JP4491639B2 - Flexible antifouling film - Google Patents

Description

  The present invention relates to a flexible membrane material that is used for, for example, a tent structure building, has non-flammability or flame retardancy, and is excellent in antifouling property. Relates to a flexible antifouling and non-flammable film material comprising a silicone resin and a photocatalytic substance and having high flameproofing and antifouling properties. In particular, the flexible antifouling non-combustible film material of the present invention conforms to the building standard law combustion test (cone calorimeter test method stipulated in ASTM-E1354) amended in 2000.

  For membrane materials for structures used in facilities that accommodate hundreds to tens of thousands of spectators, such as dome stadiums, sports stadiums, pavilions, and event venue facilities, advanced disaster prevention designs are required to ensure safety. For example, the material constituting these canopy part, roof part, and side wall part needs to have flame retardancy or incombustibility. In addition, these structural members conform to the membrane material class A or membrane material class B specified by the Japan Membrane Structure Association, and are configured by using a single registered film material or using it in combination with other building materials. Is. These membrane materials are mainly made of glass fiber fabric base fabric with a coating layer made of fluororesin, vinyl chloride resin, polyurethane resin, chloroprene rubber, etc. It is used in permanent facilities such as sports stadiums, and vinyl chloride resin-coated membrane materials are used in facilities that are supposed to be used for several years, such as exposition pavilions and event venues. In addition, a film material in which a silicone resin coating layer is provided on a glass fiber fabric base fabric as an intermediate presence between a fluororesin coating film material and a vinyl chloride resin coating film material has a high degree of flameproofing, and also during combustion. In recent years, it has been attracting attention as having a large evacuation / guidance effect in the event of a fire due to the small amount of gas generated. Recently, the demand for such a silicone resin-coated film material is increasing as an emergency fireproof shutter / smoke curtain that is installed around elevators and evacuation routes in office buildings and department stores.

  As described above, the silicone resin coating film material is an effective film material for preventing the spread of fire damage. On the other hand, the silicone resin coating layer is inferior in wear resistance and has poor dynamic durability. And oily soot (a mixture of carbon soot derived mainly from combustion exhaust gas, etc.), sand dust, and dirt). It was. As a sheet that has solved the problem of contamination of these silicone resin-coated membrane materials, the applicant previously applied the surface of a silicone resin (rubber) laminate including non-combustible fiber fabric with an acrylic resin or fluorine-containing resin to prevent contamination. The surface of a non-combustible sheet (Patent Document 1: Japanese Patent Application Laid-Open No. Sho 61-277436) imparted with a property, for example, a silicone resin (rubber) laminate including a base fabric composed of inorganic fibers and organic heat-resistant fibers, A flame retardant sheet coated with a fluorine-containing resin to impart antifouling properties (Patent Document 2: Japanese Patent Laid-Open No. 61-185443), for example, the surface of a silicone resin (rubber) laminate including a glass fiber fabric is acrylic. Non-combustible sheet (Patent Document 3: Japanese Patent Application Laid-Open No. Sho 60-244546) coated with a resin / fluorine-containing resin film to impart antifouling property, for example, an organic heat resistant fiber fabric Proposal of a flame retardant sheet (Patent Document 4: Japanese Patent Laid-Open No. Sho 61-1772736) in which the surface of a silicone resin (rubber) laminate is coated with an acrylic resin / fluorine-containing resin film to provide antifouling properties did. Certainly, these sheets have an acrylic resin layer or fluorine-containing resin layer on the surface of a flame-retardant or non-flammable laminate, so that it is easy to clean and remove dust dirt that adheres to and accumulates on the film material surface. It is possible to obtain the effect of However, since these membrane materials are not self-cleaning due to rainfall, it is necessary to perform regular cleaning maintenance in order to maintain the appearance of the membrane structure facilities. However, if regular cleaning maintenance is neglected, an antifouling layer is provided. Even the film material was contaminated with appearance due to natural accumulation of dust and oily dust. In particular, the fluorine-containing resin layer provided as an antifouling layer has hydrophobicity and good affinity with oil-based dust, so that the film material is easily soiled depending on the use environment despite the provision of the fluorine-containing resin layer. In addition, there is a problem of generating streak-like dirt on the side wall surface of the membrane structure facility, that is, so-called rain stripe dirt. Rain streak is caused by a small amount of dust dirt adhering / depositing on the surface of outdoor building materials and traffic vehicles, which is generated when the muddy water drops and falls in the direction of gravity due to rainfall. Forms a noticeable line (stripe). The dripping flow of this muddy water is dried to form rain streak stains, which are formed in irregularly spaced patterns. Once this rain streak is formed, the muddy water tends to flow along this stripe every time it rains. As a result, it gradually increases in darkness and grows into rain streak that is difficult to clean with time.

  Recently, as an antifouling technology for membrane materials for facility structures, particularly for preventing rain streak stains, the applicant has applied a membrane material for canvas tarpaulins to a medium and large tent membrane (for example, a polyester fiber fabric as a base fabric). Antifouling sheet having a photocatalytic titanium oxide layer provided on the outermost layer of a soft vinyl chloride resin-coated laminate including: Patent Document 5: JP 2001-98464 A, Patent Document 6: JP 2001-199014 A) did. Certainly, these film materials exhibit excellent self-cleaning properties due to photocatalytic action, and are film materials that have excellent aesthetic sustainability compared to conventional film materials, but also have fireproof properties that comply with the Fire Service Act, Occasionally, there was concern about evacuation safety in the event of a large amount of irritating gas containing hydrogen chloride. On the other hand, the applicant has proposed an antifouling sheet in which a photocatalytic titanium oxide layer is provided on the outermost layer of a polyolefin-based resin-coated laminate including a fiber woven fabric as a base fabric; Patent Document 7: JP-A-2002-52667). This film material does not generate a large amount of irritating gas at the time of combustion, but the combustion heat is large and the resin coating layer volatilizes and disappears. It is difficult to meet the cone calorimeter test method defined in ASTM-E1354. In addition, a sheet-like material (Patent Document 8: Japanese Patent Laid-Open No. 10-202794) has been proposed in which a photocatalyst powder is fixed to the surface of a silicone elastomer laminate including a fiber fabric to impart antifouling properties. This sheet-like material is obtained by applying a silicone elastomer composition, then attaching and supporting a titanium oxide powder having photocatalytic activity on the surface, and then curing the silicone elastomer composition. However, in the sheet-like material obtained by this method, the adhesion between the silicone elastomer composition and the titanium oxide powder is not sufficient, and therefore, when this sheet-like material is washed with an instrument, the titanium oxide powder gradually falls off due to friction, The antifouling performance could not be obtained continuously. In addition, since this sheet-like material has a tack unique to silicone rubber, a large amount of soot is adhered to cover the entire surface of the sheet-like material with soot, and the amount of ultraviolet rays that act on the photocatalyst is greatly cut, thereby self-catalysis by the photocatalyst. In reality, the cleaning effect is not exhibited, and as a result, a sufficient antifouling effect cannot be obtained. Therefore, it is a non-combustible membrane material for facility structures that conforms to the Building Standards Act fire test (cone calorimeter test method stipulated in ASTM-E1354) that was revised and implemented in 2000. In particular, there was no permanent film material excellent in rain-stain stain prevention property, in particular, a non-combustible tent film material coated with a silicone resin and an anti-fouling non-flammable film material for building materials.

JP-A 61-277436 JP-A 61-185443 JP 60-244546 A Japanese Patent Laid-Open No. 61-1772736 JP 2001-98464 A JP 2001-199014 A JP 2002-52667 A Japanese Patent Laid-Open No. 10-202794

  The present invention is a highly durable, flexible antifouling non-combustible membrane material used in membrane structure facilities that accommodate hundreds to tens of thousands of spectators such as dome stadiums, sports stadiums, pavilions, and event venue facilities, especially revised in 2000 Flexible anti-fouling and non-combustible material that conforms to the enforced building standards law combustion test (cone calorimeter test method stipulated in ASTM-E1354) and has excellent anti-stain effect and anti-rain-stain prevention by outdoor installation. The film material is to be provided.

In the present invention, as a result of intensive studies in consideration of such points, a waterproof coating layer formed of a silicone elastomer composition is provided on one or more sides of a fabric containing flame retardant fibers and / or non-combustible fibers. And on at least one surface of the waterproof coating layer, i). Photocatalytic material, ii). A silicone component-containing resin, iii). And a functional group-containing siloxane compound, iv). In an exothermic test in which a flexible sheet provided with a slippery surface layer formed from a composition containing a polyisocyanate compound is irradiated with 50 kW / m ² of radiant heat using a radiant electric heater as necessary. The total calorific value for 20 minutes after the start is 8 MJ / m ² or less, and the maximum heat generation rate does not exceed 200 kW / m ² for 20 minutes or more after the start of heating. The present invention has been completed by finding out that it is excellent in effect, in particular, excellent in preventing rain stains.

〔但し、上記式（Ｉ），（II）及び（III）において、Ｘ ¹ はハロゲン基、ＯＨ基、ＮＨ ₂ 基、ＳＨ基、ＣＯＯＨ基、アルコキシ基、エステル基、アミド基、エポキシ基、メタクリル基、メタクリロキシ基及びビニル基のいずれか１種を表し、Ｘ ² はハロゲン基、ＯＨ基、ＳＨ基、ＣＯＯＨ基、アルコキシ基、エステル基、アミド基、エポキシ基、メタクリル基、メタクリロキシ基及びビニル基の何れか１種を表し、
Ｒ_１はアルキレン基、Ｒ_２はアルキル基、アルコキシ基、及びアルキルエステル基の何れか１種を表し、ｎは１以上の整数を表し、ｍは１または２を表す。〕
から選ばれた１種以上を含むことを特徴とするものである。
本発明の可撓性防汚不燃膜材において、前記滑性表面層形成用組成物が、前記成分（Ａ-１），（Ａ-２）及び（Ａ-３）に加えて、さらに（Ａ-４）ポリイソシアネート化合物成分を含んでいてもよい。
本発明の可撓性防汚不燃膜材において、前記光触媒物質成分（Ａ-１）が、酸化チタン（ＴｉＯ_２）、過酸化チタン（ペルオキソチタン酸）、酸化亜鉛（ＺｎＯ）、酸化錫（ＳｎＯ_２）、チタン酸ストロンチウム（ＳｒＴｉＯ_３）、酸化タングステン（ＷＯ_３）、酸化ビスマス（Ｂｉ_２Ｏ_３）、酸化鉄（Ｆｅ_２Ｏ_３）、及びこれらのドーピング物質、の少なくとも１種を含有していてもよい。
本発明の可撓性防汚不燃膜材において、前記滑性表面層の静摩擦係数μが、０．３５以下（ＪＩＳ Ｋ ７１２５に準拠して測定）であることが好ましい。
本発明の可撓性防汚不燃膜材において、前記防水被覆層が、ホウ酸亜鉛、ホウ酸アルミニウム、錫酸亜鉛、ヒドロキシ錫酸亜鉛、及びクリストバライトから選ばれた１種以上の補強性充填剤粉末を含むことが好ましい。
本発明の可撓性防汚不燃膜材において、前記基布用不燃繊維が、ガラス繊維、シリカ繊維、アルミナ繊維、セラミック繊維、及び炭素繊維から選ばれた１種以上の無機繊維からなることが好ましい。
本発明の可撓性防汚不燃膜材において、前記基布用難燃繊維が、アラミド繊維、ポリベンズオキサゾール繊維、ポリベンズチアゾール繊維、及びポリフェニレンサルファイド繊維から選ばれた１種以上の有機耐熱繊維からなることが好ましい。
本発明の可撓性防汚不燃膜材において、前記基布が、モンモリロナイト、スメクタイト、及びフッ素雲母から選ばれた１種以上の層状鉱物で下処理されたものであることが好ましい。
本発明の可撓性防汚不燃膜材が、輻射電気ヒーターを用いて５０ｋＷ／ｍ^２の輻射熱を照射する発熱性試験において、加熱開始後２０分間の総発熱量が８ＭＪ／ｍ^２以下であり、かつ加熱開始後２０分間、最高発熱速度が１０秒以上継続して２００ｋＷ／ｍ^２を超えないものであることが好ましい。 The flexible antifouling and non-combustible film material of the present invention comprises a base fabric comprising a fabric containing at least one of flame retardant fibers and non-combustible fibers, and a silicone elastomer composition formed on one or more sides of the base fabric. In a flexible sheet comprising a waterproof coating layer including, and a slippery surface layer formed on at least one surface of the waterproof coating layer,
The slippery surface layer is formed from a composition comprising (A-1) a photocatalytic substance component, (A-2) a silicone component-containing resin component, and (A-3) a functional group-containing siloxane compound component. And
The silicone component-containing resin component (A-2) for the slippery surface layer is one selected from a silicone-acrylic-urethane copolymer resin, a silicone-grafted fluorine-containing copolymer, and a silicone-acrylic hybrid three-dimensional structure resin Including and
A compound in which the functional group-containing siloxane compound component (A-3) is represented by the following chemical formulas (I), (II) and (III):

[In the above formulas (I), (II) and (III), X ¹ represents a halogen group, OH group, NH ₂ group, SH group, COOH group, alkoxy group, ester group, amide group, epoxy group, methacryl group. Represents any one of a group, a methacryloxy group and a vinyl group, and X ² is a halogen group, OH group, SH group, COOH group, alkoxy group, ester group, amide group, epoxy group, methacryl group, methacryloxy group and vinyl group Any one of
R ₁ represents an alkylene group, R ₂ represents any one of an alkyl group, an alkoxy group, and an alkyl ester group, n represents an integer of 1 or more, and m represents 1 or 2. ]
It contains 1 or more types selected from.
In the flexible antifouling and non-combustible film material of the present invention, the composition for forming a slippery surface layer may further comprise (A-1), (A-2) and (A-3) in addition to (A-3). -4) A polyisocyanate compound component may be included.
In the flexible antifouling and incombustible film material of the present invention, the photocatalytic substance component (A-1) contains 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 ), and these doping substances. May be.
In the flexible antifouling and non-combustible film material of the present invention, it is preferable that the static friction coefficient μ of the slippery surface layer is 0.35 or less (measured in accordance with JIS K 7125).
In the flexible antifouling and noncombustible film material of the present invention, the waterproof coating layer is one or more reinforcing fillers selected from zinc borate, aluminum borate, zinc stannate, zinc hydroxystannate, and cristobalite. Preferably it contains a powder.
In the flexible antifouling and non-combustible film material of the present invention, the non-combustible fiber for base fabric may be composed of one or more inorganic fibers selected from glass fiber, silica fiber, alumina fiber, ceramic fiber, and carbon fiber. preferable.
In the flexible antifouling non-flammable film material of the present invention, the flame retardant fiber for the base fabric is one or more organic heat resistant fibers selected from aramid fibers, polybenzoxazole fibers, polybenzthiazole fibers, and polyphenylene sulfide fibers. Preferably it consists of.
In the flexible antifouling and non-combustible film material of the present invention, the base fabric is preferably pretreated with one or more layered minerals selected from montmorillonite, smectite, and fluorine mica.
In the exothermic test in which the flexible antifouling and non-combustible film material of the present invention is irradiated with radiant heat of 50 kW / m ² using a radiant electric heater, the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less. And, it is preferable that the maximum heat generation rate does not exceed 200 kW / m ² for 20 minutes or more after the start of heating.

  The flexible antifouling and non-combustible film material of the present invention is a flexible laminate coated with a silicone resin using a fabric containing flame retardant fibers and / or non-combustible fibers, and a photocatalyst is formed on the surface of the laminate. It is a permanent non-combustible film material with a slippery surface layer containing substances, and it only conforms to the Building Standards Act Combustion Test (Cone Calorimeter Test Method stipulated in ASTM-E1354) that was revised in 2000. In addition, the surface slipperiness is improved by including a silicone component-containing resin, a functional group-containing siloxane compound, and, if necessary, a polyisocyanate compound in the slippery surface layer and its base waterproof coating layer. This effectively reduces dust adhesion to the antifouling and non-flammable film material, thereby effectively producing the photocatalytic function without blocking the surface of the slippery surface layer containing the photocatalytic substance with dust. It is possible to, therefore antifouling incombustible film material of the present invention has a superior antifouling property, and Amesuji stain preventing property. In the antifouling and non-flammable film material of the present invention, the flexible laminate coated with the silicone resin and the slippery surface layer containing the photocatalytic substance are firmly bound to each other. Therefore, the initial appearance of the non-combustible film material can be maintained for a long time. Accordingly, the antifouling and non-combustible film material of the present invention is a non-combustible material that constitutes a canopy, a roof, and a side wall in a permanent facility such as a dome stadium, a sports stadium, a pavilion, or an event venue that accommodates hundreds to tens of thousands of spectators. It can be used as

  The flexible antifouling and non-combustible film material of the present invention is provided with a waterproof coating layer formed of a silicone elastomer composition on one or more sides of a fabric containing flame retardant fibers and / or non-combustible fibers, and , A-1) on at least one surface of the waterproof coating layer. Photocatalytic substance, A-2). Silicone component-containing resin, A-3). It is a flexible sheet provided with a slippery surface layer formed from a composition further containing a functional group-containing siloxane compound and, if necessary, a polyisocyanate compound.

  As the silicone elastomer that can be used for forming the waterproof coating layer of the antifouling and non-flammable film material of the present invention, addition reaction curable silicone elastomer, condensation reaction curable silicone elastomer, radical (peroxide crosslinking) reaction curable silicone elastomer can be used, Particularly preferred is an addition reaction curable silicone elastomer that can be diluted with toluene or the like and can be coated at a low temperature. The addition reaction curable silicone elastomer is an elastomer formed by bonding functional groups in two types of organopolysiloxane by an addition reaction to form an elastomer, such as an aliphatic unsaturated group such as a vinyl group or a hexenyl group. And silicone elastomers composed of organopolysiloxanes, organohydrogenpolysiloxanes, and platinum group compound catalysts. Aliphatic unsaturated group-containing organopolysiloxanes include vinyl dimethylsiloxy group-blocked dimethylpolysiloxane at both ends, vinyldimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends, and vinylmethylphenylsiloxy group-blocked dimethylsiloxane at both ends. -A methylphenylsiloxane copolymer is mentioned. Examples of the organohydrogenpolysiloxane include trimethylsiloxy group-blocked methylhydrogen polysiloxane at both ends, trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer at both ends, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogen at both ends. These include addition-curable curable silicone elastomers that can be cured by heating, and include additional fillers, heat-resistant agents, flame retardants, organic pigments, inorganic pigments. A pigment, an organic solvent, and the like can be contained.

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

  Examples of the radical reaction curable silicone elastomer composition include a composition comprising an organopolysiloxane, a reinforcing filler, and an organic peroxide. As an additional component, a filler, a heat-resistant agent, a flame retardant, a pigment, an organic solvent, etc. Can be contained. As organopolysiloxane, both ends are blocked with trimethylsiloxy group, dimethylvinylsiloxy group, methylphenylvinylsiloxy group or silanol group, and the main chain is dimethylpolysiloxane, dimethylsiloxane / methylphenylsiloxane copolymer, dimethylsiloxane / Examples include methyl vinyl siloxane copolymer. An example of the filler is fumed silica. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, and di-t-butyl peroxide. This radical reaction curable silicone elastomer composition can be cured by heating. The other radical reaction curable silicone elastomer composition mainly comprises an organopolysiloxane raw rubber and a reinforcing filler, and contains additional ingredients such as a filler, a heat-resistant agent, a flame retardant, a pigment, and an organic solvent. Examples thereof include compositions that are cured by irradiation with rays and γ rays, and compositions that are composed of silicon-bonded alkenyl group-containing organopolysiloxanes, sensitizers, and fillers and are cured by irradiation with ultraviolet rays. The formation thickness of the waterproof coating layer by the above-mentioned silicone elastomer (addition reaction curable type, condensation reaction curable type, radical reaction curable type) composition is preferably 50 to 300 μm, particularly preferably 100 to 200 μm. If the film thickness is less than 50 μm, the durability and waterproofness are insufficient, and if it exceeds 300 μm, the combustion test (ASTM-E1354) defined in the Building Standards Law may not be met.

In order for the antifouling and non-combustible film material of the present invention to conform to the combustion test (cone calorimeter test method stipulated in ASTM-E1354) stipulated in the Building Standard Law, zinc borate (2ZnO · 3B) is applied to the waterproof coating layer of the film material. ₂ O _3), aluminum borate _{(9Al 2 O 3 · 2B 2} O 3), zinc stannate (ZnSnO _3), zinc hydroxystannate (ZnSn _{(OH) 6),} selected from cristobalite (alpha-type or β-type) It is preferable to include any one or more reinforcing filler powders. By including these reinforcing filler powders in the waterproof coating layer, a smoke shielding effect can be obtained by forming a strong gas shielding layer by these reinforcing filler powders during combustion. In order to include the reinforcing filler powder in the waterproof coating layer, the composition obtained by uniformly dispersing the reinforcing filler powder in the silicone elastomer described above is coated on a fiber fabric substrate and cured. be able to. The compounding quantity of these reinforcing filler powders is 10-60 mass% with respect to a waterproof coating layer, Preferably it is 20-40 mass%. If the blending amount is less than 10% by mass, the obtained film material may be incompatible with the combustion test (cone calorimeter test method stipulated in ASTM-E1354) stipulated in the Building Standards Act, and obtained when it exceeds 60% by mass. Deteriorating the dynamic durability and wear resistance of the membrane material may make it unsuitable for permanent use. These reinforcing filler powders have an average particle diameter of 1 to 60 μm, preferably 2 to 30 μm, and the surface of these reinforcing filler powders has been surface-modified with a silane coupling agent, an organic titanate compound, or the like. It is preferable to use one.

〔但し、式（Ｉ），（II），（III）において、Ｘ ¹ はハロゲン基、ＯＨ基、ＮＨ ₂ 基、ＳＨ基、ＣＯＯＨ基、アルコキシ基、エステル基、アミド基、エポキシ基、メタクリル基、メタクリロキシ基及びビニル基のいずれか１種を表し、Ｘ ² はハロゲン基、ＯＨ基、ＳＨ基、ＣＯＯＨ基、アルコキシ基、エステル基、アミド基、エポキシ基、メタクリル基、メタクリロキシ基及びビニル基のいずれか１種を表し、
Ｒ_１はアルキレン基、Ｒ_２はアルキル基、アルコキシ基、又はアルキルエステル基を表し、ｎは１以上の整数を表し、ｍは１または２を表す。〕 The antifouling and non-flammable film material of the present invention is a flexible sheet in which a slippery surface layer containing a photocatalytic substance is provided on at least one surface of a silicone elastomer composition-coated laminate including a base fabric. The slippery surface layer of the membrane material of the present invention is A-1). Photocatalytic substance, A-2). Silicone component-containing resin, A-3). It is formed from a composition containing a functional group-containing siloxane compound, and the slippery surface layer can contain a polyisocyanate compound as required.
A-1) photocatalytic substances include 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 ), and at least one of these doping substances .
The silicone component-containing resin of A-2) includes silicone- urethane copolymer resin, silicone-acrylic-urethane copolymer resin, silicone-fluorine-urethane copolymer, and silicone-acrylic hybrid three-dimensional structure resin (organosiloxane). Component and reactive acrylic component form a dense organic / inorganic three-dimensional structure in the presence of a cross-linking agent), including one or more silicone component-containing resins selected from these silicone component-containing resins The amount is 5 to 50% by mass, preferably 5 to 30% by mass. These silicone component-containing resins can be blended with inorganic flame retardants, inorganic pigments, light stabilizers, sol-gel polysiloxanes, metal oxide gels, metal hydroxide gels, and the like.
The functional group-containing siloxane compound for component (A-3) is selected from the following formulas (I), (II), and (III).

[However, in the formulas (I), (II) and (III), X ¹ is a halogen group, OH group, NH ₂ group, SH group, COOH group, alkoxy group, ester group, amide group, epoxy group, methacryl group. Represents one of a methacryloxy group and a vinyl group, and X ² is a halogen group, OH group, SH group, COOH group, alkoxy group, ester group, amide group, epoxy group, methacryl group, methacryloxy group or vinyl group . Any one of them,
R ₁ represents an alkylene group, R ₂ represents an alkyl group, an alkoxy group, or an alkyl ester group, n represents an integer of 1 or more, and m represents 1 or 2. ]

As photocatalytic substances, titanium oxide (TiO ₂ ), titanium peroxide (peroxotitanic acid), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), oxidation Bismuth (Bi ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ), and these photocatalytic materials doped with metals such as Pt, Rh, RuO ₂ , Nb, Cu, Sn, NiO and metal oxides One or more selected. Further, inorganic porous fine particles carrying these photocatalytic substances 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, titanium zeolite, zirconium phosphate, calcium phosphate, calcium calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, magnesium silicate alumina, diatomaceous earth and the like. In the present invention, the photocatalytic substance includes 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, titanium hydroxide and An anatase-type peroxotitanic acid dispersion in which ultrafine titanium oxide particles 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. A photocatalytic substance having an average particle diameter of 50 nm or less, more preferably 20 nm or less is suitable because the smaller the particle diameter of the photocatalytic substance, the better the photocatalytic activity. Titanium oxide includes hydrous titanium oxide, hydrated titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide, and the like.

  The composition ratio of (A-1) the photocatalytic substance, (A-2) the silicone component-containing resin, and (A-3) the functional group-containing siloxane compound constituting the slippery surface layer of the film material of the present invention is (A -2) Silicone component-containing resin (in terms of solid content): 100 parts by mass (A-1) Photocatalytic substance: 10-100 parts by mass, preferably 25-75 parts by mass, (A-3) containing functional groups Siloxane compound (active ingredient conversion): 5 to 50 parts by mass, preferably 10 to 30 parts by mass. When the amount of the photocatalytic substance is less than 10 parts by mass, the antifouling effect of the resulting tent film material is insufficient, and when it exceeds 100 parts by mass, the photocatalytic activity increases but the flexural strength of the slippery surface layer decreases. Outdoor durability may be insufficient. Further, when the functional group-containing siloxane compound is less than 5 parts by mass, the surface of the resulting tent film material may attract dust and become easily contaminated, and when it exceeds 50 parts by mass, the wear resistance of the slipping surface layer is increased. Outdoor durability may be insufficient due to insufficient performance. 3). By adding the functional group-containing siloxane compound, it is possible to impart slipping property to the silicone elastomer of the base waterproof coating layer and to avoid attracting adhesion of dust.

  In addition to the above components (A-1) to (A-3), a polyisocyanate compound can be blended in the slippery surface layer of the film material of the present invention as necessary. The addition amount of the polyisocyanate compound (in terms of active ingredient) is (A-2) silicone component-containing resin (in terms of solid content): 1 to 30 parts by mass, preferably 3 to 15 parts by mass with respect to 100 parts by mass. . The addition effect of the polyisocyanate compound is to react with the functional group-containing siloxane compound (A-3), and by adding the polyisocyanate compound, the lubricity imparting effect (dust adhesion suppression) by the functional group-containing siloxane compound is maintained. At the same time, it has the effect of further improving the adhesion between the silicone elastomer of the base waterproof coating layer and the slippery surface layer. When the addition amount of the polyisocyanate compound exceeds 30 parts by mass, the slippery surface layer becomes hard, the bending strength of the resulting tent film material is deteriorated, and the outdoor durability may be insufficient. Specific examples of the polyisocyanate compound include hexamethylene diisocyanate (HDI), HDI-added isocyanurate-polyisocyanate, HDI-added trimethylpropane-polyisocyanate, HDI-added biuret-polyisocyanate, and blocked isocyanate groups thereof. In addition, as cycloaliphatic polyisocyanate compounds, isophorone diisocyanate (IPDI), IPDI addition type isocyanurate polyisocyanate, IPDI addition type trimethylpropane polyisocyanate, IPDI addition type biuret polyisocyanate, and these isocyanate group block bodies Etc. Isocyanate group-containing modified products in which isocyanate groups are dimerized by uretdione bonds or carbodiimide bonds, isocyanate group-containing modified products in which isocyanate groups are trimerized by isocyanurate bonds, and isocyanate group-containing modified products in which isocyanate groups are highly polymerized by uretonimine bonds It is also possible to use an isocyanate group-terminated prepolymer obtained by reacting an active hydrogen group-containing compound, or a mixture of this with an isocyanurate / urethane-modified isocyanate. Among these, preferred polyisocyanate compounds are isocyanurate-modified polyisocyanate (particularly HMDI type), burette-modified polyisocyanate (particularly HMDI type), trimethylolpropane-modified polyisocyanate (particularly HMDI type), and the like. In particular, those in which polyisocyanates are partially substituted with hydrophilic groups can be used in combination with an aqueous dispersion. In the tent film material of the present invention, the static friction coefficient μ that specifically indicates the lubricity of the lubricious surface layer is 0.35 or less (JIS K7125), preferably 0.28 or less. If the static friction coefficient μ exceeds 0.35, the dust adhesion suppressing effect may not be sufficiently obtained.

Further, the slipping surface layer of the film material of the present invention further includes a silane coupling agent and a metal oxide gel such as silica sol, alumina sol, zirconia sol, niobium oxide sol, and / or a cured product of metal hydroxide gel. May be included. The addition amount of the metal oxide gel and / or metal hydroxide gel is approximately the same amount ( + 20% by mass) as the photocatalytic material, and the addition amount of the sol-gel polysiloxane is 1/3 to 1 with respect to the photocatalytic material. The amount is preferably / 5. The metal oxide gel and / or metal hydroxide gel contained in the slippery surface layer fixes the photocatalytic substance, and is firmly adhered to the slippery surface layer. Further, these metal oxide gel and / or metal Since the hydroxide gel is porous, it has a large surface area, whereby the photocatalytic activity can be effectively exhibited.

  As a method for applying the coating agent for forming the slippery surface layer, for example, a gravure coating method, a micro gravure coating method, a comma coating method, a roll coating method, a reverse roll coating method, a bar coating method, a kiss coating method and the like are preferable. It is. The thickness of the slippery surface layer by the coating agent is preferably 1 to 25 μm. If the thickness of the slippery surface layer is less than 1 μm, the antifouling property of the obtained film material cannot be obtained sufficiently, and if it exceeds 25 μm, the slippery surface layer becomes brittle and cracks due to bending, resulting in slipperiness. The surface layer may peel off.

  The fabric comprising the flame retardant fiber and / or the flame retardant fiber used for the antifouling and non-flammable film material of the present invention will be described. The fiber fabric used as the base fabric is 1). Aramid fiber represented by poly-p-phenylene terephthalamide, poly-m-phenylene isophthalamide, copoly-p-phenylene / 3,4'-diaminodiphenylene terephthalamide, represented by poly-p-phenylene benzobisoxazole Flame retardant comprising at least one organic heat-resistant fiber selected from polybenzoxazole (PBO) fiber, polybenzthiazole (PBT) fiber represented by poly-p-phenylenebenzobisthiazole, and polyphenylene sulfide (PPS) fiber Fabric, 2). Glass fiber (sizing), silica fiber, alumina fiber, ceramic fiber (potassium titanate fiber, titania fiber, silica-titania fiber, boron nitride fiber, boron carbide fiber, zirconia fiber, silicon nitride fiber, silicon carbide fiber, silazane-nitridation Non-combustible fabric comprising at least one inorganic fiber selected from silicon fiber, silicon carbonitride fiber, alumina-boria-silica fiber), and carbon fiber (PAN-based, pitch-based), 3). Examples thereof include a blended fabric of the organic heat-resistant fiber and the inorganic fiber, or a blended fabric. This mixing can improve the bending resistance, which is a defect of inorganic fibers. The mixing ratio of the organic heat-resistant fiber is 5 to 35% by mass, preferably 10 to 25% by mass with respect to the fiber fabric. In particular, in order to register the tent film material of the present invention as a non-combustible film material, 2). Inorganic noncombustible fabrics are preferred.

These fiber fabrics are in the form of a woven fabric, a knitted fabric or a non-woven fabric. The fiber fabric used in the present invention is preferably a woven fabric or a knitted fabric. As the woven fabric, a plain woven fabric, a twill woven fabric, a satin woven fabric, a triaxial woven fabric, a tetraaxial woven fabric, a multiple woven fabric, or the like can be used. Russell knitting is preferable as the knitted fabric. The yarns constituting the warp and weft of these textile fabrics are spun at a filament diameter of 1 to 10 μm, and a single yarn obtained by twisting 0 to 5 times / inch on a strand obtained by converging 50 to 500 strands. Alternatively, a multifilament yarn such as a twisted yarn obtained by twisting two or three strands at 1 to 5 turns / inch, and a multifilament yarn having a fineness of 111 to 2222 dtex, particularly a fineness of 138 to 1111 dtex can be used. However, the organic heat resistant fiber is not limited to this, and a short fiber spun yarn can also be used. The density of the warp and weft threads of the fabric is preferably dense and free of gaps. The degree of openness (porosity) of the plain woven fabric used in the present invention is 0 to 3%, particularly when there is no fiber fabric treatment with layered minerals. Is preferably a fabric of 1.5% or less. Depending on the thickness of the waterproof coating layer and the composition of the waterproof coating layer, even if the degree of meshing is less than 3%, it may hinder smoke shielding performance in the building standard method combustion test (cone calorimeter test method prescribed in ASTM-E1354). May cause pinholes. The porosity representing the degree of cut is a value obtained by subtracting from 100 the area of the yarn occupying the unit area (preferably 10 cm × 10 cm) of the fabric as a percentage. The basis weight of the fabric used in the present invention is not particularly limited because the specific gravity varies depending on the type of fiber used, but 100 to 500 g / m ² , particularly 200 to 350 g / m ² is suitable.

The fiber fabric used for the antifouling and non-flammable film material of the present invention is preferably subjected to a pretreatment with one or more layered minerals selected from montmorillonite, smectite, and fluorine mica. Montmorillonite, smectite, fluorinated mica and the like having an average particle diameter of 0.1 to 30 μm are embedded between the multifilament yarns and the yarns-yarns, and this is a combustion test (cone as defined in ASTM-E1354). Excellent results in calorimeter test method). By using this pretreated fiber fabric, the layered mineral expands upon heating, and as a result, the membrane is accompanied by volume expansion of the multifilament yarn constituting the fiber fabric and volume expansion between the yarn and the yarn. The occurrence of pinhole depression marks on the surface of the material is suppressed, and this expansion effect makes it possible to effectively block the diffusion of combustion cracked gas and smoke. This pretreatment with layered minerals has the effect of filling the voids even in fiber fabrics with a degree of meshing of 1.5% to 3.5%, effectively generating pinholes that can cause combustion gas leakage. Therefore, it can be adapted to a combustion test (cone calorimeter test method defined in ASTM-E1354). It is also effective when the fiber fabric is composed of only organic heat-resistant fibers and does not contain inorganic fibers. As a result, it is possible to obtain non-flammability even when a fiber fabric composed only of organic heat-resistant fibers is used. As the fluorine mica, fluorine tetrasilicon mica having an average particle diameter of 10 to 30 μm obtained by organic exchange treatment of Na tetrasilicon mica can be used. Montmorillonite has an average particle size of 0.1 to 2.0 μm represented by the formula (Al _2−y Mg _y ) Si ₄ O ₁₀ (OH) _2. (M ⁺ M _{1/2 2} ⁺ ) _y nH ₂ O A dioctahedral hydrous layered silicate mineral can be used. (Y = 0.2 to 0.6, M = exchangeable cations Na, K, Ca, Mg, H, etc., n = amount of interlayer water) Smectite is composed of silica tetrahedron (tetracoordinated) and aluminum octahedron. The (hexacoordination) has a layered structure alternately, silica / aluminum having a ratio of 2: 1, and the average particle diameter is 0.1 to 2.0 μm. These layered silicate minerals can be used in combination with clay minerals such as kaolinite, vermiculite, halosite, illite and chlorite having an average particle size of 0.1 to 2.0 μm. In the non-combustible fabric with these layered minerals, the fiber fabric is impregnated with a layered mineral aqueous solution dispersed in water at a solid concentration of 3 to 30% by mass, preferably 5 to 20% by mass, and then dried. Can be done by. In order to improve the adhesion between the fiber fabric and the layered mineral, the layered mineral aqueous solution preferably contains 1 to 10% by mass of a silane coupling agent or an organic titanate compound based on the layered mineral. The layered mineral aqueous solution may contain an emulsion resin or a dispersion resin as a binder resin in a solid content of 5 to 30% by mass with respect to the layered mineral, and a silane coupling agent or an organic titanate compound is used in combination. You can also The layered mineral adhesion amount is preferably 3 to 12% by mass relative to the mass of the fiber fabric. The tent film material obtained when the adhesion amount is less than 3% by mass may not be compatible with the building standard method combustion test (cone calorimeter test method prescribed in ASTM-E1354), and the adhesion amount exceeds 12% by mass. And the adhesiveness of the waterproof coating layer formed on the fabric may be hindered, resulting in insufficient durability.

The antifouling and non-combustible film material of the present invention has a waterproof coating layer formed of a silicone elastomer composition on one or more sides of a fabric containing flame retardant fibers and / or non-combustible fibers, and On at least one surface of the waterproof coating layer, a photocatalytic substance, a silicone component-containing resin, and a functional group-containing siloxane compound, and if necessary, a slippery surface layer formed from a composition containing a polyisocyanate compound was provided. In an exothermic test (cone calorimeter test method defined in ASTM-E1354) in which a radiation electric heater is used to radiate 50 kW / m ² of radiant heat, the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less, and the heating start after 20 minutes, but not exceeding 200 kW / ^{m 2} was continued up to the heat generation rate is more than 10 seconds.

The present invention will be further described with reference to the following examples and comparative examples, but the present invention is not limited to the scope of these examples.
Explanation of test method (1). Combustion test (ASTM-E1354: Corn calorimeter test method)
In a heat generation test in which 50 kW / m ² of radiant heat from a radiant electric heater was applied to the film material for 20 minutes, the total heat generation rate and heat generation rate for 20 minutes were measured, and the appearance of the film material after the test was observed.
(A) The total calorific value: 8 MJ / m ² or less was regarded as conforming (2), and the one exceeding 8 MJ / m ² was denoted as non-conforming (1).
(B) Heat generation rate: Continuation (2) that does not exceed 200 kW / m ² continuously for 10 seconds or more,
Those that continued for 10 seconds or more and exceeded 200 kW / m ² were regarded as nonconforming (1).
(C) Appearance observation: Applicable (1) with no pinhole depressions exceeding Φ0.5mm
Those having pinhole depressions exceeding Φ0.5 mm were considered non-conforming (2) because they had poor combustion gas shielding properties.
In order to conform to the non-combustible film material, at least the above characteristics (a) and (b) must satisfy the evaluation of (2).
(2). Evaluation of Repeated Bending Fatigue Durability 10,000 bending tests specified in JIS standard K-6301 were performed, the surface condition of the sample was observed, and the bending fatigue strength of the film material was evaluated according to the following criteria. A dematcher flexing tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was used as a testing machine for evaluating repeated bending fatigue strength. The specimen mounted on the testing machine is 50 mm wide x 150 mm long so that the durability against folding and folding of the membrane material can be evaluated. The size was × 150 mm long.
The test results were evaluated and displayed as follows.
3 (conformity): There is no abnormality in the waterproof coating layer and the membrane material body.
2 (nonconformity): Can the surface of the waterproof coating be slightly cracked due to bending fatigue,
Alternatively, the waterproof coating layer is partly peeled off from the base fabric.
1 (nonconformity): Exposed base fabric due to bending fatigue is observed on the surface of the waterproof coating layer,
Alternatively, the waterproof coating layer is lifted off from the base fabric.
(3). Evaluation of abrasion resistance (surface slipperiness) The abrasion resistance of the film material surface was evaluated by the abrasion strength test C method (Taber method) defined in JIS standard L-1096.
Use a rotary abrasion tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) as a testing machine to evaluate the wear strength, and perform a wear test under conditions of wear wheel (H-18), wear load of 1 kg, and wear count of 1000 times. The difference in mass (loss of wear) between the samples before and after the test was determined and compared. The smaller the numerical value, the easier the slip of the film material surface and the less the tack.
(4). Evaluation of surface slipperiness The static friction coefficient μ defined in JIS standard K-7125 was determined as an average value of the condition of using 100 g weight and the number of repetitions of 5 times, using a friction coefficient measuring machine AB-401 manufactured by Tester Sangyo Co., Ltd. .
(5). Evaluation of antifouling property Membrane material is exposed to 30 ° and 90 ° (vertical) facing south for 1 year outdoors. The presence or absence of rain streak on the vertical surface and the degree of contamination on the 30 ° surface are the initial (blank). [Delta] E value (JIS standard Z-8729). For color difference measurement, an optical color difference meter (JP7200F) manufactured by JUKI Corporation was used. If the ΔE value exceeds 3.0, it is determined that the self-cleaning property is poor.

Reference example 1
i). Fiber fabric : 675 dtex glass fiber (multifilament) warp yarn was woven in plain weaving at a density of 45 yarns / inch per inch and 675 dtex glass fiber (multifilament) weft yarns at a density of 35 yarns / inch per inch. A glass fiber woven fabric having a mass of 205 g / m ² was used. The fiber fabric had a meshing degree of 1% or less.
This fiber fabric is immersed in a pretreatment liquid bath having the composition shown below, and this is pulled up and simultaneously pressed with a rubber mangle to a pickup rate of 40% by mass, and then dried in a hot air oven at 180 ° C. for 2 minutes to prevent the fiber base fabric from absorbing water. A glass fiber woven fabric having an applied mass of 206 g / m ² was obtained.
<Water absorption prevention pretreatment liquid composition 1>
Trademark: NK Guard NDN7E (acrylic acid perfluoroalkyl ester copolymer resin emulsion) Nikka Chemical Co., Ltd. (solid content 30% by mass) 7 parts by mass Trademark: KBM403 (γ-glycidoxypropyltriethoxysilane:
100% active ingredient) Shin-Etsu Chemical Co., Ltd. 3 parts by weight Diluted water 90 parts by weight
ii). Formation of Waterproof Coating Layer A silicone elastomer precursor composition having the following composition is prepared as i). One side of the pretreated glass fiber woven fabric obtained in (1) was knife-coated, and this was heat-treated in a hot air oven at 160 ° C. for 4 minutes to form a waterproof coating layer having a mass of 180 g / m ^2. a waterproof coating layer weight 180 g / ^{m 2} provided in the same manner to obtain a flexible substrate of the mass 566 g / ^{m 2.}
<Silicone elastomer precursor composition 1>
Trademark: Shirasukon RTV4086A (two-component addition reaction curable silicone:
100% active ingredient) 50 parts by weight of Dow Corning Asia Co., Ltd. Trademark: Shirasukon RTV4086B (two-component addition reaction curable silicone:
Active ingredient 100%) Dow Corning Asia Co., Ltd. 50 parts by mass Trademark: Arborite PF03 (Aluminum borate: average particle size 3 μm)
Reinforcing filler powder) Shikoku Kasei Kogyo Co., Ltd. 30 parts by mass Trademark: Crystal 121 (rutile titanium oxide: average particle size 0.2 μm) 5 parts by mass
Diluent manufactured by Crystal: Toluene 15 parts by mass
iii). Formation of a slippery surface layer A coating composition having the following composition was prepared as above ii). A gravure coat (80 mesh) is applied on one surface of the flexible base material obtained in the above, and this is heat-treated in a hot air oven at 110 ° C. for 1 minute to form a slippery surface layer having a mass of 3 g / m ^2. A film material (mass 569 g / m ² ) of the present invention was obtained. The evaluation results of the obtained film material are shown in Table 1.
<Coating composition 1 for forming a slippery surface layer>
Trademark: Neosilica 4000 (silicone-acrylic copolymer resin: solid content 30% by mass) 100 parts by mass
Isamu Paint Co., Ltd.
Trademark: Silaplane FM4411 (siloxane compound in which both ends X are OH groups and R ₁ is C ₃ H ₆ OC ₂ H ₄ (formula (I)) : active ingredient 100%) Chisso Corporation 5 parts by mass Trademark: Takenate D170N (HDI addition type isocyanurate polyisocyanate: active ingredient 100%) Takeda Pharmaceutical Co., Ltd. 3 parts by mass Trademark: KBM403 (γ-glycidoxypropyltriethoxysilane:
100% active ingredient) Shin-Etsu Chemical Co., Ltd. 3 parts by mass Trademark: Snowtex MEK-ST (organosilica sol: solid content 30
Mass%) Nissan Chemical Industries, Ltd. 10 parts by mass Trademark: TKP103 (anatase type photocatalytic titanium oxide: crystallite diameter 6 nm) 10 parts by mass

Reference example 2
i). Fiber fabric : 1333 dtex alumina fiber (multifilament) warp yarn was weaved in plain weave at an implantation density of 26 yarns / inch per inch, and 1333 dtex alumina fiber (multifilament) weft yarns at an implantation density of 26 yarns / inch per inch. An alumina fiber woven fabric having a mass of 280 g / m ² was used. The fiber fabric had a meshing degree of 1% or less. This was subjected to the same water absorption preventing pretreatment as in Reference Example 1 to obtain an alumina fiber woven fabric having a mass of 281 g / m ² .
ii). Formation of waterproof coating layer : In silicone elastomer precursor composition 1 of Example 1, 30 parts by mass of trademark: Arbolite PF03 (aluminum borate: Shikoku Chemicals Co., Ltd.), manufactured by Borax, Trademark: Fire Break ZB- XF (zinc borate: reinforcing filler powder having an average particle diameter of 2 μm) is the same as Reference Example 1 except that it is changed to 30 parts by mass (silicone elastomer precursor composition 2), and has a mass of 641 g / m ² . A substrate was obtained.
iii). Formation of lubricious surface layer: In slipping surface layer forming coating composition 1 of Example 1, TM: Silaplane FM4411 (at both ends X is OH group, _{R 1} is in the _C 3 _H 6 _OC 2 _{H 4} 5 parts by mass of a certain siloxane compound [Chemical Formula 1]: Chisso Corporation, trademark: Silaplane FM0411 (X is OH group, R ₁ is C ₃ H ₆ OC ₂ H ₄ , R ₂ is CH ₃ ) (Formula (II)) : 100% active ingredient: Chisso Co., Ltd. The flexible base material is the same as Reference Example 1 except that it is changed to 5 parts by mass (coating composition 2 for forming a slippery surface layer). A slipping surface layer having a mass of 3 g / m ² was formed on one surface of the film to obtain a film material (mass 644 g / m ² ) of the present invention. The evaluation results of the obtained film material are shown in Table 1.

Reference example 3
i). Fiber fabric : 555 dtex polyphenylene sulfide fiber (multifilament) warp density of 30 yarns / inch per inch, 555 dtex polyphenylene sulfide fiber (multifilament) weft yarns with a density of 29 yarns / inch A woven fabric of polyphenylene sulfide fiber having a mass of 135 g / m ² was used. The fiber fabric had a meshing degree of 1% or less. This was subjected to the same water absorption prevention treatment as in Reference Example 1 to obtain a polyphenylene sulfide fiber woven fabric having a mass of 136 g / m ² .
ii). Formation of waterproof coating layer : Using the same silicone elastomer precursor composition 1 as in Example 1 , a flexible substrate having a mass of 496 g / m ² was obtained by the same method as in Reference Example 1 .
iii). Formation of lubricious surface layer: In slipping surface layer forming coating composition 1 of Example 1, TM: Silaplane FM4411 (at both ends X is OH group, _{R 1} is in the _C 3 _H 6 _OC 2 _{H 4} 5 parts by mass of a certain siloxane compound [Chemical Formula 1]: Chisso Corp., trademark: SF8413 (X is an epoxy group, R ₁ is CH ₂ O (CH ₂ ) ₃ , R ₂ is (CH ₃ ) ₃ Siloxane compound (formula (III)) : active ingredient 100%: Toray Dow Corning Silicone Co., Ltd.) Same as Reference Example 1 except that it was changed to 5 parts by mass (coating composition 3 for forming a slippery surface layer) A film surface (mass 499 g / m ² ) of the present invention was obtained by forming a slipping surface layer having a mass of 3 g / m ^{2 on} one surface of the flexible substrate. The evaluation results of the obtained film material are shown in Table 1.

Example 4
i). Fiber fabric : 555 dtex polybenzoxazole fiber (multifilament) warp density 30 inches / inch per inch, 555 dtex polybenzoxazole fiber (multifilament) weft density 28 inches / inch per inch A polybenzoxazole fiber woven fabric having a mass of 145 g / m ² woven in a plain weave was used. The fiber fabric had a meshing degree of 1% or less. This was subjected to the same water absorption prevention treatment as in Reference Example 1 to obtain a polybenzoxazole fiber woven fabric having a mass of 146 g / m ² .
ii). Forming waterproof coating layer: except for using a silicone elastomer precursor composition 2 of Reference Example 2 as the same as in Referential Example 1 to obtain a flexible substrate of 506 g / m ^2.
iii). Formation of slippery surface layer: In the coating composition 1 for slippery surface layer formation of Reference Example 1, trademark: Neosilica 4000 (silicone-acrylic copolymer resin: solid content 30% by mass: Isamu Paint Co., Ltd.) 100% Parts: Trademark: Dialomer FF422 (silicone-fluorine-urethane copolymer): solid content 30% by mass: Dainichi Seika Kogyo Co., Ltd.) 100 parts by mass (coating composition 4 for forming a slippery surface layer) Except that, the same as in Reference Example 1, a slipping surface layer having a mass of 3 g / m ² was formed on one surface of a flexible substrate to obtain a film material of the present invention (mass 509 g / m ² ). The evaluation results of the obtained film material are shown in Table 1.

Example 5
i). Fiber fabric : In the glass fiber woven fabric used in Reference Example 1, the first, sixth, eleventh, ... (5n + 1; n = 0, 1, 2, 3, 4, 5) ...) The main piece was changed to 444 dtex polybenzoxazole fiber (multifilament), and changed to a mixed woven plain woven fabric of inorganic fibers and organic heat-resistant fibers in which polybenzoxazole fibers were inserted in a lattice shape. This mixed woven plain fabric had a warp driving density of 39 yarns / inch, a weft driving density of 30 yarns / inch, a mass of 185 g / m ² , a stitching degree of 1%, and an organic heat-resistant fiber mixture ratio of 16% by mass. . This was subjected to the same treatment for preventing water absorption as in Reference Example 1 to obtain a plain weave of 186 g / m ² of inorganic fibers and organic heat-resistant fibers.
ii). Formation of waterproof coating layer : In silicone elastomer precursor composition 1 of Reference Example 1, 30 parts by mass of trademark: Arbolite PF03 (aluminum borate: Shikoku Chemicals Co., Ltd.), manufactured by Mizusawa Chemical Co., Ltd., trademark: Alkanex ZHS (zinc hydroxystannate: reinforcing filler powder having an average particle size of 2 μm) was the same as Reference Example 1 except that the mass was changed to 30 parts by mass (silicone elastomer precursor composition 3), and the mass was 546 g / m ² . A flexible substrate was obtained.
iii). Formation of slippery surface layer: In the coating composition 1 for slippery surface layer formation of Reference Example 1, trademark: Neosilica 4000 (silicone-acrylic copolymer resin: solid content 30% by mass: Isamu Paint Co., Ltd.) 100% Except that the part was changed to 100 parts by mass (coating composition 5 for forming a slippery surface layer) of the trademark: Dia Super Serranker (Acrylic / Silicone Hybrid Resin: Solid content 25% by mass: Kowa Chemical Industry Co., Ltd.) Was the same as Reference Example 1, and a film surface (mass 549 g / m ² ) of the present invention was obtained by forming a slipping surface layer having a mass 3 g / m ^{2 on} one surface of a flexible substrate. The evaluation results of the obtained film material are shown in Table 1.

Reference Example 6
Mass of plain weaving 675 dtex glass fiber (multifilament) warp density of 43.5 yarns / inch per inch and 675 dtex glass fiber (multifilament) weft yarn density of 35 yarns / inch per inch A glass fiber woven fabric of 202 g / m ² was used. The fiber fabric had a meshing degree of 3%.
The fiber fabric was immersed in a layered mineral-containing pretreatment liquid bath having the following composition, and this was pulled up and simultaneously rubber mangled to a pickup rate of 40% by mass, and then dried in a hot air oven at 180 ° C. for 2 minutes for layered mineral treatment. A glass fiber base fabric having a mass of 205 g / m ² was obtained. A membrane material (mass 568 g / m ² ) of the present invention having a slippery surface layer was obtained in the same manner as in Reference Example 1 except for this layered mineral-containing pretreatment. The evaluation results of the obtained film material are shown in Table 2.
<Layered mineral-containing pretreatment composition 1>
Trademark: NK guard NDN7E (acrylic acid perfluoroalkyl ester copolymer resin emulsion) Nikka Chemical Co., Ltd. (solid content 30% by mass) 7 parts by mass Trademark: Nanofil 2 (montmorillonite: average particle size 8 μm, dispersed particle size 100- 500 nm layered mineral: manufactured by Sued-Chemie) 15 parts by mass Trademark: KBM403 (γ-glycidoxypropyltriethoxysilane:
100% active ingredient) Shin-Etsu Chemical Co., Ltd. 3 parts by weight Diluted water 75 parts by weight

Reference Example 7
Mass of 276 g / weave 1333 dtex alumina fiber (multifilament) warp with a weaving density of 26 yarns / inch per inch and 1333 dtex alumina fiber (multifilament) weft yarns with an impact density of 25 yarns / inch per inch An m ² alumina fiber woven fabric was used. The fiber fabric had a meshing degree of 3%.
This was subjected to the same layered mineral treatment (pretreatment composition 1) as in Reference Example 6 to obtain a layered mineral-treated alumina fiber woven fabric having a mass of 280 g / m ² . A membrane material of the present invention (mass 643 g / m ² ) having a lubricious surface layer was obtained in the same manner as in Reference Example 2 except for this layered mineral-containing pretreatment. The evaluation results of the obtained film material are shown in Table 2.

Reference Example 8
Plain weaving 555 dtex polyphenylene sulfide fiber (multifilament) warp density of 29 yarns / inch per inch, 555 dtex polyphenylene sulfide fiber (multifilament) weft yarns density of 28.5 yarns / inch per inch A polyphenylene sulfide fiber woven fabric having a mass of 131 g / m ² was used. The fiber fabric had a meshing degree of 3%. This was immersed in a layered mineral-containing pretreatment liquid bath having the following composition to obtain a layered mineral-treated polyphenylene sulfide fiber woven fabric having a mass of 134 g / m ^{2 in} the same manner as in Reference Example 6. A membrane material (mass 497 g / m ² ) of the present invention having a slippery surface layer was obtained in the same manner as in Reference Example 3 except for this layered mineral-containing pretreatment. The evaluation results of the obtained film material are shown in Table 2.
<Layered mineral-containing pretreatment composition 2>
Trademark: NK Guard NDN7E (perfluoroalkyl ester copolymer resin emulsion) Nikka Chemical Co., Ltd. (solid content 30% by mass) 7 parts by mass Trademark: Micromica MK100 (fluorine mica: layered with an average particle size of 3 μm) Mineral: Coop Chemical Co., Ltd.) 15 parts by mass Trademark: KBM403 (γ-glycidoxypropyltriethoxysilane:
100% active ingredient) Shin-Etsu Chemical Co., Ltd. 3 parts by weight Diluted water 75 parts by weight

Example 9
555 dtex polybenzoxazole fiber (multifilament) warp density of 29 yarns / inch per inch 555 dtex polybenzoxazole fiber (multifilament) weft yarn density of 27.5 yarns / inch A plain woven polybenzoxazole fiber woven fabric having a mass of 143 g / m ² was used. The fiber fabric had a meshing degree of 3%. This was subjected to the same layered mineral treatment (pretreatment composition 2) as in Reference Example 8 to obtain a polybenzoxazole fiber woven fabric having a mass of 147 g / m ² . A membrane material (mass 510 g / m ² ) of the present invention having a slippery surface layer was obtained in the same manner as in Example 4 except for this layered mineral-containing pretreatment. The evaluation results of the obtained film material are shown in Table 2.

The flexible antifouling non-combustible film material obtained in Examples 4, 5 and 9 was subjected to exothermic test (cone calorimeter test specified in ASTM-E1354) by radiating 50 kW / m ² of radiant heat using a radiant electric heater. 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 does not exceed 200 kW / m ² for 20 minutes after the start of heating for 10 seconds or more. Furthermore, no pinhole generation exceeding Φ0.5 mm was observed, and the combustion gas was excellent in smoke shielding properties. Therefore, the fiber fabric laminate obtained by surface coating with the silicone elastomer composition obtained in the present invention can be adapted to the Building Standard Law amended and enforced in 2000, so it is used as a membrane structure member for indoor and outdoor buildings. It is something that can be done. In addition, these film materials of the present invention are such that a slippery surface layer containing a silicone component-containing resin, a functional group-containing siloxane compound, and, if necessary, a polyisocyanate compound is provided on the silicone elastomer coating layer. Because the silicone elastomer coating layer tack (stickiness unique to silicone elastomer) is eliminated, and surface slipperiness is provided instead, immediately after construction, like a tent film material using conventional silicone resin (elastomer) No extremely dusty dirt was generated, and the adhesion of the dirt was very slight. Furthermore, by including photocatalytic titanium oxide as a photocatalytic substance in the slippery surface layer of the film material for tents of the present invention, organic components such as dust dirt and particularly rain streak dirt are decomposed by the photocatalytic effect, and these are separated by rainfall. For example, the initial aesthetics of the tent film material can be maintained over time.

Comparative Example 1
A film material was produced from the film material of Reference Example 1 without the slippery surface layer. The results are shown in Table 3.

Comparative Example 2
In the slippery surface layer of the film material of Reference Example 1, 100 parts by mass of trademark: Neosilica 4000 (silicone-acrylic copolymer resin: Isamu Paint Co., Ltd.) and trademark: Dianal LR-343 (acrylic resin: solid content 30) Mass%: Mitsubishi Rayon Co., Ltd.) A membrane material was produced in the same manner as in Reference Example 1 except that the mass was changed to 100 parts by mass. The results are shown in Table 3.

Comparative Example 3
In the slippery surface layer of the membrane material of Reference Example 1, the trademark: Silaplane FM4411 (siloxane compound in which both ends X are OH groups and R ₁ is C ₃ H ₆ OC ₂ H ₄ [Chemical Formula 1]: Chisso Corporation )) A membrane material was produced in the same manner as in Reference Example 1 except that 5 parts by mass was omitted. The results are shown in Table 3.

Comparative Example 4
A film material was produced in the same manner as in Reference Example 1 except that 10 parts by mass of the trademark: TKP103 (anatase type photocatalytic titanium oxide: manufactured by Crystal Co.) was omitted in the slippery surface layer of the film material of Reference Example 1. . The results are shown in Table 3.

  The film materials obtained in Comparative Examples 1 to 4 have incombustible performance as defined in the Building Standard Law, but the requirements for the slippery surface layer in the present invention, A-1). Photocatalytic substance, A-2). Silicone component-containing resin, A-3). Any one or all of the functional group-containing siloxane compounds are missing, and as a result, the film materials of Comparative Examples 1 to 4 exhibit excellent antifouling properties like the film materials of Examples. I can't. That is, since the film material of Comparative Example 1 lacks the slippery surface layer itself, the adhesive base silicone elastomer layer (waterproof coating layer) is extremely dusty and the film material of Comparative Examples 2-3 is a surface layer. However, since the adhesiveness between the base silicone elastomer layer and the slippery surface layer is insufficient due to lack of the slippery surface layer requirement A-1 or A-3, The surface-resistant surface layer is peeled off and dropped off, and when the base silicone elastomer layer is exposed after one year, the excellent antifouling property as the film material of the example cannot be exhibited for a long time. In addition, the film material of Comparative Example 4 does not have a photocatalytic substance in the surface layer, so that it cannot exhibit excellent antifouling properties like the film material of Examples for a long period of time.

  The membrane material for tents obtained by the present invention can be adapted to the Building Standard Act Combustion Test (Cone Calorimeter Test Method stipulated in ASTM-E1354), which was revised and implemented in 2000, and further smoke shielding of combustion gas Since it is excellent in property, it can be used as a non-combustible tent film material for a film structure member for indoor and outdoor buildings. In particular, the surface layer of the incombustible tent film material of the present invention contains a photocatalytic substance, so that organic components such as dust stains and particularly rain streak stains are decomposed by the photocatalytic effect, and these stains are washed away by rainfall. It is possible to maintain the initial aesthetics of the incombustible tent film material over time. Accordingly, the non-combustible tent membrane material of the present invention is used not only for general tent structures but also for membrane structure facilities that accommodate hundreds to tens of thousands of spectators such as dome stadiums, sports stadiums, pavilions, and event venue facilities. It is widely useful as an antifouling noncombustible film material for building materials.

Claims (9)

A base fabric including a fabric containing at least one of flame retardant fibers and non-combustible fibers, a waterproof coating layer formed on one or more sides of the base fabric and including a silicone elastomer composition, and at least one of the waterproof coating layers A flexible sheet comprising a slippery surface layer formed on a surface,
The slippery surface layer is formed from a composition comprising A-1) a photocatalytic substance component, A-2) a silicone component-containing resin component, and A-3) a functional group-containing siloxane compound component;
The silicone component-containing resin component (A-2) for the slippery surface layer is one selected from a silicone-acrylic-urethane copolymer resin, a silicone-grafted fluorine-containing copolymer, and a silicone-acrylic hybrid three-dimensional structure resin only it contains more than, and,
A compound in which the functional group-containing siloxane compound component (A-3) is represented by the following chemical formulas (I), (II) and (III) :

[In the above formula, X ¹ is any ^one of a halogen group, OH group, NH ₂ group, SH group, COOH group, alkoxy group, ester group, amide group, epoxy group, methacryl group, methacryloxy group and vinyl group. X ² represents a halogen group, OH group, SH group, COOH group, alkoxy group, ester group, amide group, epoxy group, methacryl group, methacryloxy group and vinyl group,
R ₁ represents an alkylene group, R ₂ represents any one of an alkyl group, an alkoxy group, and an alkyl ester group, n represents an integer of 1 or more, and m represents 1 or 2. ]
Including one or more selected from
A flexible antifouling incombustible film material. The composition for forming a slippery surface layer further comprises (A-4) a polyisocyanate compound component in addition to the components (A-1), (A-2) and (A-3). The flexible antifouling non-combustible film material according to 1. The photocatalytic substance component (A-1) is titanium oxide (TiO 2). ₂ ), Titanium peroxide (peroxotitanic acid), zinc oxide (ZnO), tin oxide (SnO) ₂ ), Strontium titanate (SrTiO) _Three ), Tungsten oxide (WO _Three ), Bismuth oxide (Bi ₂ O _Three ), Iron oxide (Fe ₂ O _Three ), And at least one of these doping substances, the flexible antifouling and non-combustible film material according to claim 1 or 2. The flexible antifouling and non-combustible film material according to any one of claims 1 to 3, wherein the sliding surface layer has a static friction coefficient µ of 0.35 or less (measured in accordance with JIS K 7125). The flexible waterproof coating according to claim 1, wherein the waterproof coating layer includes one or more reinforcing filler powders selected from zinc borate, aluminum borate, zinc stannate, zinc hydroxystannate, and cristobalite. Non-fouling film material. The flexible antifouling and non-combustible film material according to claim 1, wherein the non-combustible fiber for base fabric is composed of one or more inorganic fibers selected from glass fiber, silica fiber, alumina fiber, ceramic fiber, and carbon fiber. . 2. The flexible anti-resistance according to claim 1, wherein the flame retardant fiber for base fabric is composed of one or more organic heat resistant fibers selected from aramid fiber, polybenzoxazole fiber, polybenzthiazole fiber, and polyphenylene sulfide fiber. Non-fouling film material. The flexible antifouling and noncombustible film material according to claim 1, wherein the base fabric is pretreated with one or more layered minerals selected from montmorillonite, smectite, and fluorine mica. 50kW / m using radiant electric heater ² In the exothermic test that irradiates the radiant heat, the total calorific value for 20 minutes after the start of heating is 8 MJ / m ² 200 kW / m for 20 minutes after heating is started and the maximum heat generation rate continues for 10 seconds or more. ² The flexible antifouling incombustible film material according to any one of claims 1 to 8, which does not exceed.