JP5142002B2 - Transparent incombustible sheet and method for producing the same - Google Patents

Description

  The present invention relates to a transparent noncombustible sheet and a method for producing the same.

  The Building Standard Law and the Building Standard Law Enforcement Ordinance stipulate that smoke-exhaust equipment should be installed to prevent the flow of smoke and toxic gases generated in the event of a building fire and to facilitate evacuation and fire-fighting activities. And as a part of smoke exhausting equipment and smoke shielding equipment, smoke-proof hanging walls and smoke-shielding screens are often installed in buildings such as office buildings and shopping malls.

  Since the smoke proof wall is attached to the ceiling of a building, generally, a transparent plate glass is used so as not to obstruct the field of view. In addition, the smoke shielding screen stores a polyimide film roll in a storage box provided in a ceiling portion such as in front of an elevator so that the polyimide film can be pulled out in the event of a disaster. Sheet glass and polyimide films are excellent in nonflammability and do not burn in the event of a fire.

  However, the plate glass as the smoke-proof hanging wall may fall and crack even if measures are taken to prevent it from falling. For example, at 18:24 on May 26, 2003, the “Sanriku Minami Earthquake” occurred at the offshore boundary of Iwate and Miyagi Prefecture with a seismic intensity of M7 and a seismic intensity of less than 6. Yes. Therefore, there is a need for materials other than plate glass as smoke barriers. Moreover, although the film made from a polyimide as a smoke screen is transparent, since it is tinged with yellowishness, the further improvement of transparency is desired.

  Patent Document 1 discloses a non-combustible sheet material. In this incombustible sheet material, the difference in refractive index between the glass fiber fabric and the resin layer is not defined, and the incombustible sheet material is necessarily opaque. When an opaque incombustible sheet material is used for the smoke proof wall, the visual field is obstructed and the aesthetics of offices, commercial facilities, etc. are impaired. Therefore, a building material that is transparent, excellent in incombustibility, and does not break is desired.

JP 2003-276113 A

  In the first aspect of the present invention, a transparent noncombustible sheet comprising at least one glass fiber fabric and a pair of cured resin layers sandwiching the glass fiber fabric, the glass fiber fabric being 20 to 70 weights. And the refractive index of the glass composition that constitutes the glass fiber in the glass fiber fabric and the resin composition that constitutes the pair of cured resin layers. The difference between the glass composition constituting the glass fiber in the glass fiber fabric and the difference in Abbe number between the resin composition constituting the pair of cured resin layers is 30 or less. A sex sheet is provided.

In the present invention, in the exothermic test in which the surface of the transparent noncombustible sheet is irradiated with radiant heat of 50 kW / m ² from the radiant electric heater, the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less, Moreover, it is preferable that the maximum heat generation rate does not exceed 200 kW / m ² for 20 minutes after the start of heating for 10 seconds or more.

  Moreover, it is preferable that the total light transmittance is 80% or more and the haze is 30% or less.

  Furthermore, it is preferable that a gap between adjacent warp yarns in the glass fiber fabric is 0.5 mm or less, or a gap between adjacent weft yarns in the glass fiber fabric is 0.5 mm or less.

Furthermore, it is preferable that the weight of the pair of cured resin layers is 15 to 500 g per 1 m ^{2 of the} transparent noncombustible sheet.

  In the second aspect of the present invention, a step of applying an uncured resin composition to the first film, a step of bringing a glass fiber fabric into contact with the resin composition, and the first film and the second film are the glass. A method for producing a transparent incombustible sheet, comprising a step of sandwiching a fiber fabric, and a step of curing the resin composition in a state where the first film and the second film sandwich the glass fiber fabric. The difference in refractive index between the glass composition constituting the glass fiber in the glass fiber fabric and the cured resin composition is 0.02 or less, and the glass composition constituting the glass fiber in the glass fiber fabric There is provided a method for producing a transparent incombustible sheet, wherein the difference in Abbe number between the cured resin composition and the cured resin composition is 30 or less.

  In the 3rd side surface of this invention, the smoke-proof hanging wall which consists of a transparent noncombustible sheet in any one of the above is provided.

  According to a fourth aspect of the present invention, there is provided a smoke shielding screen comprising the transparent noncombustible sheet as described above.

  The transparent incombustible sheet of the present invention uses an incombustible glass fiber fabric, and the weight of the cured resin layer is within a predetermined range, so that it becomes incombustible. Since the difference in refractive index between the glass fiber fabric and the cured resin layer is 0.02 or less, the glass fiber fabric cannot be visually recognized and becomes transparent. Moreover, since the difference in Abbe number between the glass fiber fabric and the cured resin layer is 30 or less, scattering in the visible light region is reduced at the interface between the glass fiber fabric and the cured resin layer, and coloring can also be suppressed.

  In the method for producing a transparent incombustible sheet of the present invention, a transparent incombustible sheet can be produced efficiently.

  The smoke barrier wall and smoke screen of the present invention are colorless and transparent sheets, and can prevent falling and cracking.

  FIG. 1 shows a transparent incombustible sheet according to an embodiment of the present invention. The transparent noncombustible sheet 10 includes a glass fiber fabric 20 and a pair of cured resin layers 32 and 34 that sandwich the glass fiber fabric 20. The pair of cured resin layer 32 and cured resin layer 34 fills the gap between the glass fiber fabrics 20 and is continuous with each other.

  In the glass fiber fabric 20, a plurality of warps 22 and a plurality of wefts 24 are combined. Glass fiber fabric refers to a fabric woven using glass fibers for warp and weft. Glass fiber fabrics are sometimes called glass cloths.

  Examples of the weave structure of the glass fiber fabric include plain weave, satin weave, twill weave, oblique weave, and weave. When used as a building material, plain weave, oblique weave and woven weave are preferred.

  The gap 28 between adjacent warps 22 in the glass fiber fabric 20 is preferably 0.5 mm or less, and more preferably 0.2 mm or less. Moreover, it is preferable that the clearance gap between the adjacent wefts 24 in the glass fiber fabric 20 is 0.5 mm or less, and it is still more preferable that it is 0.2 mm or less. This is because when the gap between the warp yarns 22 or the weft yarns 24 of the glass fiber fabric is narrow, it is difficult for the flame to pass through the glass fiber fabric.

  As glass fibers in the glass fiber fabric, general-purpose non-alkali glass fibers (E glass), acid-resistant alkali-containing glass fibers (C glass), high-strength and high-modulus glass fibers (S glass, T glass, etc.), Examples include alkali-resistant glass fibers (AR glass), and it is preferable to use alkali-free glass fibers having high versatility.

  The filament diameter of the glass fiber is preferably 1 to 20 μm, and more preferably 3 to 12 μm.

  The glass fiber count is preferably 5 tex to 70 tex, more preferably 10 tex to 35 tex. The tex count of glass fiber corresponds to the number of grams per 1000 m.

  The glass fiber fabric may be woven with one type of glass fiber, or may be woven with two or more types of glass fibers. For example, the warp and the weft may be separate glass fibers. When woven with two or more types of glass fibers, the glass fiber filament diameters and counts may be the same or different. For example, the glass fiber composition may be the same, and the glass fiber diameter and count may be different.

  The glass fiber fabric is preferably surface-treated with a silane coupling agent usually used as a glass fiber treating agent for the purpose of improving the durability of the transparent noncombustible sheet. Thereby, the glass fiber fabric and the cured resin layer can be favorably bonded. Since the silane coupling agent adheres to the surface of each glass fiber, it does not substantially affect the light transmission characteristics, air permeability, etc. of the glass fiber fabric.

  In FIG. 1, the cured resin layer 32 and the cured resin layer 34 sandwich the glass fiber fabric 20 from both sides. Further, the cured resin layer 32 and the cured resin layer 34 fill the gaps of the glass fiber fabric 20 and are continuous with each other. Further, the cured resin layer 32 and the cured resin layer 34 are in contact with the glass fiber fabric 20.

  The cured resin layer may be composed of a resin composition cured by heat, or may be composed of a resin composition cured by irradiation with light such as ultraviolet rays. Some uncured resin compositions can be cured by heat or ultraviolet irradiation. Such a cured resin layer has a low viscosity in an uncured state and is easily impregnated into a glass fiber fabric.

  The cured resin layer is preferably composed of a vinyl ester resin, an unsaturated polyester resin, or an epoxy resin, and is excellent in heat resistance, chemical resistance, mechanical strength, and curing characteristics. More preferably, it is comprised.

  The cured resin layer may contain additives such as 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 surfactants.

  These additives may be in the form of particles, and in the case of particles, the particle size is preferably 10 μm or less, more preferably 5 μm or less. This is because when the particle size is small, the total light transmittance is improved and the haze is lowered.

In one embodiment of the present invention, the glass fiber fabric 20 is 20 to 70% by weight, and the pair of cured resin layers 32 and 34 is 80 to 30% by weight. When the glass fiber fabric 20 is less than 20% by weight, the amount of the cured resin layers 32 and 34 increases, and the incombustibility of the transparent incombustible sheet decreases. On the other hand, when the glass fiber fabric 20 exceeds 70% by weight, the thickness of the cured resin layers 32 and 34 may be reduced, and the pattern of the glass fiber fabric may be raised, and the transparent noncombustible sheet may be transparent. Sex is reduced.
In addition, in the exothermic test based on the evaluation method of the Building Standard Act described later, in order to suppress damage such as deformation, melting, cracks, etc., further improve the nonflammability, and to achieve a level that passes the nonflammability certification, the present invention. In the transparent noncombustible sheet, the glass fiber fabric 20 is preferably 30 to 70% by weight, and the pair of cured resin layers 32 and 34 is preferably 70 to 30% by weight.

If the weight of the pair of cured resin layers is less than 15 g per 1 m ^{2 of the} transparent incombustible sheet, the glass fiber fabric may not be sufficiently squeezed, and the pattern of the glass fiber fabric may be raised. Also, the transparency of the transparent noncombustible sheet is lowered. On the other hand, when the weight of the pair of cured resin layers is more than 500 g per 1 m ² of the transparent incombustible sheet, the incombustibility of the transparent incombustible sheet is lowered.

It is preferable that the weight of one glass fiber fabric is 20 to 150 g / m ² per 1 m ^{2 of the} transparent incombustible sheet. When the weight of one glass fiber fabric exceeds 150 g / m ² , the impregnation speed of the cured resin becomes slow, and workability may be deteriorated or impregnation failure may occur. When the weight of one glass fiber woven fabric is greater than 150 g / m ² per 1 m ^{2 of the} transparent incombustible sheet, it is preferable to use two or more glass fiber woven fabrics.

  In the present invention, the difference in refractive index between the glass composition constituting the glass fiber in the glass fiber fabric and the resin composition constituting the cured resin layer is 0.02 or less. Thus, since the difference in refractive index is small, the incombustible sheet becomes transparent. The refractive index refers to the ratio between the sine of the incident angle and the sine of the refraction angle when light is refracted at the boundary between the two media. The refractive index is equal to the ratio of the speed of light in both media.

  In the present invention, the refractive index of the glass composition constituting the glass fiber in the glass fiber fabric is not particularly limited, but is preferably in the range of 1.4 to 1.7, for example, 1.5 to 1 More preferably, it is in the range of .6. In addition, when the glass composition which comprises glass fiber is an alkali free glass, a refractive index can be made into the range of 1.55-1.57.

  The method for measuring the refractive index of the cured resin layer is in accordance with “Decision of the refractive index of plastics” of JIS K 7142. Specifically, a film of a curable resin that does not contain a glass fiber fabric is prepared under the same conditions as when a glass fiber fabric is contained, and measurement is performed using an Abbe refractometer.

  In this invention, the difference of the Abbe number of the glass composition which comprises the glass fiber in a glass fiber fabric, and the resin composition which comprises a pair of cured resin layer is 30 or less. The Abbe number is a numerical value for evaluating the chromatic aberration of the transparent body, and is used for evaluating scattering in the visible light region. The Abbe number V of the material is defined as follows.

n _D , n _F , and n _C are the refractive indices for light having a material wavelength of D-589.2 nm, F-486.1 nm, and C-656.3 nm, respectively.

  Although there is no restriction | limiting in particular in the Abbe number of the glass composition which comprises the glass fiber in a glass fiber fabric, For example, it is preferable that it is the range of 35-75, and it is still more preferable that it is the range of 50-70.

The transparent noncombustible sheet of the present invention has a total calorific value of 8 MJ / m for 20 minutes after the start of heating in a heat generation test in which 50 kW / m ² of radiant heat is irradiated from the radiation heater to the surface of the transparent noncombustible sheet. ² or less, and the heating start after 20 minutes, preferably does not exceed 200 kW / m ² was continued up to the heat generation rate is more than 10 seconds. The degree to which the transparent incombustible sheet of the present invention is specifically incombustible is numerically shown based on the evaluation method in the Building Standard Law.

  The transparent incombustible sheet of the present invention has a total light transmittance of 80% or more, preferably a haze of 30% or less, a total light transmittance of 85% or more, and 20% or less. More preferably it is. It shows numerically how much the transparent incombustible sheet of the present invention is specifically transparent.

  The measurement method of the total light transmittance of the transparent noncombustible sheet is described in “Testing Methods for Optical Properties of Plastics” in JIS K 7105, “5.5 Light Transmittance and Total Light Reflectance”. Follow. Specifically, the total light transmittance is measured by using an integrating sphere type measuring device to determine the total light transmittance.

  The method for measuring the haze of the transparent incombustible sheet follows JIS K 7105 “Testing Methods for Optical Properties of Plastics”, “6.4 haze”. Specifically, the diffuse transmittance and the total light transmittance are measured using an integrating sphere measuring device, and are expressed by the ratio.

H: Haze (%)
T _d : Diffuse transmittance (%)
T _t : Total light transmittance (%)

In another embodiment of the present invention, in the present invention, the weight of the pair of cured resin layers is 15 to 500 g and the weight of the pair of cured resin layers is 50 to 300 g per 1 m ^{2 of the} transparent noncombustible sheet. It is preferable that

  In another aspect of the present invention, a method for producing a transparent incombustible sheet is provided. In this manufacturing method, first, as shown in FIG. 2, a step of applying an uncured resin composition 44 to the first film 42 is included. After the application, it is preferable that the uncured resin composition 44 becomes a layer and covers the first film 42.

  The uncured resin composition is preferably a paste. This is because later work becomes easier. Specifically, the viscosity of the uncured resin composition is preferably 0.01 to 100 Pa · s, and more preferably 0.1 to 10 Pa · s.

  Next, as shown in FIG. 3, the glass fiber fabric 20 is brought into contact with the resin composition 44. Preferably, the glass fiber fabric 20 covers a layer made of the resin composition 44.

  In one embodiment of the present invention, the second film 46 is then brought into contact with the glass fiber fabric 20 on the opposite side of the first film 42 as shown in FIG. A glass fiber fabric 20 is sandwiched. Preferably, on the opposite side of the first film 42, the second film 46 covers the glass fiber fabric 20, and the first film 42 and the second film 44 sandwich the glass fiber fabric 20.

  Next, pressure may be applied to the first film 42 and the second film 46 with the first film 42 and the second film 46 sandwiching the glass fiber fabric. For example, a pressure may be applied to the first film 42 and the second film 46 by applying a roller over the second film 44. Alternatively, the first film 42 and the second film 46 may be passed between a pair of rollers to apply pressure to the first film 42 and the second film 46.

  Here, the glass fiber fabric 20 has a slight gap between the warp and the warp, between the weft and the weft, and between the warp and the weft. Then, by applying pressure to the first film 42 and the second film 46, the uncured resin composition passes through this gap. As a result, the uncured resin composition 44 is impregnated into the glass fiber fabric 20, and the uncured resin compositions 44a and 44b are arranged on both sides of the glass fiber fabric 20 as shown in FIG. .

  Next, the uncured resin compositions 44a and 44b are cured with the first film 42 and the second film 44 sandwiching the glass fiber fabric 20 therebetween. Preferably, the uncured resin compositions 44a and 44b are cured by heat.

  In another embodiment of the present invention, the state up to FIGS. 2 and 3 is as described above. On the other hand, as shown in FIG. 6, an uncured resin composition 47 is applied to the second film 46. After the application, it is preferable that the uncured resin composition 47 becomes a layer and covers the second film 46.

  Next, in the laminate of the first film 42, the uncured resin composition 44 and the glass fiber fabric 20 shown in FIG. 3, the second film 46 and the uncured resin composition shown in FIG. The laminate of the objects 47 is stacked so that the uncured resin composition 44 and the uncured resin composition 47 are in contact with the glass fiber fabric 20 from both sides. That is, as shown in FIG. 7, a laminate in which the first film 42, the uncured resin composition 44, the glass fiber fabric 20, the uncured resin composition 47, and the second film 46 are laminated in this order is obtained. . In FIG. 7, the first film 42 and the second film 46 sandwich the glass fiber fabric 20.

  Next, pressure is applied to the first film 42 and the second film 46 with the first film 42 and the second film 46 sandwiching the glass fiber fabric 20. Thereby, as shown in FIG. 8, the uncured resin compositions 44 and 47 fill the gaps in the glass fiber fabric.

  Next, the uncured resin compositions 44 and 47 are cured with the first film 42 and the second film 44 sandwiching the glass fiber fabric 20. Preferably, the uncured resin compositions 44 and 47 are cured by heat.

  In another embodiment of the present invention, the state up to FIGS. 2 and 3 is as described above. Next, an uncured resin composition 47 is applied on the glass fiber fabric 20, and the second film 46 is further coated on the uncured resin composition 47. Thereby, as shown in FIG. 7, the laminated body in which the first film 42, the uncured resin composition 44, the glass fiber fabric 20, the uncured resin composition 47, and the second film 46 are laminated in this order. obtain.

  Next, pressure is applied to the first film 42 and the second film 46 with the first film 42 and the second film 46 sandwiching the glass fiber fabric 20. Thereby, as shown in FIG. 8, the uncured resin compositions 44 and 47 fill the gaps in the glass fiber fabric.

  Next, the uncured resin compositions 44 and 47 are cured with the first film 42 and the second film 44 sandwiching the glass fiber fabric 20. Preferably, the uncured resin compositions 44 and 47 are cured by heat.

  In the above embodiment, a single-layer glass fiber fabric 20 was used. However, a plurality of glass fiber fabrics may be used in an overlapping manner. Further, an uncured resin composition may be applied on one layer of glass fiber fabric, and then one layer of glass fiber fabric may be placed.

  Next, the manufacturing method of the transparent incombustible sheet of the other embodiment of this invention is shown. In this embodiment, a transparent non-combustible sheet comprising two glass fiber fabrics is obtained.

  The glass fiber fabric 20 is further stacked on the laminate of the first film 42, the uncured resin composition 44, and the glass fiber fabric 20 shown in FIG. That is, as shown in FIG. 9, a laminate in which the first film 42, the uncured resin composition 44, the glass fiber fabric 20, and the glass fiber fabric 20 are laminated in this order is obtained.

  Next, the laminate of the second film 46 and the uncured resin composition 47 shown in FIG. 6 is combined with the uncured resin composition 44 and the uncured resin shown in FIG. The composition 47 is overlaid so that it contacts the glass fiber fabric 20 from both sides. That is, as shown in FIG. 10, the first film 42, the uncured resin composition 44, the glass fiber fabric 20, the glass fiber fabric 20, the uncured resin composition 47, and the second film 46 are laminated in this order. A laminated body is obtained. In FIG. 9, the first film 42 and the second film 46 sandwich the two glass fiber fabrics 20.

  Next, pressure is applied to the first film 42 and the second film 46 with the first film 42 and the second film 46 sandwiching the two glass fiber fabrics 20. Accordingly, as shown in FIG. 11, the uncured resin compositions 44 and 47 pass through the gap between the two glass fiber fabrics 20, and the uncured resin composition 48 is between the two glass fiber fabrics 20. Fill.

  Next, the uncured resin compositions 44, 47, and 48 are cured while the first film 42 and the second film 44 sandwich the glass fiber fabric 20. Preferably, the uncured resin compositions 44, 47, and 48 are cured by heat.

  In one embodiment of the present invention, the first film, the glass fiber fabric, and the second film may be continuous sheets. In this embodiment, a sheet-like transparent incombustible sheet can be produced continuously. The first film and the second film may be the same material or the same shape. The first film and the second film may be made of a thermoplastic resin. Thermoplastic resins include polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate; polyamides and the like.

  FIG. 12 is an explanatory diagram of one embodiment of the present invention. The first film 72 is pulled out from the first film roll 70, and the first film 72 is bent by the roller 90.

  Thereafter, an uncured resin composition 74 is applied to the first film 72. Specifically, the uncured resin composition 74 is supplied onto the first film 72, and then the uncured resin composition 74 is formed into a uniform thickness layer by the doctor blade 88. The layer made of the resin composition is coated on the first film 72. Here, the uncured resin composition 74 may become a resin reservoir 76 in front of the doctor blade 88.

  Next, the glass fiber fabric 62 is pulled out from the glass fiber fabric roll 60, and the glass fiber fabric 62 is brought into contact with the uncured resin composition layer on the first film 72. A layer made of a cured resin composition is coated. Then, the glass fiber fabric 62 and the first film 72 are bent by the roller 92. The glass fiber fabric 62 is pressed against the uncured resin composition by the tension applied to the glass fiber fabric 62. Since the viscosity of the uncured resin composition is low as described above, the uncured resin composition enters the gap between the glass fibers of the glass fiber fabric.

  Further, the second film 82 is pulled out from the second film roll 80. Then, on the opposite side of the first film 72, the second film 82 is brought into contact with the glass fiber fabric 62, and the first film 72 and the second film 82 sandwich the glass fiber fabric 62. Preferably, on the opposite side of the first film 72, the second film 82 covers the glass fiber fabric 62, and the first film 72 and the second film 82 sandwich the glass fiber fabric 62.

  Next, in a state where the first film 72 and the second film 82 sandwich the glass fiber fabric 62, the first film 72 and the second film 82 are passed between the pair of rollers 94 and 96, and the first film 72 and the second film 82 are passed. 2 Apply pressure to the film 82.

  Here, in the glass fiber fabric 62, there are slight gaps between the warp and the warp, between the weft and the weft, and between the warp and the weft. Then, by applying pressure to the first film 72 and the second film 82, the uncured resin composition passes through this gap, and the resin reservoir 78 is interposed between the glass fiber fabric 62 and the second film 82. Will occur. Therefore, the glass fiber fabric can be impregnated with the uncured resin composition without generating bubbles, and the uncured resin composition is arranged on both sides of the glass fiber fabric 62.

  Next, the uncured resin composition is cured with the first film 72 and the second film 82 sandwiching the glass fiber fabric 62. Preferably, the first film 72 and the second film 82 are passed through the heat-curing zone 98 with the glass fiber fabric 62 sandwiched therebetween, and the first film 72 and the second film are sandwiched with the glass fiber fabric 62, The resin composition is cured. The heat curing zone 98 is heated to a sufficient temperature for a sufficient time to cure the uncured resin composition. The temperature of the heat curing zone 98 may be constant, or the temperature may change depending on the position. For example, curing may be performed at a certain temperature for a desired time, and then curing may be performed at a temperature higher than the certain temperature for a further desired time.

  FIG. 13 shows a building having a smoke barrier 58 and a smoke screen 59 according to one aspect of the present invention. In FIG. 13, the building includes a floor 50, a ceiling 52, and walls 54 connected to the floor 50 and the ceiling 52. A smoke proof wall 58 is provided on the ceiling 52. The ceiling 52 is provided with a smoke shielding screen 59 wound and a storage box 59a for storing the smoke shielding screen 59. And the above-mentioned transparent incombustible sheet can be used as the smoke-proof hanging wall 58 and the smoke-shielding screen 59a.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail by a suitable Example, the scope of the present invention is not limited to a following example.

Examples 1-3
In Examples 1 to 3, the same glass fiber fabric and the same thermosetting resin were used, and the amount of the thermosetting resin was changed.

  A glass fiber fabric (trade name WEA116E) sold by Nitto Boseki Co., Ltd. was cut into a square of 200 mm × 200 mm. This glass fiber fabric corresponds to the glass fiber fabric standard 2116 of the American Society for Testing Material (ASTM).

This glass fiber fabric is made by weaving glass fiber, ECE225, sold by Nitto Boseki Co., Ltd., as warp and weft. 60 warps are included in 25 mm, and 58 wefts are included in 25 mm. The glass fiber fabric has a weight of 104 g / m ² , a thickness of 0.095 mm, and an air permeability of 42 cm ³ / cm ² / s. The weight, thickness and air permeability of the glass fiber fabric were measured in accordance with JIS standard R3420 “Glass fiber general test method”. Moreover, the clearance gap between adjacent warps and the clearance gap between adjacent wefts are 0.1 mm or less. These gaps were observed with an 80 times loupe.

This glass fiber fabric is heat treated to remove organic matter after the warp and weft are woven, and is surface-treated with a silane coupling agent. As the silane coupling agent, CH ₂ ═C (CH ₃ ) COOC ₃ H ₆ Si (OCH ₃ ) ₃ is used. CH ₂ ═C (CH ₃ ) COOC ₃ H ₆ Si (OCH ₃ ) ₃ has a specific gravity at 25 ° C. of 1.05, a boiling point of 255 ° C., and a refractive index at 25 ° C. of 1.43. .

The glass fiber, ECE225, is made of E glass and has a filament diameter of about 7 μm. The refractive index of E glass is 1.558, and the Abbe number is 58. The composition of E-glass is 52 to 56 wt% of _SiO 2, 12 to 16 wt% of _Al 2 _O 3, 15-25 wt% of CaO, 0 more than 6% by weight of MgO, and, more than 0 1 Contains Na ₂ O and K ₂ O in weight percent or less. The density of E glass is 2.58 g / cm ³ and the tensile strength (23 ° C.) is 3.43 GPa.

  A vinyl ester resin was prepared. 100 parts by weight of vinyl ester resin, SSP50-C06, sold by Showa Polymer Co., Ltd., 0.5 parts by weight of Perkadox P16, sold by Kayaku Akzo, Percure HO, 0.5 parts by weight, sold from) was stirred for about 20 minutes using a stirrer. And the obtained mixture was left to stand under vacuum for about 30 minutes and deaerated to obtain an uncured resin composition.

  The refractive index of SSP50-C06 is 1.558, and the Abbe number is 50.5. The viscosity of SSP50-C06 is about 0.9 Pa · s.

“Parcadox P16” is bis (4-t-butylcyclohexyl) peroxy-dicarbonate (bis- (4-t-butylcyclohexyl) peroxy-dicabonate, (CH ₃ ) ₃ C— (c—C ₆ H ₁₀ ) — O—C (═O) —OO—C (═O) —O— (c—C ₆ H ₁₀ ) —C (CH ₃ ) ₃ ), and the decomposition temperature is 44 ° C. Parkadox P16 is a white granule and has a purity of 90% or more.

“Percure HO” is t-hexyl peroxy-2-ethylhexanoate (CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) —C (═O) —OO—). C (CH ₃ ) ₂ (CH ₂ ) ₂ CH ₃ ). It is preferably used as a curing agent for unsaturated polyester resins. The purity of “Percure HO” is about 50% and is a transparent liquid. The specific gravity at 20 ° C. is 0.935.

Two polyethylene terephthalate films with a thickness of 25 μm were cut into 500 mm × 500 mm. And as shown in FIG. 2, said uncured resin composition 44 was apply | coated to the center part 200mmx200mm of one polyethylene terephthalate film 42. As shown in FIG. The coating amount was adjusted to 92 g / m ² , 300 g / m ² , and 60 g / m ² in Examples 1, 2, and 3, respectively.

  Next, as shown in FIG. 3, a 200 mm × 200 mm glass fiber fabric was placed on the applied resin composition. Next, as shown in FIG. 4, another polyethylene terephthalate film 46 was placed on the glass fiber fabric 20. The two polyethylene terephthalate films 42 and 46 had the same size, and the two sheets were just overlapped.

  From the top of the polyethylene terephthalate film 46, pressure was applied by manually rolling the glass fiber fabric 20 portion. The roller had a diameter of 16 mm and a length of 460 mm.

  Next, two polyethylene terephthalate films were sandwiched between square aluminum frames. The outer side of the aluminum frame was 400 mm × 400 mm, the inner side was 320 mm × 320 mm, and the thickness was 3 mm. Then, two polyethylene terephthalate films were fixed to the aluminum frame with a transparent adhesive tape. At this time, care was taken so that the two polyethylene terephthalate films and the glass fiber fabric sandwiched between the films were not wrinkled.

  Then, the two polyethylene terephthalate films fixed to the aluminum frame were put in an 80 ° C. hot air dryer and left for 30 minutes to cure the resin composition. Next, the temperature of the hot air dryer was raised to 100 ° C. and left for 10 minutes to further cure the resin composition.

  Two polyethylene terephthalate films fixed to the aluminum frame were taken out from the hot air dryer. Then, the two polyethylene terephthalate films were removed from the aluminum frame, and then the two polyethylene terephthalate films were removed to obtain a transparent incombustible sheet.

Comparative Example 1
The same glass fiber fabric as in Examples 1 to 3 was used, impregnated with an epoxy resin, and then cured.

  Epoxy resin manufactured by Yuka Shell Co., Ltd., 95 parts by weight of Epicoat 1001, 5 parts by weight of Epicoat A154, 5 parts by weight of dicyandiamide manufactured by Wako Pure Chemical Industries, Ltd., 0.2 part by weight of imidazole manufactured by Hiroshima Kasei, and 20 parts by weight of methyl cellosolve was stirred with a stirrer for 30 minutes to obtain an uncured epoxy resin varnish. And the glass fiber fabric was immersed in the obtained epoxy resin varnish, the excess epoxy resin varnish was scraped off with a stainless steel rod, and adjusted to 50% by weight of the epoxy resin varnish and 50% by weight of the glass fiber fabric. Then, it heated for 10 minutes with the 130 degreeC hot air dryer, and obtained the sheet | seat of the semi-hardened state.

This semi-cured sheet is sandwiched between two mirror-finished stainless steel plates, set in a flat hot press adjusted to 170 ° C., and heated and pressed at a surface pressure of 490 N / cm ² to produce an epoxy resin. Was completely cured to obtain a nonflammable sheet. In this curing condition, when the glass fiber fabric was not used, the refractive index of the cured epoxy resin sheet was 1.52.

Example 4
A transparent incombustible sheet was obtained by the same method as in Examples 1 to 3 and the same vinyl ester resin. However, Example 4 differs from Examples 1-3 in the type of glass fiber fabric and the amount of vinyl ester.

A glass fiber fabric (trade name: WLA240) sold by Nittobo Co., Ltd. was used. This glass fiber fabric is a glass fiber, ECG75, which is sold by Nitto Boseki Co., Ltd., woven using ECG37 as warp and ECG37 as weft. 44 warps are included in 25 mm, and 25 wefts are included in 25 mm. The glass fiber fabric has a weight of 240 g / m ² , a thickness of 0.23 mm, and an air permeability of 23 cm ³ / cm ² / s. The glass fibers ECG75 and ECG37 are all made of E glass, and the filament diameter is about 9 μm.

This glass fiber fabric is also heat treated to remove organic matter after the warp and weft have been woven, and surface-treated with a silane coupling agent. A silane coupling agent is the same as that of the glass fiber fabric of Examples 1-3.
Example 5

  A transparent incombustible sheet was obtained by the same method as in Examples 1 to 3 and the same vinyl ester resin. However, Example 5 was different from Examples 1 to 3 in the type of glass fiber fabric and the amount of vinyl ester, and two glass fiber fabrics were placed on the resin composition.

  In Example 5, a glass fiber fabric (trade name WE09) sold by Nitto Boseki Co., Ltd. was used. There is no standard of American Society for Testing Material (ASTM) corresponding to this glass fiber fabric.

This glass fiber fabric is woven using glass fibers, ECE225, sold by Nitto Boseki Co., Ltd., as warps and D450 as wefts. 70 warps are included in 25 mm, and 70 wefts are included in 25 mm. This glass fiber fabric has a weight of 94 g / m ² and an air permeability of 11 cm ³ / cm ² / s. Moreover, the clearance gap between adjacent warps and the clearance gap between adjacent wefts are 0.1 mm or less. Glass fiber, D450, is made of E glass and has a filament diameter of about 5 μm.

  This glass fiber fabric is also heat treated to remove organic matter after the warp and weft have been woven, and surface-treated with a silane coupling agent. A silane coupling agent is the same as that of the glass fiber fabric of Examples 1-3.

  The results of Examples 1 to 5 and Comparative Example 1 are shown in Table 1.

Exothermic test Radiant heat was applied to the surface of the transparent noncombustible sheet obtained in any of Examples 1 to 4 or Comparative Example 1 from a radiant electric heater, and radiant heat of 50 kW / m ² was applied. The calorific value was measured. Moreover, the heat generation time exceeding 200 kW / m ² was measured during 20 minutes after the start of heating.

In Table 1, when the result of the exothermic test is 8 MJ / m ² or less, the nonflammability is set as ◯, and when the result of the exothermic test is larger than 8 MJ / m ₂ , the nonflammability is set as x.

Total Light Transmittance Total light transmittance was in accordance with “Testing Methods for Optical Properties of Plastics”, “5.5 Light Transmittance and Total Light Reflectance” of JIS K 7105. Specifically, the total light transmittance was measured using an integrating sphere type measuring device to determine the total light transmittance.

Haze The method for measuring the haze of the transparent noncombustible sheet was in accordance with “6.4 haze” of “Testing Methods for Optical Properties of Plastics” of JIS K 7105. Specifically, the diffuse transmittance and the total light transmittance were measured using an integrating sphere measuring device, and expressed by the ratio.

Gurley bending resistance Measured according to JIS standard L1096 “General textile test method” bending resilience method A (Gurley method).

Visibility Judgment was made based on whether or not a glass fiber fabric was visually observed.

The transparent noncombustible sheet of the present invention can be suitably used as a smoke barrier or smoke screen.
For example, the smoke screen is housed in a rounded state in the upper part of the outside of the door of the elevator. In the event of an emergency such as a fire, the smoke shielding screen descends in front of the elevator door to prevent or reduce smoke from entering the elevator.

It is sectional drawing of the transparent noncombustible sheet of one embodiment of this invention. It is sectional drawing which shows the manufacturing method of one embodiment of this invention. It is sectional drawing which shows the manufacturing method of one embodiment of this invention. It is sectional drawing which shows the manufacturing method of one embodiment of this invention. It is sectional drawing which shows the manufacturing method of one embodiment of this invention. It is sectional drawing which shows the manufacturing method of the other embodiment of this invention. It is sectional drawing which shows the manufacturing method of the other embodiment of this invention. It is sectional drawing which shows the manufacturing method of the other embodiment of this invention. It is sectional drawing which shows the manufacturing method of the other embodiment of this invention. It is sectional drawing which shows the manufacturing method of the other embodiment of this invention. It is sectional drawing which shows the manufacturing method of the other embodiment of this invention. It is explanatory drawing which shows the manufacturing method of the other embodiment of this invention. It is sectional drawing of the building provided with the smoke proof wall and smoke screen of one embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Transparent incombustible sheet 20 Glass fiber fabric 22 Warp 24 Weft 28 Space | interval 32 Cured resin layer 34 Cured resin layer 42 1st film 44, 44a, 44b, 47 48 Uncured resin composition 46 2nd film 50 Floor 52 Ceiling 54 Wall 58 Smoke-proof wall 59 Smoke-proof screen 59a Storage box 60 Glass fiber fabric roll 62 Glass fiber 70 First film roll 72 First film 74 Uncured resin composition 76, 78 Resin pool 80 Second film roll 82 Second film 88 Doctor blade 90, 92, 94, 96 Roller 98 Heat curing zone 100 Transparent incombustible sheet

Claims (6)

A smoke-proof hanging wall made of a transparent incombustible sheet, wherein the transparent incombustible sheet is
At least one glass fiber fabric;
A pair of cured resin layers sandwiching the glass fiber fabric;
A transparent non-combustible sheet comprising
The cured resin is a vinyl ester resin;
The glass fiber fabric is 30 to 70% by weight, the pair of cured resin layers is 70 to 30% by weight,
The difference in refractive index between the glass composition constituting the glass fiber in the glass fiber fabric and the resin composition constituting the pair of cured resin layers is 0.02 or less,
The difference in Abbe number between the glass composition constituting the glass fiber in the glass fiber fabric and the resin composition constituting the pair of cured resin layers is 30 or less,
The total light transmittance is 80% or more, and the haze is 20% or less,
In the exothermic test in which the surface of the transparent noncombustible sheet is irradiated with radiant heat of 50 kW / m ² from a radiant electric heater, the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less, and for 20 minutes after the start of heating, A smoke barrier that is a transparent non-combustible sheet that has a maximum heat generation rate of 10 seconds or more and does not exceed 200 kW / m ² . In the transparent noncombustible sheet, a gap between adjacent warp yarns in the glass fiber fabric is 0.5 mm or less, or a gap between adjacent weft yarns in the glass fiber fabric is 0.5 mm or less. Item 2. A smoke barrier according to item 1. The smoke-proof hanging wall according to claim 1 or 2 , wherein the transparent non-combustible sheet has a weight of the pair of cured resin layers of 15 to 500 g per 1 m ^{2 of the} transparent non-combustible sheet. A smoke shielding screen comprising a transparent noncombustible sheet, wherein the transparent noncombustible sheet comprises:
At least one glass fiber fabric;
A pair of cured resin layers sandwiching the glass fiber fabric;
A transparent non-combustible sheet comprising
The cured resin is a vinyl ester resin;
The glass fiber fabric is 30 to 70% by weight, the pair of cured resin layers is 70 to 30% by weight,
The difference in refractive index between the glass composition constituting the glass fiber in the glass fiber fabric and the resin composition constituting the pair of cured resin layers is 0.02 or less,
The difference in Abbe number between the glass composition constituting the glass fiber in the glass fiber fabric and the resin composition constituting the pair of cured resin layers is 30 or less,
The total light transmittance is 80% or more, and the haze is 20% or less,
In the exothermic test in which the surface of the transparent noncombustible sheet is irradiated with radiant heat of 50 kW / m ² from a radiant electric heater, the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less, and for 20 minutes after the start of heating, A smoke shielding screen, which is a transparent non-combustible sheet that has a maximum heat generation rate of 10 seconds or more and does not exceed 200 kW / m ² . In the transparent noncombustible sheet, a gap between adjacent warp yarns in the glass fiber fabric is 0.5 mm or less, or a gap between adjacent weft yarns in the glass fiber fabric is 0.5 mm or less. Item 5. The smoke shielding screen according to Item 4 . Transparency incombustible sheet, the transparent incombustible sheet 1 m ² per Saegikemuri screen according to claim 4 or 5 weight of said pair of the cured resin layer is in the range of 15～500G.

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