JP2005119260A - Fire retardant film, interior material for house using it, electric product or printing film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fire retardant film reducing the load to environment while keeping the fundamental capacity of a base material film and capable of imparting fire retardancy to an arbitrary film. <P>SOLUTION: A barrier inorganic matter layer 25 is provided at least on one side of the base material film 11. The barrier inorganic matter layer 25 is an inorganic oxide layer of silicon oxide, aluminum oxide, titanium oxide or the like, an inorganic oxynitride layer of silicon oxynitride, aluminum oxynitride, titanium oxynitride or the like or a layer of an inorganic oxycarbide, inorganic nitrocarbide or inorganic oxynitride carbide and characterized in that the thickness thereof is 5-500 nm, the moisture permeability according to JIS-K 7129 thereof is 10 g/m<SP>2</SP>day or below and/or the oxygen permeability thereof according to JIS-K 7126 is 10 cm<SP>3</SP>/m<SP>2</SP>day and corresponds to UL 94 standard VTM-0 to 1. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a flame retardant film, and more specifically, lowers physical properties such as mechanical strength, transparency, and the appearance of a substrate film without significantly impairing the appearance, and reduces environmental burden and imparts flame retardancy. It is related with the flame-retardant film for doing.

  In the present specification, “ratio”, “part”, “%” and the like indicating the composition are based on mass unless otherwise specified, and the “/” mark indicates that they are integrally laminated. “CVD” is an abbreviation, functional expression, common name, or industry term for “chemical vapor deposition” and “PET” for “polyethylene terephthalate”.

(Background Technology) In recent years, with the improvement of social safety awareness and the construction of advanced social infrastructure such as high-rise buildings and high-speed railways, more diverse safety has been demanded in the material field. For example, wallpaper for indoors of high-rise buildings and printing sheets used for advertising purposes in railway vehicles have been required to be flame retardant. For flame retardancy, flame retardants are mixed in thermoplastic resins, etc., but halogen-based flame retardants that are normally used do not contain halogen-based gases such as hydrogen bromide or hydrogen chloride during molding into sheets or incineration of molded products. It has been pointed out that corrosion of equipment and effects on the human body have been pointed out, and there is also a problem of environmental pollution such as generation of dioxins.
The flame retardant film is required to have properties that are imparted with flame retardancy and have few environmental problems without significantly deteriorating the physical properties such as mechanical strength, transparency, and appearance of the base film. Yes.

(Prior Art) Conventionally, such a flame-retardant sheet or flame-retardant film is obtained by melt-kneading a halogen-based, phosphorus-based, or inorganic flame retardant into a thermoplastic resin or a thermosetting resin, and a melt extrusion molding method. It is manufactured by being formed into a sheet shape with, or a thermoplastic resin or a thermosetting resin added with the above flame retardant is provided on a base sheet (for example, See Patent Documents 1 to 4.) However, halogen-based flame retardants have been pointed out to cause corrosion of equipment and effects on human bodies due to the generation of halogen-based gases such as hydrogen bromide and hydrogen chloride during molding into sheets and incineration of molded products. There is also the problem of environmental pollution. For this reason, phosphorous and inorganic flame retardants are used as an alternative to halogen flame retardants. Phosphorus flame retardants are also suspected of generating environmental pollutants during incineration. New problems such as deterioration of mechanical properties, transparency, and markedly impaired appearance when used as a flame retardant sheet are not obtained unless it is added excessively more than halogen and phosphorus flame retardants. There is a point.
Moreover, the wallpaper and the sheet | seat for printed materials which provided the inorganic film | membrane on the one surface of the base film and made it flame-retardant are known (for example, refer patent document 5). However, only inorganic oxide films such as oxides, fluorides and metals and metal oxide sols (so-called sol-gel method) are disclosed as inorganic films. Furthermore, there is no description or suggestion about applying such a sheet to the improvement of flame retardancy, focusing on its gas permeability.

JP-A-48-90348 JP 52-47891 A JP 47-195142 A Japanese Patent Laid-Open No. 62-32955 JP 2003-33986 A

  Accordingly, the present invention has been made to solve such problems. Its purpose is to provide a vacuum thin film layer with a barrier property on the base film, so that the basic performance of the film is maintained and the flame retardant film can impart flame retardancy to any film with little impact on the environment. Is to provide.

To solve the above problem,
The flame retardant film according to the invention of claim 1 is a flame retardant film having an inorganic layer on at least one surface of a base film directly or through another layer, wherein the inorganic layer has a barrier property. An inorganic oxide layer, an inorganic nitride layer, or an inorganic oxynitride layer is used.
In the flame-retardant film according to the invention of claim 2, the material of the inorganic layer is made of silicon oxide, aluminum oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride, silicon oxynitride, aluminum oxynitride, or titanium oxynitride. It is either, and it is made so that thickness is 5-500 nm.
The flame retardant film according to the invention of claim 3 is an inorganic oxide carbide, inorganic nitride carbide or inorganic further containing carbon in the inorganic layer of the flame retardant film according to claim 1 or 2. It is like oxynitride carbide.
According to a fourth aspect of the present invention, there is provided a flame retardant film in which the material of the inorganic layer is silicon oxide carbide, aluminum oxide carbide, titanium oxide carbide, silicon nitride carbide, aluminum nitride carbide, titanium nitride carbide, silicon oxynitride carbide, silicon oxynitride It is either aluminum carbide or titanium oxynitride carbide and has a thickness of 5 to 500 nm.
The flame retardant film according to the invention of claim 5 is the flame retardant film according to any one of claims 1 to 4, wherein the moisture permeability according to JIS-K7129 is 10 g / m ² day or less and / or JIS. The oxygen permeability according to -K7126 is set to be 10 cm ³ / m ² day or less.
The flame-retardant film according to the invention of claim 6 is the flame-retardant film according to any one of claims 1 to 5 so as to have flame resistance equivalent to UL94 standard VTM-0.
A flame-retardant interior material for a house, an electrical product or a printing film according to the invention of claim 7 is obtained by using the flame-retardant film according to any one of claims 1 to 6.

(Points of the Invention) The inventors of the present invention have made extensive studies and covered the surface of the base film with an inorganic oxide layer, an inorganic nitride layer or an inorganic oxynitride layer, so that the base film of the inner layer can be obtained at high temperatures. Or the thermal adhesive layer is gradually heated to generate combustible gas,
(1) An inorganic oxide layer, an inorganic nitride layer, or an inorganic oxynitride layer becomes a barrier that shields heat and oxygen from entering from outside, and delays the generation time thereof.
(2) In order to suppress decomposition of the base film due to invading oxygen, and for excellent flame retardancy, even when a flame retardant is contained in other layers laminated as necessary, the content is reduced. Can be reduced. While maintaining the basic performance of the base film, a flame-retardant film is obtained that has a low environmental load, is excellent in environmental suitability, and has flame retardancy that can impart flame retardancy to any film. The inorganic film used in the present invention can be peeled off by chemical treatment. In particular, the inorganic substance containing silicon and aluminum used in the present invention is a hot alkali (for example, 1N aqueous sodium hydroxide solution at 60 ° C. ) Can be peeled off, and the substrate film can be recycled and reused instead of being incinerated.
(3) The generated combustible gas is shielded by an inorganic oxide layer, an inorganic nitride layer, or an inorganic oxynitride layer and is difficult to be volatilized to the outside, and an effect of suppressing the generation of combustible gas due to ignition and decomposition is found. It came.
For this reason, even if ignition, ignition, combustion, and fire spread are significantly delayed, and even if it is ignited and burnt, the inorganic oxide layer, the inorganic nitride layer, or the inorganic oxynitride layer may be partially or externally contacted. Shut off, reduce oxygen supply and prevent fire spread. Furthermore, because of the excellent flame retardancy, the content can be reduced even when the flame retardant is contained in other layers laminated as necessary. While maintaining the basic performance of the base film, a flame-retardant film is obtained that has a low environmental load, is excellent in environmental suitability, and has flame retardancy that can impart flame retardancy to any film. The above description of the inorganic oxide layer, the inorganic nitride layer, or the inorganic oxynitride layer includes an inorganic oxide layer containing carbon, an inorganic nitride layer, or an inorganic oxynitride layer.

According to the first aspect of the present invention, the flame retardant capable of remarkably delaying the combustion and its expansion and partially blocking the contact with the outside, reducing the supply of oxygen, and preventing the spread of the fire even in a burnt state. A functional film is provided.
According to the second aspect of the present invention, the inorganic oxide layer, the inorganic nitride layer, or the inorganic oxynitride layer formed by a vacuum film-forming method becomes a dense continuous layer having a small and no gap and excellent in flame retardancy. A flame retardant film is provided.
According to the third aspect of the present invention, productivity is high by continuous production by the CVD method, and the inorganic oxide layer, inorganic nitride layer, or inorganic oxynitride layer containing carbon is dense and rich in flexibility with few gaps. A flame retardant film having a continuous layer and excellent adhesion and flame retardancy is provided.
According to the fourth aspect of the present invention, the inorganic oxide carbide layer, inorganic nitride carbide layer or inorganic oxynitride carbide layer formed by a vacuum film-forming method is a dense continuous layer with a small gap and excellent in flame retardancy. A flame retardant film is provided.
According to the fifth aspect of the present invention, the flame retardant film is excellent in flame retardancy that suppresses generation of flammable gas with high productivity in continuous production, low cost, low moisture permeability and / or oxygen permeability. Is provided.
According to the sixth aspect of the present invention, a flame retardant film having a flame retardance evaluation conforming to UL's “Vertical Combustion Test for Thin Materials” corresponds to VTM-0 and excellent in reliability is provided.
According to the present invention of claim 7, there is provided a flame-retardant residential interior material, electrical product or printing film which does not discharge harmful substances such as chlorine and dioxin even when discarded and incinerated.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view of a flame retardant film showing one embodiment of the present invention.
FIG. 2 is an explanatory diagram of a CVD apparatus that can be suitably used in the present invention.

  (Invention of Material) The flame retardant film 10 of the present invention has the base film 11 and the inorganic layer 25 on one side of the base film 11 as necessary, and is provided on the other side as needed. If it is on both sides, more effective flame retardancy can be expressed. The inorganic layer 25 is composed of an inorganic oxide layer, an inorganic nitride layer, or an inorganic oxynitride layer, and is preferably silicon oxide, aluminum oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride, oxynitride Either silicon, aluminum oxynitride, or titanium oxynitride. In addition, a carbon-containing inorganic oxide layer, inorganic nitride layer, or inorganic oxynitride film layer is also suitable, and is referred to as an inorganic oxycarbide layer, an inorganic oxycarbide layer, or an inorganic oxynitride carbide layer in this specification. To do.

(Substrate film) Next, materials used in the present invention will be described.
First. As the base film 11, various materials can be applied depending on the use as long as they have excellent mechanical strength, heat resistance, chemical resistance, solvent resistance, flexibility, electrical insulation, and the like. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, nylon 6 , Polyamide resins such as nylon 66 and nylon 610, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, acrylic resins such as polyacrylate, polymethacrylate and polymethyl methacrylate, and vinyl resins such as polyvinyl chloride , Polystyrene, high impact polystyrene, AS resin, ABS resin and other styrenic resins, cellophane, cellulose triacetate, cellulose diacetate, nitrocellulose, etc. Amorphous polyolefin resin (APO) such as glass film, polycarbonate, cyclic polyolefin, polyvinyl alcohol (PVA) resin, polyvinyl alcohol resin such as ethylene-vinyl alcohol copolymer (EVOH), polyimide ( PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polyvinyl butyrate (PVB) resin, polyarylate (PAR) resin Poly resin, etc. can be applied.

  The base film 11 may be a copolymer resin containing these resins as a main component, a mixture (including alloy), or a laminate including a plurality of layers. Moreover, although it may be a stretched film or an unstretched film, a film stretched in a uniaxial direction or a biaxial direction for the purpose of improving strength is preferred. As the base film 11, polyalkylene terephthalate such as polyethylene terephthalate and polyethylene naphthalate can be preferably used from the viewpoint of mechanical strength, heat resistance, insulation, cost, etc., and polyethylene terephthalate is most suitable. The resin film may contain additives such as a filler, a plasticizer, and an antistatic agent as necessary. As the filler, moisture-resistant pigments such as silica and calcium carbonate can be applied. As the antistatic agent, nonionic surfactants, anionic surfactants, cationic surfactants, polyamides, acrylic acid derivatives, and the like can be applied. The thickness of the substrate film 11 is not particularly limited, but is usually about 1 μm to 1 mm, preferably about 5 μm to 500 μm, 10 μm to 200 μm.

(Surface Treatment of Base Film) An inorganic layer 25 is provided on one surface of the base film 11, and the inorganic oxide, inorganic nitride or inorganic oxide described later is provided on the surface of the base film 11 on which the inorganic layer 25 is provided. In order to improve the tight adhesion with the nitride film, etc., if necessary, a desired surface treatment layer (also referred to as an easy adhesion treatment) or a cleaning treatment with plasma or the like may be performed in advance.
(Surface treatment) As the surface treatment layer, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed and provided. In addition, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer, or a deposition anchor coat agent layer is optionally formed to perform surface treatment. It can also be a layer.
Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, A resin composition containing a polyolefin resin such as polyethylene or polypropylene, or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used.

(Inorganic layer) The inorganic layer 25 is composed of an inorganic oxide layer, an inorganic nitride layer, or an inorganic oxynitride layer, and is preferably silicon oxide, aluminum oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride. , Silicon oxynitride, aluminum oxynitride, or titanium oxynitride. In addition, a carbon-containing inorganic oxide layer, inorganic nitride layer, or inorganic oxynitride film layer is also suitable, and is referred to as an inorganic oxycarbide layer, an inorganic oxycarbide layer, or an inorganic oxynitride carbide layer in this specification. To do.
That is, as an inorganic substance, inorganic oxide (MOx), inorganic nitride (MNy), inorganic oxide carbide (MOxCz), inorganic nitride carbide (MNyCz), inorganic oxynitride (MOxNy), inorganic oxynitride carbide (MOxNyCz) Preferred M is Si, Al, or Ti.

(Formation of inorganic layer) Next, the inorganic layer 25 will be described. As a method for forming the inorganic layer 25, there are, for example, a vacuum deposition method, a chemical vapor deposition method, a physical vapor deposition method, a sol-gel method, and the like. However, in the present invention, it is preferable to apply a vacuum film formation method such as a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition (CVD) method, or a physical vapor deposition (PVD) method. Particularly preferred is a plasma CVD method.
According to the vacuum film-forming method, it is possible to form a continuous layer that is dense and has few gaps, and thus has low moisture permeability and / or oxygen permeability and excellent flame retardancy that suppresses the generation of flammable gases. In addition, continuous production is highly productive and low cost.
The inorganic layer 25 in the present invention may be a single layer film composed of one layer of the inorganic layer 25, or a multilayer film or a composite film composed of two or more layers, alone or in combination. Moreover, when providing the inorganic substance layer 25 on both surfaces, after forming in one surface, it should just form in the other surface similarly.

(Chemical Vapor Deposition CVD) Vacuum deposition methods such as vacuum deposition, sputtering, or PVD are well known to those skilled in the art, and the preferred chemical vapor deposition and ion plating methods of the present invention are used for inorganic layers. 25 will be further described. Examples of the inorganic film formed by chemical vapor deposition include chemical vapor deposition such as plasma chemical vapor deposition, thermal chemical vapor deposition, photochemical vapor deposition, and catalytic chemical vapor deposition (Cat-CVD). A growth method (Chemical Vapor Deposition method, CVD method) or the like can be applied. Specifically, on one surface of the base film 11, an evaporation monomer gas such as an organosilicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen Inorganic oxide or inorganic nitride such as silicon oxide, aluminum oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride, silicon oxynitride, aluminum oxynitride, or titanium oxynitride using oxygen gas as the supply gas Alternatively, an inorganic oxycarbide or inorganic nitride carbide that can form an inorganic oxynitride film and further contains carbon in the inorganic layer using a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like. Alternatively, an inorganic oxynitride carbide film can be formed. In addition, the above inorganic substance not containing carbon can be produced by an ion plating method. The non-carbon-containing inorganic material produced by this production method can have sufficient flexibility and adhesion as well as the CVD method, and can be suitably used.
As a low-temperature plasma generator, for example, generators such as high-frequency plasma, pulse wave plasma, and microwave plasma can be used. In order to obtain highly active and stable plasma, a high-frequency plasma generator is used. It is preferable to do.

FIG. 2 is an explanatory diagram of a CVD apparatus that can be suitably used in the present invention.
An example of the method of forming the inorganic 25 film by the low-temperature plasma chemical vapor deposition (referred to as plasma CVD) that can be suitably used will be described. The plasma CVD apparatus 200 includes a vacuum container 210, a gas supply unit, a vacuum pump, a power source, and a control device (not shown). The vacuum container 210 includes a paper feeding unit 211, a film forming unit 213, and a winding unit 215. ing. The film forming unit 213 includes a plurality of chambers such as a chamber 221, b chamber 223, and c chamber 225 depending on the inorganic oxide to be formed. The base film 11 is fed out from the unwinding roll disposed in the paper supply unit 211 in the vacuum vessel 210, cooled at a predetermined speed through the guide roll, and conveyed onto the circumferential surface of the electrode drum 231. The gas supply unit supplies oxygen gas, inert gas, a monomer gas such as an organosilicon compound, and the like from a gas supply device, a raw material volatilization supply device, etc., and does not adjust the single or mixed gas composition thereof. Into the vacuum vessel 210.

FIG. 2 shows an example using three kinds of gases, and the gas composition is introduced into the vacuum vessel 210 through the raw material supply nozzles 251, 253 and 255. The substrate film 11 transported on the peripheral surface of the cooling and electrode drum 221 is irradiated with plasma generated by glow discharge plasma, and an inorganic oxide such as silicon oxide, an inorganic nitride, or an inorganic oxynitride film Is formed (formed). At that time, predetermined power is applied to the cooling, electrode drum 221, a chamber electrode 251, b chamber electrode 253, and c chamber electrode 255 from a power source arranged outside the vacuum vessel 210, Further, a magnet or the like may be disposed in the vicinity of the cooling and electrode drum 221 to promote the generation of plasma. Next, the base film 11 on which the inorganic oxide, inorganic nitride, or inorganic oxynitride film is formed as described above is wound up through a guide roll, and the inorganic oxide, inorganic nitride, or inorganic oxide is formed by a plasma CVD method. A nitride film can be formed.
The inorganic oxide, inorganic nitride, or inorganic oxynitride film is not only a single layer of inorganic oxide, inorganic nitride, or inorganic oxynitride film, but also a multilayer film in which two or more layers are stacked. But you can.

  Moreover, the material to be used can also be used by 1 type, or 2 or more types of mixtures, and can also comprise the inorganic substance film mixed with the dissimilar material. By selecting a material to be used, an inorganic layer 25 such as an inorganic oxide layer, an inorganic nitride layer, an inorganic oxynitride layer, an inorganic oxycarbide layer, an inorganic oxycarbide layer, or an inorganic oxynitride carbide layer can be formed. it can.

  In addition, about the composition of the inorganic substance layer 25, surface analysis apparatuses, such as a photoelectron spectrophotometer, an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), are used, for example. By performing elemental analysis of the silicon oxide film using a method of analyzing by ion etching in the depth direction, the above-described composition ratio and physical properties can be confirmed.

  (Inorganic oxide) As the inorganic oxide film, basically any thin film on which a metal oxide is deposited can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) and other metal oxides An inorganic oxide film can be used, and an oxide of a metal such as silicon (Si), aluminum (Al), titanium (Ti), or the like is preferable. The inorganic oxide film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc., and its notation is, for example, MOx (provided that the formula is SiOx, AlOx, MgOx, etc.) M represents a metal element, and the value of X varies depending on the metal element.) Moreover, as a range of said x value, silicon (Si) is 0.1-2, aluminum (Al) is 0.1-1.5, magnesium (Mg) is 0.1-1, Calcium (Ca) is 0.1 to 1, potassium (K) is 0.1 to 0.5, tin (Sn) is 0.1 to 2, and sodium (Na) is 0.1 to 0. 5, Boron (B) is 0.1 to 1, 5, Titanium (Ti) is 0.1 to 2, Lead (Pb) is 0.1 to 1, Zirconium (Zr) is 0.1 to 2 Yttrium (Y) can take a value in the range of 0.1 to 1.5. In the above formula, when x = 0, it is a complete metal and is not transparent and cannot be used. The upper limit of the range of x is a completely oxidized value. Preferred metal oxides of the present invention are silicon (Si), aluminum (Al), and titanium (Ti) oxides. The value of x is, for example, silicon (Si) 1.0-2. If 0 is aluminum (Al), 0.5 to 1.5 can be used, and if titanium (Ti), 1.3 to 2.0 can be used.

In the present invention, the film thickness of the inorganic film varies depending on the type of metal or metal oxide to be used, for example, about 1 to 1000 nm, preferably 5 to 5 nm. It is about 500 nm, more preferably in the range of 20 to 200 nm. Above this range, cracks and the like are likely to occur in the film, and when it is less than this range, it becomes difficult to achieve a flame-retardant effect.
The thickness of the inorganic oxide film such as silicon oxide is increased by increasing the deposition rate of the inorganic oxide film, that is, by increasing the amount of monomer gas and oxygen gas or by decreasing the traveling speed of the substrate. Can be selected as appropriate. The film thickness can be measured by, for example, a fundamental parameter method, an ellipsometer UVISEL ™ (trade name) manufactured by JOBIN YVON, using a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. .

  (Aluminum oxide) An inorganic oxide film of aluminum oxide is formed by forming (forming or chemically reacting) aluminum oxide or metal aluminum in oxygen gas, and the reaction product is formed on one surface of the base film. The aluminum oxide represented by the general formula AlOx (where x represents a number of 0.5 to 1.5) is usually formed. It is a continuous thin film mainly composed of

  (Titanium oxide) Inorganic oxide film of titanium oxide is formed by forming titanium oxide or titanium metal in oxygen gas (formation or chemical reaction), and the reaction product is one side of the base film. Titanium oxide represented by the general formula TiOx (where x represents a number from 1.3 to 2.0) is usually formed. It is a continuous thin film mainly.

  (Inorganic nitride) As the inorganic nitride film, a thin film in which a metal nitride is basically deposited can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium Of metal nitrides such as (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) An inorganic nitride film can be used, and a nitride of a metal such as silicon (Si), aluminum (Al), titanium (Ti), or the like is preferable. The inorganic nitride film can be referred to as a metal nitride such as silicon nitride, aluminum nitride, titanium nitride, and the like, and its notation is, for example, MNy such as SiNy, AlNy, TiNy, etc. M represents a metal element, and the value of y is represented by a range depending on the metal element). Further, the range of the y value is y = 0.1 to 1.3 for silicon (Si), y = 0.1 to 1.1 for aluminum (Al), and y = 0 for titanium (Ti). 0.1 to 1.3 and tin (Sn) can take values in the range of y = 0.1 to 1.3. In the above formula, when y = 0, it is a complete metal and is not transparent and cannot be used. The upper limit of the range of y = is a completely nitrided value. The preferred metal nitride of the present invention is preferably an oxide of silicon (Si), aluminum (Al), or titanium (Ti). The value of y = is, for example, silicon (Si), y = 0.5. -1.3, if aluminum (Al), y = 0.3-1.0, if titanium (Ti), y = 0.5-1.3, if tin (Sn), y = 0. The thing of the range of 5-1.3 can be used. However, even a colored film may be used because it can maintain transparency if it is 3 to 15 nm.

  (Inorganic oxynitride film) As the inorganic oxynitride film, a thin film in which a metal oxynitride is basically deposited can be used. For example, silicon (Si), aluminum (Al), magnesium ( Metals such as Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) An inorganic oxynitride film of oxynitride can be used, and a metal oxynitride such as silicon (Si), aluminum (Al), titanium (Ti), or the like is preferable. The inorganic oxynitride film can be referred to as a metal oxynitride such as silicon oxynitride, aluminum oxynitride, titanium oxynitride, etc., and its notation is, for example, SiOxNy, AlOxNy, TiOxNy, etc. MOxNy (where, M represents a metal element, and the values of X and y are different depending on the metal element). Moreover, as a range of said value of x and y, silicon (Si) x = 1.0-2.0, y = 0.1-1.3, aluminum (Al) x = 0.5- 1.0, y = 0.1-1.0, magnesium (Mg) is x = 0.1-1.0, y = 0.1-0.6, calcium (Ca) is x = 0.1 1.0, y = 0.1-0.5, potassium (K) is x = 0.1-0.5, y = 0.1-0.2, tin (Sn) is x = 0.1 2.0, y = 0.1 to 1.3, sodium (Na) x = 0.1 to 0.5, y = 0.1 to 0.2, boron (B) x = 0.1 1.0, y = 0.1-0.5, titanium (Ti) x = 0.1-2.0, y = 0.1-1.3, lead (Pb) x = 0.1 1.0, y = 0.1 to 0.5, zirconium (Zr) is x = 0.1 to 2.0, y = 0.1 .0, yttrium (Y) may have a value in the range of x = 0.1~1.5, y = 0.1~1.0. In the above formula, when x = 0, it is a complete metal and is not transparent and cannot be used. Preferred metal nitrides of the present invention include silicon (Si), aluminum (Al), titanium (Ti ) And tin (Sn) oxides are preferred, and the values of x and y are, for example, silicon (Si) x = 1.0 to 2.0, y = 0.1 to 1.3, aluminum ( Al) for x = 0.5 to 1.0, y = 0.1 to 1.0, and titanium (Ti) for x = 1.0 to 2.0, y = 0.1 to 1. Those in the range of 3 can be used. However, even a colored film may be used because it can maintain transparency if it is 3 to 50 nm.

  (Inorganic oxide carbide film) As the inorganic oxide carbide film, any inorganic oxide carbide film can be used as long as it is basically a thin film in which a metal oxide carbide is deposited. For example, silicon (Si), aluminum ( Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium ( An inorganic oxide carbide film of a metal oxycarbide such as Y) can be used, and a metal oxycarbide such as silicon (Si), aluminum (Al), titanium (Ti), or the like is preferable. The inorganic oxide carbide film can be referred to as a metal oxide carbide such as silicon oxide carbide, aluminum oxide carbide, magnesium oxide carbide, etc., and its notation is, for example, MOxCz (wherein the formula is SiOxCz, AlOxCz, TiOxCz, etc.). M represents a metal element, and the values of x and z have different ranges depending on the metal element. Moreover, as a range of said x and z value, silicon (Si) is x = 0.1-1.95, z = 0.1-2.0, aluminum (Al) is x = 0.1-0.1. 1.5, z = 0.1-2.0, magnesium (Mg) x = 0.1-1.0, z = 0.1-1.5, calcium (Ca) x = 0.1 1.0, z = 0.1 to 1.5, potassium (K) x = 0.1 to 0.5, z = 0.1 to 1.0, tin (Sn) x = 0.1 2.0, z = 0.1-2.0, sodium (Na) x = 0.1-0.5, z = 0.1-1.0, boron (B) x = 0.1 1.0, z = 0.1-1.5, titanium (Ti) x = 0.1-2.0, z = 0.1-2.0, lead (Pb) x = 0.1 1.0, z = 0.1 to 2.0, zirconium (Zr) is x = 0.1 to 2.0, z = 0.1 2.0, yttrium (Y) may have a value in the range of x = 0.1~1.5, z = 0.1~2.0. In the above formula, when x = 0 and z = 0, the metal oxide is a complete metal and is not transparent and cannot be used. Preferred metal oxide carbides of the present invention include silicon (Si) and aluminum (Al). Titanium (Ti) oxide carbide is preferable, and the values of x and z are, for example, silicon (Si) x = 1.0 to 1.95, z = 0.1 to 2.0, aluminum (Al ) X = 1.0 to 1.5, z = 0.1 to 2.0, and titanium (Ti) x = 1.0 to 2.0, z = 0.1 to 2.0. The ones in the range can be used.

  (General formula SiOxCz) A preferable silicon oxide film containing carbon is mainly composed of silicon oxide and further contains a carbon element. In the general formula SiOxCz, when the amount of carbon is small (z value is small), the adhesion to the base film is lacking, and when the amount of carbon is large (z value is large), the moisture permeability and oxygen permeability are large. Since flame retardancy is lowered, in the general formula SiOxCz, x = 0.1 to 1.95 and z = 0.1 to 2.0 are preferable.

Next, as a vapor deposition monomer gas such as an organic silicon compound that forms an inorganic film not containing carbon such as silicon oxide, if it contains carbon, it will remain in the thin film. For example, monosilane, Use as a raw material in which Si, H, O, and N are combined without containing carbon, such as disilane, is a particularly preferable raw material because of its handleability and the characteristics of the formed continuous film. Moreover, in the above, as an inert gas, argon gas, helium gas, etc. can be used, for example.
Next, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms an inorganic film containing carbon such as silicon oxide carbide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethyl. Methoxysilane, vinyltrimethylsilane, tetramethoxysilane (TMOS), methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, tetraethoxysilane (TEOS), dimethyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexamethyl In addition to preferably using disilazane, trimethoxysilane, etc., it is possible to use one or more known materials such as tetramethyldisiloxane, normal methyltrimethoxysilane as a raw material. Been formed From characteristics of continued film, in particular, it is a preferred material. Moreover, in the above, as an inert gas, argon gas, helium gas, etc. can be used, for example.

  (Silicon oxide) In the present invention, an inorganic oxide film of silicon oxide formed by a vacuum film-forming method using a vapor-deposited monomer gas such as an organosilicon compound is composed of a vapor-deposited monomer gas such as an organosilicon compound and oxygen. A chemical reaction with a gas or the like, and the reaction product is tightly bonded to one surface of a base film to form a dense, flexible thin film. Usually, the general formula SiOx (however, x represents a number of 0.1 to 2), and is a continuous thin film mainly composed of silicon oxide. As the inorganic oxide film of silicon oxide, inorganic oxide of silicon oxide represented by the general formula SiOx (where x represents a number of 1.3 to 2) from the viewpoint of transparency and flame retardancy. A thin film mainly composed of a material film is preferable. The value of x varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. Generally, if the value of x decreases, the film itself becomes dense and the oxygen transmission rate decreases. The film itself is yellowish and the transparency is poor.

In addition, the silicon oxide film is mainly composed of silicon oxide, and further contains at least one compound composed of one or more of carbon, hydrogen, silicon, or oxygen, or two or more of these elements by chemical bonding or the like. May be. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the inorganic oxide film of silicon oxide can be changed by changing the conditions of the vapor deposition process.

  The content of the above-mentioned compound in the silicon oxide film is about 0.1 to 50%, preferably about 5 to 20%. In the above, if the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the inorganic oxide film of silicon oxide become insufficient, and scratches, cracks, etc. occur due to bending etc. It is easy and it becomes difficult to stably maintain the flame retardancy, and if it exceeds 50%, the flame retardancy is lowered, which is not preferable. Furthermore, in the present invention, in the silicon oxide film, the content of the above compound is preferably decreased from the surface of the silicon oxide inorganic oxide film in the depth direction. On the surface of the material film, impact resistance and the like can be enhanced by the above compound and the like. On the other hand, since the content of the above compound is small at the interface with the base film, the base film and the silicon oxide film This has the advantage that the tight adhesion of the material becomes strong.

  (Inorganic nitride carbide film) As the inorganic nitride carbide film, any inorganic nitride carbide film can be used as long as it is basically a thin film obtained by vapor deposition of metal nitride carbide. For example, silicon (Si), aluminum ( Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium ( An inorganic nitride carbide film of a metal nitride carbide such as Y) can be used, and preferably a metal nitride carbide such as silicon (Si), aluminum (Al), titanium (Ti) or the like. The inorganic nitride carbide film can be referred to as a metal nitride carbide such as silicon nitride carbide, aluminum nitride carbide, titanium nitride carbide, etc., and its notation is, for example, MNyCz (wherein the formula NnCz, where TiNyCz, etc. M represents a metal element, and the values of y and z vary depending on the metal element.) Moreover, as a range of said y and z value, silicon (Si) is y = 0.1-1.3, z = 0.1-2.0, and aluminum (Al) is y = 0.1-0.1. 1.0, z = 0.1-1.5, magnesium (Mg) is y = 0.1-1.0, z = 0.1-1.5, calcium (Ca) is y = 0.1 1.0, z = 0.1 to 1.5, potassium (K) is y = 0.1 to 0.3, z = 0.1 to 1.0, tin (Sn) is y = 0.1 1.3, z = 0.1-2.0, sodium (Na) is y = 0.1-0.3, z = 0.1-1.5, boron (B) is y = 0.1 1.0, z = 0.1-1.5, titanium (Ti) is y = 0.1-1.3, z = 0.1-2.5, lead (Pb) is y = 0.1 1.0, z = 0.1 to 1.5, zirconium (Zr) is y = 0.1 to 1.3, z = 0.1 .0, yttrium (Y) may have a value in the range of y = 0.1~1.0, z = 0.1~2.0. In the above formula, when x = 0, it is a complete metal and is not transparent and cannot be used. Preferred metal nitride carbides of the present invention include silicon (Si), aluminum (Al), titanium (Ti ) Nitrided carbide is preferred, and the values of y and z are, for example, silicon (Si), y = 1.0 to 1.4, z = 0.1 to 2.0, and aluminum (Al). If y = 0.5 to 1.0, z = 0.1 to 2.0, and titanium (Ti), y = 1.0 to 1.3 and z = 0.1 to 2.0. Things can be used. However, even a colored film may be used because it can maintain transparency if it is 3 to 30 nm.

  (Inorganic oxynitride carbide film) A preferred inorganic oxynitride (inorganic oxynitride carbide) containing carbon is mainly composed of silicon oxynitride or titanium oxynitride and further contains a carbon element. In the general formula MOxNyCz, when the amount of carbon is small (z value is small), the adhesion to the base film is lacking, and when the amount of carbon is large (z value is large), the moisture permeability and oxygen permeability are large. Flame retardancy is reduced. Examples of the M element include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium (Ti). ), Lead (Pb), zirconium (Zr), yttrium (Y), and the like can be used, and Si, Al, and Ti are preferable. However, even a colored film may be used because it can maintain transparency if it is 3 to 50 nm.

  As a preferable inorganic oxynitride carbide, for example, in the general formula SiOxNyCz, x = 0.1 to 1.95, y = 0.1 to 1.2, and z = 0.1 to 2.0 are preferable.

  In addition, in the general formula AlOxNyCz, the aluminum oxynitride thin film is formed by setting the composition in the range of x = 0.1 to 1.4, y = 0.1 to 0.9, and z = 0.1 to 2.0. A thin film with a low ratio of the residual carbon component of the titanium oxynitride thin film can suppress performance deterioration due to oxidation, and has high transparency and excellent adhesion to a CVD material (base film). .

Further, in the general formula TiOxNyCz, the titanium oxynitride thin film is obtained by setting the composition in the range of x = 1.0 to 1.8, y = 0.5 to 1.0, z = 0.3 to 1.5. A thin film with a low ratio of the residual carbon component of the titanium oxynitride thin film can suppress performance deterioration due to oxidation, and has high transparency and excellent adhesion to a CVD material (base film). . As a material constituting the thin film layer, an organic titanium compound such as titanium tetrachloride or tetraisopropoxide is suitable.
If the x value is less than this range, the Ti—O bond decreases and the film stress increases, peeling from the base film or chipping occurs in the thin film, and the barrier property decreases. Since it progresses and many functional groups are formed, it becomes a thin film lacking in heat resistance and moisture resistance, and flame retardancy deteriorates.
If the y value is less than this range, the film density is small and a dense film cannot be formed, so that the barrier property is lowered, and if it exceeds this range, the Ti-N bond increases and the thin film becomes hard, so lack of flexibility. The barrier property is likely to be lowered by external force, and the flame retardancy is deteriorated.
If the z value is less than this range, the carbon-containing component at the interface with the base film decreases, and the adhesion with the base film decreases. If the z value exceeds this range, the carbon-containing component increases, resulting in film absorption. Coloring occurs.

  (Thickness) A preferable thickness in the general formula TiOxNyCz is 5 to 500 nm. Below this range, the barrier properties are almost the same as when the TiOxNyCz layer is not present, and the barrier properties are not improved, and beyond this range, the film stress increases and cracks occur in the thin film. Does not improve.

  In the present invention, the film thickness of the inorganic layer 25 such as the inorganic oxide layer, inorganic nitride layer, inorganic oxynitride layer, inorganic oxide carbide layer, inorganic nitride carbide layer or inorganic oxynitride carbide layer as described above, Although it varies depending on the type of metal or metal oxide used, for example, it is desirable to select and form arbitrarily within a range of about 1 to 1000 nm, preferably about 5 to 500 nm, and more preferably 20 to 200 nm. . In the present invention, the inorganic oxide, the inorganic nitride, or the inorganic oxynitride film is a metal to be used, or the metal oxide is used as one kind or a mixture of two or more kinds of different materials. An inorganic oxide layer, an inorganic nitride layer, an inorganic oxynitride layer, an inorganic oxycarbide layer, an inorganic oxycarbide layer, or an inorganic oxynitride carbide layer film mixed in (1) can be formed.

  (Easily Adhesive Treatment) Further, one or a plurality of layers such as a thermal adhesive layer may be provided on the surface opposite to the inorganic layer 25 of the base film 11. Further, on the surface of the base film 11 on which the thermal adhesive layer is provided, if necessary, on the coating surface prior to coating, corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer layer (anchor coat, adhesion promoter) (Also referred to as easy-adhesive), easy-adhesion treatment such as coating treatment, pre-heat treatment, dust removal treatment, vapor deposition treatment, alkali treatment, etc. may be performed.

  (Formation of other layers) The other layers may be any layer such as heat seal layer, protective layer, antifouling layer, hard coat layer, roll coat, reverse roll coat, gravure coat, bar coat, kiss coat. It may be formed by applying and drying by a known coating method such as die coating or comma coating.

(Environmental load) Further, the inorganic thin film layer formed in the present invention is very thin, so even if it is incinerated, the environmental load is extremely small.
Furthermore, the substrate and the inorganic thin film layer can be peeled off by chemical treatment. For example, SiOxCz can be easily peeled off with a hot alkaline solution (eg, 1N NaOH aqueous solution) and AlOx can be easily peeled off with an inorganic acid (eg, 1N hydrochloric acid). it can. By separating the material constituting the layer, the substrate can be recycled and reused.

In addition, using the flame retardant film according to any one of claims 1 to 6, as another interior layer, or in combination with other members, as a housing interior material, electrical product or printing film, It can be used suitably. Residential interior materials include woodgrain film, wallpaper, ceiling materials, boards and the like. In addition, as electronic products, there are personal computers, refrigerators, washing machines, microwave ovens, rice cookers, audio, water heaters, air conditioners, mobile phones, PDAs, liquid crystal display devices, organic EL display devices, plasma displays, etc. Examples of members include printed wiring boards, flat cables, display optical members (antireflection films, color filters, polarizing plates, retardation films, diffusion films, display substrates, PDP optical filters), projection screens, housings, There are partitions, tables, etc.
Further, or as a printing film, there are in-car advertisements, posters, calendars, and the like.

The interior material for home, electrical product or printing film using the flame-retardant film of the present invention suppresses the decomposition of the base film caused by invading oxygen, so it has excellent flame retardancy, and also excellent flame retardancy. Therefore, even when the flame retardant is contained in other layers laminated as necessary, the content can be reduced.
In addition, since hazardous substances such as chlorine and dioxin are not discharged even when incinerated, it has low environmental impact and is excellent in environmental suitability.
Furthermore, in particular, the inorganic substance containing carbon used in the present invention can be peeled off with hot alkali (for example, 1N aqueous sodium hydroxide solution at 60 ° C.), and is not an incineration treatment, Reuse is also possible.

(Modification) The present invention includes the following modifications.
In the flame-retardant film of the present invention, an inorganic layer is provided on at least one surface of a base film directly or through another layer, and the base layer / printing layer / inorganic oxidation is performed using the other layer as a printing layer. It is good also as a structure of a physical layer, an inorganic nitride layer, or an inorganic oxynitride layer. An inorganic oxide layer, an inorganic nitride layer, an inorganic oxynitride layer, an inorganic oxide carbide layer, an inorganic nitride carbide layer, or an inorganic oxynitride carbide layer is highly transparent and does not use a solvent. Easy and printing effect is high. In addition, the printing layer may be provided arbitrarily, printing layer / base material / inorganic oxide layer, inorganic nitride layer, inorganic oxynitride layer, inorganic oxide carbide layer, inorganic nitride carbide layer or inorganic oxynitride carbide layer, The substrate / inorganic oxide layer, inorganic nitride layer, inorganic oxynitride layer, inorganic oxide carbide layer, inorganic nitride carbide layer, or inorganic oxynitride carbide layer / printing layer can be used.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this.

  Using a Toyobo Ester E5000 (Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, an aluminum oxide film having a thickness of 20 nm was formed by a vacuum deposition method, and the flame-retardant film of Example 1 Got.

  A flame retardant film was obtained in the same manner as in Example 1 except that the film thickness was 3 nm.

  A flame retardant film was obtained in the same manner as in Example 1 except that the film thickness was 520 nm.

  A flame retardant film was obtained in the same manner as in Example 1 except that the film thickness was changed to 20 nm.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, a 200 nm-thick silicon oxide film was formed by a vacuum deposition method to obtain a flame-retardant film.

  A TiOx film having a film thickness of 25 nm was formed by a vacuum deposition method using Toyobo Ester E5000 (manufactured by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a substrate to obtain a flame retardant film.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, a SiNy film having a thickness of 10 nm is formed by a plasma CVD method according to the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, an AlNy film having a thickness of 10 nm is formed by a plasma CVD method under the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, a TiNy film having a thickness of 10 nm is formed by a plasma CVD method under the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, a SiOxNy film having a thickness of 15 nm is formed by a plasma CVD method according to the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, an AlOxNy film having a thickness of 15 nm is formed by a plasma CVD method according to the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, a TiOxNy film having a thickness of 15 nm is formed by a plasma CVD method according to the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, a SiNyCz film having a thickness of 15 nm is formed by a plasma CVD method according to the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, an AlNyCz film having a thickness of 15 nm is formed by a plasma CVD method under the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) with a thickness of 25 μm as a base material, a TiNyCz film with a thickness of 15 nm is formed by a plasma CVD method according to the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, a SiOxCz film having a thickness of 20 nm is formed by a plasma CVD method according to the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, an AlOxCz film having a thickness of 20 nm is formed by a plasma CVD method according to the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, a TiOxCz film having a thickness of 20 nm is formed by a plasma CVD method according to the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, a SiOxNyCz film having a thickness of 15 nm is formed by a plasma CVD method according to the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, an AlOxNyCz film having a thickness of 15 nm is formed by a plasma CVD method according to the conditions described in the table, and flame retardant A characteristic film was obtained.

  Using Toyobo Ester E5000 (produced by Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a base material, a TiOxNyCz film having a thickness of 15 nm is formed by a plasma CVD method according to the conditions described in the table, and flame retardant A characteristic film was obtained.

(Comparative Example 1)
An undeposited film without a metal oxide layer was used as a flame retardant film of Comparative Example 1 using Toyobo E5000 (Toyobo Co., Ltd., trade name of PET film) having a thickness of 25 μm as a substrate.

(Evaluation method) Evaluation was carried out by a flammability test, oxygen permeability, moisture permeability, haze, total light transmittance, tensile fracture strength, tensile fracture elongation, and tensile elastic modulus.

  (1) In the flammability test, the UL94VTM rank was determined according to the vertical flammability test method of the flammability test standard UL94 of plastic materials issued by Under Laboratories. (2) Oxygen permeability conforms to JIS-K7126, (3) Moisture permeability conforms to JIS-K7129, (4) Haze conforms to JIS-K7125, (5) Total light transmittance conforms to JIS- According to K7125, (6) Tensile fracture strength, (7) Tensile fracture elongation, and (8) Tensile modulus were measured in the longitudinal direction only in accordance with JIS-K7127. The metal oxide film thickness was measured by the fluorescent X-ray method. The measurement results are shown in “Tables 1 to 3”.

  (Measurement results) In Examples 1 to 21, as compared with the film in which the metal oxide layer of Comparative Example 1 is not provided, all have optical characteristics of haze and total light transmittance, tensile breaking strength, and tensile breaking elongation. Further, no deterioration was observed in the mechanical properties of the tensile elastic modulus, and the flame retardancy was VTM-0 to 1, particularly VTM-0 in Examples 1, 4 and 5. The flame retardancy of Comparative Example 1 did not reach the VTM standard.

It is sectional drawing of the flame-retardant film which shows one Example of this invention. It is explanatory drawing of the CVD apparatus which can be used conveniently by this invention.

Explanation of symbols

10: Flame-retardant film 11: Base film 25: Metal oxide layer 200: CVD apparatus 210: Vacuum vessel 211: Paper feeding unit 213: Film forming unit 215: Winding unit 221: a chamber 223: b chamber 225: c chamber 231: Electrode drums 241, 243, 245: Electrodes 251.253, 255: Gas supply nozzles

Claims (7)

In a flame retardant film having an inorganic layer on at least one surface of a base film directly or through another layer, the inorganic layer has an inorganic oxide layer, an inorganic nitride layer, or an inorganic oxynitriding layer having a barrier property A flame retardant film characterized by being a physical layer. The material of the inorganic layer is any one of silicon oxide, aluminum oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride, silicon oxynitride, aluminum oxynitride, or titanium oxynitride, and has a thickness of 5 to 500 nm. The flame-retardant film according to claim 1. The flame retardancy characterized in that in the inorganic layer of the flame-retardant film according to any one of claims 1 to 2, the layer is an inorganic oxide carbide, inorganic nitride carbide or inorganic oxynitride carbide further containing carbon. the film. The material of the inorganic layer is any one of silicon oxycarbide, aluminum oxycarbide, titanium oxide carbide, silicon nitride carbide, aluminum nitride carbide, titanium nitride carbide, silicon oxynitride carbide, aluminum oxynitride carbide, or titanium oxynitride carbide. The flame retardant film according to claim 3, wherein the thickness is 5 to 500 nm. 5. The flame-retardant film according to claim 1, wherein the moisture permeability according to JIS-K7129 is 10 g / m ² day or less and / or the oxygen transmission rate according to JIS-K7126 is 10 cm ³ / m ^2. A flame-retardant film characterized by being not more than day. The flame-retardant film according to any one of claims 1 to 4, wherein the flame-retardant film has flame resistance equivalent to UL94 standard VTM-0. A flame-retardant interior material for a house, an electrical product or a printing film, wherein the flame-retardant film according to claim 1 is used.

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