JP5365501B2 - Non-flammable interior illuminated signboard - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film material for an internal illumination signboard that is a fiber composite film material having high light transmission and excessive light diffuseness and is made to fit for an in-combustibility test even in a using state where an overlay film for protecting a printing layer is stuck to the whole surface, and to provide an internal illumination signboard. <P>SOLUTION: An incombustible internal illumination signboard includes a sheet, in which a flame resisting resin coating layer is disposed on one surface or more of cloth obtained by arranging and knitting inorganic filament bundles without gap, and a printing layer is disposed on the surface of at least one upper layer of the flame resisting resin coating layer. The flame resisting resin coating layer has a sea-island structure by immiscible mixing of two or more kinds of synthetic resins. The island component has no flame retardant and has light diffuseness/transmission, and the sea component includes a light diffuseness/semi-transmission structure having a flame retardant. The thickness ratio of the fiber composite base material to the overlay layer is set within a range of 10:1 to 10:2.5. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a non-combustible internally illuminated signboard, and more particularly, has flexibility, high visible light transmittance, moderate light diffusibility, and particularly a printing layer such as an inkjet printing layer. A light-diffusing and permeable sheet, especially at night, convenience store eaves sign that demonstrates eye-catching by internal lighting, restaurant chain eaves sign, restaurant outdoor signage, billboard installation billboard, The present invention relates to a non-combustible flexible laminate used for advertisement signs on underground wall surfaces.

  In various sales and service industries such as convenience stores, fast food stores, pubs, karaoke stores, gas stations, and financial ATMs, internally illuminated signboards are frequently used regardless of day or night. It also functions as night lighting at the same time as the display function of the shop name and advertisement. On the other hand, the reason why the interior lighting signage is often used on the walls of the station premises, subway stations, underground shopping streets, and underground communication passages is that they also have an illumination function. These internally-lit advertising billboards are mainly printed on an acrylic resin plate by ink jetting or cut and pasted with a marking film (cutting sheet), but they are disadvantageous in that they are easily broken and flammable. . For this reason, high flameproof performance and impact strength are required for large signboards attached to buildings. For example, a fiber reinforced flexible membrane material made of polyester fiber fabric as a base material and laminated on the surface with a soft vinyl chloride resin film. Is used for internally-lit signboards, and in recent years, the non-combustibility specified in the Building Standards Law has become indispensable. As a result, non-combustible flexible membrane materials based on glass fiber fabrics have begun to be used for internally-lit signboard applications. . (Patent Documents 1, 2, 3)

  Patent Document 1 proposes a non-combustible signboard mainly composed of a non-combustible sheet material as a material suitable for a combustion test based on ASTM-E1354 “Building Material Combustibility Test Method”. An incombustible sheet for internally illuminated signboards composed of a noncombustible resin layer laminated on one or both sides of a glass cloth has been proposed as a material that conforms to the exothermic test according to Article 108-2 of the Enforcement Ordinance of the Standard Law. In Patent Document 3, as a film material to be determined as a non-combustible material prescribed in Article 2.9 of the revised Building Standards Act of 1998, one side of a glass fiber fabric is used as a flame retardant film layer, and the other A signboard film material whose surface is a coating layer mainly composed of a flame-retardant film, a thermoplastic resin, or a silicone resin has been proposed. In these combustion tests, since the acceptance rate increases as the amount of combustible components decreases, it is general that the composition is mainly composed of an inorganic material. These non-combustible film materials become materials applicable to the Building Standards Act by obtaining the Minister of Land, Infrastructure, Transport and Tourism certification number.

  According to the Examples, the film materials of Patent Documents 1 to 3 are materials that can be adapted to the nonflammability test in the state of a raw fabric. However, internally-lit signboards are used freely for each user by printing out photographs, illustrations, and trade name logos on the surface of the film material, or by marking and pasting a marking film. In particular, in competitive fields such as convenience stores, restaurant chains, gas stations, and banks, each company has a symbol color, character design, and a unique trade name logo that makes it easy to distinguish it from competitors. In order to create such an internally-illuminated signboard, a computer is used to create a decorative design that is standardized by each company. Character markings and cutout designs are made on marking films, and photographic images and illustration images are printed by inkjet printing. Design and drawing of images are efficiently performed. Especially for inkjet prints used for long periods outdoors, water resistance, weather resistance, and light fastness are required, so the entire print is coated with a transparent resin or covered with a transparent film with an adhesive layer. ing. By having such an overlay layer, an antifouling effect and an effect of preventing scratches are also exhibited. Therefore, a PVC resin film or a PET resin film having a thickness of about 50 to 100 μm is frequently used for the overlay. Since the film is flammable, it is difficult to conform to the non-flammability test when ink-jet printing is performed on the entire surface of an internally illuminated signboard and an overlay film is applied to the entire surface. There is concern about the discrepancy from the incombustibility. For this reason, it is strongly desired to meet the requirements for non-combustible materials in the revised Building Standards Law even in the state of internally-lit signboards with an overlay film attached. It is necessary to reinforce the flame retardancy of the membrane material itself, which requires the addition of a large amount of flame retardant powder. However, this increases the concealment of the film material as a negative effect due to the addition of a large amount of flame retardant powder, and significantly impedes the light transmission, thus hindering the use as an internally-lit signboard, which is substantially internally-illuminated. There was no non-combustible film material for signboards.

JP 2005-181868 A JP 2006-145910 A JP 2004-269635 A

  The present invention is a flexible fiber composite film material used for an internally-illuminated signboard, which is a printed film material having high light transmittance and appropriate light diffusibility, and has an overlay film (overlaminate) on the entire surface. Providing film materials for non-combustible interior-lit signboards that have high non-combustibility characteristics and light diffusivity, and non-combustible interior-illuminated signboards that can be applied to the non-combustible test even in affixed usage forms Is something to try.

  In order to solve the above-mentioned problems, a flame retardant resin coating layer is provided on one or more sides of a fabric formed by arranging and weaving inorganic filament bundles without gaps, and a printing layer is formed on at least one surface of the flame retardant resin coating layer. In the sheet having, the flame-retardant resin coating layer forms a sea-island structure by incompatible mixing of two or more kinds of synthetic resins, the island component does not contain a flame retardant and has light diffusion permeability, By configuring with a light diffusing semi-transmissive structure containing a flame retardant, and by setting the thickness ratio of the fiber composite base material and the overlay layer within the range of 10: 1 to 10: 2.5, The present invention has been completed by finding that it has light diffusibility suitable for an internally-lit signboard despite the overlay film sticking, and also has a high degree of nonflammability.

That is, the incombustible internally illuminated signboard of the present invention is a fiber composite base material in which a flame retardant resin coating layer is provided on one or more sides of a fabric formed by arranging and weaving inorganic filament bundles without gaps. At least on the upper surface, a printing layer is provided on the entire surface, partially or scatteredly, and the exposed portion of the flame retardant resin coating layer and an overlay layer that covers and protects the printing layer are provided. The flame retardant resin coating layer has a sea-island structure formed by incompatible mixing of two or more kinds of synthetic resins, and in this sea-island structure, the island component is a flame retardant. A light diffusion semi-transmission structure in which the sea component contains a flame retardant, and the ratio of the thickness of the fiber composite substrate to the thickness of the overlay layer is 10 Within the range of 1-10: 2.5 Rukoto is preferable. In the incombustible internally illuminated signboard of the present invention, the visible light transmittance (JIS-Z8722) ratio between the island component and the sea component is preferably within a range of 3: 2 to 3: 1. In the non-combustible internally illuminated signboard of the present invention, it is preferable from the viewpoint of antifouling properties to have a photocatalytic antifouling layer as the outermost layer of the light diffusive and transparent sheet. The non-combustible internally illuminated signboard of the present invention uses the light diffusing and permeable sheet as a test piece, and the radiant heat by a radiant electric heater to the light diffusing and transmitting sheet in the cone calorimeter test method (ASTM-E1354). Is 50 MkW / m ² , the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less, and the maximum heat generation rate is 200 kW / m ^{2 for} 20 minutes after the start of heating for 10 seconds or more. From the viewpoint of maintaining nonflammability, it is preferable to have combustion characteristics that do not exceed.

  According to the present invention, it is a flexible fiber composite film material that can be suitably used for internally-lit signboard applications, has high light transmittance and moderate light diffusibility, and in particular, an overlay film over the entire printed material. It is possible to provide a film material for internally illuminated signboards having high incombustibility characteristics and a nonflammable internally illuminated signboard system that can be adapted to the incombustibility test (Building Standards Act) even in the usage form with affixed it can. The film material of the present invention can satisfy the requirements of non-combustible materials stipulated in the revised Building Standards Law while satisfying the requirements of signboard designs by individual users, so it is a sufficient measure to prevent the spread of fire spread in downtown areas. obtain. Therefore, the incombustible interior-lit signboard of the present invention, regardless of small to large installation, convenience store eaves sign, restaurant chain eaves sign, restaurant outdoor signage, building rooftop advertising signage, underground street wall It can be widely used for advertising billboards.

The figure which shows an example of the nonflammable interior-lit signboard of this invention The figure which shows an example of the nonflammable interior-lit signboard of this invention The figure which shows an example of the incombustible internally illuminated signboard system of this invention The figure which shows the internally illuminated electric signboard model used for evaluation in an Example and a comparative example The figure shows the sea-island structure of the flame-retardant resin coating layer, and shows the structure where the island component is a light-diffusion semi-transparent structure that does not contain a flame retardant and has a light diffusibility and the sea component contains a flame retardant

  The incombustible internally illuminated signboard of the present invention is a fiber composite substrate in which a flame retardant resin coating layer is provided on one side or more of a fabric formed by arranging and weaving inorganic filament bundles without gaps. At least on the upper surface, a printing layer is provided on the entire surface, partially or scatteredly, and the exposed portion of the flame retardant resin coating layer and an overlay layer that covers and protects the printing layer are provided. The flame retardant resin coating layer has a sea-island structure formed by incompatible mixing of two or more kinds of synthetic resins. In this sea-island structure, the island component is difficult. It is a film material that has a light diffusibility and does not contain a flame retardant and has a light diffusive semi-permeable structure in which a sea component contains a flame retardant.

  The fabric used for the incombustible internally illuminated signboard of the present invention is a woven fabric or a knitted fabric obtained by arranging and weaving inorganic filament bundles without gaps. The inorganic filament bundle is an inorganic long fiber having a fineness of 138 to 2223 dtex (decitex), particularly 277 to 1112 dtex, such as glass fiber, silica fiber, alumina fiber, silica-alumina fiber, etc., and 3 to 300 filaments, particularly 50 to 150. These yarns are bundled with a book, and are yarns having a circular, elliptical, or flat cross section that are used alone, mixed, or blended with or without twisting. Examples of the woven fabric by these inorganic filament bundles include known woven fabrics such as plain weave, twill weave, satin weave, and imitation weave. Among them, plain woven fabric is particularly preferable because of excellent balance of the background of the incombustible internally illuminated signboard obtained, A knitted weft insertion tricot is preferred as the knitted fabric. These knitted fabrics are composed of warp yarns and weft yarns, each of which includes a plurality of warp yarns arranged in parallel with a close gap between yarns, and a plurality of weft yarns arranged in parallel with a close gap between yarns. A fabric made of a high-density knitted fabric having a void ratio of 0 to 3% is preferable. These fabrics are preferably treated with a silane coupling agent.

  In the incombustible internally illuminated signboard of the present invention, the flame retardant resin coating layer has a milky white to white appearance made of a melt of two or more synthetic resins or a stirred mixture of two or more liquid synthetic resins. Synthetic resins preferably used in the present invention include, for example, vinyl chloride resins, vinyl chloride copolymer resins, olefin resins (PE, PP, etc.), olefin copolymer resins, urethane resins, urethane copolymer resins. , Acrylic resin, acrylic copolymer resin, vinyl acetate resin, vinyl acetate copolymer resin, styrene resin, styrene copolymer resin, polyester resin (PET, PEN, PBT, etc.), polyester copolymer resin , Fluorine-containing copolymer resins, silicone resins, silicone rubbers, polycarbonates, polyamides, polyethers, polyester amides, polyphenylene sulfides, polyether esters and other thermoplastic resins, and vinyl ester resins.

  In the present invention, the flame retardant resin coating layer has a milky white to white appearance made of an incompatible mixture of at least two types of synthetic resins, and there is no limitation on the combination of synthetic resins as long as they are incompatible. Examples of incompatible combinations include vinyl chloride resin and polyethylene, vinyl chloride resin and polypropylene, vinyl chloride resin and polystyrene, vinyl chloride resin and silicone resin, vinyl chloride resin and fluorine-containing copolymer resin, polystyrene and polyethylene, polystyrene And polypropylene, urethane resin and polyethylene, urethane resin and polypropylene, polyester resin and polyethylene, polyester resin and polypropylene, polyamide and polycarbonate, acrylic resin and polystyrene, acrylic resin and polycarbonate, polyamide and polystyrene, polyamide and polypropylene, and the like. Another type of thermoplastic resin can also be contained with respect to these incompatible thermoplastic resin pairs.

  These incompatible mixtures exhibit a phase separation structure, and are particularly preferably sea-island structures. In this sea-island structure, the sea component and the island component are composed of different types of resins. For example, in an incompatible mixture composed of the thermoplastic resin A and the thermoplastic resin B, the ratio of the thermoplastic resin A and the thermoplastic resin B is set. The sea component can be composed of the thermoplastic resin A, the island component can be composed of the thermoplastic resin B, the sea component can be composed of the thermoplastic resin B, and the island component can be composed of the thermoplastic resin A. it can. The ratio of the resin constituting the island component is 5 to 50% by volume (preferably 10 to 30% by volume) with respect to the volume of the resin constituting the sea component, and the island component content relative to the entire flame-retardant resin coating layer is 4. 7 to 33.3% by volume (preferably 9.1 to 23.1% by volume). In addition, when another type of thermoplastic resin C is contained with respect to the incompatible thermoplastic resin pair AB, the island component is an island component by the thermoplastic resin B and an island component by the thermoplastic resin C in the sea-island structure. Similarly, the island component may be composed of an island component made of the thermoplastic resin A and an island component made of the thermoplastic resin C.

  The shape of the island component is spherical, distorted spherical, meteorite, rugby ball or the like. The average particle size of the island components is 0.1 to 50 μm, and 1 to 30 μm is particularly preferable. By making the size of the island component larger than 1 μm, it is possible to obtain a milky white to white appearance that obtains a good light diffusion effect while maintaining the total light transmittance in the flame retardant resin coating layer. In the present invention, the flame retardant resin coating layer preferably has a difference in refractive index between the synthetic resin constituting the sea component and the synthetic resin constituting the island component. If the refractive indexes are the same, the refractive scattering phenomenon does not occur at the interface between the sea component and the island component, and a sufficient light diffusion effect cannot be obtained. The refractive index difference for obtaining good light diffusibility is 0.01 or more, more preferably 0.05 or more, and the conditions constituting the refractive index difference are the refractive index on either side of the sea component and the island component. It can be high. The refractive index can be obtained by an Abbe refractometer using the D line as a light source.

  In the present invention, the flame retardant resin coating layer has a sea-island structure composed of an incompatible mixture of at least two types of synthetic resins, the sea component includes a flame retardant and is made light diffusing semi-permeable, Light diffusive transmission without flame retardant. Such a sea-island structure requirement makes it possible to obtain a flame retardant resin coating layer having a milky white to white appearance, thereby providing good light transmittance and appropriate light diffusibility. In order to obtain this sea-island structure, in the two types of synthetic resins constituting the incompatible mixture, it is set as a kneaded composition in which the flame retardant is uniformly mixed and dispersed in advance on the synthetic resin side constituting the sea component, On the side of the synthetic resin constituting the island component, a kneaded composition containing no flame retardant is used, and 5 to 50% by volume of the island component constituting synthetic resin side of the sea component constituting synthetic resin side is melted. A sea island in which the island component has light diffusibility and the sea component has light diffusibility and semi-permeability by injecting the kneaded material all at once or dividedly and mixing these two types of synthetic resin compositions incompatiblely. A structure can be obtained. The appearance of the non-combustible internally illuminated signboard of the present invention is milky white to white, improving the light diffusing effect of the internally illuminating light source, and at the same time having light source concealing property, and can also ensure good light transmittance. Higher brightness and more colorful inner lighting effect.

  Flame retardants that are uniformly dispersed in sea components are: a). Phosphorus atom-containing compounds such as metal phosphates, metal organic phosphates, phosphate derivatives, ammonium polyphosphates, and ammonium polyphosphate derivative compounds, b). Nitrogen-containing compounds such as (iso) cyanurate compounds, (iso) cyanuric acid compounds, guanidine compounds, urea compounds, and derivatives thereof, c). Inorganic compounds such as silicon compounds, metal hydroxides, metal oxides, metal carbonate compounds, metal sulfate compounds, boric acid compounds, and inorganic compound complexes; d). It is 1 or more types chosen from the organic halogen compound, and the compounding quantity with respect to 100 mass parts of synthetic resins which comprise a sea component is 10-150 mass parts, Preferably it is 30-100 mass parts.

These flame retardants are preferably white fine powdery nitrogen atom-containing compounds having an average particle size of 0.1 to 3.0 μm, and in particular, polyphosphoric acid having a degree of polymerization of n30 to 1200 represented by (NH ₄ PO ₃ ) _n. Ammonium and water-resistant ammonium polyphosphate surface-coated with melamine resin, urea resin, triazine resin, melamine-modified ammonium polyphosphate, melamine polyphosphate, (poly) phosphoric acid and melamine compound complex salt, (poly) phosphoric acid And melamine compound 2-3 trimer, phosphonic acid and melamine compound complex salt, phosphonic acid and melamine compound 2 to trimer complex salt, phosphinic acid and melamine complex salt, Complex salt of phosphinic acid and 2-mer of melamine compound, melamine cyanurate, triethyl isocyanurate, melamine (cyanuric acid Amide), guanamine, benzoguanamine, melamine sulfate, trimethylol melamine, triethyl ester of cyanuric acid, 1,3,5-triazine, dicyanamide trimer (melon), dicyandiamide, guanidine, dimethylol urea and the like. When the average particle diameter exceeds 3.0 μm, the flame retardant is kneaded into the synthetic resin, and the surface area efficiency in contact with the synthetic resin is deteriorated, and the flame retardancy may be insufficient.

  These flame retardants are preferably white fine powdery inorganic compounds having an average particle size of 0.1 to 3.0 μm, particularly aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, zinc hydroxystannate, oxidation Metal hydroxide such as tin hydrate, metal oxide such as zirconium oxide, molybdenum oxide, antimony oxide, zirconium-antimony composite oxide, boron such as zinc borate, zinc metaborate, barium metaborate, aluminum borate Examples include acid compounds, alumina hydrate, zeolite, hydrotalcite, and hydroxyapatite. When the average particle diameter exceeds 3.0 μm, the flame retardant is kneaded into the synthetic resin, and the surface area efficiency in contact with the synthetic resin is deteriorated, and the flame retardancy may be insufficient.

  These flame retardants are preferably white fine powdery organic halogen compounds having an average particle diameter of 0.1 to 3.0 μm, and in particular, decabromodiphenyl, decabromodiphenyl oxide, hexabromodiphenyl oxide, pentabromocyclohexane, ethylene Bisphenol A derivatives such as bispentabromodiphenyl, hexabromobenzene, hexabromocyclododecane, tetrabromobisphenol A, tetrabromobisphenol A-bis (bromoethyl ether), tetrabromophthalimide, ethylenebistetrabromophthalimide, and ethylenebispenta Phthalic acid derivatives such as bromophthalimide, brominated polystyrene, brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, brominated polyurea Brominated polymer compounds such as brominated polyester, low chlorinated polyethylene or low chlorinated polypropylene having a chlorine content of 25 to 45% by weight, highly chlorinated polyethylene or highly chlorinated polypropylene having a chlorine content of 60% by weight or more, etc. The chlorinated high molecular compound is mentioned. When the average particle diameter exceeds 3.0 μm, the flame retardant is kneaded into the synthetic resin, and the surface area efficiency in contact with the synthetic resin is deteriorated, and the flame retardancy may be insufficient.

  In addition, as a light diffusing particle, the sea component includes a milky white to transparent, spherical or amorphous particle-shaped inorganic compound or polymer compound having an average particle diameter of 1 to 30 μm. The light diffusing particles may be contained in an amount of 0.1 to 30% by mass, preferably 1 to 15% by mass with respect to the mass. Examples of the light diffusing particles include glass beads, hollow glass beads, glass powder, and silica (silicon oxide). Natural mica powder, synthetic mica powder, silicone resin beads, silicone resin powder, (crosslinked) acrylic resin beads, (crosslinked) acrylic resin powder, (crosslinked) polystyrene resin beads, (crosslinked) polystyrene resin powder, ( High density) polyethylene resin beads, (high density) polyethylene resin powder, epoxy resin beads, epoxy resin powder, benzoguanamine resin beads, Ben Such as guanamine resin powder.

  In the incombustible internally illuminated signboard of the present invention, the flame retardant resin coating layer may contain a known additive as required. Additives include, for example, antistatic agents, plasticizers, softeners, fillers, adhesives, crosslinking agents, UV absorbers, antioxidants, stabilizers, antibacterial agents, antifungal agents, colorants, fluorescent whitening Agents, fluorescent pigments, phosphorescent pigments and the like.

  In the present invention, the thickness of the flame retardant resin coating layer coated on the fabric is 0.01 to 0.3 mm, preferably 0.05 to 0.2 mm, and the total thickness of the resulting fiber composite substrate is 0. .2 to 0.60 mm, preferably 0.3 to 0.45 mm. If the total thickness of the fiber composite substrate exceeds 0.60 mm, the proportion of the flame retardant resin coating layer increases, and the non-combustibility standard according to the cone calorimeter test method (ASTM-E1354) may not be satisfied. Moreover, it is preferable that ratio of the visible light transmittance (JIS-Z8722) in an island component and a sea component exists in the range of 3: 2-3: 1. When the visible light transmittance increases beyond 3: 2 due to the low flame retardant content of the sea component, the brightness and color developability of the internally-illuminated signboard itself will be conspicuous, but the marking film is attached. If the visible light transmittance becomes smaller than 3: 1 due to the excessive flame retardant content of the sea component, the non-flammability with the marking film applied Although it becomes easy to adapt to the test, there is a disadvantage that the brightness and color developability of the internally illuminated signboard itself are extremely deteriorated.

  In the present invention, the flame retardant resin coating layer may be provided on the fabric by, for example, an incompatible mixture of a resin dispersed in an organic solvent, an incompatible mixture of a resin emulsion (latex), or a forced dispersion resin in water. Using a non-compatible mixture, a non-compatible mixture of paste sol mainly composed of soft polyvinyl chloride resin, an incompatible mixture mainly composed of thermosetting resin, and the like, for example, dipping (to fabric) ), Coating such as coating (single-side processing or double-side processing), and impregnation coating. Further, a film or sheet of 0.01 to 0.3 mm, preferably 0.05 to 0.2 mm, made of an incompatible thermoplastic mixture, formed by calender molding or T-die extrusion method on a fabric, and an adhesive is used. Or a method of laminating by thermal lamination, and a combination of these coating and lamination.

  The light diffusive and transmissive sheet constituting the non-combustible interior-illuminated signboard of the present invention has a front surface and a back surface, the front surface is the appearance exposed side of the signboard, and the back surface is a light source such as a fluorescent lamp or LED. The side that faces. The surface of the flame retardant resin coating layer exposed on the surface, that is, the outermost layer of the light diffusive and transparent sheet, has an antifouling layer containing a photocatalytic substance having a layer thickness of 0.05 to 3 μm, preferably 0.1 to 1 μm. Provided. Further, in the incombustible internally illuminated electric signboard of the present invention, a printing layer is provided on the entire surface side of the flame retardant resin coating layer of the light diffusive transparent sheet, or partially on the surface, and a transparent film is provided as an overlay layer on the surface. Further, an antifouling layer containing a photocatalytic substance is provided on the surface of the overlay film with a layer thickness of 0.05 to 3 μm, preferably 0.1 to 1 μm. The antifouling layer containing the photocatalytic substance is formed by spray coating on the entire interior illuminated signboard, which is completed by pasting the design by cutting out the marking film and / or cutting out the design onto the light diffusive transparent sheet. It can be performed by a known coating method such as brush coating or sponge roller coating.

  The overlay layer used in the incombustible internally illuminated electric signboard of the present invention can be formed by applying a transparent paint, forming a transparent resin layer by spraying, or attaching a transparent film with an adhesive layer or an adhesive layer. Although it can do, especially the sticking which uses a transparent film as an overlay film is preferable. Examples of the overlay film (also referred to as an overlaminate film) include soft to semi-rigid vinyl chloride resins, acrylic resins, polyethylene terephthalate resins, fluorine-containing copolymer resins, ionomer resins, and multilayer films made of these resins. These overlay layers may contain a known weather resistance improver such as an ultraviolet absorber, an antioxidant, and HALS as necessary. The thickness of the overlay layer is 25 to 120 [mu] m, preferably 60 to 100 [mu] m, including the back (adhesive) adhesive layer. The adhesive (contact) adhesive layer is provided in a thickness of 10 to 60 μm, preferably 20 to 40 μm, depending on the adhesive (contact) adhesive such as acrylic, polyurethane, polyolefin, and silicone. In the case of transparent paints, water-based paints that do not dissolve printing are preferable. Acrylic resins, acrylic acid copolymer resins, urethane resins, acrylic-urethane copolymer resins, fluorine-containing copolymer resins, acrylic-silicone copolymers Resin, silicone graft / fluorine-containing copolymer resin and the like are the main components.

  In the non-combustible interior-illuminated electric signboard of the present invention, the appearance display and the transmission display can be performed day and night by printing on the flame-retardant resin coating layer. The printing can be any of known printing, for example, gravure printing, screen printing, transfer printing, and ink jet printing. However, in the internally illuminated electric signboard of the present invention, ink is used in terms of light transmission and color development. Ink jet printing with a small coating amount is preferred. Moreover, it can be used for the interior illumination type electric signboard of this invention by using the ink which has a light transmittance also in another printing method. In addition, printing may be performed in combination with a plurality of printing methods or in combination with a marking film, and printing may be performed arbitrarily on the entire surface of the flame retardant resin coating layer, partially or scatteredly.

  In the present invention, the total thickness of the fiber composite substrate is 0.2 to 0.60 mm, preferably 0.3 to 0.45 mm. The ratio of the thickness of the fiber composite substrate and the thickness of the overlay layer is preferably 10: 1 to 10: 2.5 (that is, 10: 1 to 4: 1) from the viewpoint of nonflammability and stable maintenance. The thickness of the overlay film substrate suitably used in the present invention is 25 to 120 μm, preferably 40 to 80 μm, and the adhesive (contact) adhesive layer is 10 to 60 μm, preferably 20 to 40 μm. Therefore, the minimum thickness of the overlay layer is 35 μm and the maximum thickness is 180 μm. In the present invention, the preferred overlay film thickness is 40 to 120 μm, particularly preferably 60 to 100 μm. When the ratio of the overlay layer is less than 10: 1, that is, less than 10% of the thickness of the fiber composite base material, there is a problem that wrinkles are easily mixed in the overlay operation, and the scratch protection effect may be insufficient. is there. When the ratio of the overlay layer exceeds 10: 2.5 (that is, 4: 1), that is, when it exceeds 30% of the thickness of the fiber composite substrate, the ratio of the overlay film increases, and the cone calorimeter test method is used. The non-combustible standard according to (ASTM-E1354) may not be satisfied. In this invention, it is preferable that the test body used for the corn calorimeter test method (ASTM-E1354) can satisfy a nonflammable standard on the conditions which have an overlay layer in the test body whole surface.

In the non-combustible internally illuminated signboard of the present invention, it is preferable that the outermost layer of the light diffusive transparent sheet has a photocatalytic antifouling layer. The photocatalyst contained in the photocatalytic antifouling layer is a substance that absorbs ultraviolet rays and visible light and exhibits organic substance decomposition activity. As photocatalytic substances, 1). Titanium oxide (TiO ₂ ), titanium peroxide (peroxotitanic acid), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O) ₃ ), iron oxide (Fe ₂ O ₃ ), 2). A material obtained by doping the photocatalytic metal oxide with a simple metal such as gold, silver, copper, platinum, rhodium, palladium, ruthenium, or iridium and a metal compound thereof as a co-catalyst, 3). The photocatalytic metal oxide doped with nitrogen, carbon, sulfur, phosphorus, boron, fluorine, 4). The photocatalytic metal oxide doped with transition metal ions such as chromium, niobium, manganese, cobalt, vanadium, iron and nickel, 5). The photocatalytic metal oxide is one or more selected from those in which noble metal halides such as platinum, palladium, and rhodium are supported.

  In the present invention, in particular, as a photocatalytic substance, titanium oxide sol obtained by thermally hydrolyzing a titanium compound such as titanyl sulfate, titanium chloride, titanium alkoxide, titanium oxide obtained as an alkali neutralized product of titanium oxide sol, water, etc. Anatase type peroxotitanic acid dispersion liquid in which ultrafine particles of titanium oxide and titanium oxide are peroxylated with a peroxide such as hydrogen peroxide and dispersed in water is preferable. Titanium oxide may be any of anatase type, rutile type, and brookite type, but hydrochloric acid peptization type anatase titania sol and nitrate peptization type anatase titania sol having an average crystallite diameter of 5 to 20 nm are preferable. The smaller the particle size of the photocatalytic substance, the better the photocatalytic activity. Therefore, a photocatalytic substance having an average particle diameter of 50 nm or less, more preferably 20 nm or less is suitable. Titanium oxide includes hydrous titanium oxide, hydrated titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide, and the like. In addition, the inorganic porous fine particles supporting the above-mentioned photocatalytic substance can also be used. Specifically, the inorganic porous fine particles have an average primary particle diameter of 0.01 to 10 μm, particularly 0.05 to 5 μm silica, (synthetic) zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, diatomaceous earth and the like.

  As a method for forming a photocatalytic antifouling layer, for example, a method of forming a photocatalytic antifouling layer containing a photocatalytic substance by applying a coating agent containing particles or sol of a photocatalytic substance and a binder, photocatalytic property A method of forming a photocatalytic antifouling layer containing a photocatalyst from a solution of a substance by a sol-gel method, a method of forming a photocatalytic antifouling layer containing a photocatalytic substance by a sputtering method, an ion plating method, a CVD method, etc. It can be formed by a conventionally known method. Examples of such a binder include those that are not easily decomposed by a photocatalytic substance and that have a film-forming ability, such as organic resins such as fluorine resins, silicone resins, acrylic fluorine copolymer resins, and acrylic silicone copolymer resins. It is preferably a silicon compound condensation layer of any one or more of a binder based on polysilazane, an organic silicate compound, or a hydrolyzate of its low condensate (silanol group-containing silane compound). Any one or more of titanium sol is preferably included. The photocatalytic antifouling layer preferably contains 10 to 70 mass%, particularly 20 to 60 mass%, of photocatalyst particles or sol.

  The signboard system using the non-combustible internally illuminated signboard according to the present invention forms a signboard casing using the above-described light diffusive transmissive sheet having visible light transmittance, and a fluorescent lamp, an LED, etc. in the casing It is a structure in which the light source is arranged. The non-combustible internally illuminated electric signboard of the present invention is preferably a light diffusive and transparent sheet having a visible light transmittance (JIS-Z8722) of 10 to 60%. The visible light transmittance of itself is 30 to 60%, preferably 40 to 60%, and the visible light transmittance of the part having the printed layer, that is, the fiber composite substrate provided with the printed layer is 10 to 40%, preferably 20 to 20%. 40%. If the visible light transmittance is less than 10%, it may not be possible to obtain effective illuminance and color when used for internally illuminated signboards, and if it exceeds 60%, light sources such as fluorescent lamps and LEDs The presence and arrangement of the image may become conspicuous, and the image of advertisements and designs may be damaged.

  With respect to the non-combustible internally illuminated electric signboard of the present invention, the light diffusive and transparent sheet of FIG. 1 will be described as an example. The light diffusing and transmitting sheet (7) in FIG. 1 uses a plain woven fabric formed by knitting and arranging inorganic filament bundles without gaps as a knitted fabric (1), and laminating a flame retardant resin film thereon. As the fiber composite base material (3) in which the flame retardant resin coating layer (2) is formed on both sides of the woven fabric (1), a printing layer (4) is provided on one side, and the printing layer (4), The flame retardant resin coating layer (2) and the exposed portion (2-1) are provided with an overlay layer (5).

The non-combustible interior-illuminated electric signboard of the present invention clears the non-combustibility test stipulated by the Building Standards Law with at least the overlay film attached to the entire surface in order to use it with any overlay printing. It is preferable to do. Specifically, the non-flammability test is a heat generation test (ASTM-E1354: corn calorimeter test) in which a light diffusive transparent sheet with an overlay film attached to the entire surface is used as a test body and a radiant heat is applied to radiant heat of 50 kW / m ^2. Method), the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less, and 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. It is preferable to meet non-flammable requirements. The light diffusive and permeable sheet (7) satisfying such non-combustibility requirements is a woven fabric (1) obtained by knitting and arranging inorganic filament bundles without gaps, and is particularly high in glass fiber with a porosity of 1% or less. A density plain woven fabric is used as a base material, and a flame retardant resin coating layer (2) is provided on both sides (one side is acceptable) to form a fiber composite base material (3). On the flame retardant resin coating layer (2), a print layer (4) is provided, and an overlay layer (5) having a thickness in the range of 10 to 25% with respect to the thickness of the fiber composite substrate (3), The flame retardant resin coating layer exposed portion (2-1) and the printed layer (4) are coated, that is, the thickness ratio of the fiber composite substrate (3) to the overlay layer (5) is 10: 1. -10: 2.5.

  FIG. 3 shows an example of the non-combustible internally illuminated signboard system (10) of the present invention. The internally illuminated signboard system according to the present invention includes an internally illuminated signboard casing (8) with a light diffusive transmissive sheet (7), and a fluorescent lamp (9) inside the internally illuminated signboard casing. Is arranged. The fluorescent lamp (9) is not particularly limited as long as it is a fluorescent lamp for illumination that emits light having a wavelength of 400 nm to 800 nm, and an LED light emitter can also be used. Fluorescent lamps for illumination can be used in any form of three-wavelength fluorescent lamps, high color rendering fluorescent lamps, and general fluorescent lamps. These color temperatures are daylight (5700-7100K) and daylight white (4600-5400K). , White (3900-4500K), warm white (3200-3700K), bulb color (2600-3150K), etc., any type may be used. The signboard display surface is not limited to one side as shown in FIG. 3, but may be a double-sided display type signboard in which the light diffusion / transmission sheets (7) are mounted on both surfaces of the internally illuminated signboard casing (8). The internally illuminated signboard system of the present invention according to the present invention has non-combustibility that conforms to the guidance of the Building Standards Law, especially in busy areas, in front of stations, along roads, etc., in convenience stores, restaurants, It can be used for various shops, karaoke shops, gas stations, banks, financial ATMs, and other outdoor signboards, as well as outdoor advertising signs, and also suitable for station building information boards and underground shopping mall advertising signs. it can.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these.
In the following Examples and Comparative Examples, a glass fiber plain woven fabric obtained by arranging and weaving glass filament bundles having a filament diameter of 9 μm / 750 dtex without gap as a knitted fabric: weaving density: warp (warp) 40 / inch: weft (weft) ) 30 / inch: Sum of voids generated at the intersection of warp and weft 1%: Scouring (with heat cleaning): Silane coupling treatment with methacryloxypropyltrimethoxysilane (Z6030 manufactured by Toray Dow Corning): Dimensions: warp (warp direction) 150 cm × weft (weft direction) 150 cm was used.

  For the internally illuminated electrical signboard (light diffusive transmissive sheet) created in the examples and comparative examples, an internally illuminated electrical signboard model as shown in FIG. 4 is prepared, and the internal illumination coloration property, the visibility of the fluorescent lamp, and the nonflammability The property was evaluated as follows. The size of the light diffusing and transmitting sheet (7) used for the interior illumination type electric signboard is 150 cm long × 150 cm wide, and the printed layer (4) side of the light diffusing and transmitting sheet (7) is used as an external surface. Attached to both sides of the type signboard case (8). At this time, six 36-watt 40-type straight-tube three-wavelength daylight fluorescent lamps (9) were arranged in parallel at 25 cm intervals in the internally illuminated signboard case (8). The state where the fluorescent lamp (9) was turned on was observed in the dark interior of the internally illuminated signboard system obtained as described above. In FIG. 4, expressions of elements other than the light diffusive and transparent sheet (7) and the fluorescent lamp (fluorescent lamp fixture, power source, wiring, etc.) are omitted.

<Visibility of internal light source (fluorescent lamp)>
Observe from a position 3 m away from the printed layer of the light diffusive transparent sheet,
Evaluation was made according to the following criteria.
1: The entire surface of the light diffusing and transmitting sheet emits light almost uniformly, and the presence of a fluorescent lamp as an internal light source cannot be visually recognized, and the color and brightness of the printed layer are good.
2: The presence of the position of the internal light source (fluorescent lamp) cannot be visually recognized, but the brightness of the light diffusive and transparent sheet is insufficient, especially the color and brightness of the printed layer is insufficient.
3: The position of the internal light source (fluorescent lamp) can be clearly seen through the light diffusive transparent sheet <Illuminance>
The illuminance was measured using an illuminometer IM-2D (Irie Co., Ltd.) at a position 2 m directly below the center of the light diffusive transparent sheet.
<Visible light transmittance>
The visible light transmittance of the light diffusive transmissive sheet was measured according to JIS-Z8722 using a spectroscopic colorimeter CM-3600d (manufactured by Konica Minolta Co., Ltd.). Further, the visible light transmittance of the sea component and the island component is the composition of the synthetic resin alone constituting the sea component or the island component, respectively:
It is a measured value of a 0.12 mm sheet obtained from 2,5-13.
<Combustion test> (ASTM-E1354: Corn calorimeter test method)
The radiant heat of 50 kW / m ² by radiation electric heater irradiating the (marking film adhered to the test body all surfaces) internally illuminated illuminations signboard sheet 20 minutes, in the heating test, heat generation and gross calorific value of 20 minutes The speed was measured and the appearance of the film material after the test was observed.
(A) Total calorific value: 8 MJ / m ² or less was regarded as suitable.
(B) heating speed: 10 seconds or more continuously to the Relevant not exceed 200 kW / ^{m 2.}
(C) Appearance observation: Applicable to those with no pinhole depression exceeding 0.5 mm in diameter.

[Example 1]
Add 20% by mass of the vinyl ester resin stirring mixture of the following formulation 2 to the stirring mixture of the soft vinyl chloride resin paste with the flame retardant formulation of the following formulation 1 with respect to the mass of the vinyl chloride resin alone, and stir the vinyl ester resin. It was made to disperse | distribute uniformly and the incompatible resin mixture liquid 1 was obtained. The fabric was immersed in a bath filled with the resin mixture liquid 1, and the fabric was completely impregnated with the resin mixture liquid 1. Next, the excess resin mixture liquid 1 on both sides of the fabric was scraped off with a doctor blade and heated in an electric furnace at 180 ° C. for 5 minutes to obtain a sheet provided with a flame retardant resin coating layer on both sides of the fabric. Next, on one surface of the PET film, the resin mixture liquid 1 is coated with a thickness of 0.12 mm, and this is overlaid on one side of the previously prepared sheet and heated in an electric furnace at 180 ° C. for 5 minutes to obtain the resin mixture liquid 1 After solidifying, the PET film was removed to form a smooth flame retardant resin coating layer (construction appearance side). When this flame retardant resin coating layer is observed with a microscope, the vinyl ester resin constitutes an island component with a visible light transmittance of 82%, and the soft vinyl chloride resin has a sea component with a light diffusing semi-transmissivity (transmittance of 48%). The ratio of the visible light transmittance between the island component and the sea component was 3: 1.756. Next, a jacket image of a music CD having a size of 12 cm × 12 cm was output in full color to a size of 150 cm × 150 cm using a solvent-type ink jet printer (PJ-2216NX from Muto Kogyo Co., Ltd.) on the external observation side surface of the flame retardant resin coating layer. Next, as the overlay layer, an entire laminate layer (IJ4141: acrylic resin: 90 μm thick including the adhesive layer) of Sumitomo 3M Co., Ltd. is used to cover the entire printed layer of 150 cm × 150 cm size, The thickness ratio with the overlay layer was 10: 2.25. Furthermore, a coating solution for forming an adhesion / protection layer having the following composition 3 was applied with a 100 mesh gravure coater, dried at 100 ° C. for 1 minute and then cooled to form a 1.5 g / m ² adhesion / protection layer on one side. Furthermore, a coating solution for forming a photocatalyst antifouling layer having the following composition 4 was applied thereon with a 100 mesh gravure coater, dried at 120 ° C. for 2 minutes and then cooled to form a 1.5 g / m ² photocatalytic antifouling layer. A fiber composite substrate having a visible light transmittance of 38% and a total thickness of 0.4 mm was obtained. Using this, an internally illuminated signboard model was produced.

<Formulation 1>
Emulsion polymerization polyvinyl chloride resin (degree of polymerization 1700) 100 parts by weight Dioctyl phthalate (plasticizer) 40 parts by weight Tricresyl phosphate (plasticizer) 40 parts by weight Antimony oxide (flame retardant) 15 parts by weight Molybdenum oxide (flame retardant) 5 Parts by mass
Melamine cyanurate 10 parts by mass (Nissan Chemical Co., Ltd. flame retardant: trade name MC-640)
Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight

<Formulation 2>
100 parts by mass of vinyl ester resin (trade name: Neopole 8319, manufactured by Nippon Iupika Co., Ltd.)
Curing agent 1 part by mass (di- (4-tert-butylcyclohexyl) peroxydicarbonate)
1 parts by weight of light diffusing agent (calcium carbonate: average particle size 1 μm)

<Formulation 3> Adhesive / Protective Layer Ethanol-ethyl acetate (50/50 mass ratio) solution containing 8 mass% (solid content) of acrylic silicone resin having a silicone content of 3 mol% 100 mass parts Methyl silicate MS51 (Colcoat Co., Ltd.) )of
20% ethanol solution (polysiloxane) 8 parts by mass γ-methacryloxypropyltrimethoxysilane (silane coupling agent) 1 part by mass

<Formulation 4> Photocatalytic antifouling layer Water-ethanol (50/50 weight ratio) solution in which a nitric acid acidic titanium oxide sol corresponding to a titanium oxide content of 10% by weight is dispersed 50 parts by mass A silicon oxide content of 10% by weight 50 parts by mass of a water-ethanol (50/50 weight ratio) solution in which a corresponding nitric acid acidic silica sol is dispersed

[Example 2]
The vinyl ester resin stirring mixture of Formulation 1 of Example 1 was replaced with the silicone resin of Formulation 5 below, and 20 wt% of the vinyl chloride resin alone was added and stirred to uniformly disperse the silicone resin, thereby making the incompatible resin A mixture liquid 2 was obtained. The fabric was immersed in a bathtub filled with the resin mixture liquid 2, and the fabric was completely impregnated with the resin mixture liquid 2. Next, the excess resin mixture liquid 2 on both sides of the fabric was scraped off with a doctor blade and heated in an electric furnace at 180 ° C. for 5 minutes to obtain a sheet in which a flame retardant resin was coated on both sides of the fabric. Next, the resin mixture liquid 2 is coated on one surface of the PET film at a thickness of 0.12 mm, and this is overlaid on one side of the previously prepared sheet and heated in an electric furnace at 180 ° C. for 5 minutes to obtain the resin mixture liquid 2 After solidifying, the PET film was removed to form a smooth flame retardant resin coating layer. When this flame-retardant resin coating layer is observed with a microscope, the silicone resin constitutes an island component with a visible light transmittance of 76%, and the soft vinyl chloride resin constitutes a sea component with a light diffusing semi-transmissivity (transmittance of 48%). The ratio of the visible light transmittance between the island component and the sea component was 3: 1.895. Next, an ink jet printing layer was provided on the flame retardant resin coating layer in the same manner as in Example 1, and then an overlaminate film (IJ4116N: vinyl chloride resin: adhesive layer of Sumitomo 3M Limited) was used as an overlay layer. 80 μm) was used to coat the entire surface of the printed layer having a size of 150 cm × 150 cm, and the thickness ratio of the fiber composite substrate to the overlay layer was 10: 2. Furthermore, the adhesive / protective layer of Formulation 3 is formed at 1.5 g / m ² , and the photocatalytic antifouling layer of Formulation 4 is further formed at 1.5 g / m ² on the visible light transmittance of 39%, A fiber composite substrate having a total thickness of 0.4 mm was obtained. Using this, an internally illuminated signboard model was produced.

<Formulation 5>
Trademark: Shirasukon RTV4086A
(2-component addition reaction curable silicone resin: active ingredient 100%: manufactured by Dow Corning Asia)
50 parts by mass Trademark: Shirasukon RTV4086B
(2-component addition reaction curable silicone resin: active ingredient 100%: manufactured by Dow Corning Asia)
50 parts by mass Light diffusing agent (titanium oxide particles: average particle size 0.4 μm) 1 part by mass

[Example 3]
An incompatible resin mixture in which the vinyl chloride resin stirred mixture of the following formulation 7 is added to the stirred mixture of the silicone resin of the following formulation 6 by 10 mass% with respect to the mass of the silicone resin alone, and the vinyl chloride resin is uniformly dispersed. Liquid 3 was obtained. The fabric was immersed in a bath filled with the resin mixture liquid 3, and the fabric was completely impregnated with the resin mixture liquid 3. Next, the excess resin mixture liquid 3 on both sides of the fabric was scraped off with a doctor blade and heated in an electric furnace at 180 ° C. for 10 minutes to obtain a sheet in which a flame retardant resin was coated on both sides of the fabric. Next, the resin mixture liquid 3 is coated on one surface of the PET film at a thickness of 0.12 mm, and this is overlaid on one side of the previously prepared sheet and heated in an electric furnace at 180 ° C. for 10 minutes to obtain the resin mixture liquid 3 After solidifying, the PET film was removed to form a smooth flame retardant resin coating layer (construction appearance side). When this flame retardant resin coating layer is observed with a microscope, the vinyl chloride resin constitutes an island component with a visible light transmittance of 80%, and the silicone resin constitutes a sea component with a light diffusing semi-transmissivity (transmittance of 48%). The ratio of the visible light transmittance between the island component and the sea component was 3: 1.8. Next, in the same manner as in Example 1, an ink jet printing layer was provided on the flame retardant resin coating layer, and then an overlaminate film (IJ4114: fluorinated resin: adhesive layer of Sumitomo 3M Limited) was used as an overlay layer. 70 μm) was used to coat the entire surface of the printed layer having a size of 150 cm × 150 cm, and the thickness ratio of the fiber composite substrate to the overlay layer was set to 10: 1.75. Furthermore, the adhesive / protective layer of Formulation 3 is formed at 1.5 g / m ² , and the photocatalytic antifouling layer of Formulation 4 is further formed at 1.5 g / m ² on the visible light transmittance of 36%, A fiber composite substrate having a total thickness of 0.4 mm was obtained. Using this, an internally illuminated signboard model was produced.

<Formulation 6>
Trademark: Shirasukon RTV4086A
(2-component addition reaction curable silicone resin: active ingredient 100%: manufactured by Dow Corning Asia)
50 parts by mass Trademark: Shirasukon RTV4086B
(2-component addition reaction curable silicone resin: active ingredient 100%: manufactured by Dow Corning Asia)
50 parts by weight Magnesium hydroxide (flame retardant) 20 parts by weight Hydrotalcite (flame retardant) 5 parts by weight

<Formulation 7>
Emulsion polymerization polyvinyl chloride resin (degree of polymerization 1700) 100 parts by weight Dioctyl phthalate (plasticizer) 40 parts by weight
Tricresyl phosphate (plasticizer) 40 parts by weight zinc stearate (stabilizer) 2 parts by weight barium stearate (stabilizer) 2 parts by weight
1 parts by weight of light diffusing agent (calcium carbonate: average particle size 1 μm)

[Example 4]
To the hot-melt kneaded product of the soft vinyl chloride resin of the following formulation 8, 20% by mass of the hot-melt kneaded product of the polyethylene resin of the following formulation 9 with respect to the mass of the vinyl chloride resin alone, and hot-melt kneaded with a Banbury mixer Polyethylene resin was uniformly dispersed to obtain an incompatible resin mixture 4. This resin mixture 4 was passed through four calendar rolls set at 180 ° C. and molded into a film having a thickness of 0.12 mm. This film was laminated on both sides of the fabric as a flame retardant resin coating layer to obtain a laminate sheet. When this flame-retardant resin coating layer is observed with a microscope, the polyethylene resin constitutes an island component with a visible light transmittance of 77%, and the soft vinyl chloride resin has a sea component with a light diffusing semi-transmissivity (light transmittance of 49%). The ratio of the visible light transmittance between the island component and the sea component was 3: 1.909. Next, in the same manner as in Example 1, an ink jet printing layer was provided on the flame retardant resin coating layer, and then an overlaminate film (IJ4141: acrylic resin: adhesive layer of Sumitomo 3M Limited) was used as an overlay layer. 90 μm) was used to coat the entire surface of the printed layer having a size of 150 cm × 150 cm, and the thickness ratio of the fiber composite substrate to the overlay layer was 10: 2.25. Furthermore, the adhesive / protective layer of Formulation 3 was formed on one side at 1.5 g / m ² , and the photocatalytic antifouling layer of Formulation 4 was further formed at 1.5 g / m ² on it, and the visible light transmittance was 35%. A fiber composite substrate having a total thickness of 0.4 mm was obtained. Using this, an internally illuminated signboard model was produced.

<Formulation 8>
Polyvinyl chloride resin (degree of polymerization 1300) 100 parts by weight Dioctyl phthalate (plasticizer) 35 parts by weight Tricresyl phosphate (plasticizer) 30 parts by weight Antimony oxide (flame retardant) 10 parts by weight Molybdenum oxide (flame retardant) 5 parts by weight
Melamine cyanurate 10 parts by mass (Nissan Chemical Co., Ltd. flame retardant: trade name MC-640)
Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight

<Formulation 9>
Low-density polyethylene resin (density 0.945) 100 parts by weight Light diffusing agent (calcium carbonate: average particle diameter 1 μm) 1 part by weight

[Example 5]
To the hot melt kneaded product of the soft fluororesin of the following formulation 10 is added 10% by mass of the hot melt kneaded product of the vinyl chloride resin of the following blend 11 with respect to the mass of the soft fluororesin alone, followed by hot melt kneading with a Banbury mixer. The vinyl resin was uniformly dispersed to obtain an incompatible resin mixture 5. The resin mixture 5 was passed through four calendar rolls set at 180 ° C. to form a film having a thickness of 0.12 mm. This film was laminated on both sides of the fabric as a flame retardant resin coating layer to obtain a sheet. When this flame retardant resin coating layer is observed with a microscope, the vinyl chloride resin constitutes an island component with a visible light transmittance of 78%, and the soft fluororesin has a sea component with a light diffusive translucency (light transmittance of 47%). The ratio of the visible light transmittance between the island component and the sea component was 3: 1.807. Next, in the same manner as in Example 1, an ink jet printing layer was provided on the flame retardant resin coating layer, and then an overlaminate film (IJ4114: fluorinated resin: adhesive layer of Sumitomo 3M Limited) was used as an overlay layer. 70 μm) was used to coat the entire surface of the printed layer having a size of 150 cm × 150 cm, and the thickness ratio of the fiber composite substrate to the overlay layer was set to 10: 1.75. Furthermore, the adhesive / protective layer of Formulation 3 is formed on one side at 1.5 g / m ^2, and the photocatalytic antifouling layer of Formulation 4 is further formed at 1.5 g / m ² on the visible light transmittance of 40%, A fiber composite substrate having a total thickness of 0.4 mm was obtained. Using this, an internally illuminated signboard model was produced.

<Formulation 10>
Soft fluororesin (ethylene tetrafluoride-propylene hexafluoride-vinylidene fluoride terpolymer resin)
100 parts by mass Antimony oxide (flame retardant) 10 parts by mass Molybdenum oxide (flame retardant) 10 parts by mass

<Formulation 11>
Polyvinyl chloride resin (degree of polymerization 1300) 100 parts by weight Dioctyl phthalate (plasticizer) 35 parts by weight Tricresyl phosphate (plasticizer) 30 parts by weight
Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by weight
1 parts by weight of light diffusing agent (titanium oxide particles: average particle size 0.4 μm)

  Each of the internally illuminated electric signboard models of Examples 1 to 5 had high visible light transmittance, and had sufficient light quantity and luminance as an internally illuminated electric signboard. In these internally illuminated signboard systems, the presence of photogens such as internally arranged fluorescent lamps is hardly visible in observation from a position 3 m away, and the shadow marks caused by the cloth included in the internally illuminated signboard sheet It was excellent in light diffusing concealing properties, such as being invisible. In addition, in the internally illuminated electric signboard models of Examples 1 to 5, the visible light transmittance of ink jet printing was good, and it had sufficient brightness and color developability. Moreover, in the cone calorimeter burning test, the internally illuminated electric signboards of Examples 1 to 5 all satisfied the incombustible condition even in the state having the overlay layer on the entire surface of the test body.

[Comparative Example 1]
In Example 1, all the designs were the same as Example 1 except that the combined use of the vinyl ester resin stirring mixture of Formulation 2 was omitted. In Comparative Example 1, the sea-island structure was not formed in the flame retardant resin coating layer, and the entire flame retardant resin coating layer was a light diffusing semi-transmissive with a transmittance of 48% by the soft vinyl chloride resin. The thickness ratio between the fiber composite substrate and the overlay layer is 10: 2.25. Using this, an internally illuminated signboard model was produced.

[Comparative Example 2]
Example 1 is the same as Example 1 except that the island component formation is blended 1 and the sea component formation is blended 2 and the island component includes a flame retardant and the sea component does not include a flame retardant. Same design. When this flame retardant resin coating layer is observed with a microscope, the vinyl ester resin constitutes a sea component with a visible light transmittance of 82%, and the soft vinyl chloride resin has an island component with a light diffusive translucency (transmittance of 48%). The ratio of the visible light transmittance between the island component and the sea component was 3: 5.125. Moreover, the thickness ratio of the fiber composite substrate and the overlay layer is 10: 2.25. Using this, an internally illuminated signboard model was produced.

[Comparative Example 3]
In Example 1, Formula 1 was changed to Formula 12 below, Formula 2 was changed to Formula 13 below, and all the designs were the same as Example 1 except that the flame retardant component and the light diffusing agent component were replaced. When this flame retardant resin coating layer is observed with a microscope, the vinyl ester resin constitutes an island component with a visible light transmittance of 46%, and the soft vinyl chloride resin has a sea component with a light diffusing semi-transmissivity (transmittance of 86%). The ratio of the visible light transmittance between the island component and the sea component was 3: 5.508. Moreover, the thickness ratio of the fiber composite substrate and the overlay layer is 10: 2.25. Using this, an internally illuminated signboard model was produced.

<Formulation 12>
Emulsion polymerization polyvinyl chloride resin (degree of polymerization 1700) 100 parts by weight Dioctyl phthalate (plasticizer) 40 parts by weight Tricresyl phosphate (plasticizer) 40 parts by weight Zinc stearate (stabilizer) 2 parts by weight Barium stearate (stabilizer) 2 parts by mass
1 parts by weight of light diffusing agent (calcium carbonate: average particle size 1 μm)

<Formulation 13>
100 parts by mass of vinyl ester resin (trade name: Neopole 8319, manufactured by Nippon Iupika Co., Ltd.)
Curing agent 1 part by mass (di- (4-tert-butylcyclohexyl) peroxydicarbonate)
Antimony oxide (flame retardant) 15 parts by mass Molybdenum oxide (flame retardant) 5 parts by mass
10 parts by mass of melamine cyanurate (Nissan Chemical Co., Ltd. flame retardant: trade name MC-640)

[Comparative Example 4]
In the same manner as in Example 1, a fiber composite substrate by impregnation with the incompatible resin mixture liquid 1 was produced. However, the “resin mixture liquid 1 was coated on a surface of the PET film with a thickness of 0.12 mm on one surface of the PET film, which was overlaid on one surface of the previously prepared sheet, and heated in an electric furnace at 180 ° C. for 5 minutes. The step of solidifying the resin mixture liquid 1 and then removing the PET film to form a smooth flame-retardant resin coating layer (construction appearance side) was omitted. When this flame retardant resin coating layer is observed with a microscope, the vinyl ester resin constitutes an island component with a visible light transmittance of 82%, and the soft vinyl chloride resin has a sea component with a light diffusing semi-transmissivity (transmittance of 48%). The ratio of the visible light transmittance between the island component and the sea component was 3: 1.756. Next, as in Example 1, an inkjet printing layer is provided on the side of the external appearance observation of the flame retardant resin coating layer, and the entire surface of the printing layer is covered with the same overlay layer as in Example 1, and the thickness ratio between the fiber composite substrate and the overlay layer is determined. 10: 3.21. Further, an adhesive / protective layer was formed on one side, and a photocatalytic antifouling layer was further formed thereon to obtain a fiber composite substrate having a visible light transmittance of 45% and a total thickness of 0.28 mm. Using this, an internally illuminated signboard model was produced.

[Comparative Example 5]
In the same manner as in Example 4, a fiber composite base material by laminating the incompatible resin mixture 4 was produced. However, the laminate sheet was obtained by laminating the 0.12 mm thick film of Example 4 on the cloth only on one side. When this flame-retardant resin coating layer is observed with a microscope, the polyethylene resin constitutes an island component with a visible light transmittance of 77%, and the soft vinyl chloride resin has a sea component with a light diffusing semi-transmissivity (light transmittance of 49%). The ratio of the visible light transmittance between the island component and the sea component was 3: 1.909. Next, as in Example 1, an inkjet printing layer is provided on the side of the external appearance observation of the flame retardant resin coating layer, and the entire surface of the printing layer is covered with the same overlay layer as in Example 1, and the thickness ratio between the fiber composite substrate and the overlay layer is determined. 10: 3.21. Further, the same adhesive / protective layer as in Example 4 was formed on one side, and a photocatalyst antifouling layer was further formed thereon to obtain a fiber composite substrate having a visible light transmittance of 55% and a total thickness of 0.28 mm. Using this, an internally illuminated signboard model was produced.

  The internally illuminated electric signboard model of Comparative Example 1 was insufficient for obtaining the original color luminance of ink jet printing due to insufficient light expansion and transmission and somewhat darker illumination. The internally illuminated signboard models of Comparative Examples 2 and 3 have a flame retardant resin coating layer that contains a flame retardant in the island component and no flame retardant in the sea component, resulting in insufficient flameproofness and non-flammability. Could not fit the test. In the internally illuminated electric signboard models of Comparative Examples 4 and 5, the ratio of the overlay layer to the thickness of the fiber composite base material used in the internally illuminated electric signboard model increases, and the fiber composite base material and the overlay Since the thickness ratio with the layer exceeded 10: 2.5, the flameproofness was insufficient and could not be adapted to the incombustibility test.

  According to the present invention, it is a flexible fiber composite film material that can be suitably used for internally-lit signboard applications, has high light transmission and moderate light diffusibility, and in particular has a printed layer on the entire surface. A film material for internally illuminated signboards that has a high degree of nonflammability characteristics that enables it to conform to the nonflammability test (Building Standards Act) even in the usage form that has an overlay film that protects the printed layer. And a non-combustible internally illuminated signage system. The film material of the present invention can satisfy the requirements of non-combustible materials stipulated in the revised Building Standards Law while satisfying the requirements of signboard designs by individual users, so it is a sufficient measure to prevent the spread of fire spread in downtown areas. obtain. Therefore, the incombustible interior-lit signboard of the present invention, regardless of small to large installation, convenience store eaves sign, restaurant chain eaves sign, restaurant outdoor signage, building rooftop advertising signage, underground street wall It can be widely used for advertising billboards.

1: Woven fabric 2: Flame retardant resin coating layer (sea-island structure)
2-1: Flame retardant resin coating layer exposed portion 3: Fiber composite base material 4: Print layer 5: Overlay layer 6: Photocatalytic antifouling layer 7: Light diffusive transparent sheet
8: Internally illuminated signboard housing 9: Light source (fluorescent lamp)
10: Interior illumination type electric signboard system 11: Island component 12: Sea component

Claims (4)

  In a fiber composite base material provided with a flame retardant resin coating layer on one side or more of a fabric formed by knitting and weaving inorganic filament bundles without gaps, on the entire surface of at least one layer of the flame retardant resin coating layer, or A light diffusive and transparent sheet provided with a print layer partially or scatteredly, and provided with an exposed layer of the flame retardant resin coating layer and an overlay layer that covers and protects the print layer, The flame retardant resin coating layer has a sea-island structure formed by incompatible mixing of two or more types of synthetic resins, and in this sea-island structure, the island component does not contain a flame retardant and has light diffusion permeability. And the sea component is composed of a light diffusing semipermeable structure containing a flame retardant, and the thickness ratio of the fiber composite substrate and the overlay layer is in the range of 10: 1 to 10: 2.5 It is characterized by being Non-combustible Terushiki signboard.   The incombustible internally illuminated signboard according to claim 1, wherein a ratio of visible light transmittance (JIS-Z8722) between the island component and the sea component is within a range of 3: 2 to 3: 1.   The incombustible internally illuminated signboard according to claim 1 or 2, further comprising a photocatalytic antifouling layer as an outermost layer of the light diffusing and permeable sheet. When the light diffusible sheet is used as a test body and the radiant heat from a radiant electric heater is applied to the light diffusible sheet in a cone calorimeter test method (ASTM-E1354) at 50 kW / m ² , The total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less, and has a combustion characteristic that the maximum heat generation rate does not exceed 200 kW / m ² for 20 minutes after the start of heating for 10 seconds or more. The incombustible internally illuminated signboard according to any one of?