Foamed urethane resin composition

Abstract

To provide a foamable urethane resin composition that allows production of a polyurethane foam having resistance to burning and spreading.SOLUTION: A foamable urethane resin composition contains a polyol compound and a polyisocyanate compound. A polyurethane foam composed of the foamable urethane resin composition has an oxygen index of 26 or more as measured by JIS K 7201-2.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a foamed urethane resin composition. [Background technology]

[0002] Polyurethane foam is used in practical applications for insulation and condensation prevention in ceilings, roofs, and walls of buildings such as apartment buildings, detached houses, and commercial buildings, taking advantage of its excellent heat insulation properties. Although polyurethane foam is lightweight, it is flammable because it is an organic material. To improve this, polyurethane foam with enhanced flame retardancy is used by incorporating flame retardants into the foam. For example, Patent Document 1 describes a flame-retardant polyurethane foam obtained using ammonium polyphosphate, a urea derivative, a polyol, and an isocyanate, characterized in that the flame-retardant polyurethane foam is obtained by using ammonium polyphosphate in the range of 5 to 150 parts by weight and a urea derivative in the range of 0.001 to 15 parts by weight per 100 parts by weight of polyol. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2015-151524 [Overview of the project] [Problems that the invention aims to solve]

[0004] In recent years, there have been a relatively large number of reports of fires caused by polyurethane foam used as insulation in buildings. To address this problem, there is a need for the development of polyurethane foam that not only possesses excellent flame retardancy but also has properties that prevent the spread of fire once it starts. Therefore, the object of the present invention is to provide a foamable urethane resin composition that can produce a polyurethane foam that is resistant to flame spread. [Means for solving the problem]

[0005] As a result of diligent research, the inventors have found that the above problems can be solved by a foamable urethane resin composition containing a polyol compound and a polyisocyanate compound, wherein the oxygen index of the polyurethane foam made from the foamable urethane resin composition, as measured according to JIS K 7201-2, is 26 or higher, and have completed the present invention. That is, the present invention provides the following [1] to

[13] . [1] A foamed urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant, a blowing agent, and a catalyst, A foamable urethane resin composition wherein the oxygen index of the polyurethane foam made from the foamable urethane resin composition is 26 or higher, as measured in accordance with JIS K 7201-2. [2] The polyurethane foam made from the foaming urethane resin composition was subjected to a test in accordance with the ISO-5660 test method, with a radiant thermal intensity of 50 kW / m². 2 The total heat output when heated for 5 minutes was 8 MJ / m². 2 The foamed urethane resin composition described in [1] is as follows: [3] The polyurethane foam made from the foaming urethane resin composition was subjected to a test in accordance with the ISO-5660 test method, with a radiant thermal intensity of 50 kW / m². 2 The maximum heating rate when heated for 5 minutes was 150 kW / m². 2 The foamed urethane resin composition described in [1] or [2] below. [4] The foamed urethane resin composition according to any one of [1] to [3], wherein the chlorine concentration of the polyurethane foam made from the foamed urethane resin composition is 2.0% or more. [5] A foaming urethane resin composition according to any one of [1] to [4], wherein the isocyanate index is 200 to 700. [6] The foamed urethane resin composition according to any one of [1] to [5], wherein the polyol compound comprises a phthalic acid-based polyester polyol. [7] The expandable urethane resin composition according to any one of [1] to [6], wherein the total content of the flame retardant is 20 to 120 parts by mass based on 100 parts by mass of the polyol compound. [8] The expandable urethane resin composition according to any one of [1] to [7], wherein the flame retardant contains a liquid phosphate ester-based flame retardant. [9] The expandable urethane resin composition according to any one of [1] to [8], wherein the blowing agent contains a hydrofluoroolefin.

[10] The expandable urethane resin composition according to any one of [1] to [9], wherein the expandable urethane resin composition contains substantially no inorganic filler.

[11] The expandable urethane resin composition according to any one of [1] to

[10] , wherein the catalyst contains a trimerization catalyst.

[12] The expandable urethane resin composition according to any one of [1] to

[11] , wherein the catalyst contains a urethanization catalyst, the urethanization catalyst contains a bismuth compound, and the content of the bismuth compound is 0.1 parts by mass or more based on 100 parts by mass of the polyol compound.

[13] The expandable urethane resin composition according to any one of [1] to

[12] , which is used for spraying applications.

Effects of the Invention

[0006] According to the present invention, it is possible to provide an expandable urethane resin composition capable of producing a polyurethane foam having a property of being less likely to spread fire.

Modes for Carrying Out the Invention

[0007] [Expandable Urethane Resin Composition] The expandable urethane resin composition of the present invention is an expandable urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant, a blowing agent, and a catalyst.

[0008] (Oxygen Index) The polyurethane foam composed of the foamable urethane resin composition of the present invention has an oxygen index of 26 or more as measured in accordance with JIS K 7201-2. If the aforementioned numerical value is less than 26, the flame retardancy of the polyurethane foam will deteriorate, for example, when a fire occurs, flames tend to spread more easily, and combustion tends to continue more readily. From the viewpoint of suppressing flame spread, the oxygen index is more preferably 27 or more, and even more preferably 28 or more. The upper limit of the oxygen index is not particularly limited, but practically, it is preferably 40, for example. The oxygen index of the foam is adjusted by a combination of the type or composition of the polyol compound, the type or composition of the blowing agent, the type, composition and amount of the flame retardant, and the like. For example, the lower the content of flammable blowing agent in the blowing agent, the higher the oxygen index. In addition, the oxygen index can be increased by adding a flame retardant, particularly a phosphorus-based flame retardant having a chlorine atom or the like. In addition, the higher the density of the foam, and the higher the isocyanate index, the higher the oxygen index tends to be.

[0009] The oxygen index refers to the minimum oxygen concentration (volume%) required for a material to sustain combustion. Specifically, it can be determined by measuring the minimum oxygen concentration required for the sample to continue burning for 180 seconds or more, or to continue burning for a combustion length of 50 mm or more after flame contact, in accordance with JIS K 7201-2. The polyurethane foam used for the measurement of the oxygen index and the cone calorimeter test described later is the one produced under the conditions described in the Examples.

[0010] The polyurethane foam composed of the foamable urethane resin composition of the present invention, in accordance with the test method of ISO-5660, has a radiant heat intensity of 50kW / m 2 the total calorific value when heated for 5 minutes is 8MJ / m 2 or less. When the total calorific value is 8MJ / m 2 or less, the polyurethane foam composed of the foamable urethane resin composition of the present invention has predetermined flame retardancy, and can more effectively prevent fire spread during a fire. From the perspective of further improving the flame retardancy of the foam, the total heat release is 7.5MJ / m 2 or less, more preferably 6MJ / m 2 or less, even more preferable.

[0011] (Maximum heat release rate) For the polyurethane foam composed of the foamable urethane resin composition of the present invention, in accordance with the test method of ISO-5660, the maximum heat release rate when heated for 5 minutes at a radiant heat intensity of 50kW / m 2 is preferably 150kW / m 2 or less. When the maximum heat release rate is 150kW / m 2 or less, the polyurethane foam made of the composition has predetermined flame retardancy. In addition, by adjusting both the maximum heat release rate and the total heat release amount as described above, the flame retardancy is further improved, and fire spread in the event of a fire can be more effectively prevented. From the perspective of further improving the flame retardancy of the polyurethane foam, the maximum heat release rate is more preferably 145kW / m 2 or less, and even more preferably 130kW / m 2 or less.

[0012] The total heat release amount and the maximum heat release rate described above can be obtained by a cone calorimeter test, and specifically can be measured by the method described in the Examples. In addition, during the above cone calorimeter test, it is preferable that the polyurethane foam subjected to the test has shape stability to such an extent that it does not come into contact with the spark igniter of the cone calorimeter.

[0013] (Chlorine concentration) The polyurethane foam made from the foamable urethane resin composition of the present invention preferably has a chlorine concentration of 2.0% or higher. By setting the lower limit of the chlorine concentration to the above value, the chlorine atoms in the foam exert a radical trapping effect, which can prevent chain reactions of combustion and also increase the oxygen index of the polyurethane foam. As a result, it can play an effective role in preventing the spread of fire. Furthermore, from the viewpoint of increasing the oxygen index and effectively preventing the spread of fire, a chlorine concentration of 2.5% or higher is more preferable, and 3.0% or higher is even more preferable. Furthermore, there is no particular upper limit to the chlorine concentration, but practically, it is preferable to have a concentration of 8% or lower. The chlorine concentration (mass%) in polyurethane foam made from a foaming urethane resin composition is calculated based on the chlorine concentration and proportion of compounds other than the foaming agent (such as flame retardants) contained in the foaming urethane resin composition. The chlorine concentration of each compound can be theoretically calculated using its chemical formula. Chlorine concentration can also be determined by general ion chromatography, and in particular, it can be quantitatively analyzed from foam by pre-treating it with combustion decomposition using an automated sample combustion device.

[0014] (Polyol compounds) The polyol compounds included in the foamable urethane resin composition of the present invention include, for example, polyether polyols, polyester polyols, aromatic polyester polyols, polymer polyols, polycarbonate polyols, halogen-containing polyols, and halogen-containing aromatic polyols. While not particularly limited, polyether polyols and polyester polyols are preferred. Among these, from the viewpoint of improving the flame retardancy of the resulting polyurethane foam, polyester polyols and halogen-containing polyols, and especially aromatic polyol compounds such as aromatic polyether polyols and aromatic polyester polyols, as will be described later, are preferred. The polyol compound may also contain resin fine particles. The resin fine particles are not particularly limited, but are preferably polymers of at least one monomer selected from the group consisting of acrylonitrile, methacrylonitrile, fluorine-containing acrylonitrile, α-ethylacrylonitrile, styrene, vinyl acetate, and acrylic monomers. Among these, polymers of at least one monomer selected from the group consisting of acrylonitrile, methacrylonitrile, styrene, and fluorine-containing acrylonitrile are preferred, with polymers of acrylonitrile being preferred.

[0015] Examples of acrylic monomers include (meth)acrylates, such as alkyl (meth)acrylates including methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, and n-decyl (meth)acrylate. In addition, hydroxyl group-containing (meth)acrylates such as hydroxyalkyl (meth)acrylate can also be used. Furthermore, acrylic monomers may also be fluorine-containing monomers. Examples of fluorine-containing monomers include monomers such as the above-mentioned alkyl (meth)acrylates and hydroxyl group-containing (meth)acrylates, in which one or more hydrogen atoms constituting the monomer are substituted with fluorine atoms. Furthermore, acrylates and methacrylates, or both, are collectively referred to as (meth)acrylates.

[0016] The content of the resin fine particle-containing polyol is preferably 5 to 45 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of the polyol compound. If the content of the resin fine particle-containing polyol is above these lower limits, it becomes easier to suppress the shrinkage of the polyurethane foam, and if it is below these upper limits, it becomes easier to improve the flame-retardant properties of the polyurethane foam.

[0017] While there are no particular limitations on the type of polyol containing resin fine particles, polyether polyols are preferred from the viewpoint of suppressing shrinkage of the polyurethane foam while obtaining appropriate reactivity, and amine-based polyether polyols are more preferred among them. Examples of such amine-based polyether polyols include tolylenediamine-based polyether polyols (TDA-based polyether polyols) and Mannich-based polyether polyols, which will be described later. Furthermore, from a similar viewpoint, the hydroxyl value of the polyether polyol containing resin fine particles is preferably 250 to 550 mg KOH / g, more preferably 300 to 500 mg KOH / g. In addition, the number of functional groups (number of hydroxyl groups) of the polyether polyol containing resin fine particles is preferably 2 to 4. The hydroxyl value is measured in accordance with JIS K1557-1:2007.

[0018] Polyols containing resin microparticles can be produced by known methods. Examples include adding and mixing the resin fine powder obtained by crushing a resin produced by bulk polymerization or solution polymerization, and classifying it as needed, to a polyol; adding an emulsion containing resin microparticles obtained by emulsion polymerization directly; and dissolving or dispersing a monomer in a polyol, adding a radical polymerization initiator such as AIBN or BPO, heating, and polymerizing to produce a polyol containing resin microparticles. Among these, the method of forming resin microparticles by polymerization in a polyol is most preferred because the particles are less likely to settle even after being left for a long period of time, and a stable polyol composition can be obtained.

[0019] The following describes polyether polyols, which may be polyether polyols containing resin microparticles as described above, or polyether polyols that do not contain resin microparticles.

[0020] <Polyether polyol> Polyether polyols are polyoxyalkylene polyols obtained by ring-opening addition polymerization of alkylene oxide to an initiator having two or more active hydrogen atoms. Examples of initiators include aliphatic polyhydric alcohols (e.g., glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, cyclohexanedimethanol, etc., triols such as trimethylolpropane, glycerin, tetrafunctional alcohols such as pentaerythritol, sugars such as sucrose, sorbitol, etc.), aliphatic amines (e.g., alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, etc., alkanolamines such as monoethanolamine, diethanolamine, etc.), aromatic amines (e.g., aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, Mannich condensates), etc., and these may be used individually or in combination of two or more.

[0021] As for the polyether polyol, from the viewpoint of improving the flame retardancy of polyurethane foam, amine-based polyether polyols such as tolylenediamine-based polyether polyols and Mannich-based polyether polyols, sucrose-based polyether polyols, and sorbitol-based polyether polyols are preferred. The above-mentioned tolylenediamine-based polyether polyols refer to polyether polyols obtained using tolylenediamine as an initiator. The same applies to sucrose-based polyether polyols and sorbitol-based polyether polyols. The above-mentioned Mannich-type polyether polyols are obtained using the Mannich reaction and are Mannich condensates having two or more hydroxyl groups in the molecule, or polyether polyols obtained by adding alkylene oxide to such Mannich condensates. More specifically, they are Mannich condensates obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde and alkanolamines, or polyether polyols obtained by ring-opening addition polymerization of these compounds with at least one of ethylene oxide and propylene oxide.

[0022] The hydroxyl value of the polyether polyol is preferably 100 to 1000 mgKOH / g, and more preferably 200 to 600 mgKOH / g. The hydroxyl value is measured in accordance with JIS K1557-1:2007.

[0023] <Polyester Polyol> The polyol compound contained in the foamed urethane resin composition of the present invention preferably includes a polyester polyol. Examples of polyester polyols include aromatic polyester polyols and aliphatic polyester polyols, but when considering the flame retardancy of the resulting polyurethane foam, it is preferable to use aromatic polyester polyols. Aromatic polyester polyols are preferably condensates of aromatic dicarboxylic acids such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), and naphthalenedicarboxylic acid with glycols. In particular, from the viewpoint of improving the flame retardancy of the polyurethane foam and increasing the oxygen index value mentioned above to improve the performance of preventing the spread of flame, it is more preferable that the aromatic polyester polyol includes phthalic acid-based polyester polyols, which are condensates of phthalic acid and glycol, and even more preferable that it includes p-phthalic acid-based polyester polyols, which are condensates of p-phthalic acid and glycol. While the glycol is not particularly limited, it is preferable to use a low molecular weight aliphatic glycol known as a component of polyester polyols, such as ethylene glycol, propylene glycol, diethylene glycol, or triethylene glycol.

[0024] The polyol compound contained in the foamable urethane resin composition of the present invention is not particularly limited, but from the viewpoint of obtaining a polyurethane foam that is difficult to spread flames, it is preferable to include a phthalate-based polyester polyol. Furthermore, from the viewpoint of obtaining a polyurethane foam that is difficult to shrink and difficult to spread flames, it is more preferable for the polyol compound to contain a resin fine particle-containing polyol and a phthalate-based polyester polyol. Here, the mass ratio of the phthalate-based polyester polyol to the resin fine particle-containing polyol (phthalate-based polyester polyol / resin fine particle-containing polyol) is not particularly limited, but is preferably 95 / 5 to 55 / 45, and more preferably 90 / 10 to 60 / 40.

[0025] The hydroxyl value of the polyester polyol is not particularly limited, but from the viewpoint of enhancing the flame-retardant properties of the polyurethane foam, it is preferably 100 to 400 mg KOH / g, and more preferably 150 to 350 mg KOH / g.

[0026] (Polyisocyanate compounds) As the polyisocyanate compound contained in the foamable urethane resin composition of the present invention, various polyisocyanate compounds such as aromatic, alicyclic, and aliphatic compounds having two or more isocyanate groups can be used. Preferably, liquid diphenylmethane diisocyanate (MDI) is used due to its ease of handling, rapid reaction, excellent physical properties of the resulting polyurethane foam, and low cost. Examples of liquid MDI include crude MDI (also called polymeric MDI). Specific commercially available liquid MDI products include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.), and "Millionate MR-200" (manufactured by Nippon Polyurethane Industry Co., Ltd.). Alternatively, uretonimine-containing MDI (for example, "Millionate MTL" as a commercially available product: manufactured by Nippon Polyurethane Industry Co., Ltd.) may also be used. In addition to liquid MDI, other polyisocyanate compounds may be used in combination, and any polyisocyanate compound known in the field of polyurethanes can be used without limitation. Furthermore, a polyisocyanate may be used that has been treated in advance to increase its affinity with polyols by reacting some of the isocyanate active groups in the polyisocyanate with a hydroxyl group-containing compound.

[0027] The isocyanate index range of the foamed urethane resin composition of the present invention is, for example, 150 to 700, preferably 200 to 700, more preferably 250 to 600, and even more preferably 320 to 500. Having an isocyanate index within such a range makes it easier to adjust the oxygen index to the desired range. Furthermore, to increase the oxygen index, it is more desirable to increase both the isocyanate index and the chlorine concentration. Therefore, for example, it is preferable to have an isocyanate index of 150 to 700 and a chlorine concentration of 2.0% or higher, more preferably an isocyanate index of 250 to 600 and a chlorine concentration of 2.5% or higher, and even more preferably an isocyanate index of 320 to 500 and a chlorine concentration of 3.0% or higher.

[0028] The isocyanate index (INDEX) is calculated using the following method. INDEX = Equivalents of isocyanate / (Equivalents of polyol + Equivalents of water) × 100 Here, Equivalent weight of isocyanate = Number of parts of polyisocyanate used × NCO content (%) × 100 / Molecular weight of NCO The equivalent weight of the polyol = OHV × the amount of polyol used / molecular weight of KOH, where OHV is the hydroxyl value of the polyol (mgKOH / g). Equivalent amount of water = Number of parts of water used × Number of OH groups in water / Molecular weight of water In the above formula, the unit of the number of parts used is weight (g), the molecular weight of the NCO group is 42, the NCO content is the proportion of NCO groups in the polyisocyanate compound expressed in mass%, and for the sake of unit conversion in the above formula, the molecular weight of KOH is assumed to be 56100, the molecular weight of water is assumed to be 18, and the number of OH groups in water is assumed to be 2.

[0029] (Flame retardant) The foamed urethane resin composition of the present invention contains at least one flame retardant selected from the group consisting of liquid flame retardants at room temperature and solid flame retardants at room temperature. Here, room temperature means 23°C. Among these, it is preferable to contain a flame retardant that is liquid at room temperature. By including a liquid flame retardant at room temperature, the amount of solid flame retardant used can be reduced, improving the storage stability of the composition and reducing the likelihood of precipitation during storage. Furthermore, wear and tear on equipment used with the composition can be suppressed.

[0030] Examples of flame retardants that are liquid at room temperature include phosphate ester-based flame retardants such as monophosphate esters and condensed phosphate esters. Examples of monophosphate esters, though not particularly limited, include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, and tris(β-chloropropyl) phosphate. The condensed phosphate esters are not particularly limited, but examples include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycrezyl phosphate (trade name CR-741), and aromatic condensed phosphate esters (trade name CR747) (trade name ADEKA PFR). Among those mentioned above, phosphate esters containing a chlorine atom, such as tris(β-chloropropyl)phosphate, are preferred. When a relatively large amount of phosphate ester containing a chlorine atom is added as a liquid flame retardant, as described later, the chlorine concentration can be increased, and the oxygen index can also be easily increased. If a liquid flame retardant is included, the amount of liquid flame retardant is preferably 20 to 85 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 45 to 75 parts by mass, per 100 parts by mass of the polyol compound.

[0031] Examples of flame retardants that are solid at room temperature (solid flame retardants) include red phosphorus-based flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, chlorine-containing flame retardants, antimony-containing flame retardants, boron-containing flame retardants, needle-shaped fillers, and metal hydroxides. Solid flame retardants are, for example, in powder form.

[0032] <Red phosphorus-based flame retardant> Red phosphorus-based flame retardants may consist of pure red phosphorus, but they may also be coated with a resin, metal hydroxide, metal oxide, etc., or they may be a mixture of red phosphorus and a resin, metal hydroxide, metal oxide, etc. The resin used to coat or mix with red phosphorus is not particularly limited, but examples include thermosetting resins such as phenolic resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. From the viewpoint of flame retardancy, metal hydroxides are preferred as the compound to be coated or mixed. The metal hydroxides described later may be appropriately selected and used.

[0033] <Phosphate-containing flame retardant> Specific examples of phosphate-containing flame retardants include phosphates composed of salts of various phosphoric acids with at least one metal or compound selected from metals of groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Phosphates are not particularly limited, but examples include monophosphates, pyrophosphates, and polyphosphates. Examples of metals in groups IA through IVB of the periodic table include lithium, sodium, calcium, barium, iron(II), iron(III), and aluminum. Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and piperazine. Examples of aromatic amines include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, and 3-(trifluoromethyl)aniline. Examples of heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, and melamine.

[0034] Specific examples of phosphate-containing flame retardants include monophosphates, pyrophosphates, and polyphosphates. Here, the polyphosphate is not particularly limited, but examples include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, and aluminum polyphosphate. A phosphate-containing flame retardant may be used in combination of one or more of the above-mentioned types.

[0035] <Bromine-containing flame retardant> Bromine-containing flame retardants are not particularly limited as long as they contain bromine in their molecular structure and are solid at room temperature and pressure, but examples include aromatic compounds containing brominated aromatic rings. Examples of brominated aromatic ring-containing aromatic compounds include monomer-based organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, bis(pentabromphenoxy)ethane, ethylenebis(pentabromophenyl), and ethylenebis(tetrabromophthalimide).

[0036] Furthermore, the brominated aromatic ring-containing aromatic compound may also be a brominated polymer. Specifically, examples include polycarbonate oligomers produced using brominated bisphenol A as a raw material, brominated polycarbonates such as copolymers of the polycarbonate oligomer and bisphenol A, and diexo compounds produced by the reaction of brominated bisphenol A and epichlorohydrin. In addition, examples include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, brominated phenol condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanur chloride, and brominated polystyrene such as uncrosslinked or crosslinked brominated polystyrene. Furthermore, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may also be used. These bromine-containing flame retardants may be used individually or in combination of two or more types. Furthermore, among the above, brominated aromatic ring-containing aromatic compounds are preferred, and among these, monomer-based organic bromine compounds such as ethylenebis(pentabromophenyl) are preferred.

[0037] <Chlorine-containing flame retardant> Examples of chlorine-containing flame retardants commonly used in polyurethane foam include polychlorinated naphthalene, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene, which is sold under the trade name "Dechloran Plus." <Antimony-containing flame retardant> Examples of antimony-containing flame retardants include antimony oxide, antimonate salts, and pyroantimonate salts. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonate salts include sodium antimonate and potassium antimonate. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate. Antimony-containing flame retardants may be used alone or in combination of two or more types. The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

[0038] <Boron-containing flame retardant> Examples of boron-containing flame retardants include borax, boron oxide, boric acid, and borates. Examples of boron oxides include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide. Examples of borates include alkali metals, alkaline earth metals, elements from groups 4, 12, and 13 of the periodic table, and ammonium borates. Specifically, examples include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate; alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate; zirconium borate, zinc borate, aluminum borate, and ammonium borate. Boron-containing flame retardants may be used alone or in combination of two or more types. The boron-containing flame retardant used in the present invention is preferably a borate, and more preferably zinc borate.

[0039] <Needle-shaped filler> Examples of needle-shaped fillers include potassium titanate whiskers, aluminum borate whiskers, silicon-containing whiskers, wollastonite, sepiolite, zonolite, elestadite, boehmite, asbestos fibers, carbon fibers, graphite fibers, slag fibers, silica fibers, alumina fibers, zirconia fibers, boron nitride fibers, and stainless steel fibers. The aspect ratio (length / diameter) of the needle-shaped filler is preferably in the range of 5 to 50, and more preferably in the range of 10 to 40.

[0040] <Metal hydroxide> Examples of metal hydroxides include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, and tin hydroxide. Metal hydroxides may be used individually or in combination of two or more.

[0041] When a solid flame retardant is included, the content of the solid flame retardant is preferably 3 to 65 parts by mass, more preferably 5 to 60 parts by mass, and even more preferably 10 to 40 parts by mass, per 100 parts by mass of the polyol compound. By setting the content of the solid flame retardant above these lower limits, the effect of the solid flame retardant is more easily exhibited, and flame retardancy is enhanced. On the other hand, by setting it below the upper limit, foaming is not inhibited by the solid flame retardant.

[0042] The total content of the flame retardant is, for example, 20 parts by mass or more, preferably 33 parts by mass or more, more preferably 45 parts by mass or more, and even more preferably 60 parts by mass or more, per 100 parts by mass of the polyol compound. In this way, increasing the total content of the flame retardant increases the oxygen index, which effectively suppresses the spread of fire. Furthermore, the total content of the flame retardant is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 85 parts by mass or less, per 100 parts by mass of the polyol compound. By keeping the total content of the flame retardant below these upper limits, foaming properties and other effects can be obtained without being inhibited by the flame retardant, and effects commensurate with the amount of flame retardant can be obtained. Furthermore, flame retardants may be used individually or in combination of two or more types.

[0043] (Foaming agent) Specific examples of blowing agents include, for example, water, low-boiling-point hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, and hydrofluoroolefins. Furthermore, blowing agents include organic physical blowing agents such as mixtures of these compounds, and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Examples of the low-boiling hydrocarbons mentioned above include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Examples of the above-mentioned chlorinated aliphatic hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Examples of the fluorine compounds mentioned above include CHF3, CH2F2, and CH3F. Examples of the above-mentioned hydrochlorofluorocarbon compounds include trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane)), HCFC22 (chlorodifluoromethane), and HCFC142b (1-chloro-1,1-difluoroethane). Examples of the above-mentioned hydrofluorocarbons include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane). Examples of the ether compounds mentioned above include diisopropyl ether. Examples of the above-mentioned hydrofluoroolefins include HFO-1224yd(Z) (trans-1-chloro-2,3,3,3-tetrafluoropropene), HFO-1336mzz(Z) (cis-1,1,1,4,4,4-hexafluorobuta-2-ene), HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene), and HFO-1234yf (2,3,3,3-tetrafluoro-1-propene).

[0044] In the present invention, the foaming agent preferably contains water. As water, for example, ion-exchanged water, distilled water, etc. can be used as appropriate. From the viewpoint of foaming properties and flame retardancy, the amount of water per 100 parts by mass of the polyol compound is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and preferably 2.0 parts by mass or less, and more preferably 1.5 parts by mass or less.

[0045] In the present invention, the foaming agent preferably contains a hydrofluoroolefin, and more preferably contains both the hydrofluoroolefin and the water described above. The hydrofluoroolefin content per 100 parts by mass of the polyol compound is preferably 10 to 60 parts by mass, more preferably 15 to 50 parts by mass, and even more preferably 20 to 48 parts by mass.

[0046] (catalyst) The foamable urethane resin composition of the present invention contains a catalyst. Preferably, the catalyst contains a urethane catalyst, and also preferably a trimerization catalyst. More preferably, the catalyst contains both a urethane catalyst and a trimerization catalyst. The catalyst contained in the composition does not correspond to the inorganic filler in the present invention.

[0047] Urethane catalysts are catalysts that promote the reaction between polyol compounds and polyisocyanate compounds. Specifically, these include amino compounds, tin compounds, bismuth compounds, and acetylacetone metal salts. Furthermore, some of these catalysts are used not only for the formation of foam resin but also, due to their high activity, to improve the activity in the initial stages of foaming. Examples of the amino compounds include pentamethyldiethylenetriamine, TEDA, triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl) ether, bis(2-dimethylaminoethyl) ether, N,N,N',N'-tetramethylhexane-1,6-diamine, N,N,N',N”,N”-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl) ether, N,N-dicyclohexylmethylamine, N-methyl-N', Examples include N'-dimethylaminoethylpiperazine, imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 2,2'-dimorpholinodiethyl ether, trimethylaminoethylpiperazine, and tripropylamine. Among these, imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group, and imidazole compounds such as 1-methylimidazole are preferred.

[0048] Examples of tin compounds include stannous octoate, dibutyltin diacetate, and dibutyltin dilaurate. Examples of bismuth compounds include bismuth neodecanoate and bismuth octoate. Examples of acetylacetone metal salts include aluminum acetylacetone, iron acetylacetone, copper acetylacetone, zinc acetylacetone, beryllium acetylacetone, chromium acetylacetone, indium acetylacetone, manganese acetylacetone, molybdenum acetylacetone, titanium acetylacetone, cobalt acetylacetone, vanadium acetylacetone, and zirconium acetylacetone.

[0049] Of the urethane catalysts listed above, those containing a bismuth compound are particularly preferred. The inclusion of a bismuth compound enhances the initial activity during the reaction between the polyol compound and the polyisocyanate compound, preventing a significant loss of foaming properties. Therefore, even if a large amount of flame retardant is added, for example, or if the chlorine concentration is increased, it is possible to prevent the density of the polyurethane foam from becoming excessively high. The urethane catalyst may be used alone or in combination of two or more types. When using two or more types in combination, it is preferable to use an amino compound in addition to the bismuth compound, from the viewpoint of foaming properties and reactivity.

[0050] There are no particular limitations on the amount of urethane catalyst blended in the foamed urethane resin composition of the present invention, but it is preferably in the range of 0.5 to 30 parts by mass, more preferably in the range of 1.5 to 20 parts by mass, and even more preferably in the range of 3 to 16 parts by mass, per 100 parts by mass of the polyol compound. By keeping it within the above range, the reaction between the polyol compound and the polyisocyanate compound can be promoted at an appropriate reaction rate.

[0051] Considering the effects listed above, when a bismuth compound is included, the amount of the bismuth compound is, for example, 0.1 parts by mass or more, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 13 parts by mass, per 100 parts by mass of the polyol compound. Furthermore, when an amino compound is included in addition to the bismuth compound, the content of the amino compound is preferably 0.2 to 15 parts by mass, more preferably 0.4 to 10 parts by mass, and even more preferably 2 to 8 parts by mass, per 100 parts by mass of the polyol compound.

[0052] Trimerization catalysts are catalysts that promote trimerization, which involves the formation of isocyanurate bonds. In polyurethane resins, the flame retardancy of polyurethane foam is improved by the promotion of trimerization. As trimerization catalysts, aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, alkali metal salts such as potassium acetate, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium formate, potassium octoate, and sodium octoate, aziridines such as 2-ethylaziridine, lead compounds such as lead naphthenate and lead octoate, alkoxide compounds such as sodium methoxide, phenolate compounds such as potassium phenoxide, tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt, and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium, and tetraphenylammonium salt can be used. Trimerization catalysts may be used individually or in combination of two or more types.

[0053] The amount of trimerizing catalyst is not particularly limited, but it is preferably in the range of 0.3 to 20 parts by mass, more preferably in the range of 0.5 to 18 parts by mass, and even more preferably in the range of 1 to 15 parts by mass, per 100 parts by mass of the polyol compound. By setting the amount of trimerizing catalyst within the above range, isocyanurate bonds are appropriately formed, improving flame retardancy. Furthermore, from the viewpoint of improving the curing speed and flame retardancy of the urethane, the total amount of catalyst is preferably 1 to 35 parts by mass, more preferably 2 to 25 parts by mass, and even more preferably 7 to 20 parts by mass, per 100 parts by mass of the polyol compound.

[0054] Furthermore, these urethane catalysts and trimerization catalysts do not fall under the category of inorganic fillers described later in the present invention.

[0055] (Foam stabilizer) The foamable urethane resin composition of the present invention may optionally contain a foam stabilizer. Examples of foam stabilizers include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and surfactants such as silicone foam stabilizers such as organopolysiloxanes. However, even without a silicone component, a surfactant effect can be obtained if the molecule has a structure that includes both polar and nonpolar parts, so the invention is not limited to the above types. Furthermore, the silicone foam stabilizer may include a graft copolymer of polydimethylsiloxane and polyethylene glycol. The foam stabilizer content is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the polyol compound. The foam stabilizer may be used alone or in combination of two or more types.

[0056] The foaming urethane resin composition of the present invention may contain, to the extent that it does not impede the effects of the present invention, additives such as antioxidants such as phenolic, amine, and sulfur-based agents, heat stabilizers, light stabilizers such as hindered amines, metal damage inhibitors, antistatic agents, crosslinking agents, lubricants, softeners, pigments, tackifying resins, etc.

[0057] (Inorganic filler) The foamed urethane resin composition of the present invention may contain inorganic fillers such as the solid flame retardant described above, but it is also preferable that it substantially omits inorganic fillers. By substantially omitting inorganic fillers, it is possible to provide a foamed urethane resin composition that is less prone to precipitate formation during storage, has excellent storage stability, and can suppress wear of equipment used during use. Here, "substantially free of inorganic fillers" means that, based on the total amount of the foamed urethane resin composition, the inorganic filler content is 5% by mass or less, preferably 1% by mass or less.

[0058] Inorganic fillers are particulate inorganic compounds, and examples include solid flame retardants and inorganic fillers other than solid flame retardants. Details of solid flame retardants are as described above. In addition to solid flame retardants, other inorganic fillers include, for example, silica, diatomaceous earth, alumina, titanium dioxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, potassium salts such as calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass beads, silica powder, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon powder, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum porate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash, and the like.

[0059] The foamed urethane resin composition of the present invention may be a one-component type, but since the foamed urethane resin composition of the present invention hardens through a reaction between a polyol compound and a polyisocyanate compound, its viscosity changes over time. Therefore, before using the composition, it is preferable to divide the composition into two or more parts to prevent it from reacting and hardening. When using the composition, it is preferable to mix the two or more parts that have been divided.

[0060] When dividing the foamed urethane resin composition of the present invention into two or more parts, the components should be divided in such a way that curing does not begin with each component of the divided composition alone, but only after the components of the composition are mixed together. Typically, a two-component type is preferred, in which the composition is divided into a polyol composition containing a polyol compound and a polyisocyanate composition containing a polyisocyanate compound. In this specification, the foamed urethane resin composition is also defined as a two-component type or when it is divided into two or more parts.

[0061] The flame retardant, blowing agent, catalyst, and foam stabilizer described above may be contained in the polyol composition, in the polyisocyanate composition, or provided separately from the polyol composition and the polyisocyanate composition, but it is preferable that they be contained in the polyol composition.

[0062] [Polyurethane foam] The polyurethane foam of the present invention is formed from the above-described foamable urethane resin composition, and more specifically, is obtained by foaming and curing the foamable urethane resin composition.

[0063] The polyurethane foam of the present invention has an oxygen index of 26 or higher, as measured in accordance with JIS K 7201-2. If the value is less than 26, the flame retardancy of the polyurethane foam deteriorates, for example, in the event of a fire, the flame may spread more easily or combustion may continue more easily. From the viewpoint of suppressing the spread of fire, an oxygen index of 27 or higher is more preferable, and 28 or higher is even more preferable. There is no particular upper limit to the oxygen index, but practically speaking, for example, 40 is preferable. The oxygen index of the foam is adjusted by a combination of factors such as the type or composition of the polyol compound, the type or composition of the blowing agent, and the type or composition and amount of the flame retardant. For example, the lower the content of the flammable blowing agent in the blowing agent, the higher the oxygen index. In addition, the oxygen index can be increased by adding a flame retardant, especially a phosphorus-based flame retardant containing chlorine atoms. Furthermore, the higher the density of the foam, and the higher the isocyanate index, the higher the oxygen index of the foam tends to be.

[0064] (Total heat generation) The polyurethane foam of the present invention, according to the ISO-5660 test method, exhibits a radiant thermal intensity of 50 kW / m². 2 The total heat output when heated for 5 minutes is 8 MJ / m². 2 The following is preferable: Total heat generation is 8 MJ / m³. 2 As a result of the following, the polyurethane foam made from the foamed urethane resin composition of the present invention has predetermined flame retardancy and can more effectively prevent the spread of fire in the event of a fire. From the viewpoint of further improving the flame retardancy of the foam, the total heat output is set to 7.5 MJ / m³. 2 It is more preferable that the following conditions are met: 6 MJ / m 2 The following is even more preferable:

[0065] (Maximum heat generation rate) The polyurethane foam of the present invention, according to the ISO-5660 test method, exhibits a radiant thermal intensity of 50 kW / m². 2 The maximum heating rate when heated for 5 minutes was 150 kW / m 2 Preferably, the following: Maximum heat generation rate is 150 kW / m 2 The polyurethane foam of the present invention has a predetermined flame retardancy due to the following conditions. Furthermore, by adjusting both the maximum heat generation rate and the total heat generation amount as described above, the flame retardancy can be further improved, and the spread of fire can be more effectively prevented. From the viewpoint of further improving the flame retardancy of the foam, the above maximum heat generation rate is set to 145 kW / m². 2 It is more preferable that the following conditions are met: 130 kW / m 2 The following is even more preferable:

[0066] The total calorific value and maximum heat generation rate mentioned above are obtained by cone calorimeter testing and can be measured in detail by the method described in the examples. Furthermore, during the cone calorimeter test described above, it is preferable that the polyurethane foam used in the test has sufficient dimensional stability to avoid contact with the spark igniter of the cone calorimeter.

[0067] Furthermore, the chlorine concentration of the polyurethane foam is preferably 2.0% or higher, more preferably 2.5% or higher, and even more preferably 3.0% or higher. While there is no particular upper limit, it is practically preferable to have a concentration of 8% or lower. The density of polyurethane foam is not particularly limited, but is typically between 20 and 200 kg / m³. 3 It is preferable that the density be within this range. 3 By doing the following, the polyurethane foam becomes lighter, improving its ease of application to structures. Also, 20 kg / m 3 By doing so, the desired flame retardancy is more easily achieved. From these perspectives, the density of the polyurethane foam should be 20-100 kg / m³. 3 It is more preferable that the range be 23-80 kg / m 3 It is even more preferable that the density be within this range. The density of the polyurethane foam can be measured in accordance with JIS K7222.

[0068] The foam of the present invention is not particularly limited, but in cases where it is divided into two or more parts, such as a two-component foamable urethane resin composition, it can be obtained by, for example, preparing two or more divided parts, such as a polyol composition and a polyisocyanate composition, by mixing each component in advance, mixing them, and foaming them. The mixing and foaming of each component can be carried out by known methods. For example, it can be obtained using known equipment such as a high-pressure foamer, a low-pressure foamer, a spray foamer, or a hand mixer. In the case of a one-component type, one method is to foam the foamable urethane resin composition obtained by mixing each component constituting the foamable urethane resin composition using a known method.

[0069] (Application) The uses of the foamable urethane resin composition of the present invention and the polyurethane foam described above are not particularly limited, but they can be used to fill cavities in structures such as buildings, furniture, automobiles, trains, and ships, or to spray onto such structures. In particular, it is preferable to use them for spraying onto structures, i.e., for spraying applications. Spraying can be carried out using a spraying device (e.g., GRACO A-25) and a spray gun (e.g., Gasmar D-gun). Spraying is performed by temperature-controlled polyol composition and polyisocyanate composition in separate containers within the spraying device, mixing them by collision at the tip of the spray gun, and atomizing the mixture with air pressure. The spraying device and spray gun are well-known and commercially available. Furthermore, the stock temperature settings and pressure can be the same as those for spraying polyurethane foam. [Examples]

[0070] The present invention will be described in more detail by reference to examples, but the present invention is not limited in any way by these examples.

[0071] The details of each component used in each example and comparative example are as follows. (1) Polyol compounds (i) Polyester polyol • p-phthalate-based polyester polyol (manufactured by Hitachi Chemical Co., Ltd., product name: SV-208, hydroxyl value = 235 mg KOH / g) (ii) Polyether polyol • Mannich-type polyether polyol (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: DK3776, hydroxyl value = 350 mg KOH / g) • Resin microparticle-containing polyol (hydroxyl value = 315 mg KOH / g) The resin microparticles are a polymer of acrylonitrile, and the type of polyether polyol is a Mannich-type polyether polyol. • Sucrose-based polyether polyol (manufactured by Mitsui Chemicals, product name: GR84, hydroxyl value = 450 mg KOH / g) • Sorbitol-based polyether polyol (manufactured by Mitsui Chemicals, product name: Actcol SOR400, hydroxyl value = 400 mg KOH / g) • Ethylenediamine-based polyether polyol (manufactured by AGC Inc., product name: Exenol 750ED, hydroxyl value = 760 mg KOH / g) (2) Flame retardants • Phosphate ester-based liquid flame retardant <Tris(β-chloropropyl) phosphate> (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP, chlorine concentration 32.5% by mass) (3) Foam stabilizer • Silicone-based foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193) (4) Catalyst (i) Trimerization catalyst • Quaternary ammonium salt (manufactured by Evonik Japan, product name: TMR-7) and mixture with ethylene glycol (quaternary ammonium salt 45-55% by mass, ethylene glycol 45-55% by mass) (ii) Urethane catalyst • Imidazole compound (manufactured by Kao Corporation, product name: KL No. 390) • Bismuth compound, bismuth strioctate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600), concentration 55-58% by mass (5) Foaming agent • HFO-1233zd <Hydrofluoroolefin> (Honeywell Corporation, product name: Solstice LBA) ·water (6) Polyisocyanate compounds • MDI (manufactured by Sumika Covestro Urethane Co., Ltd., product name: 44V-20)

[0072] The methods for measuring the various physical properties and characteristics of polyurethane foam are as follows:

[0073] [Total heat generation] The total calorific value of the polyurethane foams prepared in each example and comparative example was evaluated by the following method. For each example and comparative example, polyurethane foam bonded to gypsum board as a base was cut into pieces measuring 10 cm vertically, 10 cm horizontally, and 3.25 cm thick (with 12.5 mm of gypsum board remaining) to prepare samples for cone calorimeter testing. The cone calorimeter test samples were then measured for a radiant thermal intensity of 50 kW / m² in accordance with the ISO-5660 test method. 2 The total heat generated when heated for 5 minutes was measured.

[0074] [Maximum heating speed] The maximum heat generation rate of the polyurethane foams prepared in each example and comparative example was evaluated by the following method. For each example and comparative example, polyurethane foam bonded to gypsum board as a base was cut into pieces measuring 10 cm vertically, 10 cm horizontally, and 3.25 cm thick (with 12.5 mm of gypsum board remaining) to prepare samples for cone calorimeter testing. The cone calorimeter test samples were then measured for a radiant thermal intensity of 50 kW / m² in accordance with the ISO-5660 test method. 2 The maximum heat generation rate was measured after heating for 5 minutes. Regarding the results of the corn calorie test, the maximum heating rate was 150 kW / m². 2 The following conditions apply, and the total heat output is 6 MJ / m³. 2 The following conditions are indicated by "◎", and the maximum heat generation rate is 150 kW / m². 2 The following conditions apply, and the total heat output is 8 MJ / m³. 2 The following conditions were evaluated as "○" and the other conditions as "×".

[0075] [Chlorine] The chlorine concentration and amount of each compound (flame retardant in this example) other than the blowing agent contained in the foamed urethane resin composition were calculated. The chlorine concentration of each compound was theoretically calculated using its chemical formula.

[0076] [Oxygen Index] The oxygen index was measured in accordance with JIS K 7201-2.

[0077] [density] In accordance with JIS K7222, the core portion of the spray foam was cut out and its density was measured.

[0078] [Examples 1-6, Comparative Examples 1-4] Polyol compositions obtained by mixing polyol compounds, liquid flame retardants, foam stabilizers, catalysts, and blowing agents according to the formulations shown in Table 1, and polyisocyanate compounds were supplied to separate foaming tanks. The temperature was controlled within the apparatus, and the two mixtures were mixed by impact at the tip of a spray gun. The mixture was then sprayed onto a 12.5 mm thick gypsum board to obtain polyurethane foam. Spraying was carried out using a spraying apparatus (GRACO: A-25) and a spray gun (Gasmar: D-gun). Using the obtained polyurethane foam, the maximum heat generation rate, total heat generation, oxygen index, and density were measured and evaluated according to the procedures described above. The results of the measurements and evaluations for each item are shown in Table 1. [Table 1] The numbers in parentheses in polyol compounds represent the hydroxyl value (mgKOH / g). Furthermore, in Table 1, the mass parts of each catalyst represent the mass parts of the product.

[0079] As shown in each example, the polyurethane foam formed from the foamable urethane resin composition of the present invention has a high oxygen index, which makes it difficult for flames to spread, resulting in lower maximum heat release rate and total heat release in cone calorimeter tests. In contrast, the polyurethane foam formed from the comparative example's foamable urethane resin composition was found to have a low oxygen index and to be easily flammable.

Claims

1. A foamed urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant, a blowing agent, and a catalyst, The polyol compound includes a phthalic acid-based polyester polyol. The amount of the flame retardant is 20 parts by mass or more per 100 parts by mass of the polyol compound. The blowing agent comprises a hydrofluoroolefin, The catalyst comprises a trimerizing catalyst and a urethane catalyst, the trimerizing catalyst comprises a quaternary ammonium salt, and the urethane catalyst comprises an imidazole compound and a bismuth compound. The foamed urethane resin composition may contain an inorganic filler selected from the group consisting of a flame retardant that is solid at room temperature and an inorganic filler other than the solid flame retardant. If it contains such an inorganic filler, the content of the inorganic filler is 1% by mass or less. The isocyanate index in the foamed urethane resin composition is 250 to 700. A foamable urethane resin composition wherein the oxygen index of the polyurethane foam made from the foamable urethane resin composition is 26 or higher, as measured in accordance with JIS K 7201-2.

2. The foaming urethane resin composition according to claim 1, wherein the foaming agent contains water, and the water content is 2.0 parts by mass or less per 100 parts by mass of the polyol compound.

3. The foamed urethane resin composition according to claim 1 or 2, wherein the flame retardant comprises a liquid phosphate ester-based flame retardant, and the total content of the flame retardant is 20 to 120 parts by mass per 100 parts by mass of the polyol compound.

4. The foamed urethane resin composition according to claim 3, wherein the liquid phosphate ester flame retardant is tris(β-chloropropyl) phosphate.

5. The foamable urethane resin composition according to any one of claims 1 to 4, wherein the content of the bismuth compound is 0.1 parts by mass or more per 100 parts by mass of the polyol compound.

6. A foamed urethane resin composition according to any one of claims 1 to 5, for use in spray applications.

7. The foamed urethane resin composition according to any one of claims 1 to 6, wherein the chlorine concentration of the polyurethane foam made from the foamed urethane resin composition is 2.0% by mass or more.

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