JPH0670320B2 - Composite sheet-like material and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sheet-like material having excellent fire resistance, flexibility and anti-itching property, and a method for producing the same.

In recent years, various heat insulating materials have been used in many fields due to promotion of energy saving. Among thermal insulation materials, organic foams such as polyurethane foam and polystyrene foam have a major drawback in terms of fire protection performance.For buildings and equipment that are at risk of fire, mainly inorganic fibers such as glass fiber and rock wool are used as raw materials. Insulating materials have been used. However, these very lightweight inorganic heat insulating materials generally have a non-binder or a very small amount of phenol resin adhered non-homogeneously, so they have excellent heat insulating properties but are very brittle and poor in handleability. For example, it cannot be used in places that are subject to heavy handling, such as heat insulation for folded-plate roofs. Therefore, it has been attempted to use a sheet-like material having an appropriate bendability of a thickness of about 5 to 25 mm, which is obtained by joining inorganic fibers with various binders, as a heat insulating material in the field where such heavy handling is performed. However, all such conventional sheet-like materials are sheets obtained by a manufacturing method called a dry method, and the amount of the binder is too small to uniformly cover the surface of the inorganic fiber, or the intermediate layer of the sheet-like material. Because of the lack of binder
It is not possible to improve the inherent brittleness of inorganic fibers. For example, when it is used as a heat insulating material for folded plate roofs, the fibers are crushed in the process of passing through a folded plate processing roll, which is not suitable for the use. It was suitable. Further, this pulverized product was easily scattered in the air and adhered to the human body to cause skin irritation, which gave the operator considerable discomfort. On the other hand, the technique of forming an inorganic fibrous material into a plate shape or a paper shape by a wet papermaking method has been widely used in the fields of glass paper, asbestos paper, rock wool ceiling board, asbestos slate board, etc. The paper or board obtained by the wet papermaking method of No. 1 has a small amount of binder and a specific gravity of 0.40 or more, and paper-like ones are flexible, but they are brittle and poor in flexibility, and thin and heat insulating. There is no. On the other hand, a board-shaped material is excellent in strength but not flexible, and is brittle and cannot be used as the heat insulating material for a folded plate roof as described above. Further, in order to improve such a defect, for example, a method for producing a sheet-like material in which rock wool is dispersed by using a specific surfactant described in JP-B-49-43485 and wet papermaking is known. However, it is not possible to greatly improve the basic properties of the sheet-like material by only improving the dispersibility, and a defibration / dispersion machine similar to the papermaking process using conventional pulp-based raw materials such as pulpers and beaters. Since the use of the inevitable cutting of inorganic fibers,
The sheet-like material obtained did not leave the region of the paper-like material.

In view of the present situation, the present inventors have studied to develop a heat insulating material which is excellent in fireproof property and can withstand severe handling, for example, Japanese Patent Application Nos. 55-147071 and 56-169540. I applied for a patent. However, it is insufficient in terms of itching (skin irritation caused by adhesion to the human body), and as a result of further study, it was formed by forming a wet papermaking sheet made of an organic fibrous material on the sheet-shaped material. The present invention has been found to have a remarkable effect on the anti-itching property by integrating the thin layers to be integrated. That is, the present invention relates to a sheet comprising 80 to 97% by weight of a non-combustible fibrous substance and 3 to 20% by weight of a binder containing a thermoplastic resin as a main component, and a wet papermaking comprising an organic fibrous substance on one or both sides of the sheet. It is a composite sheet-like material in which a thin layer formed by laminating a sheet is compositely integrated, and a manufacturing method by a wet papermaking method suitable for manufacturing the composite sheet-like material. Such a composite sheet can be obtained by the wet papermaking method as described below,
The present invention has the greatest points in the composite sheet-like product itself having the above-mentioned production, and is not limited to the composite sheet-like product obtained by the following production method. The present invention will be described specifically and in detail below.

Examples of the noncombustible fibrous substance used in the present invention include asbestos, rock wool, glass fibers, ceramic fibers such as aluminum silicate, and inorganic fibers such as alumina fibers and carbon fibers. In general, any substance can be used as long as it does not melt or burn at 500 ° C or less, has an average diameter of 0.1 to 20 µm, and has an average fiber length of about 1 to 30 mm. Asbestos having as long a fiber length as possible is preferable. Rockwool is the most suitable material for the purposes of the present invention, and either natural rock or mineral slag can be used as a raw material. A material having a small content of particles is preferable, and a material called granular cotton or layered cotton can be used as a starting material. As the glass fiber, chopped strand or glass wool can be used as a starting material. Further, in the present invention, within a range that does not particularly decrease the fire resistance, elasticity,
It is also possible to replace a part of the non-combustible fibrous substance with an organic fiber for the purpose of enhancing flexibility and anti-itching property. As such organic fibers, those made from vinylon, rayon, acrylic, nylon, polypropylene, vinyl chloride, ester, etc. can be used.

In the present invention, as a binder containing a thermoplastic resin as a main component, which is used for the purpose of coating the surface of the inorganic fiber and increasing the strength, elastic recovery force, and processability of the composite sheet-like product obtained by promoting the entanglement. Is preferably soluble or dispersible in water, and is preferably a water-soluble polymer, emulsion or latex resin. As the water-soluble polymer, for example, polyvinyl alcohol polymer,
Examples thereof include polyacrylic acid-based polymers, polyethylene oxide, carboxymethyl cellulose, casein, starch, and a wide variety of synthetic and natural water-soluble polymer materials can be used. Examples of the emulsion or latex resin include polyvinyl acetate and its copolymer, polyvinyl chloride and its copolymer, polyacrylic acid ester and its copolymer, polyethylene and its copolymer, polyurethane having the form of emulsion. Examples thereof include system polymers, and hydrosols such as ethylene-acrylate copolymers can be included in this category.

In the present invention, particularly in obtaining a composite sheet for use in applications requiring flexibility and flexibility, a resin having a glass transition point in the range of −50 to 30 ° C. as a thermoplastic resin is particularly preferable. It is preferably used as a binder, for example, ethylene-vinyl acetate copolymer, plasticized vinyl chloride-vinyl acetate copolymer, polyurethane, (meth)
An acrylic acid ester copolymer etc. can be mentioned.
As a method for measuring the glass transition point, for example, a method for testing the shear elastic modulus and mechanical damping of plastic by a twist pendulum of JIS K7213 or a device such as vibron can be measured, and the transition region temperature or mechanical damping of the elastic modulus can be measured. It can be represented by the peak temperature of.

In the present invention, the distribution of the binder containing the thermoplastic resin as a main component in the thickness direction of the sheet body is particularly important. The front and back skin layers are rubbed with a roller during folding plate processing, the surface for protection during handling, weather resistance, etc.
It is preferable that the amount of binder is slightly larger than or equal to that of the inner layer, and then the lower limit of the amount of binder in the intermediate layer is determined from the amount required to coat the inorganic fibers uniformly so that the inorganic fibers are not crushed during folding plate processing. , The upper limit can be determined from the fire protection performance. That is, the amount of binder in all layers of the sheet body is 3 to 20% by weight (97 to 80% by weight of noncombustible fibrous material), preferably 4 to 15% by weight, and the amount of binder in the intermediate layer is 2% by weight. Above, it is necessary to have a relatively homogeneous binder distribution of 0.25 times the average value of all layers or more.

As a method for measuring the amount of binder in the sheet described in the present invention, for example, in the case of obtaining the distribution in the thickness direction, the diameter of 20 to 20
Some 50 mm cylindrical test pieces are punched out to remove the organic fibrous material on the surface. Next, each test body was further cut into n layers (n = 3 to 8) in parallel with the surface so as to have a uniform thickness, and the respective layers were collected by layer and numbered 1 to n. here,
1 and n correspond to the surface layer, and 2 to n-1 correspond to the intermediate layer. After leaving such a sample in a desiccator at room temperature for a whole day and night and then putting it in another porcelain crucible and baking it in an electric furnace at 550 to 600 ° C. for 30 to 60 minutes, the weight loss of the m-th layer was set to Am wt%,
When the weight loss of the m-th layer obtained in the same manner for the sheet B produced by the same method without using the binder is Bm, the binder amount of the m-th layer is determined as Xm = Am-Bm. You can When the organic matter of the sheet body is only the binder, it may be determined as Xm = Am for convenience. The binder amount of the entire sheet is obtained as an average value of 1 to n, and the binder amount of the intermediate layer is obtained as an average value of 2 to n-1.

In the present invention, it is suitable for the thermoplastic resin used in order to prevent surface migration of the binder containing a thermoplastic resin as a main component, control so as to have a predetermined binder distribution, and improve water resistance, weather resistance and strength. It is an important technique to use a cross-linking agent, and in some cases, a thermoplastic resin such as self-crosslinking emulsion or heat-sensitive coagulation latex itself has a suitable cross-linking or coagulating action under certain conditions. Sometimes it works the same as using. The type of crosslinker should be selected according to the thermoplastic resin used,
For example, for polyvinyl alcohol polymers, isocyanate compounds, urea compounds, boric acid and salts thereof,
Examples thereof include zirconia compounds and titanic acid compounds. Examples of polyvinyl acetate emulsions and polyacrylic acid ester emulsions include modified polyamideimide epoxy resins and isocyanate emulsions. The addition amount of the cross-linking agent should be appropriately determined according to its efficacy, and it is generally used within the range of 0.1 to 30% by weight based on the binder containing the thermoplastic resin as the main component. The time of addition may be used as an aqueous solution which is previously mixed with a thermoplastic resin, or may be separately impregnated into a sheet-shaped material.

Further, in the present invention, an appropriate flame retardant may be used in combination in order to remarkably enhance the fire resistance and fire resistance of the obtained composite sheet. Particularly as a combination of compounds capable of exhibiting an excellent flame retardant effect suitable for the present invention, the binder 100
5 to 50 parts by weight of antimony compound, and 10
~ 100 parts by weight of a combination of aromatic bromine compounds is preferred,
A combination in which the weight ratio of the contents of the antimony compound and the aromatic bromine compound is in the range of 1: 1 to 1:10 is preferable. Examples of the antimony compound include antimony trioxide, antimony pentachloride, antimony trichloride, antimony trisulfide, or any mixture thereof, and the aromatic bromine compound has a decomposition temperature of 280 ° C. or higher and bromine. A compound having a content of 50% by weight or more is preferable, and examples thereof include compounds such as tetrabromobenzene, pentabromomethylbenzene, hexabromobenzene, hexabromodiphenyl ether, decabromodiphenyl ether, and tetrabromobisphenol A, or a mixture thereof. You can In the composite sheet material in which the flame retardant is blended, particularly the composite sheet material in which the binder amount of the main body is in the range of 4 to 8% by weight is the composite sheet material alone although the organic binder is used. The structure of a folded plate roof that has the highest level of fire protection that can pass the "non-combustible material" in the test method specified by Ministry of Construction Notification No. 1828 in 1965 and uses the composite sheet as a heat insulating material. The thing has the highest level of fire resistance that can pass "Roof 30 minutes fire resistance" by the test method instructed by Ministry of Construction Notification No. 2999 in 1969.

In the present invention, an important factor together with the binder amount of the composite sheet body and its distribution in the thickness direction is the degree of orientation of the fibrous substance in the layer of the composite sheet body.
It is preferred to have a degree of orientation of -80 degrees. The degree of orientation of the fibrous substance in the layer in the present invention can be measured by the following method. The front and back surfaces of the sheet from which the organic fibrous material on the surface of a predetermined size has been removed are bonded to a metal flat plate using an adhesive. Next, by grasping the upper and lower metal flat plates with chucks respectively and raising the crosshead at a constant speed to perform a normal interlaminar fracture strength measurement that leads to the fracture of the sample, the sheet-like material is obtained by measuring the non-combustible fibrous substance in the layer. Cutting occurs from the oriented layered interface. Here, the degree of orientation of the fibrous substance in the layer can be obtained by measuring the angle formed by the metal flat plate surface and the fracture surface of the test piece after fracture. The degree of orientation in the present invention is an important factor for the apparent density and heat insulating property, fireproof property, soundproofing property, and dewproof property of the composite sheet material, and in the paper-like sheet material obtained by the conventional technique, The degree of orientation is almost 0 degree, and the strength in the vertical direction and the horizontal direction is expressed, but the strength between layers is poor, and it is difficult to obtain a sheet-like material having a low apparent density. In addition, a bracket-shaped heat insulating material for pipes, which is obtained by cutting rock wool layered cotton into a certain length and aligning the cut edges so that the cut length becomes a thickness, is also commercially available. The apparent density is significantly reduced with time, and it is rich in flexibility, but it is very brittle and lacks handleability. For the above reasons, the orientation degree of the fibrous material in the layer of the sheet body is 3 as the composite sheet material for the above purpose.
Required to be ~ 80 degrees.

In the present invention, for the purpose of further enhancing the performance as a heat insulating material, a building material, etc., various dyes, pigments and other colorants, antifungal agents,
It is also possible to add or apply a water repellent. In addition, fillers such as aluminum hydroxide, gypsum, borax, calcium carbonate, etc. for the purpose of enhancing fire protection performance, and lightweight fillers such as pearlite, shirasu balloon, foam calculus, hollow glass spheres, and mica for the purpose of weight reduction. You may add.

The present invention is characterized by having a thin layer formed on a sheet body by forming and drying a wet papermaking sheet made of an organic fibrous material. By laminating a wet sheet that does not have the form of a layer, a part of the organic fibrous material penetrates into the sheet body, so that a thin layer is integrally formed on the sheet body with excellent adhesion. be able to. Further, since the wet papermaking sheet is combined with the sheet, it is possible to form a very thin layer (one-sided fabric weight: 3 to 30 g / m ² ) which does not become an independent sheet even when dried by itself. Therefore, the surface of the sheet body can be covered and the effect of preventing itching can be significantly enhanced without substantially lowering the fireproof property of the sheet body. When laminating a usual pre-molded sheet-like material, although the reinforcing effect is excellent, these reinforcing sheet-like materials have a large weight and cannot form a thin layer as described above, Moreover, an adhesive is often required for lamination. Such a thin layer is formed on one side or both sides of the sheet body.

Examples of the organic fibrous material used include natural pulp obtained from conifers and hardwoods, natural fibers such as cotton, wool and hemp, semi-synthetic fibers such as rayon and acetate, vinylon,
Synthetic fibers or the like made of acrylic, nylon, polypropylene, vinyl chloride, ester or the like can be used alone or as a mixture. Among these organic fibrous materials, synthetic fibers having hydrophilicity are preferable from the viewpoint of dispersibility. The organic fibrous material is preferably one having a fiber thickness of 0.1 to 5 denier and a fiber length of 1 to 35 mm. Such an organic fibrous material is dispersed in water according to a conventional method and formed into a sheet.
The paper making with the sheet body will be described later. The weight ratio of the thin layer (one side) made of the organic fibrous material to the sheet body is usually 0.001 to 0.2 times, and the basis weight of the thin layer (one side) is 3 to 30 g / m ² . When giving a reinforcing effect to such a thin layer, it is preferable to further increase the basis weight. In the present invention, in order to further enhance the adhesive strength between the sheet body and the thin layer, it is preferable to add the binder as described above to the dispersion liquid of the organic fibrous material. However, usually, as described below, the sheet body immediately after the paper making is combined with the sheet body, in which case white water containing the binder component in the sheet body rapidly permeates into the combined organic fibrous material. This improves the adhesiveness between the organic fibers and between the organic fibers and the sheet body. The amount of the binder is usually 0 to 20% by weight (in the thin layer).

In the present invention, for the purpose of enhancing the strength, water resistance, fire resistance, and moisture resistance of the composite sheet material, it is possible to further compound a sheet-like reinforcing rod on the intermediate layer or surface of the composite sheet material. As the sheet-like reinforcing material, various films or metal foils are suitable when moisture resistance and water resistance are required, and when moisture permeability and moisture absorption are required, cloth, paper, cheesecloth, non-woven fabric, mesh Porous materials such as These sheet-like reinforcing materials can be inserted into the sheet body during sheet-forming of the sheet body, or can be laminated on the surface of the composite sheet, and the obtained composite sheet material can be bound with an adhesive to form a composite. Is also possible.

Next, the method for producing a composite sheet material having excellent fire resistance, flexibility, and anti-itching properties according to the present invention will be specifically described. First, a certain amount of the above-mentioned noncombustible fibrous substance and, if necessary, the above-mentioned organic fibers and various additives, and further the above-mentioned water-soluble thermoplastic resin or emulsion or a binder containing a thermoplastic resin in a latex form as a main component. A slurry stock solution is prepared by uniformly dispersing and dissolving the thermoplastic resin in water together with a crosslinking agent or a polymer flocculant (polyacrylamide type, polyethyleneimine type, sodium polyacrylate type, etc.). At this point, a surfactant may be added as appropriate to enhance the dispersion effect. Further, in the present invention, a foam stabilizer can be used at this point for the purpose of further increasing the dehydration efficiency and controlling the binder amount of the sheet-like material. As the foam stabilizer, generally a nonionic surfactant is effective, and its action is that the slurry stock solution is formed by the action of the water-soluble thermoplastic resin or emulsion or latex-like thermoplastic resin added in the slurry stock solution. Although some bubbles are generated, it is necessary to make the bubbles uniform and fine and form an appropriate water film between the fibrous substances during dehydration under reduced pressure to prevent air from escaping and to keep the dehydration rate always constant. As a dispersion method, relatively gentle stirring with a cheest or the like is preferable, and if it is violently beaten with a device such as a beater, the fibrous substance is broken or a spherical aggregate is formed, which is not preferable. The dispersion concentration of the non-combustible fibrous substance and the binder is preferably 0.1 to 5% by weight, and should be appropriately selected depending on the purpose of use of the resulting sheet-shaped product.
Next, the slurry undiluted solution is transported from a tank by a slurry pump having a structure such that the fibrous substance does not form a spherical aggregate, or is guided from the upper part to a papermaking part by a method of falling and running or rotating, or a net-like or porous structure. It is supplied from a direction having an angle of 5 to 60 degrees, preferably 20 to 45 degrees with respect to the surface of the base material, and is sheet-formed on the base material to prepare a wet mat. In order to increase the degree of orientation of the fibers, it is also effective to supply a stock solution which is disturbed by blowing a liquid or a gas into the slurry stock solution on the surface of the base material. At this point, the white water containing the binder that has been drained from the lower surface of the base material is returned to the slurry stock solution preparation tank together with the white water in the dehydration step for reuse.

In the present invention, the method for paper-making the above-mentioned organic fibrous material into the sheet body is a wet method comprising the organic fibrous material made by a known paper-making method such as Fourdrinier or cylinder on one or both sides of the wet mat. It is possible by transferring a sheet in the state of, a dispersant, a sticking agent, or a sizing agent for the purpose of improving the dispersibility of the organic fibrous material in water, preventing reaggregation or preventing penetration, and strengthening paper strength, The use of the paper strength enhancer and the like is not limited, and known papermaking techniques can be arbitrarily applied depending on the purpose. In the present invention, unlike the case where a sheet-shaped reinforcing material that has already been formed is combined with the sheet body, it is an essential condition to combine the paper-made organic fibrous material on a wet mat in a wet state. According to such a combination, a composite sheet material in which the noncombustible fibrous material and the organic fibrous material are firmly adhered can be obtained only by drying. This effective effect is largely due to the anchoring effect of a part of the organic fibrous material entering the sheet body as described above, but when the sheet is made into a sheet body immediately after sheet making, the sheet is This is because the white water containing the binder in the main body rapidly permeates into the organic fibrous material, so that the binder effect appears even if the binder is not previously added to the dispersion liquid of the organic fibrous material. Further, the whole sheet after the combining is dehydrated under reduced pressure as described below, and the pressure effect at this time further enhances the adhesion effect between both sheets.

The wet mat of the obtained composite sheet is dehydrated by the following depressurization method. Conventionally, in the field of rock wool ceiling materials and asbestos slate boards, it is subjected to (roller) pressing in this process to impart thickness accuracy and surface smoothness or surface pattern at the same time as dehydration. In such a (roller) pressing method, it is difficult to obtain a target sheet-like article having a light weight and flexibility, and the vacuum dehydration method is the most suitable dehydration method. The wet mat after papermaking, which contains about 5 to 8 times the amount of water relative to the solid content, is sent to the decompression zone together with the mat or the base material, and the water content inside is sucked from one side or both sides, and then sent to the drying zone. If the dehydration rate is increased, the drying process can be shortened and it is economical, but since the sheet becomes fragile and the specific gravity increases, it is preferable to limit the final content to 0.5 to 2 times. In this step, the fine air bubbles inside work effectively in order to prevent the sheet from sagging and increase the dehydration rate. It is considered that the reason is that the water film formed between the fibers prevents the air from blowing through from a specific portion. The mat after dehydration is dried into a sheet by an appropriate method. As a drying method, any of a hot air shelf system, a hot air spraying system, a hot roller contact system and the like can be adopted, and a suitable drying temperature is 80 to 200 ° C.

As described above, the composite sheet material according to the present invention is flexible, fireproof, fireproof, heat insulating, dewproof, soundproof, vibration-proof, heat-resistant, fireproof, weatherproof, itchingproof, and cushiony. It is excellent in properties and the like and can be widely used in civil engineering and construction, equipment plants, home electric appliances and furniture, automobiles and other vehicle ships, and other industrial fields by utilizing such characteristics. To give an example of an application example, first, in the field of civil engineering and construction, it can be used as a fire-resistant covering material for steel frames of buildings and fire-resistant joints for fire-resistant walls by taking advantage of fire and fire resistance, and is characterized by heat insulation and dew resistance. In addition to the general ceiling / wall / floor space insulation material, the above-mentioned folded sheet roof insulation sheet, sidewall metal siding material inner coating material, hot water pool, bathroom, etc. It is a field where the characteristics of objects can be exhibited, and by further utilizing soundproofing and damping properties, metal panels for station buildings, halls, etc.
Can be used for metal shutters, inner storage / backing materials for storage boxes for shutters, deck plates, backing materials for metal floors such as emergency stairs, core materials for soundproof panels, etc., and back-up materials for PVC cushion floors, It is also effective for applications such as backing paper for fire protection wallpaper and core materials for roof and roof sealing materials. Next, in the field of factory plants, it can be used as a heat insulation material for various line pipes and a fire insulation material for various tanks by taking advantage of its heat insulation properties, and it is a lining material for air-conditioning ducts that makes good use of sound insulation and vibration control, lagging material, and air transportation. Applications include line duct lining materials, dust collector soundproofing materials, and further incinerator / combustion gas exhaust duct lining materials, air conditioning duct damper cushioning materials, and the like. Applications for equipment parts include backup materials for gas and oil heaters, air conditioners, sound absorbing and insulating materials for hot water boilers, heat insulating materials for cold storage and constant temperature freezing warehouses, as well as rock drills and handy drills by taking advantage of sound and vibration control. , Vibration control materials such as chain saws, rivets, etc. (prevention of white wax), pumps, ejectors, blowers, ball mills, hoppers, cyclones, oil separators, compressors, duster shouts, vibrating sieves, vibrating feeders, conveyors, forging machines, presses, Examples of applications include soundproofing and damping materials for housings and motor covers of various equipment such as cutters, drills, rolling mills, and generators, typewriters, line printers for computers, housing lining materials for general office equipment such as punches, etc. Can be mentioned. In the field of home appliances and furniture, fireproof sealants are used to seal bath baths, ovens that utilize heat insulation and heat resistance, cookers such as cookers, irons, heat insulators for vending machines, stainless steel sinks, and bath protection. Dew / soundproof backing material, and by making use of soundproof / vibration damping properties, housings and piping for refrigerators, air conditioners, coolers, dishwashers, etc., inner cover material for motor covers, desks, cabinets,
It is also used as a backing material for steel furniture such as rockers, as a damping material for audio products, and as a packing material and sealing material for gas appliances by impregnation. In the field of automobiles, heat insulation material for vehicle body ceiling, heat insulation and sound insulation material for partition wall between engine room and driver seat, sound insulation material for exhaust pipe, sound insulation and damping material for doors, engine rocker cover, and engine enclosure plate Material, oil pan, gas tank fire / heat insulation / vibration / insulation material, trunk room, cowl inner, sound insulation / material for front hood engine, sound / water resistant mat for floor, filter for air cleaner, etc. It can also be used as a brake lining, clutch pacing, and gasket. In the field of other large vehicles and ships, internal cover material for engine covers, heat insulation material for hot water, fuel oil and other line piping, heat insulation, dew and sound insulation materials for living areas, heat insulation materials for refrigerating ships and cold storage of refrigerated vehicles. Applications include sound absorbing materials for side walls of subways, ceilings, soundproofing of engine rooms such as motor boats and fishing boats, soundproofing of vehicle section trains such as trains and subways, soundproofing and rustproof backing of decks. In addition, it can be used as open hearth, converter, dropping lid after electric furnace, joint material of mold, soundproofing and damping material around jet engine of aircraft. The application examples described above are all examples of use of the composite sheet-like material according to the present invention alone, but the surface material of the organic foamed heat insulating material such as polyethylene foam, polystyrene foam, polyurethane foam and the like which has been widely used in the past. When it is used as, it improves the flammability, which is a drawback of the organic foam, and can be handled as a non-combustible material by a proper combination, and its application is greatly expanded.

The fireproof performance of the composite sheet material according to the present invention is a test specified in Ministry of Construction Notification No. 1828 of 1965 and Ministry of Construction Notification No. 1231 of 1976, even if the sheet is used alone or in combination with a thin metal plate. It has the ability to pass "non-combustible material" in the method. On the other hand, regarding fire resistance, the folded sheet structure roof using the composite sheet as a heat insulating material is Showa
According to the test method specified in the Ministry of Construction Notification No. 2999 in 1944, "Roof
It has the performance to pass "30 minutes fire resistance". The sheet-like material has a thermal conductivity of 0.025 to 0.06 Kcal / mh ° C, and has excellent heat insulating performance. Therefore, it is particularly effective to use the composite sheet material of the present invention as the above-mentioned various heat insulating materials. Further, the soundproofing rate of the composite sheet material is about 0.6 for a sound of 1000 Hz and about 0.8 for a sound of 1000 Hz, and it also has an excellent sound absorbing performance. Regarding the weather resistance of the composite sheet, in the weather acceleration test, there is almost no change in appearance and thickness even after 500 hours of continuous irradiation, and the conventional glass is reduced to about one-third in thickness. Very good compared to wool or rock wool insulation. As described above, the composite sheet material according to the present invention satisfies all the performances required as a building material and a heat insulating material, and can be widely used for purposes other than those described above.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the examples, all "parts" mean parts by weight unless otherwise specified.

Example 1 80 parts of a carboxyl-modified ethylene-vinyl acetate copolymer emulsion (glass transition point-10 ° C, solid content 50% by weight) as a thermoplastic resin in 18,000 parts of water, and a special polyamide epichlorohydrin resin liquid (solid content 30 as a crosslinking agent) Weight%) 18
Part, a nonionic surfactant solution consisting of polyoxyethylene nonylphenol ether as a foam stabilizer (concentration 10
5% by weight) and 10 parts of a polyacrylamide solution (concentration 0.2% by weight) as a coagulant were added and dissolved, and 180 parts of rock wool granular cotton was further added and gently stirred for 30 minutes to disperse to prepare a slurry stock solution. . Subsequently, the slurry stock solution was transported to the papermaking unit by a fixed amount using a positive displacement rotary pump, and a slide plate-shaped guide plate provided at an angle of 30 degrees with respect to a diagonally running 50 mesh stainless steel wire mesh. The paper was made on a wire mesh which was made to flow down.
During the papermaking process, a mixed powder of flame retardant antimony trioxide and pentabromomethylbenzene (decomposition temperature of 370 ° C or higher, bromine content of 82% by weight) in a weight ratio of 1: 2 was evenly distributed on the guide plate at a rate of 50 g / m ^2. Was added to. On the other hand, 0.1 part of carboxymethyl cellulose as a sticking agent was dissolved in 10,000 parts of water, and 10 parts of vinylon fiber (VPB103 manufactured by Kuraray Co., Ltd.) was added and dispersed as an organic fibrous material. The dispersion was used to make paper by a known cylinder paper machine, and was transferred to the surface of a wet mat formed into a wire mesh to prepare a paper. After a large excess of white water was mostly drained under the wire mesh, the wet mat passed between two rollers with a predetermined gap to adjust the surface smoothness and thickness unevenness, and was further sent to the vacuum dehydration zone. rate
It was dehydrated to 100% by weight (sheet base after drying). Finally, by drying with hot air at 150 ° C for 20 minutes from both sides, a composite sheet having a thickness of 5.3 mm and an apparent density of 0.16 g / cm ³ was obtained. The main body of the composite sheet material had an average binder content of 5.9% by weight, and the total organic content including the surface organic fibrous material was 8.2% by weight. The sheet body has a very uniform binder distribution in the thickness direction as shown in Table 1. The degree of orientation of the fibrous material in the layer was 14 degrees. The thermal conductivity measurement result of this composite sheet material according to JIS A1412 at 25 ° C is 0.034 Kcal / mh ° C, which is 1,00 according to JIS A1409.
The sound absorption coefficient at 0 Hz is 0.35, which means it has excellent properties as a heat insulating material and sound insulating material. Using a chloroprene-based adhesive (solid content 23% by weight, coating amount 150 g / m ² ), this long sheet is continuously machine-bonded to a color iron plate with a thickness of 0.6 mm using a laminator and bonded. After completion of the above, a folding plate was processed into a roof type 500 (working width 500 mm, mountain height 150 mm) using a roller type folding plate machine. Folded plate workability is good, cutting of corners,
There was no peeling and the like, and the elastic recovery at the portion hitting the roller was good, and there was no problem in appearance as a roofing material. In addition, there was no change in appearance even after 500 hours of the weather resistance accelerated test according to JIS A1415. This composite passed the non-combustible test in the fire protection performance test prescribed in Ministry of Construction No. 1828, 1970, tdθ in surface test was 0, CA was 18.2, temperature difference in base material test was -20 ℃. Was approved. Regarding the etching property, a 5 cm × 5 cm sample was cut out and evaluated by a sensory test, but no etching was found at all.

The sheet-like material obtained by forming a sheet without combining the above-mentioned organic fibrous material caused etching.

Example 2 Styrene-acrylic acid ester copolymer emulsion (glass transition point-6 ° C, solid content 45% by weight) in 18,000 parts of water
150 parts, 45 parts of the crosslinking agent used in Example 1 and the same amount of the foam stabilizer and coagulant used in Example 1 were added and dissolved, and further 135 parts of rock wool granular cotton and a cut length of 13 m were added.
A slurry stock solution was prepared in the same manner as in Example 1, except that 15 parts of m glass chopped strand was added. Then, using the same device as in Example 1, 45
The slurry stock solution was allowed to flow down from the angle, and white paper was blown out from below the guide plate into the slurry stock solution immediately before being transferred from the guide plate to the wire net, and papermaking was performed on the wire net. 50 g / m ² mixed powder of antimony trioxide, which is a flame retardant, and pentabromomethylbenzene (decomposition temperature 370 ° C or higher, bromine content 82% by weight) in a weight ratio of 1: 2 on the guide plate during papermaking. Then, the vinylon fibers of Example 1 were compounded in the same manner as in Example 1. Then, the same treatment as in Example 1 was carried out to obtain a composite sheet-like material having a thickness of 9.8 mm and an apparent density of 0.14 g / cm ³ . The average binder amount of the sheet body of the present composite sheet was 5.0% by weight, and the organic content including the organic fibrous substance on the surface was 7.8% by weight. The sheet body has a uniform binder distribution in the thickness direction as shown in Table 1. The degree of orientation of the fibrous substance in the layer of the sheet body is 53 degrees, and there is no etching during the hand-bonding process for the color iron plate shown in Example 1, and the thermal conductivity is 0.032Kcal / mh ° C, 1,000H.
The sound absorption coefficient at z was 0.68. This composite sheet material was used in the above-mentioned fire prevention performance test and the sheet alone
It was recognized that tdθ was 0, CA was 14.5, and the temperature difference in the base material test was −32 ° C., and passed the nonflammability. In addition, Example 1
Etching evaluation was performed in the same manner as, but no etching was found.

The sheet-like material obtained by forming a sheet without combining the above-mentioned organic fibrous material caused etching.

Example 3 All white water obtained in the filtered water and the dehydration step after obtaining the composite sheet in Example 1 were collected, and water was further added to obtain 1
23 parts of the thermoplastic resin emulsion used in Example 1, 5 parts of the crosslinking agent solution, and 5 parts of the foam stabilizer solution were added to 8,000 parts of the solution.
And 15 parts of a flocculant solution were added and dissolved, and 150 parts of rock wool granular cotton and 6 parts of chrysotile asbestos (5 class) were added to prepare a slurry stock solution in the same manner as in Example 1. The slurry stock solution was treated in the same manner as in Example 1 to obtain 2
It was guided to two discharge ports by one rotary pump, and was made to flow down from two guide plates provided so as to have an angle of 30 degrees with respect to the running wire mesh. However, in this test, between the first guide plate and the second guide plate,
By introducing a glass fiber net having an opening of 5 mm, the net was put into a layer and the papermaking was performed. Further, in this test, in the same manner as in Example 1, antimony trioxide and tetrabromobisphenol A (decomposition temperature
320 ℃, bromine content 59 wt%) 1: 5 weight ratio of mixed powder
It was added uniformly at a rate of 45 g / m ² , and the vinylon fiber of Example 1 was compounded in the same manner as in Example 1. Thereafter, the same treatment as in Example 1 was performed to give a thickness of 2.1 mm and an apparent density of 0.3.
A composite sheet having ³ g / cm ³ , a binder amount of 5.3% by weight, and a degree of orientation of the fibrous material of the sheet body of 5 degrees was obtained. The composite sheet is very strong because it is reinforced by a net,
It has a tensile strength of about 50 kg / cm ² and an elongation of about 4%, and has flameproof performance that can pass the 2-minute heating category in the test based on Article 4-3 of the Fire Service Law Enforcement Regulations. From the above, the sheet-like material can be widely used as a ceiling material for bathrooms, kitchens, etc., as a ceiling / wall surface material for public buildings, and also as a packing material for cushion floors.

Example 4 A composite folded sheet roofing material of a composite sheet material having a thickness of 5.3 mm and an apparent density of 0.16 g / cm ³ obtained in Example 1 and a color iron plate of 0.6 mm, and a thickness of 4.0 mm which was similarly trial-produced. , Apparent density 0.024
A small piece is cut out from a composite folded-plate roofing material that uses g / cm ³ polyethylene foam sheet as a heat insulating material, and the roof side of a large container controlled at room temperature of 30 ° C and relative humidity of 95 to 100% with the heat insulating material side as the inside, 3.5 ~ on the roof which is the iron plate surface
A model was used to conduct a dew condensation acceleration experiment in winter by flowing cooling water of 5.0 ℃. As a result of measuring the time until the dew condensation water finally drops on the surface of the heat insulating material, about 17 hours after in the case of the composite sheet according to the present invention, the polyethylene foam sheet reached the drop after 3 hours, Although the thermal conductivity was about the same or slightly inferior, it was clear that the composite sheet material according to the present invention was particularly excellent in dew resistance due to the moisture absorbing / releasing effect.

Example 5 Thickness 5.1 m obtained by the same composition and method as in Example 2.
0.80 mm thick composite sheet with m and apparent density of 0.14 g / cm ^3.
Combined with the zinc-iron plate and chloroprene adhesive, the mountain height is 150m
A heat-insulated roofing material with a width of 500 m and a working width of 500 mm was folded into a sheet. A part of the roofing material is cut out and modeled in 1969 by the Ministry of Construction No. 2999
In accordance with the method specified in No. 1, when heating up to 840 ° C from the sheet side for 30 minutes so that the specified indoor first-class heating curve is reached, the maximum surface temperature of the back side of the iron plate is 430 ° C. There was no red heat, no deformation, etc., and there was no drop or destruction of the sheet-like heat insulating material after the test, and the fire resistance was such that it could pass the 30-minute fire resistance of the roof.

Example 6 Using 160 parts of a bulk material of ceramic fibers (fiber diameter is 3 μm or less, fiber length is 30 mm or less), in the same manner as in Example 1,
A composite sheet having a thickness of 5.2 mm and an apparent density of 0.12 g / cm ³ was obtained. The main body of this composite sheet material has an average binder amount of 6.2% by weight, and the total organic content including the organic fibrous material on the surface is
It was 7.9% by weight. The sheet body has a very uniform binder distribution in the thickness direction as shown in Table 2.
The degree of orientation of the fibrous material in the layer was 55 degrees. The physical properties measured by the same method as in Example 1 have a thermal conductivity of 0.028 Kcal / m.
The sound absorption coefficient at h. ° C. and 1000 Hz was 0.30, and folding plate workability was also good. In addition, no change in appearance was observed after 500 hours of the accelerated weathering test, and the td in the surface test was also confirmed in the fire performance test.
0 was 0, CA was 15, and the temperature difference in the base material test was −20 ° C., and it was recognized that the material passed nonflammability. No etching was observed even in the evaluation result of the etching property.

Example 7 Using 120 parts of short carbon fibers (fiber length 3.0 mm, fiber diameter 10 μ), in the same manner as in Example 1, thickness 5.4 mm, apparent density
A sheet-like material having a weight of 0.08 g / cm ³ was obtained. The main body of the composite sheet material had an average binder content of 6.1% by weight, and the total organic content including the organic fibrous material on the surface was 7.1% by weight. The sheet has a very uniform thickness-wise binder distribution. The physical properties measured by the same method as in Example 6 are thermal conductivity.
The sound absorption coefficient at 0.025Kcal / m · h. ° C and 1000Hz was 0.33, and the folding plate processability was also good. In addition, no change in appearance was observed after 500 hours of the weather resistance accelerated test, and in the fire performance test, td0 in the surface test was 0, CA was 24, and the temperature difference in the base material test was -23 ° C. It was recognized that it passed nonflammability.
In the evaluation result of the etching property, the etching was not recognized at all.

Claims (38)

[Claims] 1. A sheet comprising 80 to 97% by weight of a non-combustible fibrous substance and 3 to 20% by weight of a binder containing a thermoplastic resin as a main component, and b) an organic fibrous substance on one or both sides of the sheet. A composite sheet-like material composed of a thin layer formed by sheet-drying a wet paper-making sheet comprising. 2. The composite sheet according to claim 1, wherein the non-combustible fibrous material of the sheet is any one of asbestos, rock wool, glass fiber, ceramic fiber, alumina fiber or carbon fiber, or a mixture thereof. Thing. 3. The thermoplastic resin has a glass transition point of −
The composite sheet material according to claim 1 or 2, which is a thermoplastic resin in the range of 50 to 30 ° C. 4. The composite sheet material according to any one of claims 1 to 3, wherein the thermoplastic resin is a self-crosslinking resin. 5. The binder is 0.1 to the thermoplastic resin.
The composite sheet material according to any one of claims 1 to 3, which contains -30% by weight of a crosslinking agent for the thermoplastic resin. 6. The composite sheet material according to claim 1, wherein the orientation degree of the non-combustible fibrous material in the layer of the sheet is 3 to 30 degrees. 7. The composite sheet material according to any one of claims 1 to 5, wherein the degree of orientation of the noncombustible fibrous substance in the layer of the sheet is 31 to 80 degrees. 8. The composite sheet according to claim 1, wherein the binder amount in the intermediate layer of the sheet is 2% by weight or more and is 0.25 times the average value of all layers or more. Thing. 9. The composite sheet material according to any one of claims 1 to 8, wherein the sheet contains the binder in an amount of 5 to 15% by weight. 10. The composite sheet material according to any one of claims 1 to 9, wherein the organic fibrous material is pulp, cellulose or synthetic fiber. 11. The composite sheet material according to any one of claims 1 to 10, wherein the organic fibrous material is bound by a binder containing a thermoplastic resin as a main component. 12. The composite sheet material according to claim 11, wherein the thermoplastic resin is a thermoplastic resin having a glass transition point in the range of −50 to 30 ° C. 13. The composite sheet material according to claim 11, wherein the thermoplastic resin is a self-crosslinking resin. 14. The binder is 0.1 to the thermoplastic resin.
The composite sheet material according to any one of claims 11 to 13, which comprises -30% by weight of a thermoplastic resin crosslinking agent. 15. The composite sheet material according to any one of claims 11 to 14, wherein the thin layer contains 0 to 20% by weight of a binder. 16. The composite sheet material, wherein the weight ratio of the thin layer (one side) to the sheet is 0.001 to 0.2 times, and the weight of the thin layer (one side) is 3 to 30 g / m ² . The composite sheet material according to any one of claims 1 to 15. 17. The composite sheet according to claim 1, wherein the composite sheet has a thickness of 0.5 to 25 mm and an apparent density of 0.08 to 0.4 g / cm ^3. Sheet material. 18. The composite sheet according to claim 1, wherein the composite sheet has a thickness of 0.5 to 50 mm and an apparent density of 0.04 to 0.2 g / cm ^3. Sheet material. 19. A) 80 to 97% by weight of non-combustible fibrous substance and 3 to 20% by weight of a binder whose main component is a thermoplastic resin.
And (b) a sheet-like reinforcing material inside or on the surface of a sheet-like material formed of a thin layer formed by composite-drying a wet paper-making sheet made of an organic fibrous material on one or both sides of the sheet. A composite sheet-like product in which are integrated. 20. The composite sheet material according to claim 19, wherein the sheet-shaped reinforcing material is a material having air permeability made of cloth, paper, cheesecloth, non-woven fabric or net. 21. The composite sheet material according to claim 19, wherein the sheet-shaped reinforcing material is a material having no air permeability made of a film or a metal foil. 22. The noncombustible fibrous material of the sheet is asbestos, rock wool, glass fiber, ceramic fiber, alumina fiber or carbon fiber, or a mixture thereof, in any one of claims 19 to 21. The composite sheet material according to 1. 23. The composite sheet material according to any one of claims 19 to 22, wherein the thermoplastic resin is a thermoplastic resin having a glass transition point in the range of -50 to 30 ° C. 24. The composite sheet material according to any one of claims 19 to 23, wherein the thermoplastic resin is a self-crosslinking resin. 25. The binder is 0.
The composite sheet material according to any one of claims 19 to 23, which contains 1 to 30% by weight of the crosslinking agent for the thermoplastic resin. 26. The composite sheet material according to any one of claims 19 to 23, wherein the orientation degree of the nonflammable fibrous substance in the layer of the sheet is 3 to 30 degrees. 27. The composite sheet material according to any one of claims 19 to 25, wherein the orientation degree of the non-combustible fibrous material in the layer of the sheet is 31 to 80 degrees. 28. The composite sheet according to any one of claims 19 to 27, wherein the amount of the binder in the intermediate layer of the sheet is 2% by weight or more and is 0.25 times the average value of all layers or more. Thing. 29. The sheet comprises 5 to 15% by weight of the binder.
29. The composite sheet material according to any one of claims 19 to 28, which contains. 30. The composite sheet material according to any one of claims 19 to 29, wherein the organic fibrous material is pulp, cellulose or synthetic fiber. 31. The composite sheet material according to any one of claims 19 to 30, wherein the organic fibrous material is bound by a binder containing a thermoplastic resin as a main component. 32. The composite sheet material according to claim 31, wherein the thermoplastic resin is a thermoplastic resin having a glass transition point in the range of −50 to 30 ° C. 33. The composite sheet material according to claim 31, wherein the thermoplastic resin is a self-crosslinking resin. 34. The binder is 0.1 to the thermoplastic resin.
The composite sheet material according to any one of claims 31 to 33, which comprises -30% by weight of a crosslinking agent for a thermoplastic resin. 35. The composite sheet material according to claim 31, wherein the thin layer contains 0 to 20% by weight of a binder. 36. The composite sheet material, wherein the weight ratio of the thin layer (one side) to the sheet is 0.001 to 0.2 times, and the weight of the thin layer (one side) is 3 to 30 g / m ² . Claim No.
The composite sheet material according to any one of items 19 to 35. 37. The composite according to claim 19, wherein the composite sheet has a thickness of 0.5 to 25 mm and an apparent density in the range of 0.08 to 0.4 g / cm ^3. Sheet material. 38. The composite sheet according to any one of claims 19 to 36, wherein the composite sheet material has a thickness of 0.5 to 50 mm and an apparent density in the range of 0.04 to 0.2 g / cm ^3. Sheet material.