JP6959647B2 - A transparent sheet, a smoke-proof hanging wall containing the transparent sheet, and a method for manufacturing the transparent sheet. - Google Patents

Description

The present invention relates to a transparent sheet, particularly a transparent sheet suitable for a smoke-proof hanging wall and the like, a smoke-proof hanging wall using the transparent sheet, and a method for manufacturing the transparent sheet.

The Building Standards Law and the Building Standards Law Enforcement Ordinance stipulate that smoke exhaust equipment should be installed to prevent the flow of smoke, toxic gas, etc. generated during a building fire and to facilitate evacuation and fire extinguishing activities. 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, transparent plate glass, a transparent 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 by the smoke-proof hanging wall or the appearance is not spoiled. The transparent resin composite of glass fiber and resin has an advantage that it is hard to break as compared with transparent plate 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.

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

However, for example, a transparent nonflammable sheet as disclosed in Patent Document 1 has a problem that although it is excellent in nonflammability, it has a high haze and insufficient transparency.

The present inventors have investigated the cause of insufficient transparency of the transparent nonflammable sheet. Then, the present inventors, for example, the transparent nonflammable sheet specifically disclosed as an example in Patent Document 1 is a relatively thick glass fiber woven fabric having a thickness of about 100 μm in order to make it excellent in nonflammability. It was found that the transparency is insufficient due to the increase in refraction and reflection of the incident light at the interface between the glass fiber and the cured resin.

Therefore, the present inventors have tried to improve the transparency by making the glass fiber woven fabric of the transparent nonflammable sheet disclosed in Patent Document 1 thinner, for example, 30 μm or less. However, it has been found that when the thickness of the glass fiber woven fabric of the transparent nonflammable sheet disclosed in Patent Document 1 is reduced, there is a problem that the tear strength, particularly the initial tear strength, tends to be inferior.

On the other hand, according to the transparent non-combustible sheet disclosed in Patent Document 2, since the reinforcing layer is integrally formed on at least one side, the tear strength of the entire transparent non-combustible sheet can be maintained high. Then, it is disclosed that, for example, a net body made of glass fiber, a vinyl chloride resin film, or the like is used alone or in combination as the reinforcing layer. However, when a net made of glass fiber is used as the reinforcing layer, there is a problem that the haze becomes high and high transparency cannot be obtained even immediately after production. Further, when a vinyl chloride resin film is used as a reinforcing layer, there are few problems in a normal environment, but for example, when it is used as a smoke-proof hanging wall in a high-temperature and high-humidity environment for a long period of time, transparency may not be maintained. There was a problem. That is, in the conventional technique of a transparent composite of glass fiber and resin, the transparency and the initial tear strength immediately after production and after long-term use in a high temperature and high humidity environment should be improved. On the other hand, there is a trade-off relationship in which the performance of the other deteriorates.

Under such circumstances, in the transparent resin composite of glass fiber and resin, when the glass fiber cloth is made thin, the initial tear strength is improved, and immediately after production and in a high temperature and high humidity environment. The main purpose is to provide a transparent sheet that can easily improve the transparency after long-term use.

The present inventors have conducted diligent studies to solve the above problems. As a result, in the transparent nonflammable sheet disclosed in Patent Document 2, the transparency can be maintained when the vinyl chloride resin film is used as a reinforcing layer and used as a smoke-proof hanging wall in a high-temperature and high-humidity environment for a long period of time. It was found that the cause of the inability to do so was the bleed-out of the plasticizer contained in the vinyl chloride resin film.

That is, the vinyl chloride resin film contains a large amount of plasticizer, and when it is laminated on the cured resin composition layer, it is used as a smoke-proof hanging wall in a high-temperature and high-humidity environment for a long period of time. It was found that the bleed-out may occur at the interface between the vinyl chloride resin film and the cured resin composition layer, and the transparency may not be maintained.

As a result of repeated studies by the present inventors, a plasticizer is not required as a layer to be laminated on the cured resin composition layer while improving the transparency immediately after production by making the glass fiber cloth having a thickness of 8 to 30 μm. By using a thermoplastic resin layer other than a polyvinyl chloride resin, it is possible to maintain the transparency immediately after production and improve the initial tear strength when used as a smoke-proof hanging wall in a high-temperature and high-humidity environment for a long period of time. I found it. The present invention is an invention completed by further studying based on these findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. A glass fiber cloth having a thickness of 8 to 30 μm, a cured resin composition layer contained in the glass fiber cloth in a state of being impregnated, and a thermoplastic other than the polyvinyl chloride resin laminated on the cured resin composition layer. A transparent sheet containing a thermoplastic resin layer containing a resin.
Item 2. Item 2. The transparent sheet according to Item 1, wherein the cured resin composition layer is a cured resin composition containing an acrylic syrup.
Item 3. The glass fiber cloth is a woven fabric, and the glass threads constituting the woven fabric have an average filament diameter of 3.5 to 4.5 μm and a number of filaments of 20 to 110, and the woven fabric has a weaving density of 80 in both warp and weft. Item 3. The transparent sheet according to Item 1 or 2, wherein the transparent sheet has a thickness of about 120 sheets / 25 mm, a thickness of 9 to 30 μm, and a mass of 9 to 35 g / m ^2.
Item 4. ^{Item 2.} The transparent sheet according to any one of Items 1 to 3, wherein the total mass of the cured resin composition layer and the thermoplastic resin layer is 150 to 300 g / m 2 in the transparent sheet.
Item 5. Item 2. Described transparent sheet.
Item 6. Item 2. The transparent sheet according to any one of Items 1 to 5, wherein the total light transmittance before and after the acceleration test is 90% or more and the haze is 3% or less.
(Promotion test method)
The transparent sheet is placed in a constant temperature and humidity chamber, heated in a moist heat environment at 50 ° C. and 90% humidity for 7 days, dried and naturally cooled.
Item 7. A smoke-proof hanging wall comprising the transparent sheet according to any one of Items 1 to 6.
Item 8. A method for producing a transparent sheet containing a glass fiber cloth, a photocurable resin composition layer contained in the glass fiber cloth in a state of being impregnated, and a thermoplastic resin layer laminated on the photocurable resin composition layer. The step A of preparing at least two light-transmitting thermoplastic resin films on which a light-transmitting cover material is laminated, and the uncured photocurable resin composition in which the glass fiber cloth is immersed are described above. The uncured photocurable resin composition was irradiated with light in a state of being sandwiched between the two thermoplastic resin films obtained in the step A so that the light-transmitting cover material was on the outside, and the uncured photocurable resin composition was irradiated with light. A method for producing a transparent sheet, which comprises a step B of curing a cured photocurable resin composition.

According to the present invention, in the composite of glass fiber and resin, when the glass fiber cloth is made thin, the initial tear strength is improved, and immediately after production and after long-term use in a high temperature and high humidity environment, It is possible to provide a transparent sheet capable of making the transparency (hereinafter, collectively abbreviated as "transparency before and after use in a high temperature and high humidity environment") easy to be excellent. Therefore, the transparent sheet of the present invention can be suitably used for, for example, a smoke-proof hanging wall.

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

The transparent sheet of the present invention is other than the glass fiber cloth having a thickness of 8 to 30 μm, the cured resin composition layer impregnated in the glass fiber cloth, and the thermoplastic resin laminated on the cured resin composition layer. It is characterized by including a thermoplastic resin layer containing the thermoplastic resin of the above.

For example, as shown in FIG. 1, the transparent sheet 1 of the present invention includes a glass fiber cloth 2, a cured resin composition layer 3 impregnated in the glass fiber cloth 2, and a thermoplastic resin 4 other than the polyvinyl chloride resin ( Hereinafter, it has a laminated structure including "thermoplastic resin layer 4"). In the transparent sheet 1, the glass fiber cloth 2 may contain at least one layer, and may contain a plurality of layers.

In FIG. 1, the cured 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 cured resin composition layer 3 and the other surface. The side portion and 32 communicate with each other through the gap portion. Further, in the transparent sheet 1 of the present invention, from the viewpoint of enhancing transparency, for example, as shown in FIG. 1, the cured resin composition layer 3 is formed on at least one surface of the layer of the glass fiber cloth 2. It is more preferable that the cured resin composition layer 3 is formed on the surface of the layer of the glass fiber cloth 2.

Further, in the transparent sheet 1 of the present invention, another layer can be laminated on the surface side of the thermoplastic resin layer 4 as needed. As the other layer, for example, as illustrated in FIG. 2, a peelable cover material 5 that is peeled off at the time of use can be laminated. Hereinafter, the composition of each layer constituting the transparent sheet 1 of the present invention will be described in detail.

(Glass fiber cloth 2)
In the transparent 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. , And preferably, non-alkali glass (E glass) having high versatility can be 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 further improving the transparency, it is preferable to select a glass material having a refractive index close to that of the cured resin composition layer 3, which will be described later.

By using a glass fiber cloth thinner than the conventional technique for a composite material of a transparent resin and a glass cloth, it is possible to improve the transparency of the transparent sheet before and after use in a high temperature and high humidity environment while maintaining the property of being hard to burn. .. The thickness is preferably 8 to 30 μm, more preferably 9 to 20 μm, and particularly preferably 9 to 13 μm.

Further, in the transparent sheet 1 of the present invention, the haze before and after use of the transparent sheet in a high temperature and high humidity environment is further reduced, and the glass fiber cloth is roughened when the resin contained in the transparent sheet is burned. From the viewpoint of making it easier to prevent, the glass fiber cloth is a woven fabric, and the glass threads constituting the woven fabric have an average filament diameter of 3.5 to 4.5 μm and a number of filaments of 20 to 110, and the woven fabric. However, it is preferable that the weaving density is 80 to 120 fibers / 25 mm, the thickness is 9 to 30 μm, and the mass is 9 to 35 g / m ^2.

Further, in the above glass fiber woven fabric, the thickness of the glass fiber woven fabric is set to the thickness of the glass filament of the warp yarn from the viewpoint of making it easier to prevent the occurrence of roughening of the glass fiber fabric when the resin contained in the transparent sheet is burned. The average number of steps shown as the value obtained by dividing the diameter by the average value of the diameter of the glass filament of the weft (glass cloth thickness / {(the diameter of the glass filament of the warp + the diameter of the glass filament of the weft) / 2}) is 2. It is preferably in the range of .5 or more and less than 3.5.

For example, when the transparent sheet 1 of the present invention is used for a smoke-proof hanging wall, the glass fiber cloth plays a role of preventing the diffusion of smoke in the event of a fire. When a fire breaks out, hot air may flow along the ceiling, and it is required to prevent this with a smoke-proof hanging wall.

On the other hand, the thickness of the glass fiber woven fabric having the above-mentioned structure is about several times the average filament diameter and about several filaments. That is, the structure of the glass fiber woven fabric also indicates that a plurality of filaments are widened in the plane direction of the glass woven fabric. By flattening glass yarn containing a specific number of filaments with a specific filament diameter so that the glass fiber woven fabric has a specific thickness, the resin component burns in the event of a fire compared to round glass yarn that is not flattened. However, the texture is less likely to shift, and it becomes easier to prevent the formation of large through holes. Further, by adopting the above-mentioned glass fiber woven fabric structure, the refraction and reflection of light incident on the transparent sheet can be reduced, and the transparency before and after use in a high temperature and high humidity environment can be further improved. As a method for producing the above-mentioned glass fiber woven fabric, for example, glass yarn having an average filament diameter of 3.5 to 4.5 μm and a number of filaments of 20 to 110 is used, and the weaving density is 80 to 120 in both warp and weft. Weaving is performed with an air jet weaving machine or the like so as to be / 25 mm, and water flow treatment is performed at a pressure of about 1 to 3 MPa while setting the tension of the glass fiber woven fabric to 50 to 100 N / m, more preferably 80 to 100 N / m in the warp direction. Therefore, it is preferable to perform the process a plurality of times.

From the same viewpoint, the glass fiber cloth is a woven fabric, and the glass threads constituting the woven fabric have an average filament diameter of 3.5 to 4.2 μm and a number of filaments of 45 to 110, and the woven fabric has a weaving density. It is more preferable that the warp and weft are 85 to 105 threads / 25 mm, the thickness is 9 to 30 μm, and the mass is 9 to 35 g / m ² , and the glass yarn constituting the woven fabric has an average filament diameter of 3. 5 to 4.5 μm, the number of filaments is 20 to 55, and the woven fabric has a weaving density of 80 to 120 fibers / 25 mm, a thickness of 9 to 13 μm, and a mass of 9 to 15 g / m ^2. The glass thread constituting the woven fabric has an average filament diameter of 3.5 to 4.2 μm and a number of filaments of 45 to 55, and the woven fabric has a weaving density of 85 to 105 in both warp and weft. It is particularly preferable that the size is 25 mm, the thickness is 9 to 13 μm, and the mass is 9 to 13 g / m ^2.

The difference in refractive index between the glass fiber cloth 2 and the cured resin composition layer 3 is preferably 0.02 or less, more preferably 0.01 or less, and even more preferably 0.005 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, with respect to 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. Using .366), using NAR-2T manufactured by Atago Co., Ltd. as an Abbe refractometer, and using a sodium D line with a wavelength of 589 nm as a light source, measurement was performed at a temperature of 23 ° C., and the average value of 5 tests was refracted. Let it be the value of the rate. Further, the refractive index of the cured resin composition 3 is measured according to the method B of JIS K 7142: 2008. Specifically, the cured cured resin composition is _{pulverized, and methylene iodide (n D} ²³ 1.747), butyl phthalate (n _D ²³ 1.491) and dimethyl carbonate (n _D ^{23) are used as immersion liquids.} Using 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., and the number of tests was 5. Let the average value of the times be the value of the refractive index.

The difference in the 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 number of abbreviations 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 and the glass fiber is measured as follows.

(Abbe number of cured resin composition)
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 line 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 (III).
Abbe number = (refractive index at wavelength 589 nm-1) / dispersion value (III)

(Abbe number of glass fiber)
A glass sheet having a width of 8 mm, a length of 20 mm, and a thickness of 5 mm is prepared using the glass material constituting the glass fiber, the surface is well polished, and the Abbe refractometer is manufactured by Atago Co., Ltd. according to the JIS K 7142A method. 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 natural light as the light source, and the Abbe number is calculated according to the above formula (III).

(Curing Resin Composition Layer 3)
In the transparent sheet 1 of the present invention, the cured resin composition layer 3 is impregnated with the glass fiber cloth 2 described later, and is formed of a cured product of the resin composition containing a curable resin. Specifically, the cured resin composition layer 3 is formed of a cured product obtained by curing the resin composition by applying energy such as light or heat to the resin composition containing the curable resin.

As the curable resin, the refractive index of the cured resin composition layer 3 and the above-mentioned glass fiber cloth 2 can be approximated from the viewpoint of further improving the transparency of the transparent sheet 1 before and after use in a high temperature and high humidity environment. Those 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, a cured resin composition containing an acrylic syrup is particularly preferable from the viewpoint of further improving the adhesiveness with the thermoplastic resin layer 4. 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-mentioned acrylic syrups, one or more kinds of 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 acid monomer is particularly preferable. In this way, when the cured resin composition layer 3 is a cured resin composition containing an acrylic syrup, the adhesion to the thermoplastic resin layer 4 is further improved, so that the transparent sheet 1 is placed in a high temperature and high humidity environment. It is preferable because the transparency before and after use is further improved.

The resin composition forming the cured resin composition layer 3 may further contain additives such as a curing accelerator, a flame retardant, an ultraviolet absorber, a filler, and an antistatic agent. 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 antistatic agent include a surfactant and the like. These additives may be used alone or in combination of two or more.

In the present invention, in order to enhance the transparency of the transparent sheet 1 before and after use in a high temperature and high humidity environment, the refractive indexes of the glass fiber cloth 2 and the cured resin composition 3 described later are set to be close to each other. From this point of view, the refractive index of the cured resin composition 3 is preferably about 1.45 to 1.65, and more preferably about 1.50 to 1.60. Further, in order to enhance the transparency of the transparent sheet 1 before and after use in a high temperature and high humidity environment, it is preferable to set the Abbe number of the glass fiber cloth 2 and the cured resin composition 3 described later to be close to each other. From this point of view, the Abbe number of the cured resin composition 3 is preferably 30 to 70, more preferably 40 to 60.

In the transparent sheet 1 of the present invention, the mass of the cured resin composition layer 3 is, for example, 20 to 100 g / m ² , from the viewpoint of achieving both transparency and nonflammability before and after use in a high temperature and high humidity environment. Therefore, 20 to 50 g / m ² is preferably mentioned. The thickness of the cured resin composition layer is, for example, 20 to 130 μm, preferably 30 to 60 μm from the viewpoint of achieving both transparency and nonflammability before and after use in a high temperature and high humidity environment. ..

In the transparent sheet 1 of the present invention, the weight ratio of the glass fiber cloth 2 and the cured resin composition layer 3 is a glass fiber cloth from the viewpoint of further achieving both transparency and nonflammability before and after use in a high temperature and high humidity environment. The ratio of the mass of the glass fiber cloth 2 to the total mass of 2 and the cured resin composition layer 3 is preferably 5 to 50% by mass, more preferably 10 to 35% by mass, and particularly preferably 10 to 25% by mass. Further, the ratio (= glass fiber cloth) of the glass fiber cloth 2 to the total mass of the transparent sheet 1 after peeling (that is, the mass excluding the peelable cover material 5) of the peelable cover material 5 that is peeled off at the time of use (= glass fiber cloth). The mass (g) of 2 / mass (g) × 100 (%) excluding the peelable cover material 5 is, for example, 3 to 20% by mass, preferably 3 to 15% by mass, and 3 More preferably, 10% by mass is mentioned.

(Thermoplastic resin layer 4)
In the transparent sheet 1 of the present invention, the thermoplastic resin layer 4 is laminated on the cured resin composition layer 3 impregnated in the glass fiber cloth 2, and is transparent when used for a long period of time in a high temperature and high humidity environment of the transparent sheet 1. It plays a role of improving the initial tear strength while maintaining the above.

The thermoplastic resin layer 4 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 plasticizing agent 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 thermoplastic resin layer 4 may not contain the polyvinyl chloride resin. From the viewpoint of further improving the initial tear strength of the transparent sheet 1, the thermoplastic resin layer 4 uses an Elemendorff tear propagation resistance (using an Elemendorff tear machine manufactured by Toyo Seiki Seisakusho Co., Ltd., JIS K7128-2.1998). The tear strength (N) is measured based on the above, and this measured value is divided by the film thickness to obtain the tear propagation resistance (N / mm). The tear strength is a test of 20 samples in each of the vertical direction and the horizontal direction. The average value of the results is used.) The one having a vertical direction and the horizontal direction of 1 N / mm or more is mentioned, the one of 3 to 20 N / mm is preferably mentioned, and the one of 5 to 15 N / mm is more preferably mentioned. .. Above all, 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, the thermoplastic resin layer 4 is made of polyester resin. It is preferable to include it. Examples of the polyester resin include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). The content of the plasticizer in the thermoplastic resin 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 or less. Particularly preferably, it is mass% or less. 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 plasticizers such as diothyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl isophthalate, -2-ethylhexyl adipate, di-2-decyl adipate, dibutyl sebatate, sebatate- Fatty acid ester plasticizers such as 2-ethylhexyl, tributyl phosphate, tri-2-ethylhexyl phosphate, -2-ethylhexyl diphenyl phosphate, tricresyl phosphate and other phosphate plasticizers, tri-2-ethylhexyl trimeritate , 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 thermoplastic resin layer 4 can be subjected to surface treatment such as corona treatment, frame treatment, and plasma treatment as needed, and is provided with various functions such as slipperiness, adhesiveness, and antistatic property. A coating layer to be formed, a hard coat layer for improving wear resistance, and the like may be provided.

Above all, when the peelable cover material 5 to be peeled off at the time of use is further laminated on the surface side of the thermoplastic resin layer 4, which will be described later, the thermoplastic resin layer 4 is at least the surface side (the thermoplastic resin layer in FIG. 2). It is preferable that the surface side portions 41 and 42) of 4 contain an antistatic agent. For example, when the transparent sheet 1 of the present invention is used as a smoke-proof hanging wall, it is preferable that the peelable cover material 5 is laminated from the viewpoint of improving the handleability at the time of construction. Then, for example, when the smoke-proof hanging wall is installed in a large facility such as a shopping mall, the cover material 5 is peeled off at the opening of the large facility (that is, when it is used as a smoke-proof hanging wall). .. On the other hand, when the cover material 5 is peeled off, friction between the thermoplastic resin layer 4 and the cover material 5 may occur, and the thermoplastic resin layer 4 may be charged with static electricity, and dust or the like existing in the air may be generated. It is possible that it adheres to the surface of the smoke-proof hanging wall. Therefore, by making the thermoplastic resin layer 4 contain an antistatic agent at least on the surface side, the generation of static electricity due to the peeling of the cover material 5 can be further suppressed, and the excellent transparency immediately after the production of the transparent sheet 1 is maintained. It will be easier.

As the antistatic agent, known ones can be used, and for example, various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and a primary to tertiary amino group; a sulfonic acid base. , Sulfate ester base, phosphate ester base, phosphonic acid base and other anionic antistatic agents; amino acid-based, aminosulfate ester-based and other amphoteric antistatic agents; aminoalcohol-based, glycerin-based, polyethylene glycol-based Various surfactant-type antistatic agents such as nonionic antistatic agents such as; Furthermore, high-molecular-weight antistatic agents obtained by increasing the amount of antistatic agents as described above, and inorganics such as silver, tin oxide, and zinc oxide. Examples include antistatic agents. Further, a monomer or oligomer having a tertiary amino group or a quaternary ammonium group and polymerizable by ionizing radiation, for example, an N, N-dialkylaminoalkyl (meth) acrylate monomer, a quaternary compound thereof, etc. Polymerizable antistatic agents can also be used. When an inorganic antistatic agent such as silver, tin oxide, or zinc oxide is used, the particle size of the inorganic fine particles is, for example, the particle size (BET particle size) obtained by the BET method as visible light. By setting the wavelength to 100 nm or less, preferably 1 to 100 nm, which is equal to or less than the wavelength of the above, it becomes easier to maintain the transparency of the transparent sheet 1.

In the transparent sheet 1 of the present invention, the mass per layer of the thermoplastic resin layer 4 is, for example, 30 to 150 g / m ² , and 50 from the viewpoint of achieving both initial tear strength and nonflammability. ~ 90 g / m ² is preferably mentioned, and 60 to 80 g / m ² is more preferably mentioned. The thickness of the thermoplastic resin layer 4 is, for example, 20 to 100 μm, preferably 30 to 70 μm, and more preferably 40 to 60 μm from the viewpoint of achieving both initial tear strength and nonflammability. Preferred. Further, for example, another layer such as a coating layer that imparts various functions such as slipperiness, adhesiveness, and antistatic property and / or a hardcoat layer that improves wear resistance is laminated on the thermoplastic resin layer 4. In this case, the thickness of the other layer is, for example, 0.1 to 3 μm, preferably 0.1 to 1 μm.

(Peelable cover material 5)
In the transparent sheet 1 of the present invention, if necessary, a peelable cover material 5 that can be peeled off at the time of use can be further laminated on the surface side of the thermoplastic resin layer 4. As a result, for example, when the transparent sheet 1 of the present invention is used as a smoke-proof hanging wall, it becomes easy to prevent the transparent sheet 1 from being scratched during construction and the transparency and aesthetics from being deteriorated.

Then, as described above, when the cover material 5 is installed in a facility where the installation of a smoke-proof hanging wall is required by the Building Standards Act, for example, after the completion of the smoke-proof hanging wall installation work (that is, smoke-proof). Peeled (when used as a hanging wall). On the other hand, when the cover material 5 is peeled off, friction between the thermoplastic resin layer 4 and the cover material 5 may occur, and the thermoplastic resin layer 4 may be charged with static electricity, and dust or the like existing in the air may be generated. It is possible that it adheres to the surface of the smoke-proof hanging wall. Therefore, when a peelable cover material 5 that is peeled off at the time of use is further laminated on the surface side of the thermoplastic resin layer 4, the cover material is provided so that the thermoplastic resin layer 4 contains at least an antistatic agent on the surface side. It is preferable because the generation of static electricity due to the peeling of 5 can be further suppressed and the excellent transparency of the transparent sheet 1 can be easily maintained.

As the peelable cover material 5, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover material 5 is peeled off, the cover material 5 and the thermoplastic are used. The adhesive strength with the resin layer 4 may be smaller than the adhesive strength between the thermoplastic resin layer 4 and the cured resin composition layer 3. Among them, if the peelable cover material 5 is a light-transmitting cover material, for example, when the resin composition forming the above-mentioned cured resin composition layer 3 is used as a photocurable cured resin composition. Also in the step of curing the cured resin composition, it is preferable in that it is easy to prevent the thermoplastic resin composition layer 4 from being scratched and the transparency and aesthetics are deteriorated. 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 cover material, 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%. The above is more preferable, and 60% or more is particularly preferable.

(Physical characteristics and performance of transparent sheet 1)
The thickness of the transparent sheet 1 of the present invention is, for example, the thickness of the transparent sheet 1 after peeling the peelable cover material 5 that is peeled off during use (that is, the thickness excluding the peelable cover material 5). Is 100 to 300 μm, preferably 150 to 200 μm. Further, as the mass of the transparent sheet 1 of the present invention, for example, the mass of the transparent sheet 1 after peeling the peelable cover material 5 that is peeled off during use (that is, the mass excluding the peelable cover material 5) is 100. ~ 400 g / m ² is mentioned, and 150 to 300 g / m ² is preferably mentioned. Further, in the transparent sheet 1 of the present invention, when the total mass of the cured resin composition layer and the thermoplastic resin layer is 150 to 300 g / m ² , more preferably 150 to 200 g / m ^2, it is nonflammable and tears. It is preferable because it makes it easier to achieve both strength and strength.

In the transparent sheet 1 of the present invention, the thickness of the glass fiber cloth is 8 to 30 μm, and since the thermoplastic resin layer 4 is laminated, the transparency before and after use in a high temperature and high humidity environment can be high. From the viewpoint of ensuring high transparency before and after use in a high temperature and high humidity environment, the total light transmittance of the transparent sheet 1 of the present invention before use in a high temperature and high humidity environment is 85% or more, preferably 90% or more. .. Further, the haze of the transparent sheet 1 of the present invention before use in a high temperature and high humidity environment is 5% or less, preferably 3% or less, and more preferably 1% or less. The total light transmittance and the haze of the transparent sheet 1 are values obtained by measuring according to JIS K73752008 "Plastic-How to obtain total light transmittance and total light reflectance", respectively.

In order to ensure high transparency before use in a high temperature and high humidity environment as described above, the thickness of the glass fiber cloth should be 8 to 30 μm, and the difference in refractive index between the glass fiber cloth 2 and the cured resin composition layer 3 The glass fiber cloth is a woven fabric, and the glass threads constituting the woven fabric have an average filament diameter of 3.5 to 4.5 μm and a number of filaments of 20 to 55. It is assumed that the weaving density is 80 to 120 fibers / 25 mm, the thickness is 9 to 15 μm, and the mass is 9 to 15 g / m ² , and the cured resin composition layer 3 is a cured resin composition containing acrylic syrup. That can be mentioned.

As the total light transmittance of the transparent sheet 1 of the present invention after use in a high temperature and high humidity environment, the total light transmittance of the transparent sheet 1 after the following acceleration test is 85% or more, preferably 90% or more. Further, as the haze after use of the transparent sheet 1 of the present invention in a high temperature and high humidity environment, the haze of the transparent sheet 1 after the following acceleration test is 5% or less, preferably 3% or less, more preferably 1% or less. ..
(Promotion test method)
Place the transparent sheet in a constant temperature and humidity chamber, heat it in a moist heat environment at 50 ° C. and 90% humidity for 7 days, dry it, and cool it naturally. Measure according to "direction".

In order to ensure high transparency after use in a high temperature and high humidity environment as described above, the method for ensuring high transparency before use in a high temperature and high humidity environment and the thermoplastic resin layer 4 are made of a thermoplastic other than a polyvinyl chloride resin. In addition to containing a resin, the amount of the plasticizer contained in the thermoplastic resin layer 4 may be reduced.

Since the transparent sheet 1 of the present invention is provided with the thermoplastic resin layer 4, the initial tear strength can be made high. From the viewpoint of ensuring high 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, test pieces of 75 mm × 150 mm were collected from a transparent sheet in the vertical direction and the horizontal direction, respectively, and two trapezoidal parts including a right angle (Fig. 3). A constant-speed load type tensile tester (Co., Ltd.) with non-slip tape (trade name 600S manufactured by Sekisui Chemical Co., Ltd.) attached to both the front and back sides (corresponding to the trapezoidal part A illustrated in). Performed using 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 transparent 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 transparent sheet 1 of the present invention is 4.10.2 heat generation in the "Fireproof Performance Test / Evaluation Business Method Manual" (revised 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 sex test / evaluation method, the maximum heat generation rate after the start of heating is 200 kW / m ^{2 continuously for 10 seconds or more.} It is preferable that the total calorific value does not exceed 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 cured resin composition layer 3 and the thermoplastic resin layer 4.

(Method for manufacturing transparent sheet of the present invention)
The method for producing the transparent 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 above-mentioned uncured cured resin composition constituting the cured resin composition layer 3 are prepared. The cured resin composition is applied to a film (for example, a polyester film) to be the thermoplastic resin layer 4, and the film is crimped from both sides of the glass fiber cloth 2 to obtain the cured resin composition from both sides of the glass fiber cloth 2. The cured resin composition was impregnated and cured by heating or light irradiation, the glass fiber cloth 2 was impregnated with the cured resin composition layer 3, and the thermoplastic resin layer 4 was laminated on the cured resin composition layer 3. A transparent sheet 1 (a transparent sheet 1 in which a cured resin composition layer 3 and a thermoplastic resin layer 4 contained in a state of being impregnated in a thermoplastic resin layer 4 / a glass fiber cloth 2 are laminated in this order) is obtained.

When the resin composition is cured by applying thermal energy, the heating temperature is not particularly limited and can be, for example, about 50 to 200 ° C. When the resin composition is cured by applying light energy, the resin composition is irradiated with light to be cured. The conditions for light irradiation can be, for example, an integrated light amount of 100 to 500 mJ / cm ² .

Further, for example, when the thermoplastic resin layer 4 contains an antistatic agent at least on the surface side, an antistatic agent may be applied after the transparent sheet 1 is manufactured, or a film to be made into the thermoplastic resin layer 4 in advance. Can also be antistatic treated. When the transparent sheet 1 of the present invention is further laminated on the surface side of the thermoplastic resin layer 4 with a peelable cover material 5 that can be peeled off during use, the transparent sheet 1 is obtained after the transparent sheet 1 is obtained. The cover material 5 can be laminated. Further, the peelable cover material 5 is laminated on the film to be the thermoplastic resin layer 4 in advance to integrate the two, so that the cover material 5 is on the outside, and the uncured cured resin composition is thermoplastic. A sheet coated on the surface of the resin layer 4 and integrated from both sides of the glass fiber cloth 2 and coated with the cured resin composition is crimped to impregnate the resin composition from both sides of the glass fiber cloth 2 to impregnate the cured resin composition. The object is cured by heating or light irradiation, the glass fiber cloth 2 is impregnated with the cured resin composition layer 3, the thermoplastic resin layer 4 is laminated on the cured resin composition layer 3, and the thermoplastic resin layer 4 is laminated. A transparent sheet 1 on which a peelable cover material 5 is laminated (a curable resin composition layer 3 / a thermoplastic resin layer contained in a state of being impregnated in a peelable cover material 5 / a thermoplastic resin layer 4 / a glass fiber cloth 2). A transparent sheet 1) laminated in the order of 4 / peelable cover material 5 is obtained.

Further, as a method for producing a transparent sheet of the present invention, a glass fiber cloth, a photocurable resin composition layer contained in the glass fiber cloth in a state of being impregnated, and a photocurable resin composition layer laminated on the glass fiber cloth. A method for producing a transparent sheet including a thermoplastic resin layer, which is a step A of preparing at least two light-transmitting thermoplastic resin films on which a light-transmitting cover material is laminated, and a step A in which the 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-transmitting cover material was on the outside. It can include a step B of irradiating the photocurable resin composition with light to cure the uncured photocurable resin composition.

(Use of the transparent sheet of the present invention)
An application of the transparent sheet of the present invention is to use it as a smoke-proof hanging wall. Above all, the transparent sheet of the present invention can be used for tension-type smoke-proof hanging walls because high-frequency welding can be performed when the outermost layer is the thermoplastic resin layer 4 when the smoke-proof hanging wall is used. , Can be preferably used. In the present invention, the tension type smoke-proof hanging wall is a hanging wall in which a transparent non-combustible sheet is stretched between two pairs of mullion. There is a smoke-proof hanging wall on the lower side of the sex sheet. again,
Since it can be a substitute for glass, it can also be applied to other applications in which glass is used, such as partitions, partitions, smoke-proof sheets, smoke-proof curtains (for example, those used in factories), touch panels, etc. can. Further, the transparent sheet 1 of the present invention is further excellent in flexibility when the mass of the curable resin composition layer 4 is, for example, 20 to 100 g / m ² , more preferably 20 to 50 g / m ^2. Since it becomes a product, it becomes easy to make a roll product. Examples of the length of the roll product in the longitudinal direction include 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.

As the cured resin composition to be impregnated in the above glass fiber cloth, acrylic syrup (trade name "Acrysil wrap XD-8005" (refractive index 1.550) manufactured by Ryokou Co., Ltd.) and "Acrysiwrap XD-8006" (refractive index 1.570) mixed at a mass ratio of 1: 1), vinyl ester resin (manufactured by Nippon Yupika Co., Ltd.), styrene monomer (manufactured by Nippon Yupika Co., Ltd.), bifunctional A mixture of (meth) acrylate and photopolymerization initiator 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 2 parts by mass with respect to 100 parts by mass in total of the vinyl ester resin, the styrene monomer, and the bifunctional (meth) acrylate. As the thermoplastic resin layer, a commercially available biaxially stretched polyester film manufactured by Toyo Boseki Co., Ltd. (trade name "Cosmo Shine (registered trademark) A4300", thickness 50 μm, mass 70 g / m ² ) is charged with tin oxide as an antioxidant. ^{A product coated with 0.5 g / m 2 of} polyester resin in which an inhibitor (particle size: 100 nm or less) is dispersed. As a vinyl chloride resin, a commercially available vinyl chloride resin film (manufactured by Okamoto Co., Ltd., general-purpose PVC # 320, thickness) 100 μm and a mass of 120 g / m ² ) were used. A polypropylene film (thickness 40 μm, mass 36 g / m ² ) is used as the peelable cover material, and an acrylic acid ester-based pressure-sensitive adhesive is used as the adhesive that allows the peelable cover material to be peelably adhered to the thermoplastic resin layer. Using.

<Example 1>
(Manufacturing of glass fiber fabric)
Weaving with an air jet loom 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 the warp and weft, the 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. Then, 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 obtained by performing the widening treatment twice while setting the tension of the glass fiber woven fabric to 100 N / m in the warp direction by water flow processing at a pressure of 1.5 MPa. The obtained glass fiber woven fabric 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 cover material on the thermoplastic resin layer)
The polyester film subjected to the antistatic treatment described above, to which the acrylic acid ester-based adhesive is applied to the polypropylene film described above on the surface side subjected to the antistatic treatment, so that the pressure-sensitive adhesive is on the polyester film side. And dried to obtain a film in which a polypropylene film was laminated on the polyester film. Two films were prepared.

(Manufacturing of transparent sheet)
The cured resin composition shown in Table 1 was applied to the polyester film surface side of one film in which a polypropylene film was laminated on the polyester film described above. Next, the obtained glass fiber cloth was placed on the cured resin composition and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths with the above resin. Next, another film in which the polypropylene film was laminated on the polyester film described above was further placed from above, and the film was pressed ^{from above with a roller so that the mass of the cured resin composition layer was 40 g / m 2. After that, the cured resin composition was irradiated with light (light irradiation condition: integrated light amount 200 mJ / cm 2} ) using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation) together with the film obtained by laminating the polypropylene film on the polyester film. The cured resin composition was cured to form a cured resin composition layer, and a transparent sheet having a laminated structure illustrated in FIG. 2 was obtained. In the obtained transparent sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both sides of the glass fiber cloth layer. A composition layer was formed.

<Example 2>
(Manufacturing of glass fiber cloth)
Weaving with an air jet loom 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 the warp and weft, the 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. Then, 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 obtained by performing the widening treatment twice while setting the tension of the glass fiber woven fabric to 100 N / m in the warp direction by water flow processing at a pressure of 1.5 MPa. The obtained glass fiber woven fabric 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 cover material on the thermoplastic resin layer)
The polyester film subjected to the antistatic treatment described above, to which the acrylic acid ester-based adhesive is applied to the polypropylene film described above on the surface side subjected to the antistatic treatment, so that the pressure-sensitive adhesive is on the polyester film side. And dried to obtain a film in which a polypropylene film was laminated on the polyester film. Two films were prepared.

(Manufacturing of transparent sheet)
The cured resin composition shown in Table 1 was applied to the polyester film surface side of one film in which a polypropylene film was laminated on the polyester film described above. Next, the obtained glass fiber cloth was placed on the cured resin composition and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths with the above resin. Next, another film in which the polypropylene film was laminated on the polyester film described above was further placed from above, and the film was pressed ^{from above with a roller so that the mass of the cured resin composition layer was 40 g / m 2. After that, the cured resin composition was irradiated with light (light irradiation condition: integrated light amount 200 mJ / cm 2} ) using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation) together with the film obtained by laminating the polypropylene film on the polyester film. The cured resin composition was cured to form a cured resin composition layer, and a transparent sheet having a laminated structure illustrated in FIG. 2 was obtained. In the obtained transparent sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both sides of the glass fiber cloth layer. A composition layer was formed.

<Example 3>
(Manufacturing of glass fiber fabric)
Weaving with an air jet loom 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 the warp and weft, the 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. Then, 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 to obtain a glass fiber woven fabric (that is, no widening treatment was performed). The obtained glass fiber woven fabric had a warp density of 95 threads / 25 mm, a weft density of 95 threads / 25 mm, a thickness of 15 μm, a mass of 12 g / m ² , and a refractive index of 1.561.

(Lamination of a peelable cover material on a thermoplastic resin layer) An acrylic acid ester-based pressure-sensitive adhesive is applied to the above-mentioned polypropylene film on the antistatic treatment surface side of the above-mentioned antistatic treatment polyester film. The applied material was laminated so that the pressure-sensitive adhesive was on the polyester film side, and dried to obtain a film in which the polypropylene film was laminated on the polyester film. Two films were prepared.

(Manufacturing of transparent sheet)
The cured resin composition shown in Table 1 was applied to the polyester film surface side of one film in which a polypropylene film was laminated on the polyester film described above. Next, the obtained glass fiber cloth was placed on the cured resin composition and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths with the above resin. Next, another film in which the polypropylene film was laminated on the polyester film described above was further placed from above, and the film was pressed ^{from above with a roller so that the mass of the cured resin composition layer was 40 g / m 2. After that, the cured resin composition was irradiated with light (light irradiation condition: integrated light amount 200 mJ / cm 2} ) using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation) together with the film obtained by laminating the polypropylene film on the polyester film. The cured resin composition was cured to form a cured resin composition layer, and a transparent sheet having a laminated structure illustrated in FIG. 2 was obtained. In the obtained transparent sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both sides of the glass fiber cloth layer. A composition layer was formed.

<Example 4>
(Manufacturing of glass fiber fabric)
Weaving with an air jet loom 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 weft 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. Then, 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 obtained by performing a widening treatment once while setting the tension of the glass fiber woven fabric to 100 N / m in the warp direction by water flow processing at a pressure of 1.5 MPa. The obtained glass fiber woven fabric 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 cover material on the thermoplastic resin layer)
The polyester film subjected to the antistatic treatment described above, to which the acrylic acid ester-based adhesive is applied to the polypropylene film described above on the surface side subjected to the antistatic treatment, so that the pressure-sensitive adhesive is on the polyester film side. And dried to obtain a film in which a polypropylene film was laminated on the polyester film. Two films were prepared.

(Manufacturing of transparent sheet)
The cured resin composition shown in Table 1 was applied to the polyester film surface side of one film in which a polypropylene film was laminated on the polyester film described above. Next, the obtained glass fiber cloth was placed on the cured resin composition and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths with the above resin. Next, another film in which the polypropylene film was laminated on the polyester film described above was further placed from above, and the film was pressed ^{from above with a roller so that the mass of the cured resin composition layer was 90 g / m 2. After that, the cured resin composition was irradiated with light (light irradiation condition: integrated light amount 200 mJ / cm 2} ) using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation) together with the film obtained by laminating the polypropylene film on the polyester film. The cured resin composition was cured to form a cured resin composition layer, and a transparent sheet having a laminated structure illustrated in FIG. 2 was obtained. In the obtained transparent sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both sides of the glass fiber cloth layer. A composition layer was formed.

<Comparative example 1>
(Manufacturing of glass fiber fabric)
Weaving with an air jet loom 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 the warp and weft, the 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. Then, 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 obtained by performing the widening treatment twice while setting the tension of the glass fiber woven fabric to 100 N / m in the warp direction by water flow processing at a pressure of 1.5 MPa. The obtained glass fiber woven fabric 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 transparent sheet)
The cured resin composition shown in Table 1 was applied to one of the above-mentioned vinyl chloride resin films. Next, the obtained glass fiber cloth was placed on the cured resin composition and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths with the above resin. Next, another sheet of the above-mentioned vinyl chloride resin film was further placed from above, and pressure was applied from above so that ^{the mass of the cured resin composition layer was 40 g / m 2.} Then, for each vinyl chloride resin film, the cured resin composition is light-irradiated (light irradiation condition: integrated light amount 200 mJ / cm ² ) using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation) to prepare the cured resin composition. It was cured to form a cured resin composition layer, and a transparent sheet was obtained. In the obtained transparent sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both sides of the glass fiber cloth layer. A composition layer was formed.

<Comparative example 2>
(Manufacturing of glass fiber fabric)
Weaving with an air jet loom 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 the warp and weft, the 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. Then, 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 obtained by performing the widening treatment twice while setting the tension of the glass fiber woven fabric to 100 N / m in the warp direction by water flow processing at a pressure of 1.5 MPa. The obtained glass fiber woven fabric 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 transparent sheet)
The cured resin composition shown in Table 1 was applied onto a PET film having a thickness of 50 μm. Next, the obtained glass fiber cloth was placed on the resin composition and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths with the resin. Next, a PET film having a thickness of 0.05 mm was placed from above, and pressure was applied from above with a roller so that the mass of the cured resin composition layer was 40 g / m ^2. Then, the resin composition was cured by ^{irradiating the resin composition with light (light irradiation condition: integrated light amount 200 mJ / cm 2} ) using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation) together with the above PET film. , A cured resin composition layer was formed. Next, two PET films were removed to obtain a transparent sheet. In the obtained transparent sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both sides of the glass fiber cloth layer. A composition layer was formed.

< Reference example 1 >
(Manufacturing of glass fiber fabric)
Weaving with an air jet loom using the trade name "ECD450 1/0 1.0Z" (average filament diameter 5 μm, average number of filaments 200, twist number 1.0Z) manufactured by Unitika Glass Fiber Co., Ltd. as the warp and weft, the warp A plain weave glass fiber woven fabric having a density of 60 threads / 25 mm and a weft density of 60 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. Then, 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 obtained by performing a widening treatment once while setting the tension of the glass fiber woven fabric to 100 N / m in the warp direction by water flow processing at a pressure of 1.5 MPa. The obtained glass fiber woven fabric had a warp density of 60 threads / 25 mm, a weft density of 60 threads / 25 mm, a thickness of 50 μm, a mass of 53 g / m ² , and a refractive index of 1.561.

(Lamination of removable cover material on the thermoplastic resin layer)
The polyester film subjected to the antistatic treatment described above, to which the acrylic acid ester-based adhesive is applied to the polypropylene film described above on the surface side subjected to the antistatic treatment, so that the pressure-sensitive adhesive is on the polyester film side. And dried to obtain a film in which a polypropylene film was laminated on the polyester film. Two films were prepared.

(Manufacturing of transparent sheet)
The cured resin composition shown in Table 1 was applied to the polyester film surface side of one film in which a polypropylene film was laminated on the polyester film described above. Next, the obtained glass fiber cloth was placed on the cured resin composition and allowed to stand for 1 minute to impregnate the gaps between the glass fiber cloths with the above resin. Next, another film in which the polypropylene film was laminated on the polyester film described above was further placed from above, and the film was pressed ^{from above with a roller so that the mass of the cured resin composition layer was 160 g / m 2. After that, the cured resin composition was irradiated with light (light irradiation condition: integrated light amount 200 mJ / cm 2} ) using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation) together with the film obtained by laminating the polypropylene film on the polyester film. The cured resin composition was cured to form a cured resin composition layer, and a transparent sheet having a laminated structure illustrated in FIG. 2 was obtained. In the obtained transparent sheet, the gaps between the glass fibers of the glass fiber cloth are impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both sides of the glass fiber cloth layer. A composition layer was formed.

In Examples , Reference Examples and Comparative Examples, the weaving density of the glass fiber woven fabric was measured and calculated according to JIS R 3420 2013 7.9. The thickness of the glass fiber woven fabric was measured and calculated according to the JIS 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 and the glass fiber woven fabric was measured and calculated by the method described above. The Abbe number of the cured resin composition and the glass fiber woven fabric was measured and calculated by the above method. The following evaluation was performed after the transparent sheet was manufactured and left indoors for one week.

(Total light transmission and haze before and after use in a hot and humid environment)
The total light transmittance and haze of the transparent sheet before use in a high temperature and high humidity environment were measured according to JIS K73752008 "Plastic-How to determine total light transmittance and total light reflectance". As for the total light transmittance and haze after use in a high temperature and high humidity environment, the transparent sheet is placed in a constant temperature and humidity chamber as an accelerated test and heated at 50 ° C. and 90% humidity for 7 days. It was measured according to K7375 2008 "Plastic-How to determine total light transmittance and total light reflectance". Those having a total light transmittance of 90% or more before and after use in a high temperature and high humidity environment and a haze of 3% or less before and after leaving in a high temperature and high humidity environment were accepted. In Examples 1 to 4 and Reference Example 1 , the transparent sheet after the peelable cover material was peeled off was evaluated.

(Initial tear strength (N))
It was measured and calculated by the method described above. Those with 50N or more were accepted. In Examples 1 to 4 and Reference Example 1 , the transparent sheet after the peelable cover material was peeled off was evaluated.

(Non-flammability evaluation)
The surfaces of the transparent sheet, with radiant electric heater irradiating radiant heat of 50 kw / m ^2, the total calorific value of the heating start after 20 minutes, the time for heating value exceeds 200 kW / m ² to the start of heating after 20 minutes It was measured. Excellent nonflammability when the total heat generation amount for 20 minutes after the start of heating is 8 MJ / m ^{2 or less and the maximum heat generation rate does not exceed 200 kW / m 2} for 10 seconds or more continuously for 20 minutes after the start of heating (◎). ). In Examples 1 to 4 and Reference Example 1 , the transparent sheet after the peelable cover material was peeled off was evaluated.

(Evaluation of rough texture of glass fiber fabric after burning resin contained in transparent sheet)
The transparent sheet was placed in a muffle furnace at a temperature of 625 ° C., heat-treated for 60 minutes, taken out, cooled to room temperature, and the state of the glass fiber cloth was visually observed and evaluated according to the following criteria. ○ The above was passed. In Examples 1 to 4 and Reference Example 1 , the transparent sheet after the peelable cover material was peeled off was evaluated.
⊚: In the weave, the occurrence of through holes with a side of 0.5 mm or more was zero, and rough texture could hardly be confirmed.
◯: In the weave, the occurrence of through holes with a side of 0.5 mm or more was zero, and although the grain was slightly rough, there was no problem in practical use.
X: Occurrence of through holes with a side of 0.5 mm or more was confirmed in the weave, and rough texture was conspicuous, which was a practically problematic level.

The results of each evaluation are shown in Table 1.

The transparent sheets of Examples 1 to 4 are laminated on the glass fiber cloth having a thickness of 8 to 30 μm, the cured resin composition layer contained in the glass fiber cloth in a state of being impregnated, and the cured resin composition layer. In addition, since it contained a thermoplastic resin layer containing at least one selected from the group consisting of polyester resin, polycarbonate resin, and polyamide resin, it was subjected to a high temperature and high humidity environment while improving the initial tear strength. It was possible to improve and maintain the transparency before and after use. Among them, in the sheets of Examples 1 and 2, the glass fiber cloth is a woven fabric, and the glass threads constituting the woven fabric have an average filament diameter of 3.5 to 4.5 μm and a number of filaments of 20 to 55. Since the woven fabric had a weaving density of 80 to 120 fibers / 25 mm, a thickness of 9 to 13 μm, and a mass of 9 to 15 g / m ² , the glass when the resin contained in the transparent sheet burned. It was intended to make it easier to prevent the occurrence of rough texture of the fiber cloth. Further, in Examples 1, 3 and 4, since the curable resin composition layer was a cured resin composition containing acrylic syrup, the transparency before and after use in a high temperature and high humidity environment was more excellent. there were. Among them, in Example 1, since the thickness of the glass fiber cloth was 13 μm or less, the transparency before and after use in a high temperature and high humidity environment was remarkably excellent.

Further, the transparent sheets of Examples 1 to 4 have excellent alkali latent resistance when the peelable cover material is peeled off, can be subjected to high-frequency welding, and generate static electricity due to the peeling of the cover material. It was also something that could be further suppressed. Further, since the transparent sheets of Examples 1 to 4 contained a cover material, particularly a light-transmitting cover material, scratches occurred in the manufacturing process of the transparent sheet and the installation work as a smoke-proof hanging wall. Was suppressed, and the handling was excellent. Further, the transparent sheets of Examples 1 to 4, especially the transparent sheets of Examples 1 to 3 have excellent flexibility, and can be made into a roll product of 5 to 300 m.

On the other hand, since the transparent sheet of Comparative Example 1 was obtained by laminating a vinyl chloride resin film on a cured resin composition layer, the plasticizer in the vinyl chloride resin migrated (bleed out) after use in a high temperature and high humidity environment. However, it oozes out at the interface between the vinyl chloride resin film and the cured resin composition layer, and transparency cannot be maintained.

The transparent sheet of Comparative Example 2 did not contain a thermoplastic resin layer containing one or more selected from the group consisting of polyester resin, polycarbonate resin, and polyamide resin laminated on the cured resin composition layer. It was inferior in initial tear strength.

Since the transparent sheet of Reference Example 1 had a thickness of the glass fiber cloth exceeding 30 μm, it was inferior in transparency before and after use in a high temperature and high humidity environment.

1 ... Transparent sheet 2 ... Glass fiber cloth 3 ... Cured resin composition layer 31, 32 ... Surface of cured resin composition layer 4 ... Thermoplastic resin layer 41, 42 ... Heat Surface side portion 5 of the plastic resin layer 4 ... Detachable cover material

Claims (7)

Glass fiber fabric and
The cured resin composition layer contained in the glass fiber cloth in a state of being impregnated,
A thermoplastic resin layer containing a thermoplastic resin other than the polyvinyl chloride resin laminated on the cured resin composition layer,
Laminated on the thermoplastic resin layer, seen including a an optically transparent cover material peelable be peeled off when using as smoke vertical wall,
A transparent sheet for smoke-proof hanging walls , in which the total light transmittance before and after the following acceleration test is 90% or more and the haze is 3% or less with the cover material peeled off.
(Promotion test method)
The transparent sheet is placed in a constant temperature and humidity chamber, heated in a moist heat environment at 50 ° C. and 90% humidity for 7 days, dried and naturally cooled. The transparent sheet for a smoke-proof hanging wall according to claim 1, wherein the cured resin composition layer is a cured resin composition containing an acrylic syrup. The glass fiber cloth is a woven fabric,
The glass threads constituting the woven fabric have an average filament diameter of 3.5 to 4.5 μm and a number of filaments of 20 to 110.
The transparent sheet for a smoke-proof hanging wall according to claim 1 or 2, wherein the woven fabric has a weaving density of 80 to 120 lines / 25 mm, a thickness of 9 to 30 μm, and a mass of 9 to 35 g / m ^2. The transparent sheet for a smoke-proof hanging wall according to any one of claims 1 to 3, wherein the total mass of the cured resin composition layer and the thermoplastic resin layer is 150 to 300 g / m ^{2 in the transparent sheet.} .. The transparent sheet for a smoke-proof hanging wall according to any one of claims 1 to 4, wherein the thermoplastic resin layer contains an antistatic agent at least on the surface side on which the cover material is laminated. A smoke-proof hanging wall comprising the transparent sheet from which the cover material is peeled off from the smoke-proof hanging wall transparent sheet according to any one of claims 1 to 5. The glass fiber cloth, the photocurable resin composition layer contained in the glass fiber cloth in a state of being impregnated, the thermoplastic resin layer laminated on the photocurable resin composition layer, and the thermoplastic resin layer laminated. been, see containing and a light permeable cover material can be peeled to be peeled off in use,
A method for producing a transparent sheet for a smoke-proof hanging wall, wherein the total light transmittance before and after the following acceleration test is 90% or more and the haze is 3% or less with the cover material peeled off.
Step A of preparing at least two light-transmitting thermoplastic resin films on which the cover material is laminated, and
The uncured photocurable resin composition in which the glass fiber cloth is immersed is sandwiched between the two thermoplastic resin films obtained in the step A so that the light-transmitting cover material is on the outside. A method for producing a transparent sheet for a smoke-proof hanging wall, comprising the step B of irradiating the uncured photocurable resin composition with light to cure the uncured photocurable resin composition.
(Promotion test method)
The transparent sheet is placed in a constant temperature and humidity chamber, heated in a moist heat environment at 50 ° C. and 90% humidity for 7 days, dried and naturally cooled.

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