Foamable polyurethane composition

Abstract

Provided is a foamable polyurethane composition capable of suppressing initial combustion at the time of ignition.　A foamable polyurethane composition according to the present invention contains a polyol compound, a polyisocyanate compound, a catalyst, a foaming agent, and a bromine-based flame retardant. The foamable polyurethane composition is substantially free of red phosphorus and has an isocyanate index of 300 or more.

Description

Foamed polyurethane composition

[0001] This invention relates to a foamed polyurethane composition.

[0002] Polyurethane foam is used in practical applications for insulation and condensation prevention in building components such as ceilings, roofs, and walls of apartment buildings, detached houses, and commercial buildings, taking advantage of its excellent thermal insulation properties. Polyurethane foam is formed by spraying a foamable polyurethane composition containing polyol compounds and polyisocyanate compounds onto the surface of each structure, and then allowing it to foam and harden.

[0003] Although polyurethane foam is lightweight, it is flammable because it is an organic material. Therefore, flame retardants are sometimes added to the raw materials of polyurethane foam to improve its flame retardancy. Among flame retardants, red phosphorus is particularly effective in imparting flame retardancy, and as disclosed in Patent Document 1, for example, red phosphorus has been widely used as a flame retardant for a long time.

[0004] Patent No. 6987732

[0005] While it is possible to impart flame retardancy to polyurethane foam by incorporating red phosphorus into the foamed polyurethane composition, which is the raw material for polyurethane foam, it has been difficult to suppress the initial combustion during ignition.

[0006] Therefore, the object of the present invention is to provide a foamed polyurethane composition that can suppress initial combustion during ignition.

[0007] As a result of diligent research, the inventors have found that the above problems can be solved by substantially omitting red phosphorus in a foamed polyurethane composition and including a large amount of brominated flame retardant. That is, the present invention provides the following [1] to

[11] .

[0008] [1] A foamed polyurethane composition comprising a polyol compound, a polyisocyanate compound, a catalyst, a blowing agent, and a brominated flame retardant, wherein the foamed polyurethane composition substantially does not contain red phosphorus and has an isocyanate index of 300 or more. [2] The foamed polyurethane composition according to [1], wherein the catalyst comprises an imidazole derivative. [3] The foamed polyurethane composition according to [1] or [2], wherein the catalyst comprises a quaternary ammonium salt. [4] The foamed polyurethane composition according to any one of [1] to [3], wherein the catalyst comprises bismuth. [5] The foamed polyurethane composition according to any one of [1] to [4], wherein the catalyst comprises a potassium salt. [6] The foamed polyurethane composition according to any one of [1] to [5], wherein the brominated flame retardant is an aromatic compound. [7] The foamed polyurethane composition according to any one of [1] to [6], wherein the brominated flame retardant is decabromodiphenylethane. [8] The foamed polyurethane composition according to any one of [1] to [7], wherein the content of the brominated flame retardant is 50 parts by mass or more per 100 parts by mass of the polyol compound. [9] Use of the foamed polyurethane composition according to any one of [1] to [8] for spraying applications.

[10] A polyurethane foam formed from the foamed polyurethane composition according to any one of [1] to [8].

[11] The polyurethane foam according to

[10] , which is a rigid polyurethane foam.

[0009] According to the present invention, it is possible to provide a foamed polyurethane composition that can suppress initial combustion during ignition.

[0010] [Foamable Polyurethane Composition] The foamable polyurethane composition of the present invention is a foamable polyurethane composition comprising a polyol compound, a polyisocyanate compound, a catalyst, a blowing agent, and a brominated flame retardant, wherein the foamable polyurethane composition substantially does not contain red phosphorus and has an isocyanate index of 300 or more. The foamable polyurethane composition of the present invention can be used for spraying applications.

[0011] <Red Phosphorus> The foamed polyurethane composition of the present invention is substantially free of red phosphorus. By substantially free of red phosphorus and containing a large amount of brominated flame retardant, it is possible to provide a foamed polyurethane composition that can suppress initial combustion at ignition. Here, substantially free of red phosphorus means that the red phosphorus content is 3 parts by mass or less per 100 parts by mass of the polyol compound, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and it is even more preferable that the red phosphorus content is 0 parts by mass per 100 parts by mass of the polyol compound. Note that red phosphorus may consist of pure red phosphorus, but it may also be red phosphorus coated with a resin, metal hydroxide, metal oxide, etc., or a mixture of red phosphorus and a resin, metal hydroxide, metal oxide, etc.

[0012] <Bromine-based flame retardants> Bromine-based flame retardants are not particularly limited as long as they contain bromine in their molecular structure and are solid at room temperature (23°C) and atmospheric pressure (1 atm). Examples include aromatic compounds containing brominated aromatic rings, which are aromatic compounds. Examples of aromatic compounds containing brominated aromatic rings include monomer-based organic bromine compounds such as 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, decabromodiphenylethane, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0013] 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 this 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, poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A and cyanur chloride condensates of brominated phenols, brominated polystyrene such as brominated (polystyrene), poly(brominated styrene), and crosslinked brominated polystyrene, and crosslinked or non-crosslinked brominated poly(methylstyrene). Furthermore, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane, tris(2,3-dibromopropyl) isocyanurate, and tris(tribromoneopentyl) phosphate may also be used. Among the above, decabromodiphenylethane, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine monomer, tris(2,3-dibromopropyl) isocyanurate, and tris(tribromoneopentyl) phosphate are preferred, and among these, brominated aromatic ring-containing aromatic compounds such as decabromodiphenylethane and 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine monomer are more preferred, and decabromodiphenylethane is even more preferred. Brominated flame retardants may be used alone or in combination of two or more types.

[0014] The content of the brominated flame retardant in the foamed polyurethane composition may be, for example, 50 parts by mass or more per 100 parts by mass of polyol, preferably 80 parts by mass or more, more preferably more than 80 parts by mass, even more preferably 100 parts by mass or more, even more preferably 150 parts by mass or more, and particularly preferably 180 parts by mass or more. If the content of the brominated flame retardant is above the lower limit of the above value, initial combustion at ignition can be suppressed. The upper limit of the content of the brominated flame retardant is not particularly limited, but it is preferably 3,000 parts by mass or less per 100 parts by mass of polyol, more preferably 2,500 parts by mass or less, even more preferably 500 parts by mass or less, even more preferably 400 parts by mass or less, and particularly preferably 300 parts by mass or less. If the content of the brominated flame retardant is below the upper limit of the above value, the increase in viscosity of the foamed polyurethane composition can be suppressed, and the sprayability when spraying the foamed polyurethane composition onto the walls of buildings, etc., can be improved.

[0015] <Catalyst> The catalyst is not particularly limited, but examples include trimerizing catalysts and resin-based catalysts. From the viewpoint of improving foaming properties and flame retardancy, it is preferable to use both trimerizing catalysts and resin-based catalysts.

[0016] (Trimerization Catalyst) The trimerization catalyst is a catalyst that promotes trimerization, which forms isocyanurate bonds, in a foamed polyurethane composition. By promoting trimerization in this way, the flame retardancy and resistance to flame spreading of the polyurethane foam are improved. The trimerization catalyst preferably contains at least one selected from amine-based catalysts, quaternary ammonium salts, and potassium salts, and more preferably contains at least one selected from quaternary ammonium salts and potassium salts.

[0017] Quaternary Ammonium Salts Examples of quaternary ammonium salts include quaternary ammonium carboxylates. The carboxylic acid in a quaternary ammonium carboxylate may have one or more carbon atoms, but it is preferable that it has two or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, and more preferably a saturated aliphatic carboxylic acid. The number of carbon atoms in the carboxylic acid is, for example, 20 or less, but is preferably 12 or less, and more preferably 8 or less. The carboxylic acid may be linear or have a branched structure, but it is preferable that it has a branched structure. Having a branched structure makes it easier to reduce the reactivity with blowing agents such as hydrofluoroolefins due to steric hindrance, thus improving the stability of the polyol composition.

[0018] Suitable specific examples of carboxylic acids in quaternary ammonium carboxylates include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. Among these, at least one selected from acetic acid and 2,2-dimethylpropanoic acid is preferred, and 2,2-dimethylpropanoic acid is more preferred.

[0019] In quaternary ammonium carboxylates, the quaternary ammonium ion is preferably a tetraalkylammonium ion or a hydroxyalkyltrialkylammonium ion, and more preferably a tetraalkylammonium ion.

[0020] Each alkyl group in the tetraalkylammonium ion is, for example, an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms, and more preferably a methyl group. Specific examples of tetraalkylammonium ions include tetramethylammonium ions and triethylmethylammonium ions.

[0021] Each alkyl group in the hydroxyalkyltrialkylammonium ion is, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, an ethyl group, or a butyl group. A hydroxyalkyl group is a group in which one of the hydrogen atoms in the alkyl group is substituted with a hydroxyl group, for example, having 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms, and more preferably 3 or 4 carbon atoms. Examples of hydroxyalkyl groups include hydroxyethyl group, hydroxypropyl group, and hydroxybutyl group. Specific examples of hydroxyalkyltrialkylammonium ions include, for example, hydroxybutyltrimethylammonium ion, hydroxypropyltrimethylammonium ion, and hydroxyethyltrimethylammonium ion.

[0022] The ammonium ion in the quaternary ammonium carboxylate is preferably at least one selected from the group consisting of triethylmethylammonium ion, tetramethylammonium ion, hydroxybutyltrimethylammonium ion, and hydroxypropyltrimethylammonium ion, more preferably at least one selected from the group consisting of triethylmethylammonium ion, tetramethylammonium ion, and hydroxybutyltrimethylammonium ion, and even more preferably tetramethylammonium ion.

[0023] Further, preferred specific examples of the quaternary ammonium carboxylate include tetramethylammonium acetate, tetramethylammonium 2,2-dimethylpropionate, triethylmethylammonium 2-ethylhexanoate, and hydroxybutyltrimethylammonium 2-ethylhexanoate. Among these, from the viewpoint of facilitating the formation of an isocyanurate bond by a trimer of polyisocyanate and easily imparting excellent flame retardancy to the polyurethane foam, at least one selected from tetramethylammonium acetate and tetramethylammonium 2,2-dimethylpropionate is preferable, and tetramethylammonium 2,2-dimethylpropionate is more preferable. In the present invention, the quaternary ammonium carboxylate may be used alone or in combination of two or more.

[0024] 《Potassium Salt》 Examples of the potassium salt include potassium carboxylate. The carboxylic acid in the potassium carboxylate may have 1 or more carbon atoms, preferably 5 or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The number of carbon atoms of the carboxylic acid is, for example, 20 or less, preferably 12 or less, more preferably 8 or less. Further, the carboxylic acid may be linear or may have a branched structure, but preferably has a branched structure. When having a branched structure, the reactivity with a blowing agent such as hydrofluoroolefin tends to be lowered due to steric hindrance, so that the stability of the polyol composition is improved.

[0025] Among them, the potassium carboxylate is preferably a potassium carboxylate represented by the following general formula (1). The potassium carboxylate represented by the following general formula (1) has an appropriate steric hindrance, so that the reaction for decomposing the blowing agent can be suppressed, and the decrease in catalytic activity can also be prevented.

[0026] (In General Formula (1), R １ and R ２ each independently represents an alkyl group, and R ３ represents a hydrogen atom or an alkyl group. Also, K ＋represents a potassium ion.)

[0027] In the general formula (1), R １ and R ２ each independently represents an alkyl group. Specifically, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 1 to 2 carbon atoms is even more preferable. The alkyl group may be linear or may have a branched structure. When the number of carbon atoms of R １ and R ２ is equal to or greater than the lower limit value, the steric hindrance becomes large, so the reaction for decomposing the hydrofluoroolefin can be suppressed. On the other hand, when the number of carbon atoms of R １ and R ２ is equal to or less than the upper limit value, it is possible to prevent the reactivity from becoming too slow because the steric hindrance does not become too large. Further, R ３ represents a hydrogen atom or an alkyl group, and a hydrogen atom is preferable. When R ３ is an alkyl group, the alkyl group preferably has 1 to 6 carbon atoms, more preferably has 1 to 4 carbon atoms, and even more preferably has 1 to 2 carbon atoms.

[0028] Preferable specific examples of the carboxylic acid in the potassium carboxylate include at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. Further, the carboxylic acid as shown in the general formula (1) is preferable, and among them, 2,2-dimethylpropanoic acid and 2-ethylhexanoic acid are more preferable, and 2-ethylhexanoic acid is even more preferable. In the present invention, the potassium carboxylate may be used alone or in combination of two or more.

[0029] The content of the trimerizing catalyst in the foamed polyurethane composition is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of polyol. Furthermore, the content of the trimerizing catalyst in the foamed polyurethane composition is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of polyol. When the content of the trimerizing catalyst is above the lower limit, trimerization of polyisocyanate occurs more easily, and the flame retardancy of the resulting polyurethane foam is improved. On the other hand, when the content of the trimerizing catalyst is below the upper limit, the reaction is easier to control. The trimerizing catalyst contained in the foamed polyurethane composition of the present invention may be used alone or in combination of two or more types.

[0030] Furthermore, the above-mentioned quaternary ammonium salt and potassium salt may contain only one of them, but it is also preferable to contain both. The content of the quaternary ammonium salt is preferably 2 parts by mass or more, more preferably 2.7 parts by mass or more, and even more preferably 3.5 parts by mass or more, per 100 parts by mass of polyol. Also, the content of the quaternary ammonium salt is preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of polyol. The content of the potassium salt is preferably 1 part by mass or more, more preferably 2.3 parts by mass or more, and even more preferably 2.5 parts by mass or more, per 100 parts by mass of polyol. Also, the content of the potassium salt is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of polyol.

[0031] (Resin-forming catalyst) The catalyst used in the present invention preferably contains a metal catalyst as a resin-forming catalyst. This metal catalyst is generally called a resin-forming metal catalyst. In the present invention, the inclusion of the above resin-forming metal catalyst promotes the reaction between the polyol and the polyisocyanate, and in particular, the initial reaction rate can be increased. Furthermore, the inclusion of the resin-forming metal catalyst makes it easier to appropriately control the reaction rate between the polyol and the polyisocyanate. From the viewpoint of foaming properties, the above resin-forming metal catalyst is preferably a bismuth compound containing bismuth or a tin compound containing tin, and a bismuth compound is more preferred. Bismuth compounds have low reactivity to HFO and high storage stability. Furthermore, they make it easier to achieve good initial activity without reducing the flame retardancy of the polyurethane foam.

[0032] The resin-based metal catalyst containing bismuth or tin is preferably an organic acid metal salt, and more preferably an organic acid bismuth salt. Specifically, examples of organic acid metal salts include metal salts of carboxylic acids. Examples of metal salts of carboxylic acids include bismuth salts and tin salts of carboxylic acids, with bismuth salts of carboxylic acids being more preferred. Bismuth salts of carboxylic acids are even more preferably bismuth salts of carboxylic acids having 5 or more carbon atoms. Having 5 or more carbon atoms in the carboxylic acid provides good stability against blowing agents, especially hydrofluoroolefins. Furthermore, from the viewpoint of catalytic activity, the number of carbon atoms in the carboxylic acid is preferably 18 or less, and more preferably 12 or less. The carboxylic acid is preferably an aliphatic carboxylic acid, and more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or have a branched structure, but it is preferable to have a branched structure.

[0033] Specific examples of carboxylic acids include octic acid, lauric acid, versatic acid, pentanoic acid, and acetic acid, with octic acid being preferred among these. That is, the resin-forming metal catalyst is preferably a metal salt of octic acid, and more preferably a bismuth salt of octic acid. These carboxylic acids may be linear as described above, but may also have a branched structure. An example of octic acid having a branched structure is 2-ethylhexanoic acid. The metal salt of the carboxylic acid may also be a carboxylic acid salt of an alkyl metal. For example, the tin carboxylic acid salt may be a dialkyltin carboxylate, and preferably a dioctyltin carboxylate. Specific examples of metal salts of carboxylic acids include bismastrioctate, dioctyltin versatate, dibutyltin dilaurate, dioctyltin dilaurate, and tin dioctylate, with bismastrioctate and dioctyltin versatate being preferred, and more preferably bismastrioctate.

[0034] The foamable polyurethane composition of the present invention may also preferably contain a heterocyclic compound having a nitrogen atom (hereinafter also referred to as "nitrogen-containing heterocyclic compound") as a resinification catalyst. Including a nitrogen-containing heterocyclic compound as a resinification catalyst improves stability with respect to hydrofluoroolefins, thereby preventing the decomposition of hydrofluoroolefins and resulting in good foaming properties. Furthermore, it is possible to maintain a reaction rate above a certain level, improving the workability when spraying the foamable polyurethane composition. Among nitrogen-containing heterocyclic compounds, imidazole derivatives are more preferable. As described above, imidazole derivatives are less affected by hydrofluoroolefins and facilitate the reaction between the polyol and polyisocyanate while increasing the stability of the polyol composition. Therefore, by containing an imidazole derivative, the polyol composition exhibits increased reactivity between the polyol and polyisocyanate, resulting in even better foaming properties. The imidazole derivative is preferably an imidazole in which the 1st and 2nd positions are independently substituted with alkyl groups having 8 or fewer carbon atoms, and the alkyl groups preferably have 6 or fewer carbon atoms, more preferably 4 or fewer carbon atoms. A suitable example of an imidazole derivative is represented by the following general formula (2).

[0035] (In general formula (2), R ４ and R ５ Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.

[0036] R in general formula (2) ４ and R ５ Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. The alkyl group and alkenyl group may be linear or have a branched structure. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, neopentyl, isopentyl, sec-pentyl, hexyl, heptyl, and octyl groups. Specific examples of alkenyl groups include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, and octenyl groups. ４ and R ５ If the number of carbon atoms in the alkyl or alkenyl group is greater than or equal to the lower limit, the steric hindrance increases, making it less susceptible to the effects of blowing agents such as hydrofluoroolefins, which is preferable. On the other hand, R ４ and R ５ If the number of carbon atoms in the alkyl group is below the aforementioned upper limit, the steric hindrance does not become excessively large, allowing the reaction between the polyol and polyisocyanate to proceed rapidly, and resulting in good foaming properties. From these viewpoints, R ４ and R ５ Each of these groups is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group.

[0037] Examples of imidazole derivatives represented by general formula (2) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Among these, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferred from the viewpoint of improving the catalytic activity in the presence of hydrofluoroolefins and allowing the reaction to proceed rapidly. Furthermore, 1,2-dimethylimidazole is even more preferred from the viewpoint of further enhancing stability.

[0038] The content of the resinified metal catalyst in the foamed polyurethane composition is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, per 100 parts by mass of polyol. Furthermore, the content of the resinified metal catalyst in the foamed polyurethane composition is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of polyol. If the resinified metal catalyst is above the lower limit, the reaction rate between the polyol and polyisocyanate is increased, making it easier to form a high-quality polyurethane foam. Furthermore, if the resinified metal catalyst is below the upper limit, the reaction rate between the polyol and polyisocyanate can be appropriately controlled. The content of the nitrogen-containing heterocyclic compound in the foamed polyurethane composition is not particularly limited, but is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of polyol. Furthermore, the content of nitrogen-containing heterocyclic compounds in the foamed polyurethane composition is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of polyol. When the content of nitrogen-containing heterocyclic compounds is above the lower limit, urethane bond formation occurs more easily, the reaction proceeds rapidly, and foaming properties are good. On the other hand, when the content of nitrogen-containing heterocyclic compounds is below the upper limit, the reaction rate is easier to control, which is preferable. The total content of resinification catalyst in the foamed polyurethane composition is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 7 parts by mass or more, per 100 parts by mass of polyol. Furthermore, the total content of resinification catalyst in the foamed polyurethane composition is preferably 25 parts by mass or less, more preferably 18 parts by mass or less, and even more preferably 13 parts by mass or less, per 100 parts by mass of polyol.

[0039] <Polyol Compounds> The polyol compounds included in the foamable polyurethane composition of the present invention are not particularly limited, but it is preferable that they include polyether polyols, polyester polyols, etc. From the viewpoint of improving the flame retardancy of the resulting polyurethane foam, it is preferable that the polyol compound includes an aromatic polyester polyol, as described later, and a phthalic acid-based polyester polyol is preferred as the aromatic polyester polyol.

[0040] (Polyester Polyol) The foamable polyurethane composition of the present invention preferably contains a polyester polyol. Including a polyester polyol makes it easier to improve flame retardancy. Examples of polyester polyols include aromatic polyester polyols and aliphatic polyester polyols. In particular, from the viewpoint of improving flame retardancy, the polyester polyol is preferably an aromatic polyester polyol. The aromatic polyester polyol is preferably a condensate of an aromatic dicarboxylic acid such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), or naphthalenedicarboxylic acid and a glycol. In particular, from the viewpoint of improving the flame retardancy of the polyurethane foam, the aromatic polyester polyol is preferably a phthalic acid-based polyester polyol, which is a condensate of phthalic acid and a glycol, and is even more preferably a p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid and a glycol. The glycol is not particularly limited, but it is preferable to use a low molecular weight aliphatic glycol known as a component of polyester polyols, such as ethylene glycol, propylene glycol, or diethylene glycol.

[0041] The hydroxyl value of the polyester polyol is preferably 100 to 400 mg KOH / g, and more preferably 150 to 350 mg KOH / g. In this specification, the hydroxyl value is the value measured in accordance with JIS K1557-1:2007.

[0042] From the viewpoint of improving the flame retardancy of the resulting polyurethane foam, the polyester polyol content on a basis of the total amount of polyol compounds is preferably more than 50% by mass, more preferably 70% by mass or more, even more preferably 75% by mass or more, even more preferably 90% by mass or more, and most preferably 100% by mass.

[0043] (Polyether Polyol) The polyol compound of the present invention preferably contains a polyether polyol. The inclusion of a polyether polyol improves the handling properties of the foamed polyurethane composition. Furthermore, the polyol compound of the present invention preferably contains both the polyester polyol and the polyether polyol described above. This improves the handling properties of the foamed polyurethane composition and enhances the flame retardancy of the resulting polyurethane foam.

[0044] 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, etc.; 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.

[0045] As for polyether polyols, tolylenediamine-based polyether polyols, Mannich-based polyether polyols, sucrose-based polyether polyols, and sorbitol-based polyether polyols are preferred from the viewpoint of improving moldability during injection when foaming a foamed polyurethane composition and workability when spraying, with Mannich-based polyether polyols being more preferred among them. These polyol compounds are preferably used in combination with the above-mentioned aromatic polyester polyols from the viewpoint of providing excellent moldability, workability, and flame retardancy.

[0046] 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-based polyether polyols refer to those obtained using the Mannich reaction, which 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 alkanolamine, or polyether polyols obtained by ring-opening addition polymerization of these compounds with at least one of ethylene oxide and propylene oxide.

[0047] The polyether polyol may be a brominated polyether polyol. A brominated polyether polyol is a polyether polyol having an aromatic ring, and having a skeleton in which at least one bromine atom is bonded to the aromatic ring.

[0048] The hydroxyl value of the polyether polyol is preferably 200 to 1000 mg KOH / g, and more preferably 300 to 600 mg KOH / g.

[0049] The polyether polyol content is preferably 5% by mass or more, preferably less than 50% by mass, more preferably 30% by mass or less, and even more preferably 25% by mass or less, based on the total amount of polyol compounds.

[0050] <Polyisocyanate Compounds> As polyisocyanate compounds contained in foamed polyurethane compositions, various polyisocyanate compounds such as aromatic, alicyclic, and aliphatic compounds having two or more isocyanate groups can be used. Examples of aromatic polyisocyanate compounds include phenylenediisocyanate, tolylenediisocyanate, xylylenediisocyanate, diphenylmethanediisocyanate, dimethyldiphenylmethanediisocyanate, triphenylmethanetriisocyanate, naphthalenediisocyanate, and polymethylenepolyphenylpolyisocyanate (also called polymeric MDI or crude MDI). Examples of alicyclic polyisocyanate compounds include cyclohexylenediisocyanate, methylcyclohexylenediisocyanate, isophoronediisocyanate, dicyclohexylmethanediisocyanate, and dimethyldicyclohexylmethanediisocyanate. Examples of aliphatic polyisocyanate compounds include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0051] Among these, aromatic polyisocyanates are preferred from the viewpoint of ease of use and availability, and diphenylmethane diisocyanate (MDI) is preferred due to its ease of handling, rapid reaction, excellent physical properties of the resulting polyurethane foam, and low cost. Crude MDI (polymeric MDI) can also be used as an MDI. It is best to use an MDI that is liquid at room temperature and atmospheric pressure. Specific commercially available liquid MDIs include "PM200" (Manka Chemical Japan Co., Ltd.), "44V-10", "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.), and "Millionate MR-200" (Nippon Polyurethane Industry Co., Ltd.). Alternatively, uretonimine-containing MDI (for example, "Millionate MTL": 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 examples of polyisocyanate compounds to be used in combination include the above-mentioned polyisocyanate compounds.

[0052] <Isocyanate Index> The isocyanate index of the foamed polyurethane composition of the present invention is 300 or higher. If the isocyanate index is less than 300, the amount of polyisocyanate relative to the polyol will not be sufficiently excessive, and isocyanurate bonds will not be sufficiently formed by the trimer of polyisocyanate, making it impossible to suppress initial combustion at ignition, resulting in insufficient flame retardancy of the polyurethane foam. The isocyanate index is more preferably 350 or higher, even more preferably 400 or higher, and even more preferably 500 or higher. Furthermore, the isocyanate index is preferably 2,000 or lower, more preferably 1,200 or lower, even more preferably 1,100 or lower, and even more preferably 1,000 or lower. If the isocyanate index is below the above upper limit, flame retardancy that is sufficiently commensurate with the manufacturing cost can be obtained.

[0053] The isocyanate index can be calculated using the following method: Isocyanate index = Equivalents of polyisocyanate / (Equivalents of polyol + Equivalents of water) × 100 Here, each equivalent can be calculated as follows: - Equivalents of polyisocyanate = Amount of polyisocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (moles) × 100 - Equivalents of polyol = OHV × Amount of polyol used (g) / Molecular weight of KOH (millimoles) OHV is the hydroxyl value of polyol (mgKOH / g). - Equivalents of water = Amount of water used (g) / Molecular weight of water (moles) × Number of OH groups in water In the above formulas, the molecular weight of NCO is 42 (moles), the molecular weight of KOH is 56,100 (millimoles), the molecular weight of water is 18 (moles), and the number of OH groups in water is 2.

[0054] <Foaming Agent> The foaming agent promotes foaming of the foamable polyurethane composition. Examples of foaming agents include water, low-boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane; chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride; ether compounds such as hydrofluoroolefins (hereinafter sometimes referred to as "HFO") and diisopropyl ether; or mixtures of these compounds; and inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Of these, it is preferable to include hydrofluoroolefins (HFO), which have high stability as a foaming agent, do not easily decrease catalytic activity, and have a low environmental impact.

[0055] Suitable HFOs as blowing agents include fluoroalkenes having approximately 3 to 6 carbon atoms. Furthermore, HFO may also be a hydrochlorofluoroolefin containing a chlorine atom, and therefore may be a chlorofluoroalkene having approximately 3 to 6 carbon atoms. Examples of HFOs include trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorodifluoropropene, chlorotrifluoropropene such as HFO-1233, and chlorotetrafluoropropene. More specifically, 3,3,3-trifluoropropene (HFO-1243zf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,1,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), trans-1,2,3,3,3-pene Examples include tafluoropropene (HFO-1225ye(E)), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,1,2,3,3-pentafluoropropene (HFO-1225yc), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), and 1,1,1,4,4,4-hexafluorobuto-2-ene (HFO-1336mzz). Among these, HFO-1233zd(E) is preferred.

[0056] The content of the blowing agent is not particularly limited, but is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more, per 100 parts by mass of polyol. Furthermore, the content of the blowing agent may be, for example, 430 parts by mass or less, preferably 110 parts by mass or less, more preferably 85 parts by mass or less, and even more preferably 78 parts by mass or less, per 100 parts by mass of polyol. If the content of the blowing agent is above the lower limit, foaming is promoted, foamability is improved, and the density of the polyurethane foam can be reduced. On the other hand, if the content of the blowing agent is below the upper limit, excessive foaming can be suppressed. In addition, by keeping the content of the blowing agent within the above range, it becomes easier to adjust the gel time of the foamable polyurethane composition to a predetermined range.

[0057] The above-mentioned foaming agents can be used one or more types. In the foamable urethane resin composition of the present invention, it is preferable to use the above-mentioned HFO in combination with other foaming agents. For example, HFO may be used in combination with water, oxygen gas, or carbon dioxide gas, which have excellent handling properties. Water is particularly preferred from the viewpoint of adjusting the isocyanate index and ease of handling. The HFO content is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more, per 100 parts by mass of polyol. The HFO content may be, for example, 420 parts by mass or less, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 75 parts by mass or less, per 100 parts by mass of polyol. The water content is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of polyol. Furthermore, the water content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, per 100 parts by mass of polyol.

[0058] (Liquid Flame Retardant) The foamed polyurethane composition of the present invention preferably contains a liquid flame retardant. Including a liquid flame retardant makes it easier to impart excellent flame retardancy to the polyurethane foam without excessively increasing the viscosity of the polyol composition, etc. A liquid flame retardant is one that becomes liquid at room temperature (25°C) and normal pressure (1 atm). The liquid flame retardant is not particularly limited, but a phosphate ester-based flame retardant is preferred.

[0059] As phosphate ester-based flame retardants, monophosphate esters, condensed phosphate esters, etc., can be used. A monophosphate ester is a phosphate ester that has one phosphorus atom in its molecule. Examples of monophosphate esters include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl) phosphate; halogen-containing phosphate esters such as tris(β-chloropropyl) phosphate; trialkoxy phosphates such as tributoxyethyl phosphate; aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, cresyldiphenyl phosphate, and diphenyl(2-ethylhexyl) phosphate; and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

[0060] Examples of condensed phosphate esters include aromatic condensed phosphate esters such as trialkyl polyphosphates, resorcinol polyphenyl phosphates, bisphenol A polycresyl phosphates, and bisphenol A polyphenyl phosphates. Examples of commercially available condensed phosphate esters include "CR-733S," "CR-741," and "CR747" from Daihachi Chemical Industry Co., Ltd., and "ADEKA Stab PFR" and "FP-600" from ADEKA Corporation.

[0061] The phosphate ester flame retardants may be used individually from the above-mentioned types, or two or more types may be used in combination. Among these, monophosphate esters are preferred from the viewpoint of making it easier to adjust the viscosity of polyol compositions and improving flame retardancy, and halogen-containing phosphate esters such as tris(β-chloropropyl) phosphate are more preferred.

[0062] The liquid flame retardant content in the foamed polyurethane composition is preferably 10 parts by mass or more, more preferably 25 parts by mass or more, even more preferably 60 parts by mass or more, and even more preferably 80 parts by mass or more, per 100 parts by mass of the polyol compound. Furthermore, the liquid flame retardant content in the foamed polyurethane composition is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, even more preferably 140 parts by mass or less, and even more preferably 120 parts by mass or less, per 100 parts by mass of the polyol compound. When the liquid flame retardant content is above these lower limits, it becomes easier to impart flame retardancy without excessively increasing the viscosity of the polyol composition. Furthermore, when the phosphate ester-based flame retardant content is below these upper limits, foaming is not inhibited by the liquid flame retardant, making it easier to manufacture polyurethane foams.

[0063] <Other Components> In addition to the above, the foamed polyurethane composition of the present invention may contain, as necessary and within the limits that do not impair its purpose, one or more additives selected from the following: flame retardants, anti-settling agents, fillers such as filler components, antioxidants such as phenolic, amine, and sulfur-based agents, foam stabilizers, heat stabilizers, metal damage inhibitors (metal deactivators), antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, plasticizers, pigments, tackifying resins, tackifying agents such as polybutene and petroleum resins.

[0064] Furthermore, it is preferable that the foamed polyurethane composition of the present invention contains little or no filler. By containing little or no filler, it is possible to include a large amount of brominated flame retardant without unnecessarily increasing the viscosity of the polyol composition, and to appropriately suppress initial combustion at ignition. Specifically, the amount of filler in the foamed polyurethane composition may be, for example, 10 parts by mass or less per 100 parts by mass of the polyol compound, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, and most preferably 0 parts by mass. The filler is a component other than the brominated flame retardant and catalyst mentioned above, which is solid at room temperature (25°C) and normal pressure (1 atm) and does not dissolve in the polyol compound, and is, for example, a component that exists as a solid in the polyol composition described later.

[0065] The foamed urethane resin composition of the present invention, when the foam obtained from the foamed urethane resin composition is subjected to a cone calorimeter test in accordance with the ISO 5660 test method, exhibits a radiant thermal intensity of 50 kW / m². ２ The maximum heating rate when heated for 10 minutes was 100 kW / m². ２ The following is preferable: 70 kW / m ２ More preferably, the following is true: 50 kW / m ２ It is even more preferable that the following conditions are met: By keeping the maximum heat generation rate below a certain level, initial combustion at ignition can be appropriately suppressed. Furthermore, the foamed urethane resin composition of the present invention, when the foam obtained from the foamed urethane resin composition is subjected to a cone calorimeter test in accordance with the ISO 5660 test method, has a radiant heat intensity of 50 kW / m². ２ The total heat generated when heated for 10 minutes was 8 MJ / m². ２ Preferably, it is 6 MJ / m ２ It is more preferable that the following conditions apply: 5 MJ / m ２ The following is even more preferable: The foamed urethane resin composition is more easily made flame retardant by keeping the total heat generation below a certain value. The polyurethane foam used when performing the cone calorimeter test may be formed from the foamed urethane resin composition by the method described in the examples.

[0066] The foamed polyurethane composition of the present invention hardens through a reaction between a polyol compound and a polyisocyanate compound, and therefore its viscosity changes over time. For this reason, before using the foamed polyurethane composition, it is preferable to divide it into two or more parts to prevent the reaction and hardening. Then, when using the foamed polyurethane composition, it is preferable to combine the two or more parts into one.

[0067] When dividing a foamed polyurethane composition into two or more parts, the curing reaction should be initiated only after the components of the divided foamed polyurethane composition are mixed, rather than each component curing on its own. Typically, a foamed polyurethane composition is divided into a polyol composition containing a polyol compound and a polyisocyanate composition containing a polyisocyanate compound.

[0068] The brominated flame retardant, catalyst, blowing agent, and optionally added liquid flame retardant and other additives described above may be contained in the polyol composition, contained 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. That is, the polyol composition is preferably a polyol premix containing a polyol compound, a catalyst, a blowing agent, a brominated flame retardant, and optionally added liquid flame retardant and other additives, and the foamed polyurethane composition of the present invention is preferably a mixture of the polyol premix and a polyisocyanate compound.

[0069] The polyurethane 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 polyurethane composition, it can be obtained by, for example, preparing two or more divided polyol compositions and polyisocyanate compositions 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, a method can be used in which the foamable polyurethane composition obtained by mixing each component constituting the foamable polyurethane composition is foamed by a known method. The polyurethane foam of the present invention is preferably a rigid polyurethane foam. That is, the foamable polyurethane composition of the present invention is preferably for forming a rigid polyurethane foam. When the polyurethane foam of the present invention is a rigid polyurethane foam, it has good thermal insulation properties, mechanical strength, etc.

[0070] (Applications) The foamable polyurethane composition of the present invention can be used for spraying applications. As means of manufacturing and producing polyurethane foam from the foamable polyurethane composition, there are two methods: obtaining polyurethane foam by spraying and foaming the foamable polyurethane composition, and obtaining polyurethane foam by foaming the foamable polyurethane composition on a factory line. In the method of obtaining polyurethane foam by foaming the foamable polyurethane composition on a factory line, the polyurethane foam is shipped in a fixed shape, which requires the effort of shaping the polyurethane foam at the installation site. On the other hand, in the method of obtaining polyurethane foam by spraying and foaming the foamable polyurethane composition, the polyurethane foam is foamed to match the shape of the structure at the installation site, which has the advantage of significantly reducing the effort of shaping the polyurethane foam on site. The foamable polyurethane composition of the present invention is preferably sprayed onto various structures such as building members such as ceilings, roofs, and walls of buildings. Spraying can be carried out using a spraying device (e.g., GRACO A-25) and a spray gun (e.g., Gasmar D-gun). The spraying process can be carried out by temperature-controlled preparation of the polyol composition and polyisocyanate composition in separate containers within a spraying apparatus, mixing them by collision at the tip of a spray gun, and atomizing the mixture using air pressure. The spraying apparatus and spray gun are well-known and commercially available products can be used.

[0071] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples.

[0072] The components used in each example and comparative example are as follows:

[0073] <Polyisocyanate> ・4,4'-diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Chemical Japan Co., Ltd., product name: PM200) <Polyol composition> (Polyol) ・p-phthalate polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g)

[0074] (Flame retardants) ・Liquid flame retardant: Phosphate ester, tris(β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP) ・Bromine flame retardant: Brominated aromatic ring-containing aromatic compound, decabromodiphenylethane (manufactured by Albemarle, Inc., product name: SAYTEX 8010) ・Bromine flame retardant: Brominated aromatic ring-containing aromatic compound, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Pyroguard SR245) ・Bromine flame retardant: Tris(tribromoneopentyl) phosphate (manufactured by Suzuhiro Chemical Co., Ltd., product name: FCP370) ・Bromine flame retardant: Tris(2,3-dibromopropyl) isocyanurate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Pyroguard SR750) • Brominated flame retardant: Ethylene bis(tetrabromophthalimide) (manufactured by Suzuhiro Chemical, product name: FCP-1010)

[0075] (Fillers) - Filler 1: Wollastonite (manufactured by Kinsei Matec, product name: SH-1250) - Filler 2: Calcium carbonate (manufactured by Calfine Co., Ltd., product name: KS-500)

[0076] (Catalysts) ・Trimerization catalyst 1: Quaternary ammonium salt, tetramethylammonium dimethylpropanoate (Air Products Co., Ltd., product name: DABCO® TMR7), concentration 45-55% by mass ・Trimerization catalyst 2: Metal catalyst, potassium 2-ethylhexanoate (Air Products Co., Ltd., product name: DABCO® K-15), concentration 70-80% by mass ・Resinization catalyst 1: Metal catalyst, bismastrioctate (Nitto Chemical Co., Ltd., product name: Neostan U-600), concentration 55-58% by mass ・Resinization catalyst 2: Amine catalyst, 1,2-dimethylimidazole (Tosoh Corporation, product name: TOYOCAT®-DM70), concentration 65-75% by mass

[0077] (Foaming agent) Water, hydrofluoroolefin (HFO), trans-1-chloro-3,3,3-trifluoropropene (manufactured by Honeywell Japan, product name: Solstice LBA)

[0078] [Measurement and Evaluation Methods for Each Physical Property] <Flame Retardancy> In each example and comparative example, polyurethane foam was produced by spraying a polyol composition and polyisocyanate onto gypsum board according to the formulations described in Table 1. The production conditions were as follows: <Production Conditions> ・Spraying machine: Graco H-25 spraying machine ・Settings (heater settings) ・Isocyanate heater: 38°C ・Premix heater (for heating the polyol composition): 38°C ・Hose heater (for heating the polyisocyanate and polyol composition before mixing): 38°C ・Substrate: Gypsum board ・Substrate temperature (temperature of the surface to be sprayed): 20°C ± 1°C

[0079] [Flame Retardancy Test (CCM: Cone Calorimeter)] A section of the polyurethane foam prepared as described above was cut out, measuring 10 cm in length, 10 cm in width, and 3.75 cm in thickness, including a gypsum board. Therefore, a portion of the cut-out sample was gypsum board, with 1.25 cm of the gypsum board and 2.5 cm of the polyurethane foam being the total thickness of the 3.75 cm sample.

[0080] <Maximum Heat Generation Rate> The cone calorimeter test sample obtained as described above was subjected to a test in accordance with ISO-5660, with a radiant heat intensity of 50 kW / m². ２ The maximum heat generation rate (kW / m) when heated for 10 minutes. ２ The following criteria were used to measure and evaluate the performance: A: Maximum heat generation rate of 100 kW / m². ２ Below, B: Maximum heating rate is 100 kW / m ２ super

[0081] <Total Heat Output> The cone calorimeter test sample obtained as described above was subjected to a test in accordance with ISO-5660, with a radiant heat intensity of 50 kW / m². ２ Total heat output (MJ / m) when heated for 10 minutes ２ The following criteria were used to measure the heat output () and evaluate the flame retardancy: A: Total heat output over 10 minutes was 8 MJ / m³. ２ Below, B: Total heat output over 10 minutes is 8 MJ / m³ ２ super

[0082]

[0083] As is clear from the above examples, polyurethane foams formed from foamable polyurethane compositions satisfying the requirements of the present invention were able to suppress initial combustion during ignition and exhibited excellent flame retardancy. In contrast, the foamable polyurethane compositions prepared in the comparative examples had an isocyanate index of 300 or higher and did not contain brominated flame retardants, resulting in poor flame retardancy as they could not suppress initial combustion during ignition.

Claims

1. A foamed polyurethane composition comprising a polyol compound, a polyisocyanate compound, a catalyst, a blowing agent, and a brominated flame retardant, wherein the foamed polyurethane composition substantially does not contain red phosphorus and has an isocyanate index of 300 or more.

2. The foamed polyurethane composition according to claim 1, wherein the catalyst comprises an imidazole derivative.

3. The foamable polyurethane composition according to claim 1 or 2, wherein the catalyst comprises a quaternary ammonium salt.

4. The foamed polyurethane composition according to any one of claims 1 to 3, wherein the catalyst comprises bismuth.

5. The foamed polyurethane composition according to any one of claims 1 to 4, wherein the catalyst comprises a potassium salt.

6. The foamed polyurethane composition according to any one of claims 1 to 5, wherein the brominated flame retardant is an aromatic compound.

7. The foamed polyurethane composition according to any one of claims 1 to 6, wherein the brominated flame retardant is decabromodiphenylethane.

8. The foamed polyurethane composition according to any one of claims 1 to 7, wherein the content of the brominated flame retardant is 50 parts by mass or more per 100 parts by mass of the polyol compound.

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