Putty-like fire-resistant composition and putty

Abstract

To provide a putty-like fire-resistant composition that excels in workability, flame retardancy, and shape stability at high temperatures.SOLUTION: The present invention provides a putty-like fire-resistant composition comprising 10 to 400 pts.mass of a radical initiator and 50 to 400 pts.mass of an inorganic compound excluding the radical initiator, based on 100 pts.mass of a liquid organic compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention mainly relates to a non-curing paste-like refractory composition used for closing the gaps of through-holes for inserting electric wires, cables, and pipes provided in firewalls, floors, etc. in buildings (such as buildings and ships), and a paste composed of the composition.

Background Art

[0002] In buildings such as buildings and ships, through-holes are drilled in fire partition bodies such as walls, floors, and ceilings that divide each facility and room, and pipes for air conditioning equipment, various electric wires and cables, etc. are inserted through the through-holes. However, when a fire breaks out in a certain space, the heat and flames cause the resin pipes, the foamed heat insulating material of the pipes of the air conditioning device, the coating of the electric wires and cables, etc. to burn or melt and disappear, so the through-hole becomes a fire path and the fire spreads from here to the adjacent facilities and rooms.

[0003] As fire prevention measures for these through-holes, pastes having fire resistance or incombustibility are used. The paste is used to fill the opening or in combination with a non-combustible board such as a calcium silicate board to close the gap. The pastes used here include a curing type paste that hardens over time after construction, and a non-curing type paste that does not dry or harden after construction.

[0004] The curing type paste has the advantage of being able to firmly hold the through-hole after construction, but has the disadvantage of not being able to cope with the replacement of wiring due to building renovation or equipment addition.

[0005] Some of the non-curing type pastes use organic compound components such as rubber and plasticizer as binders, etc. (Patent Documents 1, 2, 3).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

[0007] However, since the putties such as Patent Documents 1 to 3 use organic compound components such as rubber and plasticizers as binders, etc., they are flammable and have problems with flame retardancy. The present invention has been made in view of such circumstances, and provides a putty-shaped refractory composition excellent in workability, flame retardancy, and shape stability at high temperatures. Means for Solving the Problems

[0008] The inventors of the present invention earnestly studied to solve the above problems. As a result, they found that the above problems can be solved by using a composition with a specific formulation, and thus completed the present invention.

[0009] That is, according to the present invention, the following inventions are provided. [1] A putty-shaped refractory composition containing 10 to 400 parts by mass of a radical generator and 50 to 400 parts by mass of an inorganic compound excluding the radical generator with respect to 100 parts by mass of a liquid organic compound. [2] The putty-shaped refractory composition according to [1], wherein the liquid organic compound contains a phosphate ester-based organic compound. [3] The putty-shaped refractory composition according to [1] or [2], wherein the radical generator contains a carbonate. [4] The putty-shaped refractory composition according to any one of [1] to [3], wherein the inorganic compound excluding the radical generator contains a phosphoric acid-based inorganic compound. [5] The putty-shaped refractory composition according to any one of [1] to [4], wherein the softness when measured according to JIS A5752 at a load of 150 g and a temperature of 21°C is 50 [1 / 10 mm] or more and less than 150 [1 / 10 mm]. [6] The putty-like refractory composition according to any one of [1] to [5], which is used to close the gap of the through portion. [7] A putty composed of the putty-like refractory composition according to any one of [1] to [6].

Embodiments for Carrying Out the Invention

[0010] Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as "the present embodiments") will be described in detail. However, the present invention is not limited thereto, and various modifications are possible without departing from the gist thereof.

[0011] The putty-like refractory composition of the present embodiment contains a liquid organic compound, a radical generator, and an inorganic compound other than the radical generator. The putty-like refractory composition can be used as a putty. For example, it is used to close the gap of a through portion through which electric wires, cables, and pipes provided in a fire wall, floor, etc. in a building (such as a building or a ship) are inserted. Hereinafter, each component will be described.

[0012] <Liquid Organic Compound> In the present invention, the liquid organic compound may be any one that is fluid at normal temperature (23 °C) and normal pressure (1 atm). For example, phosphate ester-based organic compounds, process oils, mineral oils, silicone oils, liquid polyisoprene, liquid polybutadiene, liquid polychloroprene, liquid polybutene, liquid butyl rubber, plasticizers such as DOP and DOA, etc. There is no need to limit it to only one type, and two or more types may be mixed. Among these, the liquid organic compound preferably contains a phosphate ester-based organic compound from the viewpoint of flame retardancy.

[0013] Examples of the phosphate-based organic compound include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, tri(chloropropyl) phosphate, tris(tribromoneopentyl) phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, dimethyl methyl phosphate, resorcinol bis(diphenyl) phosphate, bisphenol A bis(diphenyl) phosphate, bisphenol A bis(dicresyl) phosphate, resorcinol (di-2,6-xylenyl) phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, tris(tribromopropyl) phosphate, diethyl-N,N-bis(2-hydroxyethyl) aminomethyl phosphate, non-halogenated condensed phosphate ester, and the like. These may be used alone or in combination of two or more thereof.

[0014] The paste-like refractory composition can contain 5 to 63% by mass of the liquid organic compound, preferably 10 to 30% by mass, more preferably 15 to 25% by mass. When such a range is satisfied, it has a flexibility suitable for a paste and can delay combustion. Specifically, the content of the liquid organic compound is, for example, 5, 10, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35, 40, 45, 50, 55, 60, 63% by mass, and it may be within the range between any two of the values exemplified herein.

[0015] <Radical generator> The radical generator is a component for generating aerosol (radicals) by the thermal energy generated by the combustion of a liquid organic compound or the like. Examples of the radical generator include a potassium salt-based radical generator and a sodium salt-based radical generator.

[0016] Examples of potassium salt-based radical generators include potassium acetate, potassium propionate, monopotassium citrate, dipotassium citrate, tripotassium citrate, monopotassium trihydrogen ethylenediaminetetraacetate, dipotassium dihydrogen ethylenediaminetetraacetate, tripotassium monohydrogen ethylenediaminetetraacetate, potassium ethylenediaminetetraacetate, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate, potassium hydrogen carbonate, potassium carbonate, and the like.

[0017] Examples of sodium salt-based radical generators include sodium acetate, sodium citrate, and sodium hydrogen carbonate, and the like.

[0018] Among these, from the viewpoint of flame retardancy, the radical generator preferably contains a carbonate. As the carbonate, carbonates such as potassium hydrogen carbonate, potassium carbonate, and sodium hydrogen carbonate are particularly preferable. These radical generators may be used alone or in combination of two or more.

[0019] The content of the radical generator is 10 to 400 parts by mass, preferably 55 to 320 parts by mass, and more preferably 100 to 230 parts by mass with respect to 100 parts by mass of the liquid organic compound. If the content of the radical generator is too small, the flame retardancy deteriorates. If the content of the radical generator is too large, the processability deteriorates. The content of the radical generator is, specifically, for example, 10, 20, 30, 40, 50, 55, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400 parts by mass with respect to 100 parts by mass of the liquid organic compound, and may be within the range between any two of the values exemplified here.

[0020] <Inorganic compounds other than radical generators> Examples of inorganic compounds other than radical generators 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, sericite (muscovite), illite, glauconite, chlorite, talc, zeolite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, cristobalite, smectite, kaolin, hydrotalcite, and other clay minerals; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, and barium carbonate; fibrous inorganic compounds such as glass fibers (E-glass fibers, C-glass fibers, S-glass fibers, D-glass fibers), rock wool, ceramic fibers (silica-alumina fibers, alumina fibers, silica fibers), zirconia fibers, carbon fibers, bulk alkaline earth silicate fibers, gypsum fibers, carbon fibers, metal fibers, slag fibers, basalt fibers; calcium salts such as calcium sulfate and calcium silicate, glass beads, silica 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, pearlite, pitchstone, diatomaceous earth, dehydrated sludge, boron, sodium tetraborate hydrate (borax), silica, titanium oxide, inorganic oxidants, phosphate compounds, thermally expandable graphite, vermiculite, etc. These inorganic compounds may be used alone or in combination of two or more kinds.

[0021] The content of the inorganic compound other than the radical generator is 50 to 400 parts by mass, preferably 100 to 340 parts by mass, and more preferably 150 to 270 parts by mass with respect to 100 parts by mass of the liquid organic compound. If the content of the inorganic compound other than the radical generator is too small, the shape stability at high temperature deteriorates. If the content of the inorganic compound other than the radical generator is too large, the processability deteriorates. The content of the inorganic compound other than the radical generator is, specifically, for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400 parts by mass with respect to 100 parts by mass of the liquid organic compound, and it may be within the range between any two of the numerical values exemplified here.

[0022] <Inorganic oxidizer> The inorganic oxidizer is a component that burns together with the liquid organic compound to generate thermal energy. Examples of the inorganic oxidizer include potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate, magnesium chlorate, and potassium perchlorate, etc. Among these, one kind may be used alone, or two or more kinds may be used in combination. With respect to 100% by mass in total of the radical generator and the inorganic oxidizer, the inorganic oxidizer may be, for example, less than 10% by mass, preferably 0 to 9% by mass.

[0023] <Phosphoric acid-based inorganic compound> The phosphoric acid-based inorganic compound includes, in addition to the phosphoric acid-based compound, phosphorous acid-based compound, hypophosphorous acid-based compound, metaphosphoric acid-based compound, pyrophosphoric acid-based compound, and polyphosphoric acid-based compound.

[0024] Examples of the phosphoric acid compounds include aluminum monophosphate, sodium monophosphate, potassium monophosphate, calcium monophosphate, zinc monophosphate, aluminum diphosphate, sodium diphosphate, potassium diphosphate, calcium diphosphate, zinc diphosphate, aluminum triphosphate, sodium triphosphate, potassium triphosphate, calcium triphosphate, zinc triphosphate, magnesium triphosphate, ammonium monophosphate, diammonium phosphate, tricalcium phosphate, aluminum phosphate, etc.

[0025] Examples of the phosphorous acid compounds include aluminum phosphite, aluminum hydrogen phosphite, sodium phosphite, potassium phosphite, calcium phosphite, zinc phosphite, etc.

[0026] Examples of the hypophosphorous acid compounds include aluminum hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, zinc hypophosphite, etc.

[0027] Examples of the metaphosphoric acid compounds include aluminum metaphosphate, sodium metaphosphate, potassium metaphosphate, calcium metaphosphate, zinc metaphosphate, sodium hexametaphosphate, etc.

[0028] Examples of the pyrophosphoric acid compounds include sodium pyrophosphate.

[0029] Examples of the polyphosphoric acid compounds include ammonium polyphosphate, melamine-modified ammonium polyphosphate, sodium tripolyphosphate, sodium pentapolyphosphate, sodium tetrapolyphosphate, potassium tripolyphosphate, etc.

[0030] From the viewpoint of shape stability after heat combustion, aluminum hydrogen phosphite, ammonium polyphosphate, etc. are preferable as the phosphoric acid inorganic compounds.

[0031] The content of the phosphoric acid-based inorganic compound is preferably 5 to 140 parts by mass with respect to 100 parts by mass of the liquid organic compound. By being in this range, both the shape stability at high temperatures and the flame retardancy can be achieved.

[0032] In addition, the inorganic compound other than the radical generator preferably contains a metal hydroxide. Thereby, the flame retardancy can be enhanced.

[0033] <Thermally expandable graphite> Thermally expandable graphite is obtained by surface-treating graphite powder such as natural graphite and pyrolytic graphite with inorganic acids such as sulfuric acid and nitric acid, and strong oxidizing agents such as concentrated nitric acid and permanganates, and is a crystalline compound that maintains the graphite layered structure. When these are exposed to a temperature equal to or higher than the expansion start temperature (about 200 ° C) under normal pressure, they thermally expand by 100 times or more. The graphite powder such as the natural graphite and pyrolytic graphite may be subjected to a deacidification treatment, a further neutralization treatment, or the like.

[0034] The content of the thermally expandable graphite is, for example, 0 to 100 parts by mass with respect to 100 parts by mass of the liquid organic compound, preferably 0 to 50 parts by mass, and more preferably 0 to 30 parts by mass. By being in this range, the through-hole can be blocked even if the paste-like refractory composition burns.

[0035] <Other components> In this embodiment, an organic compound other than the liquid organic compound used in a normal rubber composition may be used as long as the effects are not inhibited. Examples of the organic compound other than the liquid organic compound include elastomers, rubbers, resins, antioxidants, processing aids, lubricants, crosslinking agents, tackifiers, polyhydric alcohol compounds such as pentaerythritol, and fibrous organic compounds such as paper fibers and aramid fibers. These may be used in combination. The total amount of the organic compounds other than the liquid organic compound is, for example, 0 to 50 parts by mass with respect to 100 parts by mass of the liquid organic compound, preferably 0 to 25 parts by mass, and more preferably 0 to 9 parts by mass. By being in this range, the flame retardancy is not adversely affected.

[0036] <Properties> The paste-shaped refractory composition of this embodiment preferably has a softness of 50 [1 / 10 mm] or more and less than 150 [1 / 10 mm], more preferably 65 [1 / 10 mm] or more and less than 135 [1 / 10 mm], and even more preferably 80 [1 / 10 mm] or more and less than 120 [1 / 10 mm] when the softness is measured in accordance with JIS A5752 under a load of 150 g and a temperature of 21°C. The softness is measured by vertically penetrating a specified cone into a test piece of the paste-shaped refractory composition and measuring the penetration depth in 0.1 mm units.

[0037] <Manufacturing method> The paste-shaped refractory composition of this embodiment can be obtained by mixing the above components. Further, the paste-shaped refractory composition can be obtained, for example, by kneading using a known kneading device such as a Banbury mixer, a kneader mixer, or two-rolls.

[0038] <Paste> The paste according to an embodiment of the present invention is composed of the above paste-shaped refractory composition.

Examples

[0039] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but these Examples do not limit the present invention.

[0040] 1. Preparation of paste-shaped refractory composition The components shown in the formulations of Tables 1 to 3 were kneaded at 80°C for 10 minutes using a 3-liter kneader mixer to obtain the paste-shaped refractory compositions of Examples and Comparative Examples.

[0041] Details of the components in the table are as follows. (1) Liquid organic compound · Trimethyl phosphate: "TMP" manufactured by Daihachi Chemical Industry Co., Ltd., viscosity 2 mPa·s (25°C) · Non-halogenated condensed phosphate ester: "ADEKA STAB FP-900L" manufactured by ADEKA Corporation, viscosity 260 - 450 mPa·s (70°C) · Liquid polyisoprene: "LIR-30" manufactured by Kuraray Co., Ltd., viscosity 70 Pa·s (38 °C)

[0042] (2) Radical initiator · Potassium hydrogen carbonate: manufactured by Hayashi Pure Chemical Industries, Ltd. · Potassium carbonate: manufactured by Hayashi Pure Chemical Industries, Ltd. · Sodium hydrogen carbonate: manufactured by Hayashi Pure Chemical Industries, Ltd. · Tripotassium citrate: manufactured by Fuso Chemical Industry Co., Ltd.

[0043] <Inorganic compounds other than radical initiator> · Aluminum hydrogen phosphite: "NSF" manufactured by Taihei Chemical Industry Co., Ltd. · Aluminum hydroxide: "C-301N" manufactured by Sumitomo Chemical Co., Ltd. · Calcium carbonate: "TA-044" manufactured by Chichibu Cement Co., Ltd.

[0044] 2. Evaluation For the paste-like refractory compositions of each example and comparative example, the following measurements and evaluations were carried out as test piece pastes. The results are shown in the table.

[0045] <Workability (softness)> The softness of the test piece paste was measured at a load of 150 g and a temperature of 21 °C in accordance with JIS A5752. A specified cone was vertically penetrated into the test piece, and the penetration depth was measured in units of 0.1 mm. Then, based on the penetration depth, the workability was determined according to the following criteria. ◎: Softness is 80 [1 / 10 mm] or more and less than 120 [1 / 10 mm] ○: Softness is 65 [1 / 10 mm] or more and less than 80 [1 / 10 mm], or 120 [1 / 10 mm] or more and less than 135 [1 / 10 mm] △: Softness is 50 [1 / 10 mm] or more and less than 65 [1 / 10 mm], or 135 [1 / 10 mm] or more and less than 150 [1 / 10 mm] ×: Softness is less than 50 [1 / 10 mm] or 150 [1 / 10 mm] or more

[0046] <Flame retardancy> A 10 g spherical test piece of putty was heated at 700 °C, and the time until ignition was visually observed. ◎: The time until ignition is 5 minutes or more 〇: The time until ignition is 1 minute or more and less than 5 minutes △: The time until ignition is 30 seconds or more and less than 1 minute ×: Less than 30 seconds

[0047] <High-temperature shape stability> After heating a 10 g spherical test piece of putty at 700 °C for 20 minutes, a three-point bending test jig (upper pressing side tip R1 mm and width 80 mm, lower two-point fulcrum side R1 mm, width 80 mm, fulcrum distance 20 mm) was used to measure the breaking strength when the test piece was broken under the condition of a compression speed of 50 mm / min. Here, the greater the breaking strength, the higher the strength at high temperature. And based on the breaking strength, the high-temperature shape stability was judged according to the following evaluation criteria. 〔Evaluation criteria〕 ◎: The breaking strength is 15 [N] or more ○: The breaking strength is 10 [N] or more and less than 15 [N] △: The breaking strength is 5 [N] or more and less than 10 [N] ×: The breaking strength is less than 5 [N]

[0048]

Table 1

[0049]

Table 2

[0050]

Table 3

[0051]

Table 4

Claims

1. A paste-like refractory composition comprising 100 parts by mass of a liquid organic compound, 10 to 400 parts by mass of a radical generator, and 50 to 400 parts by mass of an inorganic compound excluding the radical generator.

2. The paste-like refractory composition according to Claim 1, wherein the liquid organic compound contains a phosphate ester-based organic compound.

3. The paste-like refractory composition according to Claim 1, wherein the radical generator contains a carbonate.

4. The paste-like refractory composition according to Claim 1, wherein the inorganic compound excluding the radical generator contains a phosphoric acid-based inorganic compound.

5. The paste-like refractory composition according to Claim 1, having a softness of 50 [1 / 10 mm] or more and less than 150 [1 / 10 mm] when measured at a load of 150 g and a temperature of 21°C in accordance with JIS A5752.

6. The paste-like refractory composition according to any one of Claims 1 to 5, which is used to close the gap of the through-hole.

7. A paste comprising the paste-like refractory composition according to any one of Claims 1 to 5.

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