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

Abstract

To provide a fire-resistant urethane foam composition having superior flexibility and flame retardancy, a method for producing the fire-resistant urethane foam composition, and a fire-resistant urethane foam joint filler composed of the fire-resistant urethane foam composition.SOLUTION: The present invention provides a fire-resistant urethane foam composition comprising 10 to 400 pts.mass of a radical generator based on 100 pts.mass of an urethane compound.SELECTED DRAWING: None

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, for part or all of the gaps of through-holes 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 Art

[0002] Fire-resistant urethane foam that takes advantage of flexibility has been used as a joint material between cables such as power cables and communication cables passing through a fire compartment and a fire wall, and piping such as air-conditioning equipment.

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

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, the flame retardancy of these technologies was not sufficient. 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 using the fire-resistant urethane foam composition.

Means for Solving the Problems

[0006] As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by using a refractory urethane foam composition having a specific composition, and have completed the present invention.

[0007] That is, according to the present invention, the following inventions are provided. [1] A refractory urethane foam composition containing 10 to 400 parts by mass of a radical generator with respect to 100 parts by mass of a urethane compound. [2] The refractory 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 refractory urethane foam composition according to [1] or [2], wherein the radical generator contains a carbonate. [4] A refractory urethane foam joint material which is a fireproof joint material using the refractory urethane foam composition according to any one of [1] to [3].

Effect of the Invention

[0008] According to the present invention, a refractory urethane foam composition excellent in flame retardancy, a method for producing the refractory urethane foam composition, and a refractory urethane foam joint material using the refractory urethane foam composition can be obtained.

Modes for Carrying Out the Invention

[0009] Hereinafter, embodiments of the present invention will be described. Various characteristic matters shown in the following embodiments can be combined with each other. Further, an invention can be established independently for each characteristic matter.

[0010] 1. Composition of Refractory Urethane Foam The refractory urethane foam composition according to one embodiment of the present invention (hereinafter, also simply referred to as "urethane foam composition") contains a urethane compound and a radical generator.

[0011] <Urethane Compound> A urethane compound is a compound having a urethane bond. The urethane compound preferably forms a urethane foam. 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 the reaction of the isocyanate group of the urethane raw material with water, and as a result of foaming, a urethane foam is obtained. The urethane foam preferably has a foaming ratio of 2 to 20 times and a density of 120 to 500 kg / m 3 is.

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

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

[0014] <Isocyanate compound> The isocyanate compound is, for example, a compound having two or more isocyanate groups. The isocyanate compound contains one or more selected from the group consisting of polyisocyanates having two or more isocyanate groups and polymers obtained by reacting a polyol with an excess of polyisocyanate and having an isocyanate group at the molecular end (urethane prepolymers).

[0015] The urethane raw material may contain a polyol in addition to the isocyanate compound. The urethane raw material can include, 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 a polyisocyanate and a polyol are added as the urethane raw material, for example, 10 to 200 parts by mass of the polyol can be added per 100 parts by mass of the polyisocyanate, and it is preferable to add 50 to 150 parts by mass of the polyol. Specifically, the addition amount of the polyol is, for example, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200 parts by mass per 100 parts by mass of the polyisocyanate, and it may be within the range between any two of the values exemplified here.

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

[0018] Examples of the aromatic isocyanate include phenylenediisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like.

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

[0020] Examples of aliphatic isocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, etc.

[0021] One or more polyisocyanates can be used.

[0022] <Urethane prepolymer> A 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 polyols include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, polyether polyols, etc.

[0024] Examples of polylactone polyols include polypropylene lactone glycol, polycaprolactone glycol, polyvalerolactone glycol, etc.

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

[0026] Examples of aromatic polyols include bisphenol A, bisphenol F, phenol novolak, cresol novolak, etc.

[0027] Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanedio, dimethyldicyclohexylmethanedio, and the like.

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

[0029] Examples of the polyester polyol 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 polyhydric alcohols.

[0030] Examples of the polymer polyol include polymers obtained by graft polymerization of ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate to aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, etc., polybutadiene polyols, modified polyols of polyhydric alcohols, or hydrogenated products thereof.

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

[0032] One kind or two or more kinds of polyols can be used.

[0033] <Foaming agent> The foaming agent promotes the foaming of 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 preferable.

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

[0035] Examples of the potassium salt-based radical generator include potassium acetate, potassium propionate, monopotassium citrate, dipotassium citrate, tripotassium citrate, monopotassium trihydrogen ethylenediaminetetraacetate, dipotassium dihydrogen ethylenediaminetetraacetate, tripotassium monohydrogen ethylenediaminetetraacetate, potassium ethylenediaminetetraacetate, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate, potassium hydrogen carbonate, potassium carbonate, etc.

[0036] Examples of the sodium salt-based radical generator include sodium acetate, sodium citrate, and sodium hydrogen carbonate.

[0037] Among these, from the viewpoint of flame retardancy, carbonates such as potassium hydrogen carbonate, potassium carbonate, and sodium hydrogen carbonate 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 with respect to 100 parts by mass of the urethane compound, preferably 40 to 300 parts by mass, and more preferably 70 to 200 parts by mass. If the content of the radical generator is too small, the flame retardancy deteriorates. If the content of the radical generator is too large, the hardness of the urethane foam becomes hard. The content of the radical generator is, specifically, for example, 10, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400 parts by mass with respect to 100 parts by mass of the urethane compound, and may be within the range between any two of the values exemplified here.

[0039] The refractory urethane foam composition can be blended with other additives as necessary, as long as its properties are not impaired. For example, inorganic compounds other than radical generators, surfactants, foam stabilizers, catalysts, blowing agents, flame retardants, stabilizers, ultraviolet absorbers, antioxidants, pigments, etc.

[0040] Examples of inorganic compounds other than radical generators include metal oxides such as alumina, aluminosilicate, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, etc.; metal hydroxides such as aluminum hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, etc.; smectite-based clays such as bentonite, montmorillonite, hectorite, fibrous clays such as palygorskite, sericite (sericite), illite, glauconite (glauconite), chlorite (chlorite), talc (talc), zeolite (zeolite), beidellite, nontronite, saponite, hectorite, sauconite, stevensite, cristobalite, smectite, kaolin, hydrotalcite, etc. Clay minerals; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, barium carbonate, etc.; fibrous inorganic compounds such as glass fibers (E glass fibers, C glass fibers, S glass fibers, D glass fibers), rock wool, ceramic fibers (silica alumina fibers, alumina fibers, silica fibers), zirconia fibers, carbon fibers, bulk alkaline earth silicate fibers, gypsum fibers, carbon fibers, metal fibers, slag fibers, basalt fibers, etc.; calcium salts such as calcium sulfate, 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, pearlite, pumice, diatomaceous earth, dehydrated sludge, boron, sodium tetraborate hydrate (borax), silica, titanium oxide, inorganic oxidants, phosphate-based 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 with respect to 100 parts by mass of the urethane compound.

[0042] <Inorganic oxidizing agent> 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 kind may be used alone, or two or more kinds may be used in combination.

[0043] <Phosphoric acid-based inorganic compound> The phosphoric acid-based inorganic compound includes, in addition to the phosphoric acid-based compound, phosphorous acid-based compounds, hypophosphorous acid-based compounds, metaphosphoric acid-based compounds, pyrophosphoric acid-based compounds, and polyphosphoric acid-based compounds.

[0044] Examples of the phosphoric acid-based compound include aluminum monophosphate, sodium monophosphate, potassium monophosphate, calcium monophosphate, zinc monophosphate, aluminum diphosphate, sodium diphosphate, potassium diphosphate, calcium diphosphate, zinc diphosphate, aluminum triphosphate, sodium triphosphate, potassium triphosphate, calcium triphosphate, zinc triphosphate, magnesium triphosphate, ammonium monophosphate, diammonium phosphate, tricalcium phosphate, and aluminum phosphate.

[0045] Examples of the phosphorous acid-based compound include aluminum phosphite, aluminum hydrogen phosphite, sodium phosphite, potassium phosphite, calcium phosphite, and zinc phosphite.

[0046] Examples of the hypophosphorous acid-based compound include aluminum hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, and zinc hypophosphite.

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

[0048] Examples of the pyrophosphate compounds include sodium pyrophosphate.

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

[0050] From the viewpoint of shape stability at high temperatures, aluminum hydrogen phosphite, ammonium polyphosphate and the like are preferable as the phosphoric acid-based inorganic compounds.

[0051] The content of the phosphoric acid-based inorganic compound is preferably 5 to 140 parts by mass with respect to 100 parts by mass of the urethane compound. When it is within this range, the shape of the urethane compound does not collapse even at high temperatures, and both flame retardancy can be achieved.

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

[0053] <Thermally expandable graphite> Thermally expandable graphite is a crystal compound obtained by subjecting graphite powder such as natural graphite and pyrolytic graphite to surface treatment using an inorganic acid such as sulfuric acid and nitric acid and a strong oxidizing agent such as concentrated nitric acid and permanganate, and maintaining the graphite layered structure. When these are exposed to a temperature equal to or higher than the expansion start temperature (about 200 ° C) under normal pressure, they thermally expand by 100 times or more. The graphite powder such as the natural graphite and pyrolytic graphite may be one that has been subjected to deacidification treatment or further neutralization treatment.

[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 with respect to 100 parts by mass of the urethane compound. By being within this range, the fire-resistant urethane composition can block the through-holes even when it burns.

[0055] <Properties of the fire-resistant urethane foam composition> The shore E hardness of the fire-resistant urethane foam composition measured in accordance with JIS K6253 under the environment of 1 kg in weight and 21 °C is 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> The manufacturing method of the fire-resistant urethane foam composition according to an embodiment of the present invention includes, for example, a compounding step of compounding a urethane raw material containing an isocyanate compound into a mixture (for example, a mixed solution such as an aqueous solution) containing a radical generator and a foaming agent. In the compounding step, foam molding is performed by compounding accompanied by addition, stirring, etc. In addition, with respect to 100 parts by mass of the isocyanate compound, the content of the foaming 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. The mixture containing the radical generator and the foaming agent may contain other additives such as inorganic compounds other than the radical generator.

[0057] In addition, the manufacturing method of the fire-resistant urethane foam composition can include a drying step of drying the urethane foam composition (foam) after foam molding when water is used as the foaming agent. The drying step can be performed, for example, at 50 to 100 °C (80 °C in one example).

[0058] 2. Fire-resistant urethane foam joint material The fire-resistant urethane foam joint material according to an embodiment of the present invention is a fireproof joint material using the above urethane foam composition. The fire-resistant urethane foam joint material can be composed of the above urethane foam composition. The fire-resistant urethane foam joint material can be used in various fields where characteristics such as its elasticity, flexibility, heat insulation, fire resistance, vibration damping, and sound insulation are required, and can also be applied to known construction methods using fireproof materials, and can be used according to the usage methods in each construction method. The use part is not particularly limited, and it can be widely used in places where fire resistance is required.

[0059] The fire-resistant urethane foam joint material is used to block part or all of the gaps of the through-holes provided in the fire compartment. It is also preferably used in the fireproof parts of the seismic isolation devices of buildings. Specifically, the gaps between the power cables, communication cables, pipes, etc. passing through the through-holes provided in the fire compartment such as firewalls and floor slabs and the firewalls can be covered with the fireproof joint material of the present invention, or gaskets formed into shapes suitable for the construction parts can be installed and used. In addition, this fireproof joint material is used between the seismic isolation device main body and the fireproof panel covering it or at the end of the fireproof panel, and is used by pasting it with an adhesive or an adhesive, or fixing it with bolts or nails.

Examples

[0060] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but these Examples do not limit the present invention. In the following description, parts and % are based on mass standards.

[0061] <Preparation of fire-resistant urethane foam composition> (A: When polyisocyanate is used as the isocyanate compound [Examples 1 to 2]) Using the compounding amounts shown in the table, water (foaming agent) was compounded into the radical generator to prepare a mixed aqueous solution of the radical generator. Polyisocyanate and polyol were added to this aqueous solution and stirred, then injected into a cylindrical mold with a diameter of 10 cm and a height of 15 cm for foam molding. By leaving it to stand in an oven at 80 °C for 3 days together with the mold, the water was evaporated to obtain a sample prototype of the urethane foam composition. The amount of water was 100 parts by mass with respect to 50 parts by mass of polyisocyanate.

[0062] (B: When using a urethane prepolymer as the isocyanate compound [Examples 3 to 12, Comparative Examples 1 to 4]) Using the compounding amounts shown in the table, water (foaming agent) was compounded into the radical generator or the flame retardant to prepare a mixed aqueous solution of the radical generator or a mixed aqueous solution of the flame retardant. Urethane prepolymer was added to this aqueous solution and stirred, then injected into a cylindrical mold with a diameter of 10 cm and a height of 15 cm for foam molding. By leaving it to stand in an oven at 80 °C for 3 days together with the mold, the water was evaporated to obtain a sample prototype of the urethane foam composition. The amount of water was 200 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

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

[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: "Sun Nix FA-195" manufactured by Sanyo Chemical Industries, Ltd.

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

[0067] <Radical generator> · Potassium hydrogen carbonate: manufactured by Hayashi Junyaku Kogyo Co., Ltd. · Potassium carbonate: manufactured by Hayashi Junyaku Kogyo Co., Ltd. · Sodium hydrogen carbonate: manufactured by Hayashi Junyaku Kogyo Co., Ltd. · Tripotassium citrate: manufactured by Fuso Chemical Industry Co., Ltd.

[0068] <Flame retardant> · Phosphate ester flame retardant tris(β-chloropropyl) phosphate: "TMCPP" manufactured by Daihachi Chemical Industry Co., Ltd. · Bromine-based flame retardant tetrabromobisphenol A bis(2,3-dibromo-2-methylpropyl) ether: "Pirogard SR-130" manufactured by Daiichi Pharmaceutical Co., Ltd.

[0069] <Blowing agent> · Water

[0070] In the examples and comparative examples, the following characteristics were evaluated and summarized in a table. The measurement methods for each characteristic are shown below.

[0071] <Hardness> The original samples of the examples and comparative examples were made into test pieces with a length of 30 mm × width of 30 mm × thickness of 10 mm. The surface with a length of 30 mm × width of 30 mm was measured according to JIS K6253 at 21°C for the Shore E hardness with a load of 1 kg. Then, based on the measured values, the hardness was determined according to the following evaluation 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] <Flammability> The original samples of the examples and comparative examples were made into test pieces with a length of 30 mm × width of 30 mm × thickness of 10 mm. These were placed in an atmosphere maintained at 700°C, and the time until ignition was visually observed. ◎: Time until ignition is 5 minutes or more 〇: Time until ignition is 1 minute or more and less than 5 minutes △: Time to ignition is 30 seconds or more and less than 1 minute ×: Time to ignition is less than 30 seconds

[0073]

Table 1

[0074]

Table 2

Claims

1. A fire-resistant urethane foam composition comprising 10 to 400 parts by mass of a radical generator with respect to 100 parts by mass of a urethane compound.

2. The fire-resistant urethane foam composition according to Claim 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 Claim 1, wherein the radical generator contains a carbonate.

4. A fire-resistant urethane foam joint material, which is a fireproof joint material using the fire-resistant urethane foam composition according to any one of Claims 1 to 3.

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