Putty-like fireproof composition, putty

Abstract

Provided is a putty-like fire-resistant composition that is excellent in processability, flame retardancy, and shape stability at high temperatures. According to the present invention, there is provided a putty-like fireproof composition containing 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.

Description

[Technical field]

[0001] The present invention relates to a non-curing, putty-like fire-resistant composition that is used mainly to seal gaps in penetrations for inserting electric wires, cables, and piping installed in fire walls, floors, etc. of buildings (buildings, ships, etc.), and a putty made of the composition. [Background technology]

[0002] 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, when a fire breaks out in a certain space, the heat and flames cause the plastic pipes, the foam insulation material of the air conditioning equipment piping, and the covering of the electric cables to burn or melt and disappear, and the penetrations become a flame path from which the fire can spread to adjacent equipment or rooms.

[0003] Fire-resistant or non-combustible putty is used as a fire prevention measure for these penetrations. The putty is used to fill the opening, or to seal the gap by combining it with a non-combustible board such as a calcium silicate board. The putty used here includes hardening putty, which hardens over time after application, and non-hardening putty, which does not dry or harden even after application.

[0004] Hardening putty has the advantage of being able to firmly hold the penetrations in place after application, but it has the disadvantage of being unable to be used when replacing wiring that accompanies building renovations or the addition of new facilities.

[0005] Some non-hardening putties use organic compound components such as rubber and plasticizers as binders (Patent Documents 1, 2, and 3). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 58-84881 [Patent Document 2] Japanese Patent Application Publication No. 5-271464 [Patent Document 3] Japanese Patent Application Publication No. 2-80468 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the putties described in Patent Documents 1 to 3 and the like are flammable because they use organic compound components such as rubber and plasticizers as binders, etc., and have a problem with flame retardancy. The present invention has been made in consideration of such circumstances, and provides a putty-like fire-resistant composition that is excellent in processability, flame retardancy, and shape stability at high temperatures. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved by using a composition with a specific blend ratio, which has led to the completion of the present invention.

[0009] That is, according to the present invention, the following inventions are provided. [1] A putty-like fireproof 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 putty-like fire-resistant composition according to [1], wherein the liquid organic compound contains a phosphate ester-based organic compound. [3] The putty-like fireproof composition according to [1] or [2], wherein the radical generator contains a carbonate. [4] The putty-like fireproof composition according to any one of [1] to [3], wherein the inorganic compound excluding the radical generator includes a phosphoric acid-based inorganic compound. [5] The putty-like fireproof composition according to any one of [1] to [4], which has a softness of 50 [1 / 10 mm] or more and less than 150 [1 / 10 mm] when measured in accordance with JISA5752 under a load of 150 g and a temperature of 21°C. [6] The putty-like fireproof composition according to any one of [1] to [5], which is used to fill a gap in a penetration part. [7] A putty comprising the putty-like fireproof composition according to any one of [1] to [6]. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Below, we will explain in detail the form for implementing the present invention (hereinafter referred to as the "present embodiment"). However, the present invention is not limited to this, and various modifications are possible without departing from the gist of the present invention.

[0011] The putty-like fireproof 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 fireproof composition can be used as a putty, and is used, for example, to block gaps in a penetration part for inserting electric wires, cables, and piping provided in a fire wall or floor in a building (such as a building or a ship). Each component will be described below.

[0012] <Liquid organic compounds> In the present invention, the liquid organic compound may be any compound that has fluidity at room temperature (23° C.) and normal pressure (1 atm), and examples thereof include phosphate organic compounds, process oils, mineral oils, silicone oils, liquid polyisoprene, liquid polybutadiene, liquid polychloroprene, liquid polybutene, liquid butyl rubber, and plasticizers such as DOP and DOA, and are not necessarily limited to one type, and two or more types may be mixed. Of these, the liquid organic compound preferably contains a phosphate organic compound from the viewpoint of flame retardancy.

[0013] Examples of phosphate organic compounds 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, and non-halogen condensed phosphate esters. These may be used alone or in combination of two or more.

[0014] The putty-like fireproof composition may contain 5 to 63 mass% of the liquid organic compound, preferably 10 to 30 mass%, more preferably 15 to 25 mass%. When the content is within such a range, the composition has a suitable softness as a putty while retarding combustion. The content of the liquid organic compound is specifically, for example, 5, 10, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35, 40, 45, 50, 55, 60, or 63 mass%, and may be within a range between any two of the numerical values ​​exemplified here.

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

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

[0017] Examples of the sodium salt radical generator include sodium acetate, sodium citrate, and sodium bicarbonate.

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

[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, based on 100 parts by mass of the liquid organic compound. If the content of the radical generator is too low, the flame retardancy is deteriorated. If the content of the radical generator is too high, the processability is deteriorated. The content of the radical generator is, 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, or 400 parts by mass relative to 100 parts by mass of the liquid organic compound, and may be within a range between any two of the numerical values ​​exemplified here.

[0020] <Inorganic compounds other than radical generators> Examples of inorganic compounds other than the radical generator 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-glass fibers) , 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), silica, titanium oxide, inorganic oxidizing agents, phosphate compounds, thermally expandable graphite, vermiculite, etc. These inorganic compounds may be used alone or in combination of two or more.

[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, relative 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 temperatures is deteriorated. If the content of the inorganic compound other than the radical generator is too large, the processability is deteriorated. The content of the inorganic compound other than the radical generator is, 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, or 400 parts by mass per 100 parts by mass of the liquid organic compound, and may be within a range between any two of the numerical values ​​exemplified here.

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

[0023] <Phosphate-based inorganic compounds> The phosphoric acid-based inorganic compounds include, in addition to phosphoric acid compounds, phosphorous acid compounds, hypophosphorous acid compounds, metaphosphate compounds, pyrophosphate compounds, and polyphosphate compounds.

[0024] Examples of phosphate 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, ammonium diphosphate, tricalcium phosphate, aluminum phosphate, etc.

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

[0026] Examples of hypophosphite compounds include aluminum hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, and zinc hypophosphite.

[0027] Examples of metaphosphate compounds include aluminum metaphosphate, sodium metaphosphate, potassium metaphosphate, calcium metaphosphate, zinc metaphosphate, and sodium hexametaphosphate.

[0028] An example of the pyrophosphate compound is sodium pyrophosphate.

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

[0030] From the viewpoint of shape stability after heating and combustion, the phosphoric acid-based inorganic compound is preferably aluminum hydrogen phosphite, ammonium polyphosphate, or the like.

[0031] The content of the phosphoric acid-based inorganic compound is preferably 5 to 140 parts by mass per 100 parts by mass of the liquid organic compound, which allows both shape stability at high temperatures and flame retardancy to be achieved.

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

[0033] <Thermal expandable graphite> Thermally expandable graphite is a crystalline compound that is obtained by surface-treating graphite powder such as natural graphite or pyrolytic graphite with an inorganic acid such as sulfuric acid or nitric acid, and a strong oxidizing agent such as concentrated nitric acid or permanganate, and that maintains a graphite layer structure. When exposed to a temperature equal to or higher than the expansion start temperature (about 200°C) under normal pressure, it thermally expands by 100 times or more. The graphite powder such as natural graphite or pyrolytic graphite may be deoxidized or further neutralized.

[0034] The content of the thermally expandable graphite is, for example, 0 to 100 parts by mass, preferably 0 to 50 parts by mass, and more preferably 0 to 30 parts by mass, relative to 100 parts by mass of the liquid organic compound. By being in this range, the penetration part can be blocked even if the putty-like fireproof composition burns.

[0035] <Other ingredients> In this embodiment, organic compounds other than the liquid organic compounds used in normal rubber compounds may be used within a range that does not impair the effect. As organic compounds other than the liquid organic compounds, for example, elastomers, rubbers, resins, antioxidants, processing aids, lubricants, crosslinking agents, tackifiers, polyhydric alcohol compounds such as pentaerythritol, fibrous organic compounds such as paper fibers and aramid fibers, etc. may be used in combination. The total amount of organic compounds other than the liquid organic compounds is, for example, 0 to 50 parts by mass, preferably 0 to 25 parts by mass, and more preferably 0 to 9 parts by mass, relative to 100 parts by mass of the liquid organic compounds. By being in this range, there is no adverse effect on flame retardancy.

[0036] <Characteristics> The putty-like fireproof composition of the present embodiment has a softness of preferably 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 according to JIS A5752 under a load of 150 g and a temperature of 21° C. The softness is measured by vertically penetrating a test piece of the putty-like fireproof composition with a specified cone and measuring the penetration depth to the nearest 0.1 mm.

[0037] <Manufacturing method> The putty-like fireproof composition of the present embodiment can be obtained by mixing the above-mentioned components. The putty-like fireproof composition can be obtained by kneading the components using a known kneading device such as a Banbury mixer, a kneader mixer, or a two-roll mill.

[0038] <Pate> A putty according to one embodiment of the present invention comprises the above putty-like fireproof composition. EXAMPLES

[0039] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

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

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

[0042] (2) Radical generator Potassium bicarbonate: Hayashi Pure Chemical Industries, Ltd. Potassium carbonate: Hayashi Pure Chemical Industries, Ltd. Sodium bicarbonate: Hayashi Pure Chemical Industries, Ltd. Tripotassium citrate: Fuso Chemical Co., Ltd.

[0043] <Inorganic compounds other than radical generators> 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 Lime Industry Co., Ltd.

[0044] 2. Evaluation The putty-like fireproof compositions of the Examples and Comparative Examples were prepared into test piece putties and subjected to the following measurements and evaluations. The results are shown in the Table.

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

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

[0047] <Shape stability at high temperatures> After heating 10 g of spherical test piece putty at 700°C for 20 minutes, a three-point bending test jig (upper pushing side tip R1 mm and width 80 mm, lower two-point support side R1 mm, width 80 mm, support distance 20 mm) was used to measure the fracture strength when the test piece was broken at a compression speed of 50 mm / min. Here, the higher the fracture strength, the higher the strength at high temperatures. Based on the fracture strength, the shape stability at high temperatures was evaluated according to the following criteria. [Evaluation Criteria] ◎: Breaking strength is 15N or more ○: Breaking strength is 10 [N] or more and less than 15 [N] △: Breaking strength is 5[N] or more and less than 10[N] ×: Breaking strength is less than 5 [N]

[0048] [Table 1]

[0049] [Table 2]

[0050] [Table 3]

[0051] [Table 4]

Claims

1. The liquid organic compound contains 10 to 400 parts by mass of a radical generator and 50 to 400 parts by mass of an inorganic compound other than the radical generator, relative to 100 parts by mass of the liquid organic compound; The putty-like fireproof composition, wherein the radical generator contains at least one of a potassium salt-based radical generator and a sodium salt-based radical generator.

2. The putty-like fire-resistant composition according to claim 1 , wherein the liquid organic compound comprises a phosphoric acid ester-based organic compound.

3. The putty-like fireproof composition according to claim 1 , wherein the radical generator comprises a carbonate.

4. The putty-like fireproof composition according to claim 1 , wherein the inorganic compound other than the radical generator includes a phosphoric acid-based inorganic compound.

5. 2. The putty-like fireproof composition according to claim 1, which has 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 putty-like fireproof composition according to any one of claims 1 to 5, which is used to seal gaps in penetration parts.

7. A putty comprising the putty-like fireproof composition according to any one of claims 1 to 5.

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