradiated with light (light irradiation conditions: cumulative light amount 200 mJ/ cm ² ) to cure the cured resin composition to form a cured resin composition layer 3, and a removable protective film 5 that is peeled off during use/an acrylic ester adhesive that can be peeled off together with the protective film 5/ Film layer 4 (vinyl chloride resin film) / Resin composition layer 3 impregnated in glass fiber cloth 2 / Film layer 4 (vinyl chloride resin film) / Acrylic acid ester adhesive that can be peeled off together with protective film 5 A nonflammable sheet of Comparative Example 3 was obtained, which had a laminated structure of a removable protective film 5 and a removable protective film 5 that was peeled off during use. In the obtained noncombustible sheet, the gaps between the glass fibers of the glass fiber cloth 2 are impregnated with a cured resin composition layer 3 (cured product of the resin composition), and the cured resin composition layer 3 (cured product of the resin composition) is impregnated on both sides of the layer of the glass fiber cloth 2. A cured resin composition layer 3 was formed thereon.

<Comparative example 4>
(Manufacture of glass fiber cloth)
The product name "ECBC3000 1/0 0.5Z" manufactured by Unitika Glass Fiber Co., Ltd. (average filament diameter 4 μm, average number of filaments 50, number of twists 0.5Z) was used as the warp and weft, and the warp was woven using an air jet loom. A plain weave glass fiber fabric having a density of 95 threads/25 mm and a weft density of 95 threads/25 mm was obtained. Then, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400° C. for 30 hours. After that, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g/L and squeezed with a padder roll. After that, it was dried and cured at 120°C for 1 minute. Then, the glass fiber fabric was widened twice by water jet processing at a pressure of 1.5 MPa while setting the tension of the glass fiber fabric to 100 N/m in the warp direction to obtain a glass fiber fabric to be used as glass fiber fabric 2. The obtained glass fiber fabric 2 had a warp density of 95/25 mm, a weft density of 95/25 mm, a thickness of 13 μm, a mass of 12 g/m ² , and a refractive index of 1.561.

(Manufacture of nonflammable sheets)
A cured resin composition as resin composition layer 3 shown in Table 1 was applied onto a 50 μm thick PET film as a removable protective film 5 that is peeled off during use. Next, the obtained glass fiber cloth 2 was placed on top of the resin composition and allowed to stand for 1 minute to impregnate the gap between the glass fiber cloth 2 with the cured resin composition. Next, another PET film of the same product as the PET film serving as the removable protective film 5 to be peeled off during use is placed on top, and the weight of the cured resin composition layer 3 is 90 g using a roller from above the PET film. / ^m2 . Thereafter, a black light fluorescent lamp (manufactured by Toshiba Corporation, product name FL15BLB) was used to coat the resin composition layer 3 while the PET film was laminated as the removable protective film 5 that was peeled off during use. The resin composition is cured by light irradiation (light irradiation conditions: cumulative light amount 200 mJ/cm ² ) to form a cured resin composition layer 3, and a removable protective film 5/glass fiber cloth 2 is peeled off at the time of use. A nonflammable sheet of Comparative Example 4 was obtained, which had a laminated structure of a resin composition layer 3 impregnated with a peelable protective film 5 that was peeled off during use. In the obtained noncombustible sheet, the gaps between the glass fibers of the glass fiber cloth 2 are impregnated with a cured resin composition layer 3 (cured product of the resin composition), and the cured resin composition layer 3 (cured product of the resin composition) is impregnated on both sides of the layer of the glass fiber cloth 2. A cured resin composition layer 3 was formed thereon.

In addition, in the examples and comparative examples, the weaving density of the glass fiber fabric is JIS R 3420.
Measured and calculated in accordance with 2013 7.9. In addition, the thickness of glass fiber fabric is JIS
Measured and calculated according to R 3420 2013 7.10.1A method. The mass of the glass fiber fabric was measured and calculated in accordance with JIS R 3420 2013 7.2. The refractive index of the cured resin composition layer 3 and the glass fiber fabric 2 was measured and calculated by the method described above. The Abbe number of the cured resin composition layer 3 and the glass fiber fabric 2 was measured and calculated by the above method. The following evaluation was performed after the noncombustible sheet was left indoors for one week after manufacturing.

(Heat cycle test and surface resistivity, total light transmittance, haze before and after the heat cycle test)
This was done using the method described above.

(Checking the degree of dust adhesion when used as a smoke-proof hanging wall for a long time)
For the obtained noncombustible sheet, remove the removable protective film 5 that is peeled off during use (if the protective film 5 contains a removable acrylic ester adhesive, remove the adhesive together) and perform the above process. A specific heat cycle test was carried out, and the nonflammable sheet was cut into 20 cm squares, and 50 pieces of paper cut into 1 mm squares were scattered in a 15 cm square on a test table, and the sheet was left standing on top of it. Afterwards, the sheet was gently pulled upward and the evaluation was made based on the number of pieces of paper that stuck to the sheet. Note that the paper used had a thickness of 0.1 mm and a mass of 70 g/m ² .
Judgment was made according to the following criteria, and a score of 3 or more was considered to be a pass.
3 points: No paper pieces were stuck. 2 points: 1 to 9 pieces of paper were stuck. 1 point: 10 or more pieces of paper were stuck.

(Initial tear strength)
This was done using the method described above.

The results of each evaluation are shown in Table 1.

In Examples 1 to 5, by setting the surface resistivity to 1×10 ¹¹ Ω or less before and after a specific heat cycle test, it is possible to reduce dust adhesion when used for a long period of time, for example, as a smoke-proof hanging wall. It was possible. On the other hand, in Comparative Examples 1 to 4, the surface resistivity exceeded 1×10 ¹¹ Ω, so it was impossible to reduce dust adhesion when used as a smoke-proof hanging wall for a long period of time. there were.

Comparing Examples 4 and 5, in Example 4, the mass (g/m ² ) of the surfactant contained in the nonflammable sheet was 1 to 1.5 g/m ² . It achieved excellent transparency while ensuring the function of reducing dust adhesion when used as a chimney wall for a long period of time. Furthermore, Examples 1 to 3 have a lower surface resistivity of 1×10 ¹⁰ Ω because they are provided with the antistatic layer 6 containing metal or metal oxide to serve as a surface layer when used as a smoke-proof hanging wall. The following features further reduce dust adhesion when used as a smoke-proof hanging wall for a long period of time, further reduce changes in surface resistivity before and after specific heat cycle tests, and achieve better transparency. It was something. Further, after a specific heat cycle test, Example 5 and Comparative Example 5 were found to be quite sticky, while Examples 1 to 3 were found to be almost not sticky. Furthermore, in Examples 1 to 3, the difference in surface resistivity before and after a specific heat cycle test (= surface resistivity after a specific heat cycle test (Ω) - surface resistivity before a specific heat cycle test (Ω)) ) was 5.0×10 ⁹ Ω or less, and it was confirmed that it had stable antistatic performance. Furthermore, since Examples 1 to 3 included the film layer 4, their initial tear strength was also excellent.

1... Nonflammable sheet 2... Glass fiber cloth 3... Resin composition layer 31, 32... Surface side portion of resin composition layer 4... Film layer 41, 42... Film layer Surface side portion 5... Peelable protective film 6 that is peeled off during use... Antistatic layer

Claims (6)

A nonflammable sheet comprising a glass fiber cloth and a resin composition layer impregnated in the glass fiber cloth,
A nonflammable sheet having a surface resistivity of 1×10 ¹¹ Ω or less before and after the following heat cycle test of the nonflammable sheet.
<Heat cycle test conditions>
The non-combustible sheet was cut into a sample with a size of 100 mm x 100 mm, and the sample was placed in a constant temperature and humidity chamber (product name: PSL, manufactured by ESPEC Co., Ltd., which was initially set to a temperature of 23°C and a relative humidity of 50% RH). -2KPH), and carry out 10 cycles in total, with the following (1) to (5) being one cycle.
(1) Transition from a temperature of 23° C. and relative humidity of 50 RH to a temperature of 60° C. and relative humidity of 50% RH with a transition time of 14 minutes.
(2) Maintain at the above temperature of 60° C. and relative humidity of 50% RH for 8 hours.
(3) Transition from the above temperature of 60° C. and relative humidity of 50% RH to temperature of 20° C. and relative humidity of 50% RH with a transition time of 45 minutes.
(4) Maintain at the above temperature of 20° C. and relative humidity of 50% RH for 8 hours.
(5) Transition from the above temperature of 20° C. and relative humidity of 50% RH to temperature of 23° C. and relative humidity of 50% RH with a transition time of 1 minute. The noncombustible sheet according to claim 1, further comprising an antistatic layer containing a metal or a metal oxide to serve as a surface layer when the noncombustible sheet is used. A layer that becomes a surface layer when the nonflammable sheet is used contains a surfactant,
The nonflammable sheet according to claim 1, wherein the mass (g/m ² ) of the surfactant in the nonflammable sheet is 0.5 to 1.5 g/m ² . The nonflammable sheet according to any one of claims 1 to 3, having a total light transmittance of 90% or more and a haze of 20% or less. The noncombustible sheet according to any one of claims 1 to 4, which is used for smokeproof hanging walls. A smoke-proof hanging wall comprising the noncombustible sheet according to any one of claims 1 to 5.