JP2004009740A - Honeycomb laminated structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a honeycomb laminated structure which delays the spread of a fire from a fire occurring place to a room of a crew and ensures the time necessary for the escape of the crew. <P>SOLUTION: An inorganic long fiber reinforced ceramic material, in particular a ceramic long fiber reinforced ceramic material 17 is laminated to both surfaces or one surface of a honeycomb 13. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a honeycomb laminated structure.

It is important to ensure the safety of occupants from fires in vehicles such as aircraft, automobiles, and trains, and in buildings such as houses, warehouses, buildings, and various storage facilities. As a vehicle fire, for example, main causes of an aircraft fire accident are ignition of an engine, leakage of electric wiring, and ignition due to contact with the ground at the time of landing. The main cause of a car fire accident is gasoline ignition caused by sparks in an electric system due to the impact of a collision. The cause of a train fire is the ignition of combustibles by the overhead wire spark. Fires in buildings include fires in kitchens, fires from stoves in living rooms, fires from oil tanks, fires from combustible materials in combustible material storage rooms, and the like.

各種 In order to protect personnel from these fire accidents, flame retardant or non-flammable materials for vehicles or buildings are being promoted.

Nevertheless, many of the materials referred to as flame retarded or non-combustible are made of plastic, so they burn at high temperatures even if they have self-extinguishing properties, The flame retardant and the resin containing halogen generate various toxic gases. Therefore, the conventional flame-retardant synthetic resin composition or non-combustible synthetic resin composition eventually burns even though it has been made flame-retardant or non-flammable, and still causes a fire.

The problem here is how to delay the burning of the material if it finally burns, and also delay the burning without generating toxic gas.

For example, if an aircraft has a fire accident on land or at sea, if there is 2 minutes to allow the fire to spread from the place of the fire to the passenger, the passenger can escape outside the aircraft, It is said that damage to passengers can be minimized.

The Federal Aviation Administration, Department of Transport Reguration # 25.803 in the U.S. states that aircraft with more than 44 seats must be able to escape within 90 seconds in an emergency. ing.

In this way, aircraft have very strict safety standards for fire personnel, for example, crew and passengers.Therefore, various materials used in aircraft are required to have sufficient characteristics to satisfy the above safety standards. is there.

The idea that such safety standards for occupants and passengers must be applied not only to aircraft but also to general vehicles such as vehicles, automobiles, trains, etc. is naturally derived from the growing awareness of safety at present. . Therefore, it is desired that various vehicles such as aircraft be made of a material that suppresses generation of toxic gas as much as possible and that delays the start of combustion as much as possible.

パ ネ ル Panels are used on various parts or inner walls of various vehicles such as aircraft. The primary function of this panel is to have impact resistance and sound insulation. Panels in aircraft and the like are also required to function as heat insulating materials. A conventional panel is configured using a honeycomb, an FRP plate, or a laminate thereof.

The cabin of an aircraft cabin (the cabin is usually located on the fuselage of the aircraft) has a honeycomb made of glass fiber and phenolic resin, an epoxy resin plate material provided on the cabin side surface, and an outermost layer on the cabin side. It is formed from decorative plastic films.

フ ェ ノ ー ル However, at the time of fire, phenolic resin is relatively hard to burn, but generates gas at high temperature, and epoxy resin and interior film are easy to burn. Therefore, fire resistance is not yet complete.

Under such circumstances, the present inventors have minimized the generation of toxic gas during combustion and minimized the generation of toxic gas during combustion. However, the combustion of the material can be suppressed as much as possible, a laminated structure suitable as a constituent material of a vehicle, a vehicle capable of suppressing the generation of toxic gas during combustion as much as possible, and suppressing the combustion of the material as much as possible. The aim was to develop building interiors, panels, and buildings that minimize the generation of toxic gases during combustion and minimize the burning of their materials.

Therefore, the inventor first focused on ceramics.

Because ceramics are lighter than metals. Therefore, ceramics is a more preferable material than metal as a material to be used for a vehicle for achieving weight reduction. Metals generally have good thermal conductivity, and ceramics have low thermal conductivity. Metals are oxidized while generating heat at high temperatures, but not in ceramics. Therefore, ceramics is a better material than metal from the viewpoint of protection from fire.

Ceramics have the advantage of being superior in heat resistance, high-temperature strength, oxidation resistance, abrasion resistance, etc. as compared with organic materials or metal materials, but have the disadvantage of low fracture toughness. As a method for improving fracture toughness, that is, toughening without losing the advantages of ceramics, a particle dispersion method, a whisker or short fiber reinforcement method, a long fiber reinforcement method, and the like have been studied.

However, the particle dispersion method and the whisker strengthening method have a drawback that, even if, for example, toughness can be achieved, if only a small part is broken, the entire part is broken at a stretch.

On the other hand, the reinforcing method using long fibers has a greater effect of improving the fracture toughness than other methods.Furthermore, in long fiber reinforced ceramics, even if a load is applied, the fiber bears the load, so the destruction can be done at once. Does not progress and can predict destruction before it is completely destroyed. This predictability of failure is a great advantage in practical use.

However, when a reinforcing method using long fibers is adopted, long fibers that maintain sufficient strength even at a temperature of 1,200 ° C. or more in air and 1,400 ° C. or more in an inert atmosphere are still in practical use. Therefore, development of a method capable of producing a composite at 1,200 ° C. or lower, preferably 1,000 ° C. or lower is desired.

製造 Manufacturing the composite at a low temperature in this way can be expected to significantly reduce the cost. Further, in order to manufacture a product having a curved shape or a complicated shape, a method of laminating and forming a prepreg having good tackiness and drapability as used in manufacturing a carbon fiber / epoxy composite or the like. Is desirable. Furthermore, for industrial production, the sintering operation can be performed in the air without replacing the atmosphere with an inert atmosphere or vacuum, and the molded body is free-standing, that is, under unconstrained conditions. Of course, it is advantageous to be able to sinter.

化学 Chemical vapor deposition and direct metal oxidation are known as methods for producing fiber-reinforced ceramics by directly forming a ceramic matrix between fibers. These methods can be applied not only to long fiber bundles and products thereof, but also to aggregates of short fibers or whiskers.

The chemical vapor deposition method is a method of depositing and depositing a ceramic as a matrix in a fiber bundle or a gap between preforms by chemical vapor deposition (CVI) (for example, JT Hoyt et al., SAMPE J. 27 No. 2, P11 (1991)). Although this method has an advantage that a ceramic matrix is formed at a relatively low temperature, for example, 1,000 to 1,200 ° C., the formation requires a long time, for example, 100 hours, and furthermore, a rate at which voids are generated (void rate) ), And it is difficult to deal with complicated shapes.

The metal oxide (Directed Metal Oxidation) method is a method in which a molten metal is brought into contact with a preform of a reinforcing fiber, and the metal is converted into ceramics by oxidation and nitridation. This method is described, for example, in MS S. Newkirk et al., J. Mater. Sci., 181 (1986). Although this method has the advantage that various ceramic matrices can be formed by changing the metal and the heating atmosphere, the metal tends to remain in the product and the strength tends to decrease at high temperatures. Also in this method, there is a great limitation in manufacturing a product having a complicated shape.

Using prepreg traditionally adopted in the composite material industry, this prepreg is laminated, molded into a predetermined shape to form a product shape, and then fired to convert the matrix component into a ceramic body. As a production method, a slurry impregnation method, a sol-gel method, and a polymer pyrolysis method are known.

The slurry impregnation method is a method in which a prepreg is prepared by impregnating fibers with a slurry liquid containing ceramic fine particles and a binder such as an organic polymer, debindered, and then hot-pressed in an inert atmosphere. This method is described, for example, in CA Doughan et al., Ceram. Eng. Sci. Proc., 10 912 (1989). According to this method, there is an advantage that a fiber-reinforced ceramic product having excellent mechanical properties can be produced, but a high temperature of 1,500 to 1,800 ° C. and a high temperature of 100 to 350 kg / cm ^2. Pressure, and the deterioration of reinforcing fibers other than carbon fibers cannot be avoided. In addition, organic substances are carbonized during binder removal and volatilized and / or thermally shrunk, thereby deteriorating matrix performance and causing cracks and voids.

In this method, water that is inexpensive and easy to remove because of its low boiling point is used as a medium in many cases, but water tends to strongly adsorb to ceramic raw materials such as metal oxides. Therefore, there is a problem that the adsorbed water is not easily removed by heating. This prepreg does not have tackiness.

In the sol-gel method, generally, a metal alkoxide, which is a liquid raw material, is converted from a sol state to a gel state by hydrolysis and condensation in the presence of an acid or an alkali, and further heat is applied to form a ceramic. Say how to let. In this method, it is possible to ceramicize even at a low temperature of 1,000 ° C. or less.

However, disadvantages of this method are the large volume shrinkage when converting a wet gel to a dry gel and the occurrence of voids, cracks and fractures due to shrinkage during firing. That is, the volume shrinkage may reach several tens% in some cases, and cracks are generated between the fibers and the fibers that do not shrink (see JP-A-63-282131).

The polymer pyrolysis method uses an organic metal polymer such as polycarbosilane or polysilazane as a matrix precursor, impregnates it into fibers, creates a prepreg, laminates, cures, and fires to form a ceramic matrix. It is a way to convert. This method is disclosed in, for example, Kiyoto Okamura, Journal of the Japan Society for Composite Materials, # 11 99 (1985). Although this method has the advantage that it can be converted to ceramics even at a temperature of 1200 ° C. or less, considerable shrinkage still occurs when the organometallic polymer is converted to a ceramic composition by thermal decomposition. In addition, these organometallic polymers cannot impart necessary tackiness, and have a problem in shapeability.

The following reports and inventions are disclosed as examples of the production of long fiber reinforced ceramics using the above three methods.

M. Chen et al. Impregnated carbon fiber or silicon carbide fiber with a sol solution mainly composed of boemite and alumina powder having a diameter of 0.5 μm, dried at 50 ° C. for 20 hours, and then dried under a nitrogen atmosphere. After heating to 1,000 ° C. and heating, the mixture was cooled and hot-pressed at 1,200 ° C. using a graphite die to prepare a fiber-reinforced ceramic. It has been concluded that the composite obtained in this way is porous, due to the large shrinkage during heating and sintering (see ECCM-3 Preprints, pp. 89-20-23 March (1989)). .

F. I. Hurwitz et al. Prepared a prepreg by a filament winding method using polysilsesquioxane as a matrix precursor and silicon carbide fibers as reinforcing fibers. The prepreg was stacked in a metal die, and the obtained laminate was kept at 70 ° C. and 689 Pa for 2 hours, and further heated to 180 ° C. and kept at 1.5 ° C. for 1.5 hours. The laminate was taken out of the die and heated to 525 ° C., 1,000 ° C., or 1200 ° C. under a stream of argon. They found that the heat shrinkage during this heating was 19% for polyvinyl (50) methyl (50) silsesquioxane and 13% for polyphenyl (50) methyl (50) silsesquioxane, A large number of cracks are observed in the matrix region between fibers (see Ceram. Eng. Sci. Proc., 10 750 (1989)).

Frank Kang Chi et al. Made a prepreg by impregnating a high modulus fiber with a thermosetting organosilicone resin dissolved in an organic solvent, and partially cured the prepreg at a temperature not higher than 300 ° C (B-Staging). ), Hardening, post-hardening, and then firing at a temperature of at least 1,000 ° C under an inert atmosphere or vacuum (Japanese Patent Publication No. 63-16350). Gazette).

They also formed prepregs by impregnating high modulus fibers with a mixture of an organic silsesquioxane sol and a colloidal metal oxide or a mixture thereof, or an organic silsesquioxane sol and a metal alkoxide or a mixture thereof. A fiber-reinforced ceramic is manufactured from this prepreg using the same hardening and firing operations and heating atmosphere as described above (see Japanese Patent Publication No. 3-77138).

At first glance, their method appears to be a method similar to carbon fiber / epoxy prepreg, but the prepreg has no effective tackiness and is difficult to handle when producing curved or complex shaped products. And peeling between the layers is likely to occur. In addition, since the flow is large, it can not be handled unless it is partially cured, and it requires three steps of curing operations including post-curing until complete curing, so it takes time and effort to manufacture Is a disadvantage. In addition, limiting the firing atmosphere to an inert atmosphere or vacuum obviously results in manufacturing restrictions and cost increases.

HAN, Jong, Hoon discloses a tacky and drapable ceramic binder composition. The composition comprises a polymer such as polymethyl methacrylate, a monomer such as trimethylolpropane trimethacrylate, a peroxide such as dicumyl peroxide and a solvent such as acetone. They composited inorganic fibers such as alumina fibers with a slurry liquid obtained by mixing the binder composition and a ceramic component such as alumina, and then further cured at 149 to 170 ° C, and then cured at a temperature of 480 ° C or less. It discloses a method for producing a fiber-reinforced ceramic in which the binder is removed by firing and the ceramic component is further sintered at 500 to 2,500 ° C. (see WO92 / 22509).

This method uses a cross-linking agent / co-cross-linking agent system commonly used in the industry for vulcanization of rubber or cross-linking of organic polymers (Takuma Matsumoto, "Rubber and organic peroxide vulcanization and co-cross-linking agent" Showa (Taiseisha Co., Ltd., issued October 10, 1 52) was used as it was as a binder for ceramic particles. Unlike the ceramic precursor binder, this method has tackiness and drapability and is expected to have good shapeability. However, this binder is not different from the polymer binder of the conventional slurry impregnation method in that all of the binder is composed of an organic substance. Therefore, after the binder is removed by thermal decomposition, the bonding strength between the ceramic particles rapidly decreases, and has good mechanical strength unless the high-temperature and high-pressure sintering method used in the conventional slurry impregnation method is used. It is difficult to obtain fiber reinforced ceramics.

As described above, the conventional method for manufacturing a reinforced ceramic molded body has the following problems.

That is, (1) a high temperature is required for sintering, (2) a long time is required for production, (3) it is difficult to fire under normal pressure and free standing, and (4) a product having a complicated shape. (5) The use of expensive inert gas is a prerequisite, (6) The matrix material shrinks greatly during heating for ceramification, and the reinforcing fibers and the matrix material are difficult to produce. Since the difference in dimensional change during heating is large, many cracks are generated in the fired body.

These problems are all disadvantages for industrial production and practical application of products, and these are the main causes that have hindered the spread of ceramic composite materials.

An object of the present invention is to provide a vehicle which is formed of a material which uses a ceramic composite material which has solved the above-mentioned problems, suppresses generation of toxic gas during combustion as much as possible, and can suppress combustion of the material as much as possible. Is to do. An object of the present invention is to use a ceramic composite material which has solved the above-mentioned problems, furthermore, suppress generation of toxic gas during combustion as much as possible, and suppress combustion of the material as much as possible. It is another object of the present invention to provide a laminated structure suitable as the above. An object of the present invention is to provide an interior component and a panel which use a ceramic composite material which has solved the above-mentioned problems, suppress generation of toxic gas during combustion as much as possible, and can suppress combustion of the material as much as possible. It is in. An object of the present invention is to provide a building that can be constructed using a material that can suppress generation of toxic gas during combustion as much as possible and that can suppress combustion of the material as much as possible.

解決 In order to solve the above problems, the present inventors have conducted intensive studies and focused on using an inorganic long fiber reinforced ceramic material for at least one of an inner wall and a floor material of a vehicle. Examples of the inorganic long fiber reinforced ceramic material include BLACKGLAS (trade name) described later and a ceramic material developed by the present inventors.

The ceramic material according to the development of the present inventors is manufactured using a prepreg obtained by impregnating or heating-infiltrating a specific matrix composition into a tow of inorganic fibers or a product of inorganic fibers. This prepreg has the same advantages of tackiness, drapeability and long out-time as prepregs for epoxy resin composites. Here, examples of the matrix composition include a composition containing the components (A) to (E) in the present invention and a solvent and an additive included as needed.

The prepreg can be used to produce a laminate having a complicated shape using the prepreg, and is further subjected to heat and pressure molding under substantially the same conditions as the prepreg for the epoxy resin composite, so that the matrix composition has a strong crosslinked structure. , And can be converted into a fiber-reinforced cured product having good bonding properties between the fiber and the matrix. This cured product has higher heat resistance than fiber-reinforced epoxy resin composite materials that are widely used at present, and has its own practicality. From this cured product, it is possible to produce a fiber-reinforced ceramic fired body even under normal pressure firing under unconstrained conditions in air, which is very easy to perform industrially. Almost no change in shape. Here, the heating under the unconstrained condition means that the cured body is heated and fired in a free standing state without taking any measures to prevent deformation such as fixing with a mold or pressing with a press. Means that.

焼 成 The fired body is further impregnated with a liquid containing at least one of the components constituting the matrix composition, and is fired again, thereby filling voids generated during firing and further improving the strength. In this way, fired fiber reinforced ceramic products having various shapes can be easily manufactured. This product can be used for heat-resistant structural members and heat shield members of aircraft and spacecraft, jet engines, rocket engines, gas turbines, and the like. Heat-resistant and heat-shielding members such as engines, turbine blades, space equipment, heater or burner members, molding jigs, tools, or high-temperature furnace members such as furnace walls, furnace core protection tubes, furnace inner vessels, etc. Can be used for

目的 The object of the present invention has been completed based on the above findings.

That is, the invention according to claim 1 is a honeycomb laminated structure in which an inorganic long fiber reinforced ceramic material is laminated on both surfaces or one surface of the honeycomb,
According to a second aspect of the present invention, the inorganic long fiber reinforced ceramic material forms a prepreg composed of a ceramic long fiber, a metal oxide, an organic polymer and / or a monomer to be an organic polymer and a curing agent thereof. The honeycomb laminated structure according to claim 1, wherein the honeycomb laminated structure is fired after curing.
The invention according to claim 3 is a matrix composition in which the inorganic long fiber-reinforced ceramic material contains the following components (A), (B), (C), (D) and (E). The honeycomb laminated structure according to claim 1 or 2, wherein a prepreg formed by impregnating or heating and impregnating the liquid or sheet-like material into a tow of inorganic fiber or a product of inorganic fiber is formed, cured, and fired. Yes,
(A) component: fine powder of metal oxide having an average particle size of 1 μm or less,
(B) component; a soluble siloxane polymer having a double-chain structure,
(C) component; trifunctional silane compound having at least one ethylenically unsaturated double bond in a molecule;
(D) component; organic peroxide,
Component (E); a radically polymerizable monomer having at least two ethylenically unsaturated double bonds in the molecule. The invention according to claim 4, wherein the amount of the component (A) in the matrix composition is 350 to 750 parts by weight,
(B) the compounding amount of the component is 80 to 170 parts by weight,
(C) a compounding amount of the component is 25 to 125 parts by weight,
The honeycomb laminated structure according to claim 3, wherein 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,
According to a fifth aspect of the present invention, the inorganic long fiber reinforced ceramic material comprises the component (A), the component (B), the component (C), the component (D) and the component (E) according to the third aspect. ,
A prepreg obtained by impregnating or heating-penetrating a liquid or sheet-like material of the matrix composition containing the content according to claim 4 into a tow of inorganic fiber or a product of inorganic fiber is formed and cured. A honeycomb laminated structure according to claim 3 or 4, wherein:
The invention according to claim 6 is that the component (A) is an oxide or a composite oxide containing at least one selected from silica, alumina, and titanium oxide;
The component (B) is a polysilsesquioxane,
The component (C) is γ- (meth) acryloxyalkyl trialkoxysilane, and the component (D) is a peroxide having a temperature of 110 ° C. or higher for obtaining a half-life of 10 hours,
The component (E) is a polyhydric alcohol di (meth) acrylate and / or a polyhydric alcohol tri (meth) acrylate,
The above-mentioned claim, wherein the inorganic fibers are at least one selected from the group consisting of glass fibers, alumina fibers, silica fibers, Tyranno fibers, and oxide-based inorganic fibers composed of various fibers containing alumina and / or silica as a main component. Item 6. The honeycomb laminated structure according to any one of Items 3 to 5,
The invention according to claim 7 is the honeycomb laminated structure according to any one of claims 1 to 6, wherein the surface of the inorganic long fiber reinforced ceramic material is coated with a fired glaze.

According to the present invention, since the inner wall material and the floor material using the ceramic long fiber reinforced ceramic material are used, it is possible to provide a vehicle and a building that protect occupants from a fire accident.

According to the present invention, it is possible to provide a honeycomb laminated structure or interior component suitable for a vehicle and a building capable of protecting personnel from a fire accident by using a ceramic long fiber reinforced ceramic material. it can.

Hereinafter, the present invention will be described in detail.
-Vehicle-
The vehicle has at least an inner wall made of an inorganic long fiber reinforced ceramic material, for example, a long ceramic fiber reinforced ceramic material.

The term vehicle refers to any vehicle in which an occupant must ride and protect the occupant from fire, such as passenger aircraft, cargo aircraft, transport aircraft, small aircraft, helicopters, amphibious boats, and combat vehicles. Aircraft such as aircraft, space shuttles, space planes such as manned rockets and spacecraft, railway vehicles such as trains and trains, automobiles such as buses, trucks, passenger cars, and special vehicles, passenger ships, cargo ships, tankers, pleasure boats And marine vessels such as hydrofoils, submarines, and submarines.

The inner wall material of the vehicle is not particularly limited as long as it is a wall material that needs to protect the occupant from fire.For example, a structural material forming a space surrounding the occupant, a space where a fire may occur, and the presence of the occupant And a structural material surrounding a space where a fire may occur in order to protect an occupant from a fire.

空間 The space surrounding the occupant includes, for example, a passenger cabin, a crew deck, a toilet, a cockpit, a cooking room (galley), and the like, and a cargo room and the like may be a space where a fire may occur.

Examples of the inner wall material include structural materials constituting a wall body, a ceiling, a storage opening / closing door, a doorway, a floor material, and the like in a space where an occupant is present or a space where a fire may occur. . In addition, floor materials and doors may not be generally referred to as walls, but in this specification, the inner wall material in the present invention is understood as a broad concept including structural materials constituting floor materials and doors. You.

態 様 FIG. 1 shows an embodiment in which this inner wall material is used. This inner wall material is used, for example, as the inner wall 3 of the cabin 2 of the passenger aircraft 1, the floor material 5 separating the cabin 2 from the cargo compartment 4, the ceiling material 6 of the cabin 2, and the like.

This inner wall material is a structural material having an inorganic long fiber reinforced ceramic material molded into a predetermined shape such as a plate shape, a curved plate shape, and a tubular shape. A member that can be fixed by an appropriate fixing means such as an adhesive, screwing, or nailing is included.

−Architecture−
The building of the present invention is provided with an inner wall material made of an inorganic long fiber reinforced ceramic material, in particular, a ceramic long fiber reinforced ceramic material (this term is used in a meaning including a floor material).

As shown in FIG. 7, the building 28 includes a vertically standing wall body 29, a floor member 30 bridged between the wall bodies 29, and a beam member 31 bridged at the upper end of the wall body 29. And a roofing material 34 mounted on an oblique material 33 supported at the upper end of the wall 29 and other portions. The wall body 29, floor material 30, ceiling material 32, and roof material 34 can be formed of an inorganic long fiber reinforced ceramic material, particularly a ceramic long fiber reinforced ceramic material, and can be formed of the above-described honeycomb laminated structure. .

−Interior goods−
The interior part is made of an inorganic long fiber reinforced ceramic material.

As the interior parts, various interior parts existing in the space where the occupants and the like exist, such as wall lining materials and floor linings, in addition to the wall and ceiling materials forming the space where the occupants and the like exist. Upholstery materials, ceiling lining materials, baggage storage shelves, various instrument panel surfaces, chairs, desks, window frames, door frames, wall surface materials, ceiling surface materials, floor surface materials, columns, ribs, dashboards, cable storage Examples include a tube and a fixed substrate for various members. In short, the interior components of the present invention are based on materials that exist in spaces where people are present, live or work, and the presence of personnel in order to effectively prevent the spread of fires in the spaces where people are present. Includes materials that exist in spaces where fire must be prevented with or without fire.

内装 The interior product may have a structure in which the surface is formed of an inorganic long fiber reinforced ceramic material. As a preferred structure, both surfaces are formed of an inorganic long fiber reinforced ceramic material, and the inside is a sheet, film, plate of a flame retardant resin or a flame retardant resin composition and / or a flame retardant resin or a flame retardant resin composition. It is formed of a foam.

There are no particular restrictions on the form of interior accessories. The shape of the inorganic long fiber reinforced ceramic material can be determined so as to have a shape corresponding to the shape originally possessed by the interior component.

例 An example of a structure suitable for interior products is shown in the drawing.

As shown in FIG. 2, in the laminated structure 7, a flame-retardant resin sheet 9 is laminated on both sides of a sheet 8 formed of a heat-resistant resin composition, and an adhesive 10 is applied to the flame-retardant resin sheet 9. An inorganic long fiber reinforced ceramic material layer 11 is formed therebetween.

The flame-retardant resin composition comprises, for example, an inorganic fiber and a heat-resistant resin. As the inorganic fibers, glass fibers, alumina fibers, silica fibers, Tyranno fibers or oxide-based inorganic fibers composed of various fibers containing alumina and / or silica as a main component, and, in some cases, carbon fibers may be used. it can.

Examples of the heat-resistant resin used in the flame-retardant resin composition include phenol resin, polyphenylene sulfide, polysulfone, polyether sulfone, wholly aromatic polyester, amorphous polyarylate, polyetheretherketone, polyimide, and epoxy resin. And the like. Preferred heat resistant resins include phenolic resins and super engineering plastics such as polyphenylene sulfide.

Examples of the flame-retardant resin used in the flame-retardant resin composition include a thermoplastic resin containing a halogen atom. Preferred examples thereof include polyvinyl fluoride, polyfluorinated ethylene-propylene copolymer, and polyfluorinated copolymer. And vinylidene.

The inorganic long fiber reinforced ceramic material will be described later.

As the adhesive, a normal adhesive called a structural adhesive, for example, an epoxy-based adhesive, a cyanoacrylate-based adhesive, or the like can be used. An epoxy adhesive or the like can be used as an adhesive suitable for forming the laminated structure.

The thickness of the sheet formed of the heat-resistant resin composition, the flame-retardant resin sheet, and the inorganic long-fiber reinforced ceramic material depends on what kind of inner wall material or interior product uses this laminated structure. It can be determined appropriately.

In this laminated structure, it is preferable that the surface of the inorganic long fiber reinforced ceramic material is coated with a sintered product of glaze. When the sintered product of the glaze is coated on the surface of the inorganic long fiber reinforced ceramic material, the laminated structure can be made gas-impermeable. Therefore, when an inner wall material or an interior part is formed of this laminated structure having a glaze sintered material on its surface, toxic gas in the event of a fire does not pass through the laminated structure, thereby ensuring the safety of occupants. be able to. In particular, by surrounding the space where the occupant is present with this laminated structure covered with the sintered product of the glaze, it is possible to prevent toxic gas in the event of a fire from entering the space, or The entry of toxic gas can be delayed.

Examples of the glaze include perhydropolysilazane, “Cosmocoat” (trade name), which can be easily obtained commercially as “polysilazane” (trade name).

-Honeycomb laminated structure-
The honeycomb laminated structure of the present invention can be used for interior parts and panels of the present invention.

Various structures can be adopted as the honeycomb laminated structure as long as the honeycomb laminated structure has a structure in which the inorganic long fiber reinforced ceramic material is laminated on both surfaces or one surface.

FIG. 3 shows a preferred embodiment of the honeycomb laminated structure. As shown in FIG. 3, in the honeycomb laminated structure 12, a sheet 14 formed of a flame-retardant resin composition is laminated on both surfaces of a honeycomb 13, and a flame-retardant resin sheet 15 is laminated on the surface of the sheet. An inorganic long fiber reinforced ceramic material 17 is laminated on the surface of the flame retardant resin sheet 15 via an adhesive 16.

材質 The material of the honeycomb is not particularly limited as long as it has a honeycomb core. Examples of the honeycomb include a structure using a metal honeycomb formed of a metal such as aluminum, an aluminum alloy, and stainless steel, and a structure using a non-metal honeycomb formed of a resin such as a flame-retardant resin or an engineering plastic. be able to.

(4) In order to further improve the flame retardancy of the honeycomb laminated structure, the honeycomb is preferably formed of a metal honeycomb, and in order to reduce the weight and increase the rigidity, the honeycomb is preferably formed of an aluminum honeycomb. In some cases, the honeycomb laminated structure may be formed of ceramics or an inorganic long fiber reinforced ceramic material.

When this honeycomb laminated structure is used in combination with a honeycomb and an inorganic long fiber reinforced ceramic material, in addition to being able to maintain lightness, strength and shock absorption, it is possible to prevent fire from spreading from a place where a fire has occurred, The combustion of the structure itself can be delayed.

This flame-retardant resin composition can be prepared by, for example, mixing inorganic fibers and a heat-resistant resin. As the inorganic fibers, glass fibers, alumina fibers, silica fibers, Tyranno fibers or oxide-based inorganic fibers composed of various fibers containing alumina and / or silica as a main component, and in some cases, carbon fibers may be used. Can be.

Examples of the heat-resistant resin used in the flame-retardant resin composition include phenol resin, polyphenylene sulfide, polysulfone, polyether sulfone, wholly aromatic polyester, amorphous polyarylate, polyetheretherketone, polyimide, and epoxy resin. And the like. Preferred heat resistant resins include phenolic resins and super engineering plastics such as polyphenylene sulfide.

Examples of the flame-retardant resin used in the flame-retardant resin composition or the flame-retardant resin used in the flame-retardant resin sheet include a thermoplastic resin containing a halogen atom. Examples thereof include polyvinyl fluoride, polyfluoroethylene propylene copolymer, polyvinylidene fluoride and the like.

The inorganic long fiber reinforced ceramic material will be described later.

Usable adhesives include ordinary adhesives called structural adhesives, such as epoxy adhesives and cyanoacrylate adhesives.

The thickness of the honeycomb, the sheet formed of the heat-resistant resin composition, the flame-retardant resin sheet, and the inorganic long-fiber reinforced ceramic material is determined by what kind of inner wall material or interior part of the honeycomb laminated structure is used. Can be determined as appropriate.

に お い て In the honeycomb laminated structure, it is preferable that the surface of the inorganic long fiber reinforced ceramic material is coated with a sintered product of glaze. When the sintered product of the glaze is coated on the surface of the inorganic long fiber reinforced ceramic material, the honeycomb laminated structure can be made gas-impermeable. Therefore, if an inner wall material or an interior part is formed of the honeycomb laminated structure having a glaze sintered material on its surface, toxic gas in the event of a fire does not pass through the honeycomb laminated structure, and the occupant's safety is reduced. Can be achieved. In particular, by surrounding the space where the occupant is present with this honeycomb laminated structure covered with the sintered product of the glaze, it is possible to prevent toxic gas in the event of a fire from entering the space, Alternatively, the entry of toxic gas can be delayed.

の 他 Another embodiment of the honeycomb laminated structure is shown in the drawings. The honeycomb laminated structure 18 shown in FIG. 4 is a sheet 20 in which a thermosetting resin such as a phenol resin is impregnated on both surfaces of a honeycomb 19 into a glass fiber sheet, for example, a glass fiber woven, knitted or nonwoven fabric sheet. Are laminated, and an inorganic long fiber reinforced ceramic material 21 is laminated on the surface of one of the sheets 20, and various patterns are printed on the surface of the inorganic long fiber reinforced ceramic material 21 for the purpose of improving the appearance, or A colored decorative sheet 22 is laminated, and a transparent protective sheet 23 is laminated on the surface of the decorative sheet 22. In addition, this honeycomb laminated structure can be used so that the transparent protective sheet 23 faces the indoor side.

ハ The honeycomb laminated structure shown in FIG. 4 can be used, for example, as an inner wall material of an aircraft door as shown in FIG. Note that the door 24 shown in FIG. 5 is a door attached to an entrance into the aircraft.

ハ The honeycomb laminated structure shown in FIG. 4 can be used, for example, as shown in FIG. 6, for an opening / closing lid of a baggage storage shelf installed in an aircraft. As shown in FIG. 6, the baggage storage shelf 25 in the aircraft has an opening / closing lid 27 that covers the shelf main body 26 and is formed to be openable and closable.

In addition to the above, these honeycomb laminated structures can be used for the inner wall material or interior parts of the present invention. The honeycomb laminated structure is suitable for flooring materials because of its strength. In a honeycomb laminated structure, an inner wall material, or an interior product, an inorganic long fiber reinforced ceramic material is laminated on a surface on a space side where a heat source such as a fire exists.

-Panel-
The panel of the present invention is formed using an inorganic long fiber reinforced ceramic material. INDUSTRIAL APPLICABILITY The panel of the present invention can be used for structural materials and interior parts constituting vehicles and buildings. The panel of the present invention is used by forming the honeycomb laminated structure on a curved surface or in a plate shape so as to conform to a predetermined structure. In particular, this panel can be suitably used as the outer surface of the fuselage of an aircraft or the inner wall of the cabin. When the panel is used to form an aircraft fuselage, the panel is mounted on an H-shaped frame assembled to form the fuselage, with the end of the panel inserted into a groove in the frame. , Or attached. Since the aircraft must keep the interior of the passenger compartment airtight, an airtight treatment is performed between the panel and an exterior material such as an aluminum plate or an alumina plate.

If this panel is mounted on the cabin side of the aircraft, and if inorganic fiber reinforced ceramic material, especially ceramic long fiber reinforced ceramic material, is facing the cabin side, the use of organic material for this panel will cause a fire. Even if smoke or gas is generated from the organic material sometimes, the inorganic long fiber reinforced ceramic material, particularly the ceramic long fiber reinforced ceramic material, can effectively prevent the smoke, gas, etc. from leaking into the passenger compartment. it can.

天井 As a building panel, as shown in FIG. 8, a ceiling panel 35, a wall panel 36, a floor panel 37, a foundation floor panel 38, a door panel 39, and the like can be given. Other panels used in buildings include fireproof wall panels and fire wall panels in kitchens.

These panels can be formed from the inorganic long fiber reinforced ceramic material, particularly the ceramic long fiber reinforced ceramic material, and can be formed from the above-described honeycomb laminated structure.

-Inorganic long fiber reinforced ceramic material-
As the inorganic long fiber reinforced ceramic material in the present invention, (1) after molding and curing a prepreg comprising an inorganic long fiber, a metal oxide, an organic polymer and / or a monomer to be an organic polymer and a curing agent and a solvent thereof A fired ceramic material (when ceramic fiber is used as the inorganic fiber, this may be referred to as a ceramic long fiber reinforced ceramic material), and (2) silicon carboxide, a silicon-based glass having a high refractive index ( SiCx Oy) and a precursor (monomer or low polymer) of a thermosetting polymer, formed of silicon carbide and carbon atom-dispersed by molding (coating, spinning, lay-up of prepreg, etc.) and firing. Ceramic composite materials can be mentioned.

と し て As the ceramic composite material, "BLACKGLAS" (trade name, manufactured by Allied-Signal Inc) can be mentioned.

The ceramic material, which is a ceramic long fiber reinforced ceramic material, can be manufactured by molding a prepreg, curing it, and firing it, as described below.

マ ト リ ッ ク ス The matrix composition used for producing the prepreg contains the following components (A), (B), (C), (D) and (E).

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

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

の Among these metal oxides, oxides containing at least one selected from alumina, silica and titanium oxide or composite oxides composed of these are preferred.

Suitable metal oxides have an average particle size of 1 μm or less, especially 0.5 μm or less. The metal oxide fine powder having such a fine particle size is densely packed by the component (B) in a three-dimensional network formed mainly by the components (C), (D) and (E). , Which facilitates sintering. When metal oxide particles having an average particle size exceeding 1 μm are used, a ceramic long fiber reinforced ceramic material having good strength may not be obtained.

金属 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. On the other hand, fine powders such as metal nitrides and metal carbides do not have sufficient hydroxyl groups on a part of their surfaces, and therefore the object of the present invention cannot always be sufficiently achieved. In addition, if it is attempted to produce a ceramic body using only the fine powder of the metal oxide, a high-temperature and high-pressure sintering operation is required, so that the effects of the present invention cannot be achieved, and therefore, the object of the present invention is achieved. I can't.

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.

Generally, 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, even when the organic polymer is a ladder type, it thermally decomposes or shrinks when heated at 500 ° C. or more and generates a large amount of gas. Therefore, such a ladder type organic polymer is used as a binder. Even if it is used to produce a prepreg fired body, many cracks and bubbles are generated in the prepreg fired body.

As a result of various studies on a binder of a fine powder of a metal oxide, the inventors have found that a siloxane homopolymer or a siloxane copolymer having a double-chain structure has a high second order transition point (glass transition point), Since it has a good joining effect, and most of it is converted to a ceramic composition after thermal decomposition, it has been recognized that it is most suitable as a binder for metal oxide fine particles 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, a chemical formula R′Si (OR) ₃ (where R is an alkyl group such as a methyl group and an ethyl group, R ′ is an alkyl group and a phenyl group And an aliphatic, alicyclic or aromatic substituent such as a vinyl group, a cyclopentyl group, a cyclohexyl group, and a methacryloyl group.).

Examples of the trialkoxysilane include methyltriethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, octyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, and γ-methacrylate. Roxypropyltrimethoxysilane and the like can be mentioned.

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

Here, 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-n- Hexylsilsesquioxane, polyphenylmethacryloxypropylsilsesquioxane and the like can be mentioned.

中 で も Among them, 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.

分子 The molecular weight of the siloxane polymer that is preferable as the binder is not particularly limited, but is generally 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 high glass transition point Tg of 300 to 400 ° C., so that heat during curing and firing is low. Deformation can be minimized. Further, even when the polymer is heated to 900 ° C., the main chain is not broken, and the polymer is converted into a ceramic structure such as amorphous silicon oxycarbide (Si—C—O) in high yield.

On the other hand, when an organic polymer is used as the 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 clear from the above description, when the soluble siloxane polymer having a double-chain structure in the present invention is used as a binder, the shrinkage is small even when heated to a high temperature, and the resin itself becomes a ceramic. Shrinkage becomes smaller. 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 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 the molecular terminal has an affinity for the component (A) having a hydroxyl group on at least a part of its surface, that is, the metal oxide fine particles and the soluble siloxane polymer, Easily inter-dispersed. In addition, they react with each other at the time of heating and combine with each other, and at the time of firing, they are integrally ceramicized.

However, even a soluble siloxane polymer having a double-chain structure with high thermal stability shows a shrinkage of about 10% when heated to a high temperature of about 1,000 ° C., causing a dimensional change in the fired body. At the same time, cracks and voids may be generated. Therefore, the object of the present invention cannot be achieved only by using the component (B).

In order to prevent the molded body from being deformed even at normal pressure and under unconstrained conditions during firing up to 1200 ° C., the present inventors have proposed that a prepreg cured body should have a strong three-dimensional It was recognized that it was effective to form a network structure.

In order to form a three-dimensional network structure, the component (C) is a trifunctional silane compound having at least one ethylenically unsaturated double bond in a molecule, and the component (D) is an organic compound. A radically polymerizable monomer having at least two ethylenically unsaturated double bonds in the molecule, which is a peroxide and a component (E).

As already described in the prior art, a cross-linking system using a combination of a rubber or polymer with a cross-linking agent (peroxide) and a co-cross-linking agent (reactive monomer) is already known. Component (C), a trifunctional silane compound having at least one ethylenically unsaturated double bond in the molecule, component (D), an organic peroxide, and component (E). A cross-linking system based on a combination with a radically polymerizable monomer having at least two ethylenically unsaturated double bonds in a molecule is not known.

The silane coupling agent is a compound having a reactive group chemically bonding to an inorganic substance such as a methoxy group and a reactive group chemically bonding to an organic substance such as a resin such as a vinyl group and an amino group in a molecule. It is widely used to improve the adhesion to organic substances such as, for example, and to increase the strength of the composite. The silane coupling agent is usually used in either or both of a method of treating the surface of the inorganic substance in advance and a method of mixing the resin with the resin.

According to the present invention, if the affinity between the components (A) and (B), which are ceramic or ceramic precursor components, and the component (E), which is an organic substance, is increased, it is easy to form a strong network structure in the matrix. It requires an action and an effect of tightening and enhancing the bondability between the matrix material and the inorganic fibers.

全 て To achieve such an effect or effect, all known silane coupling agents cannot be used. In the ceramic material as the ceramic long fiber reinforced ceramic material in the present invention, a trifunctional silane compound having at least one ethylenically unsaturated double bond in a 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 a hydroxyl group upon heating. Further, since the trifunctional silane compound as the component (C) easily reacts with the surface hydroxyl group of the inorganic fiber, 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) to be incorporated into a network structure.

Examples of the trifunctional silane compound having at least one ethylenically unsaturated double bond in a molecule include vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane. And γ-methacryloxypropyltriethoxysilane. Among them, γ-methacryloxyalkyl trialkoxysilane is preferable, and γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane are particularly preferable.

架橋 A crosslinker is required to form a network structure in the cured product that is a precursor of the ceramic long fiber reinforced ceramic material. In the present invention, the organic peroxide as the component (D) is effective as a crosslinking agent.

In order for organic peroxides to work effectively in order to obtain ceramic long fiber reinforced ceramic materials, those which decompose and generate radicals during the operation before curing are not preferred, and thus have a half-life of 10 hours. Is preferably an organic peroxide having a temperature of 110 ° C. or higher.

Examples of such organic peroxides include dicumyl peroxide, t-butylcumyl 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-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane and the like.

A matrix composition for obtaining a ceramic long fiber reinforced ceramic material comprises, as a component (D), at least two ethylenically unsaturated double bonds as a component (E), in addition to the organic peroxide serving as a crosslinking agent, It preferably contains three radically polymerizable monomers. 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 component (E) includes ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene glycol diitaconate, tetramethylene glycol diitaconate, ethylene glycol dicrotonate, ethylene glycol dimaleate, Examples thereof include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. In the above example, the expression (meth) acrylate indicates both acrylate and methacrylate.

Among these, di (meth) acrylates of polyhydric alcohols and / or polyhydric alcohols are preferable in that they are excellent in radical polymerizability, give an effective chain length, and give prepregs excellent tackiness as described later. Tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate are preferred.

各 Each component constituting the matrix composition described above is dissolved or dispersed in an organic solvent.

The solvent may be appropriately selected according to 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 acetone with a low boiling point is preferred, but not necessarily limited thereto. These solvents may be used alone or in combination of two or more.

In order to obtain a ceramic long fiber reinforced ceramic material, the components (A) to (E) are dissolved or dispersed in the solvent as uniformly as possible so as to give a dense structure to the fired ceramic matrix body. It is desirable to have. For this purpose, each of the components (B), (C), (D) and (E) is dissolved in a solvent while stirring, and the component (A) is added to the obtained solution. A method of continuing stirring until the particles are uniformly dispersed may be employed. Alternatively, a method of simultaneously adding all of the components (A) to (E) to the solvent and stirring sufficiently may be employed. Good ceramic long fiber ceramic material can be obtained. Further, a minute 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.

(4) The proportion of each component in the matrix composition is appropriately selected depending on the type of each component and the performance of a prepreg cured product or a prepreg fired product formed by combining the components. In many cases, the matrix composition has the following component proportions.

That is, the compounding amount of the component (A) is 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 component (C). Is 25 to 125 parts by weight, preferably 50 to 100 parts by weight, component (D) is 1 to 4 parts by weight, preferably 1.5 to 3 parts by weight, and component (E) is It is 25 to 125 parts by weight, preferably 50 to 100 parts by weight.

タ The tackiness of the prepreg is adjusted by the amount of the component (E) in combination with other components. Therefore, the role of the component (E) is not limited to the formation of a network structure, but also plays an important role in forming tackiness, which is an important effect of the present invention.

マ ト リ ッ ク ス The matrix composition for obtaining the ceramic long fiber reinforced ceramic material is used with a solvent as described later, or is used as a sheet after removing the solvent.

プ リ A prepreg for obtaining a ceramic long fiber reinforced ceramic material can be produced by impregnating or heating and impregnating a liquid or sheet of the matrix composition into a tow of inorganic fibers or a product thereof. A prepreg for obtaining a ceramic long fiber reinforced ceramic material can also be obtained by mixing the matrix composition with cut fibers of 1 cm or more. The ceramic long fiber reinforced ceramic material having a predetermined shape can be obtained by molding a prepreg sheet or directly molding a mixture of the matrix composition and cut fibers of 1 cm or more.

As the inorganic fiber, even in an inert atmosphere or an oxidizing atmosphere such as air, even if heated to at least 500 ° C. or less, preferably 1,000 ° C. or less, more preferably 1,200 ° C. or less, Those that maintain the strength to withstand are preferable. 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, alumina fibers, silica fibers, Tyranno fibers (Si-Ti-CO), and oxide-based inorganic fibers composed of various fibers containing alumina and / or silica as a main component. Can be. Although the glass fiber is reduced in strength at high temperatures, its strength at room temperature is higher than that of other oxide-based inorganic fibers, so that even at a temperature near 600 ° C., the ceramic long fiber has sufficient strength to achieve the object of the present invention. A reinforced ceramic material can be obtained. Although carbon fibers can be used as the inorganic fibers, the heat resistance of carbon fibers in the presence of air is 900 ° C or higher, and some fibers are not so excellent at 800 ° C or higher. It is preferable to coat with a material that does not easily diffuse air, such as glass. In addition, it is preferable to use without firing or to lower the firing temperature. Otherwise, long ceramic fibers are superior to carbon fibers.

When a commercially available inorganic fiber is used, it is preferable to use the inorganic fiber after removing the adhering sizing agent.

A filament is usually used as the inorganic fiber, but staples may be used as long as the length is 1 cm or more.

The characteristic of fiber-reinforced ceramics is that the fiber bears a load while the breaking process is controlled by the frictional force between the fiber and the matrix interface. Therefore, in the case of fiber reinforced ceramics, unlike fiber reinforced plastics and fiber reinforced metal, the bonding force at the interface between the fiber and the matrix is not too strong, and the fiber is controlled to such an extent that the pull-out of the fiber can be guaranteed. Is particularly important (see Koichi Niihara, NIKKEI / MECHANICAL / 1989/12/11 p114). This means that even if it is desired that the fiber and the matrix composition are sufficiently bonded in the prepreg and the cured prepreg, it is preferable that the fiber and the matrix are rather weakly bonded in the fired prepreg. Is shown.

炭素 Carbon and boron nitride are known as fiber surface coating agents capable of forming such an interface. In air, carbon is oxidized above about 450 ° C. and boron nitride above about 900 ° C., thereby providing a weak interface between the fibers and the matrix. It is effective to apply such a known fiber surface coating to the inorganic fiber used in the present invention in advance to further improve the mechanical properties of the fired prepreg.

Inorganic fibers are used as a towed product, or as a knit or woven fabric.

A prepreg for obtaining an inorganic long fiber reinforced ceramic material, for example, a ceramic long fiber reinforced ceramic material, includes a solvent method (also separately referred to as a wet method) and a hot melt method (which are conventionally employed in the production of an epoxy resin prepreg). It is manufactured by using a method similar to that described above.

In the method according to the solvent method, the inorganic fiber tow or its product is immersed in the liquid of the matrix composition, and after squeezing out the excess liquid, hot air is blown or passed through a drier to remove the solvent. By doing so, a prepreg is obtained.

Further, in the hot melt method, a sheet-like material having a predetermined basis weight (this term includes a film-like material as a concept) is formed from a liquid of the matrix composition, and tow of inorganic fiber or product of inorganic fiber is formed. By laminating the sheet-like material on one or both sides, or alternately laminating the sheet-like material and the inorganic fiber tow or inorganic fiber product, and heating this to a temperature of usually 120 ° C or less, the sheet-like material The prepreg is obtained by infiltrating the matrix composition between the inorganic fibers while decreasing the viscosity of the prepreg.

プ リ The prepreg thus obtained has sufficient tackiness and drapability for lamination formation and sufficient outtime for work.

This prepreg is flexible and has adhesiveness. Therefore, it is possible to sufficiently follow various complicated shapes and structures. Furthermore, even when integrated with other materials, if the mating material has heat resistance, it is integrated at the prepreg stage and then fired to reduce the adhesive that causes gas and smoke at high temperatures. It can be molded into interior parts such as panels or surface materials without using them.

Therefore, the panel formed by laminating the inorganic long fiber reinforced ceramic material, particularly the ceramic long fiber reinforced ceramic material, and the honeycomb is suitable as a favorable inner wall material, honeycomb structure, and interior product.

The prepreg manufactured in this manner is formed into a predetermined shape necessary for the inner wall material of the vehicle by using a known laminating method or a filament winding method or the like, and then heated and pressurized, that is, A curing process is applied. It should be particularly noted in the present invention that the curing reaction is sufficiently completed by one-stage curing, so that two-stage curing (including preliminary curing) and three-stage curing (including preliminary curing and post-curing) are not required. That is. However, in some cases, these pre-curing and post-curing may be performed.

Preferred curing treatment conditions include a heating temperature of 120 to 250 ° C., a pressure of ^{2 to} 10 kg / cm ² , and a treatment time of 10 to 60 minutes.

The curing operation is performed in an autoclave after a vacuum bag or by using a hot press.

The former is advantageous for industrial production because it can produce complex and large products.

The obtained cured prepreg has no shrinkage and no surface cracks, and hardly loses weight. Specifically, the cured product has a flexural strength of, for example, about 25 to 50 kg / mm ² , and hardly shrinks even when heated to 1,000 ° C. in air under normal pressure.

The reason why the prepreg hardened body hardly causes thermal shrinkage is that the solid three-dimensional network structure formed by hardening is filled with fine particles of metal oxide while maintaining a high density and sufficient contact state, In addition, it is considered that the inorganic fiber and the matrix maintain a good bonding state and do not cause separation or separation.

プ リ The obtained cured prepreg is converted to a fired body reinforced with inorganic fibers by heating to a temperature of 500 to 1,200 ° C, preferably 600 to 1,000 ° C, if necessary. The heating temperature may be a temperature exceeding 1,200 ° C., but heating to an excessively high temperature may not be preferable because the strength of the inorganic fiber may decrease. Further, deformation and cracks are effectively generated by heating at a temperature rising rate of 5 ° C./min or less, preferably 2 ° C./min or less in the temperature range up to 500 ° C. in the initial stage of the temperature rise, particularly in the temperature range of 100 to 450 ° C. Can be prevented. Under such heating conditions, the cured prepreg can be heated under normal pressure and under unrestricted conditions. The prepreg cured body heated to a predetermined temperature in this manner is cooled at a predetermined temperature for preferably 10 minutes or more, and then cooled according to a conventional method.

The heating atmosphere may be an oxidizing atmosphere, for example, any of an air and an inert gas atmosphere. However, the prepreg fired body obtained in an inert atmosphere has a carbon content remaining in the matrix without being released by thermal decomposition and exhibits a black color. When this prepreg fired body is fired again in the air, the carbon content is released and the fired prepreg becomes white. Therefore, if the prepreg fired body is used as it is in the high-temperature atmosphere in the inert atmosphere, the residual carbon content is oxidized and released as a gaseous body. In addition, a prepreg fired body in an inert atmosphere tends to have lower strength than a prepreg fired body in air. In view of these points, firing in an inert atmosphere can be performed, but is not necessarily advantageous in terms of the number of steps and performance as compared with firing in air.

One of the important effects of the present invention is that the sintering operation can be performed in air, under normal pressure, and under non-binding conditions without deformation. This makes it possible to easily manufacture a large ceramic component having a complicated shape.

In order to achieve this effect, all of the five components (A), (B), (C), (D) and (E) are essential as components of the matrix composition, If one component is missing, the object of the present invention cannot be achieved. The prepreg fired body which is the ceramic long fiber reinforced ceramic according to the present invention can be sufficiently put to practical use as it is, but its performance can be further improved by the following densification treatment.

硬化 The prepreg cured product contains an organic component in a ratio of 10 to 15%, depending on the mixing ratio of the constituent components. Some of this is taken into the ceramic composition, while the rest is released as a gas during firing, so that fine voids are formed in the fired body. This fine void is immersed in a liquid containing the components (A) to (E) constituting the matrix composition or a liquid containing at least the component (B). It can be filled, preferably by refiring at a temperature between 600 and 1200C. This densification process may be repeatedly performed. In the present invention, the prepreg fired body subjected to such densification treatment can also be suitably used as an inorganic long fiber reinforced ceramic material, for example, a ceramic long fiber reinforced ceramic material.

す る When the inorganic long fiber reinforced ceramic material thus obtained, for example, a ceramic long fiber reinforced ceramic material is laminated on another material, it is preferable to use a heat-resistant inorganic adhesive for the lamination. The use of this heat-resistant inorganic adhesive is also applicable to the formation of the honeycomb laminated structure, the interior product, and the inner wall material. When an inorganic long fiber reinforced ceramic material such as a ceramic long fiber reinforced ceramic material is laminated on another material, when an organic adhesive is used for the lamination, a phenol resin or the like is used rather than using an epoxy adhesive. It is preferable to use a phenol-based adhesive, particularly a phenol-based adhesive containing a vinyl-modified phenol resin. Such a phenol-based adhesive is preferable because it has low heat build-up and smoke emission during combustion.

-Fire evaluation method-
When inorganic long fiber reinforced ceramic materials, especially ceramic long fiber reinforced ceramic materials, are applied to the interior wall materials and interior parts used for aircraft in vehicles, the requirements for fire protection required for aircraft materials can be satisfied. .

要求 This required value is a criterion that is evaluated by the test method described in FAA Regulation 14 CFR Ch.1 (1-1-93 version) Section 25.853, Part 1.

The required values in the above test method are (1) self-extinguishing property in vertical flame test, (2) average burn length (Average Burn Length) does not exceed 6 inches, (3) remove flame source (4) The average burning time after dropping should not exceed 15 seconds on average after dripping from the sample.

The contents of this test method are as follows.
(a) Test atmosphere temperature; 70 ± 5 ° F
Humidity: 50 ± 5% RH

(b) Test execution conditions After the temperature and humidity reach the equilibrium state, or after 24 hours have elapsed, a combustion test is performed. The sample is left in the equilibrium state.

(c) Sample shape Cut out a flat plate from the product. Create a sample of the same shape. In the case of a sandwich panel, the test is performed with its structure. The sample thickness shall not exceed the minimum product thickness.

(d) Fixing the sample Fix the four corners of the sample with a metal frame. The sample surface exposed to the flame should be at least 2 inches (width) x 12 inches (length). The sample surface exposed to the flame at the time of the 45-degree combustion test described later is 8 inches (width) × 8 (length).

(e) Number of samples The number of samples shall be three or more. The test result is the average of the test results for three or more samples.

(f) Flame source Use a Bunsen burner or a Tirrill burner. The inner diameter of the burner is 3/8 inch. The height of the flame shall be 1.5 inches. As the flame temperature, the center temperature of the flame is 1550 ° F. Temperature shall be measured with a thermocouple or pyrometer.

(g) Test content
(g-1) Vertical test A flame of a burner that is leveled is sprayed on the vertical surface of a vertically erected sample. The distance between the tip of the burner and the vertical plane of the sample is 3/4 inch. The test time is 60 seconds.

(g-2) Horizontal test A burner flame is sprayed on the horizontal lower surface of the sample held horizontally. The distance between the tip of the burner and the horizontal lower surface of the sample is 3/4 inch. The test time is 15 seconds.

(g-3) 45-degree test A burner flame is sprayed on the lower surface of the sample inclined at 45 degrees. One third of the flame hits the sample. The test time is 30 seconds.

Example 1-Preparation of Matrix Composition I
400 parts by weight of alumina powder (average particle diameter: 0.4 μm), 200 parts by weight of titanium oxide powder (average particle diameter 0.4 μm), polyphenylmethylsilsesquioxane (molecular weight 2,300) Phenyl / methyl ratio = 6/4) 125 parts by weight, γ-methacryloxypropyltrimethoxysilane 40 parts by weight, trimethylolpropane trimethacrylate 25 parts by weight, 2,5-dimethyl-2,5-di (t-butyl) 2 parts by weight of peroxy) -hexyne-3 and 250 parts by weight of acetone were added and mixed by rotating a ball mill for 1 hour to obtain a liquid matrix composition I which was uniformly dissolved and dispersed.

Example 2-Preparation of Matrix Composition II
125 parts by weight of polyphenylethylsilsesquioxane (molecular weight 1,700, phenyl / ethyl ratio = 5/5) in a glass cylindrical container equipped with a stirrer, 100 parts by weight of γ-methacryloxypropyltriethoxysilane, 30 parts by weight of trimethylolpropane triacrylate, 1.3 parts by weight of dicumyl peroxide and 250 parts by weight of acetone were added and stirred until a homogeneous solution was formed. To this solution, 300 parts by weight of alumina powder (average particle size: 0.4 μm) and 200 parts by weight of silica powder (average particle size: 0.02 μm) were added with stirring, and the mixture was dispersed well by applying ultrasonic vibration to obtain a matrix composition. II was prepared.

Example 3-Preparation of Matrix Composition III
The acetone in the matrix composition was evaporated until the solution viscosity was 300 poise by slowly stirring the matrix composition prepared by the method of Example I above. As a result, a dense matrix composition III having good film-forming ability was obtained.

Example 4 Production of Prepreg I
A textile (Altex cloth, SV-600-8H, manufactured by Sumitomo Chemical Co., Ltd.) of alumina fibers (85% by weight of alumina, 15% by weight of silica) is immersed in the matrix composition I prepared in Example 1, and then squeezed. Excess matrix was removed using a roll, and the mixture was placed in a hot air circulating drier at 80 ° C. for 5 minutes to evaporate acetone, thereby producing an inorganic fiber reinforced prepreg having a matrix composition content of 60% by weight.

(4) The tackiness, drapability and out time of this prepreg were evaluated by a method similar to that of the conventional epoxy prepreg, and the results are shown in Table 1. As shown in Table 1, good results were obtained.

(Example 5-Preparation of prepreg II)
A film having a thickness of 0.15 mm was prepared from the matrix composition III prepared in Example 3 using a film coater. This film was affixed to both sides of the same alumina fiber woven fabric used in Example 4, and impregnated with a hot roll at a temperature of 120 ° C to prepare a prepreg having a matrix composition content of 50%. It was confirmed that this prepreg had tackiness, drapability and out time which passed the evaluation method shown in Example 4 above.

Example 6 Preparation of Prepreg III
A pre-degreased tow (Altex SV-10-1K, manufactured by Sumitomo Chemical Co., Ltd.) of alumina fibers (85% by weight of alumina, 15% by weight of silica) is immersed in the liquid matrix composition I prepared in Example 1. Thus, the composition I was impregnated in the tow, squeezed with a nozzle, wound around a 30 cm diameter drum around which release paper was wound with a filament winder at a pitch of 1.5 mm, cut and removed from the drum. This was put into a hot air circulating dryer at 80 ° C. for 5 minutes to evaporate acetone, thereby producing a unidirectional prepreg having a matrix composition content of 50%. It was confirmed that this prepreg also had tackiness, drapability, and out time that were acceptable by the evaluation method shown in Example 4.

(Example 7--Production of cured prepreg I)
Nine layers of the prepregs produced in Example 6 were laminated in the 0 ° direction in a vacuum bag by a conventional method, placed in an autoclave, and heated to 220 ° C. at a pressure of 7 kg / cm ² and a heating rate of 2.5 ° C./min. After holding for 30 minutes, the temperature was lowered at 4.5 ° C./min to produce a 3 mm-thick prepreg cured product plate. A test piece having a width of 4 mm and a length of 36 mm was cut out from the cured prepreg and subjected to the same bending test in the following examples in accordance with JIS R 1601, and found to have a bending strength of 57.7 kg / mm ^2. Was. In addition, the measurement values shown below this example are average values of five samples.

(Example 8--Production of cured prepreg II)
Four layers of the prepregs produced in Example 4 were laminated in the directions of 0 ° and 90 °, and a cured prepreg having a thickness of 2 mm was produced by hot pressing at 200 ° C. for 15 minutes at 3.5 kg / cm ² . . The obtained cured prepreg had good mechanical strength, no shrinkage and no surface cracks were observed, and the weight loss was 0.7%. The flexural strength of this cured prepreg was measured in the same manner as in Example 7, and was found to be 28.0 kg / mm ² .

(Example 9--Production of cured prepreg III)
Four layers of the prepregs manufactured in Example 5 were laminated in directions of 0 ° and 90 °, and a cured prepreg having a thickness of 2 mm was manufactured by hot pressing at 150 ° C. for 15 minutes at 3.5 kg / cm ² . . The obtained cured prepreg had good mechanical strength, no shrinkage and no surface cracks were observed, and the weight loss was 0.6%. The flexural strength of this cured prepreg was measured in the same manner as in Example 7 and was 32.3 kg / mm ² .

(Example 10-Firing I of Precured Prepreg)
The cured prepreg prepared in Example 7 was heated in air under normal pressure at a rate of 1 ° C./min to 500 ° C., and then heated to 1,000 ° C. at 2 ° C./min. The alumina fiber reinforced ceramic laminate (prepreg fired body) was manufactured by firing by holding for a time.

寸 法 Almost no dimensional change was observed between the cured prepreg and the fired prepreg. The weight was reduced by 7.3% compared to before the firing.

−−High temperature strength test−−
Table 2 shows the results of the high-temperature bending test performed on the laminate at 800 ° C. and 1,000 ° C. The bending test was performed according to JIS R1604. As shown in Table 2, there was a tendency for the strength to increase as the temperature increased. This is presumed to be due to the fact that the bonding property between the fiber and the matrix decreases due to the increase in temperature, the pull-out effect of the fiber increases, and / or the elongation of the matrix increases.

−−Heat cycle test−−
With respect to this laminate, the room temperature flexural strength was measured in each cycle when the thermal cycle was changed between room temperature and 1,000 ° C. to 5, 10, 15, and 20 times, and the results shown in Table 3 were obtained. Was. As shown in Table 3, no decrease in strength was observed in the heat cycle between room temperature and 1000 ° C.

(Example 11-Firing of prepreg cured product II)
The cured prepreg prepared in Example 9 was heated to 800 ° C. at a heating rate of 1.5 ° C./min. In the air at normal pressure and kept at that temperature for 1 hour for firing to obtain an alumina fiber reinforced ceramic. A laminate (prepreg fired body) was manufactured. The dimensional shrinkage between the cured prepreg and the fired prepreg was 0.03% in the length direction and 0.8% in the thickness direction.

When this laminate was subjected to a high-temperature strength test and a heat cycle test by the method shown in Example 10, as shown in Tables 4 and 5, the same tendency as shown in Tables 2 and 3 was recognized. Was done.

(Example 12-Densification treatment I)
In a glass cylindrical container equipped with a stirrer, 125 parts by weight of polyphenylmethylsilsesquioxane (molecular weight 1,700, phenyl / methyl ratio = 5/5), 100 parts by weight of γ-methacryloxypropyltrimethoxysilane, 1.3 parts by weight of dicumyl peroxide and 300 parts by weight of N-vinylpyrrolidone were added and stirred until a uniform solution was formed.

(4) The alumina fiber-reinforced ceramic laminate of Example 11 was immersed in the above-mentioned solution contained in a glass cylindrical container, and was kept under reduced pressure until no bubbles were generated. Next, the vacuum was released, the laminate was taken out, the solution adhering to the surface was removed, and the acetone was completely evaporated in a dryer at 80 ° C. The impregnated laminate was placed in an electric furnace, heated to 800 ° C. in air at a rate of 1 ° C./min, and held for 1 hour to produce a densified ceramic laminate. This sample was used as a first impregnation sample, and the same impregnation, drying, and firing operations were repeated twice and three times. These were designated as a second impregnated sample and a third impregnated sample. Table 6 shows the bending test results of each impregnated sample. It can be seen that the bending strength of the laminate improved with the number of times of impregnation.

Example 13 Densification Treatment II
The alumina fiber reinforced ceramic laminate of Example 11 was placed in a vacuum chamber, and after evacuating the inside, methylphenylvinylhydrogenpolysiloxane (H62C, manufactured by Wacker-Chemie GmbH) preheated to 80 ° C. was injected overnight. I left it. Next, after releasing the inside of the vacuum chamber to atmospheric pressure, the laminate was taken out, and the solution attached to the surface was removed. Next, the impregnated laminate was placed in an electric furnace, heated to 800 ° C. in air at a rate of 1.5 ° C./min, and kept at that temperature for 1 hour. The mechanical properties of the laminate before and after densification are described in Example 17, Table 11.

(Example 14-Densification treatment III)
The alumina fiber-reinforced ceramic laminate of Example 10 was placed in a vacuum chamber, and a densified ceramic laminate was manufactured in the same manner as in Example 13.

This sample was used as a first impregnated sample, and the same operation was repeated twice to obtain a second impregnated sample. Table 7 shows the bending test results of each impregnated sample.

(Example 15--Example in which inorganic fiber is glass fiber)
400 parts by weight of alumina powder (average particle size: 0.4 μm), 200 parts by weight of titanium oxide powder (average particle size: 0.4 μm), polyphenylsilsesquioxane (molecular weight: 1,700) were placed in a ball mill containing ceramic balls. ) 125 parts by weight, 50 parts by weight of γ-methacryloxypropyltrimethoxysilane, 50 parts by weight of trimethylolpropane triacrylate, 2 parts by weight of dicumyl peroxide and 250 parts by weight of methanol are mixed by rotating a ball mill for 1 hour. Thus, a uniformly dissolved and dispersed matrix solution was obtained.

After immersing a glass fiber fabric (6781HT-38, manufactured by Hexel Co.) in this matrix solution, excess matrix solution was removed using a squeeze roll, and dried in a hot air circulating dryer at 80 ° C. A prepreg containing 65% by weight of the matrix composition was prepared.

It was confirmed that this prepreg also had tackiness, drapeability, and outtime properties that passed the evaluation method shown in Example 4.

Eight layers of this prepreg were laminated in the directions of 0 ° and 90 °, vacuum-bagged in a usual manner, placed in an autoclave, and heated to 150 ° C. at a pressure of 5 kg / cm ² and a heating rate of 2.5 ° C./min. After holding for 15 minutes, the temperature was lowered at 4.5 ° C./minute to prepare a 3 mm-thick prepreg cured product plate.

硬化 In the obtained cured prepreg, no shrinkage and no surface cracking were observed, and the weight loss was 1.1%.

(4) The prepreg cured product was heated in air at normal pressure at a heating rate of 1.5 ° C./min to each of 400, 500, 600, and 700 ° C., and kept at that temperature for 1 hour.

(4) The weight loss rate was measured using a thermal analyzer TG / DTA30 (manufactured by Seiko Denshi Kogyo Co., Ltd.) under a stream of air at a heating rate of 1.5 ° C./min. In this case, a temperature rise test up to each temperature of 400, 500, 600, and 800 ° C. was performed. Table 8 shows the values of the weight loss rate and the bending strength of the fired laminate (fired prepreg). In addition, the weight reduction rate was shown by the value from the cured laminate.

(4) The weight loss rate increases as the temperature increases, but reaches a constant value at 600 ° C. Further, the color of the test piece after firing was still colored by the treatment at 500 ° C. for 1 hour, but turned white at 600 ° C. or more.

These results show that below 500 ° C., organic components or their decomposed products remain in the matrix, but above 600 ° C., they are completely released and converted to a ceramic composition. The bending strength of the fired product at 600 ° C. or higher is lower than that of the fired product at 500 ° C. or lower, which is considered to be due to the occurrence of defects due to the release of organic components. Note that a heat treatment time of 10 minutes or more at 600 ° C. is sufficient for releasing organic components and converting the preceramic component to a ceramic composition. This result also suggests that a firing temperature of at least 500 ° C. is required even if the heat treatment is performed at a lower temperature for a long time.

Glass fibers have a large decrease in strength with increasing temperature as compared with ceramic fibers such as alumina fibers, but since their room temperature strength is much higher than that of ceramic fibers, they have strength enough to withstand practical use even at 600 ° C (for example, tensile strength). strength: for S- glass fibers (manufactured by Owens Corning fiberglass Corp.) or T- glass fibers (Nitto Boseki Co., Ltd.)] to about 200 kg / mm ²⁾ holds. Therefore, the fact that the preceramic component, that is, the component (B) and the component (C) in the present invention can be made into a ceramic even by heat treatment at 600 ° C. for a short time means that glass fiber which has lower heat resistance than ceramic fiber but is inexpensive can be used. It shows that it is.

(Example 16--Effect of firing atmosphere)
Four layers of the prepregs produced in Example 4 were laminated and hot-pressed under the conditions of Example 9 to produce a cured laminate having a length of 160 mm, a width of 160 mm and a thickness of 2 mm, and this plate was separated into two pieces. One was heated to 800 ° C. at a rate of 1 ° C./min in air and kept at that temperature for 1 hour. The other was fired in nitrogen under the same conditions. In each case, the densification treatment under normal pressure was performed once by the same method as in Example 13.

Table 9 shows the change in weight due to baking and densification treatment (the weight of the cured product is taken as 100), and the bending test results of the densified treatment (by the method described in Example 7).

(4) The reason why the weight change in firing in nitrogen is smaller than that in firing in air is that organic components contained in the matrix components are carbonized. This was confirmed from the fact that when the fired product in black nitrogen was further fired in air at 800 ° C. for 1 hour, the color changed to the same white color as the fired product in air.

(4) The product fired in nitrogen had lower strength and higher elastic modulus than fired in air. This means that firing in air is greater in elongation than firing in nitrogen, thus indicating that the former is more tenacious than the latter.

(Example 17, Comparative Examples 1-3-Influence of matrix component I)
The adjustment of the matrix composition was performed by the method described in Example 1 using the matrix components and the mixing ratios shown in Table 10. The production of the prepreg and the cured laminate (cured prepreg) were performed by the methods described in Examples 4 and 8, respectively. For Example 17 and Comparative Example 1 shown in Table 10, each cured laminate was heated to 800 ° C. at a rate of 1.5 ° C./min in air, held at that temperature for 1 hour, and fired and laminated. A board was created. The densification treatment was performed by the method of Example 13.

比較 The following results were obtained by comparison under the same method and under the same conditions.

Comparative Example 3: The prepreg impregnated with only the component (B) had almost no tackiness, and the fibers were twisted and difficult to cut as compared with the other examples. In addition, when the temperature is increased when the prepregs are laminated and cured using a hot press, the flow of the matrix (and the fibers) is too large, the matrix (and the fibers) protrude from the mold, and it has been impossible to produce a good laminate. Therefore, the firing operation in the next step could not be performed.

Comparative Example 2: The prepreg impregnated with the component (A) and the component (B) also had poor tackiness, but could be cut easily. However, the layers of the cured product after lamination and hot pressing were separated from each other, and an integrated laminate could not be obtained. Therefore, the firing operation in the next step could not be performed.

Comparative Example 1 and Example 17: In Comparative Example 1, although the prepreg had poor tackiness and was difficult to handle, it could be easily cut, and the curing operation could be performed well, and the integrated cured laminated plate Could be obtained. Further, in Example 17, all of tackiness, cutability, and curing operation were excellent, and a favorable cured laminate could be obtained.

焼 成 These two types of cured laminates were fired and densified by the methods described in Examples 11 and 13. The measurement was carried out with respect to the shrinkage during firing and the bending strength, flexural modulus and hardness of the cured product, the fired product and the densified product. The hardness was measured using a Vickers hardness meter AVK-CT (manufactured by Akashi Seisakusho). The results are shown in Table 11.

収縮 The shrinkage ratio during firing is slightly higher in Example 17 than in Comparative Example 1. This is considered to be due to the effect that the component (E), which is an organic substance contained in the former, is released during firing. However, in both cases, the shrinkage ratio is extremely small, and it can be concluded that there is almost no dimensional change due to firing.

明瞭 A clear difference appears in the mechanical properties of the laminate in both cases. In any of the steps of curing, firing and densification, the bending strength, flexural modulus and Vickers hardness of each laminate were clearly higher in Example 17 than in Comparative Example 1, which was It means that the excellent mechanical properties of the produced cured product are maintained after firing and after densification. In particular, it was recognized that the densification treatment of Example 17 was higher than that of Comparative Example 1 in increasing the strength. That is, the flexural strength is improved by about 50% in the former, but remains at about 20% in the latter. The reason for this is not clear, but it is presumed that the fired product obtained in the former has a higher porosity than the porosity, whereas the latter has a higher porosity than the porosity. You.

The above results show that when a cured product having a complicated shape is made using the method of Example 17, the prepreg has good tackiness and is easy to handle, and because it is strong and hard, it is unconstrained. Even after the firing operation, shape deformation does not occur, that is, the self-shape retention property is effectively maintained, and there is almost no dimensional change, that is, there is no shape collapse, so that it often occurs due to shrinkage of the matrix during ceramic firing. This indicates that the generation of cracks can be minimized, and as a result, a long fiber reinforced ceramic product having good mechanical properties can be produced. That is, the addition of the component (E) not only imparts excellent mechanical properties to the laminate at each stage and facilitates the improvement of the strength by the densification treatment, but also imparts good tackiness and drapability to the prepreg. And thereby enhance the shapeability, and thus also serve to impart good mechanical properties to the product.

(Comparative Example 4--Effect of matrix component II)
The production of the prepreg, the cured prepreg and the fired prepreg was carried out by the method described in Example 17. However, of the matrix components of Example 17, mullite was used in place of the alumina and titanium oxide as the component (A). The mixing ratio of mullite (3Al ₂ O ₃ .2SiO ₂ ) was the same as the total amount of alumina and titanium oxide. As mullite, a powder having an average particle size of 1.2 μm (out of the range specified in the present invention) was used. The other components and the mixing ratio are the same as in Example 17.

When the matrix composition described in Example 17 was used, when the laminated prepreg was hot-pressed, the thickness became 1.8 mm. On the other hand, when the component (A) was changed to mullite powder, the hot-pressing under the same conditions was performed. No flow of the matrix was observed, and the thickness was limited to 3.1 mm. Also. When cutting a test piece from the fired laminated plate, it will almost broken, even test pieces were successfully cut, bending strength 1.1 kg / mm ^2, the flexural modulus exhibited low as 1370kg / mm ^2. This is attributable to the large particle size rather than the oxide composition. This result indicates that metal oxide fine particles having a particle size of 1 μm or less, preferably 0.5 μm or less should be used.

Example 18 Influence of Matrix Component III
Production of a prepreg, a prepreg cured product, a prepreg fired product, and a densified product was performed by the method described in Example 17. However, in the matrix component of Example 17, the same amount of ethylene glycol dimethacrylate was used instead of the trimethylolpropane trimethacrylate as the component (E). After the densification treatment, the laminate had a bending strength of 20.2 kg / mm ² and a flexural modulus of 5980 kg / mm ² . These values are at the same level as those obtained in Example 17, indicating that the latter compound can be used sufficiently. However, although the latter compound had no practical problem, it was recognized that the tackiness was somewhat lower than that of the former compound.

(Comparative Example 5, 6- Comparison with polymer binder)
In a conventional slurry method, a polymer binder is often used. Then, this effect was examined by using polyurethane as a polymer and combining it with the component (D) and the component (E) (Comparative Example 5). A test was also conducted on a system in which the component (C) was used in place of the polymer, and the component (D) and the component (E) were combined with the component (Comparative Example 6).

Preparation of the matrix composition was performed by the method described in Example 1. Table 12 shows the mixing ratio of the matrix components.

A prepreg was produced according to the method described in Example 4 using the above matrix liquid and the woven fabric of alumina fibers described in Example 4. The content of the matrix (solid content) was 60% by weight. Four prepregs were laminated in directions of 0 ° and 90 °, respectively, and molded and cured by hot pressing at 150 ° C. for 15 minutes under a condition of 3.5 kg / cm ² . Thereafter, it was heated to 800 ° C. at a heating rate of 1.5 ° C./min under normal pressure in air, and kept at that temperature for 1 hour.

(4) When the matrix composition of Comparative Example 5 was used, there was no flow of the matrix at all, but a certain degree of tackiness was exhibited, and molding was possible. However, when this was fired, in the obtained fired product, although the layer did not peel, only a soft material having no rigidity and flexibility was obtained, and the matrix collapsed and fell off with a slight force. . This is considered to be due to the fact that when an organic binder is used, in the case of baking at normal pressure and low temperature, after these pyrolysis release, there is no longer any force for bonding the ceramic particles. When such an organic binder is used, the normal-pressure low-temperature sintering used in the present invention is unsuitable, and shows that a high-pressure high-temperature sintering operation is necessary as used in the conventional slurry method. I have.

で も Also in Comparative Example 6, there was no flow of the matrix at all, but molding and curing were possible. However, when this was fired, the four layers were peeled off. This indicates a lack of bonding force (binding force). Therefore, this result indicates that the components (A), (B), and (C) must be used in order to achieve the objects and effects of the present invention. , (D) and (E) are essential components.

(Example 1)
In the structure shown in FIG. 2, a sheet made of polyvinyl fluoride is laminated on both sides of a sheet obtained by impregnating glass fiber with a phenol resin, and a ceramic comprising the densified ceramic laminate of Example 12 is further interposed via an epoxy adhesive. A laminated structure formed by laminating long fiber reinforced ceramic material layers was employed.

燃 焼 The laminated structure was subjected to the combustion test of FAA Regulation 14 CFR Ch.1 (1-1-93 version) Section 25.853, Part 1. In any of the vertical test, the horizontal test, and the 45-degree test, no burning, smoking, or the like of the sample was observed.

(Comparative Example 1)
In the laminated structure shown in FIG. 2, a combustion test similar to that in Example 1 was performed on a laminated structure having the same structure except that the ceramic long fiber reinforced ceramic material and the epoxy adhesive were not provided. went.

(4) As a result of the combustion test, the sheet made of polyvinyl fluoride burned and smoked, and the sheet obtained by impregnating the glass fiber with the phenol resin was carbonized to the back side.

(Example 2)
In the structure shown in FIG. 3, a sheet made of glass fiber impregnated with phenol resin is adhered to both sides of an aluminum honeycomb, and a sheet made of polyvinyl fluoride is laminated on both sides of the sheet, and the above-mentioned example is further interposed via an epoxy adhesive. A laminated structure obtained by laminating ceramic long fiber reinforced ceramic material layers composed of 12 densified ceramic laminates was employed.

燃 焼 The laminated structure was subjected to the combustion test of FAA Regulation 14 CFR Ch.1 (1-1-93 version) Section 25.853, Part 1. In any of the vertical test, the horizontal test, and the 45-degree test, no burning, smoking, or the like of the sample was observed.

(Comparative Example 2)
In the laminated structure shown in FIG. 3, a combustion test similar to that in Example 1 was performed on a laminated structure having the same structure except that the ceramic long fiber reinforced ceramic material and the epoxy adhesive were not provided. went.

(4) As a result of the combustion test, the sheet made of polyvinyl fluoride burned and smoked, and the sheet obtained by impregnating the glass fiber with the phenol resin was carbonized to the back side.

(Analysis of smoke and gas)
A prepreg (MXB6820 / 7781) made of glass fiber (181 style) impregnated with a phenol resin was analyzed for smoke generated according to JIS K7217. The smoke contained 1075 mg / g carbon dioxide and carbon monoxide. 25.5 mg / g, ethylene 41.4 mg / g, and others 3.4 mg / g. The smoke density of the prepreg measured according to ASTM F814-846 was 124.00.

A cured prepreg obtained by curing a prepreg obtained by impregnating the ceramic matrix of Example 2 into glass fiber (181 style) (curing conditions: 150 ° C., 3 kg / cm ² , curing time of 15 minutes) according to JIS K7217. Analysis of the smoke produced revealed that the smoke contained 251.5 mg / g of carbon dioxide, 4.8 mg / g of carbon monoxide, 4.3 mg / g of ethylene, and 1.7 mg / g of others. . The smoke density of the cured prepreg was measured according to ASTM F814-846 and found to be 17.3.

A prepreg cured product obtained by curing a prepreg obtained by impregnating the ceramic matrix of Example 2 into glass fiber (181 style) (curing conditions: 150 ° C., 3 kg / cm ² , curing time of 15 minutes) is further aired. When the smoke produced at 600 ° C. for 2 hours was analyzed for smoke produced according to JIS K7217, the smoke contained 0.1 mg / g or less of carbon dioxide, 1 mg / g or less of carbon monoxide, and 1 mg / g of ethylene. Below, 0.7 mg / g or less was contained in others. The smoke density of the fired product of this cured prepreg was measured according to ASTM F814-846, and was found to be 0.17.

The laminated structure and the honeycomb laminated structure using the inorganic long fiber reinforced ceramic material including the pregreg fired body obtained as described above, the interior product, and the panal have good heat resistance and flame retardancy. It is suitable as a material for protecting human bodies from fire accidents.

FIG. 1 is an explanatory longitudinal sectional view showing the inside of the aircraft. FIG. 2 is a sectional view showing a laminated structure according to one embodiment of the present invention. FIG. 3 is a sectional view showing a honeycomb laminated structure according to one embodiment of the present invention. FIG. 4 is a sectional view showing a honeycomb laminated structure according to another embodiment of the present invention. FIG. 5 is a sectional view showing a honeycomb laminated structure according to still another embodiment of the present invention. FIG. 6 is a partially sectional perspective view showing a baggage storage shelf formed by using a honeycomb laminated structure according to an embodiment of the present invention. FIG. 7 is an explanatory view schematically showing a building which is an embodiment of the present invention. FIG. 8 is a schematic perspective explanatory view showing an interior component of a building which is an embodiment of the present invention.

Explanation of reference numerals

DESCRIPTION OF SYMBOLS 1 ... Passenger aircraft, 2 ... Guest room 2, 3 ... Inner wall, 4 ... Cargo room, 5 ... Floor material, 6 ... Ceiling material, 7 ... Laminated structure, 8 ... ..Sheets 8, 9 formed of a heat-resistant resin composition: flame-retardant resin sheet, 10: adhesive, 11: ceramic long fiber reinforced ceramic material layer, 12: honeycomb laminated structure Body, 13: honeycomb, 14: sheet formed of flame-retardant resin composition, 15: flame-retardant resin sheet, 16: adhesive, 17: ceramic long fiber reinforced ceramic Material, 18: honeycomb laminated structure, 19: honeycomb, 20: sheet, 21: ceramic long fiber reinforced ceramic material, 22: decorative sheet, 23: transparent protective sheet, 24 ···················· Aircraft, ··································· -Opening / closing lid, 28-building, 29-wall, 30-floor, 31-beam, 32-ceiling, 33-inclined material, 34- -Roofing materials, 35 ... ceiling panels, 36 ... wall panels, 37 ... floor panels, 38 ... foundation floor panels, 39 ... door panels.

Claims (7)

ハ A honeycomb laminated structure in which an inorganic long fiber reinforced ceramic material is laminated on both surfaces or one surface of the honeycomb. The inorganic long fiber reinforced ceramic material is formed by molding a prepreg comprising a ceramic long fiber, a metal oxide, a monomer to be an organic polymer and / or an organic polymer, and a curing agent thereof, and after curing, firing. The honeycomb laminated structure according to claim 1. The inorganic long fiber reinforced ceramic material is prepared by mixing a liquid or sheet of a matrix composition containing the following components (A), (B), (C), (D) and (E) with inorganic fibers. 3. The honeycomb laminated structure according to claim 1, wherein a prepreg obtained by impregnating or heat-penetrating a product of tow or inorganic fiber is molded, cured, and fired.
(A) component: fine powder of metal oxide having an average particle size of 1 μm or less,
(B) component; a soluble siloxane polymer having a double-chain structure,
(C) component; trifunctional silane compound having at least one ethylenically unsaturated double bond in a molecule;
(D) component; organic peroxide,
(E) component: radically polymerizable monomer having at least two ethylenically unsaturated double bonds in the molecule 350-750 parts by weight of the component (A) in the matrix composition,
(B) the compounding amount of the component is 80 to 170 parts by weight,
(C) a compounding amount of the component is 25 to 125 parts by weight,
The honeycomb laminated structure according to claim 3, wherein the amount of the component (D) is 1 to 4 parts by weight and the amount of the component (E) is 25 to 125 parts by weight. The inorganic long-fiber-reinforced ceramic material comprises the component (A), the component (B), the component (C), the component (D), and the component (E) according to claim 3,
A prepreg formed by impregnating or heat-penetrating a liquid or sheet-like material of the matrix composition containing the content ratio according to claim 4 into a tow of inorganic fiber or a product of inorganic fiber, and curing the prepreg. The honeycomb laminated structure according to claim 3 or 4. The component (A) is an oxide or a composite oxide containing at least one selected from silica, alumina, and titanium oxide;
The component (B) is a polysilsesquioxane,
The component (C) is γ- (meth) acryloxyalkyl trialkoxysilane, and the component (D) is a peroxide having a temperature of 110 ° C. or higher for obtaining a half-life of 10 hours,
The component (E) is a polyhydric alcohol di (meth) acrylate and / or a polyhydric alcohol tri (meth) acrylate,
The above-mentioned claim, wherein the inorganic fiber is at least one selected from the group consisting of glass fibers, alumina fibers, silica fibers, Tyranno fibers, and oxide-based inorganic fibers composed of various fibers containing alumina and / or silica as a main component. Item 6. The honeycomb laminated structure according to any one of Items 3 to 5. The honeycomb laminated structure according to any one of claims 1 to 6, wherein the inorganic long fiber reinforced ceramic material has a surface coated with a fired glaze.

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