JP6371445B1 - Transparent sheet, smoke barrier wall including the transparent sheet, and method for producing the transparent sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent sheet capable of improving and maintaining transparency while improving initial tear strength when a glass fiber fabric is thin in a transparent resin composite of glass fiber and resin. The main purpose is to do.
SOLUTION: A glass fiber fabric having a thickness of 8 to 30 μm, a cured resin composition layer impregnated in the glass fiber fabric, and a polyvinyl chloride resin laminated on the cured resin composition layer And a thermoplastic resin layer containing a thermoplastic resin other than the above.
[Selection] Figure 1

Description

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

  The Building Standards Law and the Building Standards Law Enforcement Ordinance stipulate that smoke-exhaust facilities should be installed so that smoke, toxic gases, etc. generated in the event of a building fire can be prevented and evacuation and fire fighting activities can be carried out smoothly. Yes. Therefore, in buildings such as office buildings and commercial facilities, smoke barriers are often installed as smoke exhausting equipment and smoke shielding equipment.

  The smoke barrier is usually used for the purpose of temporarily blocking the flow of smoke, toxic gases, etc. in the event of a fire to the corridors and upper floors and ensuring the time required for evacuation. Attached to 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 wall so that the field of view is not hindered by the smoke proof wall and the aesthetic appearance is not impaired. The transparent resin composite of glass fiber and resin has the advantage that it is less likely to break compared to transparent plate glass. For example, Patent Document 1 discloses a transparent noncombustible sheet including a glass fiber fabric and a cured resin layer.

  For example, Patent Document 2 has a base material layer including a glass fiber fabric 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. A transparent non-combustible sheet is disclosed.

JP 2005-319746 A JP 2011-213093 A

  However, for example, the transparent noncombustible sheet as disclosed in Patent Document 1 has a problem of high haze and insufficient transparency although it is excellent in noncombustibility.

  The present inventors examined the cause of the insufficient transparency of the transparent noncombustible sheet. For example, the inventors of the present invention have disclosed a relatively thick glass fiber fabric having a thickness of about 100 μm so that the transparent non-combustible sheet specifically disclosed as an example in Patent Document 1 has excellent non-combustibility. It was found that transparency was insufficient due to increased refraction and reflection at the interface between the glass fiber and the cured resin of incident light.

  Therefore, the present inventors tried to improve transparency by making the glass fiber fabric of the transparent noncombustible sheet disclosed in Patent Document 1 thinner, for example, 30 μm or less. However, when the thickness of the glass fiber fabric of the transparent incombustible sheet disclosed in Patent Document 1 is reduced, it has been found that 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 incombustible 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 incombustible sheet can be maintained high. As a reinforcing layer, for example, a mesh body made of glass fiber, a vinyl chloride resin film, or the like is used alone or in combination. However, when a network made of glass fibers is used as the reinforcing layer, there is a problem that haze increases and high transparency cannot be obtained even immediately after production. In addition, when the vinyl chloride resin film is used as a reinforcing layer, there are few problems in a normal environment, but it may not be possible to maintain transparency when used as a smoke barrier for a long period of time in a high temperature and high humidity environment, for example. There was a problem. That is, in the prior art of transparent composites of glass fiber and resin, transparency and initial tear strength immediately after production and after long-term use in a high-temperature and high-humidity environment increase one of the performances. In other words, there is a trade-off relationship in which the other performance deteriorates.

  Under such circumstances, in the transparent resin composite of glass fiber and resin, the present invention improves the initial tear strength when the glass fiber fabric is thin, and immediately after production and under a high temperature and high humidity environment. The main object is to provide a transparent sheet capable of easily improving the transparency after long-term use.

  The inventors of the present invention have intensively studied to solve the above problems. As a result, in the transparent noncombustible sheet disclosed in Patent Document 2, the vinyl chloride resin film can be used as a reinforcing layer, for example, to maintain transparency when used for a long time as a smoke proof wall in a high temperature and high humidity environment. It has been found that the cause of the inability to do so is the bleed-out of the plasticizer contained in the vinyl chloride resin film.

  That is, a large amount of plasticizer is contained in the vinyl chloride resin film. When this is laminated on the cured resin composition layer, the plasticizer is used for a long time as a smoke-proof hanging wall in a high-temperature and high-humidity environment. Has been found to migrate (bleed out) and ooze out at the interface between the vinyl chloride resin film and the cured resin composition layer, making it impossible to maintain transparency.

  And as a result of repeated studies by the present inventors, a plasticizer is unnecessary as a layer to be laminated on the cured resin composition layer while improving the transparency immediately after production by setting the glass fiber fabric to 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 the production and improve the initial tear strength when used as a smoke proof wall for a long time in a high temperature and high humidity environment. I found it. The present invention has been completed by further studies based on these findings.

That is, this invention provides the invention of the aspect hung up below.
Item 1. A glass fiber fabric having a thickness of 8 to 30 μm, a cured resin composition layer impregnated in the glass fiber fabric, and a thermoplastic other than polyvinyl chloride resin laminated on the cured resin composition layer A transparent sheet comprising 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 obtained by curing a resin composition containing acrylic syrup.
Item 3. The glass fiber fabric is a woven fabric, the glass yarn constituting the woven fabric has an average filament diameter of 3.5 to 4.5 μm, the number of filaments of 20 to 110, and the woven fabric has a weaving density of 80 in both circumstances. The transparent sheet of claim | item 1 or 2 which are -120 piece / 25mm, thickness is 9-30 micrometers, and mass is 9-35 g / m < ² >.
Item 4. Item 4. The transparent sheet according to any one of Items 1 to 3, wherein a 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. In any one of Items 1 to 4, wherein a peelable cover material that is peeled off at the time of use is further laminated on the surface side of the thermoplastic resin layer, and the thermoplastic resin layer includes an antistatic agent at least on the surface side. The transparent sheet described.
Item 6. Item 6. The transparent sheet according to any one of Items 1 to 5, wherein the total light transmittance before and after the following accelerated test is 90% or more and the haze is 3% or less.
(Accelerated test method)
The transparent sheet is put into a constant temperature and humidity machine, heated in a humid heat environment of 50 ° C. and a humidity of 90% for 7 days, dried and naturally cooled.
Item 7. Item 7. A smoke proof wall including the transparent sheet according to any one of items 1 to 6.
Item 8. A method for producing a transparent sheet comprising a glass fiber fabric, a photocurable resin composition layer contained in an impregnated state of the glass fiber fabric, and a thermoplastic resin layer laminated on the photocurable resin composition layer The process A for preparing at least two light-transmitting thermoplastic resin films laminated with a light-transmitting cover material, and the uncured photocurable resin composition in which the glass fiber fabric is immersed, The uncured photocurable resin composition is irradiated with light in a state where the two transparent thermoplastic resin films obtained in step A are sandwiched with a light-transmitting cover material facing outside, and the uncured photocurable resin composition is irradiated with light. A process for producing a transparent sheet, comprising: a step B of curing the cured photocurable resin composition.

  According to the present invention, in the composite of glass fiber and resin, when the glass fiber fabric is thin, while improving the initial tear strength, immediately after production and after long-term use in a hot and humid environment, It is possible to provide a transparent sheet that can easily improve the transparency (hereinafter sometimes abbreviated as “transparency before and after use in a high-temperature and high-humidity environment”). Therefore, the transparent sheet of the present invention can be suitably used for, for example, a smoke proof wall.

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

  The transparent sheet of the present invention is a glass fiber fabric having a thickness of 8 to 30 μm, a cured resin composition layer impregnated in the glass fiber fabric, and a polyvinyl chloride resin laminated on the cured resin composition layer. And a thermoplastic resin layer containing the thermoplastic resin.

  For example, as shown in FIG. 1, the transparent sheet 1 of the present invention comprises a glass fiber fabric 2, a cured resin composition layer 3 impregnated in the glass fiber fabric 2, and a thermoplastic resin 4 ( Hereinafter, it may be abbreviated as “thermoplastic resin layer 4”). In the transparent sheet 1, the glass fiber fabric 2 should just contain at least 1 layer, and multiple layers may be contained.

  In FIG. 1, the cured resin composition layer 3 fills gaps between a plurality of glass fibers constituting the glass fiber fabric 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, the cured resin composition layer 3 is formed on at least one surface of the glass fiber fabric 2 as shown in FIG. It is preferable that the cured resin composition layer 3 is formed on the surface of the layer of the glass fiber fabric 2.

  Moreover, the transparent sheet 1 of this invention can laminate | stack another layer on the surface side in the said thermoplastic resin layer 4 as needed. As the another 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 fabric 2)
In the transparent sheet 1 of the present invention, the glass fiber fabric 2 is composed of a plurality of glass fibers. In the glass fiber fabric 2, the plurality of glass fibers are entangled with each other to form a single fabric. Examples of the glass fiber fabric 2 include a glass fiber fabric (glass cloth) composed of a plurality of warps and a plurality of wefts. The woven structure of the glass fiber fabric is not particularly limited, and examples thereof include plain weave, satin weave, twill weave, oblique weave, and woven weave.

  It does not restrict | limit especially as a glass material of the glass fiber which comprises the glass fiber fabric 2, For example, a well-known glass material can be used. Examples of the glass material include alkali-free glass (E glass), acid-resistant alkali-containing glass (C glass), high-strength and high-modulus glass (S glass, T glass, etc.), alkali-resistant glass (AR glass), and the like. Preferably, alkali-free glass (E glass) with high versatility is used. The glass fibers constituting the glass fiber fabric 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. Moreover, it is preferable to select the glass material which approximates the refractive index of the cured resin composition layer 3 mentioned later from a viewpoint of improving transparency more.

  In the transparent sheet 1 of the present invention, the glass fiber fabric has a thickness of 8 to 30 μm. By making the glass fiber fabric thinner than the prior art in the composite material of transparent resin and glass cloth, it becomes possible to improve the transparency of the transparent sheet before and after use in a high-temperature and high-humidity environment while maintaining the flame-resistant property. . 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 when the resin contained in the transparent sheet is burned, the glass fiber fabric is roughened. From the viewpoint of making it easier to prevent, the glass fiber fabric is a woven fabric, and the glass yarn constituting the woven fabric has an average filament diameter of 3.5 to 4.5 μm and the number of filaments of 20 to 110, and the woven fabric. However, it is preferable that the weaving density is 80 to 120 pieces / 25 mm, the thickness is 9 to 30 μm, and the mass is 9 to 35 g / m ² .

  Further, in the glass fiber woven fabric, the thickness of the glass fiber woven fabric is adjusted to the thickness of the warp glass filament from the viewpoint of making it easier to prevent the occurrence of rough glass fiber fabric when the resin contained in the transparent sheet burns. The average number of stages represented by the value divided by the average value of the diameter and the diameter of the weft glass filament (glass cloth thickness / {(diameter of warp glass filament + diameter of weft glass filament) / 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 fabric plays a role of preventing the diffusion of smoke when a fire occurs. In the event of a fire, hot air may flow along the ceiling, and it is required to prevent this with a smoke barrier.

  On the other hand, the glass fiber fabric having the above-described configuration has a thickness of about several times the average filament diameter and about several filaments. That is, the configuration of the glass fiber fabric also indicates that a plurality of filaments are widened in the glass fabric plane direction. By flattening the glass yarn containing a specific number of filaments with a specific filament diameter so that the glass fiber fabric has a specific thickness, the resin component is combusted at the time of the fire compared to the round glass yarn that is not flattened. However, the texture is more difficult to shift and it is even easier to prevent the formation of large through holes. Moreover, by setting it as the structure of the above glass fiber fabrics, the refraction and reflection of the light which injects into a transparent sheet can be reduced, and the transparency before and behind use in a hot and humid environment can further be improved. As a method for producing the glass fiber fabric as described above, for example, a glass yarn having an average filament diameter of 3.5 to 4.5 μm and a filament number of 20 to 110, and a weaving density of 80 to 120 in terms of background. Weaving with an air jet loom so as to be / 25 mm, and water flow treatment at a pressure of about 1 to 3 MPa is performed while the tension of the glass fiber fabric is 50 to 100 N / m, more preferably 80 to 100 N / m. It is preferable to perform the process a plurality of times.

From the same viewpoint, the glass fiber fabric is a woven fabric, the glass yarn constituting the woven fabric has an average filament diameter of 3.5 to 4.2 μm, the number of filaments of 45 to 110, and the woven fabric has a woven density. Is more preferably 85 to 105 yarns / 25 mm, a thickness of 9 to 30 μm, and a mass of 9 to 35 g / m ^{2. 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 weave density of 80 to 120 pieces / 25 mm in terms of background, a thickness of 9 to 13 μm, and a mass of 9 to 15 g / m ^2. More preferably, the glass yarn constituting the woven fabric has an average filament diameter of 3.5 to 4.2 μm, the number of filaments of 45 to 55, and the woven fabric has a woven density. 85 to 105 present / 25 mm, a thickness of 9～13Myuemu, it is particularly preferred that the mass is assumed to be 9~13g / ^{m 2.}

  The difference in refractive index between the glass fiber fabric 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 fabric 2 is preferably about 1.45 to 1.65, more preferably about 1.50 to 1.60.

In addition, the measurement of the refractive index of the said glass fiber fabric 2 is performed according to B method of JISK7142: 2008. Specifically, with respect to the glass fibers constituting the glass fiber fabric 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 the immersion liquid. 366), NAG-2T manufactured by Atago Co., Ltd. as an Abbe refractometer, and sodium D line with a wavelength of 589 nm as a light source, measured at a temperature of 23 ° C., and the average value of five tests is refracted The value of rate. Moreover, the measurement of the refractive index of the cured resin composition 3 is performed according to B method of JISK7142: 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 the immersion liquid. 1.366), using a small measurement microscope STM5-311 (Olympus, observation magnification: 400 times) as a microscope, using sodium D-line with a wavelength of 589 nm as a light source, and measuring at a temperature of 23 ° C. The average value of the times is taken as the refractive index value.

  The difference in Abbe number between the glass fiber fabric 2 and the cured resin composition layer 3 is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. As Abbe number of glass fiber fabric 2, 30-80 are preferred, 40-70 are more preferred, and 50-65 are still more preferred. In addition, the Abbe number of a cured resin composition and glass fiber is measured as follows.

(Abbe number of cured resin composition)
A sheet of a cured resin composition that does not contain glass fiber fabrics is prepared with the same thickness under the same conditions as when glass fiber fabrics are contained, the test piece is 8 mm wide and 20 mm long, and the surface is well polished, and JIS K According to the 7142A method, NAR-2T manufactured by Atago Co., Ltd. as an Abbe refractometer, diiodomethane as a contact liquid, sodium D-line having a wavelength of 589 nm as a light source, a measurement temperature of 23 ° C., and a refractive index at a wavelength of 589 nm are measured. . 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-1 at a wavelength of 589 nm) / dispersion value (III)

(Abbe number of glass fiber)
Using a glass material constituting the glass fiber, a glass sheet having a width of 8 mm, a length of 20 mm, and a thickness of 5 mm is prepared, and the surface is well polished. As an Abbe refractometer, manufactured by Atago Co., Ltd. according to the JIS K 7142A method. Using NAR-2T, diiodomethane as a contact liquid, sodium D-line having a wavelength of 589 nm as a light source, and measuring temperature at 23 ° C., the refractive index at a wavelength of 589 nm is measured. 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 (III).

(Curing resin composition layer 3)
In the transparent sheet 1 of the present invention, the cured resin composition layer 3 is impregnated in a glass fiber fabric 2 described later, and is formed of a cured product of a 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 and heat to the resin composition containing the curable resin.

  As the curable resin, 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, the refractive index of the cured resin composition layer 3 and the glass fiber fabric 2 described above can be approximated. Those are preferred. Preferred curable resins are those in which the curable resin composition is photocurable, such as vinyl ester resins, urethane acrylate resins, fluorene acrylate resins, unsaturated polyester resins, curable acrylic resins, and epoxy resins. It is done. Especially, what hardened | cured the resin composition containing an acrylic syrup from a viewpoint of improving adhesiveness with the thermoplastic resin layer 4 more is especially 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 acrylic syrups, at least one acrylic ester polymer selected from the group consisting of polymethyl methacrylate, methyl methacrylate / methyl acrylate copolymer, and methyl methacrylate / normal butyl acrylate copolymer is methacrylic. Acrylic syrup dissolved in an acid methyl monomer is particularly preferred. As described above, when the cured resin composition layer 3 is obtained by curing a resin composition containing acrylic syrup, the adhesiveness with the thermoplastic resin layer 4 is further improved. It is preferable because 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 phosphate ester. Examples of the ultraviolet absorber include benzotriazole. Examples of the filler include calcium carbonate, silica, and talc. Examples of the antistatic agent include a surfactant. These additives may be used individually by 1 type, and may be used in combination of 2 or more types.

  In the present invention, in order to increase the transparency of the transparent sheet 1 before and after use in a high-temperature and high-humidity environment, the refractive index of the glass fiber fabric 2 and the cured resin composition 3 described later are set to approximate. From such a viewpoint, the refractive index of the cured resin composition 3 is preferably about 1.45 to 1.65, more preferably about 1.50 to 1.60. Moreover, in order to improve the transparency of the transparent sheet 1 before and after use in a high-temperature and high-humidity environment, it is preferable that the glass fiber fabric 2 and the Abbe number of the cured resin composition 3 described later are set so as to approximate each other. From such a viewpoint, the Abbe number of the cured resin composition 3 is preferably 30 to 70, and 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 , and the viewpoint that both transparency before and after use in a high-temperature and high-humidity environment and incombustibility are more compatible. From 20 to 50 g / m ² is preferable. Moreover, as thickness of a cured resin composition layer, 20-130 micrometers is mentioned, for example, and 30-60 micrometers is mentioned preferably from a viewpoint of making the transparency and nonflammability before and after use in a hot and humid environment more compatible. .

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

(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 fabric 2 and is transparent when used for a long time in the high temperature and high humidity environment of the transparent sheet 1. While maintaining the above, it plays a role of improving the initial tear strength.

  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 plasticizer is small, and biaxial stretching including an amorphous thermoplastic resin other than the polyvinyl chloride resin. A film is preferable. Examples of the thermoplastic resin other than the polyvinyl chloride resin include a polyester resin, a polycarbonate resin, and a polyamide resin, and may include at least one of these. Further, the thermoplastic resin layer 4 may not contain a polyvinyl chloride resin. From the viewpoint of further improving the initial tear strength of the transparent sheet 1, the thermoplastic resin layer 4 is an Elmendorf tear propagation resistance (JIS K7128-2 · 1998 using an Elmendorf tearing machine manufactured by Toyo Seiki Seisakusho Co., Ltd.). The tear strength (N) is measured based on the film thickness, and the measured value is divided by the film thickness to obtain the tear propagation resistance (N / mm). The average value of the results.) The vertical direction and the horizontal direction are 1 N / mm or more, preferably 3 to 20 N / mm, more preferably 5 to 15 N / mm. . Among these, the thermoplastic resin layer 4 is made of a polyester resin from the viewpoint of further achieving both chemical resistance (including alkali detergent resistance when used as a smoke barrier), improvement in initial tear strength, and transparency. It is preferable to include. Examples of the polyester resin include polyethylene terephthalate (PET) or polyethylene naphthalate (PEN). As content of the plasticizer in the thermoplastic resin layer 4, 10 mass% or less is mentioned, for example, 5 mass% or less is preferable, 3 mass% or less is more preferable, 1 mass% or less is more preferable, 0.5 A mass% or less is particularly preferred. Examples of the plasticizer include those known as plasticizers for vinyl chloride resins, such as di-n-butyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, Phthalic acid plasticizers such as dioctyl decyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl isophthalate, 2-ethylhexyl adipate, di-2-decyl adipate, dibutyl sebacate, sebacic acid Fatty acid ester plasticizers such as 2-ethylhexyl, phosphate plasticizers such as tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyl diphenyl phosphate, and tricresyl phosphate, tri-2-ethylhexyl trimellitic acid , Trimellitic acid such as trioctyl trimellitic acid Ester plasticizers, adipate-based polyester plasticizer, polyester plasticizer such as phthalic acid type polyester plasticizer, and a terephthalic acid-based plasticizer.

  If necessary, the thermoplastic resin layer 4 can be subjected to surface treatment such as corona treatment, flame treatment, and plasma treatment, and various functions such as slipperiness, easy adhesion, and antistatic properties are imparted. A coating layer to be applied, a hard coat layer for improving wear resistance, or the like may be provided.

  In particular, 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 described later, the thermoplastic resin layer 4 is at least on the surface side (the thermoplastic resin layer in FIG. It is preferable that an antistatic agent is contained in the surface side portions 41 and 42) of the No. 4. 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 during construction. Then, for example, when the smoke proof wall is installed in a large facility such as a shopping mall, the cover material 5 is peeled off in accordance with the opening of the large facility (that is, when used as a smoke proof 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. It may be attached to the surface of the smoke barrier. Therefore, by making the thermoplastic resin layer 4 contain an antistatic agent at least on the surface side, generation of static electricity accompanying peeling of the cover material 5 can be further suppressed, and excellent transparency immediately after the production of the transparent sheet 1 can be maintained. It becomes easy.

  As the antistatic agent, known ones can be used, 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 sulfonate group , Anionic antistatic agents having anionic groups such as sulfate ester bases, phosphate ester bases, phosphonate bases; amphoteric antistatic agents such as amino acids and aminosulfate esters; amino alcohols, glycerols, polyethylene glycols Various surfactant type antistatic agents such as nonionic antistatic agents such as, and the like; and further, high molecular weight antistatic agents obtained by increasing the molecular weight of the above antistatic agents, and inorganic such as silver, tin oxide and zinc oxide And antistatic agents. Further, monomers and oligomers having a tertiary amino group or a quaternary ammonium group and capable of being polymerized by ionizing radiation, such as N, N-dialkylaminoalkyl (meth) acrylate monomers, their quaternary compounds, etc. A polymerizable antistatic agent can also be used. In addition, when an inorganic antistatic agent such as a silver-based, tin oxide-based, zinc oxide-based or the like is used, the particle diameter of the inorganic fine particles is, for example, a particle diameter (BET particle diameter) determined using the BET method is visible light. The transparency of the transparent sheet 1 can be more easily maintained by setting it to 100 nm or less, preferably 1 to 100 nm, which is equal to or less than the above wavelength.

In the transparent sheet 1 of the present invention, the mass per one layer of the thermoplastic resin layer 4 is, for example, 30 to 150 g / m ^2. From the viewpoint of making the initial tear strength and the nonflammability more compatible, 50 -90 g / m < ² > is mentioned preferably and 60-80 g / m < ² > is mentioned more preferably. Moreover, as thickness of the thermoplastic resin layer 4, 20-100 micrometers is mentioned, for example, 30-70 micrometers is mentioned preferably from a viewpoint of making initial tear strength and nonflammability more compatible, 40-60 micrometers is more. Preferably mentioned. Further, for example, another layer such as a coating layer that imparts various functions such as slipperiness, easy adhesion, and antistatic property and / or a hard coat layer that improves wear resistance is laminated on the thermoplastic resin layer 4. When doing, as thickness of the said another layer, 0.1-3 micrometers is mentioned, for example, 0.1-1 micrometer is mentioned preferably.

(Peelable cover material 5)
In the transparent sheet 1 of the present invention, a peelable cover material 5 that is peeled off at the time of use can be further laminated on the surface side of the thermoplastic resin layer 4 as necessary. Thereby, 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 transparency and aesthetics from being deteriorated due to scratches and the like on the transparent sheet 1 during construction.

  And as mentioned above, when the cover material 5 is installed in, for example, a facility that requires installation of smoke barriers according to the Building Standard Law, for example, after the installation of smoke barriers (that is, smoke protection) 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. It may be attached to the surface of the smoke barrier. Therefore, when the peelable cover material 5 which 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 obtained by making the thermoplastic resin layer 4 contain at least the antistatic agent on the surface side. 5 is preferable because the generation of static electricity associated with the peeling of 5 can be further suppressed and the excellent transparency of the transparent sheet 1 can be easily maintained.

  For example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, or the like can be used as the peelable cover material 5. When the cover material 5 is peeled off, the cover material 5 and the thermoplastic resin are used. What is necessary is just that the adhesive force with the resin layer 4 is smaller than the adhesive force between the thermoplastic resin layer 4 and the cured resin composition layer 3. In particular, when the cover material 5 that can be peeled is a light-transmitting cover material, for example, when the resin composition that forms the cured resin composition layer 3 described above is a photocurable cured resin composition. Also in the step of curing the curable resin composition, it is preferable in that it is easy to prevent the thermoplastic resin composition layer 4 from being damaged and the transparency and aesthetics from being deteriorated. The light transmittance is not particularly limited as long as it transmits light that cures the photocurable resin. For example, it transmits light with a wavelength of 100 to 400 nm, or transmits light with a wavelength of 250 to 400 nm. Is 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 50%. The above is more preferable, and 60% or more is particularly preferable.

(Physical properties and performance of transparent sheet 1)
As the thickness of the transparent sheet 1 of the present invention, for example, as the thickness of the transparent sheet 1 after peeling the peelable cover material 5 peeled off during use (that is, the thickness excluding the peelable cover material 5) Is 100 to 300 μm, preferably 150 to 200 μm. Moreover, as the mass of the transparent sheet 1 of the present invention, for example, as the mass of the peelable cover material 5 that is peeled off during use (ie, the mass excluding the peelable cover material 5) of 100, -400 g / m < ² > is mentioned, 150-300 g / m < ² > is mentioned preferably. Moreover, in the transparent sheet 1 of the present invention, if 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 , nonflammability and tearing This is preferable because it is easier to achieve both strength and strength.

  In the transparent sheet 1 of the present invention, the thickness of the glass fiber fabric is 8 to 30 μm, and the thermoplastic resin layer 4 is laminated. Therefore, 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 before use in a high-temperature and high-humidity environment of the transparent sheet 1 of the present invention is 85% or more, preferably 90% or more. . Moreover, 5% or less is mentioned as the haze before using the transparent sheet 1 of this invention in a hot and humid environment, 3% or less is preferable and 1% or less is more preferable. The total light transmittance and haze of the transparent sheet 1 are values obtained by measurement according to JIS K7375 2008 “Plastics—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 glass fiber fabric has a thickness of 8 to 30 μm, and the refractive index difference between the glass fiber fabric 2 and the cured resin composition layer 3. The glass fiber fabric is a woven fabric, the glass yarn constituting the woven fabric has an average filament diameter of 3.5 to 4.5 μm, the number of filaments of 20 to 55, and the woven fabric, The weaving density is 80 to 120 pieces / 25 mm in both circumstances, the thickness is 9 to 15 μm, the mass is 9 to 15 g / m ² , and the cured resin composition layer 3 is a cured resin composition containing acrylic syrup. And so on.

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 accelerated test is 85% or more, and preferably 90% or more. The haze of the transparent sheet 1 of the present invention after use in a hot and humid environment includes 5% or less of the haze of the transparent sheet 1 after the following acceleration test, preferably 3% or less, and more preferably 1% or less. .
(Accelerated test method)
The transparent sheet is placed in a thermo-hygrostat, heated for 7 days in a humid heat environment of 50 ° C. and 90% humidity, dried and naturally cooled, and then JIS K7375 2008 “Plastics-Determination of total light transmittance and total light reflectance. Measure in accordance with “Method”.

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

In the transparent sheet 1 of the present invention, since the thermoplastic resin layer 4 is provided, 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)
In accordance with JIS R 3420: 2013, 7.16 C method (trapezoid method), 75 mm × 150 mm test pieces were taken from the transparent sheet in the vertical direction and the horizontal direction, respectively, and two trapezoidal portions including right angles (FIG. 3). A tape (Sekisui Chemical Co., Ltd., product name 600S) is attached to each side of the back and front surfaces of each, and a constant speed load type tensile tester (Co., Ltd.) The maximum load was measured using the Orientec product name RTC-1310A), and the average value of the maximum vertical load and the maximum horizontal load (= (maximum vertical load (N) + maximum horizontal load ( N)) / 2) is the initial tear strength (N).

Since the transparent sheet 1 of the present invention includes the glass fiber fabric 2, the transparent sheet 1 can be provided with a property that does not easily burn (nonflammability). In addition, as the nonflammability of the transparent sheet 1 of the present invention, 4.10.2 heat generation in the “Fireproofing Performance Test / Evaluation Business Method Manual” (modified on March 1, 2014) of the Building Materials Testing Center In an exothermic test in which the surface of the sheet is irradiated with 50 kW / m ² of radiant heat from a radiant electric heater, measured according to the property test / evaluation method, the maximum heat generation rate after starting heating is 200 kW / m ² continuously for 10 seconds or more. And the total calorific value is preferably 8 MJ / m ² or less. In order to further improve the incombustibility, for example, in the cured resin composition layer 3 and the thermoplastic resin layer 4, a flame retardant may be added, the amount of organic substances may be reduced, and the like.

(Method for producing transparent sheet of the present invention)
The production method of the transparent sheet 1 of the present invention is not particularly limited, and examples thereof include the following production methods. First, the above-described uncured cured resin composition constituting the glass fiber fabric 2 and the cured resin composition layer 3 is prepared. The cured resin composition is applied to a film (for example, a polyester film) that forms the thermoplastic resin layer 4, and the film is pressure-bonded from both sides of the glass fiber fabric 2 to apply the cured resin composition from both sides of the glass fiber fabric 2. Impregnation and curing the cured resin composition by heating or light irradiation, the glass fiber fabric 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. Transparent sheet 1 (transparent sheet 1 laminated in the order of cured resin composition layer 3 / thermoplastic resin layer 4 contained in a state of being impregnated with thermoplastic resin layer 4 / glass fiber fabric 2) 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. Moreover, when hardening a resin composition by provision of light energy, light is irradiated and hardened | cured to a resin composition. As conditions for light irradiation, for example, the integrated light quantity can be set to 100 to 500 mJ / cm ² .

  Further, for example, when the thermoplastic resin layer 4 includes 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 used as the thermoplastic resin layer 4 in advance. An antistatic treatment can also be applied to this. Further, when the transparent sheet 1 of the present invention is further laminated with a peelable cover material 5 that is peeled off at the time of use on the surface side of the thermoplastic resin layer 4, the transparent sheet 1 is obtained after obtaining the transparent sheet 1. The cover material 5 can be laminated. In addition, the cover material 5 that can be peeled in advance is laminated on a film that forms the thermoplastic resin layer 4 and the both are integrated so that the cover material 5 is on the outside so that the uncured cured resin composition is thermoplastic. The resin layer 4 is applied to the surface, and the sheet coated with the integrated cured resin composition from both sides of the glass fiber fabric 2 is pressure-bonded and impregnated with the resin composition from both sides of the glass fiber fabric 2 to obtain a cured resin composition. The product is cured by heating or light irradiation, the glass fiber fabric 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 Transparent sheet 1 on which peelable cover material 5 is laminated (cured resin composition layer 3 / thermoplastic resin layer contained in a state of being impregnated in peelable cover material 5 / thermoplastic resin layer 4 / glass fiber fabric 2) 4 / Peelable cover 5 Laminated transparent sheet 1) is obtained.

  Moreover, as a manufacturing method of the transparent sheet of the present invention, a glass fiber fabric, a photocurable resin composition layer contained in a state impregnated in the glass fiber fabric, and a laminate of the photocurable resin composition layer, A process for preparing at least two light-transmitting thermoplastic resin films on which a light-transmitting cover material is laminated, and a glass fiber fabric soaked. The uncured photocured resin composition is sandwiched between the two thermoplastic resin films obtained in the step A so that the light-transmitting cover material is on the outside, and the uncured photocured resin composition is And 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)
As a use of the transparent sheet of the present invention, it is possible to use a smoke-proof hanging wall. Among them, the transparent sheet of the present invention is capable of high-frequency welding when the outermost layer becomes the thermoplastic resin layer 4 when the smoke-proof 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 incombustible sheet is stretched between two pairs of uprights, for example, a transparent incombustible when installed suspended from a ceiling. A smoke-proof hanging wall that does not have an eye-opening is mentioned on the lower side of the adhesive sheet. Also,
Since it can be a substitute for glass, it can also be applied to other uses where glass is used, such as partitions, partitions, smoke-proof sheets, smoke-proof curtains (for example, those used in factories), touch panels, etc. it can. Moreover, the transparent sheet 1 of this invention is further excellent in a softness | flexibility, when the mass of the curable resin composition layer 4 shall be 20-100 g / m < ² >, More preferably, 20-50 g / m < ² >, for example. It becomes easy to make a roll product. Examples of the length in the longitudinal direction of the roll product 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.

The cured resin composition impregnated in the above glass fiber fabric was made into an acrylic syrup (trade name “Acrysilup XD-8005” (refractive index: 1.550) manufactured by Ryojo Co., Ltd.) and the composition shown in Table 1. "Acrysilap XD-8006" (refractive index of 1.570) mixed at a mass ratio of 1: 1), vinyl ester resin (manufactured by Nippon Iupika Co., Ltd.), styrene monomer (manufactured by Nippon Iupika Co., Ltd.), bifunctional A mixture of (meth) acrylate and photopolymerization initiator was used. In addition, as a bifunctional (meth) acrylate which is a hardening | curing agent, the NPGDA (Neopentyl glycol diacrylate, the molecular weight 212, (made by Nippon Iupika Co., Ltd.)) of Table 1 was used. Moreover, the quantity of the photoinitiator was 2 mass parts with respect to a total of 100 mass parts of vinyl ester resin, a styrene monomer, and bifunctional (meth) acrylate. As the thermoplastic resin layer, a commercially available biaxially stretched polyester film (trade name “Cosmo Shine (registered trademark) A4300”, thickness 50 μm, mass 70 g / m ² ) manufactured by Toyobo Co., Ltd. is used as an antistatic agent and is charged with tin oxide. A polyester resin in which an inhibitor (particle size of 100 nm or less) is dispersed is applied at 0.5 g / m ^{2. As a} vinyl chloride resin, a commercially available vinyl chloride resin film (manufactured by Okamoto Co., Ltd., PVC # 320 for general use, thickness) 100 μm, mass 120 g / m ² ) was used. As the peelable cover material, a polypropylene film (thickness 40 μm, mass 36 g / m ² ), and as the pressure sensitive adhesive for releasably bonding the peelable cover material to the thermoplastic resin layer, an acrylic ester pressure sensitive adhesive is used. Using.

<Example 1>
(Manufacture of glass fiber fabrics)
As the warp and weft, we use the unit name “ECBC3000 1/0 0.5Z” (average filament diameter 4 μm, average filament number 50, twist number 0.5Z) manufactured by Unitika Glass Fiber Co., Ltd. A plain-woven glass fiber woven fabric having a density of 95/25 mm and a weft density of 95/25 mm was obtained. Subsequently, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400 ° C. for 30 hours. Thereafter, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g / L and squeezed with a padder roll. Then, it was dried and cured at 120 ° C. for 1 minute. And the widening process was performed twice by the water flow process of pressure 1.5MPa, making the tension | tensile_strength of the glass fiber fabric into the warp direction 100N / m, and the glass fiber fabric was obtained. The obtained glass fiber fabric had a warp density of 95/25 mm, a weft density of 95/25 mm, a thickness of 13 μm, a mass of 12 g / m ² and a refractive index of 1.561.

(Lamination of peelable cover material on thermoplastic resin layer)
The above-mentioned polyester film with an acrylic ester adhesive applied to the above-described polypropylene film on the surface side of the polyester film subjected to the antistatic treatment, so that the pressure-sensitive adhesive becomes 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.

(Manufacture of transparent sheets)
The cured resin composition shown in Table 1 was applied to the polyester film side of one film obtained by laminating a polypropylene film on the polyester film described above. Next, the glass fiber fabric obtained above was placed on the cured resin composition and allowed to stand for 1 minute to impregnate the resin in the gaps of the glass fiber fabric. Next, another film in which a polypropylene film was laminated on the above-described polyester film was further 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 . Thereafter, the entire film in which the polypropylene film is laminated on the polyester film and the cured resin composition are irradiated with light using a black light fluorescent lamp (trade name: FL15BLB manufactured by Toshiba Corporation) (light irradiation condition: integrated light quantity: 200 mJ / cm ² ). 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 gap between the glass fibers of the glass fiber fabric is impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both surfaces of the glass fiber fabric layer. A composition layer was formed.

<Example 2>
(Manufacture of glass fiber fabrics)
As the warp and weft, we use the unit name “ECBC3000 1/0 0.5Z” (average filament diameter 4 μm, average filament number 50, twist number 0.5Z) manufactured by Unitika Glass Fiber Co., Ltd. A plain-woven glass fiber woven fabric having a density of 95/25 mm and a weft density of 95/25 mm was obtained. Subsequently, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400 ° C. for 30 hours. Thereafter, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g / L and squeezed with a padder roll. Then, it was dried and cured at 120 ° C. for 1 minute. And the widening process was performed twice by the water flow process of pressure 1.5MPa, making the tension | tensile_strength of the glass fiber fabric into the warp direction 100N / m, and the glass fiber fabric was obtained. The obtained glass fiber fabric had a warp density of 95/25 mm, a weft density of 95/25 mm, a thickness of 13 μm, a mass of 12 g / m ² and a refractive index of 1.561.

(Lamination of peelable cover material on thermoplastic resin layer)
The above-mentioned polyester film with an acrylic ester adhesive applied to the above-described polypropylene film on the surface side of the polyester film subjected to the antistatic treatment, so that the pressure-sensitive adhesive becomes 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.

(Manufacture of transparent sheets)
The cured resin composition shown in Table 1 was applied to the polyester film side of one film obtained by laminating a polypropylene film on the polyester film described above. Next, the glass fiber fabric obtained above was placed on the cured resin composition and allowed to stand for 1 minute to impregnate the resin in the gaps of the glass fiber fabric. Next, another film in which a polypropylene film was laminated on the above-described polyester film was further 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 . Thereafter, the entire film in which the polypropylene film is laminated on the polyester film and the cured resin composition are irradiated with light using a black light fluorescent lamp (trade name: FL15BLB manufactured by Toshiba Corporation) (light irradiation condition: integrated light quantity: 200 mJ / cm ² ). 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 gap between the glass fibers of the glass fiber fabric is impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both surfaces of the glass fiber fabric layer. A composition layer was formed.

<Example 3>
(Manufacture of glass fiber fabrics)
As the warp and weft, we use the unit name “ECBC3000 1/0 0.5Z” (average filament diameter 4 μm, average filament number 50, twist number 0.5Z) manufactured by Unitika Glass Fiber Co., Ltd. A plain-woven glass fiber woven fabric having a density of 95/25 mm and a weft density of 95/25 mm was obtained. Subsequently, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400 ° C. for 30 hours. Thereafter, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g / L and squeezed with a padder roll. Then, it was dried and cured at 120 ° C. for 1 minute to obtain a glass fiber fabric (that is, no widening treatment was performed). The obtained glass fiber fabric had a warp density of 95/25 mm, a weft density of 95/25 mm, a thickness of 15 μm, a mass of 12 g / m ² , and a refractive index of 1.561.

  (Lamination of peelable cover material to thermoplastic resin layer) An acrylic ester-based pressure-sensitive adhesive is applied to the above-described polypropylene film on the surface of the polyester film subjected to the antistatic treatment, which has been subjected to the antistatic treatment. What was provided was laminated so that the pressure-sensitive adhesive would be 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.

(Manufacture of transparent sheets)
The cured resin composition shown in Table 1 was applied to the polyester film side of one film obtained by laminating a polypropylene film on the polyester film described above. Next, the glass fiber fabric obtained above was placed on the cured resin composition and allowed to stand for 1 minute to impregnate the resin in the gaps of the glass fiber fabric. Next, another film in which a polypropylene film was laminated on the above-described polyester film was further 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 . Thereafter, the entire film in which the polypropylene film is laminated on the polyester film and the cured resin composition are irradiated with light using a black light fluorescent lamp (trade name: FL15BLB manufactured by Toshiba Corporation) (light irradiation condition: integrated light quantity: 200 mJ / cm ² ). 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 gap between the glass fibers of the glass fiber fabric is impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both surfaces of the glass fiber fabric layer. A composition layer was formed.

<Example 4>
(Manufacture of glass fiber fabrics)
Weaving with an air jet loom using unit name “ECC1200 1/0 1.0Z” (average filament diameter 4.5 μm, average filament number 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 90/25 mm and a weft density of 90/25 mm was obtained. Subsequently, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400 ° C. for 30 hours. Thereafter, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g / L and squeezed with a padder roll. Then, it was dried and cured at 120 ° C. for 1 minute. Then, the glass fiber fabric was subjected to a widening process once by a water flow process at a pressure of 1.5 MPa while the tension of the glass fiber fabric was set to 100 N / m in the warp direction to obtain a glass fiber fabric. The obtained glass fiber fabric had a warp density of 90/25 mm, a weft density of 90/25 mm, a thickness of 27 μm, a mass of 30 g / m ² , and a refractive index of 1.561.

(Lamination of peelable cover material on thermoplastic resin layer)
The above-mentioned polyester film with an acrylic ester adhesive applied to the above-described polypropylene film on the surface side of the polyester film subjected to the antistatic treatment, so that the pressure-sensitive adhesive becomes 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.

(Manufacture of transparent sheets)
The cured resin composition shown in Table 1 was applied to the polyester film side of one film obtained by laminating a polypropylene film on the polyester film described above. Next, the glass fiber fabric obtained above was placed on the cured resin composition and allowed to stand for 1 minute to impregnate the resin in the gaps of the glass fiber fabric. Next, another film in which a polypropylene film was laminated on the above-described polyester film was further placed from above, and pressure was applied from above with a roller so that the mass of the cured resin composition layer was 90 g / m ² . Thereafter, the entire film in which the polypropylene film is laminated on the polyester film and the cured resin composition are irradiated with light using a black light fluorescent lamp (trade name: FL15BLB manufactured by Toshiba Corporation) (light irradiation condition: integrated light quantity: 200 mJ / cm ² ). 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 gap between the glass fibers of the glass fiber fabric is impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both surfaces of the glass fiber fabric layer. A composition layer was formed.

<Comparative Example 1>
(Manufacture of glass fiber fabrics)
As the warp and weft, we use the unit name “ECBC3000 1/0 0.5Z” (average filament diameter 4 μm, average filament number 50, twist number 0.5Z) manufactured by Unitika Glass Fiber Co., Ltd. A plain-woven glass fiber woven fabric having a density of 95/25 mm and a weft density of 95/25 mm was obtained. Subsequently, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400 ° C. for 30 hours. Thereafter, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g / L and squeezed with a padder roll. Then, it was dried and cured at 120 ° C. for 1 minute. And the widening process was performed twice by the water flow process of pressure 1.5MPa, making the tension | tensile_strength of the glass fiber fabric into the warp direction 100N / m, and the glass fiber fabric was obtained. The obtained glass fiber fabric had a warp density of 95/25 mm, a weft density of 95/25 mm, a thickness of 13 μm, a mass of 12 g / m ² and a refractive index of 1.561.

(Manufacture of transparent sheets)
The cured resin composition shown in Table 1 was applied to one vinyl chloride resin film described above. Next, the glass fiber fabric obtained above was placed on the cured resin composition and allowed to stand for 1 minute to impregnate the resin in the gaps of the glass fiber fabric. Next, another vinyl chloride resin film described above was further 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 . Thereafter, the cured resin composition is irradiated with light using a black light fluorescent lamp (trade name: FL15BLB manufactured by Toshiba Corporation) on the cured resin composition together with the vinyl chloride resin film (light irradiation condition: integrated light quantity: 200 mJ / cm ² ). Cured to form a cured resin composition layer to obtain a transparent sheet. In the obtained transparent sheet, the gap between the glass fibers of the glass fiber fabric is impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both surfaces of the glass fiber fabric layer. A composition layer was formed.

<Comparative example 2>
(Manufacture of glass fiber fabrics)
As the warp and weft, we use the unit name “ECBC3000 1/0 0.5Z” (average filament diameter 4 μm, average filament number 50, twist number 0.5Z) manufactured by Unitika Glass Fiber Co., Ltd. A plain-woven glass fiber woven fabric having a density of 95/25 mm and a weft density of 95/25 mm was obtained. Subsequently, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400 ° C. for 30 hours. Thereafter, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g / L and squeezed with a padder roll. Then, it was dried and cured at 120 ° C. for 1 minute. And the widening process was performed twice by the water flow process of pressure 1.5MPa, making the tension | tensile_strength of the glass fiber fabric into the warp direction 100N / m, and the glass fiber fabric was obtained. The obtained glass fiber fabric had a warp density of 95/25 mm, a weft density of 95/25 mm, a thickness of 13 μm, a mass of 12 g / m ² and a refractive index of 1.561.

(Manufacture of transparent sheets)
The cured resin composition shown in Table 1 was applied on a 50 μm thick PET film. Next, the glass fiber fabric obtained above was placed on the resin composition and allowed to stand for 1 minute to impregnate the resin in the gaps of the glass fiber fabric. 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, with the above PET film, the resin composition is cured by irradiating the resin composition with light using a black light fluorescent lamp (trade name FL15BLB manufactured by Toshiba Corporation) (light irradiation condition: integrated light quantity 200 mJ / cm ² ). Then, a cured resin composition layer was formed. Next, the two PET films were removed to obtain a transparent sheet. In the obtained transparent sheet, the gap between the glass fibers of the glass fiber fabric is impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both surfaces of the glass fiber fabric layer. A composition layer was formed.

<Comparative Example 3>
(Manufacture of glass fiber fabrics)
Unite glass fiber Co., Ltd. product name “ECD450 1/0 1.0Z” (average filament diameter: 5 μm, average filament number: 200, twist number: 1.0Z) is used as the warp and weft, and is woven with an air jet loom, and warp A plain-woven glass fiber woven fabric having a density of 60/25 mm and a weft density of 60/25 mm was obtained. Subsequently, the spinning sizing agent and the weaving sizing agent adhering to the obtained glass fiber fabric were removed by heating at 400 ° C. for 30 hours. Thereafter, the surface treatment agent silane coupling agent (S-350: N-vinylbenzyl-aminoethyl-γ-aminopropyltrimethoxysilane (hydrochloride) Chisso Corporation) was adjusted to a concentration of 15 g / L and squeezed with a padder roll. Then, it was dried and cured at 120 ° C. for 1 minute. Then, the glass fiber fabric was subjected to a widening process once by a water flow process at a pressure of 1.5 MPa while the tension of the glass fiber fabric was set to 100 N / m in the warp direction to obtain a glass fiber fabric. The obtained glass fiber fabric had a warp density of 60/25 mm, a weft density of 60/25 mm, a thickness of 50 μm, a mass of 53 g / m ² , and a refractive index of 1.561.

(Lamination of peelable cover material on thermoplastic resin layer)
The above-mentioned polyester film with an acrylic ester adhesive applied to the above-described polypropylene film on the surface side of the polyester film subjected to the antistatic treatment, so that the pressure-sensitive adhesive becomes 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.

(Manufacture of transparent sheets)
The cured resin composition shown in Table 1 was applied to the polyester film side of one film obtained by laminating a polypropylene film on the polyester film described above. Next, the glass fiber fabric obtained above was placed on the cured resin composition and allowed to stand for 1 minute to impregnate the resin in the gaps of the glass fiber fabric. Next, another film obtained by laminating a polypropylene film on the above-described polyester film was further placed from above, and pressure was applied from above with a roller so that the mass of the cured resin composition layer was 160 g / m ² . Thereafter, the entire film in which the polypropylene film is laminated on the polyester film and the cured resin composition are irradiated with light using a black light fluorescent lamp (trade name: FL15BLB manufactured by Toshiba Corporation) (light irradiation condition: integrated light quantity: 200 mJ / cm ² ). 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 gap between the glass fibers of the glass fiber fabric is impregnated with a cured resin composition layer (cured product of the resin composition), and the cured resin is formed on both surfaces of the glass fiber fabric layer. A composition layer was formed.

  In Examples and Comparative Examples, the woven density of the glass fiber fabric was measured and calculated according to JIS R 3420 2013 7.9. Moreover, the thickness of the glass fiber fabric was measured and calculated according to JIS R 3420 2013 7.10.1A method. The mass of the glass fiber fabric was measured and calculated according to JIS R 3420 2013 7.2. The refractive indexes of the cured resin composition and the glass fiber fabric were measured and calculated by the method described above. The Abbe number of the cured resin composition and the glass fiber fabric was measured and calculated by the above method. The following evaluation was performed after leaving the room for one week after the production of the transparent sheet.

(Total light transmittance 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 K7375 2008 “Plastics—How to obtain 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 was put into a thermo-hygrostat as an accelerated test, and the transparent sheet after heating for 7 days in a humid heat environment of 50 ° C. and 90% humidity was JIS. K7375 2008 "Plastics-Determination of total light transmittance and total light reflectance" A product 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 standing in a high temperature and high humidity environment was regarded as acceptable. In addition, about Examples 1-4 and the comparative example 3, it evaluated about the transparent sheet after peeling the cover material which can be peeled.

(Initial tear strength (N))
Measurement and calculation were performed by the method described above. The thing of 50N or more was set as the pass. In addition, about Examples 1-4 and the comparative example 3, it evaluated about the transparent sheet after peeling the cover material which can be peeled.

(Nonflammability 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 calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less and the maximum exotherm rate does not exceed 200 kW / m ² for 20 minutes or more after the start of heating for 10 seconds or more (◎ ) And evaluation. In addition, about Examples 1-4 and the comparative example 3, it evaluated about the transparent sheet after peeling the cover material which can be peeled.

(Evaluation of rough 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, then taken out and cooled to room temperature, and the state of the glass fiber fabric was visually observed and evaluated according to the following criteria. ○ The above was accepted. In addition, about Examples 1-4 and the comparative example 3, it evaluated about the transparent sheet after peeling the cover material which can be peeled.
A: The generation of through-holes with a side of 0.5 mm or more in the weave was zero, and roughening could hardly be confirmed.
○: The generation of through-holes with a side of 0.5 mm or more in the weave is zero, and the roughness is somewhat conspicuous, but it is at a level that causes no problem in practical use.
X: Generation of through-holes having a side of 0.5 mm or more was confirmed in the texture, roughening was conspicuous, and there was a problem in practical use.

  Each evaluation result is shown in Table 1.

The transparent sheets of Examples 1 to 4 are laminated on a glass fiber fabric having a thickness of 8 to 30 μm, a cured resin composition layer contained in the state impregnated in the glass fiber fabric, and the cured resin composition layer. And a thermoplastic resin layer containing at least one selected from the group consisting of a polyester resin, a polycarbonate resin, and a polyamide resin, while improving the initial tear strength and in a high temperature and high humidity environment. It was possible to improve and maintain transparency before and after use. Among them, in the sheets of Examples 1 and 2, the glass fiber fabric is a woven fabric, and the glass yarn constituting the woven fabric has an average filament diameter of 3.5 to 4.5 μm and the number of filaments of 20 to 55, Since the woven fabric had a weaving density of 80 to 120 pieces / 25 mm, a thickness of 9 to 13 μm, and a mass of 9 to 15 g / m ² , the glass contained when the resin contained in the transparent sheet burned. It was made easier to prevent the occurrence of roughening of the fiber fabric. In Examples 1, 3 and 4, since the curable resin composition layer was obtained by curing a 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 fabric was 13 μm or less, the transparency before and after use in a high temperature and high humidity environment was remarkably excellent.

  In addition, the transparent sheets of Examples 1 to 4 are excellent in alkali latent resistance when the peelable cover material is peeled off, can be subjected to high-frequency welding processing, and the generation of static electricity accompanying the peeling of the cover material is more It could be further suppressed. Moreover, since the transparent sheets of Examples 1 to 4 included a cover material, particularly a light-transmitting cover material, scratches were generated in the manufacturing process of the transparent sheet and the installation work as a smoke-proof wall. Can be suppressed, and the handleability is also excellent. Furthermore, the transparent sheet of Examples 1-4, especially the transparent sheet of Examples 1-3 were excellent also in the softness | flexibility, and it was also possible to set it as a 5-300-m roll product.

  On the other hand, since the transparent sheet of Comparative Example 1 was obtained by laminating a vinyl chloride resin film on the 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 oozed out at the interface between the vinyl chloride resin film and the cured resin composition layer, and transparency could not be maintained.

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

  The transparent sheet of Comparative Example 3 was inferior in transparency before and after use in a high-temperature and high-humidity environment because the thickness of the glass fiber fabric exceeded 30 μm.

DESCRIPTION OF SYMBOLS 1 ... Transparent sheet 2 ... Glass fiber fabric 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... Peelable cover material

Claims (10)

At the time of use as a smoke-proof hanging wall laminated on the cured resin composition layer, a cured resin composition layer contained in a state impregnated in the glass fiber fabric, a glass fiber fabric having a thickness of 8 to 30 μm A non-peelable thermoplastic resin layer containing a thermoplastic resin other than polyvinyl chloride resin, and a peelable light-transmitting cover material that is laminated on the thermoplastic resin layer and peeled off when used as a smoke barrier and, only including,
Mass of the cured resin composition layer is 20 to 100 g / ^{m 2,} a transparent sheet for smoke vertical wall. At the time of use as a smoke-proof hanging wall laminated on the cured resin composition layer, a cured resin composition layer contained in a state impregnated in the glass fiber fabric, a glass fiber fabric having a thickness of 8 to 30 μm A non-peelable thermoplastic resin layer containing a thermoplastic resin other than polyvinyl chloride resin, and a peelable light-transmitting cover material that is laminated on the thermoplastic resin layer and peeled off when used as a smoke barrier And including
The glass fiber fabric is a woven fabric,
The glass yarn constituting the woven fabric has an average filament diameter of 3.5 to 4.5 μm, and the number of filaments is 20 to 110,
The woven fabric has a weaving density of 80 to 120 pieces / 25 mm, a thickness of 9 to 30 μm, and a mass of 9 to 35 g / m. ² Transparent sheet for smoke barriers. At the time of use as a smoke-proof hanging wall laminated on the cured resin composition layer, a cured resin composition layer contained in a state impregnated in the glass fiber fabric, a glass fiber fabric having a thickness of 8 to 30 μm A non-peelable thermoplastic resin layer containing a thermoplastic resin other than polyvinyl chloride resin, and a peelable light-transmitting cover material that is laminated on the thermoplastic resin layer and peeled off when used as a smoke barrier And including
A transparent sheet for a smoke-proof hanging wall having a total light transmittance of 90% or more and a haze of 3% or less before and after the following accelerated test.
(Accelerated test method)
The transparent sheet from which the cover material has been peeled is placed in a thermo-hygrostat, heated for 7 days in a moist heat environment of 50 ° C. and 90% humidity, dried and naturally cooled. The transparent sheet for smoke-proof hanging walls according to any one of claims 1 to 3 , wherein the glass fiber fabric impregnated with the cured resin composition layer is one sheet. The ratio of the mass (g / m < ² >) of the said glass fiber fabric with respect to the total mass (g / m < ² >) of the said transparent sheet after peeling the said cover material is 3-15 mass% . The transparent sheet for smoke-proof hanging walls according to any one of the above. The ratio of the mass (g / m < ² >) of the said glass fiber fabric with respect to the total mass (g / m < ² >) of the said transparent sheet after peeling the said cover material is 3-12 mass% of Claims 1-5. The transparent sheet for smoke-proof hanging walls according to any one of the above. The transparent sheet for smoke-proof hanging walls according to any one of claims 1 to 6 , wherein the cured resin composition layer is obtained by curing a resin composition containing acrylic syrup. The said transparent sheet WHEREIN: The total mass of the said cured resin composition layer and the said thermoplastic resin layer is 150-300 g / m < ² >, The transparent sheet for smoke-proof hanging walls of any one of Claims 1-7. .   The transparent sheet for smoke-proof hanging walls according to any one of claims 1 to 8, wherein the thermoplastic resin layer contains an antistatic agent at least on the surface side. A smoke barrier wall comprising the smoke-proof wall transparent sheet according to any one of claims 1 to 9 .