JP7506122B2 - Putty-like fireproof composition - Google Patents

Description

The present invention relates to a non-curing, putty-like fire-resistant composition that is used primarily to seal gaps in fire walls and floors in buildings (buildings, ships, etc.) where electrical wires, cables, and piping pass through.

In buildings, ships, and other structures, penetrations are drilled into fire compartments such as walls, floors, and ceilings that separate each piece of equipment and room, and air conditioning equipment piping and various electric cables are inserted into these penetrations. However, if a fire breaks out in a certain space, the heat and flames will cause the plastic pipes, the foam insulation of the air conditioning equipment piping, and the coating of the electric cables to burn or melt and disappear, causing the penetrations to become a flame path and allowing the fire to spread to adjacent equipment or rooms.

Fire-resistant or non-flammable putty is used as a fire prevention measure for these penetrations. The putty is used to fill the opening, or in combination with a non-flammable board such as a calcium silicate board to seal the gap. The putty used here includes hardening putty, which hardens over time after application, and non-hardening putty, which does not dry out or harden after application. Non-hardening putty also includes expanding putty, which expands with heat, and non-expanding putty, which does not expand.

Hardening putties have the advantage of being able to firmly hold penetrations in place after application, but they have the disadvantage of being unable to accommodate things like replacing wiring that comes with building renovations or adding new facilities. Also, those that use water glass in their composition have problems with water resistance, making them vulnerable when exposed to rain, wind, and condensation outdoors.

An example of a non-hardening putty is a putty composition in which a specific amount of thermally expandable graphite is blended with a rubber component consisting of liquid rubber and butyl rubber (Patent Document 1). However, the putty composition that expands with heat is very brittle and has reduced shape stability, and when applied to a ceiling penetration, it may crumble with even a small impact. On the other hand, non-expanding putty does not expand with heat and has good shape stability, but the organic compound components such as rubber used as a binder are burned away, causing a decrease in volume, which may lead to cracks and gaps that can become a fire path (Patent Document 2).

JP 2007-254563 A Japanese Patent Application Laid-Open No. 2-80468

The present invention was made in consideration of these circumstances, and provides a putty-like fire-resistant composition that has excellent processability, non-adhesiveness, shape stability at high temperatures before combustion, thermal expansion properties, shape stability after combustion, and flame retardancy.

The inventors conducted extensive research to solve the above problems. As a result, they discovered that the above problems could be solved by using a composition with a specific blend, which led to the completion of the present invention.

That is, according to the present invention, the following inventions are provided.
[1] A putty-like fireproof composition comprising 400 to 1,200 parts by mass of an inorganic compound and 1 to 30 parts by mass of a fibrous organic compound relative to 100 parts by mass of a matrix polymer, the matrix polymer comprising a liquid rubber and a solid elastomer, and a mass ratio of the liquid rubber to the solid elastomer of 95:5 to 50:50, and the inorganic compound comprising 0.10 to 13.00% by mass of an inorganic phosphorous-based compound and 0.05 to 3.00% by mass of sepiolite.
[2] The putty-like fireproof composition according to [1], wherein the inorganic compound contains a metal hydroxide.
[3] The putty-like fireproof composition according to [1] or [2], wherein the inorganic phosphite compound contains aluminum hydrogen phosphite.
[4] The putty-like fireproof composition according to any one of [1] to [3], wherein the average fiber length of the fibrous organic compound is 0.5 to 10 mm.
[5] The putty-like fireproof composition according to any one of [1] to [4], which is used to fill a gap in a penetration portion.

The following provides a detailed explanation of the embodiment of the present invention (hereinafter referred to as the "present embodiment"); however, the present invention is not limited to this embodiment, and various modifications are possible without departing from the spirit of the present invention.

The putty-like fireproof composition of this embodiment contains a matrix polymer, an inorganic compound, and a fibrous organic compound. Each component is described below.

1. Matrix polymer The matrix polymer includes a liquid rubber and a solid elastomer, and the mass ratio of the liquid rubber to the solid elastomer is 95:5 to 50:50. This mass ratio is preferably 93:7 to 60:40, and more preferably 90:10 to 70:30. If the ratio of the liquid rubber is too high, the non-adhesiveness is poor, and if the ratio of the liquid rubber is too low, the processability is poor. If the total mass ratio of the liquid rubber and the solid elastomer is 100, the mass ratio of the solid elastomer may be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50, or may be within a range between any two of the values exemplified here. The mass ratio of the liquid rubber is the value obtained by subtracting the mass ratio of the solid elastomer from 100.

<Liquid rubber>
In the present invention, the liquid rubber may be any rubber that is fluid at room temperature. For example, liquid polyisoprene, liquid polybutadiene, liquid polychloroprene, liquid polybutene, liquid butyl rubber, etc. are used, but are not necessarily limited to one type, and two or more types may be mixed.

<Solid elastomer>
In the present invention, the solid elastomer may be any elastomer that is solid at room temperature, and examples thereof include crosslinkable rubbers such as natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, chlorinated polyethylene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber (EPDM), ethylene-vinyl acetate rubber, chloroprene rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, reclaimed rubber, silicone rubber, fluororubber, urethane rubber, and styrene-based thermoplastic elastomers.

A styrene-based thermoplastic elastomer is a thermoplastic elastomer having a monomer unit derived from a vinyl aromatic hydrocarbon. A thermoplastic elastomer is an elastomer that has the property of softening and exhibiting fluidity when heated, and can be distinguished from rubber that does not have such a property. The styrene-based thermoplastic elastomer is preferably a block copolymer consisting of a polymer block mainly composed of a vinyl aromatic hydrocarbon and a polymer block mainly composed of a conjugated diene. Examples of vinyl aromatic hydrocarbons include styrene, p-methylstyrene, α-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, etc., which may be used alone or in combination of two or more. Examples of conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, etc., which may be used alone or in combination of two or more.

Specific examples of styrene-based thermoplastic elastomers include styrene-butadiene-styrene (SBS) copolymer, styrene-isoprene-styrene (SIS) copolymer, styrene-ethylene-butylene-styrene (SEBS) copolymer, styrene-isoprene-hydrogenated styrene-isoprene-styrene (SEPS) copolymer, styrene-ethylene-propylene (SEP) copolymer, styrene-ethylene-propylene-styrene (SEPS) copolymer, styrene-ethylene-ethylene-propylene-styrene (SEEPS) copolymer, etc. The styrene content of the styrene-based thermoplastic elastomer is, for example, 15% by mass or more and 70% by mass or less, and preferably 20% by mass or more and 60% by mass or less.

The matrix polymer may be composed only of liquid rubber and solid elastomer, or may contain other polymers. Examples of other polymers include resins that are neither liquid rubber nor solid elastomers (polyolefins, polystyrene, etc.).

2. Inorganic Compound The content of the inorganic compound is 400 to 1200 parts by mass, preferably 500 to 1040 parts by mass, and more preferably 600 to 870 parts by mass, relative to 100 parts by mass of the matrix polymer. If the content of the inorganic compound is too small, the flame retardancy is deteriorated. If the content of the inorganic compound is too large, exceeding 1200 parts by mass, the flexibility is impaired and the processability is deteriorated. This content is, for example, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 870, 900, 950, 1000, 1040, 1050, 1100, 1150, or 1200 parts by mass relative to 100 parts by mass of the matrix polymer, and may be within a range between any two of the numerical values exemplified here.

The inorganic compounds include inorganic phosphorous compounds, sepiolite, and other inorganic compounds. Each component is described in detail below.

<Inorganic phosphite compounds>
Examples of inorganic phosphite compounds include aluminum phosphite, aluminum hydrogen phosphite, sodium phosphite, potassium phosphite, calcium phosphite, zinc phosphite, etc. Among these, aluminum hydrogen phosphite is preferred.

The content of the inorganic phosphite compound is preferably 0.10 to 13.00% by mass, more preferably 1.02 to 9.93% by mass, and even more preferably 1.88 to 6.85% by mass, based on the inorganic compound. The content of the inorganic phosphite compound is preferably 0.13 to 12.24% by mass, more preferably 0.88 to 8.67% by mass, and even more preferably 1.62 to 5.95% by mass, based on the entire putty-like fireproof composition. This content is, for example, 0.10, 0.13, 0.15, 0.50, 0.88, 1.00, 1.02, 1.50, 1.62, 1.88, 2.00, 2.50, 3.00, 3.50, 4.00, 4.50, 5.00, 5.50, 5.95, 6.00, 6.50, 6.85, 7.00, 7.50, 8.00, 8.50, 8.67, 9.00, 9.50, 9.93, 10.00, 10.50, 11.00, 11.24, 11.50, 12.00, 12.50, 12.80, or 13.00% by mass relative to the inorganic compound (or the entire putty-like fireproof composition), and may be within a range between any two of the numerical values exemplified here.

The content of the inorganic phosphorous-based compound is preferably 0.7 to 102 parts by mass, more preferably 1 to 100 parts by mass, even more preferably 7 to 75 parts by mass, and even more preferably 13 to 50 parts by mass, relative to 100 parts by mass of the matrix polymer. This content is, for example, 0.7, 1, 5, 7, 10, 13, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, or 102 parts by mass relative to 100 parts by mass of the matrix polymer, and may be within a range between any two of the numerical values exemplified here.

If the phosphorous acid compound content is too low, gaps will form between the walls and floors due to the volumetric reduction of the putty material during combustion. If the phosphorous acid compound content is too high, excessive expansion will occur, resulting in cracks and chips.

<Sepiolite>
The content of sepiolite is preferably 0.05 to 3.00% by mass, more preferably 0.14 to 2.24% by mass, and even more preferably 0.29 to 1.41% by mass, based on the inorganic compounds. The content of sepiolite is preferably 0.06 to 2.42% by mass, more preferably 0.12 to 1.94% by mass, and even more preferably 0.25 to 1.22% by mass, based on the entire putty-like refractory composition. This content is, for example, 0.05, 0.06, 0.07, 0.10, 0.12, 0.14, 0.20, 0.25, 0.29, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00, 1.10, 1.20, 1.22, 1.30, 1.4 0, 1.41, 1.50, 1.60, 1.70, 1.80, 1.90, 1.94, 2.00, 2.10, 2.20, 2.24, 2.30, 2.40, 2.42, 2.50, 2.60, 2.70, 2.79, 2.80, 2.90, 3.00 mass%, and may be within a range between any two of the numerical values exemplified here.

The content of sepiolite is preferably 0.4 to 22 parts by mass, more preferably 0.5 to 20 parts by mass, even more preferably 1 to 16 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the matrix polymer. This content may be, for example, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22 parts by mass relative to 100 parts by mass of the matrix polymer, and may be within a range between any two of the numerical values exemplified here.

If the sepiolite content is too low, the shape stability at high temperatures will be poor. If the sepiolite content is too high, the flexibility and workability will be poor.

<Other inorganic compounds>
Examples of other inorganic compounds include metal oxides such as alumina, aluminosilicate, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; metal hydroxides such as aluminum hydroxide, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; smectite clays such as bentonite, montmorillonite, and hectorite, fibrous clays such as palygorskite, clay minerals such as sericite, illite, glauconite, chlorite, talc, zeolite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, cristoparite, smectite, kaolin, and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, and barium carbonate; glass fibers (E Examples of the inorganic fibrous compounds include glass fiber, C-glass fiber, S-glass fiber, D-glass fiber), rock wool, ceramic fiber (silica alumina fiber, alumina fiber, silica fiber), zirconia fiber, carbon fiber, bulk alkaline earth silicate fiber, gypsum fiber, carbon fiber, metal fiber, slag fiber, basalt fiber, and other fibrous inorganic compounds; calcium sulfate, calcium silicate, and other calcium salts, glass beads, silica-based balloons, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon balloons, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, zinc borate, various magnetic powders, fly ash, inorganic hollow fillers, perlite, obsidian, perlite, rosin, diatomaceous earth, dehydrated sludge, boron, sodium tetraborate hydrate (borax), inorganic phosphate compounds other than inorganic phosphite compounds, and silica. These inorganic compounds may be used alone or in combination of two or more.

The other inorganic compound preferably contains a metal hydroxide. This can enhance flame retardancy. The content of the metal hydroxide is preferably 377 to 1177 parts by mass, more preferably 477 to 1017 parts by mass, and even more preferably 577 to 847 parts by mass, relative to 100 parts by mass of the matrix polymer. This content is, for example, 377, 400, 450, 477, 500, 550, 577, 600, 650, 700, 750, 800, 847, 850, 900, 950, 1000, 1017, 1050, 1100, 1150, or 1177 parts by mass relative to 100 parts by mass of the matrix polymer, and may be within a range between any two of the numerical values exemplified here.

3. Fibrous organic compound The shape of the fibrous organic compound may be fibrous, and examples of the cross-sectional shape of the fiber include a circle, an ellipse, and a polygon. If the average fiber length of the fibrous organic compound is L and the average diameter is D, L/D 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, 10,000. The average diameter of the fibrous organic compound is, for example, 1 to 100 μm, preferably 2 to 50 μm, and more preferably 5 to 20 μm. The average fiber length of the fibrous organic compound is, for example, preferably 0.5 to 10 mm. This value may be, for example, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0 mm, or may be within a range between any two of the values exemplified herein.

Examples of fibrous organic compounds include meta-aramid fibers, para-aramid fibers, amide fibers, cellulose fibers (e.g., pulp fibers), polyparaphenylene benzobisoxazole fibers, polyarylate fibers, polyester fibers, acrylic fibers, acrylonitrile fibers, rayon, silk, cotton, hemp, and wool.

The average fiber length and average diameter of a fibrous organic compound are determined by measuring the fiber length and diameter of a sufficiently large number of fibrous organic compounds, i.e., 20 or more fibers, and averaging the measurements.

The fiber length and diameter of fibrous organic compounds can be measured, for example, using a field emission scanning electron microscope (FE-SEM).

The content of the fibrous organic compound is 1 to 30 parts by mass, preferably 3 to 24 parts by mass, and more preferably 6 to 17 parts by mass, relative to 100 parts by mass of the matrix polymer. The content of the fibrous organic compound is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 parts by mass relative to 100 parts by mass of the matrix polymer, and may be within a range between any two of the numerical values exemplified here. If the content of the fibrous compound is too small, the shape stability at high temperatures will be poor. If the content of the fibrous compound is too high, the flexibility will be lost and the processability will be poor.

In this embodiment, a plasticizer (softener), antioxidant, processing aid, lubricant, flame retardant, tackifier, etc., which are used in normal rubber compounds, may be used in combination within a range that does not impair the effect of the other components. The total amount of the other components is, for example, 0 to 100 parts by mass, preferably 0 to 50 parts by mass, and more preferably 0 to 20 parts by mass, relative to 100 parts by mass of the matrix polymer.

The putty-like fireproof composition of this embodiment can be prepared by kneading the above-mentioned components using a known kneading device such as a Banbury mixer, kneader mixer, or two-roll mill, and then molding the mixture using a conventional molding method such as press molding, roll molding, extrusion molding, or calendar molding.

The present invention will be described in detail below with reference to examples and comparative examples, but these examples do not limit the present invention.

1. Preparation of putty-like fireproof compositions The components shown in the formulations of Tables 1 to 8 were kneaded for 10 minutes at 80° C. using a 3-liter kneader mixer to obtain putty-like fireproof compositions of the examples and comparative examples.

Details of the components in the table are as follows: The numbers in parentheses in the table for fibers indicate the average fiber length.
(1) Matrix polymer (liquid rubber)
Liquid polyisoprene: "LIR-30" manufactured by Kuraray Co., Ltd., molecular weight 28,000, Tg: -63°C, viscosity 70 Pa.s (38°C)
Liquid polybutadiene: "LBR-302" manufactured by Kuraray Co., Ltd., molecular weight 5500, Tg: -85°C, viscosity 0.6 Pa.s (38°C)
Liquid polybutene: JX Nippon Oil & Energy Corporation, "HV-100", molecular weight 980, kinetic viscosity 9,500 mm2/s (40°C)

<Solid elastomer>
Butyl rubber: "Butyl 268" manufactured by JSR Corporation, rubber-like (40°C)

(2) Inorganic compounds <Inorganic phosphite compounds>
・Aluminum hydrogen phosphite: "NSF" manufactured by Taihei Chemical Industry Co., Ltd.
・Sodium phosphite: "Sodium phosphite" manufactured by Yoneyama Chemical Industry Co., Ltd.

<Sepiolite>
・Sepiolite: "Miraclair P150" manufactured by Omi Mining Co., Ltd.

<Other inorganic compounds>
・Bentonite: "Akagi" manufactured by Hojun Co., Ltd.
Phosphate-based glass frit: "FRM" manufactured by Okaya Rika Co., Ltd.
Aluminum hydroxide: "C-301N" manufactured by Sumitomo Chemical Co., Ltd.
Magnesium hydroxide: "KISMA5A" manufactured by Kyowa Chemical Substances Co., Ltd.
Calcium carbonate: "TA-044" manufactured by Chichibu Lime Industry Co., Ltd.
Alumina fiber, average fiber length 0.5, 7, 10, 11 mm: Nichibi Co., Ltd. "Nichibi ALF"

(3) Fibrous organic compound/pulp fiber, average fiber length 1.2 mm: "Neofiber NS-10" manufactured by Oji Seibukuro Co., Ltd.
Polyarylate fiber: average fiber length 2 mm, "Vectran UM1580" manufactured by Kuraray Co., Ltd.
Aramid fiber, 0.25, 0.5, 3, 10, 12 mm: "Twaron Short Cut Fiber" manufactured by Teijin Limited

2. Evaluation The following measurements and evaluations were carried out for the fireproof materials of each of the Examples and Comparative Examples. The results are shown in Tables 1 to 8. As shown in the table, all of the Examples were good in terms of workability, non-adhesion, shape stability at high temperatures, thermal expansion, shape stability after combustion, and flame retardancy. On the other hand, all of the Comparative Examples were not good in at least one of these evaluation items. In Comparative Example 10, bentonite, which is a clay mineral like sepiolite, was blended, but the shape stability at high temperatures was not good. In Comparative Examples 13 to 16, alumina fiber, which is a fibrous inorganic compound, was blended instead of a fibrous organic compound, but the shape stability at high temperatures was not good.

<Processability (softness)>
The softness of the test piece putty was measured in accordance with JIS A5752 at a load of 150 g and a temperature of 21° C. A specified cone was vertically penetrated into the test piece, and the penetration depth was measured to the nearest 0.1 mm. Then, based on the penetration depth, the workability was judged according to the following criteria.
◎: 60 [1/10 mm] or more ○: 50 [1/10 mm] or more and less than 60 [1/10 mm] △: 40 [1/10 mm] or more and less than 50 [1/10 mm] ×: Less than 40 [1/10 mm]

<Non-adhesive>
After measuring the mass of the latex rubber glove, the glove was put on and a 100 g spherical test piece putty was gripped 10 times, after which the mass of the glove was measured and the amount of attached substance was calculated based on the following formula. Based on the amount of attached substance, the non-adhesiveness was evaluated according to the following criteria. The lower the non-adhesiveness, the easier it is to process.
Amount of attached substance (g) = (mass of glove after squeezing the putty 10 times) - (original mass of glove)
◎: Less than 0.02 g ○: 0.02 g or more and less than 0.05 g △: 0.05 g or more and less than 0.10 g ×: 0.10 g or more

<Shape stability at high temperatures>
10 g of spherical test piece putty was placed on an AL plate specified in JIS H4000 (A1050) and heated at 200° C. for 60 minutes. After that, the test piece putty was removed and the diameter of the mark left on the AL plate was measured.
◎: The mark is 10 mm or less. 〇: The mark is more than 10 mm and less than 15 mm. △: The mark is more than 15 mm and less than 20 mm. ×: The mark is more than 20 mm.

<Thermal expansion>
A test piece putty having a thickness of 4 mm, a width of 30 mm, and a length of 30 mm was heated at 800° C. for 1 hour, and then its volume was measured, and the expansion ratio was calculated from the volume. Then, based on the volume expansion ratio, the thermal expandability was evaluated according to the following criteria.
◎: 1.0 times or more ○: 0.85 times or more, less than 1.0 times △: 0.7 times or more, less than 0.85 times ×: Less than 0.7 times

<Post-combustion shape stability>
A test piece putty having a thickness of 4 mm, a width of 30 mm and a length of 30 mm was heated at 800° C. for 1 hour, and the appearance was visually observed.
◎: No cracks ○: Cracks present on the surface only ×: Cracks present inside

<Flame retardancy>
The oxygen index of the test piece putty was measured using a combustion tester (ON-1 type, manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K6269, and the flame retardancy was judged according to the following criteria. Note that a higher oxygen index indicates higher flame retardancy.
◎: Oxygen index is 65 or more. ○: Oxygen index is 60 or more and less than 65. △: Oxygen index is 55 or more and less than 60. ×: Oxygen index is less than 55.

Claims (5)

The composition contains 400 to 1200 parts by mass of an inorganic compound and 1 to 30 parts by mass of a fibrous organic compound relative to 100 parts by mass of a matrix polymer,
the matrix polymer comprises a liquid rubber and a solid elastomer, and the mass ratio of the liquid rubber to the solid elastomer is 95:5 to 50:50;
The inorganic compound includes an inorganic phosphorous compound and sepiolite,
A putty-like refractory composition , wherein the content of the inorganic phosphorous compound relative to the inorganic compounds is 0.10 to 13.00 mass %, and the content of the sepiolite relative to the inorganic compounds is 0.05 to 3.00 mass %. The putty-like fireproof composition according to claim 1, wherein the inorganic compound comprises a metal hydroxide. The putty-like fireproof composition according to claim 1, wherein the inorganic phosphite compound includes aluminum hydrogen phosphite. The putty-like fireproof composition according to claim 1, wherein the average fiber length of the fibrous organic compound is 0.5 to 10 mm. A putty-like fireproof composition according to any one of claims 1 to 4, used to seal gaps in penetrations.