Fire-resistant urethane foam composition, method for producing fire-resistant urethane foam composition, and fire-resistant urethane foam joint material

Abstract

Provided are a fire-resistant urethane foam composition having excellent flexibility and flame retardancy, a method for producing said fire-resistant urethane foam composition, and a fire-resistant urethane foam joint material made from said fire-resistant urethane foam composition. According to the present invention, there is provided a fire-resistant urethane foam composition comprising 10 to 400 parts by mass of a radical generator based on 100 parts by mass of a urethane compound.

Description

[Technical field]

[0001] The present invention relates to a fire-resistant urethane foam composition, a method for producing the fire-resistant urethane foam composition, and a fire-resistant urethane foam joint material. The fire-resistant urethane foam joint material is used, for example, in a part or all of a gap of a penetration opening provided in a fire compartment, or between a seismic isolation device and a fire-resistant panel of a building, or at the end of the fire-resistant panel. [Background technology]

[0002] Fire-resistant polyurethane foam, which takes advantage of its flexibility, has come to be used as a joint material between fire walls and cables such as power cables and communication cables that pass through fire compartments, or between pipes for air conditioning equipment, etc.

[0003] A method for producing a fire-resistant urethane foam with excellent flame retardancy has been disclosed in which a phosphorus compound or a bromine compound is blended with a flame retardant (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2023-109641 [Patent Document 2] Patent Publication No. 2023-121573 Summary of the Invention [Problem to be solved by the invention]

[0005] However, these techniques did not provide sufficient flame retardancy. The present invention provides a fire-resistant urethane foam composition having excellent flexibility and flame retardancy, a method for producing the fire-resistant urethane foam composition, and a fire-resistant urethane foam joint material made from the fire-resistant urethane foam composition. [Means for solving the problem]

[0006] As a result of extensive investigations, the inventors have discovered that the above problems can be solved by preparing a fire-resistant urethane foam composition having a specific composition, and have thus completed the present invention.

[0007] That is, according to the present invention, the following inventions are provided. [1] A fire-resistant urethane foam composition comprising 10 to 400 parts by mass of a radical generator per 100 parts by mass of a urethane compound. [2] The fire-resistant urethane foam composition according to [1], wherein the urethane compound contains a urethane prepolymer or contains a structure derived from a urethane prepolymer. [3] The fire-resistant urethane foam composition according to [1] or [2], wherein the radical generator comprises a carbonate. [4] A fireproof urethane foam joint material, which is a fireproof joint material using the fireproof urethane foam composition described in any one of [1] to [3]. Effect of the Invention

[0008] According to the present invention, a fire-resistant urethane foam composition having excellent flame retardancy, a method for producing said fire-resistant urethane foam composition, and a fire-resistant urethane foam joint material made from said fire-resistant urethane foam composition are obtained. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, embodiments of the present invention will be described. Various features shown in the following embodiments can be combined with each other. Also, each feature can be an invention independently.

[0010] 1. Composition of fire-resistant urethane foam A fire-resistant urethane foam composition according to one embodiment of the present invention (hereinafter also simply referred to as a "urethane foam composition") contains a urethane compound and a radical generator.

[0011] <Urethane compounds> The urethane compound is a compound having a urethane bond. The urethane compound preferably forms a urethane foam (foamed material). The urethane foam can be obtained, for example, by reacting a urethane raw material with a foaming agent. For example, carbon dioxide is generated by reacting the isocyanate group of the urethane raw material with water, and the urethane foam is obtained as a result of foaming. The urethane foam preferably has an expansion ratio of 2 to 20 times and a density of 120 to 500 kg / m. 3 It is.

[0012] The urethane raw material includes an isocyanate compound. The urethane compound includes an isocyanate compound or includes a structure derived from an isocyanate compound. The urethane compound preferably includes a urethane prepolymer or includes a structure derived from a urethane prepolymer.

[0013] The fire-resistant urethane foam composition may contain 20 to 91% by mass of a urethane compound, preferably 25 to 71% by mass, and more preferably 33 to 59% by mass. When the content of the urethane compound satisfies such a range, the composition has a suitable softness as a urethane foam, while retarding flame retardancy. The content of the urethane compound is, for example, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 91% by mass, and may be within a range between any two of the values ​​exemplified here.

[0014] <Isocyanate compounds> The isocyanate compound is, for example, a compound having two or more isocyanate groups. The isocyanate compound includes at least one selected from the group consisting of a polyisocyanate having two or more isocyanate groups, and a compound (urethane prepolymer) which is a polymer obtained by reacting a polyol with an excess of polyisocyanate and has an isocyanate group at the molecular end.

[0015] The urethane raw material may contain a polyol in addition to the isocyanate compound. The urethane raw material may contain, for example, a polyisocyanate and a polyol. When the urethane raw material contains a plurality of components, some or all of the components may be mixed in the reaction system.

[0016] When polyisocyanate and polyol are added as urethane raw materials, for example, 10 to 200 parts by mass of polyol can be added relative to 100 parts by mass of polyisocyanate, and it is preferable to add 50 to 150 parts by mass of polyol. The amount of polyol added is specifically, for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, or 200 parts by mass relative to 100 parts by mass of polyisocyanate, and may be within a range between any two of the numerical values ​​exemplified here.

[0017] <Polyisocyanate> Examples of the polyisocyanate include aromatic isocyanates, alicyclic isocyanates, and aliphatic isocyanates.

[0018] Examples of aromatic isocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

[0019] Examples of the alicyclic isocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0020] Examples of the aliphatic isocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0021] The polyisocyanates may be used alone or in combination.

[0022] <Urethane prepolymer> The urethane prepolymer is a polymer obtained by reacting a polyol with an excess of polyisocyanate, and is a compound having an isocyanate group at the molecular end.

[0023] <Polyol> Examples of the polyol include polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polymer polyol, and polyether polyol.

[0024] Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.

[0025] Examples of polycarbonate polyols include polyols obtained by dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with diethylene carbonate, dipropylene carbonate, and the like.

[0026] Examples of aromatic polyols include bisphenol A, bisphenol F, phenol novolac, and cresol novolac.

[0027] Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.

[0028] Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

[0029] Examples of polyester polyols include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, and condensates of hydroxycarboxylic acids and the above-mentioned polyhydric alcohols.

[0030] Examples of polymer polyols include polymers obtained by graft polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, or methacrylate with an aromatic polyol, an alicyclic polyol, an aliphatic polyol, or a polyester polyol; polybutadiene polyol; modified polyols of polyhydric alcohols; and hydrogenated products thereof.

[0031] Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one alkylene oxide, such as ethylene oxide, propylene oxide, or tetrahydrofuran, in the presence of at least one low-molecular-weight active hydrogen compound having two or more active hydrogens.

[0032] The polyols may be used alone or in combination of two or more.

[0033] <Foaming agent> The foaming agent promotes foaming of the urethane. Examples of the foaming agent include hydrofluoroolefins having 3 or 4 carbon atoms, such as trans-1-chloro-3,3,3-trifluoropropene, and water. Among these, water, in which sodium silicate is easily dissolved, is preferred.

[0034] <Radical generator> The radical generator is a component for generating an aerosol (radicals) by thermal energy generated by the combustion of a urethane compound, etc. Examples of the radical generator include potassium salt-based radical generators and sodium salt-based radical generators.

[0035] 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.

[0036] Examples of the sodium salt radical generator include sodium acetate, sodium citrate, and sodium bicarbonate.

[0037] Among these, from the viewpoint of flame retardancy, carbonates such as potassium hydrogen carbonate, potassium carbonate, sodium hydrogen carbonate, etc. are preferred. These radical generators may be used alone or in combination of two or more.

[0038] The content of the radical generator is 10 to 400 parts by mass, preferably 40 to 300 parts by mass, and more preferably 70 to 200 parts by mass, relative to 100 parts by mass of the urethane 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 hardness of the urethane foam is high. The content of the radical generator is specifically, for example, 10, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, or 400 parts by mass relative to 100 parts by mass of the urethane compound, and may be within a range between any two of the numerical values ​​exemplified here.

[0039] The fire-resistant urethane foam composition may also contain other additives as necessary within the range that does not impair the properties, such as inorganic compounds other than radical generators, surfactants, foam stabilizers, catalysts, blowing agents, flame retardants, stabilizers, UV absorbers, antioxidants, pigments, etc.

[0040] 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.

[0041] The content of the inorganic compound other than the radical generator is 0 to 400 parts by mass, preferably 0 to 200 parts by mass, and more preferably 0 to 100 parts by mass, relative to 100 parts by mass of the urethane compound.

[0042] <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.

[0043] <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.

[0044] 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.

[0045] Examples of the phosphite compounds include aluminum phosphite, aluminum hydrogen phosphite, sodium phosphite, potassium phosphite, calcium phosphite, and zinc phosphite.

[0046] Examples of hypophosphite compounds include aluminum hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, and zinc hypophosphite.

[0047] Examples of metaphosphate compounds include aluminum metaphosphate, sodium metaphosphate, potassium metaphosphate, calcium metaphosphate, zinc metaphosphate, and sodium hexametaphosphate.

[0048] An example of the pyrophosphate compound is sodium pyrophosphate.

[0049] Examples of the polyphosphate compounds include ammonium polyphosphate, melamine-modified ammonium polyphosphate, sodium tripolyphosphate, sodium pentapolyphosphate, sodium tetrapolyphosphate, and potassium tripolyphosphate.

[0050] From the viewpoint of shape stability at high temperatures, the phosphoric acid-based inorganic compound is preferably aluminum hydrogen phosphite, ammonium polyphosphate, or the like.

[0051] The content of the phosphoric acid-based inorganic compound is preferably 5 to 140 parts by mass per 100 parts by mass of the urethane compound. By being in this range, the shape of the urethane compound does not collapse even at high temperatures, and flame retardancy can be achieved at the same time.

[0052] In addition, the inorganic compound other than the radical generator preferably contains a metal hydroxide, which can enhance flame retardancy.

[0053] <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.

[0054] The content of the thermally expandable graphite is, for example, 3 to 100 parts by mass, preferably 5 to 75 parts by mass, and more preferably 10 to 50 parts by mass, relative to 100 parts by mass of the urethane compound. When the content is within this range, the penetration part can be blocked even if the fire-resistant urethane composition burns.

[0055] <Characteristics of fire-resistant urethane foam composition> The fire-resistant urethane foam composition has a Shore E hardness measured in accordance with JIS K6253 under a load of 1 kg at 21° C. of preferably less than 25, more preferably less than 20, and even more preferably less than 15. The lower limit of the Shore E hardness is not particularly limited, but is, for example, 1 or more.

[0056] <Manufacturing method> A method for producing a fire-resistant urethane foam composition according to one embodiment of the present invention includes, for example, a blending step of blending a urethane raw material containing an isocyanate compound into a mixture (for example, a mixed liquid such as an aqueous solution) containing a radical generator and a blowing agent. In the blending step, foam molding is performed by blending accompanied by addition, stirring, etc. The content of the blowing agent (for example, water) contained in the mixture is preferably 10 parts by mass or more, more preferably 50 to 500 parts by mass, and even more preferably 80 to 200 parts by mass, relative to 100 parts by mass of the isocyanate compound. The mixture containing the radical generator and the blowing agent may contain other additives such as inorganic compounds other than the radical generator.

[0057] Furthermore, when water is used as a blowing agent, the method for producing a fire-resistant urethane foam composition may include a drying step of drying the urethane foam composition (foam) after expansion molding. The drying step may be carried out at a temperature of, for example, 50 to 100°C (80°C in one example).

[0058] 2. Fire-resistant urethane foam joint material The fireproof urethane foam joint material according to one embodiment of the present invention is a fireproof joint material using the above-mentioned urethane foam composition. The fireproof urethane foam joint material can be composed of the above-mentioned urethane foam composition. The fireproof urethane foam joint material can be used in various fields that require properties such as elasticity, flexibility, heat insulation, fire resistance, vibration damping, and sound insulation, but can also be applied to known construction methods that use fireproof materials, and can be used according to the usage method in each construction method. There is no particular restriction on the area of ​​use, and it can be used widely in places where fireproofing is required.

[0059] The fireproof urethane foam joint material is used to block a part or all of the gaps of the penetration openings provided in the fireproof partition. It is also suitable for use in the fireproof portion of the seismic isolation device of a building. Specifically, the gaps between the fireproof wall and the power cable, communication cable, pipe, etc. passing through the penetration openings provided in the fireproof partition such as a fireproof wall or floor slab can be covered with the fireproof joint material of the present invention, or a gasket molded into a shape suitable for the construction part can be attached and used. The fireproof joint material of the present invention can also be used between the seismic isolation device body and the fireproof panel covering it, or at the end of the fireproof panel, and can be used by attaching it with an adhesive or adhesive, or by fixing it with a bolt or nail. EXAMPLES

[0060] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following description, parts and percentages are based on mass.

[0061] <Preparation of fire-resistant urethane foam composition> (A: When polyisocyanate is used as the isocyanate compound [Examples 1 to 2]) A radical generator mixed aqueous solution was prepared by mixing water (foaming agent) with the radical generator in the amounts shown in the table. Polyisocyanate and polyol were added to this aqueous solution, stirred, and poured into a cylindrical mold with a diameter of 10 cm and a height of 15 cm to foam mold, and the mixture was left to stand together with the mold in an oven at 80°C for three days to evaporate the water and obtain a sample raw material of a urethane foam composition. The amount of water was 100 parts by mass per 50 parts by mass of polyisocyanate.

[0062] (B: When a urethane prepolymer was used as the isocyanate compound [Examples 3 to 12, Comparative Examples 1 to 4]) A radical generator mixed aqueous solution or a flame retardant mixed aqueous solution was prepared by mixing water (foaming agent) with a radical generator or flame retardant in the amounts shown in the table. The urethane prepolymer was added to this aqueous solution, stirred, and poured into a cylindrical mold with a diameter of 10 cm and a height of 15 cm to foam mold, and the mixture was left to stand together with the mold in an oven at 80°C for three days to evaporate the water and obtain a sample raw material of the urethane foam composition. The amount of water was 200 parts by mass per 100 parts by mass of the urethane prepolymer.

[0063] The materials used in the examples and comparative examples are shown below.

[0064] <Polyisocyanate> Toluene-2,4-diisocyanate: "Cosmonate T100" manufactured by Mitsui Chemicals, Inc. Bis(4-isocyanatophenyl)methane: "Cosmonate PH" manufactured by Mitsui Chemicals, Inc.

[0065] <Polyol> Polyether polyol: Sannix FA-195 manufactured by Sanyo Chemical Industries, Ltd.

[0066] <Urethane prepolymer> Polyether type: "Hyprene EGH-401" manufactured by Mitsui Chemicals, Inc.

[0067] <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.

[0068] <Flame retardants> Phosphate ester flame retardant Tris(β-chloropropyl)phosphate: "TMCPP" manufactured by Daihachi Chemical Industry Co., Ltd. Brominated flame retardant: Tetrabromobisphenol A bis(2,3-dibromo 2-methylpropyl) ether: "Pyroguard SR-130" manufactured by Daiichi Pharmaceutical Co., Ltd.

[0069] <Foaming agent> ·water

[0070] In the examples and comparative examples, the following properties were evaluated and are summarized in Table 1. The measurement method for each property is shown below.

[0071] <Hardness> The original samples of the examples and comparative examples were cut into test pieces measuring 30 mm in length × 30 mm in width × 10 mm in thickness, and the Shore E hardness of the 30 mm in length × 30 mm in width surface was measured under a load of 1 kg in an environment of 21° C. according to JIS K6253. Then, based on the measured values, the hardness was evaluated according to the following criteria. [Evaluation Criteria] ⊚: Shore E hardness is less than 15. ◯: Shore E hardness is 15 or more and less than 20. △: Shore E hardness is 20 or more and less than 25. ×: Shore E hardness is 25 or more.

[0072] <Flame retardancy> The sample raw materials of the examples and comparative examples were cut into test pieces measuring 30 mm in length × 30 mm in width × 10 mm in thickness, which were left in an atmosphere maintained at 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 ×: Time to ignition is less than 30 seconds

[0073] [Table 1]

[0074] [Table 2]

Claims

1. containing 40 to 400 parts by mass of a radical generator relative to 100 parts by mass of a urethane compound, the radical generator includes at least one of a potassium salt-based radical generator and a sodium salt-based radical generator, The fire-resistant urethane foam composition, wherein the potassium salt-based radical generator and the sodium salt-based radical generator are carbonates.

2. 2. The fire resistant urethane foam composition of claim 1, wherein the urethane compound comprises a urethane prepolymer or comprises a structure derived from a urethane prepolymer.

3. A fireproof joint material, which is a fireproof joint material using the fireproof urethane foam composition according to claim 1 or 2.

Images