JP6896022B2 - Thermally expandable putty composition and joint material - Google Patents

Description

The present invention relates to a heat-expandable putty composition and a joint material using the same.

In general, when pipes, power cables, communication cables, and other cables are passed through the fire protection compartments, etc. specified by the Building Standards Act in buildings, etc., the fire protection compartments, etc. have a certain degree of fire resistance from the viewpoint of preventing the spread of fire. Performance is required. Therefore, between the pipes / cables in the building and the fire wall, putty-like fire-preventive agent, etc., which is a mixture of liquid polymer and metal hydrate, etc., is used as a fire-prevention joint material with fire-prevention performance. It is used (see Patent Document 1).

In addition, vermiculite, heat-expandable graphite, and microencapsulated ammonium polyphosphate are used as putty-like fireproof materials that can close the gaps created by the deformation of the pipes or the combustion of the cable coating material in the event of a fire. Is mixed with an organic resin (see, for example, Patent Document 2), or a heat-expandable composition in which a base resin is mixed with a heat-expandable graphite and a resin for preventing shape loss such as a polycarbonate resin or a polyphenylene sulfide resin (see Patent Document 2). For example, see Patent Document 3).

Japanese Unexamined Patent Publication No. 6-306364 Japanese Unexamined Patent Publication No. 10-8595 Japanese Unexamined Patent Publication No. 9-176498

From the viewpoint of workability, it is desired that the joint material for fire prevention be easy to process (processability) and that the putty does not adhere to gloves or the like (non-adhesive).

The present invention has been made in view of such circumstances, and provides a heat-expandable putty composition and a joint material capable of improving construction workability.

According to the present invention, a heat-expandable putty composition containing an organic binder, a heat-expandable compound, inorganic particles, fibers, and five components of water.
Provided is a heat-expandable putty composition in which the blending amount of the organic binder is 0.5 to 15% by mass when the total of the five components is 100% by mass.

As a result of diligent studies by the present inventor, it has been found that a heat-expandable putty composition containing an organic binder in the above proportion can solve the above-mentioned problems, and the present invention has been completed.

FIG. 1A shows an example of the shape of the inorganic particles 1, and FIG. 1B is a cross-sectional view taken along the line AA in FIG. 1A.

1. 1. Composition of Heat-Expandable Putty Composition The heat-expandable putty composition of the present invention (hereinafter referred to as putty composition) contains the first to fifth components. The first to fifth components are an organic binder, a heat-expandable compound, inorganic particles, fibers, and water, respectively. When the total of the first to fifth components is 100% by mass, the blending amount of the organic binder is 0.5 to 15% by mass.

Examples of the blending amounts of the first to fifth components are as follows.
First component (organic binder): 0.5 to 15% by mass
Second component (heat-expandable compound): 0.5 to 20% by mass
Third component (inorganic particles): 5 to 50% by mass
Fourth component (fiber): 3 to 65% by mass
Fifth component (water): 25 to 80% by mass

The putty composition may contain only the first to fifth components, or may contain other components. Other components include anti-aging agents, preservatives, surfactants and the like. The ratio of the total mass of the first to fifth components to the entire putty composition is, for example, 50 to 100% by mass, preferably 80 to 100% by mass, and preferably 100% by mass.

Hereinafter, each component will be described in detail.

<First component (organic binder)>
The organic binder is a binder composed of an organic compound, and the putty composition can be made into a hardness suitable for construction by blending an appropriate amount of the organic binder.

The organic binder preferably contains an organic polymer such as polyolefin, polyester, or polyamide. As the organic polymer, a hydrophilic polymer is preferable. Examples of the hydrophilic polymer include a water-soluble polymer that is soluble in water and a water-absorbent polymer that can absorb and expand water. Specific examples thereof include starch, cellulose derivatives, polyvinyl alcohol, and modified polymers. Acrylic acid ester-based copolymer, polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide copolymer, ethylene oxide / propylene oxide / phenylglycidyl ether copolymer, ethylene oxide / propylene oxide / allylglycidyl ether copolymer, alginic acid Examples include soda.

Examples of the cellulose derivative include carboxymethyl cellulose, hydroxyethyl cellulol, and derivatives thereof, and examples of the derivative of carboxymethyl cellulose include salts such as sodium carboxymethyl cellulose and ammonium carboxymethyl cellulose. Examples of the modified acrylic acid ester-based copolymer include a crosslinked product of a sodium salt of a sulfoethyl acrylate-acrylamide-acrylic acid copolymer.

When the total of the first to fifth components is 100% by mass, the blending amount of the organic binder is 0.5 to 15% by mass, preferably 0.7 to 10% by mass, and 1 to 6% by mass. More preferred. If the amount of the organic binder is too small, it may be too soft to be processable or non-adhesive, and the strength after drying may be insufficient. If the amount of the organic binder is too large, it may become too hard and the workability may be insufficient.

<Second component (thermally expanding compound)>
The heat-expandable compound is not particularly limited as long as it expands when heated, and examples thereof include vermiculite, kaolin, mica, and heat-expandable graphite. Among these, thermally expandable graphite is preferable because the expansion start temperature is low.

Thermally expandable graphite is a surface-treated graphite powder such as natural graphite or thermally decomposed graphite using an inorganic acid such as sulfuric acid or nitric acid and a strong oxidizing agent such as concentrated nitric acid or permanganate. , And a crystalline compound that maintains a graphite layered structure. When they are exposed to a temperature higher than the expansion start temperature (about 200 ° C.) under normal pressure, they thermally expand 100 times or more. The graphite powder such as natural graphite and pyrolytic graphite may be deoxidized, further neutralized, or the like.

The particle size of the heat-expandable graphite is preferably 20 to 400 mesh (measured by JIS Z 8901). This is because if the particle size of the heat-expandable graphite is larger than 400 mesh, the degree of expansion of the heat-expandable graphite becomes small, and the obtained heat-expandable joint material may not be sufficiently thermally expanded in the event of a fire. .. Further, if the particle size of the heat-expandable graphite is smaller than 20 meshes, the dispersibility is reduced, and the elasticity of the obtained heat-expandable joint material may be lowered. In the present invention, the means for adjusting the heat-expandable graphite to a desired particle size is not particularly limited. For example, a crusher and a classifier can be used to obtain a desired particle size.

When the total of the first to fifth components is 100% by mass, the blending amount of the heat-expandable compound is preferably 0.5 to 20% by mass, more preferably 0.7 to 10% by mass, and 1 to 8 Mass% is more preferred. If the amount of the heat-expandable compound is too small, the heat-expandability may be insufficient. If the amount of the heat-expandable compound is too large, the shape stability after expansion may deteriorate.

<Third component (inorganic particles)>
Inorganic particles are particles of inorganic substances. The shape of the particles is not particularly limited, and examples thereof include a spherical shape, an elliptical spherical shape, a cubic shape, a rectangular parallelepiped shape, and a random shape. The inorganic particles may be hollow or solid. As shown in FIG. 1, assuming that the length of the longest portion of the inorganic particle 1 is L and the diameter of the maximum circumscribed circle 1a on the plane perpendicular to the longest portion is D, the L / D is, for example, 1. It is 0 to 10.0, preferably 1.0 to 5.0.

The average particle size of the inorganic particles is, for example, 10 to 1000 μm, preferably 20 to 800 μm, more preferably 30 to 500 μm, still more preferably 40 to 200 μm. The "average particle size" means the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method.

Examples of the inorganic particles include metal oxidation of alumina, silica, aluminosilicate, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, aluminum phosphite, aluminum hydroxide, ferrites and the like. Substances: Hydrous inorganic substances such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, barium carbonate; calcium sulfate, Calcium salts such as calcium silicate; diatomaceous soil, dosonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, active white clay, sepiolite, imogolite, sericite, glass beads, silica-based balun, aluminum nitride, boron nitride, magnesium carbonate Element, carbon black, graphite, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silica carbide, zinc borate, various magnetic powders, fly ash , Inorganic hollow filler, pearlite, black rock, pearl rock, pine fat rock, diatomaceous soil, dehydrated sludge, boron, aluminum polyphosphate, sodium tetraborate hydrate (borosand) and the like.

When the total of the first to fifth components is 100% by mass, the blending amount of the inorganic particles is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass. If the amount of the inorganic particles blended is too small, the strength after drying may be insufficient. If the amount of the inorganic particles blended is too large, the thermal expansion property may be insufficient.

<Fourth component (fiber)>
The fiber contains at least one of an inorganic fiber and an organic fiber, and preferably contains both an inorganic fiber and an organic fiber. When the total of the first to fifth components is 100% by mass, the blending amount of the fibers is preferably 3 to 65% by mass.

Inorganic fibers are fibers of inorganic substances. The inorganic fiber may be fibrous, and examples of the cross-sectional shape of the fiber include a circular shape, an elliptical shape, and a polygonal shape. The L / D of the inorganic fiber is, for example, more than 10, preferably 50 or more, and more preferably 100 or more. The upper limit is not particularly specified, but is, for example, 10000. The diameter of the inorganic fiber is, for example, 1 to 100 μm, preferably 2 to 50 μm, and more preferably 5 to 20 μm. The length of the inorganic fiber is, for example, 0.5 to 100 mm, preferably 1 to 50 mm, and even more preferably 2 to 20 mm.

Examples of the inorganic fiber include ceramic fiber, glass fiber, gypsum fiber, carbon fiber, metal fiber, slag fiber and the like.

Specific examples of the ceramic fiber include silica-alumina fiber, alumina fiber, silica fiber, and zirconia fiber.

Examples of the glass fiber include E glass fiber, C glass fiber, S glass fiber, D glass fiber and the like.

When the total of the first to fifth components is 100% by mass, the blending amount of the inorganic fiber is preferably 0 to 15% by mass, more preferably 1 to 10% by mass, still more preferably 2 to 8% by mass. If the amount of the inorganic fiber blended is too small, the shape stability after expansion and the strength after drying may be insufficient. If the amount of the inorganic fiber blended is too large, the thermal expansion property may be insufficient.

Organic fibers are fibers of organic matter. The organic fiber may be fibrous, and examples of the cross-sectional shape of the fiber include a circular shape, an elliptical shape, and a polygonal shape. The L / D of the organic fiber is, for example, 5.0 or more, preferably 10.0 or more, and more preferably 20.0 or more. The upper limit is not particularly specified, but is, for example, 1000.

Examples of the organic fiber include pulp. As the pulp, wood pulp used for ordinary papermaking is used, and either chemical pulp or mechanical pulp may be used, and the type of wood or plant may be any of softwood, hardwood, kenaf, bamboo, hemp and the like. Also, used paper pulp can be used. The used paper pulp may be any of used newspaper, used printed paper, used magazine, and the like.

When the total of the first to fifth components is 100% by mass, the blending amount of the organic fiber is preferably 3 to 50% by mass, more preferably 6 to 30% by mass, still more preferably 6 to 15% by mass. If the amount of the organic fiber is too small, the strength after drying may be insufficient. If the amount of the organic fiber is too large, the shape stability after expansion may be insufficient.

<Fifth component (water)>
When the total of the first to fifth components is 100% by mass, the blending amount of water is preferably 25 to 80% by mass, more preferably 30 to 65% by mass, still more preferably 35 to 60% by mass. If the amount of water mixed is too small, it may become lumpy and workability may be poor as a putty. If the amount of water is too large, it may be too soft to maintain its shape as a putty.

The putty composition of the present invention can be used as a joint material for closing a gap between pipes / cables in a building and a fire wall or the like.

2. Method for Producing Thermally Expandable Putty Composition The putty composition of the present invention can be produced by mixing and stirring the first to fifth components using a mixer or the like.

1. 1. Preparation of Heat-Expandable Putty Composition The first to fifth components shown in Tables 1 to 3 are mixed and stirred using a mixer according to the composition (unit: mass%) in the table, and Examples / Comparative Examples The putty composition of was prepared.

The details of the components in the table are as follows.
Sodium Carboxymethyl Cellulose: Made by Hayashi Junyaku Kogyo Co., Ltd. Carboxymethyl Cellulose Ammonium: Made by Nichirin Chemical Industry Co., Ltd. Modified polyacrylic crosslinked product: Nippon Shokubai Co., Ltd., Aquaric CS6S
Thermally expandable graphite: Air Water Chemical Co., Ltd., SS-3
Vermiculite: Made by Tomoe Kogyo Co., Ltd. Aluminum hydroxide: Made by Nippon Light Metal Co., Ltd., B53
Aluminosilicate hollow particles: Fly Ash Centorite manufactured by Tomoe Chemical Industry Co., Ltd.
Glass fiber: Nitto Boseki Co., Ltd., CS13 J-917, cut length 13 mm, diameter 10 μm
Ceramic fiber: Isowool bulk, waste paper pulp manufactured by Isolite Industries Co., Ltd .: manufactured by Oji Bag Co., Ltd., neofiber citrus cellulose nanofiber: manufactured by Ehime Paper Co., Ltd.

2. Various evaluations The putty compositions of Examples and Comparative Examples were evaluated as shown below. The results are shown in Tables 1 to 3. As shown in the table, in all the examples, good results were obtained in the evaluation items of workability and non-adhesiveness related to construction workability. On the other hand, in all the comparative examples, the results of either workability and non-adhesiveness or both were poor.

-Heat-expandability Using the putty compositions of Examples and Comparative Examples, test pieces having a length of 30 mm, a width of 30 mm, and a thickness of 2 mm were prepared, and dried at 110 ° C. for 24 hours. The volume of the dried test piece after being left in an atmosphere maintained at 300 ° C. for 0.5 hours was measured. Then, the expansion ratio was calculated from the volume.

-Shape Stability Using the putty compositions of Examples and Comparative Examples, test pieces having a length of 30 mm, a width of 30 mm, and a thickness of 4 mm were prepared, and dried at 110 ° C. for 24 hours. After the dried test piece was left in an atmosphere held at 300 ° C. for 0.5 hours, a 3-point bending test jig (upper push side tip R1 mm and width 80 mm, lower 2 point fulcrum side R1 mm, width 80 mm, fulcrum) The strength (three-point bending fracture strength) when the test piece was fractured under the condition of a compression speed of 50 mm / min was measured using a distance of 20 mm), and the shape stability was evaluated according to the following criteria.

-Workability The softness of the putty composition before drying was measured at a load of 150 g and a temperature of 21 ° C. in accordance with JIS A5752. The specified cone was penetrated vertically into the test piece, and the depth thereof was measured in units of 0.1 mm.

-The weight of the deposits on the gloves was measured after wearing non-adhesive latex rubber gloves and gripping the putty 10 times.

-Strength after drying Using the putty compositions of Examples and Comparative Examples, test pieces having a length of 30 mm, a width of 30 mm and a thickness of 2 mm were prepared, and dried at 110 ° C. for 24 hours. Using a 3-point bending test jig (upper push side tip R1 mm and width 80 mm, lower 2 point fulcrum side R1 mm, width 80 mm, distance between fulcrums 20 mm), break the dried test piece under the condition of compression speed 50 mm / min. The strength at the time of bending (three-point bending fracture strength) was measured.

Claims (7)

A heat-expandable putty composition containing five components of an organic binder, heat-expandable graphite, inorganic particles, fibers, and water.
The organic binder is not the fiber
A heat-expandable putty composition in which the blending amount of an organic binder is 0.5 to 15% by mass when the total of the five components is 100% by mass. The heat-expandable putty composition according to claim 1.
The organic binder is a heat-expandable putty composition containing an organic polymer. The heat-expandable putty composition according to claim 2.
The organic polymer is a heat-expandable putty composition which is a hydrophilic polymer. The heat-expandable putty composition according to claim 3.
The hydrophilic polymer is a heat-expandable putty composition which is a cellulose derivative. The heat-expandable putty composition according to claim 4.
The cellulose derivative is a heat-expandable putty composition which is carboxymethyl cellulose or a salt thereof. The heat-expandable putty composition according to any one of claims 1 to 5.
The fibers include at least one of inorganic fibers and organic fibers.
A heat-expandable putty composition in which the blending amount of inorganic fibers is 0 to 15% by mass and the blending amount of organic fibers is 3 to 50% by mass, when the total of the five components is 100% by mass. A joint material using the heat-expandable putty composition according to any one of claims 1 to 6.

Images