JP6248266B2 - Light diffusive membrane material - Google Patents

Description

  The present invention includes a hotel, an event hall, a commercial facility, a play facility, a public facility, a station / airport facility, a ceiling lighting such as an underground shopping street, a wall lighting, a ceiling lighting such as an elevator car, a shade material for a lighting fixture, a cover material, In addition, it is a light diffusive and water-resistant film material used in various light source covers such as projection screens for projector projections, especially for LED light source covers, and has excellent dust dirt removal properties. Film material with non-combustible properties that conforms to the revised Building Standards Act burning test (cone calorimeter test method stipulated in ASTM-E1354), and Iron Transport No. 81, MLIT Decree No. 151 and JNR No. 157 And a film material for a light source cover used for in-vehicle illumination of a railway vehicle that meets non-combustibility standards based on JNR No. 124 and JNR No. 125.

  The present applicant has recently used a glass fabric as a base material, and light containing a specific amount of crushed glass powder having an aspect ratio of 1 to 1.25 and a length of 1 to 20 μm as irregular and irregularly reflecting particles on one side of the base material. A non-combustible film material for a light source cover and an optical ceiling provided with a diffusible resin coating layer (Patent Document 1) has been proposed. This film material is a film material that, when exposed to a light source, alleviates the drawbacks of woven yarn streaks, woven texture shadows and uneven shading, and produces a beautiful luminous appearance. By containing, the light-diffusion effect is largely obtained. However, on the other hand, the feel of the membrane surface is as rough as that of sandpaper, and dust or oily soot (a mixture of carbon soot derived from combustion exhaust gas, etc., sand dust / dust) is carried in the rough recess. However, the film material has a drawback that the appearance of the film material is gradually thin and difficult to remove. In particular, in the wiper wiping operation using a detergent such as synthetic detergent and alcohol or thinner, the dirt on the convex part of the film material is removed, but the dust or oily dust that has entered the concave part is pushed deeper into the concave part. This could result in random wiping traces and an unsightly appearance.

  It is a transparent incombustible material used for indoor / outdoor building materials, lighting equipment members, lighting signboards, and protective covers for solar cells, display elements, etc., lightweight, hard to break, impact resistant, and exposed to heat. A composite multilayer molded article (Patent Document 2) is disclosed in which no harmful gas is generated even if it is subjected to glass fiber reinforced plastic as a base material and a clay film laminated on the upper and lower surfaces thereof. However, the clay film, which is a constituent element of this transparent incombustible material, is a clay containing a water-soluble resin as an additive, so it is inferior in water resistance, and when it gets wet, it causes rapid volume expansion with water. As a result of generating extreme displacement energy at the interface with the fiber reinforced plastic substrate, the volume-expanded clay film is peeled off from the glass fiber reinforced plastic substrate. Therefore, the transparent incombustible material of Patent Document 2 is extremely difficult to use outdoors. According to the example of Patent Document 2, it is known that synthetic smectite is used as clay and sodium polyacrylate is used as an additive, and synthetic smectite has a property of swelling with water. In addition, since sodium polyacrylate is widely used as a water-absorbing resin in paper diapers, it is clear that a clay film obtained by mixing both of them also rapidly expands with water. For the same reason, when the transparent incombustible material of Patent Document 2 is soiled by the adhesion of dust or oily dust, the dirt and oily dust are adsorbed and permeated into the clay film swollen with moisture by removing the dirt. On the other hand, there is a concern that the clay film that has become difficult to swell and is easily swelled and embrittled by rubbing with a wiper may fall off from the glass fiber reinforced plastic substrate.

  Therefore, hotels, event halls, commercial facilities, amusement facilities, public facilities, station / airport facilities, ceiling lights such as underground street passages, ceiling lights such as elevator cars, shade materials for lighting fixtures, cover materials, and projectors Various light source covers such as projection screens, especially light diffusion transparent and water-resistant film materials used for LED light source covers, and film materials with excellent dust dirt removal properties do not yet exist It was. Furthermore, nonflammable film materials for various light source covers that conform to the Building Standard Act Combustion Test (Cone Calorimeter Test Method stipulated in ASTM-E1354) that was revised and implemented in 2000, and Iron Transport 81st, diplomatic relations There has been a demand for a non-combustible film material for a light source cover used for interior lighting of a railway vehicle that meets the non-combustible standards based on Ministerial Ordinance No. 151, JNR No. 157, JNR No. 124, and JNR No. 125. .

JP 2013-140245 A JP 2012-016875 A

  The present invention includes a hotel, an event hall, a commercial facility, a play facility, a public facility, a station / airport facility, a ceiling lighting such as an underground shopping street, a wall lighting, a ceiling lighting such as an elevator car, a shade material for a lighting fixture, a cover material, It is a light diffusive and water-resistant film material that is used for various light source covers, especially LED light source covers such as projection screens for projector projections, etc. Film materials having non-flammable properties that conform to the fire test of the Building Standard Act (cone calorimeter test method stipulated in ASTM-E1354), Iron Transport No. 81, MLIT Decree 151 and JNR 157, And a film material for a light source cover used for interior lighting of a railway vehicle that meets the non-combustibility standards based on JNR No. 124 and JNR No. 125 It is.

  As a result of repeated investigations to solve the above-mentioned problems, the present invention has a fiber fabric as a base fabric, an anchor layer formed of the synthetic resin composition (I) on one or more sides of the base fabric, and an anchor layer on the anchor layer. In the water-resistant laminate sheet having the fire-resistant layer formed, the fire-resistant layer contains a specific amount of the inorganic layered compound particles with respect to the fire-resistant layer, and the silane coupling agent is added to the total amount of the inorganic layered compound particles. By forming the synthetic resin composition (II) contained in a specific amount, particularly by making the constituent mass ratio of the anchor layer and the refractory layer a specific ratio, and further providing an antistatic incombustible layer on the refractory layer, The obtained sheet is excellent in water resistance and antifouling effect, and conforms to the building standard law combustion test (cone calorimeter test method stipulated in ASTM-E1354), which was revised in 2000, and Luck No. 81, diplomatic Ordinance No. 151 and JNR Technical No. 157, and railway Technical No. 124, and completed the present invention have found that to meet incombustible criteria based on JNR Technical No. 125.

  The light diffusive permeable membrane material of the present invention comprises a fiber fabric as a base fabric, an anchor layer formed of a synthetic resin composition (I) on one or more sides of the base fabric, and a fireproof material formed on the anchor layer. A light-resistant laminate sheet having a total light transmittance (JIS K7375) of 35 to 60% having a layer, wherein the fire-resistant layer contains 10 to 40% by mass of inorganic layered compound particles with respect to the fire-resistant layer, And it is preferable to form with the synthetic resin composition (II) which contains 1-20 mass% of silane coupling agents with respect to the total amount of this inorganic layered compound particle. This facilitates removal of adhering dust and dirt, is excellent in water resistance, and enables non-flammability characteristics that comply with ASTM-E1354 combustion tests and non-combustibility standards of National Railways, especially with silane coupling agent reactants. Synthetic resin composition (II), that is, anchoring and stabilizing inorganic layered compound particles in the anchor layer, can suppress excessive swelling of inorganic layered compound particles even when wet, and also prevent dropping To do.

  In the light diffusion / transmission film material of the present invention, it is preferable that the constituent mass ratio between the anchor layer and the refractory layer is 2: 1 to 1: 3. The film material of the present invention thus obtained is made flexible, and it is possible to realize non-flammability characteristics conforming to the ASTM-E1354 combustion test and the non-combustibility standards of National Railways, and the film material can be bent or bent. By relaxing the strain on the refractory layer when it is deformed, it becomes possible to suppress cracking of the refractory layer.

  In the light diffusive permeable membrane material of the present invention, the inorganic layered compound particles are preferably at least one selected from smectite clay mineral, synthetic smectite, sericite, and fluorine mica. By using such inorganic layered compound particles, the anchor layer is colorless or white, and at the same time exhibits light diffusibility, and further subjected to ASTM-E1354 combustion test and JNR non-combustion test. The layers of these inorganic layered compound particles are thermally peeled, the entire particle expands in volume, and the inorganic layered compounds mutually melt and fuse together to form a glassy flammable gas barrier layer. It is possible to develop non-flammable properties.

  The light diffusive permeable membrane material of the present invention is further provided with a non-combustible layer on the surface of the refractory layer, and the non-combustible layer is one or more selected from smectite clay mineral, synthetic smectite, sericite, and fluoric mica. The inorganic layered compound particles are preferably contained in an amount of 65 to 95% by mass with respect to the incombustible layer, and the silane coupling agent is preferably contained in an amount of 1 to 20% by mass with respect to the total amount of the inorganic layered compound particles. This makes it easy to remove the attached dust and dirt, makes the incombustible layer colorless or white, and at the same time increases the light diffusion permeability, and also when subjected to ASTM-E1354 combustion test and JNR noncombustion test The layers of these inorganic layered compound particles are thermally peeled, the entire particle expands in volume, and the inorganic layered compounds mutually melt and fuse together to form a glassy combustible gas barrier layer at a high density. In particular, the synthetic resin composition (II), that is, the anchoring and stabilizing of the inorganic layered compound particles in the anchor layer can be achieved especially by using the reaction product of the silane coupling agent. Even if it gets wet, it is possible to suppress excessive swelling of the inorganic layered compound particles and to prevent dropping.

  In the light diffusive permeable membrane material of the present invention, the surface resistance value of the incombustible layer (measuring method: JIS K6911, measuring condition: humidity 30% RH-temperature 23 ° C.) is preferably less than 1.0E + 12Ω. By controlling the surface resistance value of the incombustible layer by adding a surfactant, antistatic agent, etc., the film material is prevented from naturally adhering to dust and dirt. By suppressing the static electricity generated by wiping off dirt as much as possible, it is possible to prevent the reattachment of dust.

  In the light diffusive permeable membrane material of the present invention, the fiber fabric is preferably formed of one or more fiber yarns selected from glass fiber, silica fiber, alumina fiber, and ceramic fiber. This makes it possible to realize the combustion test of ASTM-E1354 and the non-flammability characteristics that meet the non-combustibility standards of JNR.

  In the light diffusive permeable membrane material of the present invention, the fiber fabric is preferably treated with one or more layered silicate compounds selected from montmorillonite, synthetic smectite, and fluorine mica. As a result, when subjected to the ASTM-E1354 combustion test and the JNR noncombustion test, the layers of these layered silicate compounds were thermally peeled, and the entire layered silicate compound expanded in volume, and each layered silica was expanded. By forming a glassy flammable gas barrier layer at high density by heat-melt fusion between acid salt compounds, filling the gaps in the fabric and suppressing leakage of combustion gas from the gaps in the fabric It is possible to develop non-flammable properties.

The light diffusive permeable membrane material of the present invention has a total calorific value of 20 minutes after the start of heating in the cone calorimeter test method stipulated in ASTM-E1354, which uses a radiant electric heater to radiate 50 kW / m ² of radiant heat. It is preferably 8 MJ / m ² or less, and has a nonflammable characteristic 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 . By conforming to the ASTM-E1354 test method, it conforms to the fire test of the Building Standards Act, which was revised and enforced in 2000, thereby ceiling lighting and wall lighting in public facilities and office buildings, as well as railway vehicles and elevators. It can be used in places where there are many users, such as ceiling lights such as baskets, and the reliability of fire and disaster prevention measures can be further increased.

  The light diffusive and permeable membrane material of the present invention has light diffusive and water resistance, is excellent in removing dust and dirt, and is in compliance with the Building Standards Act combustion test (according to ASTM-E 1354), which was revised in 2000. Film materials with non-flammable properties that conform to the prescribed corn calorimeter test method) can be obtained, so ceiling lighting and walls in hotels, event halls, commercial facilities, amusement facilities, public facilities, station / airport facilities, underground street passages, etc. Large light source cover used in places with many users such as lighting and ceiling lights such as elevator cars, etc. Especially for use as a cover for LED light sources, and also for LED lighting equipment shade materials, cover materials, projector projection In these applications, the reliability of fire countermeasures and disaster prevention measures can be further increased. It also has non-combustibility standards based on Iron Transport No. 81, MLIT Decree 151 and JNR 157, JNR 124, and JNR 125. It can be used, and the reliability of fire countermeasures and disaster prevention measures can be increased.

The figure which shows typically an example of the cross section of the light-diffusion transparent film | membrane material of this invention The figure which shows typically an example of the cross section of the light-diffusion transparent film | membrane material of this invention

  The light diffusive permeable membrane material of the present invention comprises a fiber fabric as a base fabric, an anchor layer formed of a synthetic resin composition (I) on one or more sides of the base fabric, and a fireproof material formed on the anchor layer. A water-resistant laminate sheet having a total light transmittance (JIS K7375) of 35 to 60% having a layer, the fire-resistant layer containing 10 to 40% by mass of inorganic layered compound particles with respect to the fire-resistant layer, and It is formed of a synthetic resin composition (II) containing 1 to 20% by mass of a silane coupling agent with respect to the total amount of inorganic layered compound particles, and the constituent mass ratio of the anchor layer and the refractory layer is 2: 1 to 1. : 3, which makes it easy to remove adhering dust and dirt without using detergents or solvents, has excellent water resistance, and is non-combustible that conforms to the ASTM-E1354 combustion test and the JNR combustion test. Realize the characteristics It becomes so that. And the usage method of the light diffusive permeable membrane material of the present invention, when the anchor layer and the refractory layer are provided only on one side of the base fabric, attach the refractory layer side to the lighting fixture as the appearance side, When the anchor layer and the refractory layer are provided on both sides of the base fabric, the appearance side may be any side. At this time, the surface exposed as the light source cover may contain a substance (for example, a photocatalytic substance) that can assist in removing dust and dirt.

  The fabric containing inorganic fibers used for the base material of the light diffusive permeable membrane material of the present invention is formed from one or more fiber yarns selected from glass fibers, silica fibers, alumina fibers, and ceramic fibers. A woven fabric or a knitted fabric is preferably used. When the non-flammable property suitable for the burning test of ASTM-E1354 and the burning test of JNR is not required for the light diffusive permeable membrane material of the present invention, polyester (PET, PBT, PNT) fiber, nylon fiber, polypropylene General-purpose organic synthetic fibers such as fibers, high-density polyethylene fibers, and vinylon fibers can be used. Examples of the woven fabric include general-purpose woven fabrics such as plain weave, twill weave, satin weave, imitation weave, and the woven structure is particularly warp driven: 20 to 100 pieces / 1 inch, weft driven: 20 to 100 pieces / 1. Inch plain woven fabric is preferred. The plain woven fabric is not bulky and has less surface unevenness due to its woven structure.The more yarns for warp driving and weft driving, the more the fabric texture shadows when the membrane material is placed on a light source. An inconspicuous effect is obtained. In addition, the plain woven fabric maintains the balance in physical properties (Young's modulus / elongation) with respect to the mounting tension when it is used for the light source cover, so that the shape stability of the light source cover is excellent. When such a fabric has a woven density of 0 to 2.5% of void density formed between the entanglement of the warp and weft yarns, when the film material for the light source cover is covered with a light source, the shadow of the woven structure of the fabric is removed. The effect which does not stand out is acquired highly. The porosity is most preferably 0%, but a maximum of 2.5% is acceptable depending on the fineness of the fiber yarn used. If the porosity exceeds 2.5%, when the light source cover film material is placed on the light source, only the light transmittance of the void portion increases, thereby making the shadow of the woven texture of the fabric stand out and the appearance of the light source cover is increased. May be wrong. The porosity is an area occupancy ratio by the sum of a large number of fine voids formed between the interlaces of the warp and weft yarns contained in a specific area unit of the fabric (for example, a square of 1 inch width × 1 inch length). First, the area ratio occupied by the warp and weft yarns included in a specific area unit of the fabric may be obtained and obtained by subtracting this from 100% (%). In order to improve the adhesion between the fabric and the impregnated coating layer formed of the silicone elastomer composition, the entire fabric is subjected to a surface treatment with a known silane coupling agent by an impregnation treatment with a 1 to 5% by weight solution. Is preferred.

Glass fiber, silica fiber, alumina fiber, and ceramic fiber as inorganic fiber yarns constituting the fabric are melt-spun to a filament diameter of 3 to 13 μm, and 50 to 500 strands obtained by bundling are obtained 0 to 5 times. A flat yarn having a flat cross-sectional shape with a twist of 0 / in. Glass fibers using E glass (non-alkali glass), silica fibers containing 95% by mass or more of silica (SiO ₂ ) as a main component, and boron oxide (B ₂ O ₃ ) as a subcomponent of 2.5% What contains -5 mass% is mentioned. The alumina fiber is mainly composed of 65 to 75% by mass of alumina (Al ₂ O ₃ ) and 25 to 35% by mass of silica (SiO ₂ ), and boron oxide (B ₂ O ₃ ) as subcomponents. Containing 2.5 to 10% by mass. In the present invention, the ceramic fiber is specifically one or more selected from potassium titanate fiber, titania fiber, silica-titania fiber, boron nitride fiber, zirconia fiber, silazane-silicon nitride fiber, and alumina-boria-silica fiber. It is. By using a non-twisted multifilament flat yarn, the light transmission unevenness can be eliminated, and at the same time, the porosity of the fabric can be brought close to 0 due to the wide yarn width. Therefore, when the light source cover film material is placed on the light source, the fabric The effect which does not make the shadow of the woven structure of this stand out can be set higher. If the number of strands exceeds 5 turns / inch, light refraction interferes with the spiral wave formed by twisting the multifilament, so that the light transmission shadow of the twisted portion is conspicuous and the appearance of the light source cover may be deteriorated. Moreover, although the twisted yarn etc. which twisted these strands 2 or 3 by 1-5 times / inch can be used, etc., since these become a yarn diameter large, the thickness of a fabric becomes bulky, and unevenness | corrugation increases. Shading during light transmission may be noticeable. The fineness of the inorganic fiber yarn used for the light diffusive permeable membrane material of the present invention is preferably a multifilament yarn of 150 to 1800 dtex, particularly 300 to 1350 dtex.

The above fabric is subjected to a pretreatment with one or more layered minerals selected from montmorillonite, smectite, and fluorine mica, and the average particle size between the multifilament yarns constituting the fabric and between the yarns and the yarns. It is effective in the combustion test (cone calorimeter test method defined in ASTM-E1354) that the layered mineral particles of 0.1 to 30 μm are embedded. By this means, the layered mineral is thermally exfoliated during heating and expands in volume, filling the gaps in the fabric and melting the layered mineral to form a vitreous gas barrier layer, so that the combustion gas leaks from the gaps in the fabric. This prevents smoke diffusion effectively. As the fluorine mica, fluorine tetrasilicon mica having an average particle diameter of 1 to 20 μm obtained by organic exchange treatment of Na tetrasilicon mica can be used. Montmorillonite has (Al _2−y Mg _y ) Si ₄ O ₁₀ (OH) _2. (M ⁺ M _{1/2 2} ⁺ ) _y nH ₂ O formula and has an average particle diameter of 0.01 to 3 μm. A face-piece type hydrous layered silicate mineral can be used. (Y = 0.2-0.6, M = exchangeable cations Na, K, Ca, Mg, H, etc., n = amount of interlayer water) As a smectite, silica tetrahedral (tetracoordinate) layer and aluminum It has a structure in which octahedral (hexacoordinate) layers are alternately stacked, silica / aluminum having a mass ratio of 2: 1, and the average particle diameter of smectite is 0.01 to 3 μm. The treatment of the fabric with these layered minerals is preferably carried out by impregnating the fabric with a layered mineral aqueous solution dispersed in water and then drying, and the adhesion rate is preferably 3 to 12% by mass with respect to the mass of the fabric. . In order to improve the adhesion between the fabric and the layered mineral, the layered mineral aqueous solution preferably contains 1 to 10% by mass of a silane coupling agent or an organic titanate compound based on the layered mineral.

  The fiber fabric has an anchor layer formed of the synthetic resin composition (I) and a fireproof layer formed of the synthetic resin composition (II) on the anchor layer, and includes an anchor layer and a fireproof layer. The component mass ratio is 2: 1 to 1: 3. At this time, making the main components of the synthetic resins constituting the synthetic resin composition (I) and the synthetic resin composition (II) the same increases the adhesion at the interface between the anchor layer and the fireproof layer. From the viewpoint of enhancing the durability of the light diffusive and permeable membrane material of the present invention. These synthetic resins include vinyl chloride resin (containing plasticizer), vinyl chloride copolymer resin, polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, polypropylene resin and hydrogenated styrene copolymer resin. Blends, urethane resins, urethane elastomers, acrylic resins, acrylic elastomers, polyester elastomers, fluorine elastomers, silicone elastomers, etc., and crosslinked products of these thermoplastic resins and elastomers, and combinations thereof (blend or composite Layer structure). In particular, from the viewpoint of nonflammability, silicone elastomers, fluorine elastomers, vinyl chloride resins (containing a plasticizer) and the like are preferable. The anchor layer and the refractory layer have a thickness of 0.01 mm to 1.0 mm, preferably 0.05 mm to 0.5 mm, respectively, by a calendar method, a T-die extrusion method, a casting method, a dipping method, or a coating method. The constituent mass ratio of the layer and the refractory layer is 2: 1 to 1: 3. If the constituent mass ratio of the anchor layer to the refractory layer is rich in the anchor layer, the non-flammable characteristics of the obtained film material may be insufficient, and if the refractory layer is rich, the bending resistance of the obtained film material is poor. It may be sufficient to cause cracks in the refractory layer.

  In the present invention, the anchor layer and the refractory layer are prepared by a known synthetic method such as a dipping method, a knife coating method, a gravure transfer method, and the like in a liquid synthetic resin composition (I) and a liquid synthetic resin composition (II). Preferably, the coating film is formed by coating and drying. Further, the main component of each synthetic resin constituting the liquid synthetic resin composition (I) and the liquid synthetic resin composition (II) is preferably a silicone elastomer. As these silicone elastomers, addition reaction curable silicone elastomers, condensation reaction curable silicone elastomers, radical (peroxide crosslinking) reaction curable silicone elastomers can be used. Addition-curable silicone elastomers that can be cured are preferred. The addition reaction curable silicone elastomer is an elastomer formed by bonding functional groups in two types of organopolysiloxane by an addition reaction to form an elastomer, such as an aliphatic unsaturated group such as a vinyl group or a hexenyl group. And silicone elastomers composed of organopolysiloxanes, organohydrogenpolysiloxanes, and platinum group compound catalysts. Aliphatic unsaturated group-containing organopolysiloxanes include vinyl dimethylsiloxy group-blocked dimethylpolysiloxane at both ends, vinyldimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends, and vinylmethylphenylsiloxy group-blocked dimethylsiloxane at both ends. -A methylphenylsiloxane copolymer is mentioned. Examples of the organohydrogenpolysiloxane include trimethylsiloxy group-capped methylhydrogen polysiloxane at both ends, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrol at both ends. These include addition curable silicone elastomers that can be cured by heating. In the cured product, fillers such as silica and calcium carbonate, zinc borate, Inorganic flame retardants that can form a glassy combustion gas shielding layer during combustion, such as aluminum borate, zinc stannate, zinc hydroxystannate, cristobalite, inorganic pigments such as titanium oxide, and bluing for light source covers A small amount of an organic pigment (Cyanine Blue), may contain a fluorescent brightening agent.

  Condensation reaction-curable silicone elastomers are functionalized in two types of organopolysiloxanes, or functional groups in organopolysiloxanes and silicon compounds such as silica and silane, which are bonded by a condensation reaction and crosslinked to form an elastomer. . The condensation reaction curable silicone elastomer can be any of a dehydrogenation condensation type, a dehydration condensation type, a deacetic acid condensation type, a deoxime condensation type, a dealcoholization condensation type, a deamidation condensation type, a dehydroxylamine condensation type, or a deacetone condensation type. As an additional component, it may contain an expanding filler, a heat-resistant agent, a flame retardant, a pigment, an organic solvent, and the like. Examples of the dehydrogenative condensation reaction curable silicone elastomer include a composition comprising a condensation reaction catalyst such as a diorganopolysiloxane blocked with both ends silanol groups, an organohydrogenpolysiloxane, and a heavy metal salt of an organic acid. As both-end silanol-blocked diorganopolysiloxane, both-end silanol-blocked dimethylpolysiloxane, both-end silanol-blocked dimethylsiloxane / methylphenylsiloxane copolymer, both-end silanol-blocked methyl (3,3,3-trimethyl) Fluoropropyl) polysiloxane. This diorganopolysiloxane may be an alkoxylated part of the terminal silanol group. Examples of the organohydrogenpolysiloxane that acts as a crosslinking agent include dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, trimethylsiloxy group-capped methylhydrogenpolysiloxane, and methylhydrogencyclopolysiloxane. Is mentioned. As the condensation reaction catalyst, dibutyltin dilaurate, dibutyltin dioctate, tin laurate, lead octenoate, zinc octenoate and the like can be used. These dehydrogenative condensation reaction curable silicone elastomers need to be cured by heating, but dehydration condensation type, deacetic acid condensation type, deoxime condensation type, dealcohol condensation type, deamidation condensation type, dehydroxylamine condensation type, Deacetone condensation type silicone elastomer and the like can be cured by moisture to make an elastomer. The silicone elastomer used in the present invention may be one obtained by removing water from a composition containing colloidal silica in an aqueous organopolysiloxane emulsion.

  Examples of the radical reaction curable silicone elastomer composition include a composition comprising an organopolysiloxane, a reinforcing filler, and an organic peroxide. As organopolysiloxane, both ends are blocked with trimethylsiloxy group, dimethylvinylsiloxy group, methylphenylvinylsiloxy group or silanol group, and the main chain is dimethylpolysiloxane, dimethylsiloxane / methylphenylsiloxane copolymer, dimethylsiloxane / Examples include methyl vinyl siloxane copolymer. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, and di-t-butyl peroxide. This radical reaction curable silicone elastomer composition can be cured by heating. Other radical reaction curable silicone elastomer compositions that include organopolysiloxane raw rubber as the main ingredient, compositions that are cured by irradiation with β-rays or γ-rays, and silicon-bonded alkenyl group-containing organopolysiloxanes and sensitizers, ultraviolet rays A composition that cures upon irradiation may be mentioned.

  The fireproof layer formed as described above contains 10 to 40% by weight, preferably 12.5 to 30% by weight, of the inorganic layered compound particles with respect to the fireproof layer. Such a fireproof layer is composed of the synthetic resin composition (II). Formed by. If the content is less than 10% by mass, the fire resistance may be insufficient, and if it exceeds 40% by mass, the flexibility of the refractory layer is inferior and cracks may occur when the film material is bent. As the inorganic layered compound particles, it is preferable to use one or more selected from smectite clay minerals, synthetic smectites, sericites, and fluorine mica because the appearance color of the obtained film material does not become cloudy. In particular, the smectite clay mineral preferably has an average particle size of 1 to 30 μm, and the synthetic smectite preferably has an average particle size of 0.01 to 3 μm. The smectite clay mineral is 2: 1 type smectite, and a layer composed of silicon and oxygen (silica tetrahedral layer) sandwiches a layer composed of aluminum and oxygen (aluminum octahedral layer), “silica tetrahedral layer / The “aluminum octahedral layer / silica tetrahedral layer” structure layer is a unit, and the structure layers are stacked. Further, the aluminum octahedron layer is classified into two octahedron type and three octahedron type, and specific examples of the two octahedron type smectite include montmorillonite, beidellite, nontronite, etc., as specific examples of the trioctahedral type smectite, Examples include saponite, hectorite, soconite, and stevensite. In the present invention, the inorganic layered compound particles can also use clay minerals such as talc, pyrophyllite, vermiculite, kaolinite, dickite, halloysite, mica, chlorite, serpentine, etc., and can be used in combination with the above smectite. In some cases, the appearance color of the film material obtained by being accompanied by mineral-derived coloring becomes cloudy in light earth or greenish gray. Synthetic smectite is a film material in which silica tetrahedron (tetracoordinate) layers and aluminum octahedron (hexacoordinate) layers are alternately stacked, and the use of a mass ratio of silica / aluminum of 2: 1 is obtained. This is preferable because it does not make the appearance color of turbid. Sericite (sericite) is fine muscovite and has an average particle diameter of 1 to 20 μm. Further, the fluorine mica does not make the appearance color of the film material obtained by using fluorine tetrasilicon mica having an average particle diameter of 1 to 20 μm obtained by organic exchange treatment of Na tetrasilicon mica. Moreover, since the inorganic layered compound particles used in the present invention contain exchangeable cations such as sodium ions and calcium ions between the layers, other metal ions, cationic compounds, anionic compounds, Intercalation-type inorganic layered compound particles that have been modified by incorporating a reactive compound (silane coupling agent) etc. into a substitution reaction and can be used, especially those that are hydrophilic and those that are made oleophilic Is effective for improving the dispersibility of the coating composition for forming the anchor layer and controlling the rheology, and those substituted with halogen such as Cl, Br, and F are preferred from the viewpoint of improving the nonflammability. In particular, smectite clay minerals (montmorillonite and the like) are preferably those which are substituted and modified with quaternary phosphonium compounds or quaternary ammonium compounds such as dimethylstearylammonium chloride and benzyldimethylstearylammonium chloride between the layers.

The synthetic resin composition (II) forming the fireproof layer contains a silane coupling agent, and is preferably 1 to 20% by mass, particularly 3 to 10% by mass, based on the total amount of the inorganic layered compound particles. The silane coupling agent is a compound having two or more different reactive groups in the molecule represented by the general formula: XR-Si (Y) ₃ , for example, X = amino group, vinyl group, epoxy group, A chloro group, a mercapto group, etc. (R = alkyl chain), Y = methoxy group, ethoxy group, etc. Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycol. Sidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-amino Examples include propyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane. In the obtained light diffusive transparent film material of the present invention, the silane coupling agent contained in the refractory layer reacts with the surface of the inorganic layered compound particles and / or is intercalated between the layers so that the reaction components at the ends are integrated. At the same time, the reactive component at the other end reacts with a part of the molecular chain structure of the silicone elastomer, thereby improving the wear strength and flex resistance of the refractory layer. Therefore, the blended silane coupling agent does not remain in the structure as it is in the fireproof layer of the light diffusion / transmission film material of the present invention. Therefore, if the silane coupling agent is not included, but if it is less than 1% by mass with respect to the content of the inorganic layered compound particles, the refractory layer is brittle, the refractory layer is cracked by bending, and wear deterioration is accelerated. Sometimes.

  In the light diffusive transparent film material of the present invention, a non-combustible layer is further provided on the surface of the refractory layer, and the non-combustible layer is selected from smectite clay mineral, synthetic smectite, sericite, and fluorine mica. By including 65 to 95% by mass of the above inorganic layered compound particles with respect to the incombustible layer, higher incombustibility can be obtained. As these inorganic layered compound particles, those described in paragraph [0026] are used. The incombustible layer contains 5 to 35% by mass of a binder component as a component other than the inorganic layered compound particles. This binder component is at least one of a silicone elastomer, a fluorine elastomer, and a vinyl chloride resin (containing a plasticizer), and the silane coupling agent described in paragraph [0027] has the same effect as in paragraph [0027]. For the purpose, it is preferable to contain 1 to 20% by mass, particularly 3 to 10% by mass with respect to the total amount of the inorganic layered compound particles. The incombustible layer is preferably formed into a thin film having a thickness of 0.01 to 0.2 mm, particularly 0.05 to 0.1 mm by a known coating method such as a knife coating method or a gravure transfer method. Even in this incombustible layer, the compounded silane coupling agent does not remain in the structure at the time of compounding. If the film thickness of the incombustible layer exceeds 0.2 mm, it becomes easy to crack by bending.

  The incombustible layer may further contain a photocatalytic substance, and in particular, may contain a visible light responsive photocatalyst that exhibits activity by absorbing visible light having a wavelength of 400 nm to 800 nm. These include, for example, titanium oxide, titanium peroxide (peroxotitanic acid), zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, iron oxide, and their oxides such as silver, platinum, gold, copper, rhodium. , Palladium, ruthenium, iridium, and a substance doped with one or more of transition metal ions, and the content of the nonflammable layer is 1 to 15% by mass. As a result, a part of the dust dirt adhering to the organic substance is decomposed by the photocatalytic action, so that wiping and removing performance can be further improved, and an indoor deodorizing effect can be exhibited.

  Further, the incombustible layer can further contain an inorganic colloidal substance, whereby the surface resistance value (measurement method: JIS K6911, measurement condition: humidity 30% RH-temperature 23 ° C.) of the incombustible layer is less than 1.0E + 12Ω. It provides prevention and facilitates wiping and removing dust particles adhering to the film material. Examples of the inorganic colloidal material include silica (silicon oxide) sol, alumina (aluminum oxide) sol, zirconia (zirconium oxide) sol, ceria (cerium oxide) sol, tin oxide sol (phosphoric acid dope) having a primary particle diameter of 3 to 150 nm. The content of the composite oxide (zinc oxide-antimony pentoxide composite or tin oxide-antimony pentoxide composite) sol is 1 to 15% by mass with respect to the mass of the incombustible layer.

  Further, the non-combustible layer may further contain a surfactant, whereby the surface resistance value (measurement method: JIS K6911, measurement condition: humidity 30% RH-temperature 23 ° C.) of the non-combustible layer is less than 1.0E + 12Ω. It provides prevention and facilitates wiping and removing dust particles adhering to the film material. Surfactants include anionic surfactant (carboxylate, sulfate ester, sulfonate, phosphate ester salt), cationic surfactant (amine salt type, quaternary ammonium type), amphoteric surfactant ( Amino acid type, betaine type), nonionic surfactants (polyethylene glycol type, polyhydric alcohol type) and the like can be used, and the content is 1 to 5% by mass with respect to the mass of the incombustible layer. Further, as a polymer type antistatic agent, a copolymer containing a monomer A having at least one quaternary ammonium salt in the side chain as a copolymerization component, for example, polyvinylbenzyl type, poly (meth) acrylate type, styrene- ( It is particularly preferable to use a quaternary ammonium salt type polymer such as a (meth) acrylate copolymer type, a styrene-maleimide copolymer type, or a methacrylate-methacrylimide copolymer type, which has a mass ratio of 3 to the inorganic colloid material of paragraph [0030]. : 1 to 1: 3 combination is particularly preferred.

  The light diffusive permeable film material of the present invention is a sheet having a light diffusive transmittance with a total light transmittance (JIS K7375) of 35 to 60%, preferably 40 to 55%. When the total light transmittance is less than 35%, when used for a light source cover or an optical ceiling film, the illuminance with respect to the luminance of the light source becomes low and the illumination effect becomes inefficient. On the other hand, if the total light transmittance exceeds 60%, the appearance and outline of the light source may become apparent when used for a light source cover or an optical ceiling film, thereby deteriorating the appearance of the lighting device. When the light diffusive permeable membrane material of the present invention is used for a light source cover or an optical ceiling membrane, the effect is not inferior even if any surface of the membrane material is mounted facing the light source. In addition, by applying a hidden design such as letters, designs, patterns, photographs, etc., partially or entirely on the surface facing the light source as necessary, the hidden design permeates the membrane material when the light source is turned on. It is also possible to display a line lamp on the surface. The concealed design is preferably applied by printing with a light transmissive ink. However, a Japanese paper pattern light-diffusing and permeable film material can be obtained by lightly printing a Japanese paper pattern with a light semi-transmissive white ink. Can do.

  Specifically, the light diffusive membrane material is a base light housing embedded in a ceiling of a building or railway vehicle (for example, 1 to 6 LED long bar type fluorescent lamps mounted: instrument width 15 to 45 cm x instrument length 80 to 150 cm) ) The entire surface is a film material that covers the illumination light source and the film material at a distance of 3 to 20 cm, and the coating is not limited to plane mounting, but may be curved three-dimensional mounting. In addition, a flat support frame or a three-dimensional support frame having a semicircular arc shape or a polygonal cross section is provided at the end of the film material, and the support frame is a fitting member that can be freely attached to and detached from the LED fluorescent lamp housing. It is what has. Further, specifically, it is an optical ceiling film in which a large number of lighting housings are arranged in a ceiling-embedded type or a ceiling-mounted type, and these lighting housings are collectively covered with a film material. The membrane material is increased in size by joining the original film material with a width of 1 to 3 m by sewing or bonding, or incorporating the original film material with a width of 1 to 3 m into the support frame and mechanically joining the support frames to each other. The distance between the light source and the film material is 3 to 20 cm. The shape of the ceiling is not limited to a planar shape, and may be a curved shape. Further, the light diffusive and permeable membrane material of the present invention can also be used as a light source cover for an externally attached internal signboard attached to a building. Further, the light diffusive and permeable membrane material of the present invention can be used as a desktop or stand type LED lamp shade by giving an arbitrary three-dimensional design. The light source suitable for the light diffusive transparent film material of the present invention is an incandescent lamp, a halogen lamp, a long bar fluorescent tube, a circle fluorescent tube, a ball built-in fluorescent tube, a long bar LED fluorescent tube, a ball built-in LED fluorescent tube, There are no limitations on the types and forms of light sources such as a circle-type LED fluorescent tube, a light emitter in which a number of LEDs are arbitrarily arranged, and an organic EL element.

In the non-combustible property (cone calorimeter test: ASTM-E1354 or ISO 5660-1) in the Building Standard Law, when radiant heat from an electric heater is irradiated at 50 kW / m ² toward the test body, 20 minutes after the start of heating. The total calorific value is 8 MJ / m ² or less, and the combustion requirement is such that the maximum heat generation rate does not exceed 200 kW / m ² continuously for 10 minutes or more for 20 minutes after the start of heating. In addition, the interior materials for railway vehicles include non-combustibility based on iron transportation No. 81, MLIT Decree 151 and JNR 157, JNR 124, JNR 125, and alcohol as a combustion source. The combustion behavior of the test specimen is divided into five stages, and the highest rank is satisfied.

[Nonflammability evaluation]
A) Corn calorimeter test (ASTM-E1354)
A test film material having a vertical surface of about 100 mm and a thickness of up to 50 mm and a flat surface is used for 10 minutes at a radiant heat of 50 KW / m ² . In the test, it was confirmed that the difference between the average value of the maximum heat generation rates of the three test membrane materials and the maximum heat generation rate of each test membrane material was less than 10%. Adopt data of test membrane material. If 10% or more, further test three test film materials, and among these six test film materials, four test film materials excluding the maximum and minimum maximum heat generation rates Data. Combustion determination is performed based on the total calorific value (MJ / m ² ), maximum heat generation rate (KW / m ² ), and ignition time (seconds) measured during the test time. The ignition time (seconds) is the time from the start of the test until the first ignition is confirmed, assuming that a flame exists for 10 seconds or more after the flame is confirmed from the test piece.
(A) Total calorific value: 8 MJ / m ² or less conforms (b) Heat generation rate: Conforms not to exceed 200 kW / m ² continuously for 10 seconds or more (c) Appearance observation: Pinhole exceeding 0.5 mm in diameter Fits no dents
B) Material combustion test for railway vehicles: Iron fortune No. 81 (May 15, 1969)
B5 size test membrane material (182mm x 257mm) is held at a 45 ° inclination so that the center of the bottom of the fuel container is 25.4mm (1 inch) vertically below the center of the bottom surface of the test membrane material Next, place it on a base made of a material having low thermal conductivity such as cork, put 0.5 cc of pure ethyl alcohol, ignite, and leave it until the fuel is burned out. Combustion judgment is divided into alcohol combustion and after combustion. During combustion, the film material is observed for ignition, ignition, smoke generation, flame condition, etc. After combustion, afterflame and residual dust are observed. Investigate the state of carbonization and deformation, and perform a five-step evaluation of “non-flammability”, “extreme flame retardancy”, “flame retardance”, “slow burnability” and “flammability”.
* "Nonflammable" requirements During combustion: Ignition (none), Flame (none), Smoke (slight), Fire (-)
After combustion: Residual flame (-), residual dust (-), carbonization (change of 100mm or less
Color), deformation (surface deformation of 100mm or less), melt dripping (none)
[Dust removal evaluation]
A) The test film material is stretched and fixed for 1 month on an outdoor exposure table with an outdoor exposure inclination angle of 30 degrees, and dust particles adhering to the surface are wiped off with a wiping cloth (trade name: Savina: manufactured by KB Seiren) to remove dust particles. Sex was determined as follows. (Implemented in Soka City, Saitama Prefecture in December 2013)
1: Excellent removability (appearance of membrane material returned to initial level)
2: Even after repeated wiping, the dust and dirt remains slightly unchanged.
3: Even after repeated wiping, dust stains do not clear and the traces of wiping are unsightly.
4: The fireproof layer peels off and falls due to rain and cannot be evaluated
B) Dirt chamber diameter 20cm x height 25cm in a cylindrical sealed container with a sample film piece affixed to the inner wall, 1g of copier carbon toner and 50g of dry river sand, and the cylindrical sealed container lying sideways After rotating the cylindrical airtight container on a pair of rotating rolls (counterclockwise) at a rotation speed of 60 times / min for 10 minutes, the membrane material piece is taken out and dust dirt adhering to the surface is wiped off with a wiping cloth ( The product was wiped with a trade name Zavina (manufactured by KB Seiren Co., Ltd.), and dust removal was determined as follows.
1: Excellent removability (appearance of membrane material returned to initial level)
2: Even after repeated wiping, the dust and dirt remains slightly unchanged.
3: Even after repeated wiping, dust stains do not clear and the traces of wiping are unsightly.
[Evaluation of light source cover]
Using the membrane material prepared in the examples and comparative examples, the whole surface of the ceiling-embedded fluorescent lamp housing (equipped with two 36 watt 40 type white fluorescent tubes: instrument width 25 cm x instrument length 125 cm) is covered flat, The distance of the film material was 3 cm. Visually observe the light transmission appearance of the membrane material at a distance of 50 cm from the surface of the membrane material when the fluorescent lamp is lit. A). Visibility of fluorescent tube (light source), B). The light diffusivity was evaluated visually. The mounting of the membrane material on the housing was evaluated by mounting with the impregnated coating layer side exposed to the outside.
A) Hot spot visibility of fluorescent tube (light source)
1: It has sufficient illuminance and the presence of a fluorescent tube (light source) is not visible
2: Although it has sufficient illuminance, the position of the fluorescent tube (light source) can be visually recognized.
3: Although it has sufficient illuminance, the position of the fluorescent tube (light source) is clearly visible
4: Existence of fluorescent tube (light source) is not visible, but illuminance is insufficient
B) Light diffusivity
1: Sufficient illuminance and excellent light diffusibility
2: It has sufficient illuminance, but is slightly inferior in light diffusivity and slightly shaded
3: Although it has sufficient illuminance, it is inferior in light diffusibility and has shading.
4: Illuminance is insufficient
[Evaluation of water resistance]
Small pieces (5 cm × 5 cm) of the film material prepared in Examples and Comparative Examples were immersed in a petri dish filled with 100 ml of pure water at 20 ° C. for 60 minutes, and the surface of the film material was wetted immediately after pulling up the small piece. Observed.
1: Slightly swollen, but fireproof layer is held firmly
2: The fireproof layer swelled more than twice, and peeled off when touched with a finger
3: The refractory layer was peeled or dissolved, dropped off, and the anchor layer was exposed
[Evaluation of bent cracks in refractory layers]
A small piece (2 cm × 10 cm) of the film material prepared in the example and the comparative example is folded in two at a position of 5 cm (the refractory layer side is mountain-folded), and a weight of 500 g is placed on the folded portion at 20 ° C. After leaving still for 60 seconds, the fire-resistant layer was colored with red ink, and the image was observed with a digital magnifier (magnification 50 times) to determine the presence or absence of cracks.
1: No cracks are observed
2: Acknowledgment of cracks

[Example 1]
A flat yarn single yarn with a fineness of 67.5 tex consisting of 400 filaments of 9 μm diameter made of E glass is used as warp and weft, and the porosity is 0% due to a weaving density of 44 yarns / inch and a weft density of 33 yarns / inch. A glass plain weave fabric (mass 210 g / m ² ) as a base material (1), and a synthetic resin composition (I) for forming an anchor layer according to <Formulation 1> on one side of the base material (1) by a knife coating method The film was uniformly coated, and an anchor layer was provided at an adhesion amount of 32 g / m ² through a heat treatment curing process at 180 ° C. for 3 minutes in an electric furnace.
Next, on this anchor layer, the synthetic resin composition (II) for forming a refractory layer according to <Formulation 2> is uniformly applied by a knife coating method, and a heat treatment curing process at 180 ° C. for 3 minutes in an electric furnace is performed. Then, a fireproof layer was provided with an adhesion amount of 26 g / m ² . The constituent mass ratio of the anchor layer to the refractory layer was 2: 1.625, and the obtained film material had a thickness of 0.2 mm, a mass of 268 g / m ² , and a total light transmittance of 44.3%.
<Formulation 1> Synthetic resin composition (I)
Product Name: Shirasukon RTV4086A
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
50 parts by mass Product name: Shirasukon RTV4086B
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
50 parts by mass Product name: SRX212 CATALYST (manufactured by Toray Dow Corning) 1 part by mass Toluene (diluent) 100 parts by mass

<Formulation 2> Synthetic resin composition (II)
Product Name: Shirasukon RTV4086A
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
50 parts by mass Product name: Shirasukon RTV4086B
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
50 parts by mass Product name: SRX212 CATALYST (manufactured by Dow Corning Toray) 1 part by mass Product name: Nanofil 9: (Montmorillonite: average particle size 8 μm: manufactured by Sud Chemie Catalyst)
* Inorganic layered compound particles = smectite clay mineral = montmorillonite 20 parts by mass Product name: KBM903 (silane coupling agent: manufactured by Shin-Etsu Silicone) 2 parts by mass * γ-aminopropyltrimethoxysilane (active ingredient 100%)
100 parts by weight of toluene (diluent)

[Example 2]
Constituent mass of the anchor layer and the refractory layer in the same manner as in Example 1 except that <Formulation 2> as the synthetic resin composition (II) for forming the refractory layer in Example 1 was changed to <Composition 3> below. A film material having a ratio of 2: 1.625, a thickness of 0.2 mm, a mass of 268 g / m ² , and a total light transmittance of 48.5% was obtained.
<Formulation 3> Synthetic resin composition (II)
Product Name: Shirasukon RTV4086A
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
50 parts by mass Product name: Shirasukon RTV4086B
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
50 parts by mass product name: SRX212 CATALYST (manufactured by Dow Corning Toray) 1 part by mass product name: Lucentite SAN: lipophilic synthetic smectite: manufactured by Corp Chemical Co.)
* Inorganic layered compound particles = synthetic smectite 20 parts by mass Product name: KBM903 (silane coupling agent: manufactured by Shin-Etsu Silicone) 2 parts by mass * γ-aminopropyltrimethoxysilane (active ingredient 100%)
100 parts by weight of toluene (diluent)

[Example 3]
Constituent mass of the anchor layer and the refractory layer in the same manner as in Example 1 except that <Formulation 2> as the synthetic resin composition (II) for forming the refractory layer in Example 1 was changed to <Composition 4> below. A film material having a ratio of 2: 1.625, a thickness of 0.2 mm, a mass of 268 g / m ² , and a total light transmittance of 48.6% was obtained.
<Formulation 4> Synthetic resin composition (II)
Product Name: Shirasukon RTV4086A
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
50 parts by mass Product name: Shirasukon RTV4086B
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
50 parts by mass product name: SRX212 CATALYST (manufactured by Dow Corning Toray) 1 part by mass product name: Shimasov MTE: organically treated fluoromica: manufactured by Coop Chemical Co., Ltd.
* Inorganic layered compound particles = Fluorine mica: Average particle size 5 μm 20 parts by mass Product name: KBM903 (silane coupling agent: manufactured by Shin-Etsu Silicone) 2 parts by mass * γ-aminopropyltrimethoxysilane (active ingredient 100%)
100 parts by weight of toluene (diluent)

[Example 4]
Constituent mass of the anchor layer and the refractory layer in the same manner as in Example 1 except that <Formulation 2> as the synthetic resin composition (II) for forming the refractory layer in Example 1 was changed to <Composition 5> below. A film material having a ratio of 2: 1.625, a thickness of 0.2 mm, a mass of 268 g / m ² , and a total light transmittance of 47.7% was obtained.
<Formulation 5> Synthetic resin composition (II)
Product Name: Shirasukon RTV4086A
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
50 parts by mass Product name: Shirasukon RTV4086B
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
50 parts by mass product name: SRX212 CATALYST (manufactured by Toray Dow Corning) 1 part by mass product name: sericite powder: manufactured by Horie Chemical Co., Ltd.
* Inorganic layered compound particles = sericite (sericite): average particle size 5-8 μm 20 parts by mass Product name: KBM903 (silane coupling agent: manufactured by Shin-Etsu Silicone) 2 parts by mass * γ-aminopropyltrimethoxysilane (effective) 100% ingredient)
100 parts by weight of toluene (diluent)

[Example 5]
An incombustible layer according to the following <Composition 6> was formed on the entire surface of the fire-resistant layer of the film material of Example 1. The incombustible layer is formed by gravure transfer coating using an 80 mesh gravure roll, and is subjected to a heat treatment curing process at 180 ° C. for 1 minute in an electric furnace to form an anchor layer as an incombustible layer having an adhesion amount of 4 g / m ^2. And a refractory layer having a constituent mass ratio of 2: 1.625, a thickness of 0.21 mm, a mass of 272 g / m ² , and a total light transmittance of 41.7% were obtained.
<Formulation 6> Composition for forming a noncombustible layer Product name: Shirasukon RTV4086A
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
10 parts by mass Product name: Shirasukon RTV4086B
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
10 parts by mass Product name: SRX212 CATALYST (manufactured by Toray Dow Corning) 0.2 parts by mass Product name: Nanofil 9: (Montmorillonite: average particle size 8 μm: manufactured by Sued Chemie Catalysts)
* Inorganic layered compound particles = smectite clay mineral = montmorillonite 50 parts by mass Product name: KBM903 (silane coupling agent: manufactured by Shin-Etsu Silicone) 5 parts by mass * γ-aminopropyltrimethoxysilane (active ingredient 100%)
Product name: Celnax CX-S401M (Antistatic agent: manufactured by Nissan Chemical Industries)
* Phosphate doped tin oxide sol with 40% active ingredient and average particle size of 5 to 20 nm 6 parts by weight Copper oxide doped tungsten oxide (visible light responsive photocatalyst) fine particles 1 part by weight Toluene (diluent) 100 parts by weight

[Example 6]
An incombustible layer according to the following <Composition 7> was formed on the entire surface of the fire-resistant layer of the film material of Example 2. The incombustible layer is formed by gravure transfer coating using an 80 mesh gravure roll, and is subjected to a heat treatment curing process at 180 ° C. for 1 minute in an electric furnace to form an anchor layer as an incombustible layer having an adhesion amount of 4 g / m ^2. And a refractory layer having a composition mass ratio of 2: 1.625, a thickness of 0.21 mm, a mass of 272 g / m ² , and a total light transmittance of 47.3% were obtained.
<Formulation 7> Composition for forming noncombustible layer Product name: Shirasukon RTV4086A
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
10 parts by mass Product name: Shirasukon RTV4086B
(Two-component addition reaction curable silicone resin: 100% active ingredient: Toray Dow Corning)
10 parts by mass Product name: SRX212 CATALYST (manufactured by Dow Corning Toray) 0.2 parts by mass Product name: Lucentite SAN: (lipophilic synthetic smectite: manufactured by Corp Chemical)
* Inorganic layered compound particle = synthetic smectite 50 parts by mass Product name: KBM903 (silane coupling agent: manufactured by Shin-Etsu Silicone) 5 parts by mass * γ-aminopropyltrimethoxysilane (active ingredient 100%)
Product name: Celnax CX-S401M (Antistatic agent: manufactured by Nissan Chemical Industries)
* Phosphate doped tin oxide sol with 40% active ingredient and average particle size of 5 to 20 nm 6 parts by weight Copper oxide doped tungsten oxide (visible light responsive photocatalyst) fine particles 1 part by weight Toluene (diluent) 100 parts by weight

[Example 7]
An incombustible layer according to <Formulation 6> used in Example 5 was formed on the entire surface of the refractory layer of the film material of Example 3. The incombustible layer was formed in the same manner as in Example 5. An incombustible layer having an adhesion amount of 4 g / m ² was provided, the constituent mass ratio of the anchor layer to the refractory layer was 2: 1.625, and the thickness was 0.21 mm. A film material having a mass of 272 g / m ² and a total light transmittance of 45.3% was obtained.

[Example 8]
An incombustible layer according to <Formulation 7> used in Example 6 was formed on the entire surface of the fireproof layer of the film material of Example 4. The incombustible layer was formed in the same manner as in Example 6. An incombustible layer with an adhesion amount of 4 g / m ² was provided, the constituent mass ratio of the anchor layer to the refractory layer was 2: 1.625, and the thickness was 0.21 mm. A film material having a mass of 272 g / m ² and a total light transmittance of 46.5% was obtained.

[Examples 9 to 16]
Except having changed the base material (1) used for Examples 1-8 into the following base material (2), it was the same as that of Examples 1-8, and obtained the film material of Examples 9-16, respectively. Example 1 corresponds to Example 9, Example 2 corresponds to Example 10, Example 3 corresponds to Example 11, and so on.
Base material (2)
The base yarn (1) is a flat yarn single yarn having a fineness of 67.5 tex, in which 400 filaments of 9 μm diameter made of E glass are bundled, and is used as warp and weft. The warp drive density is 44 yarns / inch and the weft drive density is 33 yarns / inch. A glass plain woven fabric (mass 210 g / m ² ) having a porosity of 0% with a woven structure of the above is immersed in a layered mineral-containing pretreatment liquid bath of <Formulation 8> below, and simultaneously with this, the rubber mangle is pressed to a pickup rate of 40% by mass. Then, it was dried in a hot air oven at 180 ° C. for 2 minutes to obtain a layered mineral-treated glass fiber fabric having a mass of 214 g / m ² and used as the substrate (2).
<Formulation 8: Layered mineral-containing pretreatment solution>
Product name: Nanofil9 (montmorillonite: manufactured by Zude Chemie Catalysts Co., Ltd.) 25 parts by mass * Layered mineral with an average particle size of 8 μm and dispersed particle size of 100-500 nm Product name: KBM403 (manufactured by Shin-Etsu Silicone) 3 parts by mass * γ-glycidoxypropyl Triethoxysilane: 100% active ingredient
72 parts by weight of dilution water

  The film materials of Examples 1 to 16 have sufficient illuminance when used for ceiling lighting, wall lighting, ceiling lighting such as railcars and elevator cars, shade materials for lighting fixtures, cover materials, and projection screens for projector projection. It has excellent light diffusibility, and the presence (hot spot) of fluorescent tubes (especially LED light sources) is not visually recognized. These film materials are used as cone calorimeter tests. (ASTM-E1354) conforms to the incombustibility or conforms to the incombustibility of railway vehicle material combustion test (Tetsunyu 81), especially ceiling lighting and wall lighting in public facilities and office buildings It was the most suitable as a light source cover for use in railway vehicle ceiling lighting. In particular, since the film materials of Examples 5 to 8 are obtained by further adding a non-combustible layer to the surface of the film materials of Examples 1 to 4, the results of conformity of the above non-flammability test to those of the film materials of Examples 1 to 4 are improved. It was excellent in numerical value. In addition, the film materials of Examples 9 to 16 were obtained by treating glass fiber fabrics with a layered silicate compound, so that they were superior in the numerical values of the conformity results of the above nonflammability test than the film materials of Examples 1 to 8. Furthermore, the film materials of Examples 13 to 16 were superior to the film materials of Examples 9 to 12 in the numerical values of the conformity results of the nonflammability test. In other words, the order of increasing incombustibility was generally in the relationship of Examples 13 to 16 group> Examples 5 to 12 group> Examples 1 to 4 group. In addition, the film materials of Examples 1 to 16 were excellent in the removal of dust dirt, but in particular, the film materials of Examples 5 to 8 and Examples 13 to 16 were phosphate-doped tin oxide sols in the incombustible layer. In addition, the antistatic effect on the surface of the film material is excellent, and the antistatic effect of 1.0E + 9Ω to 10Ω is obtained. The removability of dust dirt was superior to the film materials of Examples 9-12. At the same time, oil-based dust dirt (volatile cooking oil and tobacco spear) caused by copper oxide-doped tungsten oxide (visible light responsive photocatalyst) contained in the incombustible layers of the film materials of Examples 5 to 8 and Examples 13 to 16 It is considered that the removal effect of dust dirt was more excellent due to the action of the decomposition effect. It is also effective in reducing the odor concentration of odors (body odor, animal odor, food odor, tobacco odor, chemical odor, etc.) that come into contact with the lighting cover (or optical ceiling film material) by the photocatalytic action of copper oxide doped tungsten oxide. It was. In comparison with the film materials of Examples 1 to 4 and Examples 9 to 12 that do not contain copper oxide-doped tungsten oxide, the time until the odor concentration attenuates to 1/2 is reduced to Examples 1 to 4 and Example 9. The time required for the film materials of Examples 5 to 8 and Examples 13 to 16 was about 22 minutes with respect to the film material of ˜12 for about 34 minutes.

[Comparative Example 1]
In Example 1, the thickness was 0.2 mm and the mass was 248 g, except that 20 parts by mass of the inorganic layered compound particles (Nanofil 9: average particle diameter 8 μm) included in the fireproof layer <Formulation 2> was omitted. / M ² , a flame retardant film material having a total light transmittance of 68.2% was obtained. Since the film material obtained in Comparative Example 1 did not contain inorganic layered compound particles in the refractory layer, it was inferior in the removability of dust adhering dirt. Further, when used for a light source cover, the light diffusibility is inferior and the appearance of the light source position (hot spot) is unclear.

[Comparative Example 2]
In Example 1, except that 20 parts by mass of inorganic layered compound particles (Nanofil 9: average particle size 8 μm) included in the fireproof layer <Formulation 2> were changed to 20 parts by mass of magnesium hydroxide particles (flame retardant). In the same manner as in Example ¹ , an extremely flame retardant film material having a thickness of 0.2 mm, a mass of 268 g / m ² , and a total light transmittance of 46.3% was obtained. The film material obtained in Comparative Example 2 was inferior also in the removability of dust adhering dirt.

[Comparative Example 3]
Same as Example 1. However, in the same manner as in Example 1 except that 20 parts by mass of the inorganic layered compound particles (Nanofil 9: average particle diameter of 8 μm) included in the fireproof layer <Formulation 2> were changed to 5 parts by mass, the thickness was 0.2 mm and the mass A flame retardant film material having a light transmittance of 64.3% was obtained at 251 g / m ² . The film material obtained in Comparative Example 3 is inferior in dust removability due to the small amount of inorganic layered compound particles contained in the refractory layer, and inferior in light diffusibility when used in a light source cover, and in a light source position (hot spot). Appearance was unsightly as if it were exposed.

[Comparative Example 4]
Same as Example 1. However, in the same manner as in Example 1 except that 20 parts by mass of the inorganic layered compound particles (Nanofil 9: average particle diameter 8 μm) included in the fireproof layer <Formulation 2> were changed to 100 parts by mass, the thickness was 0.2 mm and the mass An incombustible film material having 285 g / m ² and a total light transmittance of 12.4% was obtained. The film material obtained in Comparative Example 4 is inferior in water resistance because the amount of inorganic layered compound particles contained in the refractory layer is too large, and the total light transmittance is too low to be used for a light source cover, making the illumination dim. Met.

[Comparative Example 5]
In Example 1, except that 2 parts by mass of the silane coupling agent (KBM903: γ-aminopropyltrimethoxysilane) contained in the fireproof layer <Formulation 2> was omitted, the thickness was 0.2 mm. , A mass of 268 g / m ² , and a non-combustible film material having a total light transmittance of 44.2%. Since the film material obtained in Comparative Example 5 does not contain a silane coupling agent in the refractory layer, the refractory layer is inferior in water resistance. When exposed to rain in an outdoor exposure test, the refractory layer swells and anchors. It peeled off from the layer and dropped off spontaneously. Further, when the dust stain was wiped with water, the dust stain was permeated and adsorbed in the swollen refractory layer.

[Comparative Example 6]
In Example 1, the thickness was changed in the same manner as in Example 1 except that the amount of silane coupling agent (KBM903: γ-aminopropyltrimethoxysilane) contained in the fireproof layer <Formulation 2> was changed to 20 parts by mass. A film material having a thickness of 0.2 mm, a mass of 261 g / m ² and a total light transmittance of 42.3% was obtained. Since the film material obtained in Comparative Example 6 contains an excess of the silane coupling agent in the refractory layer, the silane coupling agent component in an unreacted or hydrolyzed state bleeds on the surface of the obtained film material. The surface of the film material became wet soon after the start of use, so that dust dirt was violently adhered and it was difficult to wipe off. Moreover, since it contains an excessive amount of flammable silane coupling agent, it became incompatible with the non-flammability of the cone calorimeter test (ASTM-E1354), and the rail vehicle material combustion test (Tetsunyu No. 81) became flammable. .

  According to the present invention, it has light diffusibility and water resistance, is excellent in dust dirt removal performance, and is subjected to the amendment and enforcement of the Building Standard Act in 2000 (cone calorimeter specified in ASTM-E1354). Film materials with non-combustible properties that meet the test method) can be obtained. Ceiling lighting and wall lighting for hotels, event halls, commercial facilities, amusement facilities, public facilities, stations and airport facilities, underground passages, and elevators It can be used not only as a large light source cover used in places with many users such as ceiling lighting such as baskets, but it can also be used for lighting equipment shade materials, cover materials, projection screens for projector projection, etc. Can improve the reliability of fire and disaster prevention measures. It also has non-combustibility standards based on Iron Transport No. 81, MLIT Decree 151 and JNR 157, JNR 124, and JNR 125. It can be used, and the reliability of fire countermeasures and disaster prevention measures can be increased.

1: Light diffusive permeable membrane material 2: Fiber fabric (base fabric)
2-1: Layered silicate compound 3: Anchor layer: Synthetic resin composition (I)
4: Fireproof layer: Synthetic resin composition (II)
4-1: Inorganic layered compound particles 4-2: Silane coupling agent 5: Incombustible layer 5-1: Inorganic layered compound particles 5-2: Silane coupling agent 5-3: Antistatic agent 6: Light source (LED fluorescent tube) )

Claims (8)

  A total light transmittance (JIS K7375) having an anchor layer formed of a synthetic resin composition (I) on at least one surface of the base fabric and a fireproof layer formed on the anchor layer, using a fiber fabric as a base fabric. ) Is a water-resistant laminate sheet of 35 to 60%, wherein the refractory layer contains 10 to 40% by mass of the inorganic layered compound particles with respect to the refractory layer, and the total amount of the inorganic layered compound particles The light diffusive and permeable film material is formed of a synthetic resin composition (II) containing 1 to 20% by mass of a silane coupling agent.   2. The light diffusive permeable film material according to claim 1, wherein the constituent mass ratio of the anchor layer to the refractory layer is 2: 1 to 1: 3.   The light diffusive permeable membrane material according to claim 1 or 2, wherein the inorganic layered compound particles are at least one selected from smectite clay minerals, synthetic smectites, sericite, and fluorine mica.   A non-combustible layer is further provided on the surface of the refractory layer, and the non-combustible layer contains one or more inorganic layered compound particles selected from smectite clay mineral, synthetic smectite, sericite, and fluorine mica with respect to the non-combustible layer. The light-diffusing and permeable film material according to any one of claims 1 to 3, further comprising 65 to 95% by mass and 1 to 20% by mass of a silane coupling agent with respect to the total amount of the inorganic layered compound particles. .   5. The light diffusive permeable membrane material according to claim 4, wherein the non-combustible layer has a surface resistance value (measuring method: JIS K6911, measuring condition: humidity 30% RH-temperature 23 ° C.) of less than 1.0E + 12Ω.   The light diffusive permeable film according to any one of claims 1 to 5, wherein the fiber fabric is formed of one or more fiber yarns selected from glass fiber, silica fiber, alumina fiber, and ceramic fiber. Wood.   The light diffusive permeable membrane material according to claim 6, wherein the fiber fabric is treated with one or more layered silicate compounds selected from montmorillonite, synthetic smectite, and fluorine mica. In the cone calorimeter test method stipulated in ASTM-E1354, radiating heat of 50 kW / m ² using a radiant electric heater, the total calorific value for 20 minutes after starting heating is 8 MJ / m ² or less, and heating is started. The light diffusive permeable membrane material according to claim 6 or 7, which has non-flammability characteristics in which the maximum heat generation rate continues for 10 seconds or more for 20 minutes and does not exceed 200 kW / m ² .