JPH08276536A - Laminate for interior decoration and its manufacture - Google Patents

Abstract

PURPOSE: To prevent heat from being conducted to the inside of a metal foil i.e., a wall side even though intense heat exists on the sheet side of a laminate for interior decoration. CONSTITUTION: A laminate for interior decoration wherein a sheet formed of ceramic fiber, and matrix containing metal oxide and organic polymer, and at least a metal foil selected in a group consisting of aluminum, gold, and silver are laminated, and its manufacturing method are obtained. Therefore, though there is small problem on heat resisting property of a wall material, a wall is not heated for a specific time. When it is used as a substitution for an inner wall of a chamber of an airplane, a ceiling, a partition, and other wall paper, fire extending at one breath from an intial burning, i.e., a flashover phenomenon is prevented by inhibiting spreading of a fire and generation of gas caused by heating the wall.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate for interior and a method for producing the same, and more specifically, it can prevent the spread of fire and the generation of gas when a fire occurs in a room.
In particular, the present invention relates to an interior laminate useful and suitable as a wallpaper and a simple method for producing the same.

[0002]

2. Description of the Related Art In recent years, various safety requirements are increasing. In particular, in order to prevent the occurrence of fires, the spread of fires, and the generation of toxic and flammable gases in the rooms where people gather and live, for example, in passenger cabins of passenger aircraft, safety standards are becoming stricter year by year. ing.

Therefore, there are many cases in which a material that has passed the old standard fails the new standard. Aircraft that fail the new standard are not immediately banned, but they must pass the new standard when refurbishing unsafe parts. That is, the wall itself must meet the new standard when replacing interior decorations on the wall, such as wallpaper, that met the old standard.

Walls manufactured under the old standard are relatively vulnerable to fire because their materials themselves are not very sensitive to fire. In that case, compared to the case of using a material that has been sufficiently considered, the new interior, that is, the wallpaper, is required to have an extra capacity to prevent such fire spread and gas generation. For example, as a wall material for aircraft,
Conventionally, a honeycomb panel using an epoxy resin has been used. Although the wall material for aircraft currently used is being changed to a honeycomb panel using a safer phenolic resin, there are still many cases where an epoxy resin is still used.

The present invention has been completed based on the above circumstances. An object of the present invention is to solve the above problems.
An object of the present invention is to provide an interior product having a sufficient function to make up for the drawbacks of fire-sensitive materials.

[0006]

The invention according to claim 1 for solving the above-mentioned problems is a sheet formed of ceramic fibers and a matrix containing a metal oxide and an organic polymer, and aluminum. 3. A laminate for interior, which is formed by laminating at least a metal foil selected from the group consisting of, gold and silver.
The invention according to claim 3, wherein the content of the metal oxide is 50 to 80% by weight with respect to the matrix, which is the interior laminate according to claim 1 or 2. Is the interior laminate according to claim 1 or 2, wherein the ceramic fiber has a ferrous iron content of at most 0.5% by weight, and the invention according to claim 4 relates to the metal. The laminate for interior according to any one of claims 1 to 3, wherein the foil is embossed, and the invention according to claim 5 has the sheet as an interior side and the metal foil as an interior substrate. The laminated body for interior according to any one of claims 1 to 4, wherein the sheet is a ceramic fiber, a metal oxide, and an organic material. Polymer and / or organic polymer formable monomers and hardeners The laminate for interior according to any one of claims 1 to 5, which is obtained by curing a prepreg containing an agent, and the invention according to claim 7 is the side opposite to the sheet of the metal foil. The laminated body for interior according to any one of claims 1 to 6, wherein a foamed resin layer and / or a ceramic balloon layer are formed on the sheet. A tow of ceramic fibers or a product thereof is impregnated or heated and permeated with a liquid or sheet of a matrix composition containing the components (A), (B), (C), (D) and (E). A cured product of a prepreg formed by
(A) component; fine powder of metal oxide having an average particle size of 1 μm or less; (B) component; soluble siloxane polymer having a double chain structure; Component; at least one ethylenically unsaturated double bond
A trifunctional silane compound contained in an individual molecule, (D) component; organic peroxide, (E) component; at least two ethylenically unsaturated double bonds.
A radical polymerizable monomer contained in an individual molecule.

The invention according to claim 9 provides a prepreg containing a ceramic fiber, a metal oxide, an organic polymer and / or a monomer and a curing agent capable of forming an organic polymer, aluminum, gold and Laminating at least a metal foil selected from the group consisting of silver, on the outer surface of the sheet, press the uneven mold to heat cure under pressure,
The method for producing an interior laminate, which comprises embossing, according to the invention of claim 10, wherein the prepreg is a component (A); a fine powder of a metal oxide having an average particle size of 1 μm or less, and a component (B). A soluble siloxane polymer having a double chain structure, component (C); at least one ethylenically unsaturated double bond
A trifunctional silane compound contained in an individual molecule, (D) component; organic peroxide, (E) component; at least two ethylenically unsaturated double bonds.
10. The laminate for interior according to claim 9, wherein the tow of ceramic fibers or a product thereof is impregnated or heated and permeated with a liquid or sheet of a matrix composition containing a radically polymerizable monomer contained in individual molecules. It is a method of manufacturing a product.

The interior laminate of the present invention is formed by laminating a specific sheet and a specific metal foil (hereinafter referred to as a metal foil). Therefore, the present invention will be described according to the following table of contents.

(A) Sheet (b) Suitable example of sheet (c) Metal foil (d) Production of interior laminate (e) Use of interior laminate

(A) Sheet The sheet used in the interior laminate of the present invention is a sheet formed of ceramic fibers and a matrix containing a metal oxide and an organic polymer.

Examples of the ceramic fibers include ceramic fibers and whiskers. For example, glass fibers, alumina fibers, silica fibers, tyranno fibers or various fibers containing alumina and / or silica as a main component, or short fibers or long fibers. Examples thereof include oxide-based inorganic fibers made of fibers.

Among the glass fibers, glass fibers containing at most 0.5% by weight of ferrous iron are preferred, and glass fibers containing at most 0.1% by weight are particularly preferred.
The glass fiber containing the ferrous atom in a proportion exceeding 0.5% by weight has a large amount of absorbing far infrared rays emitted from the fire source at the time of a fire, and thus the fire resistance of the interior laminate of the present invention is improved. It is not preferable because it lowers. Here, the first
Iron atoms may exist in the glass in the form of ions,
It may also exist in non-ionic form.

The ceramic fiber used in this invention is
The short fibers or long fibers may be randomly dispersed in the sheet, but it is preferable to have a product form such as a woven fabric, a knitted fabric or a nonwoven fabric. The woven fabric may have a known weaving structure such as plain weave, twill weave, and satin weave.

Examples of the metal oxide contained in the matrix include silica, alumina, titanium oxide,
Lithium oxide, zinc oxide, tin oxide, calcium oxide,
Single oxides such as magnesium oxide, boron trioxide, zirconia, partially stabilized zirconia, vanadium pentoxide, barium oxide, yttria and ferrite, as well as mullite, steatite, forsterite, cordierite, aluminum titanate, titanium. There may be mentioned complex oxides such as barium acid salt, strontium titanate, potassium titanate and lead zirconate titanate. One of these may be used alone, or two or more thereof may be used in combination.

Among these metal oxides, the preferable one is
An oxide containing at least one selected from alumina, silica and titanium oxide or a composite oxide composed of these.

The organic polymer contained in the matrix is not particularly limited, but preferably a polymer obtained by polymerizing the component (B) and the component (C), which will be described in detail later, and the component (E). A polymer obtained by polymerizing The polymer obtained by polymerizing the component (E) is preferably a polymer obtained by polymerizing an ester of a polymerizable unsaturated carboxylic acid, particularly an ester of a polyhydric alcohol.

The mixing ratio of the metal oxide and the organic polymer in the matrix is usually 3 for the metal oxide.
50 to 750 parts by weight, preferably 450 to 650 parts by weight, the organic polymer is 130 to 420 parts by weight, preferably 2
It is from 00 to 350 parts by weight.

In some cases, the content of the metal oxide in the matrix is usually 50 to 80% by weight, preferably 60 to 70% by weight. When the content of the metal oxide is within the above range, the object of the present invention is well achieved.

The content of the ceramic fiber contained in the sheet composed of the ceramic fiber and the matrix is usually 10 to 60% by weight, preferably 30 to 5%.
0% by weight.

The matrix may contain, together with the organic polymer or instead of the organic polymer, a monomer that leads to the organic polymer, such as the component (C) or the component (E), and a curing agent.

Some monomers have already been described. The component (C) or the component (E) will be described later. As the curing agent, a usual polymerization initiator, especially a radical polymerization initiator can be used.

The thickness of the specific sheet used in the interior laminate of the present invention is appropriately determined depending on the use of the interior laminate. When it is used as a surface coating material, the thickness is at least 1.5 mm, preferably 0.5 to 1.5 mm.

In the sheet according to the present invention, the ceramic fibers are dispersed in the matrix, or a prepreg obtained by impregnating the matrix with a product such as a woven fabric, a knitted fabric or a non-woven fabric made of the ceramic fibers is heat-cured. It can be prepared.

(B) Suitable Examples of Sheets Suitable sheets used for the interior laminate of the present invention are:
A ceramic fiber tow or inorganic fiber product is impregnated with a liquid or sheet of a matrix composition containing the following components (A), (B), (C), (D) and (E). Alternatively, it is a cured product of a prepreg obtained by heating and permeating.

Component (A): fine powder of metal oxide having an average particle size of 1 μm or less, component (B): soluble siloxane polymer having a double chain structure, component (C): ethylenically unsaturated double bond At least 1
A trifunctional silane compound contained in an individual molecule, (D) component; organic peroxide, (E) component; at least two ethylenically unsaturated double bonds.
A radical polymerizable monomer contained in an individual molecule.

As the metal oxide as the component (A),
Single oxides such as silica, alumina, titanium oxide, lithium oxide, zinc oxide, tin oxide, calcium oxide, magnesium oxide, boron trioxide, zirconia, partially stabilized zirconia, vanadium pentoxide, barium oxide, yttria and ferrite And complex oxides such as mullite, steatite, forsterite, cordierite, aluminum titanate, barium titanate, strontium titanate, potassium titanate and lead zirconate titanate. One of these may be used alone, or two or more thereof may be used in combination.

Among these metal oxides, the preferable one is
An oxide containing at least one selected from alumina, silica and titanium oxide or a composite oxide composed of these.

Suitable metal oxides have an average particle size of 1 μm.
m or less, particularly 0.5 μm or less. The fine powder of the metal oxide having such a fine particle diameter is mainly composed of the component (C),
It is included in the three-dimensional network structure formed by the component (D) and the component (E) in a densely bonded state by the component (B), and therefore has excellent physical properties and is easily formed into a thin sheet. be able to.

The soluble siloxane polymer having a double chain structure which is the component (B) may be a homopolymer or a copolymer. The component (B) acts as a binder for the metal oxide. The soluble siloxane polymer having a double chain structure in the present invention includes what is called an oligomer.

A raw material for preparing a siloxane polymer having a double-chain structure is represented by the chemical formula R'Si (OR) ₃
(Wherein R is an alkyl group such as a methyl group or an ethyl group,
R ′ represents an aliphatic, alicyclic, or aromatic substituent such as an alkyl group, a phenyl group, a vinyl group, a cyclopentyl group, a cyclohexyl group, and a methacryloyl group. )).

As this trialkoxysilane, methyltriethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, octyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like can be mentioned.

The soluble siloxane polymer having a double chain structure which is the component (B) is, for example, JFB Brown et at., J.
Prepared by hydrolyzing and condensing one or more trialkoxysilanes using an acid catalyst by a known method described in Polymer Sci., Part C No.1 p.83 (1963). be able to. These are also called polysilsesquiosans, and are generally represented by the following chemical formula.

[0033]

Embedded image

However, R ¹ represents a hydrogen atom or R in the chemical formula R′Si (OR) ₃ , and R ² and R ³ represent R ′ in the chemical formula R′Si (OR) ₃ .

Examples of the polysilsesquioxane include polymethylsilsesquioxane, polyphenylsilsesquioxane, polyvinylmethylsilsesquioxane, polyphenylmethylsilsesquioxane, polyphenylpropylsilsesquioxane and polymethyl. Examples thereof include -n-hexylsilsesquioxane and polyphenylmethacryloxypropylsilsesquioxane.

Of these, polyphenylsilsesquioxane, polyphenylmethylsilsesquioxane and polyphenylethylsilsesquioxane are preferable. In the case of a copolymer, the molar ratio of phenyl group to methyl group or ethyl group (phenyl group / methyl group or ethyl group) is preferably 2/1 to 1/2. This is because these materials have a small heat shrinkage ratio during heating and are easy to manufacture.

The molecular weight of the siloxane polymer which is preferable as the binder is not particularly limited, but it is usually preferably 1,000 or more, and particularly preferably 1,500 or more.

As the trifunctional silane compound having at least one ethylenically unsaturated double bond as the component (C), vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, Examples thereof include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane. Among these, γ-methacryloxyalkyltrialkoxysilane is preferable, and γ-methacryloxypropyltrimethoxysilane and γ are particularly preferable.
Methacryloxypropyltriethoxysilane is preferred.

As the organic peroxide which is the component (D),
Dicumyl peroxide, t-butyl cumyl peroxide, di-t-butyl peroxide, α, α-bis (t-butylperoxyisopropyl) benzene, di-
t-butyl peroxydiisopropylbenzene, 2,5
-Dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,1-bis (t-butylperoxy)-
3,3,5-Trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-
Butyl peroxy) octane and the like can be mentioned.

These peroxides function as a polymerization initiator of the above-mentioned components (C) and (E) when heated for curing.

Examples of the component (E) include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene glycol diitaconate, tetramethylene glycol diitaconate, ethylene glycol dicrotonate and ethylene glycol di. Esters of polymerizable unsaturated carboxylic acids such as maleate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, especially polyvalent Mention may be made of esters with alcohols. In the above example, the expression (meth) acrylate indicates both acrylate and methacrylate.

Among these, in forming a crosslinked structure by the component (C) by curing, the chain length of crosslinking is appropriately lengthened, and the sheet before curing has excellent tackiness, that is, the sheet has tackiness. It is excellent in the effect for the purpose of adding this component that it has a property of adhering by laminating sheets and pressurizing them, and because of excellent radical polymerizability, di (meth) acrylate of polyhydric alcohol and And / or tri (meth) acrylates of polyhydric alcohols such as trimethylolpropane tri (meth) acrylate are preferred.

The components constituting the matrix composition described above are dissolved or dispersed in an organic solvent.

The type of the solvent may be appropriately selected depending on the type of each constituent and the mixing ratio thereof. Solvents suitably used in the present invention are selected from alcohols, aromatic hydrocarbons, alkanes, ketones, nitriles, esters, glycol esters and the like. It is preferred that the solvent be completely removed prior to curing, and thus a solvent such as low boiling acetone is preferred, but not necessarily limited thereto. These solvents may be used alone or in combination of two or more.

With respect to the proportion of each component in the matrix composition, the amount of the component (A) is usually 350 to 750 parts by weight, preferably 450 to 650 parts by weight, and the amount of the component (B) is 80 to 170. Parts by weight, preferably 100-150
Parts by weight, the amount of component (C) is 25 to 125 parts by weight, preferably 50 to 100 parts by weight, and the amount of component (D) is 1
-4 parts by weight, preferably 1.5-3 parts by weight and (E)
The blending amount of the components is 25 to 125 parts by weight, preferably 50 to
It is 100 parts by weight.

Examples of the ceramic fiber include glass fiber, alumina fiber, silica fiber, and tyranno fiber (Si-T).
i-CO), and oxide-based inorganic fibers made of various fibers containing alumina and / or silica as a main component. Among these, glass fibers are preferable, and glass fibers having a content of ferrous iron atoms of at most 0.5% by weight are preferable.

When a commercially available ceramic fiber is used, it is preferable to remove the adhering sizing agent before use.

The ceramic fibers are used as a tow draw product or in the form of products such as knitted fabric, woven fabric and non-woven fabric.

The prepreg is prepared by immersing a ceramic fiber tow or a product thereof in a liquid of a matrix composition,
After squeezing out excess liquid, by blowing hot air or passing through a dryer to remove the solvent,
Obtainable.

When the whiskers and / or short fibers are used, the whiskers and / or short fibers are mixed with the liquid of the matrix composition, the resulting mixture is cast on a predetermined plane, and the solvent is dried and removed to prepare the prepreg. You can also get

Alternatively, a sheet-like material having a predetermined basis weight (this term conceptually includes a film-like material) is formed from the liquid of the matrix composition, and the tow of the ceramic fiber or the ceramic fiber is formed. A sheet is prepared by stacking the sheet-like material on one or both sides of the product, or alternately stacking the sheet-like material and a tow of ceramic fibers or a product of ceramic fibers, and heating the sheet to a temperature of usually 120 ° C. or lower. A sheet-shaped prepreg is obtained by infiltrating the matrix composition between the ceramic fibers while reducing the viscosity of the sheet.

When the ceramic fibers are short fibers, the ceramic fibers are uniformly dispersed and mixed in the liquid of the matrix composition, spread on a flat surface or a net in a sheet shape, and the solvent is removed to form a sheet shape. The prepreg can be obtained.

The prepreg thus obtained has sufficient tackiness and drapeability for forming a laminate, and sufficient outtime performance in operation.

The preferred sheet according to the present invention is obtained by heat-curing the prepreg. The heat curing conditions will be described in detail in the section "(d) Manufacturing of laminate for interior".

(C) Metal Foil Metal foil in the interior laminate according to the present invention (hereinafter referred to as
Sometimes referred to as metal foil. ) Is a metal foil selected from the group consisting of aluminum, gold and silver. It is preferable that the surface of each of these metal foils, which is bonded to the sheet, is uneven. When the metal foil surface is uneven, the adhesiveness with the sheet is improved. In order to form unevenness on the metal foil surface to be bonded to the sheet, it is preferable to emboss this metal foil.

However, the metal foil before being attached to the sheet does not necessarily need to have an uneven surface, and for example, the metal foil has a smooth surface without being uneven. The prepreg may be overlapped with the above prepreg, and the resulting superposed product may be heated under pressure with a mold having an uneven surface. As a result, in the obtained interior laminate, the interface between the metal foil and the sheet becomes uneven, and the adhesiveness between the metal foil and the sheet is further improved.

The metal foil may have a glossy surface and a non-glossy surface. In that case, it is preferable to stack the sheet or prepreg on the glossy side, and the inner layer laminate may be used so that the glossy side of the metal foil faces the indoor side. When the interior laminate is used with the glossy surface of the metal foil facing the interior, heat rays or far infrared rays emitted from the flame generated in the interior are effectively blocked or reflected.

The thickness of the metal foil is usually 10 to 30 μm, preferably 15 to 25 μm. A metal foil having this thickness is lightweight and has good adhesion to a sheet.

(D) Manufacture of Interior Laminate The interior laminate of the present invention is obtained by stacking the prepreg and the metal foil, and heat-curing the resulting laminate, preferably by pressure heat-curing. Can be done.

The prepreg to be laminated with the metal foil may be a single layer, or may be a laminated prepreg obtained by laminating a plurality of prepregs.

As the curing condition, a heating temperature of 120 is used.
To 250 ° C., the pressure may be ^{2 to} 10 kg / cm ² , and the treatment time may be 10 to 60 minutes.

Examples of the curing treatment include a curing treatment in which the above-mentioned laminate is vacuum-packed with a soft film and cured in an autoclave, and a treatment in which it is pressure-cured by a hot press.

The mold used for the hot pressing is a flat plate-shaped press in which the surface sandwiching the laminate of the sheet and the metal foil is a smooth surface, or the surface in contact with the metal foil is formed to be uneven. It may be a mold or a press mold having an inner surface that follows the shape of the interior base material to which the interior laminate is attached.

The obtained laminate for interior is one in which shrinkage and surface cracks are not observed, and the weight is hardly reduced. Specifically, this laminate for interior is, for example, 25
It has a bending strength of about 50 kg / mm ² and maintains its shape-retaining property even at a high temperature at which the metal foil does not melt.

The heating atmosphere may be an oxidizing atmosphere such as air or an inert gas atmosphere.

The thickness of the obtained laminate for interior is preferably at most 1.5 mm, particularly 0.5 to 1.5 m.
It is preferably m.

The thus-obtained interior laminate of the present invention is usually formed by laminating the sheet and the metal foil, and the surface of the metal foil opposite to the sheet is a foamed resin and / or ceramic. By stacking balloon-containing layers,
It is also preferable to reduce the thermal conductivity from the metal foil to the inner wall base material or the inner wall material.

The foamed resin is a foamed resin. Examples of the resin used for the foamed resin include epoxy resin,
Silicone resin etc. can be mentioned. Of these, silicone resin is preferable.

The ceramic balloon-containing layer is a resin or ceramic containing hollow ceramic spheres.

The diameter of the hollow ceramic sphere is usually 20-50.
μm. Further, as the hollow ceramics, commercially available shirasu balloons and glass balloons can be adopted.

The ceramic balloon-containing layer is a mixture of the hollow ceramic spheres and the liquid of the matrix composition,
The resulting mixture can be formed by applying the mixture to the back side of the metal foil, that is, the surface of the metal foil on which the sheets are not laminated, and drying and then heat-curing it. Further, an uncured thermosetting resin and the hollow ceramic can be formed. It can also be formed by mixing spheres, applying the resulting mixture to the back side of the metal foil, and curing by heating. In addition, the ceramic balloon-containing layer can be formed by mixing hollow ceramic spheres with a solution of a solvent-soluble resin having a certain degree of heat resistance and drying the mixture.

(E) Use of Interior Laminate The interior laminate of the present invention is used for vehicles such as airplanes, automobiles, railway vehicles, general residences, commercial buildings, and unmanned facilities such as substation facilities and warehouses. Can be suitably used as an interior material for buildings. Among these, it is preferable to use the interior laminate of the present invention for interiors of airplanes, especially passenger planes.

The interior laminate may be provided on the surface of the interior article or may form the interior article itself. Interior products include wall materials and ceiling materials that form a space in which personnel exist, or various interior products that exist in a space in which personnel exist, such as wall lining materials, floor lining materials, and ceiling lining materials. , Luggage storage shelves, various instrument panels, chairs,
Examples include desks, window frame bodies, door frame bodies, wall surface materials, ceiling surface materials, floor surface materials, columns, ribs, panels, cable storage tubes, and fixed substrates for various members.

The interior laminate of this invention is used with the sheet facing the interior.

[0075]

[Examples] 400 parts by weight of alumina powder (particle size; 0.4 μm), 200 parts by weight of titanium oxide powder (average particle size; 0.4 μm), polyphenylsilsesquioxane (molecular weight) ; 1,700) 1
25 parts by weight, 50 parts by weight of γ-methacryloxypropyltrimethoxysilane, 25 parts by weight of trimethylolpropane triacrylate, 2 parts by weight of dicumyl peroxide and 250 parts by weight of acetone were added, and the contents were obtained by rotating the ball mill for 10 hours. A liquid of the matrix composition which was mixed and dispersed and dissolved was obtained.

A glass fiber woven fabric (KS1581, manufactured by Kanebo Glass Co., Ltd., glass composition; SiO ₂ 54%, Al ₂ O ₃ 15%, CaOP 1) was added to this matrix composition liquid.
7%, MgO 5%, B ₂ O ₃ 8%, Na ₂ O 0.6
%) Soaked. Then, a squeeze roll was used to remove excess liquid of the matrix composition, which was then placed in a hot air circulation dryer at 80 ° C. and dried to obtain a sheet-like prepreg having a matrix composition content of 60%. Obtained.

This prepreg and one embossed aluminum foil having a thickness of 25 μm were superposed, vacuum packed with a nylon film by a conventional method, placed in an autoclave, pressure 3.5 kg / cm ² , temperature rising rate 2.5 ° C. / Min at 150 ℃
And then maintained at that temperature for 15 minutes. Then, the temperature was lowered at 4.5 ° C./min to obtain a laminate having a thickness of 0.35 mm.

Foamed silicon (Tosfoam 5310, manufactured by Toshiba Silicon Co., Ltd.) was applied to the surface of the aluminum foil of this laminate to form a foamed silicon layer having a thickness of 1 mm to obtain an interior laminate of the present invention.

The interior laminate was adhered to a 10 mm-thick epoxy resin honeycomb panel with a double-sided adhesive tape made by coating a glass fiber tape with a silicon-based adhesive to obtain a wall material sample as a test sample. Obtained.

This wall material sample was subjected to the University of Ohio heat release rate test apparatus shown in FIG. 1 to measure the maximum heat release rate, total heat release amount, and optical maximum smoke density, to thereby prevent the spread of fire of this wall material sample. Was evaluated. As a result, the maximum heat generation rate of the wall material sample was 30 kW / m ² , and the total heat generation amount was 32.
The kW · min / m ² and optical maximum smoke density was 150.

The fire spread prevention property is evaluated by the maximum heat generation rate of the sample. This fire spread preventive evaluation method is defined in 1988, and is applied to all airplanes manufactured after 1990 in FAR25-853 AMEND. 25-7
It is 2. According to this evaluation method, the maximum heat release rate measured using the Ohio University heat release rate test apparatus shown in FIG. 1 must be 65 kW / m ² or less.

FIG. 1 shows an outline of the University of Ohio heat generation rate test apparatus.

As shown in FIG. 1, in this Ohio University heat generation rate test apparatus 1, a test sample 3 is arranged in a vertical chamber 2 having a rectangular horizontal cross section. The test sample 3 is held vertically by the sample holder 4. The lower part of the test sample 3 is heated by the lower pilot frame 6 injected from the lower pilot combustion pipe 5. An upper pilot combustion pipe 8 for ejecting an upper pilot frame 7 for combusting gas generated from the test sample 3 is arranged above the test sample 3. A radiant heat adjusting baffle plate 9 is arranged in front of the test sample 3 in the horizontal direction, and four heating heaters 10 are arranged between the radiant heat adjusting baffle plate 9 and the wall surface of the vertical chamber 2. The heat rays or far infrared rays emitted from the heater 10 for heating are reflected by the reflector 11
Is reflected by and is directed to the test sample 3. A combustion chamber ventilation air dispersion plate 12 is provided below the vertical chamber 2, and a lower air supply pipe 13 is disposed at the bottom of the vertical chamber 2 and blown out from the lower air supply pipe 13. Air is introduced into the combustion chamber 14 through a vent provided in the combustion chamber ventilation air dispersion plate 12. Five lower thermocouples 15 are arranged on the bottom surface of the vertical chamber 2 to measure the temperature. This lower thermocouple 15
As one arrangement mode, one lower thermocouple 15 is arranged at the intersection of the diagonal lines of the rectangle which is the shape of the bottom surface, and four lower thermocouples 15 are arranged on the diagonal line of the rectangle at a position at a predetermined equidistant distance from the intersection of the diagonal lines. The lower thermocouple 15 of is arranged. A quadrangular pyramid-shaped ceiling plate 16 is provided above the combustion chamber 14 of the vertical chamber 2, and an opening 17 is provided at the top of the combustion chamber 14 so that gas and smoke generated in the combustion chamber 14 become an updraft. Are being distributed. An exhaust port 18 having a rectangular planar shape is provided in the upper portion of the vertical chamber 2. Five upper thermocouples 19 are arranged at the exhaust port 18, and the temperature of the gas passing through the exhaust port 18 is measured. The upper thermocouple 19 is connected to the exhaust port 18
One is arranged at the intersection of the diagonal lines of the rectangular rectangular shape, and four are arranged at a position equidistant from the intersection of the diagonal lines on the diagonal. Further, a light source 20 and a light receiving portion 21 are arranged at the exhaust port 18 so as to face each other, and smoke passing through the exhaust port 18 is detected. The upper thermocouple 19 and the light receiving section 21 are connected to a data analysis computer 22 via a signal line, and the result of data analysis is displayed on the output device 23. An upper cooling air supply pipe 24 is disposed between the ceiling 16 and the vertical chamber 2 to prevent the vertical chamber 2 from being unnecessarily heated.

In this Ohio University heat generation rate test apparatus, air is supplied at a constant flow rate (10 liters / second) through the lower air supply pipe 13, and the combustion chamber 14 is in circulation.
Inside the test sample 4 (15 × 15
cm) is held vertically.

The test sample 4 is exposed to a radiant heat source adjusted to 3.5 W / cm ² and ignited by the lower pilot flame 6 ejected from the lower pilot combustion pipe 5. The generated combustible gas is combusted in the upper pilot flame 7 ejected from the upper pilot combustion pipe 8.

Upper thermocouple 19 set at exhaust port 18
Thus, the exhaust temperature is continuously measured. Measurement time is 5
Minutes.

The heat generation rate is obtained from the air flow rate and the exhaust gas temperature, and the maximum value is the maximum heat generation rate. Normally, the output of the thermocouple is input to the computer so that the progress of the heat generation rate can be illustrated and the maximum heat generation rate can be directly displayed.

[0088]

According to the present invention, the interior laminate can prevent heat from being conducted to the inner side of the metal foil, that is, the wall side, even if high heat is present on the sheet side. Therefore, even if there is a slight problem with the heat resistance of the wall material, the wall will not be heated for a certain period of time, and will be used in place of, for example, the interior wall of an aircraft room, ceiling, bulkhead or other wallpaper. At this time, by suppressing the spread of fire and the generation of gas due to the heating of the wall, it is possible to prevent a so-called flashover phenomenon in which the initial combustion burns and spreads at a stretch, and it is possible to secure the escape time for passengers and passengers. Even if it is a wall material made of conventional epoxy resin used for aircraft, the above-mentioned FAR is obtained by using the interior laminate of the present invention.
25-853 AMEND. It also passes US standards 25-72.

Normally, a material containing an organic substance is vulnerable to a fire, and it is expected that the material will start burning within a short period of time. It is marvelous to pass the above US standards, despite having The reason why the interior laminate of the present invention thus passes the above US standard despite containing the organic substance is considered as follows.

In the flashover phenomenon described above, the wall body is heated by heat conduction from the wall surface, the material composing the wall is thermally decomposed by the heating, and the decomposed gas is generated, and a large amount of the generated decomposed gas is generated all at once. It is considered to be generated by burning. Therefore, in the prior art, the technique for preventing such a flashover phenomenon has focused on reducing the thermal conductivity of the wall material. In the present invention, the direction in which such conventional technology is aimed is completely different. The laminate for interior of the present invention has good heat resistance because the metal foil increases reflection of heat rays and far infrared rays, and the sheet laminated on the metal foil has high far infrared transmittance. It is considered to be a thing.

Furthermore, this interior laminate has good mechanical properties such as lightness and strength.

Since this laminate for interior is sufficiently flexible, it can be easily adapted to a surface other than a flat surface, that is, a curved surface. Therefore, the interior laminate can be mounted on the outer surface of many interior products.

Even if a fire occurs, the organic substance in the sheet changes into a ceramic, so that the interior laminate of the present invention retains further excellent lightness, strength and heat resistance.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an outline of an Ohio University heat generation rate test apparatus.

[Explanation of symbols]

1 ... University of Ohio heat rate tester, 2 ... Vertical chamber 3 ... Test sample, 4 ... Sample holder, 5 ... Lower pilot combustion tube, 6 ... Lower pilot frame, 7 ... Upper pilot frame, 8
... Upper pilot combustion tube, 9 ... Radiant heat adjusting baffle plate, 10 ... Heating heater, 11 ... Reflector plate, 1
2 ... Combustion chamber ventilation air dispersion plate, 13 ... Lower air supply pipe, 14 ... Combustion chamber, 15 ... Lower thermocouple, 1
6 ... Ceiling plate, 17 ... Opening part, 18 ... Exhaust port, 19 ... Upper thermocouple, 20 ... Light source, 21 ...
・ Light receiving part, 22 ・ ・ ・ Data analysis computer, 23 ・
..Output devices, 24 ... Air supply pipes for upper cooling.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B32B 27/20 B32B 27/20 Z 31/20 7148-4F 31/20

Claims (10)

[Claims] 1. A laminate of a sheet made of ceramic fibers and a matrix containing a metal oxide and an organic polymer, and a foil of at least a metal selected from the group consisting of aluminum, gold and silver. An interior laminate characterized by the above. 2. The interior laminate according to claim 1, wherein the content of the metal oxide is 50 to 80% by weight based on the matrix. 3. The interior laminate according to claim 1 or 2, wherein the ceramic fiber has a content of ferrous iron atoms of at most 0.5% by weight. 4. The laminate for interior according to claim 1, wherein the metal foil is embossed. 5. The laminate for interior according to any one of claims 1 to 4, wherein the sheet is laminated on the interior side and the metal foil is laminated on the interior base material side. 6. The sheet according to claim 1, wherein the sheet is obtained by curing a prepreg containing a ceramic fiber, a metal oxide, an organic polymer and / or a monomer capable of forming an organic polymer, and a curing agent. The laminate for interior according to any one of to 5. 7. The laminate for interior according to claim 1, wherein a foamed resin layer and / or a ceramic balloon layer is formed on the side of the metal foil opposite to the sheet. 8. The sheet comprises the following component (A):
Curing of a prepreg obtained by impregnating or heating-permeating a liquid or sheet of a matrix composition containing the component (B), the component (C), the component (D) and the component (E) into a ceramic fiber tow or a product thereof. Claim 1 which is a thing
The laminate for interior according to any one of to 7. (A) component: fine powder of metal oxide having an average particle diameter of 1 μm or less, (B) component: soluble siloxane polymer having a double-chain structure, (C) component: at least one ethylenically unsaturated double bond.
A trifunctional silane compound contained in an individual molecule, (D) component; organic peroxide, (E) component; at least two ethylenically unsaturated double bonds.
A radical polymerizable monomer contained in an individual molecule. 9. A prepreg formed from a ceramic fiber and a metal oxide, an organic polymer and / or a monomer capable of forming an organic polymer and a curing agent is selected from the group consisting of aluminum, gold and silver. A method for producing an interior laminate, which comprises laminating at least a metal foil, pressing an uneven mold on the outer surface of the sheet precursor, heat-curing the composition under pressure, and embossing. Wherein said prepreg, the following (A), (B) component, (C) component, (D) component and (E)
The method for producing a laminate for interior according to claim 9, which is formed by impregnating or heating and impregnating a tow of ceramic fibers or a product thereof with a liquid or sheet of a matrix composition containing components. (A) component: fine powder of metal oxide having an average particle diameter of 1 μm or less, (B) component: soluble siloxane polymer having a double-chain structure, (C) component: at least one ethylenically unsaturated double bond.
A trifunctional silane compound contained in an individual molecule, (D) component; organic peroxide, (E) component; at least two ethylenically unsaturated double bonds.
A radical polymerizable monomer contained in an individual molecule.