JP2019162831A - Transparent noncombustible sheet, smokeproof hanging wall using the transparent noncombustible sheet, smokeproof screen and curtain, and manufacturing method of transparent noncombustible sheet - Google Patents

Abstract

To provide a transparent noncombustible sheet capable of being manufactured easily, in which a resin composition easily impregnates in a glass fiber fabric, excellent in flexibility, cutting property, transparency and processability, and maintaining peel strength equal to conventional articles.SOLUTION: In a transparent noncombustible sheet formed by laminating a thermoplastic resin layer on both surfaces of a glass cloth via an adhesive layer, the adhesive layer consists of a resin composition containing a polyvinyl chloride (PVC) paste resin and at least one kind of plasticizer, K value of the polyvinyl chloride (PVC) paste resin is 50 to 70, and all light ray transmittance of the sheet is 75% or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transparent incombustible sheet in which a thermoplastic resin film is laminated on both surfaces of a glass cloth via an adhesive layer, a method for producing the same, a smoke-proof hanging wall using the transparent incombustible sheet, and a smoke-proof screen curtain. .

  In recent years, a fiber reinforced resin sheet obtained by reinforcing a resin with glass fiber has nonflammability that does not easily generate heat even in a high temperature environment such as a fire, and therefore, the demand for a glass substitute material is increasing. The fiber reinforced resin sheet is often used as a construction material such as a smoke proof wall, a smoke shielding screen, a curtain, or a partition sheet. Further, in general, in this type of application, it is often required to be a transparent member so that it can be lit even in a closed state and the other side can be seen through the sheet.

  As the fiber reinforced resin sheet, for example, a transparent incombustible sheet in which a glass fiber fabric is impregnated with a curable resin (for example, Patent Document 1), a transparent incombustible sheet in which a glass fiber fabric is impregnated with a vinyl chloride resin (for example, Patent document 2) is known.

JP 2015-42794 A Japanese Patent No. 5604874

  The transparent incombustible sheet described in Patent Documents 1 and 2 is a process of adding an organic solvent to a resin composition and impregnating the prepared resin solution into the glass fiber fabric, and volatilizing the solvent in the resin solution impregnated into the glass fiber fabric. It is manufactured through a drying step, and a step of heat-pressing a resin film on the upper and lower surfaces of the resin-impregnated glass fiber fabric obtained after drying. In some cases, when the glass fiber fabric is impregnated with the resin solution, a step of thermocompression bonding between both sides with a process film such as polyethylene terephthalate and a step of curing the resin-impregnated glass fiber fabric with heat or light energy are added. As described above, the conventional transparent non-combustible sheet has the problems that the manufacturing process is complicated, the manufacturing process is inferior, and the manufacturing cost is high, since the above process is essential.

  Further, the transparent non-combustible sheet disclosed in Patent Document 1 has the advantages of having transparency and non-combustibility and high mechanical strength, but it has poor flexibility and the sheet is hard. There is a problem that workability is poor because it is necessary to cut many times when cutting.

  The inventors of the present invention have worked on solving the problems of the prior art described above, found a method that can simplify the manufacturing process and can be easily manufactured, and have developed the highest level of transparent non-combustible sheet in the conventional laminate non-combustible sheet (pending) No. 2017-145525). However, since this method simplifies the production process, the impregnation time of the resin composition into the glass fiber fabric is shortened, and thus a new problem has been found that the impregnation property of the resin composition is lowered.

  The present invention has been made in order to solve the above-described problems of the prior art, and can be easily manufactured. The glass fiber fabric can be easily impregnated with a resin composition, and has flexibility, cutability, transparency and processability. An object of the present invention is to provide a transparent noncombustible sheet that is excellent and maintains the same peel strength as that of a conventional product, and a method for producing the same.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have paid attention to the composition of the resin composition constituting the adhesive layer and the bonding process thereof, and the adhesive layer made of the predetermined composition is subjected to a predetermined condition. It was found that the non-combustible sheet can be produced by forming the glass cloth with a superior resistance to impregnation, workability and transparency of the adhesive layer to the glass cloth and maintaining the same peel strength as the conventional product. It came to complete.
That is, the present invention is a transparent non-combustible sheet obtained by laminating a thermoplastic resin film on both surfaces of a glass cloth with an adhesive layer interposed between the glass cloth and the polyvinyl chloride (PVC) paste resin. The polyvinyl chloride (PVC) paste resin has a K value of 50 to 70, and the total light transmittance of the sheet is 75% or more. To do.

  The transparent noncombustible sheet of the present invention (hereinafter also referred to as “the sheet of the present invention”) has a glass fiber count of 3 to 20 tex in the glass cloth, and a total density of warp and weft is 80/25 mm to 190. / 25 mm is preferable.

  Further, in the sheet of the present invention, the difference between the refractive index of the plasticizer, the refractive index of the glass fiber constituting the glass cloth, and the refractive index of the polyvinyl chloride (PVC) paste resin is ± 0.06 or less. It is preferable that

  In the sheet of the present invention, the plasticizer is preferably a plasticizer mainly composed of a phthalate ester plasticizer.

  In the sheet of the present invention, the thermoplastic resin film is composed of a resin composition containing a polyvinyl chloride resin and a plasticizer, and the content of the plasticizer with respect to the total mass of the thermoplastic resin film is 50% by mass. The following is preferable.

  In the sheet of the present invention, the thermoplastic resin film preferably has a thickness of 0.05 to 0.20 mm.

In the sheet of the present invention, the coating amount of the adhesive layer is preferably 10.0 to 60.0 g / m ² .

  Moreover, it is preferable that the thickness of the sheet | seat of this invention is 0.45 mm or less.

  Moreover, it is preferable that the sheet | seat of this invention is used for any of a smoke-proof hanging wall, a smoke-shielding screen, a smoke-proof partition wall, and a smoke-proof curtain.

  Moreover, the sheet | seat of this invention is used suitably for a smoke-proof hanging wall and a smoke-proof screen curtain.

  In the sheet manufacturing method of the present invention, a first thermoplastic resin film in which an adhesive layer made of a resin composition containing a polyvinyl chloride (PVC) paste resin and at least one plasticizer is formed on at least one surface of the sheet. A step of conveying, a step of heating and conveying the second thermoplastic resin film, and a step of laminating the glass cloth and the second thermoplastic resin film in this order on the adhesive layer of the first thermoplastic resin film. And heat laminating the first thermoplastic resin film, the adhesive layer, the glass cloth, and the second thermoplastic resin film.

  In the sheet manufacturing method of the present invention, it is preferable that the processing temperature when the second thermoplastic resin film is heated and conveyed is 78 ° C. or higher.

  According to the sheet of the present invention, it is easy to manufacture and low cost, the impregnation property of the adhesive layer into the glass cloth is excellent, the nonflammability, the flexibility and the cutting property are maintained, and the peel strength equivalent to the conventional product is maintained. Thus, a transparent non-combustible sheet having high transparency can be provided.

It is a conceptual diagram which shows the suitable embodiment of this invention. 2 is a stereomicrograph showing impregnation evaluation in Example 1. FIG. 3 is a stereoscopic micrograph showing impregnation evaluation in Example 2. FIG. 4 is a stereomicrograph showing impregnation evaluation in Example 3. FIG. 3 is a stereomicrograph showing impregnation evaluation in Comparative Example 1. 4 is a stereomicrograph showing impregnation evaluation in Comparative Example 2. 10 is a stereomicrograph showing impregnation evaluation in Comparative Example 3.

Hereinafter, a transparent incombustible sheet as an example of an embodiment of the present invention will be described.
However, the scope of the present invention is not limited to the embodiments described below. Unless otherwise specified, the notation “A to B” for numerical values A and B means “A to B”. In this notation, when a unit is attached to only the numerical value B, the unit is also applied to the numerical value A.

  A first aspect of the present invention is a transparent noncombustible sheet formed by laminating a thermoplastic resin film on both surfaces of a glass cloth with an adhesive layer interposed between the glass cloth and the polyvinyl chloride (PVC) paste resin. A resin composition comprising at least one plasticizer, wherein the polyvinyl chloride (PVC) paste resin has a K value of 50 to 70 and a total light transmittance of 75% or more. It is a transparent non-combustible sheet.

  For example, as FIG. 1 shows, the sheet | seat 10 of this invention is equipped with the 1st thermoplastic resin film which provided the adhesive layer 4 on the single side | surface on the both surfaces of the glass cloth 3, and a 2nd thermoplastic resin film. Have

(Glass cloth)
The glass cloth 3 used in the sheet 10 of the present invention is composed of a glass fiber fabric. Examples of the glass fiber fabric include one woven with warp and weft glass fibers, one in which a plurality of glass fibers in one direction are arranged in a direction in which the glass fibers intersect with each other, and a glass fiber orthogonal laminated net. Among these, those woven with glass fiber warp and weft are preferable. Examples of the woven structure by weaving include plain weave, satin weave, twill weave, oblique weave, and weave. The weaving structure by weaving is not particularly limited, but plain weaving is preferable in that uniform tensile strength can be obtained in any direction.

  Moreover, as glass fiber in a glass fiber fabric, general-purpose non-alkali glass fiber (E glass), acid-resistant alkali-containing glass fiber (C glass), high-strength and high-modulus glass fiber (S glass, T glass, etc.) ), Alkali-resistant glass fiber (AR glass) and the like. Among them, the use of alkali-free glass fibers having high versatility is preferable. The glass fibers constituting the glass cloth 3 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.

  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 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 cloth 3 used in the sheet 10 of the present invention is subjected to fiber opening treatment, heat treatment, and silane coupling agent treatment for the purpose of ensuring adhesion and transparency. In the fiber opening treatment, it is possible to expect the effect of facilitating the impregnation of the resin by flattening the yarn and expanding the warp and weft stitches.

  As for the density of the glass fiber in the glass fiber fabric, the total warp and weft density is 80/25 mm or more, preferably 90/25 mm or more, and preferably 95/25 mm or more. The higher the density of the glass fiber, the higher the nonflammability, but the lower the transparency. Therefore, the upper limit of the density is preferably 190/25 mm or less, and more preferably 180/25 mm or less.

  The thickness (tex count) of the glass fiber is 3 tex or more, preferably 4 tex or more, more preferably 5 tex or more, and the upper limit is 20 tex or less, preferably 15 tex or less, more preferably 12 tex or less. One type of glass fiber count may be used alone, or two or more types may be combined. The tex count of the glass fiber corresponds to the number of grams per 1000 m.

  The gap between adjacent warp yarns in the glass fiber fabric is preferably 0.5 mm or less, and more preferably 0.3 mm or less. Moreover, it is preferable that the clearance gap between the adjacent wefts in a glass fiber fabric is 0.5 mm or less, and it is still more preferable that it is 0.3 mm or less. When the gap between the warp or weft of the glass fiber fabric is narrow, the flame may be difficult to pass through the glass fiber fabric. Therefore, the gap between the warp and the weft is preferably within the above range.

  The thickness of the glass cloth 3 is not particularly limited, but is usually preferably 0.3 mm or less. The thicker the glass cloth 3 is, the higher the mechanical strength such as tear strength and rigidity of the transparent non-combustible sheet 10 is, and the non-flammability is enhanced. On the other hand, the thinner the glass cloth 3 is, the more the adhesive layer 4 becomes. It becomes easy to impregnate a glass fiber fabric, it becomes easy to discharge | release the bubble contained between glass fibers outside, and the transparency of the transparent nonflammable sheet | seat 10 can be improved more. From these viewpoints, the thickness of the glass cloth 3 in the transparent incombustible sheet 10 is preferably 0.06 mm or less, more preferably 0.04 mm or less, and further preferably 0.03 mm or less. In particular, when the thickness of the glass cloth 3 is 0.03 mm or less, the flexibility of the transparent incombustible sheet 10 can be further increased. For example, when the transparent incombustible sheet 10 is used for a smoke shielding sheet or the like, It can be easily wound around the feeding portion and can be easily cut during processing. In addition, as a lower limit of the thickness of the glass cloth 3, it can be about 0.01 mm, for example.

  The surface of the glass cloth 3 is preferably subjected to a silane coupling agent treatment. Examples of the silane coupling agent treatment include treatment using an aminosilane-based silane coupling agent. By this treatment, the impregnation property of the thermoplastic resin composition constituting the adhesive layer into the glass cloth 3 can be improved. 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 cloth 3.

  Although it does not restrict | limit especially as a refractive index of the glass fiber which comprises the glass cloth 3, From the viewpoint of improving transparency, it is preferable to make it close with the refractive index of the thermoplastic resin composition which is an adhesive layer. Specifically, the refractive index of the glass fiber constituting the glass cloth 3 is about 1.40 to 1.70, more preferably about 1.50 to 1.60.

(Adhesive layer)
The adhesive layers 4 and 4 used in the sheet 10 of the present invention are made of a thermoplastic resin composition containing a polyvinyl chloride (PVC) paste resin and at least one plasticizer. Preferred is a PVC paste sol in which a polyvinyl chloride (PVC) paste resin is dispersed in a plasticizer. When the PVC paste sol is heated, absorption of the plasticizer into the PVC particles proceeds to change from a sol state to a gel state. If heating is further continued, melting proceeds and a good adhesive layer can be formed.
The polyvinyl chloride (PVC) paste resin used in the adhesive layers 4 and 4 has a K value of 70 or less, preferably 65 or less, and more preferably 60 or less. The lower limit of the K value of the vinyl chloride (PVC) paste resin is not particularly limited, but the K value is preferably 50 or more from the viewpoint of maintaining good adhesiveness.
The K value is a value measured in accordance with ISO 1628-2 (JIS K7367-2 Plastic-Determination of viscosity of polymer diluted solution using capillary viscometer-Part 2: Vinyl chloride resin). is there.

  Further, the plasticizer used in the adhesive layers 4 and 4 of the sheet 10 of the present invention is not particularly limited. For example, dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), phthalate Phthalic acid ester compounds such as butyl benzyl acid (BBP), dibutyl phthalate (DBP), dimethyl phthalate (DMP), diethyl phthalate (DEP); diallyl phthalate (DAP), diallyl isophthalate, diallyl terephthalate Phthalic acid diallyl ester compounds; adipic acid ester compounds such as diisononyl adipate (DINA), diisodecyl adipate (DIDA), dioctyl adipate (DOA), benzoic acid ester compounds such as benzoic acid glycol ester (DEDB); tris phosphate (TXP), phosphorus Phosphate ester compounds such as tricresyl (TCP), triphenyl phosphate (TPP), cresyl diphenyl phosphate (CDP), resorcinol bisdiphenyl phosphate (RDP), and bisphenol A bisdiphenyl phosphate (BDP); . These plasticizers may be used alone or in combination of two or more.

  The plasticizer used in the adhesive layers 4 and 4 has a refractive index difference of ± 0 from the refractive index of the glass fiber constituting the glass cloth 3 and the polyvinyl chloride (PVC) paste resin used in the adhesive layers 4 and 4. 0.06 or less, more preferably ± 0.05 or less, and even more preferably ± 0.03 or less. Therefore, the refractive index range of the plasticizer itself is preferably 1.44 to 1.66, more preferably 1.45 to 1.65, and further preferably 1.47 to 1.63. preferable. When the refractive indexes of the adhesive layers 4 and 4 are in the above range, the transparency can be improved.

  In order to make the difference in refractive index between the resin composition (that is, the PVC paste resin and the plasticizer) constituting the adhesive layers 4 and 4 and the glass cloth 3 within the above range, the plasticizer used in the adhesive layers 4 and 4. In order to make the refractive index of the glass fiber 3 close to the refractive index of the glass fiber 3, it is preferable to use butylbenzyl phthalate (BBP) as the plasticizer.

  The content of the plasticizer contained in the resin composition constituting the adhesive layers 4 and 4 is not particularly limited, but is preferably 30% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, The upper limit is 80% by mass or less, preferably 70% by mass or less. If the content of the plasticizer contained in the adhesive layer 3 is in the above range, the glass fiber fabric can be easily impregnated in a sol state with the resin composition constituting the adhesive layers 4 and 4.

  For the adhesive layers 4 and 4, other synthetic resins and, if necessary, stabilizers, UV absorbers, hindered amine light stabilizers, antioxidants, slip agents, and colorants as long as the effects of the present invention are not impaired. A filler, a nucleating agent, a flame retardant, an antibacterial agent, a refractive index adjusting agent, and the like may be added.

The coating amount of the adhesive layer 4, 4 10.0 g / ^{m 2} or more, preferably 20.0 g / ^{m 2} or more, further preferably 30.0 g / ^{m 2} or more, 60.0 g / ^{m 2} or less, preferably it is 50.0 g / ^{m 2,} more preferably not more than 40.0 g / ^{m 2.} If the coating amount of the adhesive layers 4 and 4 is within the above range, it is preferable to prevent the adhesive layer from being impregnated into the glass cloth and the excess portion from overflowing.

(First and second thermoplastic resin films)
Examples of the thermoplastic resin used in the first thermoplastic resin film 1 and the second thermoplastic resin film 2 (hereinafter collectively referred to as “thermoplastic resin films 1 and 2”) of the sheet 10 of the present invention. The thermoplastic resin composition constituting the adhesive layers 4 and 4 and the glass fiber of the glass cloth 3 can be approximated to the refractive index of the glass fiber 3 without particular limitation. Preferred thermoplastic resins include, for example, polyvinyl chloride resins (polyvinyl chloride resins, polyvinylidene chloride resins, chlorinated polyolefin resins, etc.), polyester resins, polyolefin resins (polyethylene resins, polypropylene resins, ethylene-α -Olefin copolymer etc.), acrylic resin, polycarbonate resin, polyvinyl alcohol resin, ethylene vinyl acetate copolymer, polyamide resin, polyarylate resin and the like. For example, when non-alkali glass fibers are used as the glass fibers constituting the glass fiber fabric, from the viewpoint of refractive index, among these, polyvinyl chloride resins, polyester resins, acrylic resins are preferable, and polyvinyl chloride resins are used. A resin is more preferable. A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types from which refractive index differs in order to approximate the refractive index of the glass fiber to be used.

  The thermoplastic resin films 1 and 2 may contain a plasticizer for imparting flexibility. The plasticizer used in the thermoplastic resin films 1 and 2 is not particularly limited. Examples include phthalic acid ester compounds, adipic acid ester compounds, trimetic acid ester compounds, adipic acid polyester compounds, phthalic acid polyester compounds, terephthalic acid ester compounds, phosphoric acid ester compounds, etc. From the viewpoint of versatility and cold resistance Diisononyl adipate (DINA) is preferred.

  The plasticizer contained in the thermoplastic resin films 1 and 2 can be used as long as the properties of the thermoplastic resin to be used are not impaired, and preferably the total amount of the resin composition constituting the thermoplastic resin films 1 and 2. On the other hand, it is 50% by mass or less, and preferably 35% by mass or less from the viewpoint of preventing blocking of the noncombustible sheet.

  In addition, the thermoplastic resin films 1 and 2 include, for example, a flame retardant, an ultraviolet absorber, a hindered amine light stabilizer, a filler, an antistatic agent, and a colorant in addition to the plasticizer to the extent that the effects of the present invention are not impaired. Further, additives such as antibacterial agents, stabilizers, slip agents and the like may be further contained.

  The thermoplastic resin films 1 and 2 are embossed on the surface of the adhesive layers 4 and 4 for the purpose of improving adhesiveness with the glass cloth 3 and infiltrating the thermoplastic resin composition of the adhesive layers 4 and 4 into the glass cloth 3. It is preferable to apply. Specifically, the surface roughness Ra on the adhesive layers 4 and 4 side of the thermoplastic resin films 1 and 2 is 0.5 μm or more, preferably 1.0 μm or more, more preferably 3.0 μm or more, and 15. It is desirable that the thickness be 0 μm or less, preferably 12.0 μm or less, and more preferably 10.0 μm or less.

  The thickness of the thermoplastic resin films 1 and 2 is not particularly limited, but from the viewpoint of maintaining transparency and nonflammability, it is about 0.05 to 0.20 mm, preferably 0.08 to 0.15 mm. . If the thermoplastic resin films 1 and 2 are too thick, the incombustibility is lowered. On the other hand, if the thermoplastic resin films 1 and 2 are too thin, wrinkles easily occur, and the uneven shape of the glass cloth tends to appear on the surface of the transparent incombustible sheet.

(Non-combustible sheet)
The thickness of the entire sheet 10 of the present invention is not particularly limited, but is 0.45 mm or less, preferably 0.40 mm or less, more preferably 0.35 mm from the viewpoint of maintaining transparency, flexibility and cutting properties. It is as follows.

The sheet 10 of the present invention may be at least partly, preferably the whole is transparent, and the total light transmittance at an average value of wavelengths of 400 nm to 700 nm is 75% or more, preferably 80% or more, more preferably 85% or more. It is. In order to further improve the transparency, the refractive index of the glass fiber constituting the glass fiber fabric, the refractive index of the thermoplastic resin composition (PVC paste resin and plasticizer) constituting the adhesive layer, and the thermoplastic resin film It is desirable that the difference from the refractive index of the thermoplastic resin composition constituting 1 and 2 is ± 0.06 or less, preferably ± 0.05 or less, more preferably ± 0.03 or less.
Moreover, a part may be opaque by printing or coloring. In addition, various surface treatments such as hairline treatment, embossing treatment, hard coat treatment, antifouling treatment, antistatic treatment, and heat shielding treatment may be performed.

  The incombustibility of the sheet 10 of the present invention varies depending on the composition of the adhesive layers 4 and 4 and the thermoplastic resin films 1 and 2, but the thermoplastic resin films 1 and 2 are obtained so as to obtain desired incombustibility and transparency. The thickness of the glass cloth 3, the weave density, the composition of the adhesive layers 4 and 4 can be set.

In the sheet 10 of the present invention, in the exothermic test in which the surface of the sheet is irradiated with 50 kw / m ² of radiant heat, the total calorific value at the start of heating for 20 minutes is 8 MJ / m ² or less, and the maximum at the start of heating for 20 minutes. The heat generation rate can continue for 10 seconds or more and impart incombustibility of less than 200 kw / m ² . Such a non-combustible transparent non-combustible sheet is preferable because it can be certified as a non-combustible material as stipulated in the Building Standard Law.

  The sheet 10 of the present invention can be used as a smoke-proof hanging wall, a smoke-shielding screen, a smoke-proof partition wall, a smoke-proof curtain, a sheet used for a partition of a warehouse / factory, a transparent blind, or the like. The sheet 10 of the present invention is suitably used for a smoke barrier, a smoke screen, a smoke partition, or a smoke screen curtain.

[Method for Producing Sheet of the Present Invention]
The manufacturing method of the sheet | seat 10 of this invention is from the resin composition containing the polyvinyl chloride (PVC) paste resin of K value 50-70 and at least 1 sort (s) of plasticizer in the at least single side | surface of a 1st thermoplastic resin film. Forming an adhesive layer and transporting the adhesive layer; heating and transporting the second thermoplastic resin film; and a glass cloth and the second heat on the adhesive layer of the first thermoplastic resin film. And a step of laminating the plastic resin films in this order, and a step of thermally laminating the first thermoplastic resin film, the glass cloth, and the second thermoplastic resin film.

  As a specific example, a polyvinyl chloride (PVC) paste resin having a K value of 50 to 70 and at least one plasticizer (preferably having a molecular weight of 380 or less are provided on one side of a first thermoplastic resin film as a thermoplastic resin film. ) -Containing resin composition is formed to form an adhesive layer 4, and a glass cloth 3 and then a second thermoplastic resin film are laminated on the adhesive layer 4 in a thermocompression bonding state. Then, the transparent non-combustible sheet 10 is obtained by pasting them together.

  Moreover, since the resin composition which comprises the contact bonding layers 4 and 4 can be impregnated and solidified in the gel form by using the heat and pressure at the time of bonding, heat energy and light can be obtained in a separate process. There is no need to cure by applying energy, and power costs can be reduced. Further, bubbles contained in the glass cloth 3 can be discharged and removed to the outside by heating and pressing.

  A transparent non-combustible sheet in which a conventional glass fiber fabric is placed inside a curable resin plate is coated with a curable resin on one side of a process film such as a polyethylene terephthalate film, and the curable resin layer is formed on the formed curable resin layer. A glass fiber fabric is stacked, and a new process film is stacked on the glass fiber fabric, and the glass fiber fabric is impregnated with the curable resin of the curable resin layer by pressing. Next, after the curable resin is cured by heat or light, the process films on both sides are peeled off, and then a reinforcing sheet made of, for example, a flame retardant vinyl chloride resin is pasted on both sides using a urethane adhesive. It was manufactured by the method of attaching.

  Since the transparent noncombustible sheet obtained by the conventional manufacturing method has many steps and used a process film, it is necessary to dispose of the peeled process film. For this reason, the conventional manufacturing method has a problem that the manufacturing cost and the disposal cost are required. Moreover, in the conventional manufacturing method, since it was necessary to harden | cure by giving a thermal energy and light energy, there also existed a problem that electric power cost started.

  In the present invention, the glass cloth 3, the adhesive layers 4 and 4, and the thermoplastic resin films 1 and 2 can be manufactured by the above-described process, so that it is not necessary to use a process film. It is possible to easily produce a transparent incombustible sheet that suppresses the above.

  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.

<Material constituting each layer>
1. Thermoplastic resin film [thermoplastic resin]: polyvinyl chloride resin (TK1000S; manufactured by Shin-Etsu Chemical Co., Ltd.)
[Plasticizer 1]: Diisononyl adipate (DINA; manufactured by JPLUS)
[Flame Retardant]: Phosphate ester (Reophos-65; manufactured by Ajinomoto Fine Techno Co., Ltd.)
[Stabilizer]: Ba—Zn stabilizer (manufactured by ADEKA)
[Ultraviolet absorber]: Benzophenone ultraviolet absorber (Kimasoap 81; manufactured by BASF Japan Ltd.)
[Pigment]: MP MKV 073 Blue (manufactured by Dainichi Seika Kogyo Co., Ltd.)

2. Material used for adhesive layer [polyvinyl chloride (PVC) paste resin]: PSL-675 (manufactured by Kaneka Corporation)
[Polyvinyl chloride (PVC) paste resin 2]: PSH-180 (manufactured by Kaneka Corporation)
[Plasticizer 2]: Butylbenzyl phthalate (BBP) (manufactured by Ferro Japan)
[Stabilizer]: Ba—Zn stabilizer (manufactured by ADEKA)

3. Glass cloth 1067 (Chongqing Tenjin Co., Ltd.)

<Example>
[Production of thermoplastic resin film]
66.0% by mass of polyvinyl chloride resin, 13.2% by mass of plasticizer 1, 2.64% by mass of stabilizer, 0.65% by mass of UV absorber, 17.2% by mass of flame retardant, charging Add 0.07% by weight of inhibitor, 0.03% by weight of slip agent, and 0.12% by weight of pigment, mix using a Henschel mixer, and use a calendering machine to make a polyvinyl chloride resin film. Produced.

[Coating adhesive layer]
Polyvinyl chloride (PVC) paste resin 1 or polyvinyl chloride (PVC) paste resin 2 and plasticizer 2 are blended in the proportions shown in Table 1, and 1% by mass of Ba-Zn stabilizer is added and mixed. A resin composition for an adhesive layer was prepared, and an adhesive layer was formed using the resin composition.

[Production of transparent noncombustible sheet]
A resin composition constituting the adhesive layer shown in Table 1 is applied to the thermoplastic resin film, and the adhesive layer and the thermoplastic resin film are heated on one side of the glass cloth and the other side is heated. A laminate with a film was prepared. Thereafter, a transparent non-combustible sheet was produced by nip-bonding between a metal roll and a rubber roll set at 160 ° C. and thermocompression bonding the thermoplastic resin film, the adhesive layer, and the glass cloth.
The following evaluation was performed about the obtained transparent noncombustible sheet. The evaluation results are shown in Table 1.

<Evaluation of nonflammability>
Beyond the produced transparent incombustible surface of the sheet, in radiant electric heater irradiating radiant heat of 50 kw / m ^2, the total calorific value of the heating start after 20 minutes, the heating value in the start of heating after 20 minutes a 200 kW / m ² The time was measured. If the total calorific value is 8 MJ / m ² or less and the time exceeding 200 kw / m ² continues for less than 10 seconds, the nonflammability evaluation is “◯”, and if it exceeds, “×” It was.

<Evaluation of transparency>
The total light transmittance (average value of wavelengths 400 to 700 nm) of the produced transparent noncombustible sheet was measured using a spectrophotometer UV-3500 manufactured by Hitachi, Ltd. When the total light transmittance is 90% or more, the transparency is evaluated as “◎”. When the total light transmittance is 80% or more and less than 90%, “◯”, and when it is 60% or more and less than 80%, “△”. , “X” when less than 60%.

<Evaluation of impregnation>
The impregnation property of the produced transparent incombustible sheet was evaluated by observation of the appearance after the production of the transparent incombustible sheet. Appearance observation was performed with a stereomicroscope. The results are shown in FIGS.
As shown in FIG. 2 to FIG. 7, when the glass cloth part impregnated with the resin composition in the transparent incombustible sheet has an area of the resin non-impregnated part (white stripes) of less than 20%, The case where the area of the part (white streaks) was 20% or more and less than 50% was designated as “◯”, and the case where the resin non-impregnated part was 50% or more was designated as “Δ”.

<Evaluation of peel strength>
The peel strength of the produced transparent noncombustible sheet was evaluated by the degree of peeling of the polyvinyl chloride resin film. For the evaluation, a sample in which a transparent incombustible sheet was cut and formed into 25 mm × 250 mm was used. Specifically, when the polyvinyl chloride resin film is peeled off from the sample with a scribing stick, whether or not the polyvinyl chloride resin film is peeled off, and if it is peeled off, whether or not the polyvinyl chloride resin film remains on the peeled surface Evaluated. ◎ if the polyvinyl chloride resin film cannot be peeled off with a scribing stick, ○ if it can be peeled off with a scribing stick but part of the polyvinyl chloride resin film remains on the peeled surface, peel off with a scribing stick The case where the polyvinyl chloride resin film did not remain on the peeled surface was marked as x.

<Evaluation of flexibility>
The flexibility of the produced transparent noncombustible sheet was evaluated by the JIS L 1096A method (45 ° cantilever method). Place the test piece on a smooth horizontal platform with a 45 ° slope, align one end of the test piece with the boundary with the slope, hold the test piece gently with a metal plate, and center the tip of the test piece. The scale when touching the slope was read. When the scale was 40 mm or less, “◎”, when it was larger than 40 mm but not more than 60 mm, “◯”, when it was larger than 60 mm and not more than 80 mm, “Δ”, when it was larger than 80 mm, “×”.

As shown in Table 1, the incombustible sheet specified in the present invention is a low-cost incombustible sheet having transparency, flexibility, and incombustibility (Examples 1 to 3). On the other hand, when the K value of the PVC paste resin constituting the adhesive layer exceeded 70, the non-flammable sheet was inferior in transparency (Comparative Examples 1 and 2). Moreover, when an adhesive layer was not a polyvinyl chloride (PVC) paste resin, it was inferior to a softness | flexibility and resulted in a manufacturing cost rising (comparative example 3).
As shown in FIGS. 2 to 6, it can be seen that the sheet of the present invention has fewer bubbles (white portions in the photograph) contained in the sheet than the sheets of Comparative Examples 1 and 2, and is more transparent.

  The non-combustible sheet of the present invention is a transparent non-combustible sheet that is easy to manufacture and low in cost, does not generate waste in the manufacturing process, and has excellent transparency, non-combustibility, flexibility, and cutting properties. It can be suitably used for smoke barriers and smoke screens / curtains.

DESCRIPTION OF SYMBOLS 1 1st thermoplastic resin film 2 2nd thermoplastic resin film 3 Glass cloth 4 Adhesive layer 10 Transparent incombustible sheet

Claims (13)

A transparent non-combustible sheet formed by laminating a thermoplastic resin film on both sides of a glass cloth with an adhesive layer,
The adhesive layer is made of a resin composition containing a polyvinyl chloride (PVC) paste resin and at least one plasticizer, and the K value of the polyvinyl chloride (PVC) paste resin is 50 to 70, and
A transparent incombustible sheet, wherein the sheet has a total light transmittance of 75% or more.   The transparent incombustible sheet according to claim 1, wherein the glass fiber count in the glass cloth is 3 to 20 tex, and the total density of warp and weft is 80/25 mm to 190/25 mm.   The difference between the refractive index of the plasticizer, the refractive index of the glass fiber constituting the glass cloth, and the refractive index of the polyvinyl chloride (PVC) paste resin is ± 0.06 or less. Transparent incombustible sheet as described in 1.   The transparent incombustible sheet according to any one of claims 1 to 3, wherein the plasticizer is a plasticizer mainly composed of a phthalate ester plasticizer.   The thermoplastic resin film is composed of a resin composition containing a polyvinyl chloride resin and a plasticizer, and the plasticizer content relative to the total mass of the thermoplastic resin film is 50% by mass or less. 4. The transparent noncombustible sheet according to any one of 4 above.   The transparent noncombustible sheet according to any one of claims 1 to 5, wherein the thermoplastic resin film has a thickness of 0.05 to 0.20 mm. The coating amount of the adhesive layer is 10.0~60.0g / ^{m 2,} transparency incombustible sheet according to any one of claims 1 to 6.   The transparent noncombustible sheet according to any one of claims 1 to 7, wherein the entire sheet has a thickness of 0.45 mm or less.   The transparent incombustible sheet according to any one of claims 1 to 8, which is used for any one of a smoke proof wall, a smoke proof screen, a smoke proof partition wall, and a smoke proof curtain.   A smoke barrier wall using the transparent noncombustible sheet according to claim 1.   A smoke-proof screen curtain using the transparent non-combustible sheet according to claim 1. An adhesive layer made of a resin composition containing a polyvinyl chloride (PVC) paste resin having a K value of 50 to 70 and at least one plasticizer is formed on at least one surface of the first thermoplastic resin film and conveyed. And a process of
Heating and conveying the second thermoplastic resin film;
A step of laminating a glass cloth and the second thermoplastic resin film in this order on the adhesive layer of the first thermoplastic resin film;
And a step of thermally laminating the first thermoplastic resin film, the glass cloth, and the second thermoplastic resin film.   The manufacturing method of the transparent nonflammable sheet | seat of Claim 12 whose processing temperature at the time of carrying out heating conveyance of said 2nd thermoplastic resin film is 78 degreeC or more.

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