JP7090885B2 - Non-combustible sheet, smoke-proof hanging wall containing the non-combustible sheet - Google Patents

Description

The present invention relates to a non-combustible sheet, and particularly to a non-combustible sheet suitable for a smoke-proof hanging wall or the like, and a smoke-proof hanging wall using the same.

The Building Standards Law and the Building Standards Law Enforcement Ordinance stipulate that smoke exhaust equipment should be installed so that evacuation and fire extinguishing activities can be carried out smoothly by hindering the flow of smoke, toxic gas, etc. generated during a building fire. There is. Therefore, in buildings such as office buildings and commercial facilities, smoke-proof hanging walls and the like are often installed as smoke exhaust equipment and smoke-shielding equipment.

Smoke-proof hanging walls are usually used for the purpose of temporarily blocking the flow of smoke, toxic gas, etc. in the event of a fire to the corridors and upper floors, and ensuring the time required for evacuation. It is mounted on the ceiling. For this reason, a 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 appearance is not spoiled by the smoke-proof hanging wall. The resin composite of glass fiber and resin has an advantage that it is hard to break as compared with flat glass. For example, Patent Document 1 discloses a transparent nonflammable sheet containing a glass fiber woven 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 surface of the base material layer. The transparent nonflammable sheet is disclosed.

Further, for example, Patent Document 3 describes a nonflammable laminate in which an adhesive-impregnated coated glass cloth is used as a base material and soft vinyl chloride resin transparent layers are provided on both sides thereof, wherein the adhesive-impregnated coated glass cloth is provided. However, it is a composite intermediate obtained by impregnating and curing an adhesive component containing a triisocyanate compound and a binder resin in a mass ratio of 1: 5 to 1:35 on a glass cloth treated with a silane coupling agent. Further, a transparent non-combustible sheet is disclosed, wherein the triisocyanate compound is at least one selected from isocyanurate-modified triisocyanate, bullet-modified triisocyanate, and trimethylolalkyl-modified triisocyanate.

Japanese Unexamined Patent Publication No. 2005-319746 Japanese Unexamined Patent Publication No. 2011-213093 Japanese Unexamined Patent Publication No. 2014-76663

As a result of examination by the present inventors, the non-combustible sheet described in Patent Documents 1 to 3 is, for example, in the air in a building installed as a smoke-proof hanging wall when used as a smoke-proof hanging wall for a long period of time. It has been found that there is a problem that the existing dust adheres to the surface of the nonflammable sheet and the appearance is deteriorated. Under such circumstances, the present invention comprises a non-combustible sheet made of a glass cloth and a resin, for example, a non-combustible sheet for reducing the adhesion of dust when used as a smoke-proof hanging wall for a long period of time, and the non-combustible sheet. The purpose is to provide a smoke wall.

As a result of studies by the present inventors in order to solve the above problems, for example, the nonflammable sheet as disclosed in Patent Documents 1 to 3 has a surface resistivity of about 1 × 10 ¹⁵ Ω, which is caused by this. As a result, it was found that the adhesion of dust existing in the air could not be sufficiently prevented. Therefore, as a result of diligent studies by the present inventors, it has been found that the adhesion of dust 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 is an invention completed by further studies based on these findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. A nonflammable sheet comprising a glass fiber cloth and a resin composition layer impregnated in the glass fiber cloth, and having a surface resistivity of 1 × before and after the following heat cycle test of the nonflammable sheet. 10 ¹¹ Ω or less, nonflammable sheet.
<Heat cycle test conditions>
The nonflammable sheet was cut into a size of 100 mm × 100 mm and used as a sample, and the sample was initially set to a temperature of 23 ° C. and a relative humidity of 50% RH. -2KPH), and the following (1) to (5) are regarded as one cycle, and a total of 10 cycles are performed.
(1) The transition is performed from a temperature of 23 ° C. and a relative humidity of 50 RH to a temperature of 60 ° C. and a relative humidity of 50% RH with a transition time of 14 minutes.
(2) Hold at the above temperature of 60 ° C. and a relative humidity of 50% RH for 8 hours.
(3) The transition time is 45 minutes from the temperature of 60 ° C. and relative humidity of 50% RH to the temperature of 20 ° C. and relative humidity of 50% RH.
(4) Hold at the above temperature of 20 ° C. and a relative humidity of 50% RH for 8 hours.
(5) The transition is performed from the temperature of 20 ° C. and a relative humidity of 50% RH to a temperature of 23 ° C. and a 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 so as to be a surface layer when the nonflammable sheet is used.
Item 3. The layer that becomes the surface layer when the nonflammable sheet is used contains a surfactant, and the mass (g / m ² ) of the surfactant in the nonflammable sheet is 0.5 to 1.5 g / m ² . , Item 1. The nonflammable sheet according to Item 1.
Item 4. Item 6. The nonflammable sheet according to any one of Items 1 to 3, wherein the total light transmittance is 90% or more and the haze is 20% or less.
Item 5. Item 6. The nonflammable sheet according to any one of Items 1 to 4, which is used for a smoke-proof hanging wall.
Item 6. A smoke-proof hanging wall provided with the non-combustible 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 the adhesion of dust when used as a smoke-proof hanging wall for a long period of time, for example. ..

It is a schematic sectional drawing which shows an example of the nonflammable sheet of this invention. It is a schematic sectional drawing which shows an example of the nonflammable sheet of this invention. It is a schematic sectional drawing which shows an example of the nonflammable sheet of this invention. It is a schematic sectional drawing which shows an example of the nonflammable sheet of this invention. It is a schematic plan view explaining the method of measuring the initial tear strength of this invention.

The nonflammable sheet of the present invention is a nonflammable sheet containing a glass fiber cloth and a resin composition layer impregnated in the glass fiber cloth, and is a nonflammable sheet before and after the following heat cycle test of the nonflammable sheet. The surface resistivity is 1 × 10 ¹¹ Ω or less.
<Heat cycle test conditions>
The nonflammable sheet was cut into a size of 100 mm × 100 mm and used as a sample, and the sample was initially set to a temperature of 23 ° C. and a relative humidity of 50% RH. -2KPH), and the following (1) to (5) are regarded as one cycle, and a total of 10 cycles are performed.
(1) The transition time is 14 minutes from a temperature of 23 ° C. and a relative humidity of 50% RH to a temperature of 60 ° C. and a relative humidity of 50% RH.
(2) Hold at the above temperature of 60 ° C. and a relative humidity of 50% RH for 8 hours.
(3) The transition time is 45 minutes from the temperature of 60 ° C. and relative humidity of 50% RH to the temperature of 20 ° C. and relative humidity of 50% RH.
(4) Hold at the above temperature of 20 ° C. and a relative humidity of 50% RH for 8 hours.
(5) The transition is performed from the temperature of 20 ° C. and a relative humidity of 50% RH to a temperature of 23 ° C. and a relative humidity of 50% RH with a transition time of 1 minute.

For example, as shown in FIGS. 1 to 4, the nonflammable sheet 1 of the present invention has a laminated structure including a glass fiber cloth 2 and a resin composition layer 3 impregnated in the glass fiber cloth 2. In the nonflammable sheet 1, the glass fiber cloth 2 may contain at least one layer, and may contain a plurality of layers.

Further, as shown in FIGS. 2 to 4, the nonflammable sheet 1 of the present invention has a glass fiber cloth 2, a resin composition layer 3 impregnated in the glass fiber cloth 2, and at least one surface of the resin composition layer 3. Above, preferably, a laminated structure including the film layer 4 may be formed on both sides. Further, as shown in FIGS. 3 and 4, the nonflammable sheet 1 of the present invention is 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. A peelable protective film 5 that can be peeled off can be included.

In FIGS. 1 to 4, the resin composition layer 3 fills the gaps between the plurality of glass fibers constituting the glass fiber cloth 2, and one surface side portion 31 of the resin composition layer 3 and the other surface. The side portion and 32 communicate with each other through the gap portion. Further, in the nonflammable sheet 1 of the present invention, from the viewpoint of enhancing transparency, for example, as shown in FIGS. 1 to 4, the resin composition layer 3 is placed on at least one surface of the layer of the glass fiber cloth 2. It is preferably formed, and it is more preferable that the resin composition layer 3 is formed on both sides of the layer of the glass fiber cloth 2.

When the film layer 4 shown in FIG. 1 is not laminated, the surface side of the resin composition layer 3 (31, 32 side in FIG. 1), or when the film layer 4 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 (41, 42 side in FIGS. 2 and 3) of the film layer 4. This makes it possible to further reduce the surface resistivity before and after the specific heat cycle test, further reduce the change in the surface resistivity before and after the 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 arranged so as to be a surface layer when the nonflammable sheet 1 is used, for example, when it is used as a smokeproof hanging wall. Hereinafter, the composition of each layer constituting the nonflammable sheet 1 of the present invention will be described in detail.

(Glass fiber cloth 2)
In the nonflammable 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 a glass fiber woven fabric (glass cloth) composed of a plurality of warp threads and a plurality of weft threads. The weaving structure of the glass fiber woven fabric is not particularly limited, and examples thereof include plain weave, satin weave, twill weave, diagonal weave, and ridge weave.

The glass material of the glass fiber constituting the glass fiber cloth 2 is not particularly limited, and for example, a known glass material can be used. Examples of the glass material include non-alkali glass (E glass), acid-resistant alkali-containing glass (C glass), high-strength and high-elasticity glass (S glass, T glass, etc.), alkali-resistant glass (AR glass), and the like. However, preferably, non-alkali glass (E glass) having high versatility is mentioned. The glass fiber constituting the glass fiber cloth 2 may be made of one kind of glass material, or may be a combination of two or more kinds of glass fibers made of different glass materials. Further, from the viewpoint of improving transparency, it is preferable to select a glass material which is similar to the refractive index 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. The count of the glass fiber is preferably 20 tex or less, preferably 3 to 6 tex, and more preferably 3 to 5 tex, from the viewpoint of improving transparency. The count of the glass fiber may be one type alone or a combination of two or more types. The tex count of the glass fiber corresponds to the number of grams per 1000 m.

As the glass fiber constituting the glass fiber cloth 2, a glass yarn in which a plurality of single fibers, which are long glass fibers, are twisted together is preferable. The number of single fibers in the glass yarn is preferably about 30 to 400, more preferably about 40 to 120. The diameter of the single fiber 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 the color bleeding of the nonflammable sheet 1 is suppressed by keeping the diameter of the single fiber 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 a condition, the shrinkage at the interface between the glass yarn and the resin composition layer 3 is more effectively suppressed, and as a result, the color bleeding of the nonflammable sheet 1 is suppressed.

In the nonflammable sheet 1, the ratio (mass%) of the glass fiber cloth 2 is 20 to 50% by mass in the total amount of the glass fiber cloth 2 and the resin composition layer 3 described later from the viewpoint of suppressing color bleeding. Preferably, 20 to 40% by mass is more preferable, and 20 to 30% by mass is more preferable. The mass (g / m ² ) of one piece of the glass fiber cloth 2 is preferably 10 to 120 (g / m ² ), more preferably 10 to 60 (g / m ² ), and 10 to 40 (g / m 2). m ² ) is more preferable.

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

The refractive index of the glass fiber cloth 2 is measured according to the B method of JIS K 7142: 2008. Specifically, regarding 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) are used as immersion liquids. .366) was used, NAR-2T manufactured by Atago Co., Ltd. was used as an Abbe refractometer, and a sodium D line with a wavelength of 589 nm was used as a light source for measurement at a temperature of 23 ° C., and the average value of 5 tests was refracted. The value of the rate. Further, the refractive index of the resin composition 3 is measured according to the B method 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 ) are used as immersion liquids. ²³ 1.366), a small measuring microscope STM5-311 (manufactured by Olympus, observation magnification 400 times) was used as a microscope, and a sodium D line having a wavelength of 589 nm was used as a light source for measurement at a temperature of 23 ° C. Let the average value of 5 times be the value of the refractive index.

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

(Abbe number of cured resin composition layer)
A sheet of the cured resin composition containing no glass fiber cloth was prepared under the same conditions as when the glass fiber cloth was contained, and the test piece was made to have a width of 8 mm and a length of 20 mm, and the surface was well polished. According to the 7142A method, NAR-2T manufactured by Atago Co., Ltd. is used as an Abbe refractometer, diiodomethane is used as a contact liquid, and sodium D-ray having a wavelength of 589 nm is used as a light source, and the refractive index is measured at a wavelength of 589 nm at a measurement temperature of 23 ° C. .. Subsequently, the dispersion value is measured and calculated using the light source as natural light, 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 having 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 fiber, and the surface was well polished. Using NAR-2T, diiodomethane as a contact liquid, and sodium D-ray having a wavelength of 589 nm as a light source, the refractive index is measured at a wavelength of 589 nm at a measurement temperature of 23 ° C. Subsequently, the dispersion value is measured and calculated using the light source as natural light, 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 ratio of 38% or more 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 a fiber opening treatment.

Glass volume (%) = (A / (B × C)) × 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 with the glass fiber cloth 2 and is formed by curing or solidifying the resin composition containing the resin. Specifically, the resin composition layer 3 can be a curable resin composition layer or a thermoplastic resin composition layer. In the case of forming a cured resin composition layer, a cured product (photo-cured resin composition or thermosetting) in which the resin composition is cured by applying energy such as light or heat to the resin composition containing the curable resin. Resin composition). When the thermoplastic resin composition layer is used, it can be a cured product obtained by drying and solidifying the thermoplastic resin composition.

As the curable resin, the refractive index of the resin composition layer 3 and the glass fiber cloth 2 described above are approximated from the viewpoint of further improving the transparency of the nonflammable sheet 1 before and after the specific heat cycle test described above. Those that can be used are preferable. Preferred curable resins include those in which the curable resin composition is photocurable, and examples thereof include vinyl ester resin, urethane acrylate resin, fluorene acrylate resin, unsaturated polyester resin, curable acrylic resin, and epoxy resin. Be done. Among them, when the film layer 4 is provided, a curable acrylic resin is more preferable from the viewpoint of further improving the adhesiveness with the film layer 4, and a cured resin composition containing an 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 / normal butyl acrylate copolymer are methacrylic. Acrylic syrup dissolved in a methyl acrylate monomer is particularly preferable. As described above, when the cured resin composition layer 3 is a cured resin composition containing acrylic syrup, the adhesion to the film layer 4 is further improved, so that the above-mentioned specific heat of the nonflammable sheet 1 is further improved. It is preferable because the transparency before and after the cycle test is further improved.

As the thermoplastic resin, the refractive index of the resin composition layer 3 and the glass fiber cloth 2 can be approximated from the viewpoint of further improving the transparency of the nonflammable sheet 1 before and after the specific heat cycle test described above. What can be done is preferable. Preferred thermoplastic resins include, for example, polyvinyl chloride resin, saturated polyester resin, polyolefin resin, thermoplastic acrylic resin, polycarbonate resin, polyvinyl alcohol resin, ethylene vinyl acetate copolymer, polyamide resin, polyarylate resin and the like. For example, when E glass is used as the glass material of the glass fiber constituting the glass fiber cloth 2, from the viewpoint of refractive index, polyvinyl chloride resin, saturated polyester resin, thermoplastic acrylic resin and the like are preferable. 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 to be used. In the nonflammable sheet 1 of the present invention, when the resin composition layer 3 is used as the thermoplastic resin composition layer, the portion impregnated in the glass fiber cloth 2 is a thermoplastic resin composition in the form of a sol or dissolved in a solvent. Is impregnated and solidified (solidified by heating or solidified by drying). Further, 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 the form of a sol or dissolved in a solvent and solidified (solidified by heating or solidified by drying). It may be formed by a film-like thermoplastic resin composition.

When it is necessary to join the nonflammable sheets, for example, when the nonflammable sheets are used as a tension type smoke-proof hanging wall, which will be described later, and the ends of the nonflammable sheets are joined by high-frequency welding. When the resin composition layer 3 impregnated with the glass fiber cloth 2 is a cured resin composition layer, it becomes easier to maintain the transparency before and after the welding process at the end of the nonflammable sheet to be subjected to the high frequency welding process. It is 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 a phosphate ester. Examples of the ultraviolet absorber include benzotriazole and the like. Examples of the filler include calcium carbonate, silica, talc and the like. Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane-1-. On, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hirodoxy-1- {4- [4- (2-hydroxy-) 2-Methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl]- Examples thereof include 1-butanone, 2,4,6, -trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphin oxide and the like. Above all, when a curable acrylic resin is used 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 non-combustible sheet 1 of the present invention, for example, when the film layer 4 is not laminated as in the embodiment shown in FIG. 1, from the viewpoint of reducing the adhesion of dust when used as a smoke-proof hanging wall for a long period of time, for example, from the viewpoint of reducing the adhesion of dust. The resin composition layer 3 can contain a surfactant. That is, when the effect of the present invention is to reduce the adhesion of dust when used as a smoke-proof hanging wall for a long period of time by using a surfactant, for example, an interface is formed on the surface layer at the time of use. It can contain an activator. In other words, when the effect of the present invention is to be achieved by using a surfactant, for example, to reduce the adhesion of dust when used as a smoke-proof hanging wall for a long period of time, the layer to be the surface layer at the time of use is used. It is necessary to contain a surfactant.

In the present invention, the surfactants include cationic surfactants, anionic surfactants, nonionic (nonionic) surfactants, amphoteric surfactants, fluorosurfactants, and reactive surfactants. Can be mentioned. For example, examples of anionic surfactants include sulfate ester salts of higher alcohols, higher alkyl sulfonic acids and salts thereof, alkylbenzene sulfonic acids and salts thereof, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, and vinyl sulfos. Examples thereof include succinate, polyoxyalkylene alkyl ether sulfate, and examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, and ethylene oxide propylene oxide block copolymer. Examples thereof include sorbitan derivatives such as polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide copolymer and polyoxyethylene sorbitan fatty acid ester, and examples of the amphoteric surfactant include laurylbetaine and lauryldimethylamine oxide. Examples of the reactive surfactant include alkylpropenylphenol polyethylene oxide adducts and sulfate ester salts thereof, allylalkylphenol polyethyleneoxide adducts and sulfate ester salts thereof, allyldialkylphenol polyethyleneoxide adducts and sulfate ester salts thereof. Examples include compounds having a reactive double bond. Above all, the polyoxyalkylene alkyl ether sulfate is preferable from the viewpoint of further achieving both transparency and antistatic property 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 later contains an excessive amount of a surfactant, the transparency of the nonflammable sheet 1 may be impaired. This is because the surfactant is generally inferior in compatibility with the resin. Therefore, for example, from the viewpoint of obtaining excellent transparency while ensuring the function of reducing the adhesion of dust when used as a smoke-proof hanging wall for a long period of time, the resin composition layer 3 or the film layer which becomes the surface layer at the time of 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 0. It is more preferably .5 to 0.75% by mass. Further, from the same viewpoint as above, the mass (g / m ² ) of the surfactant contained in the layer to be the surface layer at the time of use is 0.5 to 2.0 g / m ² in the nonflammable sheet. 0.5 to 1.5 g / m ² is preferable, 0.5 to 1.0 g / m ² is more preferable, and 0.5 to 0.75 g / m ² is even more preferable.

As will be described later, in the nonflammable sheet of the present invention, for example, in order to reduce the adhesion of dust when 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 must be less than or equal to Ω. The surface resistivity can be achieved by containing only the surfactant in the resin composition layer 3 when the film layer 4 is not laminated, or in the film layer 4 when the film layer 4 is laminated, as described above. Will be.

On the other hand, while lowering the upper limit of the surface resistivity (1 × 10 ¹¹ Ω) before and after the specific heat cycle test, the change in the surface resistivity is further reduced before and after the specific heat cycle test, and From the viewpoint of obtaining better transparency, for example, rather than containing a surfactant in the resin composition layer 3 or the film layer 4 which is the surface layer when used as a smoke-proof hanging wall, for example, the figure. As shown in 4, the surface side of the resin composition layer 3 when the film layer 4 is not laminated, or the surface side of the film layer 4 when the film layer 4 is laminated, contains a metal or a metal compound described later. It is preferable to provide the layer 6, and it is more preferable to provide the antistatic layer 6 containing the metal fine particles or the metal compound fine particles. The reason for this is that, according to the study by the present inventors, first, the resin composition layer 3 is used when the above-mentioned film layer 4 is not laminated, or the film layer 4 is used when the film layer 4 is laminated. When only contained, the surface resistance before and after a specific heat cycle test is 1 × 10 ¹⁰ Ω or less, which is higher performance, and the total light transmittance is 90% or more, and the haze is 20% or less, which is higher transparency. It turned out that I couldn't. On the other hand, in the case where 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. Was found to be able to achieve both of the above performances. Secondly, when the above-mentioned film layer 4 is not laminated, the resin composition layer 3 is used, or when the film layer 4 is laminated, the film layer 4 contains only the surfactant, by a specific heat cycle test. It has been found that the surfactant may bleed out and the surface resistivity may change easily before and after a specific heat cycle test. On the other hand, in the case where 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 was found that the change in surface resistivity can be further reduced before and after a specific heat cycle test because there is no risk of bleed-out. In addition, thirdly, when the above-mentioned film layer 4 is not laminated, the resin composition layer 3 is used, or when the film layer 4 is laminated, the film layer 4 contains only the surfactant, especially the interface. It has been found that the bleed-out of the activator may cause stickiness on the surface of the nonflammable sheet 1 when used as a smoke-proof hanging wall, for example. When the stickiness occurs, once the dust adheres, it may not be easily removed. 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, for example, as shown in FIG. 1, when the film layer 4 is not laminated, the nonflammable sheet 1 of the present invention further lowers the surface resistance before and after the specific heat cycle test, and before and after the specific heat cycle test. From the viewpoint of further reducing the change in the surface resistance and obtaining more excellent transparency, it is preferable to provide the antistatic layer 6 containing a metal or a metal compound on the surface side of the resin composition layer 3. In the case, the resin composition layer 3 is the 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, further 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 is, for example, when the film layer 4 shown in FIGS. 2 and 3 is provided, and when the film layer 4 contains a surfactant and is used as a smoke-proof hanging wall for a long period of time. In order to reduce the adhesion of dust, the mass (g) of the surfactant contained in the resin composition layer with respect to the total mass (g / m ² ) of the resin composition layer 3 excluding the glass fiber cloth 2. The ratio of / 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 further preferably 0% by mass. preferable. Further, the nonflammable sheet 1 of the present invention may be provided with, for example, the film layer 4 shown in FIG. 4, and the antistatic layer 6 containing a metal or a metal compound may be provided on the surface side of the resin composition layer 3. 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. Is preferable, 0.3% by mass or less is more preferable, 0.1% by mass or less is further preferable, 0.01% by mass or less is particularly preferable, and 0% by mass is further preferable.

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

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 glass from the viewpoint of further 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. Further, when the form layer 4 is provided, the total mass of the nonflammable sheet 1 after peeling off the peelable protective film 5 of the glass fiber cloth 2 (that is, the peelable protection that is peeled off at the time of use). The ratio in the mass excluding the film 5 (= mass (g) of the glass fiber cloth 2 / mass excluding the peelable protective film 5 that is peeled off during use (g) × 100 (%)) is, for example, 3. It is preferably up to 20% by mass, preferably 3 to 15% by mass, and more preferably 3 to 10% by mass.

(Film layer 4)
In the nonflammable sheet 1 of the present invention, the film layer 4 is laminated on the resin composition layer 3 impregnated in the glass fiber cloth 2 as needed, and before and after the above-mentioned specific heat cycle test of the nonflammable sheet 1. It plays a role in further improving the initial tear strength while further improving the transparency of the resin.

The film layer 4 is not particularly limited, but preferably contains a thermoplastic resin other than the polyvinyl chloride resin. Examples of the thermoplastic resin other than the polyvinyl chloride resin include those that can be formed into a film even if the amount of the plasticizer is small, and biaxially stretched containing an amorphous thermoplastic resin other than the polyvinyl chloride resin. Films are preferred. Examples of the thermoplastic resin other than the polyvinyl chloride resin include polyester resin, polycarbonate resin, and polyamide resin, and at least one of these may be contained. Further, the film layer 4 may not contain the polyvinyl chloride resin. From the viewpoint of further improving the initial tear strength of the nonflammable sheet 1, the film layer 4 has an Elemendorff tear propagation resistance of 1 N / mm or more in both the vertical direction and the horizontal direction, and 3 to 3 to 20 N / mm is preferable, and 5 to 15 N / mm is more preferable. Above all, the film layer 4 contains a polyester resin from the viewpoint of further achieving both chemical resistance (including alkali detergent resistance when used as a smoke-proof hanging wall), improvement of initial tear strength and transparency. It is preferable to use a detergent. Examples of the polyester resin include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). For the Elemendorff tear propagation resistance, the tear strength (N) was measured based on JIS K7128-2.1998 using an Elemendorff tear machine manufactured by Toyo Seiki Seisakusho Co., Ltd., and this measured value was divided by the film thickness. It means tear propagation resistance (N / mm). The tear strength shall be the average value of the test results of 20 samples in each of the vertical direction and the horizontal direction.

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, still 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, for example, di-n-butyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, and the like. Phthrate-based plasticizers such as diothyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl isophthalate, -2-ethylhexyl adipate, di-2-decyl adipate, dibutyl sebatate, sebatic acid- Fatty acid ester plasticizers such as 2-ethylhexyl, tributyl phosphate, tri-2-ethylhexyl phosphate, -2-ethylhexyldiphenyl phosphate, tricresyl phosphate and other phosphate ester plasticizers, tri-2-ethylhexyl trimellitic acid , Trimellitic acid ester-based plasticizers such as trioctyl trimellitic acid, adipic acid-based polyester plasticizers, polyester-based plasticizers such as phthalic acid-based polyester plasticizers, and terephthalic acid-based plasticizers.

The film layer 4 has calcium carbonate, magnesium carbonate, calcium oxide, and oxidation on the surface of the resin composition layer 3 on the side (the surface in contact with the surface side portions 31 and 32 of the resin composition layer 3 in FIGS. 2 to 4). 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 type It can contain particles made of inorganic particles or organic particles such as a crosslinked polymer, a silicone resin, a fluororesin, a benzoguanamine resin, a phenol resin, and a nylon resin. As a result, the adhesion between the resin composition layer 3 and the film layer 4 is improved. For example, when the protective film 5 described later is peeled off when the nonflammable sheet 1 is used, the resin composition layer 3 and the film layer 4 are separated from each other. It becomes difficult to peel off. This effect becomes even more remarkable when the antistatic layer 6 containing the metal or metal compound fine particles described later is laminated on the surface side of the film layer 4. That is, when the antistatic layer 6 containing the metal or metal compound fine particles described later 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 is somewhat peeled off from the antistatic layer 6. Where it may be difficult, by incorporating the inorganic particles or organic particles on the surface of the film layer 4 on the resin composition layer 3 side as described above, the anchor effect of the inorganic particles or organic particles works, and the resin The 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, frame treatment, plasma treatment, etc., if necessary, and is a coating layer that imparts various functions such as slipperiness and adhesiveness, and wear resistance. A hard coat layer or the like for improving the properties may be provided.

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, a specific heat cycle test is performed while the surface resistance is further lowered before and after the specific heat cycle test. From the viewpoint of further reducing the change in surface resistance before and after and obtaining more excellent transparency, the mass of the surfactant contained in the film layer 4 with respect to the total mass (g / m ² ) of the film layer 4 ( The ratio of 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, the film used as the film layer 4 is preferably excellent in transparency and smoothness. As the transparency of the film to be used as the film layer 4, for example, the total light transmittance (JIS K 7105: 1981) is preferably 90% or more, and more preferably 91 to 98%. Further, for example, haze (JIS K 7105: 1981) is preferably 1.5% or less, more preferably 0.3 to 1.0%.

(Antistatic layer 6 containing a metal or a 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-mentioned specific heat cycle test. Then, as described above, the surface resistivity is set to 1 × 10 ¹⁰ Ω or less, which further reduces the adhesion of dust when used as a smoke-proof hanging wall for a long period of time, and further, the surface resistance before and after a specific heat cycle test. From the viewpoint of further reducing the change in resistivity and obtaining more excellent 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 the film layer 4 shown in FIGS. 2 and 3 is laminated, the antistatic layer 6 containing a metal or a metal oxide is provided on the surface side portion (41, 42 in FIGS. 2 and 3) of the film layer 4. It is preferable to include it.

Examples of the metal element contained in the antistatic layer 6 containing a metal or a metal compound include Ag, Ni, Cu, Sn, Sb, Al, In, Ti and the like, and the standard electrode potential when the metal is used alone. 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 and the like). Further, the antistatic layer 6 may be free of fine particles made of barium sulfate, calcium carbonate, aluminum oxide, magnesium silicate, glass and the like. Examples of the contained form of the metal or the metal compound include a thin film of the metal or the metal compound by vapor deposition, sputtering, plating, or the like, or a layer in which the metal or the fine particles of the metal compound are dispersed in the fixed resin. Examples of the shape of the metal or metal compound fine particles include granules, flakes, and needles (fibrous). The average particle size of the metal or metal compound fine particles is, for example, calculated as the average particle size by a conventional method from the average particle size (specific surface area (m ² / g) measured by the nitrogen gas adsorption method) obtained by the BET method. By setting the specific surface area diameter) to 100 nm or less, preferably 1 to 100 nm, which is equal to or less than the wavelength of visible light, it becomes easier to maintain the transparency of the nonflammable sheet 1.

When the antistatic layer 6 containing a metal or a metal compound contains a metal or metal compound fine particles, it is preferable to contain a fixing resin for fixing the metal or the metal compound fine particles to the base material. That is, it is preferable that the antistatic layer 6 is a layer containing the fixing resin and the metal or metal compound fine particles dispersed in the fixing 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, pentaerythritol and the like. In particular, polyurethane-based resins, polyester-based resins, and acrylic-based resins are preferable. As the acrylic resin, for example, a modified acrylic resin (urethane modification, polyester modification, polycarbonate modification, fluorine modification, etc.) can be used. 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 resistance and transparency before and after the specific heat cycle test described above. 0.1 to 5 g / m ² is preferred, 0.1 to 3 g / m ² is more preferred, and 0.1 to 1 g / m ² is particularly preferred. Further, the metal or the metal compound can be present on the surface of the resin composition layer 3 or the film layer 4. Then, the thickness of the resin composition layer 3 or the film layer 4 provided with the antistatic layer 6 containing a metal or a metal compound is within a range of 10% from the center in the thickness direction of the layer (for example, the resin composition layer 3 or the film layer 4). When the thickness of the film layer 4 is 100 μm, the content of the metal or the metal compound is the said in the range of 40 to 60 μm from the one surface, centering on the distance of 50 μm from one surface in the thickness direction. For example, 1% by mass or less, 0.1% by mass or less, and 0.01% by mass or less are mentioned with respect to the mass of the layer included in the range. 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 and the metal or metal compound fine particles in the antistatic layer 6 (mass of the fixed resin (g / m ² ): mass of the metal or metal compound fine particles (g / m ² )) is as described above. From the viewpoint of achieving both surface resistance 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. Especially preferable. Further, examples of the surface smoothness when the antistatic layer 6 containing a metal or a metal compound is provided include a surface roughness Ra of 1 to 200 nm. The ratio of the mass (g / m ² ) of the metal and the metal compound fine particles to the total mass (g / m ² ) of the antistatic layer 6 is 50 to 10% by mass, and 30 to 20% by mass. Preferred.

(Removable protective film 5 that is peeled off during use)
The nonflammable sheet 1 of the present invention is further provided on the surface side of the resin composition layer 3 or the film layer 4 (when the antistatic layer 6 is provided on the surface side of the resin composition layer 3 or the film layer 4, if necessary. A peelable protective film 5 that can be peeled off during use can be further laminated on the surface side of the antistatic layer 6). As a result, for example, when the non-combustible sheet 1 of the present invention is used as a smoke-proof hanging wall, it becomes easy to prevent the non-combustible sheet 1 from being scratched during construction and the transparency and aesthetics from being deteriorated.

As the peelable protective film 5 that can be peeled off during use, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyester film, or the like can be used. Among them, if the protective film 5 that can be peeled off at the time of use is a light-transmitting protective film, for example, the resin composition forming the resin composition layer 3 described above is a photocurable cured resin composition. In the case of The light transmittance is not particularly limited as long as it transmits light that cures the photocurable resin, but for example, one that transmits light having a wavelength of 100 to 400 nm and one that transmits light having a wavelength of 250 to 400 nm. Can be mentioned. As the light transmittance of the protective film 5, for example, the average transmittance between the measurement wavelengths of 250 to 400 nm measured by a UV transmittance measuring device (trade name UV3150 manufactured by Shimadzu Corporation) is preferably 40% or more, and is 50. % Or more is more preferable, and 60% or more is particularly preferable.

Since the peelable protective film 5 that is peeled off during use is peeled off during use, for example, a smoke-proof hanging wall, the transparency and smoothness are not particularly limited. 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 characteristics and performance of nonflammable sheet 1)
Before and after the following heat cycle test of the nonflammable sheet, it is necessary that the surface resistivity is 1 × 10 ¹¹ Ω or less.
<Heat cycle test conditions>
The nonflammable sheet was cut into a size of 100 mm × 100 mm and used as a sample, and the sample was initially set to a temperature of 23 ° C. and a relative humidity of 50% RH. -2KPH), and the following (1) to (5) are regarded as one cycle, and a total of 10 cycles are performed.
(1) The transition time is 14 minutes from a temperature of 23 ° C. and a relative humidity of 50% RH to a temperature of 60 ° C. and a relative humidity of 50% RH.
(2) Hold at the above temperature of 60 ° C. and a relative humidity of 50% RH for 8 hours.
(3) The transition time is 45 minutes from the temperature of 60 ° C. and relative humidity of 50% RH to the temperature of 20 ° C. and relative humidity of 50% RH.
(4) Hold at the above temperature of 20 ° C. and a relative humidity of 50% RH for 8 hours.
(5) The transition is performed from the temperature of 20 ° C. and a relative humidity of 50% RH to a temperature of 23 ° C. and a relative humidity of 50% RH with a transition time of 1 minute.

As a result of examination by the present inventors, for example, the nonflammable sheet disclosed in Patent Documents 1 to 3 has a surface resistivity of about 1 × 10 ¹⁵ before and after the specific heat cycle test, which is the cause. As a result, it was found that the adhesion of dust existing in the air could not be sufficiently prevented. Therefore, as a result of diligent studies by the present inventors, it was found that the adhesion of dust can be reduced by setting the surface resistivity to 1 × 10 ¹¹ Ω or less before and after the specific heat cycle test. The surface resistivity is more preferably 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 for example, 1 × 10 ⁵ Ω or more can be mentioned, and from the viewpoint of further improving transparency, 1.0 × 10 ⁷ Ω or more, more preferably 1.0 × 10 ⁸ Ω or more. , More preferably 1.0 × ¹⁰⁹ Ω or more.

The surface resistivity is measured according to 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 an applied voltage of 100 V × 1 minute.

Further, from the viewpoint of ensuring that the change in surface resistivity is further reduced before and after the specific heat cycle test, the difference in surface resistivity before and after the specific heat cycle test (= surface resistivity after the specific heat cycle test). (Ω) -The 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 nonflammable sheet 1 of the present invention is, for example, the thickness of the nonflammable sheet 1 after peeling the peelable protective film 5 that is peeled off during use (that is, the peelable protective film that is peeled off during use). Examples of the thickness) excluding 5 include 100 to 500 μm, preferably 150 to 300 μm. Further, as the mass of the nonflammable sheet 1 of the present invention, for example, the mass of the nonflammable sheet 1 after peeling off the peelable protective film 5 at the time of use (that is, the peelable protective film 5 peeled off at the time of use). As the mass excluding), 100 to 500 g / m ² is mentioned, and 150 to 300 g / m ² is preferably mentioned. Further, 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 obtained. It is preferable because it makes it easier to achieve both.

In the nonflammable sheet 1 of the present invention, from the viewpoint of ensuring the 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 is mentioned. 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%. The following are particularly preferable, and 1% or less is more preferably mentioned. The total light transmittance and the haze of the nonflammable sheet 1 are the values obtained by measuring according to JIS K73782008 "Plastic-How to determine the total light transmittance and the total light reflectance", respectively.

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

In the nonflammable sheet 1 of the present invention, if the film layer 4 is provided, the initial tear strength can be made higher. From the viewpoint of ensuring a 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 the C method (trapezoid method) of 7.16 of JIS R 3420: 2013, 75 mm × 150 mm test pieces were collected from a nonflammable sheet in the vertical and horizontal directions, respectively, and two trapezoidal parts including a right angle (Fig.) A tape for non-slip (trade name 600S manufactured by Sekisui Chemical Co., Ltd.) is attached to each of the trapezoidal parts A exemplified in 5), and a constant-speed load type tensile tester (stock) is attached without making a cut. Performed using the company Orientec product name RTC-1310A), measure the maximum load, and average the maximum load in the vertical direction and the maximum load in the horizontal direction (= (maximum load in the vertical direction (N) + maximum load in the horizontal direction). Let (N)) / 2) be the initial tear strength (N).

Since the non-combustible sheet 1 of the present invention contains the glass fiber cloth 2, it can have a property of being hard to burn (non-combustible). The nonflammability of the nonflammable sheet 1 of the present invention is 4.10.2 in the "Fireproof Performance Test / Evaluation Business Method Manual" (revised on March 1, 2014) of the Building Materials Testing Center. In the heat generation test in which the surface of the sheet is irradiated with radiant heat of 50 kW / m ² from the radiant electric heater, which is measured according to the heat generation test / evaluation method, the maximum heat generation rate after the start of heating is 200 kW / m continuously for 10 seconds or more. It is preferable that the total calorific value does not exceed ² and is 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 producing the nonflammable sheet 1 of the present invention is not particularly limited, and examples thereof include the following production methods. First, the above-mentioned glass fiber cloth 2 and the 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) to be a film layer 4, a glass fiber cloth 2 is placed on 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, pressure is applied from the surfaces of the two film layers 4, and the glass fiber cloth 2 is further impregnated with the cured resin composition to further impregnate the cured resin composition. Is hardened by heating or light irradiation, the glass fiber cloth 2 is impregnated with the cured resin composition layer 3, and the film layer 4 is laminated on the cured resin composition layer 3 to obtain a nonflammable sheet 1 (film layer 4 /). A nonflammable sheet 1) laminated in the order of the resin composition layer 3 and the film layer 4 contained in the glass fiber cloth 2 in a state of being impregnated can be obtained. If the nonflammable sheet 1 does not contain the film layer 4, a protective film 5 that is peeled off at the time of use may be used instead of the film layer 4, and the protective film 5 may be peeled off.

Further, as a method for producing the nonflammable sheet 1 of the present invention, the following production method can also be mentioned. First, the above-mentioned glass fiber cloth 2 and the thermoplastic resin composition constituting the resin composition layer 3 are prepared. Next, two films to be used as the film layer 4 are prepared, the thermoplastic resin composition is applied to the film, the glass fiber cloth 2 is placed on the thermoplastic resin composition, and the thermoplastic resin is placed on the glass fiber 2. The composition is impregnated, and another film to be used as the film layer 4 is placed on the glass fiber cloth 2, and pressure is applied from the surfaces of the two film layers 4 to further apply the cured resin composition to the glass fiber cloth 2. By impregnating, drying and solidifying the thermoplastic resin composition, the glass fiber cloth 2 is impregnated with the thermoplastic resin composition layer 3, and the film layer 4 is laminated on the thermoplastic resin composition layer 3, which is nonflammable. A sex sheet 1 (a nonflammable sheet 1 laminated in the order of the resin composition layer 3 / the film layer 4 contained in the film layer 4 / the glass fiber cloth 2 in the impregnated state) is obtained.

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

Further, as a method for producing a nonflammable sheet of the present invention, the glass fiber cloth, the photocurable resin composition layer contained in the glass fiber cloth in a state of being impregnated, and the photocurable resin composition layer are laminated. A step of preparing at least two light-transmitting thermoplastic resin films on which a light-transmitting protective film is laminated, which is a method for manufacturing a nonflammable sheet including a film layer, and a step A in which a glass fiber cloth is immersed. The uncured photocurable resin composition was sandwiched between the two thermoplastic resin films obtained in the step A so that the light transmissive protective film was on the outside, and the uncured resin composition was sandwiched between the two thermoplastic resin films. It can include a step B of irradiating the photocurable resin composition with light to cure the uncured photocurable resin composition.

(Use of the nonflammable sheet of the present invention)
Applications of the nonflammable sheet of the present invention include a smoke-proof hanging wall that is hung and attached to the ceiling of a building. Examples of the smoke-proof hanging wall include known ones using a nonflammable sheet of glass cloth and resin. For example, a mounting rail arranged on the ceiling surface of a building and an upper end portion held by the mounting rail. A flexible non-combustible sheet suspended from the floor and a pair of end mullion arranged on both sides of the non-combustible sheet, and the non-combustible sheet and the end mullion are provided. Examples thereof include smoke-proof hanging walls that are freely joined together. Above all, in the non-combustible sheet of the present invention, when the outermost layer is a layer made of a thermoplastic resin when the smoke-proof hanging wall is used, high-frequency welding processing is possible, so that the tension-type smoke-proof hanging wall can be used. It can be suitably used for use. In the present invention, the tension type smoke-proof hanging wall is a hanging wall in which a non-combustible sheet is stretched between two pairs of mullion. There is a smoke-proof hanging wall on the lower side of the building. In addition, since it can be a substitute for glass when it is made more transparent, it can be used in other applications where glass is used, such as partitions, partitions, smoke-proof sheets, and smoke-proof curtains (for example, those used in factories, etc.). ) Etc. can also be applied. Further, the nonflammable sheet 1 of the present invention becomes even more flexible 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 . Since it is excellent, it is easy to make it into a roll product. Examples of the length in the longitudinal direction of the roll product include, for example, 5 to 300 m.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

The resin composition constituting the resin composition layer 3 to be impregnated with the above glass fiber cloth 2 has the composition shown in Table 1 and is made of acrylic syrup (trade name "Acrysilup XD-8005" manufactured by Ryokou Co., Ltd.). (Refractive index 1.550) and "Acrylic wrap XD-8006" (refractive index 1.570) mixed so as to have a mass ratio of 1: 1), vinyl ester resin (manufactured by Nippon Yupica Co., Ltd.), styrene Monomer (manufactured by Nippon Yupica Co., Ltd.), bifunctional (meth) acrylate, photopolymerization initiator (Omnirad 184 manufactured by IGM) or surfactant as antistatic agent ("Electro Stripper ME-2" manufactured by Kao Co., Ltd., solid A mixture of 50% by mass) was used. As the bifunctional (meth) acrylate as the curing agent, NPGDA (neopentyl glycol diacrylate, molecular weight 212, (manufactured by Japan U-Pica Co., Ltd.)) shown in Table 1 was used. The amount of the photopolymerization initiator was 3 parts by mass with respect to 100 parts by mass of acrylic syrup or 100 parts by mass of the total of vinyl ester resin, styrene monomer and bifunctional (meth) acrylate. The film layer 4 is a commercially available biaxially stretched polyester film manufactured by Toyobo Co., Ltd. (trade name "Cosmo Shine (registered trademark) A4300", thickness 50 μm, mass 70 g / m ² , total light transmittance (JIS K 7105: 1981). ) 93%, Haze (JIS K 7105: 1981) 0.9%), As a vinyl chloride resin, a commercially available vinyl chloride resin film (manufactured by Okamoto Co., Ltd., general-purpose PVC # 320, thickness 100)
μm, mass 120 g / m ² ) was used. Protective film that can be peeled off during use 5
The polypropylene film (thickness 40 μm, mass 36 g / m ² ) is coated with an acrylic acid ester adhesive that can be peelably adhered to the film layer 4 on one surface, and a PET film (thickness). 50 μm, total light transmittance 93%, haze 4%) was used.

<Example 1>
(Manufacturing of glass fiber cloth 2)
Weaving with an air jet weaving machine using the trade name "ECC1200 1/0 1.0Z" (average filament diameter 4.5 μm, average number of filaments 100, twist number 1.0Z) manufactured by Unitica Fiberglass Co., Ltd. as warp and weft. , A plain weave glass fiber woven fabric having a warp density of 90 threads / 25 mm and a warp density of 90 threads / 25 mm was obtained. Then, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber woven 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 Co., Ltd.) 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 woven fabric was subjected to a widening treatment once while the tension of the glass fiber woven fabric was set to 100 N / m in the warp direction by water flow processing at a pressure of 1.5 MPa to obtain a glass fiber woven fabric to be used as the glass fiber cloth 2. The obtained glass fiber woven fabric 2 had a warp density of 90 threads / 25 mm, a weft density of 90 threads / 25 mm, a thickness of 27 μm, a mass of 30 g / m ² , and a refractive index of 1.561.

(Laminating the antistatic layer 6 on the film layer 4)
The antistatic layer 6 was laminated on one surface of Cosmo Shine (registered trademark) A4300 as the film layer 4. The antistatic layer 6 has tin oxide fine particles (average particle diameter of 20 nm) in the polyester resin as the fixing resin, and the mass ratio of the fixing resin to the tin oxide fine particles (fixed resin: tin oxide fine particles) is 75:25. In this way, the mixed and dispersed antistatic agent was applied and dried on one surface of Cosmoshine (registered trademark) A4300 as the film layer 4. The mass of the antistatic layer 6 provided was 0.5 g / m ² , and the thickness was 0.4 μm.

(Laminating the peelable protective film 5 that is peeled off during use on the film layer 4 (antistatic layer 6 side))
The peelable protective film 5 to be peeled off at the time of use described above on the antistatic layer 6 of Cosmoshine (registered trademark) A4300 having the antistatic layer 6 provided on one surface as the film layer 4. A polypropylene film to which an acrylic ester-based adhesive is applied is laminated on one surface of the polypropylene film so that the adhesive is on the antistatic layer 6 side, dried, and peeled off during use. A laminated body A having a laminated structure of Cosmo Shine (registered trademark) A4300 having a protective film 5 / acrylic acid ester adhesive / antistatic layer 6 / film layer 4 was obtained. Two layers A were prepared.

(Manufacturing of nonflammable sheets)
Table 1 shows the resin composition layer 3 on the Cosmo Shine (registered trademark) A4300 side (that is, the side opposite to the peelable protective film 5 that can be peeled off during use) of the obtained laminate A1. The described cured resin composition was applied. Next, the obtained glass fiber cloth 2 is placed on the cured resin composition to be the resin composition 3 and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths 2 with the cured resin composition. I let you. Next, of the obtained laminate A, the other is the Cosmoshine (registered trademark) A4300 surface side of the laminate A (that is, the side opposite to the peelable protective film 5 that is peeled off during use). Was placed on the cured resin composition 3 side and pressed from above the laminate A with a roller so that the mass of the cured resin composition layer 3 was 90 g / m ² . After that, while the peelable protective film 5 that is peeled off during use is laminated, the cured resin composition as the resin composition layer 3 is irradiated with light (light) using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation). Irradiation conditions: Cumulative light amount 200 mJ / cm ² ) to cure the cured resin composition to form the cured resin composition layer 3, and the laminated structure exemplified in FIG. 4 (the peelable protective film 5 peeled off during use). / Acrylic acid ester adhesive that can be peeled off together with the protective film 5 / Antistatic layer 6 / Film layer 4 (Cosmo Shine (registered trademark) A4300) / Resin composition layer 3 contained in the glass fiber cloth 2 in a state of being impregnated / Film layer 4 (Cosmo Shine (registered trademark) A4300) / Antistatic layer 6 / Acrylic acid ester-based adhesive that can be peeled off together with the protective film 5 / Protective film 5 that can be peeled off during use) Got In the obtained nonflammable sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with the cured resin composition layer 3 (cured product of the resin composition), and the layers on both sides of the glass fiber cloth are impregnated. The cured resin composition layer 3 was formed.

<Example 2>
(Manufacturing of glass fiber cloth 2)
Weaving with an air jet weaving machine using the trade name "ECBC3000 1/0 0.5Z" (average filament diameter 4 μm, average number of filaments 50, twist number 0.5Z) manufactured by Unitika Glass Fiber Co., Ltd. as warp and weft, warp A plain weave glass fiber woven 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 woven 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 Co., Ltd.) 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 woven fabric was subjected to the widening treatment twice while the tension of the glass fiber woven fabric was set to 100 N / m in the warp direction by the water flow processing at a pressure of 1.5 MPa to obtain the glass fiber woven fabric to be the glass fiber cloth 2. The obtained glass fiber woven fabric 2 had a warp density of 95 threads / 25 mm, a weft density of 95 threads / 25 mm, a thickness of 13 μm, a mass of 12 g / m ² , and a refractive index of 1.561.

(Laminating the antistatic layer 6 on the film layer 4)
The antistatic layer 6 was laminated on one surface of Cosmo Shine (registered trademark) A4300 as the film layer 4. The antistatic layer 6 has tin oxide fine particles (average particle diameter of 20 nm) in the polyester resin as the fixing resin, and the mass ratio of the fixing resin to the tin oxide fine particles (fixed resin: tin oxide fine particles) is 75:25. In this way, the mixed and dispersed antistatic agent was applied and dried on one surface of Cosmoshine (registered trademark) A4300 as the film layer 4. The mass of the antistatic layer 6 provided was 0.5 g / m ² , and the thickness was 0.4 μm.

(Laminating the peelable protective film 5 that is peeled off during use on the film layer 4 (antistatic layer 6 side))
The peelable protective film 5 to be peeled off at the time of use described above on the antistatic layer 6 of Cosmoshine (registered trademark) A4300 having the antistatic layer 6 provided on one surface as the film layer 4. A polypropylene film to which an acrylic ester-based adhesive is applied is laminated on one surface of the polypropylene film so that the adhesive is on the antistatic layer 6 side, dried, and peeled off during use. A laminated body A having a laminated structure of Cosmo Shine (registered trademark) A4300 having a protective film 5 / acrylic acid ester adhesive / antistatic layer 6 / film layer 4 was obtained. Two layers A were prepared.

(Manufacturing of nonflammable sheets)
Table 1 shows the resin composition layer 3 on the Cosmo Shine (registered trademark) A4300 side (that is, the side opposite to the peelable protective film 5 that can be peeled off during use) of the obtained laminate A1. The described cured resin composition was applied. Next, the obtained glass fiber cloth 2 is placed on the cured resin composition to be the resin composition 3 and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths 2 with the cured resin composition. I let you. Next, of the obtained laminate A, the other is the Cosmoshine (registered trademark) A4300 surface side of the laminate A (that is, the side opposite to the peelable protective film 5 that is peeled off during use). Was placed on the cured resin composition 3 side and pressed from above the laminate A with a roller so that the mass of the cured resin composition layer 3 was 90 g / m ² . After that, while the peelable protective film 5 that is peeled off during use is laminated, the cured resin composition as the resin composition layer 3 is irradiated with light (light) using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation). Irradiation conditions: Cumulative light amount 200 mJ / cm ² ) to cure the cured resin composition to form the cured resin composition layer 3, and the laminated structure exemplified in FIG. 4 (the peelable protective film 5 peeled off during use). / Acrylic acid ester adhesive that can be peeled off together with the protective film 5 / Antistatic layer 6 / Film layer 4 (Cosmo Shine (registered trademark) A4300) / Resin composition layer 3 contained in the glass fiber cloth 2 in a state of being impregnated / Film layer 4 (Cosmo Shine (registered trademark) A4300) / Antistatic layer 6 / Acrylic acid ester-based adhesive that can be peeled off together with the protective film 5 / Protective film 5 that can be peeled off during use) Got In the obtained nonflammable sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with the cured resin composition layer 3 (cured product of the resin composition), and the layers on both sides of the glass fiber cloth are impregnated. The cured resin composition layer 3 was formed.

<Example 3>
(Manufacturing of glass fiber cloth 2)
Weaving with an air jet weaving machine using the trade name "ECBC3000 1/0 0.5Z" (average filament diameter 4 μm, average number of filaments 50, twist number 0.5Z) manufactured by Unitika Glass Fiber Co., Ltd. as warp and weft, warp A plain weave glass fiber woven 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 woven 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 Co., Ltd.) 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 woven fabric was subjected to the widening treatment twice while the tension of the glass fiber woven fabric was set to 100 N / m in the warp direction by the water flow processing at a pressure of 1.5 MPa to obtain the glass fiber woven fabric to be the glass fiber cloth 2. The obtained glass fiber woven fabric 2 had a warp density of 95 threads / 25 mm, a weft density of 95 threads / 25 mm, a thickness of 13 μm, a mass of 12 g / m ² , and a refractive index of 1.561.

(Laminating the antistatic layer 6 on the film layer 4)
The antistatic layer 6 was laminated on one surface of Cosmo Shine (registered trademark) A4300 as the film layer 4. The antistatic layer 6 has tin oxide fine particles (average particle diameter of 20 nm) in the polyester resin as the fixing resin, and the mass ratio of the fixing resin to the tin oxide fine particles (fixed resin: tin oxide fine particles) is 75:25. In this way, the mixed and dispersed antistatic agent was applied and dried on one surface of Cosmoshine (registered trademark) A4300 as the film layer 4. The mass of the antistatic layer 6 provided was 0.5 g / m ² , and the thickness was 0.4 μm.

(Laminating the peelable protective film 5 that is peeled off during use on the film layer 4 (antistatic layer 6 side))
The peelable protective film 5 to be peeled off at the time of use described above on the antistatic layer 6 of Cosmoshine (registered trademark) A4300 having the antistatic layer 6 provided on one surface as the film layer 4. A polypropylene film to which an acrylic ester-based adhesive is applied is laminated on one surface of the polypropylene film so that the adhesive is on the antistatic layer 6 side, dried, and peeled off during use. A laminated body A having a laminated structure of Cosmo Shine (registered trademark) A4300 having a protective film 5 / acrylic acid ester adhesive / antistatic layer 6 / film layer 4 was obtained. Two layers A were prepared.

(Manufacturing of nonflammable sheets)
Table 1 shows the resin composition layer 3 on the Cosmo Shine (registered trademark) A4300 side (that is, the side opposite to the peelable protective film 5 that can be peeled off during use) of the obtained laminate A1. The described cured resin composition was applied. Next, the obtained glass fiber cloth 2 is placed on the cured resin composition to be the resin composition 3 and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths 2 with the cured resin composition. I let you. Next, of the obtained laminate A, the other is the Cosmoshine (registered trademark) A4300 surface side of the laminate A (that is, the side opposite to the peelable protective film 5 that is peeled off during use). Was placed on the cured resin composition 3 side and pressed from above the laminate A with a roller so that the mass of the cured resin composition layer 3 was 40 g / m ² . After that, while the peelable protective film 5 that is peeled off during use is laminated, the cured resin composition as the resin composition layer 3 is irradiated with light (light) using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation). Irradiation conditions: Cumulative light amount 200 mJ / cm ² ) to cure the cured resin composition to form the cured resin composition layer 3, and the laminated structure exemplified in FIG. 4 (the peelable protective film 5 peeled off during use). / Acrylic acid ester adhesive that can be peeled off together with the protective film 5 / Antistatic layer 6 / Film layer 4 (Cosmo Shine (registered trademark) A4300) / Resin composition layer 3 contained in the glass fiber cloth 2 in a state of being impregnated / Film layer 4 (Cosmo Shine (registered trademark) A4300) / Antistatic layer 6 / Acrylic acid ester-based adhesive that can be peeled off together with the protective film 5 / Protective film 5 that can be peeled off during use) Got In the obtained nonflammable sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with the cured resin composition layer 3 (cured product of the resin composition), and the layers on both sides of the glass fiber cloth are impregnated. The cured resin composition layer 3 was formed.

<Example 4>
(Manufacturing of glass fiber cloth 2)
Weaving with an air jet weaving machine using the trade name "ECC1200 1/0 1.0Z" (average filament diameter 4.5 μm, average number of filaments 100, twist number 1.0Z) manufactured by Unitika Glass Fiber Co., Ltd. as warp and weft. , A plain weave glass fiber woven fabric having a warp density of 90 threads / 25 mm and a warp density of 90 threads / 25 mm was obtained. Then, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber woven 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 Co., Ltd.) 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 woven fabric was subjected to a widening treatment once while the tension of the glass fiber woven fabric was set to 100 N / m in the warp direction by water flow processing at a pressure of 1.5 MPa to obtain a glass fiber woven fabric to be used as the glass fiber cloth 2. The obtained glass fiber woven fabric 2 had a warp density of 90 threads / 25 mm, a weft density of 90 threads / 25 mm, a thickness of 27 μm, a mass of 30 g / m ² , and a refractive index of 1.561.

(Manufacturing of nonflammable sheets)
The cured resin composition used as the resin composition layer 3 shown in Table 1 was applied onto a PET film having a thickness of 50 μm, which is a peelable protective film 5 that is peeled off during use. Next, the obtained glass fiber cloth 2 was placed on the resin composition and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths 2 with the cured resin composition. Next, another PET film of the same product as the PET film used as the peelable protective film 5 to be peeled off during use is placed from above, and the weight of the cured resin composition layer 3 is 90 g from above the PET film with a roller. The pressure was increased to / m ² . After that, a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation) was used for the resin composition to be the resin composition layer 3 while the PET film to be the peelable protective film 5 to be peeled off at the time of use was laminated. The resin composition is cured by light irradiation (light irradiation condition: integrated light amount 200 mJ / cm ² ) to form a cured resin composition layer 3, and a peelable protective film 5 / glass fiber cloth 2 that is peeled off during use. A nonflammable sheet having a laminated structure of a resin composition layer 3 contained in a state of being impregnated with the resin / a protective film 5 that can be peeled off at the time of use was obtained. In the obtained nonflammable sheet, the gaps between the glass fibers of the glass fiber cloth 2 are impregnated with the cured resin composition layer 3 (cured product of the resin composition) on both sides of the glass fiber cloth layer. The cured resin composition layer 3 was formed.

<Example 5>
(Manufacturing of glass fiber cloth 2)
Weaving with an air jet weaving machine using the trade name "ECC1200 1/0 1.0Z" (average filament diameter 4.5 μm, average number of filaments 100, twist number 1.0Z) manufactured by Unitica Fiberglass Co., Ltd. as warp and weft. , A plain weave glass fiber woven fabric having a warp density of 90 threads / 25 mm and a warp density of 90 threads / 25 mm was obtained. Then, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber woven 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 Co., Ltd.) 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 woven fabric was subjected to a widening treatment once while the tension of the glass fiber woven fabric was set to 100 N / m in the warp direction by water flow processing at a pressure of 1.5 MPa to obtain a glass fiber woven fabric to be used as the glass fiber cloth 2. The obtained glass fiber woven fabric 2 had a warp density of 90 threads / 25 mm, a weft density of 90 threads / 25 mm, a thickness of 27 μm, a mass of 30 g / m ² , and a refractive index of 1.561.

(Manufacturing of nonflammable sheets)
The cured resin composition used as the resin composition layer 3 shown in Table 1 was applied onto a PET film having a thickness of 50 μm, which is a peelable protective film 5 that is peeled off during use. Next, the obtained glass fiber cloth 2 was placed on the resin composition and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths 2 with the cured resin composition. Next, another PET film of the same product as the PET film used as the peelable protective film 5 to be peeled off during use is placed from above, and the weight of the cured resin composition layer 3 is 90 g from above the PET film with a roller. The pressure was increased to / m ² . After that, a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation) was used for the resin composition to be the resin composition layer 3 while the PET film to be the peelable protective film 5 to be peeled off at the time of use was laminated. The resin composition is cured by light irradiation (light irradiation condition: integrated light amount 200 mJ / cm ² ) to form a cured resin composition layer 3, and a peelable protective film 5 / glass fiber cloth 2 that is peeled off during use. A nonflammable sheet having a laminated structure of a resin composition layer 3 contained in a state of being impregnated with the resin / a protective film 5 that can be peeled off at the time of use was obtained. In the obtained nonflammable sheet, the gaps between the glass fibers of the glass fiber cloth 2 are impregnated with the cured resin composition layer 3 (cured product of the resin composition) on both sides of the glass fiber cloth layer. The cured resin composition layer 3 was formed.

<Comparative Example 1>
In Example 1, the antistatic layer 6 was not laminated except that the antistatic layer 6 was not laminated, and the same procedure as in Example 1 was carried out. Agent / film layer 4 (Cosmo Shine (registered trademark) A4300) / resin composition layer 3 (Cosmo Shine (registered trademark) A4300) / protective film 5 contained in the glass fiber cloth 2 in a state of being impregnated. A nonflammable sheet of Comparative Example 1 having a laminated structure of a peelable acrylic acid ester adhesive / a peelable protective film 5 that can be peeled off at the time of use was obtained.

<Comparative Example 2>
(Manufacturing of glass fiber cloth 2)
Weaving with an air jet weaving machine using the trade name "ECC1200 1/0 1.0Z" (average filament diameter 4.5 μm, average number of filaments 100, twist number 1.0Z) manufactured by Unitica Fiberglass Co., Ltd. as warp and weft. , A plain weave glass fiber woven fabric having a warp density of 90 threads / 25 mm and a warp density of 90 threads / 25 mm was obtained. Then, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber woven 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 Co., Ltd.) 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 woven fabric was subjected to a widening treatment once while the tension of the glass fiber woven fabric was set to 100 N / m in the warp direction by water flow processing at a pressure of 1.5 MPa to obtain a glass fiber woven fabric to be used as the glass fiber cloth 2. The obtained glass fiber woven fabric 2 had a warp density of 90 threads / 25 mm, a weft density of 90 threads / 25 mm, a thickness of 27 μm, a mass of 30 g / m ² , and a refractive index of 1.561.

(Lamination of removable protective film 5 that is peeled off when used on the film layer 4)
The above-mentioned Cosmoshine (registered trademark) A4300 as the film layer 4 is provided with an acrylic acid ester adhesive on one surface of the above-mentioned polypropylene film as the peelable protective film 5 which is peeled off during use. Is laminated so that the pressure-sensitive adhesive is on the Cosmo Shine (registered trademark) A4300 side, dried, and used as a peelable protective film 5 / acrylic acid ester-based pressure-sensitive adhesive / film layer 4. A laminated body B having a laminated structure of Shine (registered trademark) A4300 was obtained. Two pieces of the laminated body B were prepared.

(Manufacturing of nonflammable sheets)
Table 1 shows the resin composition layer 3 on the Cosmo Shine (registered trademark) A4300 side (that is, the side opposite to the peelable protective film 5 that can be peeled off during use) of the obtained laminate B1. The described cured resin composition was applied. Next, the obtained glass fiber cloth 2 is placed on the cured resin composition to be used as the resin composition layer 3, and the glass fiber cloth 2 is allowed to stand for 1 minute to allow the cured resin composition to be placed in the gaps between the glass fiber cloths 2. Impregnated. Next, of the obtained laminate B, the other is the Cosmoshine (registered trademark) A4300 surface side of the laminate B (that is, the side opposite to the peelable protective film 5 that is peeled off during use). Was placed on the cured resin composition 3 side and pressed from above the laminate B with a roller so that the mass of the cured resin composition layer 3 was 90 g / m ² . After that, while the peelable protective film 5 that is peeled off during use is laminated, the cured resin composition as the resin composition layer 3 is irradiated with light (light) using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation). Irradiation conditions: Cumulative light amount 200 mJ / cm ² ) to cure the cured resin composition to form a cured resin composition layer 3, which can be peeled off together with the peelable protective film 5 / protective film 5 which is peeled off during use. Acrylic acid ester-based pressure-sensitive adhesive / film layer 4 (Cosmo Shine (registered trademark) A4300) / resin composition layer 3 / film layer 4 (Cosmo Shine (registered trademark) A4300) contained in a state of being impregnated in the glass fiber cloth 2. / A nonflammable sheet of Comparative Example 2 having a laminated structure of an acrylic acid ester-based pressure-sensitive adhesive that can be peeled off together with the protective film 5 / a protective film 5 that can be peeled off during use was obtained. In the obtained nonflammable sheet, the gaps between the glass fibers of the glass fiber cloth 2 are impregnated with the cured resin composition layer 3 (cured product of the resin composition) on both sides of the glass fiber cloth layer. The cured resin composition layer 3 was formed.

<Comparative Example 3>
(Manufacturing of glass fiber cloth 2)
Weaving with an air jet weaving machine using the trade name "ECBC3000 1/0 0.5Z" (average filament diameter 4 μm, average number of filaments 50, twist number 0.5Z) manufactured by Unitika Glass Fiber Co., Ltd. as warp and weft, warp A plain weave glass fiber woven 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 woven 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 Co., Ltd.) 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 woven fabric was subjected to the widening treatment twice while the tension of the glass fiber woven fabric was set to 100 N / m in the warp direction by the water flow processing at a pressure of 1.5 MPa to obtain the glass fiber woven fabric to be the glass fiber cloth 2. The obtained glass fiber woven fabric 2 had a warp density of 95 threads / 25 mm, a weft density of 95 threads / 25 mm, a thickness of 13 μm, a mass of 12 g / m ² , and a refractive index of 1.561.

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

(Manufacturing of nonflammable sheets)
The curing according to Table 1 in which the resin composition layer 3 is formed on the vinyl chloride resin film surface side (that is, the side opposite to the peelable protective film 5 that is peeled off during use) of the obtained laminate C1 sheet. A resin composition was applied. Next, the obtained glass fiber cloth 2 is placed on the cured resin composition to be the resin composition layer 3, allowed to stand for 1 minute, and the cured resin composition is placed in the gaps between the glass fiber cloths 2. Impregnated. Next, of the obtained laminate C, the other side of the laminate C is a cured resin on the vinyl chloride resin film surface side (that is, the side opposite to the peelable protective film 5 that is peeled off during use). The film was placed so as to be on the composition 3 side, and was pressed from above the laminate C with a roller so that the mass of the cured resin composition layer 3 was 40 g / m ² . After that, while the peelable protective film 5 that is peeled off during use is laminated, the cured resin composition is irradiated with light using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation) (light irradiation condition: integrated light amount 200 mJ / cm ² ) The cured resin composition is cured to form the cured resin composition layer 3, and the peelable protective film 5 / the protective film 5 and the peelable acrylic acid ester-based pressure-sensitive adhesive / Acrylic acid ester adhesive that can be peeled off together with the film layer 4 (vinyl chloride resin film) / resin composition layer 3 (vinyl chloride resin film) / protective film 5 impregnated in the glass fiber cloth 2. A nonflammable sheet of Comparative Example 3 having a laminated structure of a protective film 5 that can be peeled off at the time of agent / use was obtained. In the obtained nonflammable sheet, the gaps between the glass fibers of the glass fiber cloth 2 are impregnated with the cured resin composition layer 3 (cured product of the resin composition) on both sides of the layer of the glass fiber cloth 2. The cured resin composition layer 3 was formed on the surface.

<Comparative Example 4>
(Manufacturing of glass fiber cloth)
Weaving with an air jet weaving machine using the trade name "ECBC3000 1/0 0.5Z" (average filament diameter 4 μm, average number of filaments 50, twist number 0.5Z) manufactured by Unitika Glass Fiber Co., Ltd. as warp and weft, warp A plain weave glass fiber woven 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 woven 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 Co., Ltd.) 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 woven fabric was subjected to the widening treatment twice while the tension of the glass fiber woven fabric was set to 100 N / m in the warp direction by the water flow processing at a pressure of 1.5 MPa to obtain the glass fiber woven fabric to be the glass fiber cloth 2. The obtained glass fiber woven fabric 2 had a warp density of 95 threads / 25 mm, a weft density of 95 threads / 25 mm, a thickness of 13 μm, a mass of 12 g / m ² , and a refractive index of 1.561.

(Manufacturing of nonflammable sheets)
The cured resin composition used as the resin composition layer 3 shown in Table 1 was applied onto a PET film having a thickness of 50 μm, which is a peelable protective film 5 that is peeled off during use. Next, the obtained glass fiber cloth 2 was placed on the resin composition and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths 2 with the cured resin composition. Next, another PET film of the same product as the PET film used as the peelable protective film 5 to be peeled off during use is placed from above, and the weight of the cured resin composition layer 3 is 90 g from above the PET film with a roller. The pressure was increased to / m ² . After that, a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation) was used for the resin composition to be the resin composition layer 3 while the PET film to be the peelable protective film 5 to be peeled off at the time of use was laminated. The resin composition is cured by light irradiation (light irradiation condition: integrated light amount 200 mJ / cm ² ) to form a cured resin composition layer 3, and a peelable protective film 5 / glass fiber cloth 2 that is peeled off during use. A nonflammable sheet of Comparative Example 4 having a laminated structure of a resin composition layer 3 contained in a state of being impregnated with the resin / a protective film 5 that can be peeled off at the time of use was obtained. In the obtained nonflammable sheet, the gaps between the glass fibers of the glass fiber cloth 2 are impregnated with the cured resin composition layer 3 (cured product of the resin composition) on both sides of the layer of the glass fiber cloth 2. The cured resin composition layer 3 was formed on the surface.

In the examples and comparative examples, the weaving density of the glass fiber woven fabric is JIS R 3420.
Measured and calculated according to 2013 7.9. The thickness of the glass fiber woven fabric is JIS.
Measurements and calculations were made according to the R 3420 2013 7.10.1A method. The mass of the glass fiber woven fabric was measured and calculated according to JIS R 3420 2013 7.2. The refractive index of the cured resin composition layer 3 and the glass fiber woven fabric 2 was measured and calculated by the above-mentioned method. The Abbe numbers of the cured resin composition layer 3 and the glass fiber woven fabric 2 were measured and calculated by the above method. The following evaluation was performed after the nonflammable sheet was manufactured and left indoors for one week.

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

(Confirmation of the degree of dust adhesion when used as a smoke-proof hanging wall for a long period of time)
With respect to the obtained nonflammable sheet, the peelable protective film 5 that is peeled off during use is peeled off (if the protective film 5 and the peelable acrylic acid ester adhesive are contained, the peelable adhesive is peeled off) as described above. A specific heat cycle test was performed, and the nonflammable sheet was cut into 20 cm squares, and 50 pieces of paper cut into 1 mm squares were sprayed in a 15 cm square on a test table and allowed to stand on it. After that, the evaluation was made based on the number of pieces of paper stuck to the sheet when the sheet was gently pulled upward. The paper used was 0.1 mm thick and 70 g / m ² in mass.
Judgment was made according to the following criteria, and a score of 3 or higher was regarded as a pass.
3 points ... 2 points where the pieces of paper did not stick at all ... 1 to 9 pieces of paper that stuck 1 point ... 10 or more pieces of paper that stuck

(Initial tear strength)
It was done by the method described above.

The evaluation results 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 the adhesion of dust when used as a smoke-proof hanging wall for a long period of time, for example. It was possible. On the other hand, in Comparative Examples 1 to 4, since the surface resistivity exceeded 1 × 10 ¹¹ Ω, it was not possible to reduce the adhesion of dust when used as a smoke-proof hanging wall for a long period of time. there were.

Comparing Examples 4 and 5, in Example 4, since the mass (g / m ² ) of the surfactant contained in the nonflammable sheet was 1 to 1.5 g / m ² , it was prevented. It was able to obtain excellent transparency while ensuring the function of reducing the adhesion of dust when used as a smoke wall for a long period of time. Further, in Examples 1 to 3, since the antistatic layer 6 containing a metal or a metal oxide is provided so as to be a surface layer when used as a smoke-proof hanging wall, the surface resistivity is lower 1 × 10 ¹⁰ Ω. As described below, the adhesion of dust when used as a smoke-proof hanging wall for a long period of time is further reduced, the change in surface resistivity is further reduced before and after a specific heat cycle test, and more excellent transparency is obtained. It was a thing. Further, after the specific heat cycle test, the stickiness was considerably observed in Examples 5 and Comparative Example 5, while the stickiness was hardly observed in Examples 1 to 3. Further, in Examples 1 to 3, the difference in surface resistivity before and after the specific heat cycle test (= surface resistivity after the specific heat cycle test (Ω) -surface resistivity before the specific heat cycle test (Ω)). ) Was 5.0 × ¹⁰⁹ Ω or less, and it was confirmed that it had stable antistatic performance. Further, since Examples 1 to 3 contained the film layer 4, the initial tear strength was also excellent.

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

Claims (6)

A nonflammable sheet comprising a glass fiber woven fabric and a curable resin composition layer contained in the glass fiber woven fabric in a state of being impregnated.
An antistatic layer containing a metal or a metal oxide is provided so as to be a surface layer when the nonflammable sheet is used.
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 nonflammable sheet was cut into a size of 100 mm × 100 mm and used as a sample, and the sample was initially set to a temperature of 23 ° C. and a relative humidity of 50% RH. -2KPH), and the following (1) to (5) are regarded as one cycle, and a total of 10 cycles are performed.
(1) The transition is performed from a temperature of 23 ° C. and a relative humidity of 50 RH to a temperature of 60 ° C. and a relative humidity of 50% RH with a transition time of 14 minutes.
(2) Hold at the above temperature of 60 ° C. and a relative humidity of 50% RH for 8 hours.
(3) The transition time is 45 minutes from the temperature of 60 ° C. and relative humidity of 50% RH to the temperature of 20 ° C. and relative humidity of 50% RH.
(4) Hold at the above temperature of 20 ° C. and a relative humidity of 50% RH for 8 hours.
(5) The transition is performed from the temperature of 20 ° C. and a relative humidity of 50% RH to a temperature of 23 ° C. and a relative humidity of 50% RH with a transition time of 1 minute. A nonflammable sheet comprising a glass fiber woven fabric and a curable resin composition layer contained in the glass fiber woven fabric in a state of being impregnated.
As a layer to be a surface layer when the nonflammable sheet is used, the curable resin composition layer or a film layer containing a thermoplastic resin other than a polyvinyl chloride resin is included.
Before and after the following heat cycle test of the nonflammable sheet, the surface resistivity was 1 × 10. ¹¹ Non-combustible sheet with Ω or less.
<Heat cycle test conditions>
The nonflammable sheet was cut into a size of 100 mm × 100 mm and used as a sample, and the sample was initially set to a temperature of 23 ° C. and a relative humidity of 50% RH. -2KPH), and the following (1) to (5) are regarded as one cycle, and a total of 10 cycles are performed.
(1) The transition is performed from a temperature of 23 ° C. and a relative humidity of 50 RH to a temperature of 60 ° C. and a relative humidity of 50% RH with a transition time of 14 minutes.
(2) Hold at the above temperature of 60 ° C. and a relative humidity of 50% RH for 8 hours.
(3) The transition time is 45 minutes from the temperature of 60 ° C. and relative humidity of 50% RH to the temperature of 20 ° C. and relative humidity of 50% RH.
(4) Hold at the above temperature of 20 ° C. and a relative humidity of 50% RH for 8 hours.
(5) The transition is performed from the temperature of 20 ° C. and a relative humidity of 50% RH to a temperature of 23 ° C. and a relative humidity of 50% RH with a transition time of 1 minute. A surfactant is contained in the layer that becomes the surface layer when the nonflammable sheet is used, and the surface layer is contained.
The nonflammable sheet according to claim 2 , wherein the mass (g / m ² ) of the surfactant in the nonflammable sheet is 0.5 to 2.0 g / m ² . The nonflammable sheet according to any one of claims 1 to 3 , wherein the total light transmittance is 90% or more and the haze is 20% or less. The nonflammable sheet according to any one of claims 1 to 4 , which is for a smoke-proof hanging wall. A smoke-proof hanging wall comprising the nonflammable sheet according to any one of claims 1 to 5 .

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