Refractory composition and member

Abstract

Provided is a refractory composition excellent in processability, workability, thermal expansion, shape stability after thermal expansion, and adhesion after thermal expansion.　According to the present invention, there is provided a refractory composition containing a matrix polymer component and a phosphoric acid-based inorganic compound. With respect to 100 parts by mass of the matrix polymer component, the content of the phosphoric acid-based inorganic compound is more than 120 parts by mass and 2000 parts by mass or less, the content of a thermally expandable layered inorganic compound is less than 10 parts by mass, and the content of a polyhydric alcohol compound having a molecular weight of 500 or less is less than 30 parts by mass. The matrix polymer component includes a liquid rubber and solid elastomer, and the mass ratio of the liquid rubber to the solid elastomer is 95:5 to 5:95.

Description

Refractory composition, member

[0001] The present invention relates to a refractory composition mainly used for filling an opening of a penetration portion of an electric wire, cable, or pipe provided in a fire wall, floor, etc. in a building (such as a building or a ship), or a refractory composition for battery use, and a member including these refractory compositions.

[0002] In buildings such as buildings and ships, through holes are formed 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, and the coating of the electric wires and cables to burn or melt and disappear, so the through hole becomes a flame path and the fire spreads from here to the adjacent facilities and rooms.

[0003] As fire prevention measures for these penetration parts, putties having fire resistance or incombustibility are used. The putty is used to fill the opening or in combination with a non-combustible board such as a calcium silicate board to close the gap.

[0004] As such a putty, for example, a rubber component composed of liquid rubber and butyl rubber is blended with a specific amount of thermally expandable graphite, aluminum phosphite, and aluminum hydroxide, which expands thermally when a fire occurs, prevents flames from flowing in from the gap, and further, a thermally expandable putty composition having sufficient shape stability such that the residue after combustion does not collapse is known (Patent Document 1).

[0005] In recent years, thermally expandable refractory materials have also been used for battery members. In various battery cells represented by lithium ion batteries, disasters such as ignition and smoke generation may occur at high temperatures. In order to suppress damage when fire breaks out from the battery cell, a thermally expandable refractory material may be used around the battery cell. For example, Patent Document 2 exemplifies a thermally expandable refractory sheet containing a matrix resin and thermally expandable graphite, containing 5% by mass or more of the thermally expandable graphite, and specifying the relationship between the thickness of the thermally expandable refractory sheet and the average aspect ratio of the thermally expandable graphite.

[0006] Japanese Patent Publication No. 2007-254563, Japanese Patent Publication No. 2018-115319

[0007] The thermally expandable graphite described in Patent Document 1 is obtained by treating powders such as natural graphite or pyrolysis graphite with inorganic acids such as sulfuric acid and nitric acid, and strong oxidizing agents such as concentrated nitric acid and permanganate, resulting in a flattened crystalline compound that maintains a graphite layered structure. When exposed to temperatures of around 200°C or higher, it expands thermally, for example, by more than 100 times in an accordion-like manner. There is a trade-off relationship between this thermal expandability and the dimensional stability that allows it to maintain its shape, and it has not been possible to achieve both properties simultaneously. Similarly, the thermally expandable fire-resistant sheet described in Patent Document 2 also failed to achieve both thermal expandability and dimensional stability. Furthermore, the residue after thermal expansion has poor adhesion to non-combustible boards such as calcium silicate boards, and to metals and resins that serve as substrates for batteries, etc. In particular, vertical sections and those installed upside down are prone to falling off due to the intensity of the fire, wind, or deformation of the adherend during a fire, which has been a problem.

[0008] Therefore, the present invention provides a fire-resistant material composition that is excellent in processability, workability, thermal expansion, shape stability after thermal expansion, and adhesion after thermal expansion.

[0009] The inventors diligently studied to solve the above problems. As a result, they discovered that the above problems could be solved by using a specific compound composition, and thus completed the present invention.

[0010] In other words, the present invention provides the following inventions: [1] A fire-resistant material composition comprising a matrix polymer component and a phosphate-based inorganic compound, wherein the content of the phosphate-based inorganic compound is more than 120 parts by mass and 2000 parts by mass or less per 100 parts by mass of the matrix polymer component, the content of the thermally expandable layered inorganic compound is less than 10 parts by mass, the content of the polyhydric alcohol compound having a molecular weight of 500 or less is less than 30 parts by mass, the matrix polymer component comprises liquid rubber and a solid elastomer, and the mass ratio of the liquid rubber to the solid elastomer is 95:5 to 5:95. [2] The fire-resistant material composition according to [1], comprising 1 to 30 parts by mass of a fibrous organic compound per 100 parts by mass of the matrix polymer component. [3] The fire-resistant material composition according to [1] or [2], wherein the phosphate-based inorganic compound comprises at least one selected from aluminum hydrogen phosphite or disaluminum phosphate. [4] The fire-resistant material composition according to [1] or [2], wherein the content of the thermally expandable layered inorganic compound is less than 3 parts by mass. [5] The fire-resistant material composition according to [1] or [2], wherein the content of the thermally expandable layered inorganic compound is 0 parts by mass. [6] The fire-resistant material composition according to [1] or [2], wherein the content of the phosphoric acid-based inorganic compound is 220 to 1500 parts by mass. [7] The fire-resistant material composition according to [1] or [2], wherein the content of the phosphoric acid-based inorganic compound is 360 to 1000 parts by mass. [8] A member comprising the fire-resistant material composition according to any one of [1] to [7]. [9] The member according to [8], used to close a gap in a penetration.

[10] The member according to [8], used in a battery.

[0011] The present invention provides a fire-resistant material composition that is excellent in processability, workability, thermal expansion, shape stability after thermal expansion, and adhesion after thermal expansion. Such a fire-resistant material composition can be used, for example, in gaps in penetrations or in components used in batteries.

[0012] Figure 1A is a schematic diagram showing the process of applying a putty-like fire-resistant material composition to the surface of a cylindrical battery cell. Figure 1B is a schematic diagram showing the state after the putty-like fire-resistant material composition has been applied to the surface of the cylindrical battery cell. This diagram illustrates the test method for adhesion after thermal expansion.

[0013] The following describes in detail an embodiment for carrying out the present invention (hereinafter referred to as "this embodiment"), but the present invention is not limited thereto, and various modifications are possible without departing from its essence.

[0014] The fire-resistant material composition of this embodiment comprises a matrix polymer component and a phosphate-based inorganic compound, wherein the amount of the phosphate-based inorganic compound is more than 120 parts by mass and not more than 2000 parts by mass per 100 parts by mass of the matrix polymer component, the content of the thermally expandable layered inorganic compound is less than 10 parts by mass, and the content of the polyhydric alcohol compound with a molecular weight of 500 or less is less than 30 parts by mass. The matrix polymer comprises liquid rubber and solid elastomer, and the mass ratio of liquid rubber to solid elastomer is 95:5 to 5:95. Such a composition is a composition with excellent processability and can be used as a putty that is easy to use according to the shape. For example, it can be used in gaps in penetrations and in components used in batteries. That is, the composition can also be provided as a putty-like fire-resistant material composition. The following describes each component.

[0015] <Matrix Polymer Components> The matrix polymer components include liquid rubber and solid elastomer, with a weight ratio (liquid rubber:solid elastomer) of 95:5 to 5:95, preferably 93:7 to 30:70, and more preferably 90:10 to 40:60. If the proportion of liquid rubber exceeds 95% by mass, workability (non-adhesion) deteriorates, and if the proportion of liquid rubber is less than 5% by mass, processability deteriorates. If the total mass ratio of liquid rubber and solid elastomer is 100, the mass ratio of solid elastomer can be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and may be within the range of any two of the values ​​exemplified here. The mass ratio of liquid rubber is the value obtained by subtracting the mass ratio of solid elastomer from 100.

[0016] <Liquid Rubber> In the present invention, liquid rubber refers to any rubber that is fluid at room temperature (25°C). For example, liquid polyisoprene, liquid polybutadiene, liquid polychloroprene, liquid polybutene, liquid butyl rubber, etc., can be used, but it is not limited to one type, and two or more types may be mixed.

[0017] <Solid Elastomer> In the present invention, the solid elastomer can be any elastomer that is solid at room temperature (25°C), and examples include 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, recycled rubber, and other crosslinkable rubbers, as well as silicone rubber, fluororubber, urethane rubber, and styrene-based thermoplastic elastomers.

[0018] Styrene-based thermoplastic elastomers are thermoplastic elastomers having monomer units derived from vinyl aromatic hydrocarbons. Thermoplastic elastomers are elastomers that soften and become fluid when heated, and can be distinguished from rubber which does not have such properties. Styrene-based thermoplastic elastomers are preferably block copolymers consisting of a polymer block mainly composed of vinyl aromatic hydrocarbons and a polymer block mainly composed of conjugated dienes. Examples of vinyl aromatic hydrocarbons include styrene, p-methylstyrene, α-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, etc., and these may be used individually 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., and these may be used individually or in combination of two or more.

[0019] 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-ethylenepropylene (SEP) copolymer, styrene-ethylenepropylene-styrene (SEPS) copolymer, and styrene-ethylene-ethylenepropylene-styrene (SEEPS) copolymer. 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.

[0020] The matrix polymer component may consist only of liquid rubber and solid elastomer, or it may contain other polymers. Examples of other polymers include thermoplastic elastomers other than styrene-based (olefin-based, PVC-based, urethane-based, ester-based, amide-based, etc.) and resins that are not elastomers (polyolefin, polystyrene, etc.).

[0021] The content of the matrix polymer component in 100% by mass of the refractory material composition may be, for example, 5 to 91% by mass, preferably 5 to 25% by mass. Specifically, the content of the matrix polymer component in 100% by mass of the refractory material composition may be, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91% by mass, and may be within the range of any two of the values ​​exemplified here.

[0022] <Phosphoric Acid-Based Inorganic Compounds> Phosphoric acid-based inorganic compounds are used as thermally expandable compounds to provide shape stability to refractory material compositions that undergo significant thermal expansion and maintain their expanded form when exposed to high temperatures such as 600°C. Preferably, the phosphate-based inorganic compound includes at least one of the following: phosphate compounds, phosphite compounds, hypophosphite compounds, metaphosphate compounds, pyrophosphate compounds, and polyphosphate compounds.

[0023] Examples of phosphate compounds include monoaluminum phosphate, monosodium phosphate, monopotassium phosphate, monocalcium phosphate, monozinc phosphate, dialuminum phosphate, disodium phosphate, dipotassium phosphate, dicalcium phosphate, dizinc phosphate, trialuminum phosphate, trisodium phosphate, tripotassium phosphate, tricalcium phosphate, trizinc phosphate, trimagnesium phosphate, monoammonium phosphate, diammonium phosphate, tricalcium phosphate, and aluminum phosphate.

[0024] Examples of phosphite compounds include aluminum phosphite, aluminum hydrogen phosphite, sodium phosphite, potassium phosphite, calcium phosphite, and zinc phosphite.

[0025] Examples of hypophosphite compounds include aluminum hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, and zinc hypophosphite.

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

[0027] Examples of pyrophosphate compounds include sodium pyrophosphate.

[0028] Examples of polyphosphate compounds include ammonium polyphosphate, melamine-modified ammonium polyphosphate, sodium tripolyphosphate, sodium pentapolyphosphate, sodium tetrapolyphosphate, and potassium tripolyphosphate.

[0029] The content of the phosphoric acid-based inorganic compound is more than 120 parts by mass and 2000 parts by mass or less per 100 parts by mass of the matrix polymer component, preferably 220 to 1500 parts by mass, and more preferably 360 to 1000 parts by mass. If the content of the phosphoric acid-based inorganic compound is 120 parts by mass or less, the thermal expansion properties will be poor. If the content of the phosphoric acid-based inorganic compound exceeds 2000 parts by mass, the processability will be poor. The content of the phosphoric acid-based inorganic compound is, specifically, 121, 125, 157, 200, 220, 250, 300, 350, 360, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950, and 2000 parts by mass per 100 parts by mass of the matrix polymer component, and may be within the range of any two of the values ​​exemplified herein.

[0030] The phosphate-based inorganic compound preferably contains a phosphite compound and a phosphate compound, and more preferably contains aluminum hydrogen phosphite or disaluminum phosphate. The inclusion of aluminum hydrogen phosphite or disaluminum phosphate tends to improve shape retention after thermal expansion.

[0031] These phosphate-based inorganic compounds can be used individually or in combination of two or more.

[0032] <Thermally Expandable Compounds> In addition to phosphoric acid-based inorganic compounds, thermally expandable compounds may also be used to assist the thermal expansion of phosphoric acid-based inorganic compounds. There are no particular limitations on thermally expandable compounds other than phosphoric acid-based inorganic compounds as long as they expand when heated, but for example, thermally expandable layered compounds and thermally expandable non-layered compounds can be used. One or more of these thermally expandable compounds can be used. When using thermally expandable compounds other than phosphoric acid-based inorganic compounds, thermally expandable non-layered compounds are preferred from the viewpoint of shape retention after thermal expansion or adhesion to the substrate after thermal expansion. Examples of thermally expandable non-layered compounds other than phosphoric acid-based inorganic compounds include thermally expandable non-layered organic compounds such as microspheres and nitrogen-containing blowing agents, and thermally expandable non-layered inorganic compounds such as bicarbonates.

[0033] As thermally expandable layered compounds, particularly thermally expandable layered inorganic compounds, any known inorganic compound having a layered structure that expands when heated can be used, such as vermiculite, kaolin, mica, and thermally expandable graphite. Thermally expandable graphite is a crystalline compound that maintains a graphite layered structure, obtained by treating powders of natural graphite, pyrolysis graphite, etc., with inorganic acids such as sulfuric acid and nitric acid, and strong oxidizing agents such as concentrated nitric acid and permanganate. When exposed to temperatures of around 200°C or higher, these expand, for example, by more than 100 times. In addition to deacidification treatment, various types of powders of natural graphite, pyrolysis graphite, etc., are available, including those that have undergone neutralization treatment, and all types can be used.

[0034] The thermally expandable graphite used in this invention preferably has an average aspect ratio of 20 or more. An average aspect ratio of 20 or more allows for sufficient filling of the frame structure constituting the opening frame of building components such as fire-resistant resin sashes, and it can also be suitably used for steel frame covering.

[0035] The average aspect ratio is the ratio of the average horizontal diameter to the vertical thickness. Since the thermally expandable graphite used in this invention is generally flat, the vertical direction can be considered to coincide with the thickness direction and the horizontal direction with the diameter direction. Therefore, the aspect ratio is calculated by dividing the maximum horizontal dimension by the vertical thickness. The aspect ratio is then measured for a sufficiently large number of graphite pieces, i.e., 10 or more, and the average value is taken as the average aspect ratio. The average particle size of the thermally expandable graphite can also be determined as the average value of the maximum horizontal dimension. The maximum horizontal dimension and thickness of the thermally expandable graphite can be measured, for example, using a field emission scanning electron microscope (FE-SEM).

[0036] Examples of nitrogen-containing foaming agents include melamine, azo compounds, nitroso compounds, and hydrazine derivatives.

[0037] Examples of bicarbonates include sodium bicarbonate.

[0038] The content of thermally expandable compounds other than phosphate-based inorganic compounds is preferably less than 10 parts by mass, more preferably less than 5 parts by mass, even more preferably less than 3 parts by mass, and particularly preferably 0 parts by mass, per 100 parts by mass of the matrix polymer component. When the content of thermally expandable compounds other than phosphate-based inorganic compounds is 10 parts by mass or more, the shape stability after thermal expansion tends to deteriorate. Specifically, the content of thermally expandable compounds other than phosphate-based inorganic compounds is, for example, 0, 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 1.5, 1.8, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 19, and 20 parts by mass per 100 parts by mass of the matrix polymer component, and may be within the range between any two of the values ​​exemplified here, or within the range less than either of them.

[0039] The content of the thermally expandable layered inorganic compound is less than 10 parts by mass, preferably less than 5 parts by mass, more preferably less than 3 parts by mass, and even more preferably 0 parts by mass, per 100 parts by mass of the matrix polymer component. If the content of the thermally expandable layered inorganic compound is 10 parts by mass or more, the shape stability after thermal expansion deteriorates. Specifically, the content of the thermally expandable layered inorganic compound is, for example, 0, 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, or 9 parts by mass per 100 parts by mass of the matrix polymer component, and may be within the range between any two of the values ​​exemplified here, or less than either of them.

[0040] Furthermore, the content of thermally expandable non-layered compounds other than phosphate-based inorganic compounds is preferably less than 10 parts by mass, more preferably less than 5 parts by mass, even more preferably less than 3 parts by mass, and even more preferably 0 parts by mass, per 100 parts by mass of the matrix polymer component. Having the content of thermally expandable non-layered compounds other than phosphate-based inorganic compounds within this range provides a good balance between thermal expandability and shape stability after thermal expansion. Specifically, the content of thermally expandable non-layered compounds other than phosphate-based inorganic compounds is, for example, 0, 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 19, and 20 parts by mass per 100 parts by mass of the matrix polymer component, and may be within the range between any two of the values ​​exemplified here, or less than either of them.

[0041] Furthermore, the content of the nitrogen-containing blowing agent is preferably less than 10 parts by mass, more preferably less than 5 parts by mass, even more preferably less than 3 parts by mass, and even more preferably 0 parts by mass, per 100 parts by mass of the matrix polymer component. When the content of the nitrogen-containing blowing agent is 10 parts by mass or more, the shape stability after thermal expansion tends to deteriorate. Specifically, the content of the nitrogen-containing blowing agent is, for example, 0, 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 19, or 20 parts by mass per 100 parts by mass of the matrix polymer component, and may be within the range between any two of the values ​​exemplified here, or within the range less than either of them.

[0042] <Fibrous organic compound> The shape of the fibrous organic compound only needs to be fibrous, and examples of the cross-sectional shape of the fiber include circular, elliptical, polygonal, etc. If the average fiber length of the fibrous organic compound is L and the average diameter is D, then L / D is, for example, more than 10, preferably 50 or more, and more preferably 100 or more. The upper limit is not particularly defined, but is, for example, 10000. 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 preferably, for example, 0.25 to 12 mm. The average fiber length is, for example, 0.25, 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, 12.0 mm, and may also be within the range between any two of the values exemplified herein.

[0043] Examples of the fibrous organic compound include meta-aramid fiber, para-aramid fiber, amide fiber, cellulose fiber (e.g., pulp fiber), polyparaphenylene benzobisoxazole fiber, polyarylate fiber, polyester fiber, acrylic fiber, acrylonitrile fiber, rayon, silk, cotton, hemp, wool, etc.

[0044] For the fibrous organic compound, the average fiber length and the average diameter are numbers large enough, that is, the fiber length and the diameter are measured for 20 or more fibrous organic compounds, and the average value thereof is taken as the average fiber length and the average diameter.

[0045] The fiber length and the diameter of the fibrous organic compound can be measured, for example, using a field emission scanning electron microscope (FE-SEM).

[0046] The content of the fibrous organic compound is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, based on 100 parts by mass of the matrix polymer component. 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, 30 parts by mass based on 100 parts by mass of the matrix polymer component, and may be within the range between any two of the values exemplified herein. By having the content of the fibrous compound within this range, it is possible to achieve both shape stability and processability at high temperatures (for example, 200 °C).

[0047] <Low molecular weight polyhydric alcohol compound> The low molecular weight polyhydric alcohol compound can be added for the purpose of improving the compatibility (miscibility) between materials. However, from the viewpoint of flame retardancy and the like, it may be preferable not to add a large amount. The content of the low molecular weight polyhydric alcohol compound is less than 30 parts by mass, preferably less than 10 parts by mass, and more preferably 0 parts by mass, based on 100 parts by mass of the matrix polymer component. Specifically, the content of the low molecular weight polyhydric alcohol compound is, for example, 0, 5, 10, 15, 20, 25, 29 parts by mass based on 100 parts by mass of the matrix polymer component, and may be within the range between any two of the values exemplified herein or less than any of them.

[0048] The low molecular weight polyhydric alcohol is a compound having two or more hydroxyl groups in the molecule and a molecular weight of 500 or less. Examples of the low molecular weight polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, glycerin, butylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, inositol, mannitol, glucose, fructose, and the like. The molecular weight of the low molecular weight polyhydric alcohol is, for example, 50 to 500, and for example, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, and may be within the range between any two of the values exemplified herein.

[0049] <Other Components> In this embodiment, plasticizers (softeners), antioxidants, processing aids, lubricants, tackifiers, other inorganic compounds (excluding the phosphorus-based inorganic compounds and other thermally expandable compounds) commonly used in rubber compounding, softeners, vulcanizing agents, crosslinking agents, carbonizing agents, flame retardants, etc., may be used in combination, to the extent that they do not impair the effect.

[0050] <Other Inorganic Compounds> The shapes of other inorganic compounds include, for example, spherical, ellipsoidal, cuboidal, rectangular, random, and fibrous shapes, and they may be hollow or solid. The average particle size of particulate inorganic compounds is, for example, 10 to 1000 μm, preferably 20 to 800 μm, more preferably 30 to 500 μm, and even more preferably 40 to 200 μm. "Average particle size" refers to the particle size at 50% of the cumulative value in the particle size distribution determined by laser diffraction / scattering. These may be used individually or in combination of two or more.

[0051] Other inorganic compounds include, for example, metal oxides such as alumina, silica, aluminosilicate, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; hydrated inorganic substances such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, and barium carbonate; calcium salts such as calcium sulfate and calcium silicate; 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, pitchstone, diatomaceous earth, dewatered sludge, boron, sodium tetraborate hydrate (borax), and the like. These may be used individually or in combination of two or more. From the viewpoint of flame retardancy, the inorganic compound preferably contains aluminum hydroxide.

[0052] The content of other inorganic compounds is 10 to 500 parts by mass per 100 parts by mass of the matrix polymer component, preferably 70 to 440 parts by mass, and more preferably 130 to 270 parts by mass.

[0053] <Plasticizers (Softeners)> Plasticizers (softeners) are not particularly limited, but examples include rapeseed oil, cottonseed oil, palm oil, coconut oil, peanut oil, sub(factis), tall oil, pine tar, process oils (paraffinic oils, naphthenic oils, and aromatic process oils), carboxylic acid ester plasticizers (phthalate esters, adipic acid esters, sebacate esters, maleate esters, fumarate esters, trimellitic acid esters, citrate esters, oleate esters, ricinoleate esters, stearic acid esters, glycolic acid esters, etc.), and phosphate ester plasticizers (tritolyl phosphate, triisopropylphenyl phosphate, etc.). Softeners may be used alone or in combination of two or more.

[0054] In this embodiment, vulcanizing agents and vulcanization accelerators commonly used in rubber compounding may be included, to the extent that they do not impair the effect. The vulcanizing agents and vulcanization accelerators improve the degree of crosslinking of the vulcanizable rubber and improve the strength of the rubber itself. The strength of the rubber can be evaluated by its hardness. However, the refractory material of the present invention does not have to contain vulcanizing agents and vulcanization accelerators. In other words, the refractory material of the present invention does not have to be vulcanized.

[0055] The carbonizing agent generally has the effect of forming a thick foamed layer with superior heat insulation properties by dehydrating and carbonizing itself along with the carbonization of the binder due to fire. The carbonizing agent is not particularly limited as long as it has this effect, and the same carbonizing agents as those used in known foamed refractory materials can be used. Examples include polyhydric alcohols such as pentaerythritol, dipentaerythritol, and trimethylolpropane, as well as starch and casein. These can be used one or more at a time. Among these, dipentaerythritol is particularly preferred because it has excellent dehydration cooling effect and foamed layer formation effect.

[0056] Examples of flame retardants include organophosphorus compounds such as tricresyl phosphate and diphenylcresyl phosphate; chlorine compounds such as chlorinated polyphenyls, chlorinated polyethylenes, diphenyl chloride, triphenyl chloride, pentachloride fatty acid esters, perchloropentacyclodecane, chlorinated naphthalene, and tetrachlorophthalic anhydride; antimony compounds such as antimony trioxide and antimony pentachloride; phosphorus compounds such as phosphorus trichloride and phosphorus pentachloride; and other inorganic compounds such as zinc borate and sodium borate.

[0057] When both a carbonizing agent and a flame retardant are included, the weight ratio is preferably 2:8 to 8:2, and more preferably 3:7 to 7:3. Furthermore, the total amount of the carbonizing agent and flame retardant is preferably 10 to 1500 parts by mass per 100 parts by mass of the matrix polymer component.

[0058] The refractory material composition of this embodiment can be obtained by kneading the above components using a known kneading device such as a Banbury mixer, kneader mixer, or double-roll mixer. Alternatively, the kneaded material can be formed into a sheet using a conventional molding method such as press molding, roll molding, extrusion molding, or calendering to obtain a sheet-like molded body.

[0059] <Other Embodiments> A member according to another embodiment of the present invention comprises the above-described fire-resistant composition. The fire-resistant composition may be used as a fire-resistant material on its own to constitute a member, or the member may be formed together with the fire-resistant material and other components. The member may be used, for example, to seal gaps in penetrations or to cover batteries.

[0060] The component may consist of a layer made of a fire-resistant material based on a fire-resistant composition and layers of other components laminated together. For example, a base material may be provided on at least one side of the fire-resistant material. The base material may be a combustible material layer, a semi-noncombustible material layer, or a noncombustible material layer. A release treatment such as silicone may be applied to the side of the base material opposite to the side on which the fire-resistant material is laminated. The thickness of the base material is not particularly limited, but is, for example, 5 μm to 2 mm. Examples of materials used for the combustible material layer include one or more types of materials such as cloth, paper, wood, and resin film. When the base material is a semi-noncombustible material layer or a noncombustible material layer, examples of materials used include metals and inorganic materials, and more specifically, woven or nonwoven fabrics made of glass fibers, ceramic fibers, carbon fibers, and graphite fibers may be used as materials for the semi-noncombustible material layer or noncombustible material layer. Furthermore, the material for the semi-noncombustible material layer or noncombustible material layer may be a composite material of these fibers and metals, for example, aluminum glass cloth is preferred. An adhesive layer may also be laminated onto the fire-resistant material. The use of an adhesive layer makes it possible to easily adhere the fire-resistant material to the desired location. The adhesive layer may be provided on the base material or formed directly on the surface of the fire-resistant material. Alternatively, a double-sided adhesive tape (double-sided tape) with adhesive layers on both sides of the base material may be used. In this case, one adhesive layer is attached to the fire-resistant material, and the other adhesive layer is used to attach it to other components.

[0061] Furthermore, a battery according to another embodiment of the present invention comprises a component made of the above composition. The battery typically has at least one battery cell 3, and the above urethane foam composition is attached to the battery as a component 1 such as a protective material or fire-resistant material (Figure 1). The urethane foam composition is typically attached to the surface of the battery cell. The battery may have one battery cell or two or more battery cells.

[0062] Battery cells include, but are not limited to, lithium-ion batteries, lithium-ion polymer batteries, nickel-metal hydride batteries, lithium-sulfur batteries, nickel-cadmium batteries, nickel-iron batteries, nickel-zinc batteries, sodium-sulfur batteries, lead-acid batteries, and air batteries.

[0063] Batteries are used in, for example, small electronic devices such as mobile phones and smartphones, laptop computers, automobiles, power tools, and the like, but are not limited to these.

[0064] The present invention will be described in detail below with reference to examples and comparative examples, but these examples are not intended to limit the present invention.

[0065] 1. Preparation of the refractory material composition The components shown in Tables 1 to 5 were kneaded in a 3-liter kneader mixer at 80°C for 10 minutes to obtain a putty-like refractory material composition.

[0066] The details of the ingredients in the table are as follows: [Matrix Polymer Components] ・Polyisoprene rubber: "LIR-30" manufactured by Kuraray Co., Ltd., molecular weight 28,000, Tg -63°C, viscosity 70 Pa.s (38°C) ・Polybutadiene rubber: "LBR-302" manufactured by Kuraray Co., Ltd., molecular weight 5,500, Tg -85°C, viscosity 0.6 Pa.s (38°C) ・Polybutene: "HV-100" manufactured by JX Energy Corporation, molecular weight 980, kinematic viscosity 9,500 mm² / s (40°C) ・Butyl rubber: "Butyl 268" manufactured by JSR Corporation, rubbery (40°C) [Phosphoric acid-based inorganic compounds] ・Aluminum hydrogen phosphite (Hydrogen phosphite AL): "NSF" manufactured by Taihei Chemical Industry Co., Ltd. ・Disaluminum phosphate (Disaluminum phosphate AL): manufactured by Taihei Chemical Industry Co., Ltd. ・Sodium phosphite (Na phosphite): manufactured by Taihei Chemical Industry Co., Ltd. ・Ammonium polyphosphate (Polyphosphate NH4): SCM Industrial Chemical Co. , Ltd. , "HP-APP II" [Fibrous organic compounds] ・Pulp fibers, average fiber length 2 mm: "Neofiber NS-10" manufactured by Oji Seibutsu Co., Ltd. ・Polyarylate fibers: average fiber length 2 mm, "Vectran UM1580" manufactured by Kuraray Co., Ltd. ・Aramid fibers, average fiber lengths 0.25, 0.5, 3, 10, 12 mm: "Twaron Short Cut Fiber" manufactured by Teijin Limited [Thermal expandable compounds (other than phosphorus-based inorganic compounds)] (Thermal expandable layered inorganic compounds) ・Thermal expandable graphite: ADT501 (aspect ratio 25.2): "ADT501" manufactured by ADT, aspect ratio 25.2 (Thermal expandable non-layered organic compounds) ・Organic compound-based blowing agent (melamine): "Melamine" manufactured by Hayashi Pure Chemical Industries, Ltd. ・Organic compound-based blowing agent (azo compound): "Cellmic C-1" manufactured by Sankyo Kasei Co., Ltd. - Microspheres: "FN-180D" manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd. (thermally expandable non-layered inorganic compound) - Inorganic compound-based foaming agent (sodium bicarbonate): "Cellmicron 266" manufactured by Sankyo Chemical Co., Ltd.

[0067] 2. Evaluation The following measurements and evaluations were performed on the fire-resistant material compositions (test piece putty) of each example and comparative example. The results are shown in Tables 1 to 5.

[0068] <Processability (Softness)> The softness of the test putty was measured in accordance with JIS A5752 under a load of 150g and a temperature of 21°C. A specified cone was inserted perpendicularly into the test piece, and the penetration depth was measured in units of 0.1 mm. Based on the penetration depth, the processability was judged according to the following criteria: ◎: 60 [1 / 10 mm] or more ○: 50 [1 / 10 mm] or more, less than 60 [1 / 10 mm] △: 40 [1 / 10 mm] or more, less than 50 [1 / 10 mm] ×: Less than 40 [1 / 10 mm]

[0069] <Workability (Non-adhesion)> Latex rubber gloves were worn, and the weight of the material adhering to the gloves after squeezing 100g of test putty 10 times was measured. The weight of the material adhering was calculated based on the following formula. Based on the weight of the material adhering, non-adhesion was judged according to the following criteria. Note that lower non-adhesion indicates easier work. Weight of material adhering (g) = (Weight of gloves after squeezing putty 10 times) - (Weight of original gloves) ◎: Less than 0.2 [g] ○: 0.2 [g] or more, less than 0.4 [g] △: 0.4 [g] or more, less than 0.6 [g] ×: 0.6 [g] or more

[0070] <Shape Stability at High Temperatures> A 10g spherical test piece of putty was placed on an aluminum plate as defined by JIS H4000 (A1050P) and heated at 200°C for 60 minutes. After that, the test piece of putty was removed and the diameter of the mark left on the aluminum plate was measured. ◎: Mark 10mm or less 〇: Mark greater than 10mm but 15mm or less △: Mark greater than 15mm but 20mm or less ×: Mark greater than 20mm

[0071] <Thermal Expansion> A test piece of putty measuring 2 mm thick, 30 mm long, and 30 mm wide was heat-treated at 600°C for 0.5 hours, and its expansion ratio was measured. Specifically, the volume expansion ratio was calculated by dividing the volume after heat treatment by the volume before heat treatment, and the thermal expansion properties were judged according to the following criteria. Note that the volume was calculated by actually measuring the pressure, width, and length. ◎: Volume expansion ratio of 6 times or more ○: Volume expansion ratio of 4 times or more and less than 6 times △: Volume expansion ratio of 2 times or more and less than 4 times ×: Volume expansion ratio less than 2 times

[0072] <Shape Stability After Thermal Expansion> After evaluating the thermal expansion properties described above, a three-point bending test fixture (upper pressing tip R1 mm and width 80 mm, lower two-point support side R1 mm, width 80 mm, distance between supports 20 mm) was used to measure the strength (three-point bending fracture strength) of the thermally expanded test specimen when it was fractured under the condition of a compression rate of 50 mm / min. The shape retention after thermal expansion was then determined according to the following criteria: ◎: Three-point bending fracture strength of 15 [N] or more ○: Three-point bending fracture strength of 10 [N] or more and less than 15 [N] △: Three-point bending fracture strength of 5 [N] or more and less than 10 [N] ×: Three-point bending fracture strength less than 5 [N]

[0073] <Adhesion after thermal expansion> Using the test piece putty from the examples and comparative examples, a test piece measuring 30 mm in length, 30 mm in width, and 2 mm in thickness was prepared and placed on a calcium silicate board. This was then left in an atmosphere maintained at 600°C for 0.5 hours to allow thermal expansion. As shown in Figure 2, the surface of the calcium silicate board to which the sample was attached was fixed parallel to the vertical direction. The thermally expanded sample was then pressed against the boundary between the calcium silicate board and the expanded sample using the upper pressing jig (tip radius 1 mm and width 80 mm) of a three-point bending test jig at a speed of 50 mm / min, and the adhesion strength was measured when the thermally expanded sample was peeled off. Based on the adhesion strength, the adhesion after thermal expansion was judged according to the following criteria. If the thermally expanded sample fell before the upper pressing jig was pressed, the adhesion strength was set to 0.0 [N]. ◎: 1.5 [N] or more ○: 1.0 [N] or more, less than 1.5 [N] △: 0.5 [N] or more, less than 1.0 [N] ×: Less than 0.5 [N]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] 1: Components 3: Battery cell

Claims

1. A fire-resistant composition comprising a matrix polymer component and a phosphate-based inorganic compound, wherein the content of the phosphate-based inorganic compound is more than 120 parts by mass and 2000 parts by mass or less per 100 parts by mass of the matrix polymer component, the content of the thermally expandable layered inorganic compound is less than 10 parts by mass, and the content of the polyhydric alcohol compound having a molecular weight of 500 or less is less than 30 parts by mass, and the matrix polymer component comprises liquid rubber and a solid elastomer, with the mass ratio of the liquid rubber to the solid elastomer being 95:5 to 5:

95.

2. The fire-resistant material composition according to claim 1, comprising 1 to 30 parts by mass of a fibrous organic compound with respect to 100 parts by mass of the matrix polymer component.

3. The fire-resistant material composition according to claim 1, wherein the phosphate-based inorganic compound comprises at least one selected from aluminum hydrogen phosphite or disaluminum phosphate.

4. The fire-resistant material composition according to claim 1, wherein the content of the thermally expandable layered inorganic compound is less than 3 parts by mass.

5. The fire-resistant material composition according to claim 1, wherein the content of the thermally expandable layered inorganic compound is 0 parts by mass.

6. The fire-resistant material composition according to claim 1, wherein the content of the phosphoric acid-based inorganic compound is 220 to 1500 parts by mass.

7. The fire-resistant material composition according to claim 1, wherein the content of the phosphoric acid-based inorganic compound is 360 to 1,000 parts by mass.

8. A member comprising the fire-resistant material composition according to any one of claims 1 to 7.

9. The member according to claim 8, used for closing the gap in a penetration.

10. The component according to claim 8, used in a battery.

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