JP4394587B2 - Thermally expansive inorganic material - Google Patents

Description

  The present invention relates to a thermally expandable inorganic material.

Conventionally, as a sheet material such as a sealing material for a fire door gap or a fireproof felt, a thermally expandable inorganic material made of inorganic fiber, thermally expandable graphite, a sinterable inorganic material, or the like has been proposed (
Patent Document 1, Patent Document 2, and Patent Document 3).
These thermally expansive inorganic materials have a function of expanding due to heat at the time of a fire to close the opening and preventing the spread of fire and the diffusion of smoke accompanying the fire.
Japanese Patent No. 2516556 Japanese Patent No. 2619818 JP 2000-199194 A

When using these thermally expandable inorganic materials to cover building members such as walls with openings such as ventilation holes, the material portions at positions corresponding to the openings are removed from the thermally expandable inorganic material. There is a need to.
However, the above-described thermally expandable inorganic material has a problem that even if it receives heat such as a fire, the opening portion remaining after removing the material portion is not sufficiently blocked.
An object of the present invention is to provide a thermally expandable inorganic material in which the opening portion remaining after the removal of a part of the material is exposed to heat such as a fire, and the opening portion is blocked by heat. .

As a result of intensive studies to solve the above problems, the inventor of the present invention is suitable for the purpose of the present invention, in which the inorganic fiber in the sheet material is substantially oriented in the normal direction to the surface of the sheet material. As a result, the present invention has been completed.

That is, the present invention
55-85 wt% inorganic fiber, 5-30 wt% thermally expandable inorganic material, 5-25 sinterable inorganic material
A sheet material comprising wt% and an organic binder of 5 to 15 wt%, wherein the inorganic fiber is substantially oriented in a normal direction with respect to the surface of the sheet material. Is.

ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where the opening part which remains after removing a part of material is exposed to heat, such as a fire, the said thermally expansible inorganic material with which the said opening part is obstruct | occluded with a heat can be provided. .

First, the inorganic fibers used in the present invention will be described.
The inorganic fibers used in the present invention are not particularly limited, and examples thereof include ceramic fibers.
Specific examples of such ceramic fibers include silica alumina fibers, alumina fibers, silica fibers, and zirconia fibers.
Such ceramic fibers preferably have a melting point of 1300 ° C. or higher from the viewpoint of heat resistance,
If it is 1500 degreeC or more, it is still more preferable.
In the present invention, the melting point means a melting point for a substance that clearly shows the melting point, such as a pure substance, and a substance that does not clearly show the melting point, such as a mixture, in JIS R3103-1. It shall mean the softening point measured accordingly.

  The said inorganic fiber can use 1 type, or 2 or more types.

The compounding quantity of the inorganic fiber used for this invention needs to be 55 to 85 weight% on the basis of the weight of the thermally expansible inorganic material of this invention.
When the amount of the inorganic fiber is less than 55% by weight, the shape retention of the heat insulating layer is lowered, and when it exceeds 85% by weight, the workability of the thermally expandable inorganic material of the present invention is lowered.
The amount of the inorganic fiber used in the present invention is preferably in the range of 60 to 80% by weight.

The diameter of the inorganic fiber is usually in the range of 0.01 to 100 μm, preferably 0.1 to 100 μm.
The range is 30 μm. In addition, the inorganic fiber may be a bundle of a plurality of fibers combined with a sizing agent such as a silane coupling agent.

There is no limitation on the production method for obtaining the inorganic fiber, for example, a rod method for winding the fiber obtained by softening and drawing the inorganic fiber raw material, discharging the molten raw material from the nozzle, Obtained by a method such as a pot method for winding the obtained fiber, a precursor polymer method for winding the fiber obtained by sintering the precursor of the raw material dissolved in an organic solvent as a precursor, and the like. A thing etc. can be obtained as a commercial item.

Next, the thermally expandable inorganic substance used in the present invention will be described.
The thermally expandable inorganic compound used in the present invention is not particularly limited as long as it expands when heated, and examples thereof include vermiculite, kaolin, mica, and thermally expandable graphite. Among these, heat-expandable graphite is preferable because the foaming start temperature is low.

The heat-expandable graphite is a conventionally known substance, and powders such as natural scaly graphite, pyrolytic graphite and quiche graphite are mixed with inorganic acids such as concentrated sulfuric acid, nitric acid and selenic acid, concentrated nitric acid, perchloric acid, It is a crystalline compound that maintains the carbon layer structure by producing a graphite intercalation compound by treatment with a strong oxidizing agent such as chlorate, permanganate, dichromate, or hydrogen peroxide. .

The heat-expandable graphite obtained by acid treatment as described above is preferably further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like.

Examples of the aliphatic lower amine include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, and butylamine. Examples of the alkali metal compound and alkaline earth metal compound include hydroxides such as potassium, sodium, calcium, barium, and magnesium, oxides, carbonates, sulfates, and organic acid salts.

The thermal expandable graphite preferably has a particle size in the range of 20 to 200 mesh. Granularity is 2
If it is smaller than 00 mesh, the degree of expansion of graphite is small and a sufficient fireproof heat insulating layer cannot be obtained. If the particle size is larger than 20 mesh, there is an advantage that the degree of expansion of graphite is large. It becomes difficult to be held inside.

As a commercial item of the said thermal expansion graphite by which the neutralization process was carried out, for example, UCAR CARBON
“GRAFGUARD” manufactured by the company, “GREP-EG” manufactured by Tosoh Corporation, and the like.

  The said thermally expansible inorganic substance can use 1 type, or 2 or more types.

The blending amount of the thermally expandable inorganic material used in the present invention needs to be 5 to 30% by weight based on the weight of the thermally expandable inorganic material of the present invention.

When the blending amount of the heat-expandable inorganic material is less than 5% by weight, the expansion volume after combustion is small, and a sufficient fireproof heat insulating layer cannot be obtained. On the other hand, when it exceeds 30% by weight, the strength of the thermally expandable inorganic material after expansion is lowered.
The amount of the thermally expandable inorganic material used in the present invention is preferably in the range of 10 to 25% by weight.

Next, the sinterable inorganic material used in the present invention will be described.
The sinterable inorganic material used in the present invention is not particularly limited, and examples thereof include boron compounds such as boric acid and borax, low melting point frit, water glass, electrically insulating glass, colloidal silica and the like. it can.

Among these, since the heat-expandable inorganic material of the present invention is excellent in shape retention after being expanded by heat, electrically insulating glass, colloidal silica and the like are preferable, and an electrically insulating glass is more preferable.

As the electrically insulating glass, for example, silicon dioxide is specifically 50 to 60% by weight.
Examples include E-glass containing 10 to 20% by weight of aluminum oxide, 10 to 20% by weight of calcium oxide, 1 to 10% by weight of magnesium oxide, and 8 to 13% by weight of boron oxide. be able to.

Examples of the colloidal silica include ordinary colloidal silica mainly composed of water glass, and high purity obtained by treating water glass with an oxidizing agent such as hydrogen peroxide and then treating with an ion exchange resin. Examples include high-purity colloidal silica obtained by hydrolyzing colloidal silica, tetraalkoxysilane, and the like.

The sinterable inorganic material used in the present invention is preferable if the content of the lead metal salt and the alkali metal oxide is less than 1% by weight with respect to the weight of the sinterable inorganic material.
As the lead metal salts, for example, a _{PbO, PbO 2, Pb 3 O} 4 or the like.
Examples of the alkali metal oxide include Na ₂ O and K ₂ O.

The sinterable inorganic material used in the present invention is preferably one that melts in a temperature range of 650 to 1000 ° C. Thereby, even after the heat-expandable inorganic material of the present invention is expanded by heat such as a fire, the inorganic fibers and the like contained in the heat-expandable inorganic material can be kept in a single unit.
The temperature range is preferably 700 to 900 ° C, and more preferably 750 to 850 ° C.

The sinterable inorganic material having a desired melting point can be obtained by adjusting the components contained in the sinterable inorganic material.
For example, in the case of the E glass, specifically, silicon dioxide is 55% by weight, aluminum oxide is 15% by weight, calcium oxide is 15% by weight, magnesium oxide is 5% by weight,
When boron oxide is contained at 10% by weight or the like, the melting point is 700 ° C. By increasing the amount of calcium oxide, magnesium oxide and the like contained in the E glass, the ratio of covalent bonds such as silicon dioxide contained in the E glass can be reduced. It becomes possible to lower the temperature below ℃.
Conversely, by reducing the amount of calcium oxide, magnesium oxide, etc., the proportion of covalent bonds such as silicon dioxide contained in this E glass can be increased, so that the melting point can be raised to 700 ° C. or higher. Become.

The compounding quantity of the sinterable inorganic material used for this invention needs to be 5-25 weight% on the basis of the weight of the thermally expansible inorganic material of this invention.
When the amount of the sinterable inorganic material is less than 5% by weight or more than 25% by weight, when the thermally expandable inorganic material of the present invention is exposed to a high temperature for a long time, its shape retention is reduced To do.
The amount of the sinterable inorganic material used in the present invention is preferably in the range of 10 to 15% by weight.

The shape of the sinterable inorganic material is not particularly limited, and examples thereof include a fiber-shaped body, a wool-shaped body in which the fiber-shaped body is intertwined, and a powder-shaped body.
When a fiber shaped body is used as the sinterable inorganic material, the diameter of the fiber is usually 0.
. The range is from 01 to 100 μm, preferably from 0.1 to 30 μm. In this case, as the fiber shaped body, a plurality of fibers combined into one by a sizing agent such as a silane coupling agent can be used.

The method for obtaining such a fiber-shaped body is not particularly limited. For example, the rod method of winding the fiber obtained by softening and drawing the raw material of the sinterable inorganic material, the molten raw material What was obtained by methods, such as the pot method discharged | emitted from a nozzle and winding up the obtained fiber, can be obtained as a commercial item.

Moreover, when using a powder-shaped body as said sinterable inorganic material, the average particle diameter of the said powder-shaped body is the range of 5-500 micrometers normally. The powdery body can usually be obtained as a commercial product.

  The said sinterable inorganic material can use 1 type, or 2 or more types.

Next, the organic binder used in the present invention will be described.
The organic binder used in the present invention is not particularly limited. For example, specifically, polyolefin resins such as polypropylene resins, polyethylene resins, poly (1-) butene resins, polypentene resins, polystyrene resins, Acrylonitrile-butadiene-styrene resin, methyl methacrylate-butadiene-styrene resin, ethylene-vinyl acetate resin, ethylene-propylene resin, polycarbonate resin, polyphenylene ether resin, acrylic resin, polyamide resin, polyvinyl chloride resin, etc. Thermoplastic resins,
Natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-polybutadiene rubber (1,2-BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR) ), Butyl rubber (IIR), ethylene-propylene rubber (EPR, EPDM), chlorosulfonated polyethylene (CSM), acrylic rubber (
ACM, ANM), epichlorohydrin rubber (CO, ECO), polyvulcanized rubber (T), silicone rubber (Q), fluoro rubber (FKM, FZ), rubbers such as urethane rubber (U),
Thermosetting resins such as polyurethane resin, polyisocyanate resin, polyisocyanurate resin, phenol resin, epoxy resin,
Latexes such as the above thermoplastic resins and rubbers,
Examples thereof include emulsions such as the above thermoplastic resins and rubbers.

Of these, rubber latexes, ethylene-vinyl acetate resins, acrylic resin emulsions, and the like are preferable from the viewpoint of handleability.

  The organic binder can be used alone or in combination of two or more.

The compounding quantity of the organic binder used for this invention needs to be 5 to 15 weight% on the basis of the weight of the thermally expansible inorganic material of this invention.
When the blending amount of the organic binder is less than 5% by weight, workability for producing the thermally expandable inorganic material of the present invention is lowered. On the other hand, when the content exceeds 15% by weight, the shape-retaining property is lowered when the thermally expandable inorganic material of the present invention is exposed to a high temperature for a long time.
The amount of the organic binder used in the present invention is preferably in the range of 5 to 10% by weight.

In addition, various additives such as a colorant, an antioxidant, a flame retardant, and an inorganic filler can be used for the thermally expandable inorganic material of the present invention as long as the object of the present invention is not impaired.

Next, a method for producing the thermally expandable inorganic material of the present invention will be described.
As a manufacturing method of the thermally expansible inorganic material of this invention, the method by the adsorption molding method is mentioned, for example.

An embodiment of this adsorption molding method is exemplified as follows with reference to FIG.
(1) For example, a solvent that does not dissolve each component of the thermally expandable inorganic material is prepared,
A slurry 1 is prepared in which the constituent components of the thermally expandable inorganic material are suspended in such a solvent.
(2) In order to separate the components of the thermally expandable inorganic material from the frame suction port 2 for sucking the slurry 1 and the slurry 1 provided on one side of the frame suction port 2 The slurry is sucked by an adsorption molding device 5 including the filter member 3 and a suction device 4 for recovering the solvent from the slurry 1 through the filter member 3.
(3) Between the frame body inlet 2 of the adsorption molding device 5 and the filtering means 3, for example,
A partition for orienting the inorganic fibers contained in the slurry 1 in one direction can be provided (not shown). Since this partition is provided with one side of each section sufficiently longer than the other side, the inorganic fibers 6 are sequentially deposited from the filtration member 3 side along the direction of the long side in the suction molding apparatus 5. .
For convenience of explanation, in FIG. 1, the length of the inorganic fiber is drawn longer than the actual length.
The partition is pulled out from the frame body suction port 2 after the suction operation is completed or while performing the suction operation, so that a filtered material in which the inorganic fibers are substantially oriented in a certain direction is formed inside the adsorption molding device 5. .
(4) After suction, the solvent contained in the obtained filtrate is removed by means such as suction, compression, centrifugation, heating, and air blowing.
(5) Subsequently, it can be formed into a desired shape using means such as cutting.

  Through the above steps, the thermally expandable inorganic material of the present invention can be obtained.

Examples of the filtering member include means for filtering with a filter paper, a filter cloth, a filter, a metal mesh, and the like. The solvent is not particularly limited as long as it does not dissolve each component of the heat-expandable inorganic material of the present invention. Specific examples thereof include water and methyl alcohol.
The solvent is preferably water from the viewpoint of handleability.

A heat-expandable inorganic material having a desired shape can be obtained by appropriately selecting the shape of the frame inlet.

When sucking the slurry by the above operation, the orientation direction of the inorganic fibers can be aligned in the suction direction, and the inorganic fibers contained in the sheet-like thermally expandable inorganic material are in the normal direction to the surface of the material. Can be substantially oriented.
When the inorganic fibers are substantially oriented in the normal direction with respect to the surface of the material, the thermally expandable inorganic material of the present invention expands greatly in the sheet surface direction as compared with the sheet thickness direction.
Thereby, even if it is a case where an opening part exists in a part of thermally expandable inorganic material of this invention, the said opening part can be obstruct | occluded by expansion | swelling based on heat, such as a fire.

The shape of the thermally expandable inorganic material of the present invention can be appropriately determined according to the purpose, but is usually a sheet shape.
The thickness of the thermally expandable inorganic material in the form of a sheet is usually in the range of 0.1 to 100 mm, preferably 3 to 10 mm.

The bulk density of the thermally expandable inorganic material of the present invention is usually in the range of 0.10 to 0.40 g / cm ^3, preferably ranges from 0.15~0.35g / cm ^3.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Ceramic fibers (“SC bulk” manufactured by Nippon Kayaku Thermal Ceramics Co., Ltd.), thermally expandable graphite (“GREP-EG” manufactured by Tosoh Corporation), glass fibers (“Glasslon Chopped Strand” manufactured by Asahi Fiber Glass Co., Ltd.) Glass long fiber, fiber diameter: about 10 μm, fiber length: about 3 mm), glass wool (“Glasslon Wool” manufactured by Asahi Fiber Glass Co., Ltd.)
Fiber diameter: about 4-7 μm), acrylic resin latex (“LX87” manufactured by Nippon Zeon Co., Ltd.)
4 ”) was dispersed in water at the compounding ratio shown in Table 1 to prepare a slurry. A heat-expandable inorganic material having a predetermined bulk density in which inorganic fibers are oriented in a substantially constant direction by suction (adsorption molding method) from a thickness direction by a papermaking method using a mold of width 300 mm × length 450 mm × thickness 30 mm Then, the sample was sliced in the direction perpendicular to the orientation method of the inorganic fibers to obtain a thermally expandable inorganic material sample having a predetermined thickness.

About the produced sample, volume expansion magnification was evaluated.
[Evaluation of the obtained sample]
The above sample of 50 mm square was heated in an electric furnace at a temperature of 1000 ° C. for 1 hour, and the width, length, and thickness were measured. Calculated as (after volume / volume before heating).
The heated sample preferentially expanded mainly in a direction parallel to the fiber direction, but expansion was also observed in the fiber direction, that is, the thickness direction.

The schematic cross section which shows the outline of the apparatus for manufacturing the thermally expansible inorganic material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Slurry 2 Frame body inlet 3 Resin 4 Suction apparatus 5 Adsorption molding apparatus 6 Inorganic fiber 7 Piping 8 Slurry tank

Claims (1)

55-85 wt% inorganic fiber, 5-30 wt% thermally expandable inorganic material, 5-2 inorganic binder
A heat-expandable inorganic material, which is a sheet material composed of 5 wt% and 5-15 wt% of an organic binder, wherein the inorganic fibers are substantially oriented in a normal direction to the surface of the sheet material.