JP2651361B2 - Ceramic fire protection sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic fire-resistant protective sheet, and more particularly to a fire-resistant protective sheet having excellent fire resistance and excellent flexibility. The present invention relates to a ceramic fire-resistant protective sheet capable of providing fire resistance.

[0002]

2. Description of the Related Art Conventionally, phenol resin is impregnated into glass fiber as an organic flame retardant on the surface of an aramid honeycomb (Nomex, etc.) as an interior material of an aircraft. There is known an interior material including a cured sheet, a printed polyvinyl fluoride (Tedlar or the like) film, and a non-printed transparent polyvinyl fluoride film in this order.

[0003] Sheets or films made of such materials are used as surface covering materials because of their excellent flexibility and easy handling.

[0004] However, such interior materials using organic flame retardants have a problem that a large amount of smoke and toxic gas is generated when a fire occurs.

[0005] For example, in the Chinese aircraft accident that occurred at Nagoya Airport in April 1994, it is considered that the fire that occurred in addition to the impact of the crash caused a great deal of casualties. Conventional interior materials composed of organic flame retardants and wallpaper generate a large amount of smoke and toxic gas, which makes it impossible to evacuate quickly.

In recent years, higher fire resistance has been required for aircraft interior materials.

[0007] For example, the latest standards of the Federal Aviation Administration (FAA) for cabin interior materials include standards for smoke density (Ds) in addition to conventional standards such as maximum heat release. Therefore, when retrofitting old interior materials (for example, side panels), it is necessary to satisfy the latest standards. For this purpose, it is conceivable to change all of them to new ones, but there is a great problem in terms of cost. In addition, it is very difficult to satisfy such requirements by a method of further coating a conventional organic material on a surface coating material of an old interior material. Further, it is expected that interior materials will be required to have increasingly higher fire resistance performance in the future due to demands for improved safety.

[0008] Such a demand for improvement in fire resistance performance is not limited to aircraft, and similarly exists for interior materials of other vehicles and buildings.

The present invention has been completed based on such circumstances. That is, an object of the present invention is to solve the above problems. An object of the present invention is to provide a ceramic refractory protection sheet having excellent fire resistance and excellent flexibility. The object of the present invention is to
An object of the present invention is to provide a ceramic fire-resistant protective sheet capable of imparting extremely excellent fire resistance performance to the protected member by bonding to the protected member. Further, an object of the present invention is to remarkably improve the fire resistance of the interior material by a very simple process of attaching it to the surface of the interior material of an aircraft, and to greatly improve the safety of the ceramic fire protection sheet. Is to provide. Another object of the present invention is to provide a ceramic refractory protective sheet having a low thermal conductivity and generating very little gas during combustion.

[0010]

Means for Solving the Problems The constitution of the invention according to claim 1 for solving the above-mentioned problems comprises the following component (A):
Prepreg prepared by impregnating or heat-penetrating a liquid or sheet of a matrix composition containing component (B), component (C), component (D) and component (E) into a tow of inorganic fibers or a product of inorganic fibers. Are laminated or formed into a sheet, at a temperature of 120 to 250 ° C. and a pressure of 2 to 10 kg /
A ceramic refractory protective sheet characterized by being cured by heating and pressing under conditions of cm ² .

Component (A): fine powder of a metal oxide having an average particle size of 1 μm or less; component (B): a soluble siloxane polymer having a double-chain structure; component (C): an ethylenically unsaturated double bond. At least one
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.

A first aspect of the present invention will now be described with reference to a preferred embodiment of the present invention.
The amount of the component (A) in the matrix composition is 35
0 to 750 parts by weight, the compounding amount of the component (B) is 80 to 170
Parts by weight, the compounding amount of the component (C) is 25 to 125 parts by weight,
A ceramic refractory protective sheet having a compounding amount of the component (D) of 1 to 4 parts by weight and a compounding amount of the component (E) of 25 to 125 parts by weight. 2. In the invention according to any one of the above items 2, the inorganic fiber is a group consisting of a glass fiber, an alumina fiber, a silica fiber, a Tyranno fiber, and an oxide-based inorganic fiber composed of various fibers containing alumina and / or silica as a main component. A third aspect is the invention according to any one of claims 1 to 3, wherein the product of the inorganic fibers is a towed product and a knitted fabric. A fourth aspect of the present invention is the ceramic fire-resistant protective sheet according to any one of claims 1 to 4, wherein the thickness of the fire-resistant protective sheet is 0.1 mm.
A ceramic refractory protection sheet having a thickness of 1 mm to 5 mm. In a fifth aspect, in the invention according to any one of claims 1 to 5, the component (A) is selected from silica, alumina, and titanium oxide. A sixth aspect of the present invention is the ceramic refractory protection sheet which is an oxide or a composite oxide containing at least one of the above. A seventh aspect of the present invention is a ceramic refractory protective sheet that is a sesquioxane, wherein the component (B) is a polyphenylsilsesquioxane, a polyethylsilsesquioxane, a polymethylsilsesquioxane, and a composition thereof. The sixth ceramic refractory protection sheet, which is at least one selected from the group consisting of monomer copolymers, A ninth aspect of the present invention is the ceramic fire-resistant protective sheet according to any one of claims 1 to 5, wherein the component (C) is γ- (meth) acryloxyalkyl trialkoxysilane. Is
The ceramic refractory protective sheet according to any one of claims 1 to 5, wherein the component (D) is a peroxide whose temperature for obtaining a half-life of 10 hours is 110 ° C or higher. , A tenth aspect of the present invention, wherein:
In the invention according to any one of the above, the component (E) is a polyhydric alcohol di (meth) acrylate and / or a polyhydric alcohol tri (meth) acrylate.

Hereinafter, the present invention will be described in detail.

The matrix composition used for producing the ceramic refractory protective sheet of the present invention contains the following components (A), (B), (C), (D) and (E). I do.

Component (A): fine powder of a metal oxide having an average particle diameter of 1 μm or less; component (B): a soluble siloxane polymer having a double-chain structure; component (C): an ethylenically unsaturated double bond. At least one
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 can be used alone, or two or more of them can be used in combination.

Preferred among these metal oxides are:
An oxide containing at least one selected from alumina, silica and titanium oxide or a composite oxide composed of these.

The metal oxide used in the present invention has an average particle size of 1 μm or less, preferably 0.5 μm or less. The fine powder of the metal oxide having such a fine particle size is densely packed by the component (B) in the three-dimensional network mainly formed by the components (C), (D) and (E). It is included in a joined state. Therefore, when a metal oxide having the above average particle size is used, a ceramic refractory protective sheet having excellent properties such as fracture toughness can be obtained.
On the other hand, when a metal oxide having an average particle size exceeding 1 μm is used, a ceramic refractory protective sheet having good strength cannot be obtained.

Since the metal oxide fine powder stored in the atmosphere has a hydroxyl group on at least a part of its surface, it effectively functions for the bonding effect described later. In contrast,
Fine powders such as metal nitrides and metal carbides cannot be used for producing the ceramic refractory protective sheet of the present invention, because they do not have sufficient hydroxyl groups on a part of the surface.

The soluble siloxane polymer having a double chain structure as the component (B) may be a homopolymer or a copolymer. This component (B) functions as a binder for the metal oxide.

In general, a so-called ladder-type organic polymer having a double-chain structure is considered to be excellent in heat resistance, rigid and small in heat shrinkage as compared with a linear organic polymer. However, organic polymers, even ladder-type,
When heated at a temperature of not less than ° C., it thermally decomposes or shrinks and generates a large amount of gas, which is not preferable for producing the ceramic refractory protective sheet of the present invention.

The present inventors have conducted various studies on binders of fine powders of metal oxides. As a result, siloxane homopolymers or siloxane copolymers having a double-chain structure have a high secondary transition point (glass transition point), It has been found that it has a good bonding effect on oxides, and most of it is converted to a ceramic composition after thermal decomposition, so that it is most suitable as a binder for metal oxide fine particles used in the present invention. The soluble siloxane polymer having a double-chain structure in the present invention includes what is called an oligomer.

As a raw material for preparing a siloxane polymer having a double-chain structure, 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 the 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 as the component (B) is described, for example, in JFB Rown et at.
Polymer Sci., Part C No. 1 p. 83 (1963), prepared by hydrolyzing one or more trialkoxysilanes using an acid catalyst and condensing them by a known method described in (1963). be able to. These are also called polysilsesquiosans, and are generally represented by the following chemical formula.

[0026]

Embedded image

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

Examples of the polysilsesquioxane include polymethylsilsesquioxane, polyphenylsilsesquioxane, polyvinylmethylsilsesquioxane, polyphenylmethylsilsesquioxane, polyphenylpropylsilsesquioxane, and polymethylsilsesquioxane. -N-hexylsilsesquioxane, polyphenylmethacryloxypropylsilsesquioxane, and the like.

Among these, preferred are polyphenylsilsesquioxane, polyphenylmethylsilsesquioxane, and polyphenylethylsilsesquioxane. 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. These are because the heat shrinkage rate during heating is small and the production is easy.

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

For example, polyphenylsilsesquioxane is soluble in a solvent, can form a tough film from the solution, and has a glass transition point Tg of 300.
To 400 ° C., so that thermal deformation during curing can be minimized.

This siloxane polymer does not break its main chain even when heated to 900 ° C., and is converted into a ceramic structure such as amorphous silicon oxycarbide (Si—CO) in high yield. I do. On the other hand, when an organic polymer is used as a binder, the organic polymer is thermally decomposed in the process of baking at normal pressure, the bonding strength between metal oxides is lost, and cracks are generated.

As is apparent from the above description, the soluble siloxane polymer having a double chain structure in the present invention is:
When used as a binder, shrinkage is small even when heated to a high temperature, and the heat-resistant protective sheet shrinks less because it is itself ceramicized. Therefore, the soluble siloxane polymer having a double-chain structure is particularly advantageous for a calcination operation under normal pressure and under unrestricted conditions. Here, the normal pressure includes a case where the operation of increasing or decreasing the pressure is not intentionally performed.

In the present invention, among the above-mentioned soluble siloxane polymers having a double-chain structure, those having a silanol group or an alkoxy group at the molecular terminal are particularly advantageous. The soluble siloxane polymer having a silanol group or an alkoxy group at a molecular terminal has an affinity for the component (A) having a hydroxyl group on at least a part of its surface, that is, fine particles of metal oxide and the soluble siloxane polymer, Easily inter-dispersed. Further, they react and bond with each other during the heating and pressurizing treatment, and are integrally ceramicized during the firing.

In the present invention, the mutual affinity between the component (A) and the component (B) and the component (E) which is an organic substance are increased, and the formation of a strong network structure in the matrix is facilitated, and the matrix material and Not all known silane coupling agents can be used arbitrarily in order to achieve the function and effect of enhancing the bonding property with the inorganic fiber.

In the present invention, a trifunctional silane compound having at least one ethylenically unsaturated double bond in the molecule is used as the component (C). The component (C) easily bonds to the molecular terminals of the soluble siloxane polymer having a double-chain structure, which is the component (B), and the metal oxide fine particles. These bonds are formed by dehydration condensation of hydroxyl groups upon heating. In addition, the trifunctional silane compound as the component (C) easily reacts with the surface hydroxyl group of the inorganic fiber, so that the bonding property between the matrix composition and the inorganic fiber can be improved. Therefore, in this regard, oxide-based inorganic fibers are preferable to nitride-based inorganic fibers and carbide-based inorganic fibers. Further, the ethylenically unsaturated double bond contained in the component (C) reacts with the radical catalyst as the component (D) and is incorporated into a network structure.

The trifunctional silane compound having at least one ethylenically unsaturated double bond in a molecule includes vinyl tris (β-methoxyethoxy) silane, vinyl trimethoxy silane, vinyl triethoxy silane, γ-methacryloxypropyl Examples thereof include trimethoxysilane and γ-methacryloxypropyltriethoxysilane. Among them, γ-methacryloxyalkyl trialkoxysilane is preferable, and γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane are particularly preferable.

In order to form a network structure in the cured product, a crosslinking agent is required. In the present invention, the organic peroxide as the component (D) is effective as a crosslinking agent.

In the present invention, in order for the organic peroxide to work effectively, it is not preferable that the organic peroxide decomposes during the operation before curing to generate radicals. Is preferably 110 ° C. or higher.

Such organic peroxides include dicumyl peroxide, t-butylcumyl peroxide,
Di-t-butyl peroxide, α, α-bis (t-butylperoxyisopropyl) benzene, di-t-butylperoxydiisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy ) Hexin-
3,1,1-bis (t-butylperoxy) -3,3,3
Examples thereof include 5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, and 2,2-bis (t-butylperoxy) octane.

The matrix composition according to the present invention comprises:
In addition to the organic peroxide which is a cross-linking agent as the component (D), a radical polymerizable monomer having at least two, preferably three ethylenically unsaturated double bonds as the component (E) is contained. . This component (E), as a co-crosslinking agent, contributes to the formation of a stronger three-dimensional network structure by curing. The matrix composition containing the component (E) contains fine particles of metal oxide and changes to a network structure having an effective and sufficient chain length that does not deform when heated.

The components (E) include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene glycol diitaconate, tetramethylene glycol diitaconate, ethylene glycol dicrotonate, and ethylene glycol dicrotonate. Maleate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like can be mentioned. In the above example,
The expression (meth) acrylate refers to both acrylate and methacrylate.

Among these, it is excellent in radical polymerizability,
Di (meth) acrylates of polyhydric alcohols and / or tri (meth) acrylates of polyhydric alcohols, such as trimethylolpropanetriene, provide an effective chain length and excellent tackiness to a prepreg as described below. (Meth) acrylates 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 component 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. Preferably, the solvent is completely removed prior to curing, and thus a solvent such as, but not limited to, acetone with a low boiling point is preferred. These solvents may be used alone or in combination of two or more.

In the present invention, the component (A)
It is desirable that the component (E) is dissolved or dispersed in the solvent as uniformly as possible so as to give a dense structure to the ceramic refractory protective sheet. For this purpose, the components (B), (C), (D) and (E)
A method of dissolving each component in a solvent with stirring, adding the component (A) to the obtained solution, and continuing stirring until each component is uniformly dispersed may be adopted.
All of the components (A) to (E) are simultaneously added to the solvent,
The effect of the present invention can be achieved even if a method of sufficiently stirring is adopted. Further, a trace amount of a dispersion stabilizer such as a known surfactant may be added. Furthermore, as long as the properties of the matrix composition are not impaired, addition of known additives is not prevented.

The ratio of each component in the matrix composition is as follows:
It is appropriately selected depending on the type of each component and the performance of the ceramic refractory protective sheet composited therewith. In many cases, the matrix composition has the following component proportions.

That is, the amount of the component (A) is from 350 to
750 parts by weight, preferably 450 to 650 parts by weight,
The compounding amount of the component (B) is 80 to 170 parts by weight, preferably 100 to 150 parts by weight, and the compounding amount of the component (C) is 25 to 1
25 parts by weight, preferably 30 to 80 parts by weight, the compounding amount of the component (D) is 1 to 4 parts by weight, preferably 1.5 to 3 parts by weight, and the compounding amount of the component (E) is 25 to 125 parts by weight; Preferably it is 25 to 100 parts by weight.

As will be described later, the matrix composition used in the present invention can be used with a solvent, or can be used as a sheet after removing the solvent.

The prepreg used in the present invention is produced by impregnating or heating-infiltrating a liquid or sheet of the matrix composition into a tow of inorganic fibers or a product thereof.

The inorganic fibers may be heated to at least 500 ° C. or lower, preferably 1,000 ° C. or lower, more preferably 1200 ° C. or lower in either an inert atmosphere or an oxidizing atmosphere such as air. It is preferable to use a material which has sufficient strength for practical use. Examples of materials satisfying such conditions include nitride-based inorganic fibers, carbide-based inorganic fibers, oxide-based inorganic fibers, and carbon fibers. These inorganic fibers have sufficient heat resistance and reinforcing effect required in the present invention.

Preferred inorganic fibers include glass fibers and
Alumina fiber, silica fiber, Tyranno fiber (Si-Ti-
CO), and oxide-based inorganic fibers composed of various fibers containing alumina and / or silica as a main component.

In the present invention, glass fibers such as E glass fiber and S glass fiber are particularly preferable, and E glass fiber is particularly preferable. Generally, glass fiber has higher room temperature strength than other oxide-based inorganic fibers, so that a thin ceramic refractory protective sheet can be obtained while maintaining a certain fracture toughness. It can be suitably used.

When a commercially available inorganic fiber is used,
It is preferable that the sizing agent attached is removed before use. The inorganic fiber is used as a towed product, or as a knitted or woven fabric.

The prepreg in the present invention includes a solvent method (also separately referred to as a wet method) and a hot melt method (separately referred to as a dry method) employed in the production of a conventional epoxy resin prepreg. It can be manufactured using a similar technique.

In a method according to the solvent method, a tow of inorganic fiber or a product thereof is immersed 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,
A prepreg is obtained.

In the hot melt method, a sheet material having a predetermined basis weight (this term includes a film material as a concept) is formed from a liquid of the matrix composition, and the inorganic fiber tow or the inorganic fiber is formed. By laminating the sheet-like material on one or both surfaces of the product, or alternately laminating the sheet-like material and the inorganic fiber tow or inorganic fiber product, and heating it to a temperature of usually 120 ° C or less. A prepreg can be obtained by infiltrating the matrix composition between the inorganic fibers while lowering the viscosity of the sheet material. The prepreg thus obtained has sufficient tackiness and drapability for lamination formation and sufficient outtime for work.

The prepreg manufactured in this manner is
The sheet is formed into a sheet by a known laminating method or a filament winding method, and then subjected to a heating and pressing treatment, that is, a curing treatment. It should be noted that in the present invention, the curing reaction is sufficiently completed by the one-stage curing, so that the two-stage curing (including the preliminary curing) and the three-stage curing (including the preliminary curing and the post-curing) are not required. That is. However, in some cases, these pre-curing and post-curing may be performed.

The conditions for the heating and pressurizing treatment are as follows:
20-250 ° C., preferably 130-180 ° C., pressure 2-10 kg / cm ² , preferably 3-5 kg / cm <sup>2
2. The</sup> processing time is 10 to 60 minutes, preferably 15 to 30 minutes.

This heating and pressurizing treatment is performed in an autoclave after the vacuum bag or by using a hot press. The latter is advantageous because sheets having a uniform thickness can be produced.

The thus obtained ceramic refractory protective sheet has a thickness of usually 0.1 to 5 mm, preferably 0.1 to 3 mm. When the thickness is within the above range, sufficient fire resistance can be imparted to the interior material, and a certain degree of flexibility is ensured, and workability when attaching the interior material is excellent.

In the ceramic refractory protective sheet of the present invention, shrinkage and surface cracks are not observed, and usually 25 to
It has a bending strength of about 50 kg / mm ² , and hardly shrinks when heated to 700 ° C. in air under normal pressure.

The reason that the ceramic refractory protective sheet hardly causes heat shrinkage is that metal oxide fine particles are filled in a strong three-dimensional network structure formed by curing while maintaining a high density and sufficient contact state. This is considered to be due to the fact that the inorganic fiber and the matrix maintain a good bonding state and do not cause separation or separation.

The ceramic refractory protective sheet of the present invention is used as follows. That is, the ceramic refractory protection sheet of the present invention is usually affixed or adhered to an object to which fire resistance is to be imparted or a surface of a protected member to be protected.

The object to which the ceramic fire-resistant protective sheet of the present invention is applied is not particularly limited as long as fire resistance is required and the ceramic fire-resistant protective sheet of the present invention can be stuck or adhered. From the viewpoint of the above, there may be mentioned interior materials of vehicles and buildings that require improvement of fire resistance performance.

Among the above vehicles, interior materials for aircraft which are required to be lightweight and have extremely high fire resistance,
For example, the ceramic fire-resistant protective sheet of the present invention can be particularly suitably used for ceilings, storages, wall panels, and the like in the machine.

A specific method of using the ceramic refractory protection sheet of the present invention will be described by taking as an example a case where the method is applied to an aircraft wall panel.

FIG. 1 is a sectional view schematically showing an example of a conventional wall panel. The wall panel 1 has a cured sheet 3 made of glass fiber impregnated with phenolic resin, a printed film 4 made of polyvinyl fluoride (Tedlar or the like), and a print on the surface of an aramid honeycomb (Nomex or the like) 2. A transparent film 5 made of the same polyvinyl fluoride which is not applied is provided in this order.

As shown in FIG. 2, for example, the ceramic refractory protection sheet 6 of the present invention can be used by directly affixing it to the surface of the film 5 of the wall panel 1 with an adhesive. The ceramic refractory protection sheet of the present invention can impart a high level of fire resistance to interior materials by such an extremely simple operation.

The ceramic refractory protective sheet of the present invention is characterized in that the sintered ceramic material has a large number of micropores on its surface, whereas the surface of the ceramic refractory protective sheet of the present invention is extremely smooth. Yes, clear printing can be directly applied to the surface. Further, the ceramic refractory protective sheet of the present invention has excellent flexibility as compared with a sintered ceramic material, and thus can be easily attached to a curved surface.

Therefore, when changing the design of the interior of an old model machine, the design can be changed by performing a very simple operation such as simply attaching a printed ceramic refractory protection sheet to the interior material before renovation. At the same time, the latest fire resistance standards can be sufficiently satisfied. This economic benefit is huge.

The method of applying the ceramic refractory protection sheet of the present invention to the wall panel 1 is as follows. Only the film 5 is peeled off, or both the film 5 and the film 4 are peeled off. May be attached. Further, the cured body sheet 3 may also be removed and directly attached to the aramid honeycomb 2.

The ceramic refractory protective sheet of the present invention can impart a high level of fire resistance to the interior material, regardless of whether it is used in any of the above embodiments. Also,
Another surface protective coating may be applied to the surface of the ceramic refractory protective sheet of the present invention.

As an adhesive for bonding the ceramic refractory protective sheet of the present invention to an object or a member to be protected, or a surface protective coating agent for applying the surface protective coating, a silicon-based adhesive having high heat resistance is used. Agents and surface protective coating agents can be suitably used.

The ceramic refractory protection sheet of the present invention can be used for imparting heat resistance to interior materials of buildings. For example, a metal plate may be provided around a device that generates heat, such as a gas range, in order to prevent the surrounding walls and the like from burning or burning due to the heat.

However, since such a metal has a high thermal conductivity, even if the surface does not change, it is subjected to heat for a long period of time and the wood inside thereof is carbonized, causing a fire or a strength. May collapse due to a decrease in

On the other hand, the ceramic refractory protective sheet of the present invention has an extremely low thermal conductivity. Accordingly, heat is blocked by the ceramic refractory protection sheet, and inconveniences such as carbonization of the wood inside are prevented. Table 1 shows the thermal conductivity of the ceramic refractory protective sheet and the metal plate of the present invention.

Further, since the ceramic refractory protective sheet has flexibility like paper, it can be applied very easily regardless of whether the surface of the member to be protected is flat or curved.

[0079]

[Table 1]

[0080]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described more specifically below with reference to embodiments of the present invention. It goes without saying that the present invention is not limited to the following embodiments.

Example 1 Preparation of Matrix Composition 400 parts by weight of alumina powder (average particle diameter: 0.4 μm) and 200 parts by weight of titanium oxide powder (average particle diameter: 0.4 μm) were placed in a ball mill containing ceramic balls. Parts, 125 parts by weight of polyphenylmethylsilsesquioxane (molecular weight 2,300, phenyl / methyl ratio = 6/4), 40 parts by weight of γ-methacryloxypropyltrimethoxysilane, 50 parts by weight of trimethylolpropane trimethacrylate , 5
-Dimethyl-2,5-di (t-butylperoxy) -hexyne-3 (2 parts by weight) and acetone (250 parts by weight) were added and mixed by rotating a ball mill for 1 hour.
A liquid matrix composition uniformly dissolved and dispersed was obtained.

(Example 2--Preparation of Test Specimen) The matrix composition prepared in Example 1 was mixed with an E glass fiber woven fabric (KS-1).
200, manufactured by Kanebo Glass Co., Ltd.), and the excess matrix was removed using a squeeze roll.
5 minutes in a hot air circulating dryer to evaporate the acetone,
An inorganic fiber reinforced prepreg having a matrix composition content of 65% by weight was produced.

The prepreg is rotated by 2 ° in the direction of 0 ° / 90 °.
0 layers are laminated, and at 150 ° C. for 15 minutes, 3.5 kg / cm ²
By a hot press under the conditions described above, a ceramic refractory protective sheet having a thickness of 3 mm was produced. A test piece having a width of 4 mm and a length of 36 mm was cut out from the ceramic refractory protection sheet and used in the following evaluation tests.

--Strength Evaluation Test-- Using the test piece obtained in Example 2, a bending test was performed according to JIS R1601. As a result, the bending strength is
It was 33.8 kg / mm ² .

--Combustion Gas Test-- A combustion gas test was conducted using the ceramic refractory protection sheet obtained in Example 2 to obtain a cured product of a phenolic resin / glass fiber fabric used in conventional aircraft interior parts. Was compared with the case of burning. The results are shown in Table 2. The combustion gas test was performed according to JIS K 7217. As shown in Table 2, in the ceramic refractory protective sheet of the present invention, the amount of generated gas at the time of combustion was 1/5 to 1/10 of that of the conventional phenol resin / glass fiber fabric cured product for any gas. This indicates that the fire safety is high.

[0086]

[Table 2]

--Smoke test-- Using the ceramic refractory protective sheet obtained in Example 2 and the conventional cured product of phenolic resin / glass fiber fabric in the same manner as in the above combustion gas test, according to ASTM F814. A smoke test was performed. Table 3 shows the results. The fireproof sheet made of ceramics of the present invention has a smoke density of 1/7 or less as compared with the conventional phenolic resin / glass fiber woven fabric when burned. It has been shown to be excellent in properties.

[0088]

[Table 3]

The extremely low smoke density during combustion is extremely advantageous when used for interior materials of aircraft.
That is, the current fire resistance standard of the FAA stipulates that the smoke density (Ds) is 200 or less, and the conventional cured product of phenolic resin / glass fiber fabric also satisfies this standard. However, considering the transition of the above standards up to the present, the standards required for interior materials are expected to become even more stringent in the future, and there are times when the use of conventional cured products of phenolic resin / glass fiber fabric is no longer accepted. This is because it is not far away. Table 4 shows the FAA
The outline of the transition of the fire resistance standard is shown below.

[0090]

[Table 4]

--- HEAT RELEASE RATE TES
T) --- The current FAA fire resistance standards include the heat release rate (HEAT RELEAS
Standards for E) are specified. It was examined how the heat release rate changes by attaching the ceramic refractory protection sheet of the present invention to a conventional interior material.

The tests used aircraft side panels manufactured at a time when the heat release rate of the FAA was not met. That is, the side panel was used as a sample as it was and the ceramic refractory protection sheet obtained in Example 2 was adhered to the surface of the sample, and the heat release rate of each of these was measured by OSU (Ohio State University) HEAT RELEASE CHAMBER.
It measured using.

Table 5 shows the results. The conventional side panel does not satisfy the current requirements for the heat release rate of the fire resistance standard. However, the heat release rate of the conventional side panel can be sufficiently reduced by merely attaching the ceramic fire protection sheet of the present invention to the current side. It has been shown that the rate can be reduced.

[0094]

[Table 5]

[0095]

According to the ceramic refractory protection sheet of the present invention, an extremely high level of fire resistance can be imparted to the object by an extremely simple operation of sticking it to the surface of the object.

According to the ceramic refractory protection sheet of the present invention, when the design of the interior material of an aircraft is changed, the standard relating to the fire resistance can be cleared only by sticking to the interior material, so that the cost is significantly reduced. be able to.

By applying the ceramic refractory protection sheet of the present invention to an interior material of an aircraft, it is possible to greatly reduce the generation of toxic gas and smoke when a fire occurs. Therefore, when a fire occurs, quick evacuation becomes possible. In addition, it is possible to reduce the number of evacuation openings, thereby reducing the manufacturing cost of the aircraft.

The ceramic refractory protective sheet of the present invention has a smooth surface and can be directly printed.
Able to withstand aesthetic requirements.

Since the ceramic refractory protective sheet of the present invention has flexibility like paper, it can be stuck even on a curved surface, or is very excellent in handleability.

The ceramic fire-resistant protective sheet of the present invention has an extremely low thermal conductivity in addition to excellent fire resistance, and is therefore suitable for protecting interior materials of buildings from heat.

[0101]

[Brief description of the drawings]

FIG. 1 is a sectional view schematically showing an example of a conventional wall panel.

FIG. 2 is a schematic sectional view showing an example in which a ceramic refractory protection sheet according to one embodiment of the present invention is attached to a conventional wall panel.

[Explanation of symbols]

1 ... wall panel 1, 2 ... aramid honeycomb, 3
..Cured sheets, 4 ... printed films, 5
... Transparent film without printing, 6 ... Ceramic fireproof protective sheet.

Claims (5)

(57) [Claims] 1. The following components (A), (B) and (C)
Laminating or molding a prepreg obtained by impregnating or heating-penetrating a liquid or sheet-like material of a matrix composition containing the component, component (D) and component (E) into a tow of inorganic fibers or a product of inorganic fibers. And temperature 120 ~
A ceramic refractory protective sheet obtained by heating and pressing at 250 ° C. and a pressure of ^{2 to} 10 kg / cm ² . (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. 2. The amount of component (A) in the matrix composition is 350 to 750 parts by weight, the amount of component (B) is 80 to 170 parts by weight, and the amount of component (C) is 25 to 1 part by weight.
The ceramic refractory protective sheet according to claim 1, wherein 25 parts by weight, the compounding amount of the component (D) is 1 to 4 parts by weight, and the compounding amount of the component (E) is 25 to 125 parts by weight. 3. The inorganic fiber is at least selected from the group consisting of a glass fiber, an alumina fiber, a silica fiber, a Tyranno fiber, and an oxide-based inorganic fiber composed of various fibers containing alumina and / or silica as a main component. The ceramic refractory protection sheet according to any one of claims 1 and 2, which is a kind. 4. The ceramic fire-resistant protective sheet according to claim 1, wherein the inorganic fiber product is one of a towed product and a knitted fabric. 5. The ceramic refractory protective sheet according to claim 1, which has a thickness of 0.1 mm to 5 mm.