JPH0333838B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides sheet-like materials with excellent fire retardancy and flexibility;
It relates to its manufacturing method. More specifically, it is a sheet with a thickness of 0.5 to 25 mm and an apparent density of 0.08 to 0.4 g/cm3, consisting of a) 80 to 97% by weight of a nonflammable fibrous material and b) ³ to 20% by weight of a binder resin. a) the degree of orientation of the fibrous material in the layer of the sheet-like material with respect to the sheet surface is 3 to 30 degrees;
b) the amount of binder in the intermediate layer of the sheet-like material is 2% by weight or more and 0.25 times or more the average value of all the layers, and c) the nonflammable woven material is bonded by a binder resin crosslinked sheet-like materials,
The sheet-like material further contains as a flame retardant (c) 5 to 50 parts by weight of an antimony compound and 10-100 parts by weight of an aromatic bromine compound based on 100 parts by weight of the binder; The present invention relates to a manufacturing method using a wet paper-forming method suitable for manufacturing a sheet-like article, and a heat-insulating material made of the sheet-like article, and the sheet-like article has fireproofing properties, fire resistance, heat insulation properties, soundproofing properties, dew proofing properties, It is a heat insulating material and construction material with excellent weather resistance, mechanical strength, and foldability, and can be widely applied to buildings and various branded equipment. In recent years, with the promotion of energy conservation, various types of insulation materials have been used in many fields. Among insulation materials, organic foams such as polyurethane foam and polystyrene foam have major drawbacks in terms of fire protection performance, and for buildings and equipment that are at risk of fire, inorganic fibers such as glass fiber and rock wool are mainly used as raw materials. Insulating materials are being used. However, these extremely lightweight inorganic insulation materials generally have no binder or have a very small amount of phenolic resin adhered non-uniformly, so although they have excellent insulation properties, they are extremely brittle and difficult to handle. For example, it cannot be used in areas subject to severe handling, such as insulation for folded roofs. Therefore, attempts have been made to use sheet-like materials having a thickness of about 5 to 25 mm and having appropriate flexibility, which are made by bonding inorganic fibers with various binders, as heat insulating materials in fields that are subject to such severe handling. but,
All of these conventional sheet-like materials are sheets obtained by a manufacturing method called a dry method, and the amount of binder is too small to uniformly cover the surface of the inorganic fibers, or the binder in the middle layer of the sheet-like material is Because of the lack of , it was unsuitable for this purpose. On the other hand, the technology of forming inorganic fibrous materials into plate or paper shapes by wet papermaking has been widely used in the fields of glass paper, asbestos paper, rock wool ceiling panels, asbestos slate panels, etc. Both paper and board obtained by conventional wet papermaking methods have a small amount of binder and a specific gravity of 0.40 or more, and although paper-like products are flexible, they are brittle, have poor flexibility, and are thin. No insulation. On the other hand, board-shaped materials have excellent strength, but are not flexible and brittle, and cannot be used as insulation materials for folded-plate roofs as described above. In order to improve this drawback, there are also known methods for producing sheet-like products, such as those described in Japanese Patent Publication No. 49-43485, in which Rokuu is dispersed using a specific surfactant and wet-formed. However, it is not possible to significantly improve the basic properties of sheet materials by simply improving dispersibility, and it is not possible to significantly improve the basic properties of sheet materials. Since the inorganic fibers were used, cutting of the inorganic fibers was unavoidable, and the sheet-like material obtained did not go beyond the paper-like region. In view of the current situation, the inventors of the present invention have conducted intensive studies to develop a heat insulating material that has excellent fire retardant properties and can withstand severe handling, and as a result has arrived at the present invention. That is, the present invention consists of a) 80 to 97% by weight of a nonflammable fibrous material and b) 3 to 20% by weight of a binder resin, with a thickness of 0.5 to 25 mm, and an apparent density of 0.08 to 0.4 g/
cm ³ sheet-like material, wherein: a) the degree of orientation of the fibrous material in the layer of the sheet-like material with respect to the sheet surface is 3 to 3;
30 degrees, and b) the amount of binder in the middle layer of the sheet is 2% by weight or more and 0.25% of the average value of all layers.
(c) A sheet-like material bonded by a binder resin in which a non-flammable fibrous material is cross-linked; 5 to 50 parts by weight of an antimony compound and 10 to 50 parts by weight
A sheet-like product containing 100 parts by weight of an aromatic bromine compound, a manufacturing method using a wet paper-making method suitable for producing the sheet-like product, particularly having a thickness of 0.5 to 25 mm,
Sheet materials with an apparent density in the range of 0.08 to 0.4 g/ ^cm3 are excellent as heat insulating materials, and can be used as building materials such as fireproofing, fireproofing, heat insulation, soundproofing, weather resistance, water resistance, dew proofing, etc. It satisfies all the performance requirements for a heat insulating material. For example, the sheet-like material is folded at an angle of 60 degrees to 90 degrees by being composited with a thin metal plate or a thin metal plate with polyethylene foam sandwiched between intermediate layers, and then passed through a folding roller. The sheet material on the surface does not suffer any damage even when bent, and has excellent thickness resilience, and can withstand such harsh handling and processing. It provides excellent performance as a thermal insulator, base material, dew proofing material, soundproofing material, and fireproof coating material. Such a sheet-like product can be obtained by a wet papermaking method as described below, but the main point of the present invention is the sheet-like product itself having the above structure,
The present invention is not limited to sheet-like products obtained by the manufacturing method described below. The present invention will be described in detail below. Examples of the noncombustible fibrous material used in the present invention include asbestos, rock wool, glass fiber, ceramic fibers such as aluminum silicate, alumina fibers, and carbon fibers. Others generally do not melt or burn at temperatures below 500℃, and have an average diameter of 0.1~
Any fibrous material can be used as long as it has a diameter of 20 μm and an average fiber length of about 1 to 30 mm. It is preferable to use asbestos with fibers as long as possible. Rock wool is the most suitable material for the purpose of the present invention, and it can be used regardless of whether it is made from natural rock or slag. It is preferable to use a material with a small content of particles, and a material called granular cotton or layered cotton can be used as a starting material. As the glass fiber, chopped strands or glass wool can be used as a starting material. Further, in the present invention, it is also possible to replace a part of the nonflammable fibrous material with organic fibers for the purpose of reducing elasticity, flexibility, and irritation to the skin, within a range that does not particularly reduce fire protection. As such organic fibers, those made from vinylon, rayon, acrylic, nylon, polypropylene, vinyl chloride, ester, etc. can be used. In the present invention, the binder whose main component is a thermoplastic resin is used for the purpose of coating the surface of inorganic fibers and promoting entanglement to increase the strength, elastic recovery power, and processability of the obtained sheet-like product. It is preferable to use a substance that can be dissolved or dispersed in water, and water-soluble polymers, emulsions, or latex-like resins are preferable. Examples of water-soluble polymers include polyvinyl alcohol polymers, polyacrylic acid polymers, polyethylene oxide,
Examples include carboxymethyl cellulose, casein, starch, etc., and a wide variety of synthetic and natural water-soluble polymer materials can be used. Examples of emulsion or latex-like resins include polyvinyl acetate and copolymers thereof, polyvinyl chloride and copolymers thereof, polyacrylic acid esters and copolymers thereof, polyethylene and copolymers thereof, and polyurethane in the form of emulsions. Hydrosols such as ethylene-acrylate copolymers can also be included in this category. In the present invention, in order to obtain a sheet material for use in applications requiring particular flexibility and flexibility, a thermoplastic resin whose glass transition point is within the range of -50 to 30°C is used as a binder. For example, ethylene-vinyl acetate copolymer, plasticized vinyl chloride-vinyl acetate copolymer, polyurethane, (meth)acrylic acid ester copolymer, etc. can be mentioned. For example, JISK7213 is a method for measuring the glass transition point.
The shear modulus and mechanical damping of plastics can be measured using a torsion pendulum test method or a device such as a pipe lon, and can be represented by the transition region temperature of the elastic modulus or the peak temperature of mechanical damping. In the present invention, the distribution of the binder containing the thermoplastic resin as a main component in the sheet-like material in the thickness direction is particularly important. It can be an effective sheet material that can withstand handling. First, it is preferable that the front and back skin layers contain slightly more binder than the inner layer, or the same amount, in order to protect the surface from rubbing by rollers during folded plate processing, protect the surface during handling, and weather resistance. The lower limit of the amount of binder in the intermediate layer is determined from the amount necessary to uniformly coat the inorganic fibers to the extent that the inorganic fibers are not crushed during folded plate processing, and the upper limit is determined from the viewpoint of fire protection performance.
That is, the amount of binder in all layers of the sheet material is in the range of 3 to 20% by weight, preferably 5 to 15% by weight, and the amount of binder in the intermediate layer is 2% by weight or more and 0.25 times the average value of all layers. The above-mentioned conditions can be satisfied if the binder has a relatively homogeneous distribution in the amount or more. As a method for measuring the amount of binder in a sheet-like material as described in the present invention, for example, when determining the distribution in the thickness direction, a spread sheet A with a diameter of 20 to 50 mm centered on an arbitrary point is used. Several cylindrical test specimens were punched out, and then each test specimen was further cut into n layers (n = 3 to 8) parallel to the surface so that the thickness was uniform.After collecting each layer separately, Number n. Here, 1 and n correspond to the surface layer, and 2-
n-1 corresponds to the middle layer. After leaving such samples in a desiccator at room temperature for a day and night, they were placed in separate porcelain crucibles and baked in an electric furnace at 550 to 600°C for 30 to 60 minutes.The weight loss of the m-th layer was defined as Am weight %, and the same If the weight loss of the m-th layer obtained in the same manner for the sheet-like material B produced without using the binder by the method is Bm, the amount of binder in the m-th layer is Xm = Am - Bm. You can ask for it.
When the organic content in the sheet-like material is only the binder, it may be determined as Xm=Am for convenience.
The amount of binder in the entire sheet-like material is an average value of 1 to n, and the amount of binder in the intermediate layer is determined as an average value of 2 to n-1. In the present invention, heat is used to prevent the migration of the binder mainly composed of thermoplastic resin to the surface of the sheet material, to control the predetermined binder distribution, and to improve the water resistance, weather resistance, and strength of the sheet material. The use of suitable cross-linking agents for plastic resins has become an important technique, and in some cases, the thermoplastic resins used themselves, such as self-cross-linking emulsions or heat-coagulated latexes, can be cross-linked or cross-linked under certain conditions. It may also cause a coagulating effect, resulting in the same effect as using a crosslinking agent. The type of crosslinking agent should be selected depending on the thermoplastic resin used; for example, for polyvinyl alcohol polymers, isocyanate compounds, urea compounds, boric acid and its salts,
Examples include zirconia compounds and titanic acid compounds, and examples of polyvinyl acetate emulsions and polyacrylic ester emulsions include modified polyamideimide epoxy resins and isocyanate emulsions. The amount of the crosslinking agent added should be appropriately determined depending on its effectiveness, and is generally used within the range of 0.1 to 30% by weight based on the binder whose main component is a thermoplastic resin. At the time of addition, it may be used as an aqueous solution mixed with a thermoplastic resin in advance, or it may be impregnated into a sheet-like material. In addition, in the present invention, it is preferable to use an appropriate flame retardant in order to significantly improve the fireproofing properties and fire resistance of the obtained sheet material. In particular, a combination of compounds suitable for the present invention that can exhibit excellent effects is a combination of 5 to 500 parts by weight of an antimony compound and 10 to 100 parts by weight of an aromatic odor compound based on 100 parts by weight of the binder. Preferably, a combination in which the weight ratio of the antimony compound and the aromatic bromine compound is in the range of 1:1 to 1:10 is preferable. If more than 50 parts by weight of the antimony compound and 100 parts by weight of the aromatic bromine compound are added to 100 parts by weight of the binder, the flame retardance will further improve, but flexibility will decrease, which is not preferable. Examples of the antimony compound include antimony trioxide, antimony pentachloride, antimony trichloride, and antimony trisulfide, or a mixture thereof.
In addition, the aromatic bromine compound has a particularly high decomposition temperature.
Compounds with a temperature of 280°C or higher and a bromine content of 50% by weight or higher are preferred, such as tetrabromobenzene, pentabromomethylbenzene, hexabromobenzene, hexabromo diphenyl ether,
Examples include compounds such as decabromodiphenyl ether and tetrabrombisphenol A, or mixtures thereof. Among sheet materials containing such flame retardants, those with a binder content in the range of 4 to 8% by weight were constructed in 1972 even though organic binders were used. The folded plate roof structure, which has the highest level of fire resistance that passes the test method specified in Ministry Notice No. 1828 as a "noncombustible material," and uses the sheet material as a heat insulating material, was constructed in 1962. Ministry Notice No.
"Roof 30 minute fire resistance" according to the test method specified in No. 2999
It has the highest level of fire resistance that can pass the standards. In the present invention, an important factor in addition to the amount of binder in the sheet-like material and its distribution in the thickness direction is the degree of orientation of the fibers in the layer of the sheet-like product with respect to the sheet surface, and is 3 to 30%. Preferably 5~
It is essential to have a degree of orientation of 15 degrees. The degree of orientation of the fibrous material within a layer as used in the present invention can be measured by the following method. The front and back surfaces of the sheet-like material of a predetermined size are bonded to a flat metal plate using an adhesive. Next, the upper and lower metal plates are grasped with a chuck, and the crosshead is raised at a constant speed to cause the sample to break. By doing the usual interlaminar breaking strength measurement, the sheet-like material can be measured using the nonflammable fibrous material in the layers. Cutting occurs from the oriented layered interface.
The degree of orientation of the fibrous material within the layer can be determined by measuring the angle between the flat metal plate surface of the test piece after fracture and the fracture surface. The degree of orientation in the present invention is an important factor for the apparent density, heat insulation, fireproofing, soundproofing, and dewproofing properties of the sheet material, and in the case of paper-like sheet materials obtained by conventional techniques, The degree of orientation is almost 0 degrees, and although strength in the vertical and horizontal directions is exhibited, interlayer strength is poor, and it is difficult to obtain a sheet-like product with a low apparent density. Bracket-shaped insulation materials for piping are also commercially available, which are made by cutting rock wool layered cotton into a certain length and pasting them together with the cut ends aligned so that the cut length corresponds to the thickness. The apparent density is greatly reduced, and although it has good flexibility, it is extremely brittle and lacks ease of handling. For the above reasons, the degree of orientation of the fibrous material in the layer relative to the sheet surface is 3 to 30 degrees, preferably 5 to 15
A sheet material having such a degree of orientation can be obtained, for example, by the manufacturing method described below. In the present invention, it is also possible to add or coat coloring agents such as various dyes and pigments, fungicides, and water repellents for the purpose of enhancing the performance as a heat insulating material, building material, etc. In addition, aluminum hydroxide, gypsum dihydrate, borax,
Fillers such as calcium carbonate, and lightweight fillers such as barlite, shirasu balloons, foamed vermiculite, hollow glass spheres, and mica may be added for the purpose of weight reduction. In the present invention, the strength and water resistance of the sheet-like material,
It is also possible to compound a sheet-like reinforcing material on the intermediate layer or surface of the sheet-like product for the purpose of improving fireproofing and moisture-proofing properties. As sheet-like reinforcing materials, various films and metal foils are suitable especially when moisture-proofing and waterproofing properties are required, while cloth, paper, cheesecloth, non-woven fabric, and netting are suitable when moisture-permeable and moisture-absorbing properties are required. Porous materials such as the like are suitable. These sheet-like reinforcing materials can be molded and composited at the same time during paper forming, or they can be composited by applying an adhesive to the obtained sheet-like material. Next, a method for manufacturing a sheet-like article having excellent fire resistance and flexibility according to the present invention will be explained in detail. First, a certain amount of the above-mentioned athermal fibrous substance, the above-mentioned organic fibers and various additives as necessary, and a binder whose main component is the above-mentioned water-soluble thermoplastic resin, emulsion, or latex-like thermoplastic resin are added. A slurry stock solution is prepared by uniformly dispersing and dissolving the thermoplastic resin in water together with a crosslinking agent or 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 dewatering efficiency and controlling the amount of binder in the sheet material. Nonionic surfactants are generally effective as this foam stabilizer, and their action is due to the action of the water-soluble thermoplastic resin, emulsion, or latex-like thermoplastic resin added to the slurry stock solution. It will foam up a bit, but this is done by making the bubbles uniform and fine, forming an appropriate water film between the fibrous materials during vacuum dehydration, preventing air from escaping, and keeping the dehydration rate constant. . As for the dispersion method, relatively gentle stirring using a chieste or the like is preferable; vigorous crushing using a Peter or other device is not preferable because the fibrous material may break or form spherical aggregates. The dispersion concentration of the nonflammable fibrous material and the binder is preferably 0.1 to 5% by weight, and should be appropriately selected depending on the purpose of use of the obtained sheet material. Next, the slurry stock solution is transported from the tank with a slurry pump having a structure that prevents the fibrous materials from forming spherical aggregates, or is guided to the papermaking section by dropping it from the top, and is passed through a running or rotating net-like or porous material. The material is supplied from a direction having an angle of 5 to 60 degrees, preferably 20 to 45 degrees with the surface of a shaped base material, and is formed into a sheet on the base material to produce a wet mat having an orientation of 3 to 30 degrees. do. At this point, the white water containing the binder drained from the surface of the substrate is returned to the slurry stock solution adjustment tank together with the white water from the dehydration step and reused. The resulting wet mat of non-combustible fibrous material is then dehydrated using a vacuum method. Conventionally, in the field of rock wool ceiling materials and asbestos slate boards, etc., a (roller) press is applied in this process to impart thickness and thinness precision, surface smoothness, or surface pattern at the same time as dewatering, but in the production of sheet-like products according to the present invention. With such a (roller) pressing method, it is not possible to obtain the desired lightweight and flexible sheet-like material, and therefore, a vacuum dehydration method is most suitable as a dehydration method. The wet mat after papermaking, which contains about 5 to 8 times as much water as the solid content, is sent to a reduced pressure zone either alone or together with the base material, and after the internal moisture is sucked out from one or both sides, it is sent to a drying zone. Although the drying process to increase the water removal rate can be shortened and is economical, the final water content is preferably kept at 0.5 to 2 times because the sheet becomes stale and the specific gravity increases. In this process, the fine air bubbles inside work effectively to prevent the sheet from sagging and to increase the dehydration rate. The reason for this is thought to be that the water film formed between the fibers prevents air from blowing through from specific locations. After dehydration, the pine is dried by an appropriate method to form a sheet. The drying method may be a hot air tray method, a hot air blowing method, a hot roller contact method, etc., and the suitable drying temperature is 80 to 200°C. In the present invention, the above-mentioned flame retardant can be added internally when preparing the slurry stock solution or coated on the surface before drying. The method of adding and mixing and paper-forming together provides the best dispersion with the binder component and is effective in increasing the flame retardant effect. Furthermore, in the present invention, the method of combining the sheet-like material and the sheet-like reinforcing material, if necessary, is as described above. As mentioned above, the sheet-like product according to the present invention has the following features:
It has excellent flexibility, fireproofing, fire resistance, heat insulation, dew proofing, soundproofing, vibration damping, heat resistance, water and weather resistance, cushioning properties, etc., and these characteristics can be used for civil engineering construction, equipment plants, etc. It can also be widely used in household appliances, furniture, automobiles and other vehicles, ships, and other industrial fields. To give an example of its application, first of all, in the field of civil engineering and construction, it can be used as a fireproof coating for steel frames of buildings, etc., and as a fireproof joint material for fireproof walls, making use of its fire prevention and fire resistance. In addition to heat insulating materials for ceilings, walls, and floor spaces, the sheet-like material of the present invention can be used as the above-mentioned heat insulating sheets for folded-plate roofs, inner lining materials for side wall metal siding materials, and water drop prevention materials for heated pools, bathrooms, etc. This is a field in which it can demonstrate its characteristics, and by taking advantage of its soundproofing and vibration damping properties, it can be used as an inner lining material for metal panels and shelters in station buildings, halls, etc., as an inner lining material for flat doors, metal shutters, shutter storage boxes, etc. Can be used as deck plates, backing materials for metal floors such as emergency stairs, core materials for soundproof panels, etc., backing materials for PVC cushion floors, backing paper for fireproof wallpaper, core materials for roof/rooftop sealing materials, etc. It is also effective for applications such as Next, in the field of factories, it can be used as a heat insulating material for various line piping due to its insulation properties, and as a fireproof insulation material for various tanks.It can also be used as a lining material for air conditioning ducts, a lagging material, and pneumatic transportation material that takes advantage of its soundproofing and vibration damping properties. Applications include line duct lining material and air conditioning duct damper cushion material.
Applications to equipment parts include bulk up materials for gas and oil heaters, sound absorbing and insulating materials for air conditioners and hot water boilers, insulating materials for cold storage warehouses and fixed-temperature freezer warehouses, as well as rock drills and hand drills that utilize sound insulation and vibration damping properties. ,
Damping materials for chainsaws, rivets, etc. (to prevent white wax), pumps, ejectors, blowers, ball mills, hoppers, cyclones, oil separators, compressors, duster chute, vibrating screens, vibrating feeders, conveyors, forging machines, presses, cutters Application examples include soundproofing and vibration damping materials such as housings and motor covers for various equipment such as drills, rolling mills, and generators, and housing lining materials for general office equipment such as typewriters, line printers for computers, and drilling machines. It will be done. In the field of home appliances and furniture, we take advantage of our fire resistance to use sealants for bathtubs, insulation, and
Cooking devices such as ovens and ranges that take advantage of their heat resistance,
Insulating materials for irons, vending machines, etc., dew-proofing and soundproofing lining materials for stainless sinks and baths, and housings, piping, and motors for refrigerators, air conditioners, air conditioners, dishwashers, etc. that take advantage of their soundproofing and vibration-damping properties. It can also be used as an inner lining material for covers, as a lining material for steel furniture such as desks, cabinets, and lockers, and as a damping material for audio products.It can also be used as a packing material and sealing material for gas appliances after being impregnated. In the automotive field, insulation materials for car body ceilings,
Insulating and sound-absorbing material for the partition wall between the engine room and the driver's seat,
Soundproofing materials for exhaust pipes, soundproofing and vibration-damping interior materials for doors, engine locker covers, engine enclosure panel interior materials, fireproof and heat-insulating vibration-proofing materials for oil pans, gasoline tanks, trunk rooms, cowl inners, In addition to soundproofing material for the engine part of front hoods, soundproofing/waterproofing mats for floors, and filters for air cleaners, it can also be used as brake linings, clutch facings, and gaskets by impregnation. In the field of other large vehicles and ships, we use inner lining materials for engine covers, insulation materials for line piping for warm fresh water, fuel oil, etc., heatproofing, dewproofing, and soundproofing materials for living areas, insulation materials for refrigerator compartments of refrigerated cars, subways, etc. side walls, ceiling sound absorbing materials, motor boards,
Soundproofing materials for engine rooms of fishing boats, etc., soundproofing materials for wheel shelters of trains, subways, etc., soundproofing materials for decks, etc.
Examples of uses include rust-proof backing material. Other open hearth,
It can also be used as a dropper for converters, electric furnaces, etc., as a joint material for molds, and as a soundproofing/vibration damping material around aircraft jet engines. The above-mentioned application examples are all examples of the use of the sheet-like product of the present invention alone, but it can also be used as a surface material for organic foam insulation materials such as polyethylene foam, polystyrene foam, and polyurethane foam, which have been widely used in the past. When used, the flammability, which is a drawback of the organic foam, can be improved, and by appropriate combination, it can be treated as a non-combustible material, and its uses will be greatly expanded. The fire retardant performance of the sheet-like material according to the present invention is determined by the test method specified in Ministry of Construction Notification No. 1828 of 1971 and Ministry of Construction Notification No. 1231 of 1976, whether the sheet is used alone or in a composite with a thin metal plate. It has the performance to pass the "noncombustible material" test. On the other hand, in terms of fire resistance, folded plate roofs that use the sheet material as a heat insulator have the ability to pass the "roof 30 minute fire resistance" test method specified in Ministry of Construction Notification No. 2999 of 1962. have. The thermal conductivity of the sheet-like material is 0.025 to 0.06 Kcal/mh℃,
It has excellent heat insulation performance. Therefore, it is particularly effective to use the sheet-like material of the present invention as the various heat insulating materials mentioned above. In addition, the sound absorption coefficient of the sheet-like material is approximately 0.6 for sound at 1000 Hz for a sheet with a thickness of 10 mm, and approximately 0.8 for a sheet-like material with a thickness of 25 mm, so it also has excellent sound-absorbing performance. Regarding the weather resistance of the sheet, there was almost no change in appearance or thickness even after continuous irradiation for 500 hours in a weather accelerated test, and the thickness was reduced to about one-third compared to conventional glass. Much better than wool or rock wool insulation. The sheet material according to the present invention satisfies all the performances required as a building material and a heat insulating material, and can be used in a wide range of applications other than those described above. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples in any way. In the examples, unless otherwise specified, "part"
All numbers refer to parts by weight. Example 1 108 parts of carboxyl-modified ethylene-vinyl acetate copolymer emulsion (glass transition point -10°C, solid content 50% by weight) as a thermoplastic resin in 18000 parts of water,
25 parts of special polyamide epichlorohydrin resin liquid (solid content 30% by weight) as a crosslinking agent, 5 parts of a nonionic surfactant solution (concentration 10% by weight) consisting of polyoxyethylene nonylphenol ether as a foam stabilizer, polyacrylamide as a flocculant. Add and dissolve 15 parts of the solution (concentration 0.2% by weight), then add 180 parts of Rockwool granular cotton, and gently stir
The mixture was stirred for a minute to disperse it, and a slurry stock solution was prepared. Next, the slurry stock solution was transported to the papermaking department in fixed quantities using a liquid-dispersion type rotary pump, and 30%
The paper was made to flow down a slide-like guide plate set at an angle of 100 degrees, and then formed onto a wire mesh. After most of the excess white water has been filtered under the wire mesh, the Ettomatsuto is passed between two rollers with a predetermined gap to smooth out the surface smoothness and smooth the thickness, and then sent to a vacuum dehydration zone to absorb moisture. rate 100
% by weight (sheet base after drying). Finally, by drying both sides with hot air at 150℃ for 20 minutes, the thickness is 5.3mm and the apparent density is 0.16g/
A sheet of cm ³ was obtained. This sheet-like material has an average binder content of 8.4% by weight, and has a very uniform binder distribution in the thickness direction as shown in Table 1. The degree of orientation of the fibrous material within the layer was 14 degrees.
The heat conductivity measurement result of this sheet-like material at 25℃ according to JISA1412 is 0.034Kcal/mh℃,
The sound absorption coefficient at 1000Hz according to JISA1409 is 0.35,
It has excellent properties as a heat insulator and sound insulator.
Using a chloroprene adhesive (solid content 23% by weight, coating amount 150g/m ² ), this long sheet was continuously mechanically pasted onto a 0.6mm thick colored iron plate using a laminator. After this is completed, use a roller-type folding machine to fold the roof into a 500-type roof (working width 500mm, height 150mm).
mm). Folded plate workability is good,
There were no cuts or peeling at the corners, and the elastic recovery properties of the areas hit by the rollers were good, so there were no problems with the appearance as a roofing material. Furthermore, there was no change in appearance even after 500 hours of accelerated weather resistance test according to JISA1415. This composite passed the fire protection performance test stipulated in Ministry of Construction Notification No. 1828 of 1970, with tdθ of 0 in the surface test, CA of 13.1, and temperature difference of -24°C in the base material test, making it nonflammable. It was recognized that the Example 2 18,000 parts of water, 150 parts of styrene-acrylic ester copolymer emulsion (glass transition point -6°C, solid content 45% by weight), crosslinking agent used in Example 1
45 parts and the foam stabilizer and flocculant used in Example 1 were added and dissolved in the same amounts as in Example 1, and further 135 parts of rock wool granular cotton and 15 parts of glass chopped strands with a cut length of 13 mm were added. A slurry stock solution was prepared in the same manner as in Example 1. Subsequently, using the same apparatus as in Example 1, the slurry stock solution was allowed to flow down at an angle of 45 degrees onto a moving stainless wire gauze, and was formed into a sheet. However, in this test, a mixed powder of antimony trioxide, a flame retardant, and pentaprom methylbenzene (decomposition temperature 370°C or higher, bromine content 82% by weight) in a weight ratio of 1:2 was placed on the guide plate.
It was added uniformly at a rate of 60 g/m ² . The subsequent steps were carried out in the same manner as in Example 1 to obtain a sheet-like product having a thickness of 9.8 mm and an apparent density of 0.14 g/cm ³ . The average amount of binder in this sheet-like material was 7.6% by weight, and it had a uniform binder distribution in the thickness direction as shown in Table 1. The degree of orientation of the fibrous material within the layer is
The temperature is 23 degrees, and the thermal conductivity is 0,032 Kcal/mh℃.
The sound absorption coefficient at 1000Hz was 0.68. In the above-mentioned fire protection performance test, this sheet-like material was found to pass the test as nonflammable, with tdθ of 0 in the surface test, CA of 9.5, and temperature difference of 41°C in the base material test. Comparative Example 1 After preparing a slurry stock solution in exactly the same manner as in Example 1, the slurry stock solution was sent to a normal Fourdrinier paper machine, and the slurry stock solution was dropped from directly above a wire mesh running horizontally, and the slurry stock solution was placed at a 90 degree angle. It was produced at. The surface smoothness of the wet mat after papermaking was very poor, and it was necessary to pass it between rollers many times to form a sheet of constant thickness, resulting in an increase in sheet density. Furthermore, the fibrous material was uneven and the dewatering efficiency was poor, resulting in a large amount of binder in the obtained sheet. The thickness of the sheet after drying is 3.2 mm, and the apparent density is
0.35, and the average binder amount was 21.5% by weight. As shown in Table 1, the binder distribution is relatively uniform, but the degree of orientation of the fibrous material within the layer is 0.
Although the amount of binder was large, it felt stiff, and when a composite folded plate processing test was conducted with a 0.60 mm thick color steel plate in the same way as in Example 1, cracks were found in the sheet-like material. occured. In addition, in the above-mentioned fire protection performance test, the sheet alone or the steel plate composite did not pass the mark as non-combustible, and the thermal conductivity was also low.
The temperature was 0.069Kcal/mh℃, and the surface was severely rough and the appearance was poor, making it unsuitable as an insulation material for folded steel roofs. Comparative Example 2 Completely saponified polyvinyl alcohol (concentration 10% by weight) in which 200 parts of Rockwool granular cotton was mixed with 5000 parts of water.
200 parts of the slurry, 200 parts of corn starch (concentration 10% by weight), and 2.0 parts of a cationic nonionic surfactant were uniformly dispersed to prepare a slurry stock solution. Wet pine was made from this slurry stock solution in the same manner as in Comparative Example 1, and this pine was further dehydrated under reduced pressure and at the same time using a roller press, and then dried with hot air in the same manner to obtain a thickness of 7.5 mm and an apparent density of 0.40 g/cm ² A sheet-like product was obtained. This sheet-like material was obtained in the same manner as conventional rock wool ceiling panels, but because the binder was not cross-linked in the sheet, the binder migrated to the surface during drying, and as shown in Table 1. It has a non-uniform binder distribution as shown.
In addition, the degree of orientation of the fibrous material in the layer is 0, it is hard and has low interlayer strength, and when folded by a folding plate processing roller, the surface cracks and delamination occurs, making it unsuitable as a heat insulating material for folded plates. It was appropriate. Comparative Example 3 100 parts of Rockwool granular cotton was added to 10,000 parts of water together with 3 parts of a dioxyethylene stearylamimine cationic surfactant (concentration 10% by weight), and the mixture was beaten and dispersed for 30 seconds with a Peter. Example 1
In this case, 10 parts of the crosslinking agent used in the above was added as a fixing agent and stirred, and then 60 parts of polyvinyl acetate resin emulsion (glass transition point 35°C, solid content 45% by weight) was added and thoroughly stirred to form a slurry stock solution. adjusted. The slurry stock solution was paper-formed, dehydrated, and dried in the same manner as in Comparative Example 1 to obtain a sheet-like product having a thickness of 1.7 mm and an apparent density of 0.49 g/cm ² . The sheet-like material is a well-known
Although it was produced according to No. 49-43485, it has a disadvantage that the dispersion is good because a cationic surfactant is used, and the apparent density is therefore high. Furthermore, due to beating by the Peter, cutting of the fibrous material cannot be avoided, the entanglement of the fibrous material is eliminated, and furthermore, since the ordinary fourdrinier papermaking method is used, the degree of orientation of the fibrous material within the layer is 0. The sheet-like material obtained due to this reason became a paper-like hard and brittle material. When the sheet material was subjected to a folded plate processing test in the same manner as in Example 1,
Cracks occurred in the sheet-like material, making it unsuitable for the same purpose. Based on the above, the
The sheet-like product obtained by No. 43485 has an inappropriate degree of orientation of the fibrous material in the layer, and the sheet-like product that is the object of the present invention cannot be obtained by known manufacturing methods. Comparative Example 4 While continuously dropping defibrated Canadian chrysotile asbestos (class 3), No. 1 sodium silicate aqueous solution (concentration 40% by weight) was added at a ratio of 25 parts to 100 parts of asbestos. After spraying a certain amount at a time to form a pine, a roller press was applied to form a homogeneous wet pine. Further, this Etomatsu was dried in a hot air dryer at 160° C. for about 40 minutes to obtain a sheet-like product having a thickness of 5.0 mm and an apparent density of 0.09 g/cm ³ . Since the sheet-like material uses an inorganic binder, it is impossible to measure the binder distribution using the method described above, but the binder migrates to the surface rapidly, giving it a rough feel, and the sheet is likely to peel during folding. Problems such as getting caught. It also has poor weather resistance, with a rating of 200 in the weather acceleration test.
After some time, the sheets came undone and scattered.
From the above, the properties of the sheet-like material obtained in the comparative example as a building material and a heat insulating material are inferior to those of the sheet-like material according to the present invention.

[Table] Example 3 All of the white water obtained in the filtration and dehydration process after obtaining the sheet-like material in Example 1 was collected, and water was added to make a solution of 18,000 parts. 23 parts of thermoplastic resin emulsion, 5 parts of crosslinking agent solution
A slurry stock solution was prepared in the same manner as in Example 1 by adding and dissolving 5 parts of foam stabilizer solution, 15 parts of flocculant solution, and further adding 150 parts of rock wool granular cotton and 6 parts of chrysotile asbestos (class 5). did. As in Example 1, the slurry stock solution was guided to two discharge ports using two rotary pumps and allowed to flow down over two guide plates installed at an angle of 30 degrees with respect to the running wire mesh. I made a paper. However, in this test, a glass fiber net with an opening of 5 mm was introduced between the first guide plate and the second guide plate, and the net was inserted into the layer and the sheets were combined. . Furthermore, in this test, the flame retardant antimony trioxide and tetrabromobisphenol A (decomposition temperature 320°C, bromine content 59% by weight) were mixed in a weight ratio of 1:5 using the same method as in Example 2.
The mixed powder was uniformly added at a rate of 45 g/m ² . After that, the process was carried out in the same manner as in Example 1, and the thickness was
A sheet-like product having a diameter of 2.1 mm, an apparent density of 0.33 g/cm ² , a binder content of 5.3% by weight, and a degree of orientation of the fibrous material of 5 degrees was obtained. The sheet-like material is very strong because it is reinforced with a net, with a tensile strength of about 50 kg/cm ³ and an elongation of about 4%, and it was heated for 2 minutes in a test based on Article 4-3 of the Fire Service Act Enforcement Regulations. It has flame retardant performance that can pass. From the above, the sheet-like material can be widely used as a ceiling material in bathrooms, kitchens, etc., and as a ceiling/wall material in public buildings, and can also be used as a backing material for cushion floors, etc. Example 4 Thickness 5.3 mm and apparent density obtained in Example 1
Composite folded plate roofing material made of 0.16g/ ^cm3 sheet material and 0.6mm colored iron plate, and a similar prototype with a thickness of 4.0mm.
mm, an apparent density of 0.024 g/cm ³ A small piece is cut from a composite folded plate roofing material with an apparent density of 0.024 g/cm 3 as a heat insulating material, and a large piece is kept at a room temperature of 30°C and a relative humidity of 95 to 100% with the insulating material side inside. Use the roof lid of the container and place 3.5~ on the roof, which is an iron plate surface. 0
We conducted a model experiment to accelerate dew condensation in winter by flowing cooling water at ℃. As a result of measuring the time it takes for the water condensed on the surface of the insulation material to finally drip, it was found that the sheet material according to the present invention started dripping after about 17 hours, but the polyethylene foam sheet started dripping after 3 hours, and the heat Although the conductivity was approximately the same or slightly inferior, it was clear that the sheet-like material according to the present invention was particularly excellent in dew-proofing properties due to its moisture absorption and desorption effect. Example 5 A sheet-like material with a thickness of 5.1 mm and an apparent density of 0.14 g/cm ³ obtained using the same composition and method as in Example 2 was composited with a galvanized iron plate with a thickness of 0.80 mm and a chloroprene adhesive, and a height of 150 mm was obtained. , we processed folded plates into an insulating roofing material with a working width of 500 mm. Cut out a part of the roofing material and heat it for 30 minutes from the sheet-like material side so that the model has the specified indoor class 1 heating curve according to the method specified in Ministry of Construction Notification No. 2999 of 1962. When heated to 840℃, the maximum temperature of the back iron plate surface was 430℃.
There was no red heat or deformation, and the sheet-like insulation material did not fall off or break after the test, and it had a fire resistance that could pass the 30-minute roof fire resistance test. Example 6 Bulk ceramic fiber (fiber diameter 3 μm)
Below, using 160 parts of fibers with a fiber length of 30 mm or less,
Same as Example 1, thickness 6.2mm, apparent density
A sheet material weighing 0.11 g/cm ³ was obtained. The physical properties of this sheet-like material are shown in Table 2. The sheet has a very uniform binder distribution through the thickness. The thermal conductivity measurement result of this sheet-like material at 25℃ according to JISA1412 is 0.027Kcal/m・h・℃,
The sound absorption coefficient at 1000Hz according to JISA1409 is 0.37,
It has excellent properties as a heat insulator and sound insulator.
As in Example 1, the folded plate workability is also good,
No change in appearance was observed after 500 hours of accelerated weather resistance test according to JISA1415. Steel plate (thickness 0.6mm)
Composite materials with
is 0, CA is 12.5, temperature difference in base material test is -25℃
It was recognized as being non-combustible. Example 4 Short carbon fiber (fiber length 3.0mm, fiber diameter 10μ)
Using 120 parts, the thickness was 6.0 in the same manner as in Example 1.
A sheet-like material with an apparent density of 0.08 g/cm ³ was obtained. The sheet has a very uniform binder distribution through the thickness as shown in Table 1. The physical properties measured in the same manner as in Example 6 were thermal conductivity
The sound absorption coefficient at 0.025 Keal/m·h·°C and 1000 Hz was 0.35, and the workability into folded plates was also good. In addition, no change in appearance was observed after 500 hours of accelerated weather resistance test.
In the fire protection performance test, the TDO in the surface test was O,
The CA was 18, the temperature difference in the base material test was -24°C, and it was recognized as being nonflammable.

【table】

【table】

Claims (1)

[Scope of Claims] 1. A thickness consisting of (a) 80 to 97% by weight of a nonflammable fibrous material and (b) 3 to 20% by weight of a binder resin.
0.5~25mm, apparent density 0.08~0.4g/ ^cm3
A sheet-like article, wherein (a) the degree of orientation of the fibrous material in the layer of the sheet-like article with respect to the sheet surface is 3 to 3;
30 degrees, and (b) the amount of binder in the intermediate layer of the sheet-like product is 2% by weight or more and the average value of all layers.
0.25 times or more, and (c) a sheet-like article characterized in that the non-flammable fibrous material is bonded by a binder resin in which the non-combustible fibrous material is cross-linked. However, the intermediate layer referred to in the present invention refers to n layers (n=3
-8) and number each layer from 1 to n.
In this case, 2 to n-1 are intermediate layers. 2 The non-combustible fibrous material is asbestos, rock wool,
The sheet-like article according to claim 1, which is any one of glass fiber, ceramic fiber, alumina fiber, or carbon fiber, or a mixture thereof. 3. The sheet-like material according to claim 1 or 2, wherein the degree of orientation of the fibrous material in the layer of the sheet-like material with respect to the sheet surface is 5 to 15 degrees. 4. The sheet-like article according to claim 1, 2 or 3, containing the binder in an amount of 5 to 15% by weight. 5. The sheet-like article according to claim 1, 2, 3, or 4, wherein a sheet-like reinforcing material is integrally integrated inside or on the sheet-like article. 6. The sheet-like material according to claim 5, wherein the sheet-like reinforcing material is a breathable material made of cloth, paper, cheesecloth, nonwoven fabric, or net. 7. The sheet-like article according to claim 5, wherein the sheet-like reinforcing material is a non-air permeable material made of a film or metal foil. 8 (a) consisting of 80 to 97% by weight of a non-combustible fibrous material and b) 3 to 20% by weight of a binder resin, and c)
The binder contains 5 to 50 parts by weight of an antimony compound and 10 to 100 parts by weight of an aromatic bromine compound, has a thickness of 0.5 to 25 mm, and has an apparent density of 0.08 to 0.4 g/cm ³ A sheet-like article, wherein a) the degree of orientation of the fibrous material in the layer of the sheet-like article with respect to the sheet surface is 3 to 30 degrees, and b) the amount of binder in the middle layer of the sheet-like article is 2% by weight. % or more and 0.25 times or more the average value of all layers, c)
A sheet-like article characterized in that a nonflammable fibrous material is bonded by a cross-linked binder resin. 9 The noncombustible fibrous material is asbestos, rock wool,
The sheet material according to claim 8, which is any one of glass fiber, ceramic fiber, alumina fiber, or carbon fiber, or a mixture thereof. 10. The sheet-like material according to claim 8 or 9, wherein the degree of orientation of the fibrous material in the layer of the sheet-like material with respect to the sheet surface is 5 to 15 degrees. 11. The sheet material according to claim 8, 9 or 10, containing 4 to 8% by weight of the binder. 12 The antimony compound is antimony trioxide,
The sheet material according to claim 8, 9, 10, or 11, which is antimony pentachloride, antimony trichloride, antimony trisulfide, or a mixture thereof. 13 The aromatic bromine compound is tetrabromobenzene, pentabromomethylbenzene, hexabromobenzene, hexabromo diphenyl ether, decabromo diphenyl ether, tetrabromo bisphenol A, or a mixture thereof, and the decomposition temperature is 280 ℃ or higher, and the bromine content is
Claim 8, which is a compound with a content of 50% by weight or more,
9, 10, 11 or 12. 14. The sheet form according to claim 8, 9, 10, 11, 12 or 13, wherein the weight ratio of the content of the antimony compound and the aromatic bromine compound is in the range of 1:1 to 1:10. thing. 15. The sheet-like article according to claim 8, 9, 10, 11, 12, 13, or 14, wherein a sheet-like reinforcing material is integrally integrated inside or on the sheet-like article. 16. The sheet-like material according to claim 15, wherein the sheet-like reinforcing material is a breathable material made of cloth, paper, cheesecloth, nonwoven fabric, or net. 17. The sheet-like material according to claim 15, wherein the sheet-like reinforcing material is a non-air permeable material made of a film or metal foil. 18 a) A nonflammable fibrous substance and b) a binder whose main component is a water-soluble thermoplastic resin or an emulsion or latex-like thermoplastic resin is dispersed and dissolved in water together with a crosslinking agent or a polymer flocculant for the thermoplastic resin. A slurry stock solution is prepared, and the slurry stock solution is supplied from a direction having an angle of 5 to 60 degrees with the surface of a moving or rotating net-like or porous base material to form a sheet-like product on the base material. , followed by dehydration and drying a) non-flammable fibrous material 80-97% by weight and b)
Thickness 0.5~20% by weight of binder resin
25 mm and an apparent density of 0.80 to 0.4 g/cm ³ , a) the degree of orientation of the fibrous material in the layer of the sheet to the sheet surface is 3 to 30 degrees, and b ) the amount of binder in the intermediate layer of the sheet-like product is 2% by weight or more and 0.25 times or more the average value of all layers; A method of manufacturing sheet-like products. However, the intermediate layer referred to in the present invention refers to n layers (n=3
-8) and number each layer from 1 to n.
In this case, 2 to n-1 are intermediate layers. 19. The method for manufacturing a sheet-like article according to claim 18, wherein the slurry stock solution is supplied from a direction having an angle of 20 to 45 degrees with the surface of the substrate to form a sheet onto the substrate. 20. The method for producing a sheet-like product according to claim 18 or 19, wherein the slurry stock solution is supplied, a flame retardant is added and mixed immediately before paper-making, and the same is carried out by paper-making. 21 Claim 1: When preparing the slurry stock solution, a surfactant having foam stability is further added and mixed to prepare the slurry stock solution.
8, 19 or 20. 22 The thermoplastic resin has a glass transition point of -
22. The method for producing a sheet material according to claim 18, 19, 20 or 21, which is a thermoplastic resin having a temperature in the range of 50 to 30C. 23. The method for producing a sheet-like article according to claim 18, 19, 20 or 21, wherein the thermoplastic resin is a self-crosslinking resin. 24 The binder has a ratio of 0.1 to the thermoplastic resin.
Claims 18, 19, 20, 2 containing ~30% by weight of a crosslinking agent for the thermoplastic resin
24. The method for producing a sheet-like product according to 1, 22 or 23. 25 Claims 18, 19, 20, 21, 22, in which a sheet-like reinforcing material is further compositely integrated into or on the surface of the sheet-like material when the fibrous material is made into a sheet or after it is formed into a sheet-like material.
25. The method for producing a sheet-like product according to 23 or 24.