JP2014201024A - Natural lighting nonflammable sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a natural lighting nonflammable sheet in which a fabrication quality such as cutting and deposition, and handleability at installation time are largely improved, and further a stain adherence preventing property at long-term service time, and a stain wiping property by an organic solvent or the like are improved without damaging a natural lighting property, and incombustibility.SOLUTION: A natural lighting nonflammable sheet is that glass fiber cloth is embedded in an inside of a curable resin layer, and an ethylene-vinyl alcohol copolymer resin layer is laminated on at least one face of the curable resin layer through or not through a layer other than the ethylene-vinyl alcohol copolymer resin layer.

Description

  The present invention relates to an incombustible sheet having improved antifouling properties, welder weldability, and surface tackiness, and excellent transparency and daylighting.

  In order to partition the space of a large building, the partition that reaches the ceiling and the ceiling is often used. In the space partitioned by the partition, a small private space is often formed by partitions or low partitions. The partition is not limited to partitioning the office space, and it is necessary to partition the space for ensuring the safety of various manufacturing machines in the manufacturing plant and stabilizing the quality, and glass and resin sheets are used.

  Also, glass and resin sheets are used for lighting covers, back-illuminated advertising covers, and flame-proof banners. However, they are burned by fires, malfunctioned equipment, damaged by earthquakes, and injured by scattering. There were fundamental problems with glass and resin sheets, such as the occurrence of

  Therefore, recently, a product made by impregnating and curing a glass fiber fabric with a resin or laminating a glass fiber fabric with a flameproof resin sheet is commercially available as a resin-made sheet with non-flammability and good daylighting. However, when these sheets are used for a long period of time, there are problems such as stain penetration, accumulation, poor welder welding, or very poor workability and handling due to surface tack.

  In order to solve the above problems, Patent Document 1 and the like disclose a light-emitting incombustible sheet material in which a glass fiber fabric is impregnated with a resin and cured, or a resin sheet is laminated to improve transparency. . However, the disclosed daylighting non-combustible sheet may have its outermost layer covered with a vinyl chloride resin, an acrylic resin, etc., and as described above, dirt is likely to adhere and is difficult to remove. There is also a problem that the surface tack is strong and the secondary processability such as cutting and welding and the handling property at the time of installation are inferior. Patent Document 2 discloses a daylighting incombustible sheet coated with a fluoric resin, a silicon resin, an acrylic resin, etc. for surface modification, and although an improvement in antifouling property is recognized, welder welding is disclosed. There is a problem that the coating property and surface tackiness are deteriorated by coating.

  Patent Document 3 discloses a daylighting incombustible sheet in which a glass fiber fabric is impregnated with a fluorine-based resin or a silicon-based resin for imparting antifouling properties. However, there was a problem that a sheet satisfying both the antifouling property, the welder weldability and the surface tackiness and a method for producing the same were not found.

JP 2001-348411 (UV curing) JP 2010-52370 (PVC impregnation) JP2001-311235 (Fluorine series)

  The non-combustible sheet having the lighting property obtained by impregnating and curing the resin to the glass fiber fabric used in the office or the manufacturing factory has the above-mentioned problems, and the object of the present invention is to prevent stains, welder welding and surface tack. An object of the present invention is to provide a non-combustible sheet that is greatly improved.

That is, according to the present invention, a glass fiber fabric is embedded in a cured resin layer, and an ethylene-vinyl alcohol copolymer resin layer other than the ethylene-vinyl alcohol copolymer resin layer is formed on at least one surface of the cured resin layer. This is a daylighting incombustible sheet that is laminated with or without intervening layers and satisfies the following (a) to (f).
(A): Mass ratio of the glass fiber constituting the glass fiber fabric to the cured resin constituting the cured resin layer is 20:80 to 70:30.
(B): Ratio of ethylene-vinyl alcohol copolymer resin in ethylene-vinyl alcohol copolymer resin layer is 75% by mass or more (c): Movement of outer surface of ethylene-vinyl alcohol copolymer resin layer according to JIS K 7125 (D): Total light transmittance is 75% or more (e): Haze degree is 30% or less (f): High frequency welder welding strength is 4 kg / 30 mm width or more

  The daylighting incombustible sheet of the present invention has good light transmission, dirt is less likely to adhere, surface tackiness is reduced, and heat-fusability between sheets during processing (welder weldability) is also good. It has sufficient nonflammability and further transparency.

FIG. 1 is a schematic cross-sectional view of an embodiment of the daylighting incombustible sheet of the present invention. FIG. 2 is a schematic cross-sectional view of a laminate obtained as an intermediate product at the time of manufacturing the daylighting incombustible sheet (Example 1) of the present invention. FIG. 3 is a schematic cross-sectional view of a laminated sheet obtained as an intermediate product during the manufacture of the daylighting incombustible sheet (Example 1) of the present invention. FIG. 4 is a schematic cross-sectional view of an ethylene-vinyl alcohol copolymer resin layer laminate obtained as an intermediate product during the manufacture of the daylighting incombustible sheet (Example 1) of the present invention. FIG. 5 is a schematic cross-sectional view of an embodiment of the daylighting incombustible sheet (Example 1) of the present invention.

  In the present invention, a glass fiber fabric is embedded in a cured resin layer, and an ethylene-vinyl alcohol copolymer (hereinafter sometimes referred to as EVOH) resin layer is formed on at least one surface of the cured resin layer. It is a daylighting incombustible sheet formed by being laminated with or without a layer other than the vinyl alcohol copolymer resin layer.

  FIG. 1 is a schematic cross-sectional view of an embodiment of the daylighting incombustible sheet of the present invention. The daylighting incombustible sheet includes a glass fiber fabric 3 and a cured resin layer 5 in which the glass fiber fabric is embedded. The cured resin layer 5 preferably fills the gaps in the glass fiber fabric 3 and is at least partially continuous. An ethylene-vinyl alcohol copolymer resin layer 14 is formed on at least one surface of the cured resin layer 5. The thermoplastic resin layer 9 may be provided between the cured resin layer 5 and the EVOH resin layer 14 for the purpose of improving the flexibility and workability of the daylighting incombustible sheet, and further, for example, improving the peel resistance. Thus, the adhesive-1 layer 8 is formed between the cured resin layer 5 and the thermoplastic resin layer 9, or the adhesive-2 layer 13 is formed between the EVOH resin layer 14 and the thermoplastic resin layer 9. May be. The EVOH resin layer 14 and the cured resin layer 5 may be bonded via the adhesive-2 layer 13.

  The shape of the glass fiber fabric 3 constituting the present invention is not particularly limited to a shape such as a woven fabric, a knitted fabric, a non-woven fabric, and paper, but is a woven fabric from the viewpoint that it is easy to ensure the transparency of the sheet of the present invention. Preferably there is.

  In the glass fiber fabric, a plurality of warps 1 and a plurality of wefts 2 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 between adjacent warps 1 in the glass fiber fabric 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 2 in a glass fiber fabric is 0.5 mm or less, and it is more preferable that it is 0.2 mm or less. Satisfying the above-mentioned gap is preferable from the viewpoint of ensuring that the flame does not easily pass through the glass fiber fabric and ensures nonflammability.

  Glass fibers in the glass fiber fabric 3 include general-purpose non-alkali glass fibers (E glass), acid-resistant alkali-containing glass fibers (C glass), and high-strength / high-modulus glass fibers (S glass, T glass, etc.) Alkali-resistant glass fiber (AR glass) and the like can be mentioned, but use of alkali-free glass fiber having high versatility is preferable.

  The filament diameter of the glass fiber is preferably 1 to 20 μm from the viewpoint of achieving both strength properties and workability of the glass fiber fabric, and more preferably 3 to 12 μm. Further, the count of the glass fiber 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 3 is preferably surface-treated with a silane coupling agent usually used as a glass fiber treating agent for the purpose of improving the transparency and the bending whitening resistance of the daylighting incombustible sheet of the present invention. . Thereby, the glass fiber fabric 3 and the curable resin 4 can be bonded satisfactorily. As the silane coupling agent, an acrylic silane coupling agent, a styrene silane coupling agent, a vinyl silane coupling agent, an amine silane coupling agent and the like are preferable, and an acrylic silane coupling agent and a styrene silane are preferable. A coupling agent is more preferable.

It is preferable that the mass of the glass fiber fabric 3 per 1 m ² in the daylighting incombustible sheet of the present invention, that is, the basis weight of the glass fiber fabric 3 is 20 to 150 g / m ² . If the basis weight of the glass fiber fabric 3 is more than 150 g / m ^2, the impregnation rate of the uncured resin 4 becomes slow, lowered workability, it may cause impregnation defects in the case of less than 20 g / m ² May cause problems with nonflammability, and each is not preferred. Note When more than 150 g / m ² basis weight of the glass fiber cloth 3 in daylight incombustible sheet, it is preferable to use two or more glass fiber cloth 3.

  The cured resin layer 5 may be composed of a curable resin that is cured by heat, or may be composed of a curable resin that is cured by irradiation with light such as ultraviolet rays. Among the curable resins, there are those that can be cured by heat or ultraviolet irradiation. However, such a curable resin is preferable because it has a low viscosity in an uncured resin state and is easily impregnated into glass fibers.

  The curable resin 4 is preferably composed of a vinyl ester resin, an unsaturated polyester resin, an epoxy resin, or the like. Among them, the heat resistance, chemical resistance, mechanical strength, and curing characteristics are excellent. More preferably, it is made of a vinyl ester resin.

  The curable resin 4 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 a particle shape, and in the case of a particle shape, a particle size of 10 μm or less is preferable from the viewpoint of improving the total light transmittance of the obtained sheet and reducing haze, and 5 μm or less. More preferably.

Lighting incombustible sheet of the present invention preferably has a basis weight of the cured resin layer 5 is in the range of 15~500g / ^{m 2,} and more preferably in the range of 50 to 300 g / ^{m 2.} When the basis weight of the cured resin layer 5 is less than 15 g / m ² , the glass fiber fabric 3 cannot be sufficiently packed, and the pattern of the glass fiber fabric 3 may be raised, and the transparency is high. Decreasing and not preferable. On the other hand, when the basis weight of the cured resin layer 5 is more than 500 g / m ² , the nonflammability is lowered, which is not preferable.

In the daylighting incombustible sheet of the present invention, it is important that the mass ratio of the glass fiber constituting the glass fiber fabric 3 and the curable resin constituting the cured resin layer 5 is 20:80 to 70:30. When the mass ratio of the glass fibers is less than 20, the amount of the cured resin layer 5 increases and the nonflammability decreases. On the other hand, when the mass ratio of the glass fibers exceeds 70, the thickness of the cured resin layer 5 becomes thin, and the pattern of the glass fiber fabric 3 may be raised, resulting in a decrease in transparency.
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 and cracking, further improve nonflammability, and to achieve a level that passes the nonflammability certification, The mass ratio between the fiber and the curable resin is preferably 30:70 to 70:30.

  In the daylighting incombustible sheet of the present invention, the difference in refractive index between the glass composition constituting the glass fiber in the glass fiber fabric 3 and the curable resin 4 constituting the cured resin layer 5 is preferably 0.02 or less. The smaller the difference in refractive index between the two, the better the transparency of the sheet, which is preferable.

  The EVOH resin used for the EVOH resin layer 14 constituting the daylighting incombustible sheet of the present invention is an ethylene content of 20 to 55 mol%, particularly 25 to 50 mol%, particularly a saponification of a vinyl acetate component, in terms of water resistance and strength. A saponified ethylene-vinyl acetate copolymer (ie EVOH) having a degree of 90 mol% or more, particularly 95 mol% or more, and having an intrinsic viscosity in the range of 0.7 to 1.56 dL / g is particularly preferable. When the ethylene content is less than 20 mol%, the water resistance under high humidity is inferior, and when the ethylene content exceeds 55 mol%, the antifouling property is insufficient. Moreover, when the saponification degree of a vinyl acetate component is less than 90 mol%, there exists a problem inferior to solvent resistance, and it is unpreferable. Further, if the intrinsic viscosity is less than 0.7 dL / g, the mechanical strength is insufficient, and those having an intrinsic viscosity exceeding 1.5 dL / g are not practical because of difficulty in production. Here, the intrinsic viscosity is a value measured at a temperature of 30 ° C. in a mixed solvent of water / phenol having a mass ratio of 15/85.

  EVOH is obtained by saponification of an ethylene-vinyl acetate copolymer. The ethylene-vinyl acetate copolymer should be produced by any known polymerization method, for example, solution polymerization, suspension polymerization, emulsion polymerization, etc. The saponification of the ethylene-vinyl acetate copolymer can also be performed by a known method.

  Further, within the range not impairing the gist of the present invention, the α-olefin, the unsaturated carboxylic acid compound, the unsaturated sulfonic acid compound, (meth) if the EVOH resin constituting the EVOH layer is less than 50% by mass. EVOH resins copolymerized and modified with other comonomers such as acrylonitrile, (meth) acrylamide, vinyl ether, vinylsilane compounds, vinyl chloride, styrene, etc. can be used, and post-modified EVOH such as urethanization, acetalization, and cyanoethylation A resin may be used.

  The daylighting incombustible sheet of the present invention is characterized in that the EVOH resin layer is laminated, but it is important that the ratio of the EVOH resin in the EVOH resin layer is 75% by mass or more. When the proportion of EVOH resin is 75% by mass or more, the obtained daylighting incombustible sheet has sufficient light transmittance, while ensuring antifouling properties against dirt such as organic solvents, and further the tackiness of the daylighting incombustible sheet. It can be lowered to a state that does not hinder the secondary processing.

  As a method of laminating EVOH resin on the non-flammable sheet of the present invention without using a layer other than the EVOH resin or through an adhesive-2 layer 13 as necessary, melt extrusion by laminating a melt extruded EVOH film Method, coating method in which an EVOH resin solution is coated on a fine unevenness forming cover film 15 such as polyethylene terephthalate, dried and then transferred to a laminate, and a coating method in which an EVOH resin solution is directly coated on a laminated sheet. is not.

  In general, a melt extrusion method capable of easily increasing the thickness of the EVOH resin layer is suitable for taking advantage of the properties of the outermost EVOH resin and imparting surface hardness and scratch resistance. On the other hand, when the flexibility of the EVOH resin laminate is required, it is better to make the outermost EVOH resin layer thinner, and a transfer method and a solution coating method are used.

  The thickness of the EVOH resin layer is preferably 0.1 to 20 μm, and more preferably 0.2 to 15 μm. If the thickness is less than 0.1 μm, the anti-fouling property deteriorates due to insufficient permeation prevention of the plasticizer, unreacted monomer, etc. from the inner layer resin. Has a problem of partial desorption. On the other hand, if it exceeds 20 μm, the rigidity is excessively increased, and there may be problems in workability and handleability, which is not preferable.

  As the melt extrusion method, an extrusion film formation method in which an EVOH resin or an EVOH resin and an adhesive resin as an adhesive are laminated on the outermost layer of the daylighting incombustible sheet through a multi-layer T die with a melt extruder. Is a preferred example. Further, in order to reduce the thickness of the EVOH layer, an extrusion laminating method in which a film is nipped by a transfer cover film and a cooling roll in a molten film state and cooled and solidified simultaneously with the lamination is also suitably used.

  The EVOH resin used in the extrusion film forming method and the extrusion laminating method is a blend of a carboxylic acid-modified polyethylene resin within a range of 20 parts by mass or less with respect to 100 parts by mass of the EVOH resin as long as the gist of the present invention is not impaired. The glossiness may be controlled. When it exceeds 20 parts by mass, the surface tackiness is greatly improved, but there is a problem that the total light transmittance is deteriorated, and it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

The carboxylic acid component constituting the carboxylic acid-modified polyethylene resin is an α, β-unsaturated carboxylic acid having 3 to 10 carbon atoms or the carboxylic anhydride, such as acrylic acid, methacrylic acid, ethacrylic acid, maleic acid. Itaconic acid, maleic anhydride, itaconic anhydride and the like can be mentioned, among which maleic anhydride and itaconic anhydride are preferred. Examples of the polyethylene resin include high density polyethylene, low density polyethylene, and linear low density polyethylene.
Although there is no restriction | limiting in particular in the manufacturing method of carboxylic acid modification polyethylene resin used by this invention, The method of graft-polymerizing (alpha), (beta) -unsaturated carboxylic acid or this carboxylic acid anhydride to polyethylene is preferable.

  The adhesive resin used in the extrusion laminating method and serving as an adhesive between the EVOH resin layer 14 and the cured resin layer 5 or the thermoplastic resin layer 9 and providing the adhesive-2 layer 13 is urethane, polyester, or epoxy. , Acrylic, polyester polyol-acrylic copolymer, polyester polyol-acrylic copolymer, vinyl chloride-vinyl acetate copolymer and polyolefin resin, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, itaconic acid, Graft polymerized resins such as maleic anhydride, itaconic anhydride, boric acid compounds can be used.

The EVOH resin solution used for the transfer method and the solution coating method is prepared by dissolving the EVOH resin in a solvent. The solvent used is preferably water / alcohol, among which water / isopropanol, water / n-propanol, water / n-butanol, water / sea-butanol, water / isobutanol are the stability of the resulting EVOH resin solution. Further, it is more preferable from the viewpoints of handleability and economics. In the case of a water / alcohol solvent, the water / alcohol mass ratio in the solvent is preferably 20/80 to 80/20 from the viewpoint of stability and transparency of the EVOH resin solution.
Mixing formic acid, phenol, dimethylformamide, N-methylpyrrolidone and the like in the above solvent in a proportion of 1 to 30% by mass improves the solution stability and transparency, and is more preferable.

  If the concentration of the EVOH resin in the EVOH resin solution is less than 1% by mass, the coating layer after drying becomes too thin, the surface becomes cloudy and the transparency is impaired. On the other hand, if the concentration exceeds 20% by mass, the workability during coating is inferior because the solution concentration is high, and gloss unevenness due to uneven drying of the coating layer is likely to occur, and the solution concentration should be selected from the range of 1 to 20% by mass. Is desirable.

  In order to improve the sliding property of the daylighting incombustible sheet of the present invention, the EVOH resin layer preferably contains fine particles. For example, by adding fine particles to the EVOH resin solution, the EVOH resin layer can contain fine particles.

  The proportion of the fine particles in the EVOH resin layer is preferably 0.1 to 12 parts by mass of the fine particles with respect to 100 parts by mass of the EVOH resin. When the proportion of the fine particles is less than 0.1 parts by mass, the tackiness of the EVOH resin layer surface is increased, and the handleability when processing and constructing the daylighting incombustible sheet is unfavorable. When the proportion of the fine particles exceeds 12 parts by mass, the transparency may decrease, which is not preferable.

  The average particle diameter of the fine particles is preferably 2 μm or less, more preferably 0.05 to 2 μm, and still more preferably 0.1 to 1 μm. If it exceeds 2 μm, there is a problem that transparency and daylighting of the daylighting incombustible sheet are deteriorated, which is not preferable. Even when the average particle diameter of the fine particles is 2 μm or less, if there are coarse particles of 5 μm or more in the EVOH resin layer, the total light transmittance is lowered or the haze value is increased (transparency is lowered). Therefore, it is preferable that the average particle diameter of the fine particles is 2 μm or less, and the particles having a particle diameter of 5 μm or more in the EVOH resin layer are 1 part by mass or less with respect to 100 parts by mass of the EVOH resin. In order to reduce the secondary aggregation of the fine particles and sharpen the particle size distribution, when the fine particles are dispersed in a solvent, the surface state of the fine particles may be made hydrophilic or hydrophobic with a silane coupling agent or the like. desirable. Further, stirring for dispersion is an important factor, and strong stirring by using a homogenizer or the like is desirable as much as possible.

  As fine particles, aluminum, titanium, iron, cerium, yttrium, manganese, silicon, tin, zinc, copper, bismuth, cobalt, and composites of these metal oxides, and the surface of the metal oxide are coated with an organic substance. As long as it is a fine particle imparted with hydrophilicity or hydrophobicity, it is not particularly limited.

  There are no particular restrictions on the method of creating the fine particles, and there are pulverization methods that physically apply at low temperatures, precipitation methods from solutions, plasma evaporation / cooling solidification methods, evaporation / chemical reactions / cooling solidification methods, and the like. . The latter three methods are preferably used to obtain fine particles having an average particle diameter of 0.05 to 2 μm.

  For the purpose of preventing secondary aggregation and improving compatibility with the EVOH resin, the fine particle is preferably a slurry dispersion to which various surfactants and silane coupling agents are added. As the silane coupling agent, those having a (meth) acryloxy group include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethethoxysilane, 3-meta Acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane; p-styryltrimethoxysilane as styryl group; amino group N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3- Aminopropyltri Ethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane ; Having a urea group, 3-ureidopropyltriethoxysilane; having an isocyanate group, 3-isocyanatopropyltriethoxysilane; and the like can be mentioned, but is not limited thereto. It is also possible to use it individually or in combination of 2 or more types.

  The surfactant is not particularly limited, but there are anionic surfactants, cationic surfactants, and nonionic surfactants depending on the dispersion solvent to be used. As anionic surfactants, Kao Corporation Fatty acid salt surfactant commercially available from the company; NS soap, KS soap, KS-soap L-18, OS soap, alkenyl succinate surfactant; Ramtel ASK, Ramtel DSK, higher alcohol sulfate ester salt type Emar O, Emar 10 needle, Emar 10 powder, Emar 2F needle, Emar 2F-G, Emar 2F-30, alkylbenzene sulfonic acid type; Neopex G-65, Neopex G-25, Neopex G-15, Alkyl Sulfonate salt; Ramtel PS, alkyl diphenyl ether sulfone Perex SS-L, Perex SS-H, naphthalenesulfonic acid formalin condensate type; Demol N, Demol NL, Demol T, Demol T-45, Special carboxylic acid polymer surfactant type; Poise 500 series, Demol EP, Reactive surfactant type; Ramtel PD-104, Ramtel S-180, Ramtel S-180A, commercially available from Asahi Denka Kogyo Co., Ltd., sulfate type; Adeka Hope MS-30C, Adeka Hope MS-90P, Adeka Hope YES- 25, sulfonate type; ADEKA HOPE HAN-40, ADEKA HOPE SAN-40PD, sulfated oil; ADEKA HOPE TR-45, phosphate ester type; ADEKA COAL TS-230E, ADEKA COAL CS-141E, ADEKA COAL CS-1361E, ADEKA COAL CS-279 , Adekaco Le PS-440E, ADEKA COL PS-509E, ADEKA COL PS-807, ADEKA COL PS-984, sulfosuccinate type; Adekacol EC-4500, Adekacol EC-8600, polypeptide type; ADECANOL AP-1240E, and the like.

  As the cationic surfactant, an alkylamine salt type commercially available from Kao Corporation; acetamine 24, acetamine 86, quaternary ammonium salt type; coatamine 24P, coatamine 86P conch, coatamine 60W, coatamine 86W, coatamine D86P, Alkyl ether quaternary ammonium salt type, benzalkonium chloride type; Sanizol B-50, alkyl cation type commercially available from Asahi Denka Kogyo Co., Ltd .; Adecamine 4MAC-30, 4DAC-80, 4DAC-85, MT-50, Amide type, ester cation type; adecamine SF-101, SF-201, SF-106, amino oxide type; adecamine LDM, PMS-100, and the like.

  As the amphoteric surfactant, an alkylbetaine type commercially available from Kao Corporation; Amphitol 20BS, Amphitol 24B, Amphitol 86B, an alkylamine oxide type; Amphitol 20N, Adeka Anhhot PB commercially available from Asahi Denka Kogyo Co., Ltd. -30L, AB-35L, and the like.

  In addition, the method for dispersing the fine particle dispersed slurry in the EVOH solution is not particularly limited. However, if the solvent composition of the fine particle dispersed slurry and the EVOH solution are greatly different or the concentration difference between the two is large, It causes deterioration of transparency and appearance due to secondary aggregation and poor dispersion. Therefore, in order to sufficiently increase the dispersion of the solution, it is preferable to use a homomixer having high stirring efficiency.

  When using the transfer method when manufacturing the daylighting incombustible sheet of the present invention, the EVOH resin solution is solidified by coating the EVOH resin solution on the fine unevenness forming cover film 15 having fine unevenness formed on the surface. After forming an EVOH resin layer having fine irregularities on the surface and applying adhesive-2 on the surface of the EVOH resin layer opposite to the fine irregularity forming cover film 15 as necessary, the fine irregularity forming cover film 15 / The cured resin layer 5 or the cured resin layer 5 / thermoplastic resin layer 9 is formed of the EVOH resin layer 14 or the slightly uneven formed multilayer film 16 having a laminated structure such as the slightly uneven formed cover film 15 / EVOH resin layer 14 / adhesive-2 layer. Then, after overlapping with a laminated sheet having a laminated structure such as cured resin layer 5 / adhesive-1 layer 8 / thermoplastic resin layer 9 and the like, peel off the outermost fine unevenness forming cover film 15. The lighting incombustible sheet may be manufactured by a method for. Here, the fine unevenness forming cover film 15 is not particularly limited, but is polyolefin such as polyethylene, polypropylene, polynorbornene, polystyrene, polyvinyl chloride, acrylic resin, methacrylic resin, polytetrafluoroethylene (PTFE), Perfluoroalkoxyalkane (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin), fluororesin such as ethylene-tetrafluoroethylene copolymer, perfluoroethylene-propene copolymer, polyester such as polymethyl methacrylate (PMMA); aliphatic polyamide, Examples thereof include polyamides such as aromatic polyamides. Of these, polyester films (hereinafter sometimes referred to as PET films) are preferable in terms of performance and cost.

  Although it does not specifically limit as thickness of the fine unevenness formation cover film 15, It is 12-200 micrometers, More preferably, it is 20-150 micrometers. When the thickness is less than 12 μm, it is not only difficult to ensure the flatness of the EVOH resin layer and thus the daylighting incombustible sheet, but the fine unevenness forming cover film 15 may be broken when the fine unevenness forming cover film 15 is peeled off. There is. On the other hand, when it exceeds 200 μm, not only the process passability is inhibited, but also there is a problem in cost.

The fine unevenness forming cover film 15 has a rough surface because the surface of the fine unevenness forming cover film 15 is easy to impart designability, post-processability by tack reduction, and handleability to the daylighting incombustible sheet of the present invention. It is preferable that it is processed. The degree of roughening of the fine unevenness forming cover film 15 is such that the glossiness specified by JIS Z 8741 is 40% or more, more preferably 50% or more. If the glossiness is less than 40%, the haze of the obtained daylighting incombustible sheet becomes high and the transparency is lowered, which is not preferable.
The fine unevenness forming cover film 15 is provided with a corona treatment, a silicon-based or a fluorine-based film within the range not inhibiting the present invention in order to prevent the coating liquid from being peeled off or to facilitate the peeling of the cover film from the daylighting incombustible sheet. You may perform the process by a mold release agent.

  For example, regarding the EVOH resin having the fine unevenness formed on the surface by the above method using the fine unevenness forming cover film 15, the daylighting incombustible sheet in which the EVOH resin layer is laminated so that the fine unevenness forming surface becomes the outer surface is as follows: Since the total light transmittance is high and the haze is low, the sheet has both translucency and transparency.

  In the daylighting incombustible sheet of the present invention, a thermoplastic resin layer 9 may be laminated between the cured resin layer 5 and the EVOH resin layer. Although it does not specifically limit as a thermoplastic resin which forms the thermoplastic resin layer 9, Polyolefin, such as polyethylene, a polypropylene, a polynorbornene; Polystyrene; Polyvinyl chloride; Acrylic resin; A methacrylic resin; Polytetrafluoroethylene ( PTFE), perfluoroalkoxyalkane (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin), fluororesin such as ethylene-tetrafluoroethylene copolymer and perfluoroethylene-propene copolymer, polyester such as polymethyl methacrylate (PMMA); fat And polyamides such as aromatic polyamides and aromatic polyamides. Among these, polyvinyl chloride is more preferable in terms of cost and performance.

  Among polyvinyl chloride resins, vinyl chloride polymers, vinyl chloride / vinyl acetate copolymers, vinyl chloride / acrylic ester copolymers, and vinyl chloride / vinylidene chloride copolymers are economical and workable. It is preferable at a point and these may be used independently and may mix and use two or more types.

  The thermoplastic resin layer 9 may contain components other than the thermoplastic resin, and a plasticizer is preferably contained in order to ensure the flexibility of the obtained sheet.

  When the thermoplastic resin layer 9 is made of a polyvinyl chloride resin, the amount of the plasticizer added to the polyvinyl chloride resin is preferably 30 to 150 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. It is more preferable that it is 35-120 mass parts. If it is less than 30 parts by mass, it will be excessively hard and will not be able to follow movement such as bending, and cracks will easily occur. On the other hand, if it exceeds 150 parts by mass, the strength of the resin is lowered, the strength of the heat-sealed part becomes insufficient, and the plasticizer may cause problems such as contamination of the film material.

  There are no particular restrictions on the plasticizer that can be used for the polyvinyl chloride resin, but dibutyl phthalate, diethyl phthalate, dihebutyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-phthalate as the phthalate ester plasticizer. Nonyl phthalate, di-n-decyl phthalate, diisodecyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, etc. are used, and adipic acid is 2-methyl-1,8-octanediol, 1,2 as a polyester plasticizer. -Products esterified with one or more of glycols such as propanediol, 1,3-butanediol, 2-ethylhexanol, and n-octanol can be used. Further, as a trimellitic acid plasticizer, , Tri-2-ethylhexyltri Relate, and the like can be used triisodecyl trimellitate rate, other plasticizers, pyromellitic acid plasticizers such as 2-ethylhexyl pyromellitate rate can also be used. As the polymer having a plasticizing action, an ethylene-vinyl acetate copolymer and / or a polymer obtained by introducing carbon monoxide into an ethylene-acrylic acid ester copolymer can be used. Such a polymer includes Elvalloy 742 (trademark) manufactured by Mitsui DuPont Chemical.

  The flame retardant for the polyvinyl chloride resin is preferably 3 to 150 parts by mass, more preferably 5 to 120 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. When the blending amount of the flame retardant is less than 3 parts by mass, the flame resistance of the polyvinyl chloride resin layer becomes insufficient, and when a corn calorimeter test based on ISO 5660 and Part 1 is performed, Pinholes are likely to occur, which is not preferable. Moreover, when it exceeds 150 mass parts, the softness | flexibility and resin strength of a polyvinyl chloride-type resin layer will fall, and peeling strength with the cured resin layer 5 etc. may fall, and it is unpreferable.

As the flame retardant used for the polyvinyl chloride resin, an inorganic flame retardant is preferable because high flame retardancy can be secured. Among them, a combined flame retardant in which an antimony compound and a molybdenum compound are used in combination is used. Antimony compounds impart high flame retardancy to polyvinyl chloride resins and have a strong effect of preventing the spread of flames. Molybdenum compounds reduce combustion heat, reduce smoke generation, reduce harmful combustion gases, and promote carbonization. And it has the effect | action which suppresses generation | occurrence | production of the pinhole in a base fabric, and is used preferably.
Examples of the antimony compound include antimony trioxide and antimony pentoxide.
Examples of the molybdate compound include calcium zinc molybdate, potassium molybdate, sodium molybdate, calcium molybdate carbonate, and ammonium molybdate.
The inorganic flame retardant used in the present invention may be subjected to a silane coupling treatment in advance to improve adhesion with the resin.

Furthermore, as flame retardants other than the above, the total calorific value and the rate of heat generation during the burning of the film material do not exceed the standard values of ISO5660Part1, for example, bromo flame retardants, phosphate esters, halogenated phosphate esters, chlorination Flame retardants can be used in addition to paraffin.
Decabromodiphenyl ether, pentabromomethylbenzene, hexabromobenzene and the like can be used as the bromide flameproofing agent.
As the phosphate ester, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate and the like can be used.

  Furthermore, for polyvinyl chloride resin layers, stabilizers such as calcium / zinc-based, barium / zinc-based, cadmium / barium-based, lead-based, organic tin laurate-based, organic tin mercaptite-based, and epoxy-based stabilizers Can be used alone or in admixture of two or more. The blending amount of the stabilizer is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin.

The basis weight of the thermoplastic resin layer 9 is preferable in order to achieve both the transparency and strength characteristics of a sheet obtained in the range of 60 to 400 g / m ² .

As long as the effect of the present invention is not hindered, use of an adhesive in the laminated portion of the daylighting incombustible sheet is not restricted. For example, an adhesive is used between the cured resin layer 5 and the thermoplastic resin layer 9. -1 layer 8 is provided, or an adhesive-2 layer 13 is provided between the EVOH resin layer 14 and the thermoplastic resin layer 5 or between the EVOH resin layer 14 and the cured resin layer 5, and lighting is performed. You may improve the peeling-proof characteristic of a nonflammable sheet.
The adhesive to be used is not particularly limited, and vinyl chloride-based, urethane-based, polyester-based, epoxy-based and acrylic-based adhesives can be used, and vinyl chloride-based and urethane-based materials are preferable.
When the anti-peeling property of the daylighting incombustible sheet is particularly important, a curing agent such as an epoxy type or an isocyanate type may be used as an adhesive and cured. The application amount of the adhesive is 0.1 to 20 g / m ² , more preferably 0.2 to 10 g / m ² in the drying stage. In consideration of process passability during production, it is more preferable that there is almost no tack at room temperature. For example, when the adhesive-1 layer 8 and the adhesive-2 layer 13 are provided using an adhesive at two or more places, the brand of the adhesive may be the same or different.

  The daylighting incombustible sheet of the present invention has a slip coefficient (sliding property) of the daylighting incombustible sheet, which is the object of the present invention, that the dynamic friction coefficient of the outermost layer of the EVOH resin layer according to JIS K 7125 is 2 or less. The daylighting incombustible sheet is important in terms of improving work characteristics when performing secondary processing such as product processing, and the dynamic friction coefficient is preferably 1.5 or less. The dynamic friction coefficient is an index of the degree of unevenness of the sheet surface. For example, the EVOH resin layer can be moved by adding fine particles to the EVOH resin layer or forming fine unevenness on the EVOH resin layer with a fine unevenness forming cover film. It is possible for the coefficient of friction to be 2 or less.

In addition, in the daylighting incombustible sheet of the present invention, it is important for ensuring the transparency of the sheet that the total light transmittance is 75% or more and the haze is 30% or less. It is preferably 85% or more and 20% or less. Here, the value of the total light transmittance is defined in “Testing Methods for Optical Properties of Plastics”, “5.5 Light Transmittance and Total Light Reflectance” of JIS K 7105. Specifically, this is a value obtained by measuring the total light transmission amount using an integrating sphere measuring device and obtaining the total light transmittance, and the haze value is defined in “Optical of plastic” in JIS K 7105. In accordance with “6.4 Haze”, specifically, diffuse transmittance and total light transmittance are measured using an integrating sphere type measuring device, and “Testing Methods for Optical Properties of Plastics”. It is a value obtained by the ratio.
In order that the daylighting incombustible sheet of the present invention is provided with an EVOH resin layer, the light transmittance is 75% or more and the haze satisfies 30% or less, when the EVOH resin layer has fine particles, The average particle diameter of the fine particles is preferably 2 μm or less, and further, the daylighting incombustible sheet preferably has a thermoplastic resin layer.

  Further, the daylighting incombustible sheet of the present invention has a high-frequency welder welding strength of 4 kg / 30 mm width or more, and is excellent in heat weldability when the daylighting incombustible sheets or the daylighting incombustible sheet and other sheets are thermally welded. Therefore, the width is preferably 5 kg / 30 mm or more. By providing the EVOH resin layer in the daylighting incombustible sheet of the present invention, the high-frequency welder welding strength can be 4 kg / 30 mm width or more.

The daylighting non-combustible sheet of the present invention has a total calorific value of 20 MJ / m ² or less in 20 minutes after the start of heating in a heat generation test in which 50 kW / m ² of radiant heat is applied to the surface of the sheet from a radiant electric heater. In addition, it is preferable from the viewpoint of nonflammability of the sheet that the maximum heat generation rate continues for 10 seconds or more for 20 minutes after the start of heating and does not exceed 200 kW / m ² . This parameter is a numerical value indicating how incombustible the sheet of the present invention is based on the evaluation method in the Building Standard Law.

  Although it does not specifically limit as embodiment of the lighting noncombustible sheet | seat of this invention, EVOH resin layer 14 / adhesive agent-2 layer 13 / cured resin layer 5, EVOH resin layer 14 / adhesive agent-2 layer 13 / Cured resin layer 5 / adhesive layer-2 layer 13 / EVOH resin layer 14, EVOH resin layer 14 / adhesive layer-2 13 / thermoplastic resin layer 9 / cured resin layer 5, thermoplastic resin layer 9 / cured resin layer 5 / adhesive layer-2 layer 13 / EVOH resin layer 14, EVOH resin layer 14 / adhesive agent-2 layer 13 / thermoplastic resin layer 9 / cured resin layer 5 / adhesive layer-2 layer 13 / EVOH resin layer 14 EVOH resin layer 14 / adhesive-2 layer 13 / thermoplastic resin layer 9 / adhesive-1 layer 8 / cured resin layer 5; thermoplastic resin layer 9 / adhesive-1 layer 8 / cured resin layer 5 / adhesive Agent-2 layer 13 / EVOH resin layer 14, EVOH resin layer 14 / adhesive 2 layers 13 / thermoplastic resin layer 9 / adhesive-1 layer 8 / cured resin layer 5 / adhesive-2 layer 13 / EVOH resin layer 14, EVOH resin layer 14 / adhesive-2 layer 13 / thermoplastic resin layer 9 / adhesive-1 layer 8 / cured resin layer 7 / adhesive-1 layer 8 / thermoplastic resin layer 9, EVOH resin layer 14 / adhesive-2 layer 13 / thermoplastic resin layer 9 / adhesive-1 layer 8 / cured resin layer 5 / adhesive-1 layer 8 / thermoplastic resin layer 9 / adhesive-2 layer 13 / EVOH resin layer 14 and the like. When transporting the daylighting incombustible sheet or the like, the cover film 11 or / and the fine unevenness forming cover film 15 are left laminated on at least one of the outermost layers of the daylighting incombustible sheet. Alternatively, a method of peeling the fine unevenness forming cover film 15 may be employed.

Although it will not specifically limit as a manufacturing method of the lighting non-combustible sheet of this invention if the effect of this invention is obtained, For example, the following manufacturing method etc. are selected preferably.
First, when the glass fiber fabric 3 is impregnated with the curable resin 4 and then cured with light or heat, in order to facilitate the flatness and handleability of the cured resin layer 5, an uncured state is formed on the cover film 11. After applying the curable resin 4, the glass fiber fabric 3 may be embedded and then cured to form a laminate. Alternatively, the thermoplastic resin layer 9 is laminated on the cover film 11 for the purpose of ensuring the thickness uniformity of the daylighting incombustible sheet, the daylighting property, and the productivity, and further curing the uncured state on the side of the thermoplastic resin layer 9. Curable resin 4 is applied by applying pressure from above and below the laminated structure of cover film 11 / thermoplastic resin layer 9 / curable resin embedded with glass fiber fabric after glass fiber fabric 3 is embedded. May be cured to form a laminate. Thereafter, the cover film 11 is peeled from the laminate, and the EVOH resin layer is formed on the obtained laminate sheet by the above-described melt extrusion method, transfer method, coating method, etc., to obtain the daylighting incombustible sheet of the present invention. it can.
For the laminate, for example, cover film 11 / cured resin layer 5, cover film 11 / thermoplastic resin layer 9 / cured resin layer 5, cover film 11 / thermoplastic resin layer 9 / adhesive-1 layer 8 / cured. Resin layer 5, cover film 11 / thermoplastic resin layer 9 / adhesive-1 layer 8 / cured resin layer 7 / adhesive-1 layer 8 / thermoplastic resin layer 9 / cover film 11, cover film 11 / thermoplastic resin The layer 9 / adhesive-1 layer 8 / cured resin layer 5 / cover film 11 can be selected.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely and in detail, the scope of the present invention is not limited to a following example.

Description of test method Dynamic coefficient of friction (slip property): When JIS K 7125 “Plastic film and sheet friction coefficient test method” is used, a test piece of 63 mm square is subjected to a load of 200 g and pulled at a speed of 100 mm / min. The value obtained by dividing the tension by the load was defined as the dynamic friction coefficient.

  Total light transmittance: According to “Testing methods for Optical Properties of plastics” of JIS K 7105, “5.5 Light transmittance and total light reflectance”. Specifically, the total light transmittance was measured using a direct reading haze meter manufactured by Toyo Seiki, which is an integrating sphere measuring device, and the total light transmittance was determined.

  Haze: The method for measuring the haze of the transparent noncombustible sheet was in accordance with “6.4 haze” in “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.

Flammability test: A corn calorimeter test according to ISO 5660 Part 1 was performed under the conditions of a heating intensity of 50 kW / m ² and a test time of 20 minutes, and the total calorific value and the heat generation rate were measured.
The acceptance criteria as a non-combustible film material were a total calorific value of 8 MJ / m ² or less, a heating rate exceeding 10 seconds and not exceeding 200 kW / m ² , and that no pinholes were confirmed in the sample after the test. The test results were evaluated as follows.
Total calorific value 8 MJ / m ² or less: Pass, Exceed 8 MJ / m ² : Fail Heat generation rate Exceed 10 seconds and do not exceed 200 kW / m ² : Pass
Over 10 seconds and over 200 kW / m ² : Fail Pinhole Not recognized: Pass, Accepted: Fail

Flame retardancy test: Flame retardancy was evaluated according to JIS L 1091 “Flammability test for textile products”. The test results were displayed as follows.
○: Category 3 passed, ×: Category 3 failed

Antifouling property: The multilayer film cut into a size of 2 cm × 2 cm was wiped off with oily red ink (Mitsubishi Marker, Mitsubishi Pencil Co., Ltd.) and gauze with benzine attached after 24 hours. Moreover, soy sauce (Kikkoman Co., Ltd. Kikkoman deep mouth) was applied, and 24 hours later, it was wiped off with gauze moistened with Mama lemon (synthetic detergent for kitchen) of Lion Corporation.
Judgment criteria A (pass): No dirt remains B (pass): Unclean dirt remains.
C (failure): Clear dirt remains D (failure): After wiping remains or the surface layer is detached.

  High frequency welder: Two A4 size test pieces are superposed, YE7000A manufactured by Yamamoto Vinita Co., Ltd. is used, and the test pieces are heat-sealed by heating them to a 250 mm x 50 mm width electrode at a current of 1 A for 5 seconds. I let you. The heat-sealed test piece was cut to a width of 30 mm, 90-degree T-type peeling was performed at a peeling speed of 200 mm / min, and welder fusion peeling strength was measured.

Example 1
As glass fiber fabric 3, glass cloth H350F3 manufactured by Unitika Glass Fiber Co., Ltd. (the number of warps and wefts to be driven is 32/25 mm, 31/25 mm, the thickness is 0.3 mm, and the basis weight is 250 g / m ² ) Was heated in a heating furnace at 370 ° C. for 2 minutes to remove the sizing agent attached to the glass cloth. Thereafter, a styrene-based silane coupling agent (trade name: KBM1403) manufactured by Shin-Etsu Silicon Co., Ltd. was diluted to 5% with a 30% aqueous methanol solution, and then the glass fiber fabric 3 was immersed and dehydrated, followed by hot air at 100 ° C. It dried for 30 minutes with the dryer.

  As curable resin 4, 100 parts by mass of an orthophthalic acid unsaturated polyester resin (trade name: Rigolac 1635) sold by Showa High Polymer Co., Ltd. and a polymerization initiator sold by Nippon Oil & Fats Co., Ltd. And 0.5 parts by mass of methyl ethyl ketone peroxide (trade name: Permec N) were stirred for about 3 minutes using a stirrer. And the obtained mixture was left to stand under vacuum for about 5 minutes and deaerated to obtain an uncured curable resin 4.

  As the cover film 11, two PET films having a thickness of 100 μm were used.

One cover film 11 was thermocompression bonded with a vinyl chloride film having the following composition as a thermoplastic resin 9 using a 120 ° C. heat laminating roll. Thereafter, a urethane adhesive (Sanplex 435A) manufactured by Murayama Chemical Co., Ltd. was diluted to a concentration of 20% with a 20% aqueous isopropyl alcohol solution, and further 5% of a block isocyanate curing agent manufactured by DIC was added, followed by vinyl chloride. 10 g / m ^{2 is} applied to the film side, dried at 80 ° C. for 5 minutes to form an adhesive-1 layer 8, and a cover film 11 / thermoplastic resin layer 9 / adhesive-1 layer 8 is laminated. A laminated film 12 was obtained.
65% by mass of vinyl chloride resin
Di-2-ethylhexyl phthalate 15% by mass
Phosphoric ester flame retardant plasticizer 15% by mass
Ba-Zn stabilizer 3% by mass
UV absorber, light stabilizer, lubricant 2% by mass
Inorganic colorant Trace amount (0.005% by mass)

On the adhesive-1 layer 8 side of the laminated film 12 cut to 200 mm × 300 mm, the uncured curable resin 4 is applied in an amount of 150 g / m ² in a central area of 150 mm × 250 mm, and then applied. The glass fiber fabric 3 having a size of 150 mm × 250 mm was placed on the curable resin 4 in a state. Leave for about 5 minutes, and after confirming that the uncured curable resin 4 is sufficiently impregnated into the glass fiber cloth 3 and degassed, the other of the uncured curable resin 4 including the glass fiber cloth 3 is removed. The other cover film 11 on the surface is in contact with the uncured curable resin 4 and is laminated so that no bubbles are mixed in the uncured curable resin 4 and has the form shown in FIG. Got.

  The thus obtained curable resin 4 in an uncured state is obtained by applying pressure by applying a roller by hand from above the outermost layer cover films 11 of the laminate including the uncured resin 4. Removal of bubbles remaining between the glass fiber fabric 3 and the thickness of the uncured curable resin 4 were made uniform. The diameter of the roller was 20 mm and the length was 200 mm.

  Next, the laminate containing the uncured curable resin 4 was put under pressure in a hot press machine at 80 ° C. and left for 30 minutes to cure the uncured curable resin 4. Next, the temperature of the hot air dryer was raised to 100 ° C. and left for 10 minutes for further curing.

After cooling the laminated body including the curable resin 4 taken out from the hot air dryer, the cover films 11 of both outermost layers of the laminated body were peeled off to obtain a laminated sheet having the structure shown in FIG.
As shown in Table 1, the obtained laminated sheet 10 had good flame retardancy, non-flammability, and daylighting properties, but there were problems with poor antifouling properties, surface tackiness, and the like.

Next, 10 g / m ^{2 of the} same adhesive used for forming the adhesive-1 layer 8 was applied to the outermost thermoplastic resin layer 9 side of the laminated sheet 10 and dried at 80 ° C. for 5 minutes for adhesion. After forming the agent-2 layer 13, an EVOH resin (trade name: Eval E105) having an ethylene content of 44 mol% and a saponification degree of 99% manufactured by Kuraray Co., Ltd. was obtained by a T-die melt extrusion lamination method. A 2 μm EVOH film 14 was laminated onto the adhesive-2 layer.

On the other hand, the composition shown below is formed on the fine uneven surface side of a polyethylene terephthalate mat (trade name: Lumirror # 50-X44) made of Toray with a fine unevenness on the surface and having a glossiness of 55% as the fine unevenness forming cover film 15. The EVOH solution was applied at 10 g / m ^2, dried at 120 ° C. for 3 minutes to form the EVOH resin layer 14, and the adhesive used above was applied at 10 g / m ^{2 on} the outermost layer of the EVOH resin layer 14. Drying at 80 ° C. for 5 minutes forms an adhesive-2 layer 13, and a fine unevenness forming multilayer film 16 having a laminated structure of fine unevenness cover film 15 / EVOH resin layer 14 / adhesive-2 layer 13 is obtained. It was.

  Then, the cured resin layer on the side opposite to the side on which the thermoplastic resin layer 9 of the laminated sheet 10 is laminated is brought into contact with the adhesive 2 layer 13 side of the fine unevenness-formed multilayer film 16 and heat laminated at 130 ° C. 4 to obtain an EVOH resin layer laminate having the form shown in FIG. 4, and then removing the outermost fine unevenness forming cover film 15 to obtain the daylighting incombustible sheet of Example 1 having the form shown in FIG. 5. It was.

  As shown in Table 1, the daylighting incombustible sheet of Example 1 has high-frequency welder properties with improved antifouling properties and surface tackiness, and is excellent in daylighting and incombustibility.

Example 2
In Example 1, instead of heat laminating the EVOH film 14 at 130 ° C., an EVOH solution having the composition shown below was applied at 10 g / m ² and then dried at 120 ° C. . The evaluation results are shown in Table 1, and show good performance as described above.

As a composition of the EVOH solution used above,
EVOH resin (Kuraray E105, ethylene content 44 mol%) 5% by mass
n-propanol 52% by mass
33% by weight of water
N-methylpyrrolidone 5% by mass
Fine particles (SIRW 15W% -H06, average particle size 0.3μm) 5% by mass
Then, after adding and stirring the fine particle dispersion of the above composition into a mixed solvent composed of n-propanol, water and N-methylpyrrolidone of the above composition, the EVOH resin of the above composition was added, and the mixture was heated and stirred in a 75 ° C. hot water bath. A fresh EVOH solution was prepared. The ratio of the particles of 5 μm or more in the EVOH solution constituting the EVOH resin layer 14 was less than 0.1% by mass.

Example 3
In Example 1, in producing a laminate, instead of laminating the cover film 11 on the uncured curable resin 4 impregnated with the glass fiber fabric 3, a laminated film 12 was laminated (ie, Except that the laminated film 12 was laminated on both sides of the curable resin 4 in an uncured state), the same daylighting incombustible sheet of Example 3 was obtained. The evaluation results are shown in Table 1, and show good performance as described above.

Example 4
In Example 1, in producing the laminate, instead of laminating the laminated film 12, the cover film 11 was laminated (that is, the cover film 11 was laminated on both sides of the uncured curable resin 4). Otherwise, the same procedure as in Example 1 was performed to obtain a daylighting incombustible sheet of Example 4. The evaluation results are shown in Table 1, and show good performance as described above.

Example 5
In Example 3, in preparing the laminate, the curable resin 4 was made of 100 parts by mass of epoxy acrylate resin (NEOPOL 8126) manufactured by Nippon Iupika Co., Ltd., 20 parts of styrene monomer, and 1 part by mass of photosensitized catalyst. A lighting incombustible sheet of Example 5 was obtained in the same manner as in Example 3 except that it was changed to a curable resin and was cured with an ultraviolet irradiator for curing the curable resin 4 in an uncured state. The evaluation results are shown in Table 1, and show good performance as described above.

Comparative Example 1
When the laminated sheet of Example 1 was used as a lighting incombustible sheet, as shown in Table 1, the antifouling property, surface tackiness, and welder weldability were poor. There are also problems in terms of workability and handling.

Comparative Example 2
On both surfaces of the laminated sheet used in Example 1, 40 g% by weight of SQ100 manufactured by Tokiki, 10% by weight of the curing agent UXA615, and 4 g / m of a silicone coating agent prepared by adjusting the dilution solvent methyl ethyl ketone at a ratio of 50% by weight. after ² applied to obtain a sheet of Comparative example 2 was dried at 120 ° C.. The evaluation results are shown in Table 1. Although it looks good at first glance, such as antifouling property, the coating layer detachment by an organic solvent such as methyl ethyl ketone and welder weldability are poor, and there is a problem in the performance as a daylighting incombustible sheet. Including.

Comparative Example 3
A sheet of Comparative Example 3 was obtained in the same manner as in Example 2 except that the fine particles used in the EVOH solution were changed to Gantz Pearl GM-0401S (average particle size, 4 μm) manufactured by Gantz Chemical. . The evaluation results are shown in Table 1. The antifouling property, surface tackiness, and welder weldability are good, but the daylighting property (total light transmittance) and transparency (haze degree) are poor, and it is used as a daylighting incombustible sheet. Includes performance issues.

Comparative Example 4
In Example 1, EVOH resin and maleic anhydride-modified polyethylene resin were melt-mixed at a mass ratio of 70:30 instead of EVOH resin melt-formed film, and a 3 μm film was laminated by melt extrusion laminating method. Except having carried out, it carried out similarly to Example 1 and the sheet | seat of the comparative example 5 was obtained. The evaluation results are shown in Table 1. The antifouling property, surface tackiness, and welder weldability are good, but the transparency (haze degree) is poor, and the performance as a daylighting incombustible sheet is problematic.

1. Glass fiber (warp)
2. Glass fiber (weft)
3. 3. Glass fiber fabric 4. Curable resin Hardened resin layer8. Adhesive-1 layer9. Thermoplastic resin layer 10. Laminated sheet 11. Cover film13. Adhesive-2 layer14. EVOH resin layer 15. 15. Micro uneven forming cover film Slightly uneven multilayer film

The lighting non-combustible sheet of the present invention can be suitably used as a space partition, a smoke-proof hanging wall, and a smoke-proof screen, and is installed in an office space, a specific space partition in a manufacturing plant, for example, an automobile assembly line. It is effective in preventing injury and injury of workers and visitors walking along the passage due to welding spatter from the robot and malfunction of the assembly robot.
Further, the smoke shielding screen comprising the daylighting non-combustible sheet of the present invention can be stored in a rolled state, for example, in the upper part outside the door of the elevator, and the smoke shielding screen can be used in an emergency such as a fire. It is possible to prevent or reduce the intrusion of smoke into the elevator.

Claims (3)

A glass fiber fabric is embedded in the cured resin layer, and an ethylene-vinyl alcohol copolymer resin layer is disposed on at least one surface of the cured resin layer via a layer other than the ethylene-vinyl alcohol copolymer resin layer or A daylighting incombustible sheet which is laminated without being interposed and satisfies the following (a) to (f).
(A): Mass ratio of the glass fiber constituting the glass fiber fabric to the cured resin constituting the cured resin layer is 20:80 to 70:30.
(B): The proportion of the ethylene-vinyl alcohol copolymer resin in the ethylene-vinyl alcohol copolymer resin layer is 75% by mass or more. (C): of the outer surface layer of the ethylene-vinyl alcohol copolymer resin layer according to JIS K 7125 Dynamic friction coefficient is 2 or less (d): Total light transmittance is 75% or more (e): Haze degree is 30% or less (f): High frequency welder welding strength is 4 kg / 30 mm width or more   The ethylene-vinyl alcohol copolymer resin layer is composed of an ethylene-vinyl alcohol copolymer resin and fine particles having an average particle diameter of 2 μm or less, and the fine particles are 0.1% with respect to 100 parts by mass of the ethylene-vinyl alcohol copolymer resin. The daylighting incombustible sheet according to claim 1, which is contained in an amount of ˜12 parts by mass.   The daylighting incombustible sheet according to claim 1 or 2, wherein the outer surface of the ethylene-vinyl alcohol copolymer resin layer has fine irregularities.

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