Polyol composition, polyurethane foam-forming composition, polyurethane foam, flame retardant composition, and solid flame retardant composition

Abstract

To provide a polyol composition with good redispersibility and a polyurethane foam-forming composition that contributes to the production of polyurethane foams with good flame retardancy. [Solution] A polyol composition comprising a solid flame retardant and a liquid flame retardant, The solid flame retardant includes a bromine-containing flame retardant. The bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant. The first bromine-containing flame retardant is one selected from the following three: (a) to (c): (a) Aliphatic bromine-containing compounds, (b) aromatic bromine-containing low molecular compound, (c) aromatic bromine-containing polymer compound; A polyol composition comprising the second bromine-containing flame retardant, which is selected from two of the three (a) to (c) other than one selected from the three (a) to (c).

Description

[Technical Field]

[0001] This disclosure relates to polyol compositions, polyurethane foam-forming compositions, polyurethane foams, flame retardant compositions, and solid flame retardant compositions. [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 thermal insulation properties. Although lightweight, polyurethane foam is flammable because it is an organic material. To improve this, polyurethane foam with enhanced flame retardancy is used, incorporating flame retardants and other additives. For example, Patent Document 1 describes a flame-retardant polyurethane foam obtained using a bromine-containing flame retardant, a polyol compound, a blowing agent, a catalyst, a foam stabilizer, and a polyisocyanate compound. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 03-140363 [Overview of the project] [Problems that the invention aims to solve]

[0004] The polyurethane foam described in Patent Document 1 has excellent flame retardancy due to the inclusion of a large amount of bromine-containing flame retardant. However, in recent years, the market demand for flame retardancy has increased, and the flame retardancy of these polyurethane foams is insufficient, requiring further improvement. Furthermore, bromine-containing flame retardants have a high specific gravity, and polyol compositions containing bromine-containing flame retardants are prone to caking due to the sedimentation and aggregation of the bromine-containing flame retardant over time. Therefore, there has been a need to improve the redispersibility of polyol compositions containing bromine-containing flame retardants.

[0005] Therefore, one aspect of this disclosure aims to provide a polyol composition with good redispersibility and a polyurethane foam-forming composition that contribute to the production of a polyurethane foam having good flame retardancy. Another aspect of this disclosure aims to provide a flame retardant composition and a solid flame retardant composition that contribute to the production of a polyurethane foam having good flame retardancy and a polyol composition with good redispersibility. Yet another aspect of this disclosure aims to provide a polyurethane foam having good flame retardancy. [Means for solving the problem]

[0006] This disclosure provides the following aspects. [1] A polyol composition comprising a solid flame retardant, a liquid flame retardant, and a polyol compound, The solid flame retardant includes a bromine-containing flame retardant. The bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant. The first bromine-containing flame retardant is one selected from the following three: (a) to (c): (a) Aliphatic bromine-containing compounds, (b) aromatic bromine-containing low molecular compound, (c) aromatic bromine-containing polymer compound; A polyol composition wherein the second bromine-containing flame retardant comprises one selected from the other two, excluding one selected from the three (a) to (c). [2] The polyol composition according to [1], wherein the first bromine-containing flame retardant comprises the (c) aromatic bromine-containing polymer compound. [3] The polyol composition according to [1] or [2], wherein the second bromine-containing flame retardant comprises the aliphatic bromine-containing compound (a) described above. [4] A polyol composition comprising a solid flame retardant, a liquid flame retardant, and a polyol compound, The solid flame retardant includes a bromine-containing flame retardant. The bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant. The first bromine-containing flame retardant is one selected from the following three (i) to (iii): (i) A bromine-containing flame retardant having a decomposition temperature of less than 370°C, (ii) A bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, (iii) A bromine-containing flame retardant having a decomposition temperature of 450°C or more; A polyol composition, wherein the second bromine-containing flame retardant comprises one selected from the remaining two of the three (i) to (iii) other than the one selected as the first bromine-containing flame retardant. [5] The polyol composition according to [4], wherein the first bromine-containing flame retardant comprises the bromine-containing flame retardant (iii) having a decomposition temperature of 450°C or more. [6] The polyol composition according to [4] or [5], wherein the second bromine-containing flame retardant comprises the bromine-containing flame retardant (i) having a decomposition temperature of less than 370°C. [7] The polyol composition according to any one of [1] to [6], further comprising a polyol compound, a foam stabilizer, a foaming agent, and a catalyst. [8] A polyurethane foam-formable composition comprising the polyol composition according to [7]. [9] A sample for cone calorimeter test produced from the polyurethane foam-formable composition under the following production conditions has a total heat release after 10 minutes of 8.0 MJ / m when heated at a radiant heat intensity of 50 kW / m in accordance with the test method of ISO-5660 2 2 or less, the polyurethane foam-formable composition according to [8]. [Conditions for producing sample for cone calorimeter test] (1): The polyurethane foam-formable composition is stirred for 5 seconds with a lab disperser. (2): After (1), the resulting mixture is immediately poured into a mold having a height × depth × width of 150 mm × 150 mm × 150 mm to obtain a polyurethane foam. (3): The polyurethane foam is cut into a size of 10 cm in length, 10 cm in width and 2.5 cm in thickness to obtain a sample for cone calorimeter test.

[10] A polyurethane foam, which is a foam of the polyurethane foam-formable composition according to [8].​

[11] A solid flame retardant composition comprising a first bromine-containing flame retardant and a second bromine-containing flame retardant, wherein the first bromine-containing flame retardant is one selected from the following three (a) to (c): (a) an aliphatic bromine-containing compound, (b) a low-molecular aromatic bromine-containing compound, (c) a high-molecular aromatic bromine-containing compound; and the second bromine-containing flame retardant comprises one selected from the remaining two of the three (a) to (c) other than the one selected for the first bromine-containing flame retardant.

[12] The solid flame retardant composition according to

[11] , wherein the first bromine-containing flame retardant comprises the (c) high-molecular aromatic bromine-containing compound.

[13] The solid flame retardant composition according to

[11] or

[12] , wherein the second bromine-containing flame retardant comprises the (a) aliphatic bromine-containing compound.

[14] A solid flame retardant composition comprising a first bromine-containing flame retardant and a second bromine-containing flame retardant, wherein the first bromine-containing flame retardant is one selected from the following three (i) to (iii): (i) a bromine-containing flame retardant having a decomposition temperature of less than 370°C, (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°C, (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or higher; and the second bromine-containing flame retardant comprises one selected from the remaining two of the three (i) to (iii) other than the one selected for the first bromine-containing flame retardant.

[15] The solid flame retardant composition according to

[14] , wherein the first bromine-containing flame retardant comprises the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or higher.

[16] The solid flame retardant composition according to

[14] or

[15] , wherein the second bromine-containing flame retardant comprises the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C.

[17] The solid flame retardant composition according to any one of

[11] to

[16] , which is for a polyurethane foam-formable composition.

[18] The solid flame retardant composition according to any one of

[11] to

[16] , which is for a polyurethane foam.

[19] A solid flame retardant composition according to any one of

[11] to

[16] , which is for spraying to adhere the solid flame retardant composition to an object. A flame retardant composition comprising a solid flame retardant composition described in any one of items

[20]

[11] to

[16] and a liquid flame retardant. [Effects of the Invention]

[0007] According to one aspect of this disclosure, a polyol composition with good redispersibility and a polyurethane foam-forming composition can be provided, which contribute to the production of a polyurethane foam having good flame retardancy. Furthermore, a flame retardant composition and a solid flame retardant composition can be provided, which contribute to the production of a polyurethane foam having good flame retardancy and a polyol composition with good redispersibility. Moreover, according to yet another aspect of this disclosure, a polyurethane foam having good flame retardancy can be provided. [Modes for carrying out the invention]

[0008] Exemplary embodiments for carrying out each aspect of this disclosure will be described in further detail. However, this disclosure is not limited to the following embodiments. In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with the values ​​shown in the examples. Furthermore, the upper and lower limits described individually can be combined in any way.

[0009] [Mechanism of flame retardancy derived from flame retardants] When polymer materials are heated, they melt, decompose, and volatilize, and the resulting flammable gases ignite in the presence of oxygen, initiating combustion. Flame retardants primarily exhibit flame-retardant effects through flame-retardant mechanisms in the gas phase or solid phase. The flame-retardant effect in the gas phase tends to increase with the amount of trapped OH radicals, which have a high combustion traction force generated during the combustion of organic matter. On the other hand, the flame-retardant effect in the solid phase tends to increase with the amount of highly flame-retardant graphite-like carbon layer (carbonized layer) produced. Furthermore, the carbonized layer tends to form a multilayer structure with the interposition of phosphorus, further improving its flame retardancy.

[0010] In each aspect of this disclosure, the inventors speculate that by using at least two bromine-containing flame retardants with different decomposition temperatures as trappers for OH radicals, it becomes possible to trap OH radicals with high combustion traction over a wider temperature range than with a single bromine-containing flame retardant, thereby obtaining a polyurethane foam with superior flame retardancy compared to the case where only one bromine-containing flame retardant is used. In other words, the inventors speculate that when two or more bromine-containing flame retardants exhibit flame retardancy, unlike when only one bromine-containing flame retardant is used, flame retardancy is brought to the polyurethane foam by different actions, resulting in unexpectedly superior flame retardancy.

[0011] The decomposition temperature of bromine-containing flame retardants depends on the form of the carbon atom to which the bromine atom is bonded. Carbon-bromine bonds derived from aromatic compounds result in a higher decomposition temperature than carbon-bromine bonds derived from aliphatic compounds. Furthermore, carbon-bromine bonds derived from high molecular weight compounds result in a higher decomposition temperature than carbon-bromine bonds derived from low molecular weight compounds. Therefore, the decomposition temperature of bromine-containing flame retardants depends on the form of the carbon atom to which the bromine atom is bonded and / or its molecular weight.

[0012] [Polyol composition] A polyol composition according to one aspect of the present disclosure is a polyol composition comprising a solid flame retardant, a liquid flame retardant, and a polyol compound, The solid flame retardant includes a bromine-containing flame retardant. The bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant. The first bromine-containing flame retardant is one selected from the following three: (a) to (c): (a) Aliphatic bromine-containing compounds, (b) aromatic bromine-containing low molecular compound, (c) aromatic bromine-containing polymer compound; The second bromine-containing flame retardant includes one selected from the other two, excluding one selected from the three (a) to (c).

[0013] The polyol composition may further contain one or more additives selected from the group consisting of solid flame retardants other than bromine-containing flame retardants, foam stabilizers, blowing agents, catalysts, inorganic fillers, settling inhibitors, dispersion stabilizers, and other additives.

[0014] Here, the polyol composition forms a polyurethane foam by mixing it with the polyisocyanate composition. It is preferable to use the polyol composition as the first liquid of the polyurethane foam-forming composition. In other words, during distribution, it is desirable to use a two-component or multi-component form that combines a first liquid containing a polyol composition, a second liquid containing a polyisocyanate composition, and, in the case of a multi-component type, a third liquid (and fourth or more liquids) containing components other than the polyol composition and the polyisocyanate composition. When forming the foam, it is desirable to mix these first and second liquids, and in the case of a multi-component type, the third liquid (and fourth or more liquids). The polyol composition contains a polyol compound as an essential component.

[0015] The polyol composition, by including a solid flame retardant and a liquid flame retardant, improves the flame retardancy of the resulting polyurethane foam. Here, a solid flame retardant refers to a flame retardant that is solid at 23°C, and a liquid flame retardant refers to a flame retardant that is liquid at 23°C.

[0016] [Polyisocyanate composition] The polyisocyanate composition contains a polyisocyanate compound. The polyisocyanate composition may further contain one or more additives selected from the group consisting of solid flame retardants, liquid flame retardants, blowing agents, foam stabilizers, catalysts, inorganic fillers, settling inhibitors, dispersion stabilizers, and other additives.

[0017] [Polyurethane foam-forming composition] Other embodiments of the present disclosure include polyurethane foam-forming compositions comprising the polyol composition described above and a polyisocyanate composition. Furthermore, the polyurethane foam-forming composition includes a polyol compound, a polyisocyanate compound, a bromine-containing flame retardant, and a liquid flame retardant. In addition, the polyurethane foam-forming composition may include one or more additives selected from the group consisting of solid flame retardants other than bromine-containing flame retardants, foam stabilizers, blowing agents, catalysts, inorganic fillers, settling inhibitors, dispersion stabilizers, and other additives.

[0018] Here, the polyurethane foam-forming composition may be a two-component type or a multi-component type with two or more components. "Two-component type" means a form in which a first liquid containing a polyol composition and a second liquid containing a polyisocyanate composition are stored separately and mixed when foam is formed. "Multi-component type" means, for example, a form in which a first liquid containing a polyol composition, a second liquid containing a polyisocyanate composition, and a third liquid (and fourth or more liquids) containing components other than the polyol composition and polyisocyanate composition are stored separately and mixed when foam is formed. Note that the polyol composition contains a polyol compound, and the polyisocyanate composition contains a polyisocyanate compound.

[0019] [Polyurethane foam] Another aspect of the present disclosure is a polyurethane foam made from the polyurethane foam-forming composition described above.

[0020] [Solid flame retardant composition] Solid flame retardant compositions in other embodiments of this disclosure include: A first bromine-containing flame retardant and a second bromine-containing flame retardant are included. The first bromine-containing flame retardant is one selected from the following three: (i) to (iii): (i) Bromine-containing flame retardants with a decomposition temperature of less than 370°C (ii) Bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C, (iii) Bromine-containing flame retardants with a decomposition temperature of 450°C or higher; The second bromine-containing flame retardant includes one selected from the other two, excluding one selected from the three (i) to (iii).

[0021] The solid flame retardant composition may further contain solid flame retardants such as phosphorus-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxide-based flame retardants.

[0022] [Flame retardant composition] Flame retardant compositions of other embodiments of this disclosure include the above-mentioned solid flame retardant composition and a liquid flame retardant. [Solid flame retardant] The polyol composition and the solid flame retardant composition contain a solid flame retardant. The composition may contain both a polyol composition and a polyisocyanate composition. Preferably, only the polyol composition contains the solid flame retardant.

[0023] (Bromine-containing flame retardant) The bromine-containing flame retardant comprises two or more bromine-containing flame retardants having different forms of carbon atoms to which bromine atoms are bonded and / or different molecular weights, or two or more bromine-containing flame retardants having different decomposition temperatures, and includes at least two types consisting of a first bromine-containing flame retardant and a second bromine-containing flame retardant.

[0024] Bromine-containing flame retardants are not particularly limited as long as they are compounds that contain bromine atoms in their molecular structure. Examples include compounds containing aliphatic carbon-bromine atom bonds (aliphatic bromine-containing compounds), compounds that do not contain aliphatic carbon-bromine atom bonds but contain aromatic carbon-bromine atom bonds and have three or fewer aromatic rings (aromatic bromine-containing low molecular weight compounds), and compounds that contain aromatic carbon-bromine bonds and have an average of more than three aromatic rings within the molecule (aromatic bromine-containing high molecular weight compounds).

[0025] Bromine-containing flame retardants tend to produce polyurethane foams with even better flame retardancy than when using a single bromine-containing flame retardant, as well as polyol compositions and polyurethane foam-forming compositions with suppressed caking and excellent redispersibility, when two or more bromine-containing flame retardants with different carbon atom configurations and / or molecular weights are used in combination. In particular, by including two or more compounds selected from the group consisting of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing high molecular weight compounds, it is easier to obtain polyurethane foams with particularly excellent flame retardancy, as well as polyol compositions and polyurethane foam-forming compositions that suppress caking and have excellent redispersibility.

[0026] In other words, the first bromine-containing flame retardant is one selected from the following three: (a) to (c): (a) Aliphatic bromine-containing compounds, (b) aromatic bromine-containing low molecular compound, (c) aromatic bromine-containing polymer compound; It is preferable that the second bromine-containing flame retardant is one selected from the other two, excluding the one selected from the three (a) to (c).

[0027] Examples of compounds containing aliphatic carbon-bromine atom bonds (aliphatic bromine-containing compounds) include low molecular weight organic bromine compounds such as 2,4,6-tris(2,4-dibromopropyl)-1,3,5-triazine (Piroguard SR-750), 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] (Piroguard SR-720), and 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2-methyl-2,3-dibromopropyloxy)benzene] (Piroguard SR-130). Among these, 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] is preferred.

[0028] Specific examples of low molecular weight organic bromine compounds that do not contain aliphatic carbon-bromine atom bonds, contain aromatic carbon-bromine atom bonds, and have three or fewer aromatic rings (aromatic bromine-containing low molecular weight compounds) include, for example, hexabromobenzene, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (Pyroguard SR-245), pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), tetrabromobisphenol A, and other low molecular weight organic bromine compounds. Among these, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine and ethylenebis(pentabromophenyl) are preferred.

[0029] Specific examples of compounds containing aromatic carbon-bromine atom bonds and having an average of more than three aromatic rings within the molecule (aromatic bromine-containing polymer compounds) include homopolymers derived from 2,6-dibromophenol or 2,4-dibromophenol (Piroguard SR-460B), polycarbonate oligomers produced using brominated bisphenol A as a raw material, brominated polycarbonates such as copolymers of the said polycarbonate oligomer and bisphenol A (FG-8500, FG-7500, FG-7000), and brominated polymers produced by the reaction of brominated bisphenol A with 1,2-dichloroethane. Examples include brominated epoxy compounds such as diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin, monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin, poly(brominated benzyl acrylate), brominated polyphenylene ether, cyanur chloride and condensates of brominated phenols, brominated polystyrenes such as brominated (polystyrene), poly(brominated styrene), and crosslinked brominated polystyrene, halogenated brominated compound polymers such as crosslinked or non-crosslinked brominated poly(α-methylstyrene), and any combination of two or more of these. Among these, brominated polycarbonates such as homopolymers derived from 2,6-dibromophenol and 2,4-dibromophenol, polycarbonate oligomers produced using brominated bisphenol A as a raw material, and copolymers of the said polycarbonate oligomer and bisphenol A are preferred.

[0030] The upper limit of the content of the bromine-containing flame retardant may be 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 67 parts by mass or less, 64 parts by mass or less, 61 parts by mass or less, 58 parts by mass or less, 55 parts by mass or less, 52 parts by mass or less, 49 parts by mass or less, 46 parts by mass or less, 43 parts by mass or less, 40 parts by mass or less, 37 parts by mass or less, 34 parts by mass or less, 31 parts by mass or less, 28 parts by mass or less, 25 parts by mass or less, 22 parts by mass or less, 19 parts by mass or less, 15 parts by mass or less, 14.5 parts by mass or less, 14 parts by mass or less, 13.5 parts by mass or less, 13 parts by mass or less, 12.5 parts by mass or less, 12 parts by mass or less, 11.5 parts by mass or less, 11 parts by mass or less, or 10.5 parts by mass or less, relative to 100 parts by mass of the polyol compound. The lower limit of the content of the bromine-containing flame retardant may be 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, 5 parts by mass or more, 6 parts by mass or more, 7 parts by mass or more, 8 parts by mass or more, 9 parts by mass or more, 9.5 parts by mass or more, 10 parts by mass or more, 10.5 parts by mass or more, 11 parts by mass or more, 11.5 parts by mass or more, 12 parts by mass or more, 12.5 parts by mass or more, 13 parts by mass or more, 13.5 parts by mass or more, 14 parts by mass or more, 14.5 parts by mass or more, 15 parts by mass or more, 19 parts by mass or more, 22 parts by mass or more, 25 parts by mass or more, 28 parts by mass or more, 31 parts by mass or more, 34 parts by mass or more, 37 parts by mass or more, 40 parts by mass or more, 43 parts by mass or more, or 46 parts by mass or more, relative to 100 parts by mass of the polyol compound. The content of the bromine-containing flame retardant may be 1 to 100 parts by mass, 2 to 90 parts by mass, 3 to 80 parts by mass, 4 to 70 parts by mass, 5 to 67 parts by mass, 6 to 64 parts by mass, 7 to 61 parts by mass, 8 to 58 parts by mass, 9 to 55 parts by mass, 9.5 to 52 parts by mass, 10 to 49 parts by mass, 10.5 to 46 parts by mass, 11 to 43 parts by mass, 11.5 to 40 parts by mass, 12 to 37 parts by mass, 12.5 to 34 parts by mass, 13 to 31 parts by mass, 13.5 to 28 parts by mass, 14 to 25 parts by mass, 14.5 to 22 parts by mass, or 15 to 19 parts by mass, relative to 100 parts by mass of the polyol compound. Furthermore, the lower limit of the bromine-containing flame retardant content may be, for example, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 1.0% by mass or more, 1.5% by mass or more, 2.0% by mass or more, 2.5% by mass or more, 3.0% by mass or more, 3.5% by mass or more, 4.0% by mass or more, 4.5% by mass or more, 5.0% by mass or more, 5.5% by mass or more, 6.0% by mass or more, 6.5% by mass or more, 7.0% by mass or more, 7.5% by mass or more, 8.0% by mass or more, 8.5% by mass or more, 9.0% by mass or more, 9.5% by mass or more, 10.0% by mass or more, 10.5% by mass or more, 11.0% by mass or more, or 11.5% by mass or more, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The upper limit of the bromine-containing flame retardant content may be, for example, 12.0% by mass or less, 11.8% by mass or less, 11.7% by mass or less, 11.5% by mass or less, 11.0% by mass or less, 10.5% by mass or less, 10.0% by mass or less, 9.5% by mass or less, 9.0% by mass or less, 8.5% by mass or less, 8.0% by mass or less, 7.5% by mass or less, 7.0% by mass or less, 6.5% by mass or less, 6.0% by mass or less, 5.5% by mass or less, 5.0% by mass or less, 4.5% by mass or less, 4.0% by mass or less, 3.5% by mass or less, 3.0% by mass or less, 2.5% by mass or less, 2.0% by mass or less, 1.5% by mass or less, or 1.0% by mass or less, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The content of the bromine-containing flame retardant may be, for example, 0.1% to 12.0% by mass, 0.3% to 11.8% by mass, 0.5% to 11.7% by mass, 1.0% to 11.5% by mass, 1.5% to 11.0% by mass, 2.0% to 10.5% by mass, 2.5% to 10.0% by mass, 3.0% to 9.5% by mass, 3.5% to 9.0% by mass, 4.0% to 8.5% by mass, 4.5% to 8.0% by mass, 5.0% to 7.5% by mass, 5.5% to 7.0% by mass, or 6.0% to 6.5% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. When the content of the bromine-containing flame retardant is within the aforementioned range, it is easier to obtain a polyurethane foam with excellent flame retardancy, a polyol composition and a polyurethane foam-forming composition that suppress caking and have excellent redispersibility.When the content of the bromine-containing flame retardant is below the upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy, as well as polyol compositions and polyurethane foam-forming compositions with suppressed caking and excellent redispersibility, tend to be obtained. When the content of the bromine-containing flame retardant is above the lower limit, the flame retardant effect derived from the bromine-containing flame retardant is more easily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0031] In polyurethane foams according to yet another embodiment of this disclosure, for example, the polyurethane foam is produced under conditions where there is a large excess of isocyanate groups relative to the active hydrogen-containing component (polyol compound, water). In the production of polyurethane foam under these conditions, some of the isocyanate groups react with the active hydrogen-containing component to produce urethane or urea groups, while the remaining unreacted isocyanate groups are converted to isocyanurate groups. Since isocyanurate groups have a much higher decomposition temperature compared to urethane or urea groups, the more isocyanurate groups there are, the better the flame retardancy of the polyurethane foam obtained. On the other hand, the unreacted isocyanate groups react with moisture in the air to form amino groups, and these amino groups react with carbonyl bonds in the polyurethane foam, causing decomposition of the polyurethane resin. Generally, the higher the molecular weight of the polyurethane resin, the better the flame retardancy tends to be. Therefore, the higher the rate of conversion from unreacted isocyanate groups to isocyanurate groups, the better the flame retardancy of the polyurethane foam obtained.

[0032] In this specification, "polyurethane foam components of a polyurethane foam-forming composition" refers to the components that make up the polyurethane foam. For example, among liquid flame retardants, solid flame retardants, polyol compounds, polyisocyanate compounds, foam stabilizers, blowing agents, catalysts, and other additives, the components that make up the polyurethane foam are considered "polyurethane foam components of a polyurethane foam-forming composition." Furthermore, the blowing agent is entirely or largely discharged from the system as bubbles and does not constitute the polyurethane foam. For example, of the water used as a blowing agent, the hydrogen atoms constitute part of the urea bonds in the polyurethane foam, but the oxygen atoms become CO2 and do not constitute the polyurethane foam itself. For this reason, in this specification, the blowing agent is not included in the "polyurethane foam components of the polyurethane foam-forming composition."

[0033] The upper limit of the content of the aliphatic bromine-containing compound may be 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 63 parts by mass or less, 60 parts by mass or less, 57 parts by mass or less, 54 parts by mass or less, 51 parts by mass or less, 48 parts by mass or less, 45 parts by mass or less, 42 parts by mass or less, 39 parts by mass or less, 36 parts by mass or less, 33 parts by mass or less, 30 parts by mass or less, 27 parts by mass or less, 24 parts by mass or less, 21 parts by mass or less, 18 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 8 parts by mass or less, 7.6 parts by mass or less, 7.2 parts by mass or less, 6.8 parts by mass or less, 6.4 parts by mass or less, 6 parts by mass or less, 5.6 parts by mass or less, or 5.2 parts by mass or less, relative to 100 parts by mass of the polyol compound. The lower limit of the content of the aliphatic bromine-containing compound may be 0.01 parts by mass or more, 0.1 parts by mass or more, 0.4 parts by mass or more, 0.8 parts by mass or more, 1.2 parts by mass or more, 1.6 parts by mass or more, 2 parts by mass or more, 2.4 parts by mass or more, 2.8 parts by mass or more, 3.2 parts by mass or more, 3.6 parts by mass or more, 4 parts by mass or more, 4.4 parts by mass or more, 4.8 parts by mass or more, 5.2 parts by mass or more, 5.6 parts by mass or more, 6 parts by mass or more, 6.4 parts by mass or more, 6.8 parts by mass or more, 7.2 parts by mass or more, 7.6 parts by mass or more, 8 parts by mass or more, 12 parts by mass or more, 15 parts by mass or more, 18 parts by mass or more, 21 parts by mass or more, 24 parts by mass or more, 27 parts by mass or more, 30 parts by mass or more, or 33 parts by mass or more, relative to 100 parts by mass of the polyol compound. The content of the aliphatic bromine-containing compound may be 0.01 parts by mass to 100 parts by mass, 0.1 parts by mass to 90 parts by mass, 0.4 parts by mass to 80 parts by mass, 0.8 parts by mass to 70 parts by mass, 1.2 parts by mass to 63 parts by mass, 1.6 parts by mass to 60 parts by mass, 2 parts by mass to 57 parts by mass, 2.4 parts by mass to 54 parts by mass, 2.8 parts by mass to 51 parts by mass, 3.2 parts by mass to 48 parts by mass, 3.6 parts by mass to 45 parts by mass, 4 parts by mass to 42 parts by mass, 4.4 parts by mass to 39 parts by mass, 4.8 parts by mass to 36 parts by mass, 5.2 parts by mass to 33 parts by mass, 5.6 parts by mass to 30 parts by mass, 6 parts by mass to 27 parts by mass, 6.4 parts by mass to 24 parts by mass, 6.8 parts by mass to 21 parts by mass, 7.2 parts by mass to 18 parts by mass, 7.6 parts by mass to 15 parts by mass, or 8 parts by mass to 12 parts by mass, relative to 100 parts by mass of the polyol compound. Furthermore, the lower limit of the content of aliphatic bromine-containing compounds may be, for example, 0.001% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, 0.9% by mass or more, 1.1% by mass or more, 1.3% by mass or more, 1.5% by mass or more, 1.7% by mass or more, 1.9% by mass or more, 2.1% by mass or more, 2.3% by mass or more, 2.5% by mass or more, 2.7% by mass or more, 2.9% by mass or more, 3.2% by mass or more, 3.5% by mass or more, 3.8% by mass or more, 4.3% by mass or more, 4.8% by mass or more, 5.3% by mass or more, 5.8% by mass or more, or 7.0% by mass or more, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The upper limit of the content of the aliphatic bromine-containing compound is, for example, 12.0% by mass or less, 11.0% by mass or less, 10.0% by mass or less, based on the mass of the polyurethane foam component of the polyurethane foam-forming composition. 0 mass% or less, 9.0 mass% or less, 8.0 mass% or less, 7.0 mass% or less, 6.5 mass% or less, 6.0 mass% or less, 5.5 mass% or less, 5.0 mass% or less, 4.5 mass% or less, 4.0 quality % by mass or less, 3.5% by mass or less, 3.3% by mass or less, 3.1% by mass or less, 2.9% by mass or less, 2.7% by mass or less, 2.5% by mass or less, 2.3% by mass or less, 2.1% by mass or less, 1.9% by mass The content may be 1.7% by mass or less, 1.5% by mass or less, 1.3% by mass or less, 1.2% by mass or less, 1.0% by mass or less, 0.8% by mass or less, 0.6% by mass or less, or 0.4% by mass or less.The content of aliphatic bromine-containing compounds is, for example, 0.001% to 12.0% by mass, 0.01% to 11.0% by mass, 0.03% to 10.0% by mass, 0.05% to 9.0% by mass, 0.07% to 8.0% by mass, 0.09% to 7.0% by mass, 0.1% to 6.5% by mass, and 0.3% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The content of the aliphatic bromine-containing compound may be between % and 6.0% by mass, between 0.5% by mass and 5.5% by mass, between 0.7% by mass and 5.0% by mass, between 0.9% by mass and 4.5% by mass, between 1.1% by mass and 4.0% by mass, between 1.3% by mass and 3.5% by mass, between 1.5% by mass and 3.3% by mass, between 1.7% by mass and 3.1% by mass, between 1.9% by mass and 2.9% by mass, between 2.1% by mass and 2.7% by mass, or between 2.3% by mass and 2.5% by mass. When the content of the aliphatic bromine-containing compound is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the content of the aliphatic bromine-containing compound is below the above upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content of aliphatic bromine-containing compounds is above the aforementioned lower limit, the flame-retardant effect derived from the aliphatic bromine-containing compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0034] The upper limit of the content of low molecular weight compounds in aromatic odorants is defined as follows: below 100%, below 90%, below 80%, below 70%, below 63%, below 60%, below 57%, below 54%, below 51%, below 48%, below 45%, below 42%, below 39%, and below 3%. 6 quality department and below, 33 quality department and below, 30 quality department and below, 27 quality department and below, 24 quality department and below, 21 quality department and below, 18 quality department and below, 15 quality department and below, 12 quality department and below, 8 quality department and below, 7.6 quality department and below, 7.2 quality department and below, 6.8 quality department and below, 6.4 quality department and below, 6 quality department and below, 5.6 quality department and below, also 5.2 quality department and below, de àtte yoi. The lower limit of the content of low molecular weight compounds in aromatic odorants is defined as follows: 0.01% or more, 0.1% or more, 0.4% or more, 0.8% or more, 1.2% or more, 1.6% or more, 2% or more, 2.4% or more, 2.8% or more, 3.2% or more, 3.6% or more, 4% or more, and 4.4% or more. Above, 4.8 quality department or above, 5.2 quality department or above, 5.6 quality department or above, 6 quality department or above, 6.4 quality department or above, 6.8 quality department or above, 7.2 quality department or above, 7.6 quality department or above, 8 quality department or above, 12 quality department or above, 15 quality department or above, 18 quality department or above, 21 quality department or above, 24 quality department or above, 27 quality department or above, 30 quality department or above, also 33 quality department or above, de àtte yoi. The content of aromatic odorants containing low molecular weight compounds is defined as follows: 0.01 to 100% of the total mass, 0.1 to 90% of the total mass, 0.4 to 80% of the total mass, 0.8 to 70% of the total mass, 1.2 to 63% of the total mass, 1.6 to 60% of the total mass, 2 to 57% of the total mass, 2.4 to 54% of the total mass, 2.8 to 51% of the total mass, and 3.2 to 48% of the total mass. Below, 3.6 quality department or above 45 quality department or below, 4 quality department or above 42 quality department or below, 4.4 quality department or above 39 quality department or below, 4.8 quality department or above 36 quality department or below, 5.2 quality department or above 33 quality department or below, 5.6 quality department or above 30 quality department or below, 6 quality department or above 27 quality department or below, 6.4 quality department or above 24 quality department or below, 6.8 quality department or above 21 quality department or below, 7.2 quality department or above 18 quality department or below, 7.6 quality department or above 15 quality department or below, also 8 quality department or above 12 quality department or below, de àtte yoi.Furthermore, the lower limit of aromatic bromine-containing low molecular weight compounds may be, for example, 0.001% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, 0.9% by mass or more, 1.1% by mass or more, 1.3% by mass or more, 1.5% by mass or more, 1.7% by mass or more, 1.9% by mass or more, 2.1% by mass or more, 2.3% by mass or more, 2.5% by mass or more, 2.7% by mass or more, 2.9% by mass or more, 3.2% by mass or more, 3.5% by mass or more, 3.8% by mass or more, 4.3% by mass or more, 4.8% by mass or more, 5.3% by mass or more, 5.8% by mass or more, or 7.0% by mass or more, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The upper limit of the content of the aromatic bromine-containing low-molecular compound is, for example, 12.0% by mass or less, 11.0% by mass or less, 1 0.0 mass% or less, 9.0 mass% or less, 8.0 mass% or less, 7.0 mass% or less, 6.5 mass% or less, 6.0 mass% or less, 5.5 mass% or less, 5.0 mass% or less, 4.5 mass% or less, 4.0 Mass% or less, 3.5 mass% or less, 3.3 mass% or less, 3.1 mass% or less, 2.9 mass% or less, 2.7 mass% or less, 2.5 mass% or less, 2.3 mass% or less, 2.1 mass% or less, 1.9 mass% % or less, 1.7 mass% or less, 1.5 mass% or less, 1.3 mass% or less, 1.2 mass% or less, 1.0 mass% or less, 0.8 mass% or less, 0.6 mass% or less, or 0.4 mass% or less.The content of aromatic bromine-containing low molecular weight compounds is, for example, 0.001% to 12.0% by mass, 0.01% to 11.0% by mass, 0.03% to 10.0% by mass, 0.05% to 9.0% by mass, 0.07% to 8.0% by mass, 0.09% to 7.0% by mass, 0.1% to 6.5% by mass, and 0.3% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The content may be between % by mass and 6.0% by mass, 0.5% by mass and 5.5% by mass, 0.7% by mass and 5.0% by mass, 0.9% by mass and 4.5% by mass, 1.1% by mass and 4.0% by mass, 1.3% by mass and 3.5% by mass, 1.5% by mass and 3.3% by mass, 1.7% by mass and 3.1% by mass, 1.9% by mass and 2.9% by mass, 2.1% by mass and 2.7% by mass, or 2.3% by mass and 2.5% by mass. When the content of aromatic bromine-containing low molecular weight compounds is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the content of aromatic bromine-containing low molecular weight compounds is below the above upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content of aromatic bromine-containing low molecular weight compounds is above the aforementioned lower limit, the flame retardant effect derived from the aromatic bromine-containing low molecular weight compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0035] The upper limit of the content of the aromatic bromine-containing polymer compound is 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 63 parts by mass or less, 60 parts by mass or less, 57 parts by mass or less, 54 parts by mass or less, 51 parts by mass or less, 48 ​​parts by mass or less, 45 parts by mass or less, 42 parts by mass or less, 39 parts by mass or less, 36 parts by mass. The following may be 33 parts by mass or less, 30 parts by mass or less, 27 parts by mass or less, 24 parts by mass or less, 21 parts by mass or less, 18 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 8 parts by mass or less, 7.6 parts by mass or less, 7.2 parts by mass or less, 6.8 parts by mass or less, 6.4 parts by mass or less, 6 parts by mass or less, 5.6 parts by mass or less, 5.2 parts by mass or less, or 4.8 parts by mass or less. The lower limit of the content of the aromatic bromine-containing polymer compound may be 0.01 parts by mass or more, 0.1 parts by mass or more, 0.4 parts by mass or more, 0.8 parts by mass or more, 1.2 parts by mass or more, 1.6 parts by mass or more, 2 parts by mass or more, 2.4 parts by mass or more, 2.8 parts by mass or more, 3.2 parts by mass or more, 3.6 parts by mass or more, 4 parts by mass or more, 4.4 parts by mass or more, 4.8 parts by mass or more, 5.2 parts by mass or more, 5.6 parts by mass or more, 6 parts by mass or more, 6.4 parts by mass or more, 6.8 parts by mass or more, 7.2 parts by mass or more, 7.6 parts by mass or more, 8 parts by mass or more, 12 parts by mass or more, 15 parts by mass or more, 18 parts by mass or more, 21 parts by mass or more, 24 parts by mass or more, 27 parts by mass or more, 30 parts by mass or more, 33 parts by mass or more, or 36 parts by mass or more, per 100 parts by mass of the polyol compound.The content of aromatic odorants containing high molecular weight compounds is defined as follows: 0.01% to 100%; 0.1% to 90%; 0.4% to 80%; 0.8% to 70%; 1.2% to 63%; 1.6% to 60%; 2% to 57%; 2.4% to 54%; 2.8% to 51%; 3.2% to 48% and below. Below, 3.6 quality department or above 45 quality department or below, 4 quality department or above 42 quality department or below, 4.4 quality department or above 39 quality department or below, 4.8 quality department or above 36 quality department or below, 5.2 quality department or above 33 quality department or below, 5.6 quality department or above 30 quality department or below, 6 quality department or above 27 quality department or below, 6.4 quality department or above 24 quality department or below, 6.8 quality department or above 21 quality department or below, 7.2 quality department or above 18 quality department or below, 7.6 quality department or above 15 quality department or below, also 8 quality department or above 12 quality department or below, de àtte yoi. Furthermore, the lower limit of aromatic bromine-containing polymer compounds may be, for example, 0.001% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, 0.9% by mass or more, 1.1% by mass or more, 1.3% by mass or more, 1.5% by mass or more, 1.7% by mass or more, 1.9% by mass or more, 2.1% by mass or more, 2.3% by mass or more, 2.5% by mass or more, 2.7% by mass or more, 2.9% by mass or more, 3.2% by mass or more, 3.5% by mass or more, 3.8% by mass or more, 4.3% by mass or more, 4.8% by mass or more, 5.3% by mass or more, 5.8% by mass or more, or 7.0% by mass or more, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The upper limit of the content of the aromatic bromine-containing polymer compound is, for example, 12.0% by mass or less, 11.0% by mass or less, 1% by mass or less, based on the mass of the polyurethane foam component of the polyurethane foam-forming composition. 0.0 mass% or less, 9.0 mass% or less, 8.0 mass% or less, 7.0 mass% or less, 6.5 mass% or less, 6.0 mass% or less, 5.5 mass% or less, 5.0 mass% or less, 4.5 mass% or less, 4.0 Mass% or less, 3.5 mass% or less, 3.3 mass% or less, 3.1 mass% or less, 2.9 mass% or less, 2.7 mass% or less, 2.5 mass% or less, 2.3 mass% or less, 2.1 mass% or less, 1.9 mass% % or less, 1.7 mass% or less, 1.5 mass% or less, 1.3 mass% or less, 1.2 mass% or less, 1.0 mass% or less, 0.8 mass% or less, 0.6 mass% or less, or 0.4 mass% or less.The content of aromatic bromine-containing polymer compounds is, for example, 0.001% to 12.0% by mass, 0.01% to 11.0% by mass, 0.03% to 10.0% by mass, 0.05% to 9.0% by mass, 0.07% to 8.0% by mass, 0.09% to 7.0% by mass, 0.1% to 6.5% by mass, and 0.3% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The content may be between % by mass and 6.0% by mass, 0.5% by mass and 5.5% by mass, 0.7% by mass and 5.0% by mass, 0.9% by mass and 4.5% by mass, 1.1% by mass and 4.0% by mass, 1.3% by mass and 3.5% by mass, 1.5% by mass and 3.3% by mass, 1.7% by mass and 3.1% by mass, 1.9% by mass and 2.9% by mass, 2.1% by mass and 2.7% by mass, or 2.3% by mass and 2.5% by mass. When the content of aromatic bromine-containing polymer compounds is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the content of aromatic bromine-containing polymer compounds is below the above upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content of aromatic bromine-containing polymer compounds is above the aforementioned lower limit, the flame retardant effect derived from the aromatic bromine-containing polymer compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0036] The content ratios of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing high molecular weight compounds in polyol compositions, polyurethane foam-forming compositions, polyurethane foams, flame retardant compositions, and solid flame retardant compositions are, for example, within the following ranges. The lower limit of the content ratio of aliphatic bromine-containing compounds may be, for example, 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing high molecular weight compounds. The upper limit of the content ratio of aliphatic bromine-containing compounds may be, for example, 99% by mass or less, 96% by mass or less, 93% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing high molecular weight compounds. The content ratio of aliphatic bromine-containing compounds may be, for example, 1% to 99% by mass, 2% to 96% by mass, 3% to 93% by mass, 5% to 90% by mass, 10% to 85% by mass, 15% to 80% by mass, 20% to 75% by mass, 25% to 70% by mass, 30% to 65% by mass, 35% to 60% by mass, 40% to 55% by mass, or 45% to 50% by mass, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing high molecular weight compounds. When the content ratio of aliphatic bromine-containing compounds is within the aforementioned range, a polyurethane foam with excellent flame retardancy, a polyol composition and polyurethane foam-forming composition with suppressed caking and excellent redispersibility tend to be obtained due to the synergistic effect of the flame retardant effect derived from the aliphatic bromine-containing compound and the aromatic bromine-containing low molecular weight compound and / or aromatic bromine-containing high molecular weight compound.When the content ratio of aliphatic bromine-containing compounds is below the upper limit, the flame retardant effect derived from aromatic bromine-containing low molecular weight compounds and / or aromatic bromine-containing high molecular weight compounds tends to be more readily exhibited, resulting in a polyurethane foam with particularly excellent flame retardancy, as well as a polyol composition and polyurethane foam-forming composition that suppress caking and exhibit excellent redispersibility. When the content ratio of aliphatic bromine-containing compounds is above the lower limit, the flame retardant effect derived from aliphatic bromine-containing compounds tends to be more readily exhibited, resulting in a polyurethane foam with particularly excellent flame retardancy, as well as a polyol composition and polyurethane foam-forming composition that suppress caking and exhibit excellent redispersibility.

[0037] The lower limit of the content ratio of aromatic bromine-containing low molecular weight compounds may be, for example, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 4% by mass or more, 8% by mass or more, 12% by mass or more, 16% by mass or more, 20% by mass or more, 24% by mass or more, 28% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing high molecular weight compounds. The upper limit of the content ratio of aromatic bromine-containing low molecular weight compounds may be, for example, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 52% by mass or less, 48% by mass or less, 44% by mass or less, 40% by mass or less, 36% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing high molecular weight compounds. The content ratio of aromatic bromine-containing low molecular weight compounds may be, for example, 1% to 95% by mass, 1.5% to 90% by mass, 2% to 80% by mass, 4% to 70% by mass, 8% to 60% by mass, 12% to 52% by mass, 16% to 48% by mass, 20% to 44% by mass, 24% to 40% by mass, or 28% to 36% by mass, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing polymer compounds. When the content ratio of aromatic bromine-containing low molecular weight compounds is within the above range, a polyurethane foam with excellent flame retardancy, a polyol composition and polyurethane foam-forming composition with suppressed caking and excellent redispersibility tend to be obtained due to the synergistic effect of the flame retardant effect derived from the aromatic bromine-containing low molecular weight compounds, aliphatic bromine-containing compounds and / or aromatic bromine-containing polymer compounds.When the content ratio of aromatic bromine-containing low molecular weight compounds is below the upper limit, the flame retardant effect derived from aliphatic bromine-containing compounds and / or aromatic bromine-containing high molecular weight compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy, as well as polyol compositions and polyurethane foam-forming compositions with suppressed caking and excellent redispersibility, tend to be obtained. When the content ratio of aromatic bromine-containing low molecular weight compounds is above the lower limit, the flame retardant effect derived from aromatic bromine-containing low molecular weight compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy, as well as polyol compositions and polyurethane foam-forming compositions with suppressed caking and excellent redispersibility, tend to be obtained.

[0038] The lower limit of the content ratio of aromatic bromine-containing polymer compounds may be, for example, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 4% by mass or more, 8% by mass or more, 12% by mass or more, 16% by mass or more, 20% by mass or more, 24% by mass or more, 28% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing polymer compounds. The upper limit of the content ratio of aromatic bromine-containing polymer compounds may be, for example, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 52% by mass or less, 48% by mass or less, 44% by mass or less, 40% by mass or less, 36% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing polymer compounds. The content ratio of aromatic bromine-containing polymer compounds may be, for example, 1% to 95% by mass, 1.5% to 90% by mass, 2% to 80% by mass, 4% to 70% by mass, 8% to 60% by mass, 12% to 52% by mass, 16% to 48% by mass, 20% to 44% by mass, 24% to 40% by mass, or 28% to 36% by mass, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing polymer compounds. When the content ratio of aromatic bromine-containing polymer compounds is within the above range, a synergistic effect of the flame-retardant effect derived from aromatic bromine-containing polymer compounds, aliphatic bromine-containing compounds, and / or aromatic bromine-containing low molecular weight compounds tends to make it easier to obtain polyurethane foams with excellent flame retardancy, polyol compositions and polyurethane foam-forming compositions with suppressed caking and excellent redispersibility.When the content ratio of aromatic bromine-containing polymer compounds is below the upper limit, the flame retardant effect derived from aliphatic bromine-containing compounds and / or aromatic bromine-containing low molecular weight compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy, as well as polyol compositions and polyurethane foam-forming compositions with suppressed caking and excellent redispersibility, tend to be obtained. When the content ratio of aromatic bromine-containing polymer compounds is above the lower limit, the flame retardant effect derived from aromatic bromine-containing polymer compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy, as well as polyol compositions and polyurethane foam-forming compositions with suppressed caking and excellent redispersibility, tend to be obtained.

[0039] Bromine-containing flame retardants, when used in combination with two bromine-containing flame retardants having different decomposition temperatures, tend to produce polyurethane foams with even greater flame retardancy than when using a single bromine-containing flame retardant, as well as polyol compositions and polyurethane foam-forming compositions that suppress caking and have excellent redispersibility. In particular, by including two or more bromine-containing flame retardants selected from the group consisting of bromine-containing flame retardants with a decomposition temperature of less than 370°C, bromine-containing flame retardants with a decomposition temperature of 370°C or more but less than 450°C, it is easier to obtain polyurethane foams with particularly excellent flame retardancy, as well as polyol compositions and polyurethane foam-forming compositions that suppress caking and have excellent redispersibility.

[0040] In other words, the first bromine-containing flame retardant is one selected from the following three: (i) to (iii): (i) Bromine-containing flame retardants with a decomposition temperature of less than 370°C (ii) Bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C, (iii) Bromine-containing flame retardants with a decomposition temperature of 450°C or higher; It is preferable that the second bromine-containing flame retardant is one selected from the other two, excluding the one selected from the three (i) to (iii).

[0041] Here, the difference between the decomposition temperature of the first bromine-containing flame retardant and the decomposition temperature of the second bromine-containing flame retardant may be 15°C or higher, 20°C or higher, 25°C or higher, 30°C or higher, 35°C or higher, 40°C or higher, 45°C or higher, or 50°C or higher, and may be 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 90°C or lower, 80°C or lower, 70°C or lower, or 60°C or lower.

[0042] Examples of bromine-containing flame retardants with a decomposition temperature of less than 370°C include 2,4,6-tris(2,4-dibromopropyl)-1,3,5-triazine (Pyroguard SR-740N), 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] (Pyroguard SR-720), and 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2-methyl-2,3-dibromopropyloxy)benzene] (Pyroguard SR-130). Among these, 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] is preferred.

[0043] Examples of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C include 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (Pyroguard SR-245) and ethylenebis(pentabromophenyl).

[0044] Examples of bromine-containing flame retardants with a decomposition temperature of 450°C or higher include homopolymers derived from 2,6-dibromophenol and 2,4-dibromophenol (Pyroguard SR-460B), polycarbonate oligomers produced using brominated bisphenol A as a raw material, and brominated polycarbonates such as copolymers of polycarbonate oligomers and bisphenol A (FG-8500, FG-7500, FG-7000).

[0045] The upper limit of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C is 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, based on 100 parts by mass of the polyol compound. , 63 parts by mass or less, 60 parts by mass or less, 57 parts by mass or less, 54 parts by mass or less, 51 parts by mass or less, 48 ​​parts by mass or less, 45 parts by mass or less, 42 parts by mass or less, 39 parts by mass or less, 36 parts by mass or less , 33 parts by mass or less, 30 parts by mass or less, 27 parts by mass or less, 24 parts by mass or less, 21 parts by mass or less, 18 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 8 parts by mass or less, 7.6 parts by mass or less , 7.2 parts by weight or less, 6.8 parts by weight or less, 6.4 parts by weight or less, 6 parts by weight or less, 5.6 parts by weight or less, 5.2 parts by weight or less, 4.8 parts by weight or less, or 4.4 parts by weight or less. The lower limit of the content of a bromine-containing flame retardant with a decomposition temperature of less than 370°C may be 0.01 parts by mass or more, 0.1 parts by mass or more, 0.4 parts by mass or more, 0.8 parts by mass or more, 1.2 parts by mass or more, 1.6 parts by mass or more, 2 parts by mass or more, 2.4 parts by mass or more, 2.8 parts by mass or more, 3.2 parts by mass or more, 3.6 parts by mass or more, 4 parts by mass or more, 4.4 parts by mass or more, 4.8 parts by mass or more, 5.2 parts by mass or more, 5.6 parts by mass or more, 6 parts by mass or more, 6.4 parts by mass or more, 6.8 parts by mass or more, 7.2 parts by mass or more, 7.6 parts by mass or more, 8 parts by mass or more, 12 parts by mass or more, 15 parts by mass or more, 18 parts by mass or more, 21 parts by mass or more, 24 parts by mass or more, 27 parts by mass or more, 30 parts by mass or more, 33 parts by mass or more, or 36 parts by mass or more, per 100 parts by mass of the polyol compound.The content of the bromine-containing flame retardant having a decomposition temperature of less than 370°C may be 0.01 to 100 parts by mass, 0.1 to 90 parts by mass, 0.4 to 80 parts by mass, 0.8 to 70 parts by mass, 1.2 to 63 parts by mass, 1.6 to 60 parts by mass, 2 to 57 parts by mass, 2.4 to 54 parts by mass, 2.8 to 51 parts by mass, 3.2 to 48 parts by mass, 3.6 to 45 parts by mass, 4 to 42 parts by mass, 4.4 to 39 parts by mass, 4.8 to 36 parts by mass, 5.2 to 33 parts by mass, 5.6 to 30 parts by mass, 6 to 27 parts by mass, 6.4 to 24 parts by mass, 6.8 to 21 parts by mass, 7.2 to 18 parts by mass, 7.6 to 15 parts by mass, or 8 to 12 parts by mass, relative to 100 parts by mass of the polyol compound. Furthermore, the lower limit for bromine-containing flame retardants with a decomposition temperature of less than 370°C is, for example, 0.001% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, and 0.9% by mass or more, relative to the mass of the polyurethane foam component of the polyurethane foam forming composition. It may be 1.1% by mass or more, 1.3% by mass or more, 1.5% by mass or more, 1.7% by mass or more, 1.9% by mass or more, 2.1% by mass or more, 2.3% by mass or more, 2.5% by mass or more, 2.7% by mass or more, 2.9% by mass or more, 3.2% by mass or more, 3.5% by mass or more, 3.8% by mass or more, 4.3% by mass or more, 4.8% by mass or more, 5.3% by mass or more, 5.8% by mass or more, or 7.0% by mass or more. The upper limit for the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C may be, for example, 12.0% by mass or less, 11.0% by mass or less, 10.0% by mass or less, 9.0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.5% by mass or less, 6.0% by mass or less, 5.5% by mass or less, 5.0% by mass or less, 4.5% by mass or less, 4.0% by mass or less, 3.5% by mass or less, 3.3% by mass or less, 3.1% by mass or less, 2.9% by mass or less, 2.7% by mass or less, 2.5% by mass or less, 2.3% by mass or less, 2.1% by mass or less, 1.9% by mass or less, 1.7% by mass or less, 1.5% by mass or less, 1.3% by mass or less, 1.2% by mass or less, 1.0% by mass or less, 0.8% by mass or less, 0.6% by mass or less, or 0.4% by mass or less, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition.The content of bromine-containing flame retardants with a decomposition temperature of less than 370°C is, for example, 0.001% to 12.0% by mass, 0.01% to 11.0% by mass, 0.03% to 10.0% by mass, 0.05% to 9.0% by mass, 0.07% to 8.0% by mass, 0.09% to 7.0% by mass, 0.1% to 6.5% by mass, and 0% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam forming composition. The amount may be 0.3% by mass or more and 6.0% by mass or less, 0.5% by mass or more and 5.5% by mass or less, 0.7% by mass or more and 5.0% by mass or less, 0.9% by mass or more and 4.5% by mass or less, 1.1% by mass or more and 4.0% by mass or less, 1.3% by mass or more and 3.5% by mass or less, 1.5% by mass or more and 3.3% by mass or less, 1.7% by mass or more and 3.1% by mass or less, 1.9% by mass or more and 2.9% by mass or less, 2.1% by mass or more and 2.7% by mass or less, or 2.3% by mass or more and 2.5% by mass or less. When the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C is below the above upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C is above the aforementioned lower limit, the flame retardant effect derived from the bromine-containing flame retardants with a decomposition temperature of less than 370°C is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0046] The upper limit of the content of bromine-containing flame retardants with a decomposition temperature of 370°C or more and less than 450°C is 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 63 parts by mass or less, 60 parts by mass or less, 57 parts by mass or less, 54 parts by mass or less, 51 parts by mass or less, 48 ​​parts by mass or less, 45 parts by mass or less, 42 parts by mass or less, 39 parts by mass or less Parts by weight or less, 36 parts by weight or less, 33 parts by weight or less, 30 parts by weight or less, 27 parts by weight or less, 24 parts by weight or less, 21 parts by weight or less, 18 parts by weight or less, 15 parts by weight or less, 12 parts by weight or less, 8 parts by weight or less, 7.6 parts by weight or less, 7.2 parts by weight or less, 6.8 parts by weight or less, 6.4 parts by weight or less, 6 parts by weight or less, 5.6 parts by weight or less, or 5.2 parts by weight or less. The lower limit of the content of a bromine-containing flame retardant with a decomposition temperature of 370°C or higher and less than 450°C may be 0.01 parts by mass or more, 0.1 parts by mass or more, 0.4 parts by mass or more, 0.8 parts by mass or more, 1.2 parts by mass or more, 1.6 parts by mass or more, 2 parts by mass or more, 2.4 parts by mass or more, 2.8 parts by mass or more, 3.2 parts by mass or more, 3.6 parts by mass or more, 4 parts by mass or more, 4.4 parts by mass or more, 4.8 parts by mass or more, 5.2 parts by mass or more, 5.6 parts by mass or more, 6 parts by mass or more, 6.4 parts by mass or more, 6.8 parts by mass or more, 7.2 parts by mass or more, 7.6 parts by mass or more, 8 parts by mass or more, 12 parts by mass or more, 15 parts by mass or more, 18 parts by mass or more, 21 parts by mass or more, 24 parts by mass or more, 27 parts by mass or more, 30 parts by mass or more, or 33 parts by mass or more, per 100 parts by mass of the polyol compound.The decomposition temperature is 370℃ or higher. The content of odorant (not fully decomposed at 450℃) and flame retardant is: 100% by mass of polyol compound; 0.01% to 100% by mass; 0.1% to 90% by mass; 0.4% to 80% by mass; 0.8% to 70% by mass; 1.2% to 63% by mass; 1.6% to 60% by mass; 2% to 57% by mass; 2.4% to 54% by mass; 2.8% to 51% by mass; 3.2% or higher by mass. 48 quality department and below, 3.6 quality department and above, 45 quality department and below, 4 quality department and above, 42 quality department and below, 4.4 quality department and above, 39 quality department and below, 4.8 quality department and above, 36 quality department and below, 5.2 quality department and above, 33 quality department and below, 5.6 quality department and above, 30 quality department and below, 6 quality department and above, 27 quality department and below, 6.4 quality department and above, 24 quality department and below, 6.8 quality department and above, 21 quality department and below, 7.2 quality department and above, 18 quality department and below, 7.6 quality department and above, 15 quality department and below, and also 8 quality department and above, 12 quality department and below. Furthermore, the lower limit for bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C is, for example, 0.001% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, and 0.9% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. It may be % or more, 1.1% by mass or more, 1.3% by mass or more, 1.5% by mass or more, 1.7% by mass or more, 1.9% by mass or more, 2.1% by mass or more, 2.3% by mass or more, 2.5% by mass or more, 2.7% by mass or more, 2.9% by mass or more, 3.2% by mass or more, 3.5% by mass or more, 3.8% by mass or more, 4.3% by mass or more, 4.8% by mass or more, 5.3% by mass or more, 5.8% by mass or more, or 7.0% by mass or more. The upper limit for the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C is, for example, 12.0% by mass or less, 11.0% by mass or less, 10.0% by mass or less, 9.0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.5% by mass or less, 6.0% by mass or less, 5.5% by mass or less, 5.0% by mass or less, and 4.5% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. 4.0% by mass or less, 3.5% by mass or less, 3.3% by mass or less, 3.1% by mass or less, 2.9% by mass or less, 2.7% by mass or less, 2.5% by mass or less, 2.3% by mass or less, 2.1% by mass or less, 1. It may be 9% by mass or less, 1.7% by mass or less, 1.5% by mass or less, 1.3% by mass or less, 1.2% by mass or less, 1.0% by mass or less, 0.8% by mass or less, 0.6% by mass or less, or 0.4% by mass or less.The content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C is, for example, 0.001% to 12.0% by mass, 0.01% to 11.0% by mass, 0.03% to 10.0% by mass, 0.05% to 9.0% by mass, 0.07% to 8.0% by mass, 0.09% to 7.0% by mass, and 0.1% to 6.5% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The following may be the amounts: 0.3% by mass or more and 6.0% by mass or less, 0.5% by mass or more and 5.5% by mass or less, 0.7% by mass or more and 5.0% by mass or less, 0.9% by mass or more and 4.5% by mass or less, 1.1% by mass or more and 4.0% by mass or less, 1.3% by mass or more and 3.5% by mass or less, 1.5% by mass or more and 3.3% by mass or less, 1.7% by mass or more and 3.1% by mass or less, 1.9% by mass or more and 2.9% by mass or less, 2.1% by mass or more and 2.7% by mass or less, or 2.3% by mass or more and 2.5% by mass or less. When the content of a bromine-containing flame retardant with a decomposition temperature of 370°C or more and less than 450°C is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C is below the upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C is above the lower limit, the flame retardant effect derived from the bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C tends to be more readily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0047] The upper limit of the content of the bromine-containing flame retardant with a decomposition temperature of 450°C or higher is 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 63 parts by mass or less, 60 parts by mass or less, 57 parts by mass or less, 54 parts by mass or less, 51 parts by mass or less, 48 ​​parts by mass or less, 45 parts by mass or less, 42 parts by mass or less, 39 parts by mass or less, 36 Parts by mass or less, 33 parts by mass or less, 30 parts by mass or less, 27 parts by mass or less, 24 parts by mass or less, 21 parts by mass or less, 18 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 8 parts by mass or less, 7 .6 parts by weight or less, 7.2 parts by weight or less, 6.8 parts by weight or less, 6.4 parts by weight or less, 6 parts by weight or less, 5.6 parts by weight or less, 5.2 parts by weight or less, or 4.8 parts by weight or less. The lower limit of the content of a bromine-containing flame retardant with a decomposition temperature of 450°C or higher may be 0.01 parts by mass or more, 0.1 parts by mass or more, 0.4 parts by mass or more, 0.8 parts by mass or more, 1.2 parts by mass or more, 1.6 parts by mass or more, 2 parts by mass or more, 2.4 parts by mass or more, 2.8 parts by mass or more, 3.2 parts by mass or more, 3.6 parts by mass or more, 4 parts by mass or more, 4.4 parts by mass or more, 4.8 parts by mass or more, 5.2 parts by mass or more, 5.6 parts by mass or more, 6 parts by mass or more, 6.4 parts by mass or more, 6.8 parts by mass or more, 7.2 parts by mass or more, 7.6 parts by mass or more, 8 parts by mass or more, 12 parts by mass or more, 15 parts by mass or more, 18 parts by mass or more, 21 parts by mass or more, 24 parts by mass or more, 27 parts by mass or more, 30 parts by mass or more, 33 parts by mass or more, or 36 parts by mass or more, per 100 parts by mass of the polyol compound.The content of the bromine-containing flame retardant having a decomposition temperature of 450°C or higher may be 0.01 to 100 parts by mass, 0.1 to 90 parts by mass, 0.4 to 80 parts by mass, 0.8 to 70 parts by mass, 1.2 to 63 parts by mass, 1.6 to 60 parts by mass, 2 to 57 parts by mass, 2.4 to 54 parts by mass, 2.8 to 51 parts by mass, 3.2 to 48 parts by mass, 3.6 to 45 parts by mass, 4 to 42 parts by mass, 4.4 to 39 parts by mass, 4.8 to 36 parts by mass, 5.2 to 33 parts by mass, 5.6 to 30 parts by mass, 6 to 27 parts by mass, 6.4 to 24 parts by mass, 6.8 to 21 parts by mass, 7.2 to 18 parts by mass, 7.6 to 15 parts by mass, or 8 to 12 parts by mass, relative to 100 parts by mass of the polyol compound. Furthermore, the lower limit for bromine-containing flame retardants with a decomposition temperature of 450°C or higher is, for example, 0.001% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, and 0.9% by mass or more, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. It may be 1.1% by mass or more, 1.3% by mass or more, 1.5% by mass or more, 1.7% by mass or more, 1.9% by mass or more, 2.1% by mass or more, 2.3% by mass or more, 2.5% by mass or more, 2.7% by mass or more, 2.9% by mass or more, 3.2% by mass or more, 3.5% by mass or more, 3.8% by mass or more, 4.3% by mass or more, 4.8% by mass or more, 5.3% by mass or more, 5.8% by mass or more, or 7.0% by mass or more. The upper limit for the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher may be, for example, 12.0% by mass or less, 11.0% by mass or less, 10.0% by mass or less, 9.0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.5% by mass or less, 6.0% by mass or less, 5.5% by mass or less, 5.0% by mass or less, 4.5% by mass or less, 4.0% by mass or less, 3.5% by mass or less, 3.3% by mass or less, 3.1% by mass or less, 2.9% by mass or less, 2.7% by mass or less, 2.5% by mass or less, 2.3% by mass or less, 2.1% by mass or less, 1.9% by mass or less, 1.7% by mass or less, 1.5% by mass or less, 1.3% by mass or less, 1.2% by mass or less, 1.0% by mass or less, 0.8% by mass or less, 0.6% by mass or less, or 0.4% by mass or less, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition.The content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is, for example, 0.001% to 12.0% by mass, 0.01% to 11.0% by mass, 0.03% to 10.0% by mass, 0.05% to 9.0% by mass, 0.07% to 8.0% by mass, 0.09% to 7.0% by mass, 0.1% to 6.5% by mass, 0 The amount may be 0.3% by mass or more and 6.0% by mass or less, 0.5% by mass or more and 5.5% by mass or less, 0.7% by mass or more and 5.0% by mass or less, 0.9% by mass or more and 4.5% by mass or less, 1.1% by mass or more and 4.0% by mass or less, 1.3% by mass or more and 3.5% by mass or less, 1.5% by mass or more and 3.3% by mass or less, 1.7% by mass or more and 3.1% by mass or less, 1.9% by mass or more and 2.9% by mass or less, 2.1% by mass or more and 2.7% by mass or less, or 2.3% by mass or more and 2.5% by mass or less. When the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is below the above upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is above the aforementioned lower limit, the flame retardant effect derived from the bromine-containing flame retardants with a decomposition temperature of 450°C or higher is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0048] The content ratios of bromine-containing flame retardants with a decomposition temperature of less than 370°C, bromine-containing flame retardants with a decomposition temperature of 370°C or more and less than 450°C, and bromine-containing flame retardants with a decomposition temperature of 450°C or more in polyol compositions, polyurethane foam-forming compositions, polyurethane foams, flame retardant compositions, and solid flame retardant compositions are, for example, within the following ranges. The lower limit of the content ratio of bromine-containing flame retardants with a decomposition temperature of less than 370°C may be, for example, 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or more and less than 450°C, and the content of bromine-containing flame retardants with a decomposition temperature of 450°C or more. The upper limit for the content ratio of bromine-containing flame retardants with a decomposition temperature of less than 370°C may be, for example, 99% by mass or less, 96% by mass or less, 93% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or more and less The content ratio of bromine-containing flame retardants with a decomposition temperature of less than 370°C may be, for example, 1% to 99% by mass, 2% to 96% by mass, 3% to 93% by mass, 5% to 90% by mass, 10% to 85% by mass, 15% to 80% by mass, 20% to 75% by mass, 25% to 70% by mass, 30% to 65% by mass, 35% to 60% by mass, 40% to 55% by mass, or 45% to 50% by mass, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, bromine-containing flame retardants with a decomposition temperature of 370°C or more and less than 450°C, and bromine-containing flame retardants with a decomposition temperature of 450°C or more.When the content ratio of bromine-containing flame retardants with a decomposition temperature of less than 370°C is within the aforementioned range, a synergistic effect of flame retardant effects derived from bromine-containing flame retardants with a decomposition temperature of less than 370°C, bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C, and / or bromine-containing flame retardants with a decomposition temperature of 450°C or higher tends to be obtained, resulting in a polyurethane foam with excellent flame retardancy, and a polyol composition and polyurethane foam-forming composition with suppressed caking and excellent redispersibility. When the content ratio of bromine-containing flame retardants with a decomposition temperature of less than 370°C is below the aforementioned upper limit, the flame retardant effect derived from bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C, and / or bromine-containing flame retardants with a decomposition temperature of 450°C or higher tends to be more readily exhibited, resulting in a polyurethane foam with particularly excellent flame retardancy, and a polyol composition and polyurethane foam-forming composition with suppressed caking and excellent redispersibility. When the content ratio of bromine-containing flame retardants with a decomposition temperature of less than 370°C is above the aforementioned lower limit, the flame retardant effect derived from the bromine-containing flame retardants with a decomposition temperature of less than 370°C is more likely to be exhibited, and it is easier to obtain polyurethane foams with particularly excellent flame retardancy, as well as polyol compositions and polyurethane foam-forming compositions that suppress caking and have excellent redispersibility. The lower limit of the content ratio of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C may be, for example, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 4% by mass or more, 8% by mass or more, 12% by mass or more, 16% by mass or more, 20% by mass or more, 24% by mass or more, 28% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher. The upper limit of the content ratio of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C may be, for example, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 52% by mass or less, 48% by mass or less, 44% by mass or less, 40% by mass or less, 36% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C, and the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher. The content ratio of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C may be, for example, 1% by mass or more and 95% by mass or less, 1.5% by mass or more and 90% by mass or less, 2% by mass or more and 80% by mass or less, 4% by mass or more and 70% by mass or less, 8% by mass or more and 60% by mass or less, 12% by mass or more and 52% by mass or less, 16% by mass or more and 48% by mass or less, 20% by mass or more and 44% by mass or less, 24% by mass or more and 40% by mass or less, or 28% by mass or more and 36% by mass or less, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C, and the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher.When the content ratio of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C is within the aforementioned range, a synergistic effect of flame retardant effects derived from bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C and bromine-containing flame retardants with a decomposition temperature of less than 370°C and / or bromine-containing flame retardants with a decomposition temperature of 450°C or higher tends to result in a polyurethane foam with excellent flame retardancy, as well as a polyol composition and polyurethane foam-forming composition with suppressed caking and excellent redispersibility. When the content ratio of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C is below the aforementioned upper limit, the flame retardant effect derived from bromine-containing flame retardants with a decomposition temperature of less than 370°C and / or bromine-containing flame retardants with a decomposition temperature of 450°C or higher tends to be more readily exhibited, resulting in a polyurethane foam with particularly excellent flame retardancy, as well as a polyol composition and polyurethane foam-forming composition with suppressed caking and excellent redispersibility. When the content ratio of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C is above the aforementioned lower limit, the flame retardant effect derived from the bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C is more likely to be exhibited, and a polyurethane foam with particularly excellent flame retardancy, as well as a polyol composition and polyurethane foam-forming composition that suppress caking and have excellent redispersibility, tend to be obtained. The lower limit of the content ratio of bromine-containing flame retardants with a decomposition temperature of 450°C or higher may be, for example, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 4% by mass or more, 8% by mass or more, 12% by mass or more, 16% by mass or more, 20% by mass or more, 24% by mass or more, 28% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or more and the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher. The upper limit of the content ratio of bromine-containing flame retardants with a decomposition temperature of 450°C or higher may be, for example, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 52% by mass or less, 48% by mass or less, 44% by mass or less, 40% by mass or less, 36% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher. The content ratio of bromine-containing flame retardants with a decomposition temperature of 450°C or higher may be, for example, 1% to 95% by mass, 1.5% to 90% by mass, 2% to 80% by mass, 4% to 70% by mass, 8% to 60% by mass, 12% to 52% by mass, 16% to 48% by mass, 20% to 44% by mass, 24% to 40% by mass, or 28% to 36% by mass, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, bromine-containing flame retardants with a decomposition temperature of 370°C or higher or less than 450°C, and bromine-containing flame retardants with a decomposition temperature of 450°C or higher.When the content ratio of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is within the aforementioned range, a synergistic effect of flame retardant effects derived from bromine-containing flame retardants with a decomposition temperature of 450°C or higher, bromine-containing flame retardants with a decomposition temperature of less than 370°C, and / or bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C tends to result in a polyurethane foam with excellent flame retardancy, as well as a polyol composition and polyurethane foam-forming composition with suppressed caking and excellent redispersibility. When the content ratio of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is below the aforementioned upper limit, the flame retardant effect derived from bromine-containing flame retardants with a decomposition temperature of less than 370°C and / or bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C tends to be more readily exhibited, resulting in a polyurethane foam with particularly excellent flame retardancy, as well as a polyol composition and polyurethane foam-forming composition with suppressed caking and excellent redispersibility. When the content ratio of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is above the aforementioned lower limit, the flame retardant effect derived from the bromine-containing flame retardants with a decomposition temperature of 450°C or higher is more likely to be exhibited, and it is easier to obtain polyurethane foams with particularly excellent flame retardancy, as well as polyol compositions and polyurethane foam-forming compositions that suppress caking and have excellent redispersibility.

[0049] The polyol composition may contain solid flame retardants other than bromine-containing flame retardants. Either the polyisocyanate composition or the polyol composition may contain solid flame retardants other than bromine-containing flame retardants, or both may contain them. Examples of solid flame retardants other than bromine-containing flame retardants include solid phosphorus-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, metal hydroxide-based flame retardants, phosphazene, silicone-based flame retardants, and organic sulfonate-based flame retardants. Two or more of these solid flame retardants may be used in combination.

[0050] (Solid phosphorus-containing flame retardant) Examples of solid phosphorus-containing flame retardants include red phosphorus, phosphinic acid-based flame retardants, and phosphate-containing flame retardants.

[0051] <Red phosphorus> There are no restrictions on the type of red phosphorus used; for example, commercially available products can be selected and used as appropriate.

[0052] <Phosphinic acid-based flame retardant> As phosphinic acid-based flame retardants, one or more selected from phosphinic acid-based flame retardants represented by formula (A-1) or formula (A-2), and polymers thereof, are preferred.

[0053] [ka]

[0054] [ka]

[0055] In the formula, R 1 , R 2 R is either the same or different, and is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms; 3 is a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 20 carbon atoms, or an arylalkylene group having 7 to 20 carbon atoms; M is Na, Li, K, Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base; m is an integer selected from 1 to 4, n is an integer selected from 1 to 4, and x is an integer selected from 1 to 4.

[0056] R 1 , R 2 Preferably, these are the same or different groups, and are a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, or a phenyl group. 3Preferably, M is a methylene group, ethylene group, n-propylene group, i-propylene group, n-butylene group, t-butylene group, n-pentylene group, n-octylene group, n-dodecylene group, phenylene group, naphthylene group, methylphenylene group, ethylphenylene group, t-butylphenylene group, methylnaphthylene group, ethylnaphthylene group, t-butylnaphthylene group, phenylmethylene group, phenylpropylene group, or phenylbutylene group. The above M is preferably Mg, Ca, Al, Sn, Ti, Zn, Fe, or Zr.

[0057] Such phosphinic acid-based flame retardants can be obtained, for example, by reacting alkyl sulfonates and / or phosphinic acids and / or their alkali metal salts with olefins in the presence of a free radical initiator to obtain phosphinic acids and / or their alkali metal salts, and then further reacting them with a metal compound. Specifically, examples of phosphinate-based flame retardants include aluminum phosphinate, sodium phosphinate, calcium phosphinate, potassium phosphinate, aluminum tris(diethylphosphinate), potassium tris(diethylphosphinate), calcium tris(diethylphosphinate), sodium tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(butylethylphosphinate), aluminum tris(diphenylphosphinate), zinc bis(diethylphosphinate), zinc bis(methylethylphosphinate), zinc bis(diphenylphosphinate), titanyl bis(diethylphosphinate), titanium tetrakis(diethylphosphinate), titanyl bis(methylethylphosphinate), titanium tetrakis(methylethylphosphinate), titanyl bis(diphenylphosphinate), titanium tetrakis(diphenylphosphinate), etc., and any combination of two or more of these. Among these, aluminum phosphinate; sodium phosphinate; and tris(phosphinate)aluminum selected from tris(diethylphosphinate)aluminum, tris(methylethylphosphinate)aluminum, tris(butylethylphosphinate)aluminum, and tris(diphenylphosphinate)aluminum are particularly preferred.

[0058] [Phosphate-containing flame retardant] Examples of phosphate-containing flame retardants include phosphates consisting of a salt of phosphoric acid with at least one metal or compound selected from metals of groups IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. While there are no particular limitations on phosphoric acid, various types such as monophosphate, pyrophosphate, and polyphosphate are examples. Examples of metals of groups IA to 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, piperazine, and any combination of two or more of these. Examples of aromatic amines include pyridine, triazine, and melamine. Furthermore, phosphate-containing flame retardants may be subjected to known water-resistance-improving treatments such as silane coupling agent treatment or coating with melamine resin.

[0059] Specific examples of phosphate-containing flame retardants include monophosphates, pyrophosphates, and polyphosphates.

[0060] The monophosphates are not particularly limited, but examples include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite; and any combination of two or more of these.

[0061] Polyphosphates are not particularly limited, but examples include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, aluminum polyphosphate, and any combination of two or more of these.

[0062] Among these, the use of polyphosphates is preferable because it improves the self-extinguishing properties of phosphate-containing flame retardants, and the use of ammonium polyphosphate is even more preferable.

[0063] (Boron-containing flame retardant) Examples of boron-containing flame retardants 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, ammonium borate, and any combination of two or more of these. Among these, zinc borate is preferred.

[0064] [Antimony-containing flame retardant] Examples of antimony-containing flame retardants include antimony oxide, antimonate salts, pyroantimonate salts, and any combination of two or more of these. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonate salts include sodium antimonate and potassium antimonate, and any combination of two or more of these. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate, and any combination of two or more of these. Antimony-containing flame retardants are preferably antimony oxide.

[0065] [Metal hydroxide-based flame retardants] Examples of metal hydroxide-based flame retardants include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, and any combination of two or more of these.

[0066] [Liquid flame retardant] The polyol composition contains a liquid flame retardant. Either the polyisocyanate composition or the polyol composition may contain a liquid flame retardant, or both may contain one. Examples of liquid flame retardants include phosphate ester-based flame retardants such as monophosphate esters and condensed phosphate esters. In particular, it is preferable to use phosphate ester-based flame retardants as the liquid flame retardant. Examples of monophosphate esters, though not particularly limited, include trimethyl phosphate, triethyl phosphate, tributoxyethyl phosphate, tributyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresylphenyl phosphate, dimethylmethyl phosphonate, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, tris(β-chloropropyl) phosphate, and any combination of two or more of these. The condensed phosphate esters are not particularly limited, but examples include resorcinol polyphenyl phosphate (product name CR-733S, manufactured by Daihachi Chemical Co., Ltd.), bisphenol A polycresyl phosphate (product name CR-741, manufactured by Daihachi Chemical Co., Ltd.), and aromatic condensed phosphate esters. Among these, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, and tris(β-chloropropyl) phosphate are preferred.

[0067] The upper limit of the content of liquid flame retardant is 300 parts by mass or less, 280 parts by mass or less, 260 parts by mass or less, 240 parts by mass or less, 220 parts by mass or less, 200 parts by mass or less, 180 parts by mass or less, 160 parts by mass or less, 140 parts by mass or less, 135 parts by mass or less, 130 parts by mass or less, 125 parts by mass or less, 120 parts by mass or less Parts by weight or less, 115 parts by weight or less, 110 parts by weight or less, 105 parts by weight or less, 100 parts by weight or less, 95 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 77 parts by weight or less, 74 parts by weight or less, 71 parts by weight or less, 68 parts by weight or less, 65 parts by weight or less, 60 parts by weight or less, 55 parts by weight or less, 50 parts by weight or less, or 45 parts by weight or less. The lower limit of the liquid flame retardant content may be 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, 55 parts by mass or more, 60 parts by mass or more, 65 parts by mass or more, 68 parts by mass or more, 71 parts by mass or more, 74 parts by mass or more, 77 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, 95 parts by mass or more, 100 parts by mass or more, 105 parts by mass or more, 110 parts by mass or more, 115 parts by mass or more, 120 parts by mass or more, 125 parts by mass or more, 130 parts by mass or more, or 135 parts by mass or more, per 100 parts by mass of the polyol compound. The liquid flame retardant content is as follows, per 100 parts by mass of the polyol compound: 1 to 300 parts by mass, 5 to 280 parts by mass, 10 to 260 parts by mass, 15 to 240 parts by mass, 20 to 220 parts by mass, 25 to 200 parts by mass, 30 to 180 parts by mass, 35 to 160 parts by mass, and 40 to 140 parts by mass. Below, 45 parts to 135 parts by mass, 50 parts to 130 parts by mass, 55 parts to 125 parts by mass, 60 parts to 120 parts by mass, 65 parts to 115 parts by mass, 68 It may be at least 71 parts by mass and at most 105 parts by mass, at least 74 parts by mass and at most 100 parts by mass, at least 77 parts by mass and at most 95 parts by mass, or at least 80 parts by mass and at most 90 parts by mass. Furthermore, the lower limit of the liquid flame retardant content may be, for example, 1% by mass or more, 2% by mass or more, 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 8% by mass or more, 9% by mass or more, 10% by mass or more, 11% by mass or more, 12% by mass or more, 13% by mass or more, 14% by mass or more, 15% by mass or more, 16% by mass or more, 17% by mass or more, 18% by mass or more, 19% by mass or more, 20% by mass or more, 22% by mass or more, 24% by mass or more, 26% by mass or more, 28% by mass or more, or 30% by mass or more, relative to the mass of the polyurethane foam component of the polyurethane foam forming composition. The upper limit of the liquid flame retardant content may be, for example, 36% by mass or less, 34% by mass or less, 32% by mass or less, 30% by mass or less, 28% by mass or less, 26% by mass or less, 25% by mass or less, 24% by mass or less, 23% by mass or less, 22% by mass or less, 21% by mass or less, 20% by mass or less, 19% by mass or less, 18% by mass or less, 17% by mass or less, 16% by mass or less, 15% by mass or less, 14% by mass or less, 13% by mass or less, 12% by mass or less, 11% by mass or less, 9% by mass or less, 7% by mass or less, or 5% by mass or less, relative to the mass of the polyurethane foam component of the polyurethane foam forming composition. The liquid flame retardant content may be, for example, 1% to 36% by mass, 2% to 34% by mass, 4% to 32% by mass, 5% to 30% by mass, 6% to 28% by mass, 7% to 26% by mass, 8% to 25% by mass, 9% to 24% by mass, 10% to 23% by mass, 11% to 22% by mass, 12% to 21% by mass, 13% to 20% by mass, 14% to 19% by mass, 15% to 18% by mass, or 16% to 17% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. When the liquid flame retardant content is within the above range, it tends to be easier to obtain a polyurethane foam with excellent flame retardancy. When the liquid flame retardant content is below the upper limit, the rate of conversion from unreacted isocyanate groups to isocyanurate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the liquid flame retardant content is above the lower limit, the flame retardant effect derived from the flame retardant is more easily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0068] The upper limit of the total content of solid flame retardant and liquid flame retardant is 400 parts by mass or less, 380 parts by mass or less, 360 parts by mass or less, 340 parts by mass or less, 320 parts by mass or less, 300 parts by mass or less, 280 parts by mass or less, 260 parts by mass or less, 240 parts by mass or less, 220 parts by mass or less, 200 parts by mass or less, It may be 190 parts by mass or less, 180 parts by mass or less, 170 parts by mass or less, 160 parts by mass or less, 150 parts by mass or less, 140 parts by mass or less, 130 parts by mass or less, 125 parts by mass or less, 120 parts by mass or less, 115 parts by mass or less, 110 parts by mass or less, 105 parts by mass or less, 100 parts by mass or less, 90 parts by mass or less, or 80 parts by mass or less. The lower limit of the total content of solid and liquid flame retardants may be 1 part by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, 100 parts by mass or more, 105 parts by mass or more, 110 parts by mass or more, 115 parts by mass or more, 120 parts by mass or more, 125 parts by mass or more, 130 parts by mass or more, 140 parts by mass or more, 150 parts by mass or more, 160 parts by mass or more, 170 parts by mass or more, 180 parts by mass or more, 190 parts by mass or more, 200 parts by mass or more, 220 parts by mass or more, or 240 parts by mass or more, per 100 parts by mass of the polyol compound. The total content of solid and liquid flame retardants may be 1 to 400 parts by mass, 10 to 380 parts by mass, 20 to 360 parts by mass, 30 to 340 parts by mass, 40 to 320 parts by mass, 50 to 300 parts by mass, 60 to 280 parts by mass, 70 to 260 parts by mass, 80 to 240 parts by mass, 90 to 220 parts by mass, 100 to 200 parts by mass, 105 to 190 parts by mass, 110 to 180 parts by mass, 115 to 170 parts by mass, 120 to 160 parts by mass, 125 to 150 parts by mass, or 130 to 140 parts by mass per 100 parts by mass of the polyol compound. Furthermore, the lower limit of the total content of solid and liquid flame retardants may be, for example, 5% by mass or more, 7% by mass or more, 10% by mass or more, 12% by mass or more, 14% by mass or more, 16% by mass or more, 18% by mass or more, 20% by mass or more, 22% by mass or more, 24% by mass or more, 26% by mass or more, 28% by mass or more, 30% by mass or more, 32% by mass or more, 34% by mass or more, 37% by mass or more, 40% by mass or more, 43% by mass or more, 46% by mass or more, 49% by mass or more, or 52% by mass or more, relative to the mass of the polyurethane foam component of the polyurethane foam forming composition. The upper limit of the total content of solid and liquid flame retardants may be, for example, 57% by mass or less, 54% by mass or less, 51% by mass or less, 48% by mass or less, 45% by mass or less, 42% by mass or less, 39% by mass or less, 36% by mass or less, 33% by mass or less, 30% by mass or less, 28% by mass or less, 26% by mass or less, 24% by mass or less, 22% by mass or less, 20% by mass or less, 18% by mass or less, 16% by mass or less, 14% by mass or less, 12% by mass or less, or 10% by mass or less, relative to the mass of the polyurethane foam component of the polyurethane foam forming composition. The total content of solid and liquid flame retardants may be, for example, 5% to 57% by mass, 7% to 54% by mass, 10% to 51% by mass, 12% to 48% by mass, 14% to 45% by mass, 16% to 42% by mass, 18% to 39% by mass, 20% to 36% by mass, 22% to 33% by mass, 24% to 30% by mass, or 26% to 28% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. When the total content of solid and liquid flame retardants is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the total content of solid and liquid flame retardants is below the above upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the total content of solid and liquid flame retardants is above the aforementioned lower limit, the flame retardant effect derived from the flame retardants is more easily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0069] [Polyurethane foam] A polyurethane foam in yet another aspect of this disclosure is a foam of the polyurethane foam-forming composition described above.

[0070] <Polyol compounds> The polyol composition contains a polyol compound. The polyol compound is not particularly limited, but it is preferable that it contains polyether polyols and polyester polyols. Among these, it is preferable that it contains aromatic polyols such as aromatic polyether polyols and aromatic polyester polyols from the viewpoint of improving the flame retardancy of the resulting polyurethane foam. Furthermore, it is particularly preferable that it contains terephthalic acid-based polyester polyols from the viewpoint of improving the flame retardancy of the resulting polyurethane foam.

[0071] (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. Specific examples of initiators include aliphatic polyhydric alcohols, aliphatic amines, aromatic amines, and any combination of two or more of these. Examples of aliphatic polyhydric alcohols include glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, and cyclohexanedimethanol; triols such as trimethylolpropane and glycerin; and tetrafunctional alcohols such as pentaerythritol. Examples of aliphatic amines include alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine; and alkanolamines such as monoethanolamine and diethanolamine. Examples of aromatic amines include aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, and Mannich condensates.

[0072] As for polyether polyols, aromatic polyether polyols having an aromatic ring in the molecule are preferred from the viewpoint of improving the flame retardancy of polyurethane foams, and among these, amine-based polyether polyols such as tolylenediamine-based polyether polyols and Mannich-based polyether polyols are preferred, with Mannich-based polyether polyols being more preferred. The tolylenediamine-based polyether polyol mentioned above refers to a polyether polyol obtained using tolylenediamine as an initiator. The Mannich-based polyether polyol mentioned above refers to a polyether polyol produced using the Mannich reaction with phenols, primary or secondary amines, and aldehydes, such as a polyether polyol obtained using a Mannich condensate as an initiator.

[0073] The hydroxyl value of the polyether polyol is preferably 200 to 1000 mg KOH / g, and more preferably 300 to 600 mg KOH / g. The hydroxyl value is measured in accordance with JIS K1557-1:2007.

[0074] (Polyester polyol) 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 glycol. Among these, from the viewpoint of improving the flame retardancy of the polyurethane foam, phthalic acid-based polyester polyols, which are condensates of at least one of o-phthalic acid, m-phthalic acid, and p-phthalic acid with glycol, are preferred, and p-phthalic acid-based polyester polyols, which are condensates of p-phthalic acid and glycol, are more preferred. 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, or diethylene glycol.

[0075] Among the polyol compounds described above, it is preferable to include an aromatic polyester polyol from the viewpoint of improving the flame retardancy of the polyurethane foam, and it is more preferable that the aromatic polyester polyol contains at least one of a terephthalic acid-based polyester polyol and an amine-based polyether polyol.

[0076] The hydroxyl value of the polyester polyol is preferably 100 to 400 mg KOH / g, and more preferably 150 to 350 mg KOH / g.

[0077] The lower limit of the aromatic polyester polyol content may be, for example, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, or 85% by mass or more, relative to the polyol compound content. The upper limit of the aromatic polyester polyol content may be, for example, 100% by mass or less, 99% by mass or less, 98% by mass or less, 96% by mass or less, 94% by mass or less, 92% by mass or less, 90% by mass or less, or 88% by mass or less, relative to the polyol compound content. The content of aromatic polyester polyol may be, for example, 50% to 100% by mass, 55% to 99% by mass, 60% to 98% by mass, 65% to 96% by mass, 70% to 94% by mass, 75% to 92% by mass, 80% to 90% by mass, or 85% to 88% by mass, relative to the content of the polyol compound. When the content of aromatic polyester polyol is within the above range, it is easier to obtain a polyol composition with excellent handling properties due to reduced viscosity and a polyurethane foam with excellent flame retardancy. When the content of aromatic polyester polyol is below the upper limit, it is easier to obtain a polyol composition with excellent handling properties due to reduced viscosity. Furthermore, when the content of aromatic polyester polyol is above the lower limit, it is easier to obtain a polyurethane foam with excellent flame retardancy.

[0078] The lower limit of the terephthalic acid-based polyester polyol content may be, for example, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, or 65% by mass or more, relative to the polyol compound content. The upper limit of the terephthalic acid-based polyester polyol content may be, for example, 100% by mass or less, 98% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, or 70% by mass or less, relative to the polyol compound content. The terephthalic acid-based polyester polyol may be present in amounts of, for example, 30% to 100% by mass, 35% to 98% by mass, 40% to 95% by mass, 45% to 90% by mass, 50% to 85% by mass, 55% to 80% by mass, 60% to 75% by mass, or 65% to 70% by mass, relative to the polyol compound content. When the terephthalic acid-based polyester polyol content is within the above range, it tends to be easier to obtain a polyol composition with excellent handling properties due to reduced viscosity and a polyurethane foam with excellent flame retardancy. When the terephthalic acid-based polyester polyol content is below the above upper limit, it tends to be easier to obtain a polyol composition with excellent handling properties due to reduced viscosity. Furthermore, when the terephthalic acid-based polyester polyol content is above the above lower limit, it tends to be easier to obtain a polyurethane foam with excellent flame retardancy.

[0079] [Polyisocyanate composition] Polyisocyanate compositions can form polyurethane foams by mixing them with polyol compositions. It is preferable to use the polyisocyanate composition as the second liquid in a two-component or multi-component polyurethane foam-forming composition. Specifically, during distribution, it is desirable to have a two-component or multi-component form combining a first liquid containing the polyol composition, a second liquid containing the polyisocyanate composition, and, in the case of a multi-component type, a third liquid (and fourth or more liquids) containing components other than the polyol composition and the polyisocyanate composition. When forming the foam, it is preferable to mix these first and second liquids, and in the case of a multi-component type, the third liquid (and fourth or more liquids). Polyisocyanate compositions contain a polyisocyanate compound as an essential component.

[0080] <Polyisocyanate compounds> As the polyisocyanate compound included in the polyisocyanate composition, 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 MR200" (manufactured by Tosoh Corporation). Alternatively, uretonimine-containing MDI (for example, "Millionate MTL": manufactured by Tosoh Corporation, a commercially available product) 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.

[0081] The lower limit of the isocyanate index (NCO INDEX) is not particularly limited, but may be 150 or higher, 180 or higher, 210 or higher, 240 or higher, 270 or higher, 310 or higher, 340 or higher, 370 or higher, 390 or higher, 420 or higher, 450 or higher, 480 or higher, 510 or higher, 540 or higher, 570 or higher, or 600 or higher. The upper limit of the isocyanate index may be, for example, 800 or lower, 700 or lower, 610 or lower, 570 or lower, 540 or lower, 510 or lower, 470 or lower, 440 or lower, 410 or lower, 390 or lower, 360 or lower, 330 or lower, 300 or lower, 270 or lower, 240 or lower, or 210 or lower. The isocyanate index content may be, for example, 150 to 800, 180 to 700, 210 to 610, 240 to 570, 270 to 540, 310 to 510, 340 to 470, 370 to 440, or 390 to 410. When the isocyanate index is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the isocyanate index is above the lower limit, the amount of isocyanate nurate groups produced increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. Furthermore, when the isocyanate index is below the upper limit, the rate of conversion from unreacted isocyanate groups to isocyanurate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0082] (Inorganic filler) The polyol composition may contain an inorganic filler, to the extent that it does not impair the effects of one aspect of the present disclosure. Either the polyisocyanate composition or the polyol composition may contain an inorganic filler, or both may contain one. Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, 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, gypsum fiber, potassium salts such as calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica pulp, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon pulp, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum porate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, etc., and any combination of two or more of these.

[0083] From the viewpoint of foamability of the polyurethane foam, the content of the inorganic filler is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, even more preferably 3 to 20% by mass, particularly preferably 4 to 15% by mass, and most preferably 5 to 10% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam forming composition.

[0084] (Anti-settling agent) The polyol composition may contain a settling inhibitor. Either the polyisocyanate composition or the polyol composition may contain a settling inhibitor, or both may contain one. Examples of settling inhibitors include organic bentonite, aliphatic amide, hydrogenated castor oil wax, carbon black, silica powder, and any combination of two or more of these. Examples of aliphatic amides include ASA T-1700 (manufactured by Ito Oil Co., Ltd.), ASA T-1800 (manufactured by Ito Oil Co., Ltd.), ASA T-2800 (manufactured by Ito Oil Co., Ltd.), and Disparon 6100 (manufactured by Kusumoto Chemical Co., Ltd.). Among these, ASA T-1700 is preferred. By including a settling inhibitor, the settling of powder particles with a high specific gravity, such as solid flame retardants, in the polyol composition can be suppressed.

[0085] The content of the settling inhibitor is preferably 0.1 to 3.0% by mass, more preferably 0.2 to 2.5% by mass, even more preferably 0.3 to 2.0% by mass, particularly preferably 0.4 to 1.5% by mass, and most preferably 0.5 to 1.0% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. When the content of the settling inhibitor is above the lower limit, a polyol composition in which the settling of the solid flame retardant is suppressed tends to be obtained. Also, when the content of the settling inhibitor is below the upper limit, a polyurethane foam with excellent flame retardancy tends to be obtained.

[0086] (Dispersant) The polyol composition may contain a dispersant. Either the polyisocyanate composition or the polyol composition may contain a dispersant, or both may contain one. The dispersant is a material for improving the redispersibility of the solid flame retardant. Examples of dispersants include alkylammonium salts, organic ammonium salts, phosphate esters, and phosphate ester salts of acidic copolymers having hydroxyl groups. Examples of organic ammonium salts include alkylammonium salts, alkylol ammonium salts, and any combination of two or more of these. Examples of phosphate ester salts include lecithin. Among these, lecithin is preferred.

[0087] The dispersant content is preferably 0.01 to 3.0% by mass, more preferably 0.03 to 2.5% by mass, even more preferably 0.05 to 2.0% by mass, particularly preferably 0.07 to 1.5% by mass, and most preferably 0.09 to 1.0% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. When the dispersant content is above the lower limit, a polyol composition with excellent dispersion stability tends to be obtained. Conversely, when the dispersant content is below the upper limit, a polyurethane foam with excellent flame retardancy tends to be obtained.

[0088] <Foam stabilizer> The polyol composition may contain a foam stabilizer. Either the polyisocyanate composition or the polyol composition may contain a foam stabilizer, or both may contain one. Examples of foam stabilizers include surfactants such as polyoxyalkylene foam stabilizers like polyoxyalkylene alkyl ethers and silicone foam stabilizers like organopolysiloxanes, and any combination of two or more of these. Furthermore, the silicone foam stabilizer may include a graft copolymer of polydimethylsiloxane and polyethylene glycol.

[0089] The content of the foam stabilizer is not particularly limited, but is preferably 0.05 to 4.0% by mass, more preferably 0.1 to 3.0% by mass, even more preferably 0.15 to 2.5% by mass, particularly preferably 0.2 to 2.0% by mass, and most preferably 0.25 to 1.5% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam forming composition.

[0090] <Foaming agent> The polyol composition may contain a blowing agent. Either the polyisocyanate composition or the polyol composition may contain a blowing agent, or both may contain one. Preferably, only the polyol composition contains a blowing agent. Examples of blowing agents include water and / or physical blowing agents.

[0091] Specific examples of physical blowing agents include, for example, low-boiling-point hydrocarbon compounds, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbon compounds, ether compounds, and hydrofluoroolefin compounds. Furthermore, physical 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 hydrocarbon compounds 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, and dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)). Examples of the above-mentioned hydrofluorocarbon compounds 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 hydrofluoroolefin compounds include HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene) and HFO-1234yf (2,3,3,3-tetrafluoro-1-propene). These physical blowing agents may be used individually or in any combination of two or more. Among these, hydrofluoroolefin compounds are preferred.

[0092] The upper limit of the foaming agent content may be 100 parts by mass or less, 95 parts by mass or less, 90 parts by mass or less, 85 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, 45 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less, per 100 parts by mass of the polyol compound. The lower limit of the foaming agent content may be 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 60 parts by mass or more, 65 parts by mass or more, 70 parts by mass or more, 75 parts by mass or more, or 80 parts by mass or more, per 100 parts by mass of the polyol compound. The foaming agent content may be 5 to 100 parts by mass, 10 to 95 parts by mass, 15 to 90 parts by mass, 20 to 85 parts by mass, 25 to 80 parts by mass, 30 to 75 parts by mass, 35 to 70 parts by mass, 40 to 65 parts by mass, or 45 to 60 parts by mass per 100 parts by mass of the polyol compound. Furthermore, the lower limit of the foaming agent content may be, for example, 1.0% by mass or more, 2.0% by mass or more, 3.0% by mass or more, 4.0% by mass or more, 5.0% by mass or more, 6.0% by mass or more, 7.0% by mass or more, 8.0% by mass or more, 9.0% by mass or more, 10.0% by mass or more, 11.0% by mass or more, 12.0% by mass or more, 13.0% by mass or more, or 14.0% by mass or more, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The upper limit of the foaming agent content may be, for example, 18.0% by mass or less, 17.0% by mass or less, 16.0% by mass or less, 15.0% by mass or less, 14.0% by mass or less, 13.0% by mass or less, 12.0% by mass or less, 11.0% by mass or less, 10.0% by mass or less, 9.0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.0% by mass or less, or 5.0% by mass or less, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The foaming agent content may be, for example, 1.0% to 18.0% by mass, 2.0% to 17.0% by mass, 3.0% to 16.0% by mass, 4.0% to 15.0% by mass, 5.0% to 14.0% by mass, 6.0% to 13.0% by mass, 7.0% to 12.0% by mass, 8.0% to 11.0% by mass, or 9.0% to 10.0% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. When the foaming agent content is within the above range, it is easier to obtain a polyurethane foam with improved mechanical properties such as compressive strength, dimensional stability, and adhesion, as well as reduced raw material costs. When the foaming agent content is below the above upper limit, it is easier to obtain a polyurethane foam with particularly excellent mechanical properties such as compressive strength, dimensional stability, and adhesion. Furthermore, when the foaming agent content is above the aforementioned lower limit, polyurethane foams with particularly reduced raw material costs tend to be obtained. When the foaming agent content is within the aforementioned range, polyurethane foams with improved mechanical properties such as compressive strength, dimensional stability, and adhesion, as well as reduced raw material costs, tend to be obtained. When the foaming agent content is below the aforementioned upper limit, polyurethane foams with particularly excellent mechanical properties such as compressive strength, dimensional stability, and adhesion tend to be obtained. Furthermore, when the foaming agent content is above the aforementioned lower limit, polyurethane foams with particularly reduced raw material costs tend to be obtained.

[0093] The upper limit of the water content is 10 parts by mass or less, 9 parts by mass or less, 8 parts by mass or less, 7 parts by mass or less, 6 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1 part by mass or less, 0.9 parts by mass or less, 0.8 parts by mass or less. 0.7 parts by mass or less, 0.6 parts by mass or less, 0.5 parts by mass or less, 0.29 parts by mass or less, 0.27 parts by mass or less, 0.25 parts by mass or less, 0.23 parts by mass or less, 0.21 parts by mass or less, 0.19 parts by mass or less, 0.17 parts by mass or less, or 0.15 parts by mass or less. The lower limit of the water content may be 0.01 parts by mass or more, 0.03 parts by mass or more, 0.05 parts by mass or more, 0.07 parts by mass or more, 0.09 parts by mass or more, 0.11 parts by mass or more, 0.13 parts by mass or more, 0.15 parts by mass or more, 0.17 parts by mass or more, 0.19 parts by mass or more, 0.21 parts by mass or more, 0.23 parts by mass or more, 0.25 parts by mass or more, 0.27 parts by mass or more, 0.29 parts by mass or more, 0.5 parts by mass or more, 0.6 parts by mass or more, 0.7 parts by mass or more, 0.8 parts by mass or more, 0.9 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass or more, per 100 parts by mass of the polyol compound. The content of water is 0.01 parts by mass or more and 10 parts by mass or less, 0.03 parts by mass or more and 9 parts by mass or less, 0.05 parts by mass or more and 8 parts by mass or less, 0.07 parts by mass or more and 7 parts by mass or less, 0.09 parts by mass or more and 6 parts by mass or less, 0.11 parts by mass or more and 5 parts by mass or less, 0.13 parts by mass or more and 4 parts by mass or less, and 0.15 parts by mass or more, with respect to 100 parts by mass of the polyol compound. It may be at least 0.17 parts by mass and at most 2 parts by mass, at least 0.19 parts by mass and at most 1 part by mass, at least 0.21 parts by mass and at most 0.9 parts by mass, at least 0.23 parts by mass and at most 0.8 parts by mass, at least 0.25 parts by mass and at most 0.6 parts by mass, or at least 0.29 parts by mass and at most 0.5 parts by mass. Furthermore, the lower limit of the water content may be, for example, 0.01% by mass or more, 0.02% by mass or more, 0.03% by mass or more, 0.04% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, 0.11% by mass or more, 0.13% by mass or more, 0.16% by mass or more, 0.19% by mass or more, 0.22% by mass or more, 0.25% by mass or more, 0.28% by mass or more, 0.31% by mass or more, 0.34% by mass or more, or 0.37% by mass or more, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The upper limit of the water content may be, for example, 0.55% by mass or less, 0.50% by mass or less, 0.45% by mass or less, 0.40% by mass or less, 0.35% by mass or less, 0.30% by mass or less, 0.25% by mass or less, 0.20% by mass or less, 0.15% by mass or less, 0.13% by mass or less, 0.11% by mass or less, 0.09% by mass or less, 0.07% by mass or less, 0.05% by mass or less, or 0.03% by mass or less, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The water content may be, for example, 0.01% to 0.55% by mass, 0.02% to 0.50% by mass, 0.03% to 0.45% by mass, 0.04% to 0.40% by mass, 0.05% to 0.35% by mass, 0.07% to 0.30% by mass, 0.09% to 0.25% by mass, 0.11% to 0.20% by mass, or 0.13% to 0.15% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. When the water content is within the above range, polyurethane foams with excellent mechanical properties such as flame retardancy and compressive strength tend to be obtained. When the water content is below the above upper limit, polyurethane foams with particularly excellent flame retardancy tend to be obtained. Furthermore, when the water content is above the above lower limit, polyurethane resins with particularly excellent mechanical properties such as compressive strength tend to be obtained.

[0094] The upper limit of the physical blowing agent content may be 100 parts by mass or less, 95 parts by mass or less, 90 parts by mass or less, 85 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, 45 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less, per 100 parts by mass of the polyol compound. The lower limit of the physical blowing agent content may be 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 60 parts by mass or more, 65 parts by mass or more, 70 parts by mass or more, 75 parts by mass or more, or 80 parts by mass or more, per 100 parts by mass of the polyol compound. The amount of physical blowing agent may be 5 to 100 parts by mass, 10 to 95 parts by mass, 15 to 90 parts by mass, 20 to 85 parts by mass, 25 to 80 parts by mass, 30 to 75 parts by mass, 35 to 70 parts by mass, 40 to 65 parts by mass, or 45 to 60 parts by mass per 100 parts by mass of the polyol compound. Furthermore, the lower limit of the physical blowing agent content may be 1.0% by mass or more, 2.0% by mass or more, 3.0% by mass or more, 4.0% by mass or more, 5.0% by mass or more, 6.0% by mass or more, 7.0% by mass or more, 8.0% by mass or more, 9.0% by mass or more, 10.0% by mass or more, 11.0% by mass or more, 12.0% by mass or more, 13.0% by mass or more, or 14.0% by mass or more, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The upper limit of the physical blowing agent content may be, for example, 18.0% by mass or less, 17.0% by mass or less, 16.0% by mass or less, 15.0% by mass or less, 14.0% by mass or less, 13.0% by mass or less, 12.0% by mass or less, 11.0% by mass or less, 10.0% by mass or less, 9.0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.0% by mass or less, or 5.0% by mass or less, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. The content of the physical blowing agent may be, for example, 1.0% to 18.0% by mass, 2.0% to 17.0% by mass, 3.0% to 16.0% by mass, 4.0% to 15.0% by mass, 5.0% to 14.0% by mass, 6.0% to 13.0% by mass, 7.0% to 12.0% by mass, 8.0% to 11.0% by mass, or 9.0% to 10.0% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. If the physical blowing agent contains chlorine atoms in its molecule, it also exhibits a flame-retardant effect. When the content of the physical blowing agent is within the above range, it is easier to obtain a polyurethane foam with excellent mechanical properties such as compressive strength, dimensional stability, and adhesion, as well as flame retardancy. When the content of the physical blowing agent is below the above upper limit, it is easier to obtain a polyurethane foam with particularly excellent mechanical properties such as compressive strength, dimensional stability, and adhesion. Furthermore, when the content of the physical blowing agent is above the aforementioned lower limit, polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0095] If the blowing agent contains water and a physical blowing agent, the lower limit of the physical blowing agent content may be 40 mol% or more, 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, 83 mol% or more, 85 mol% or more, 87 mol% or more, 89 mol% or more, 91 mol% or more, 93 mol% or more, 95 mol% or more, 97 mol% or more, or 99 mol% or more, relative to the sum of the water content and the physical blowing agent content. The upper limit of the physical blowing agent content may be, for example, 99 mol% or less, 98 mol% or less, 97 mol% or less, 96 mol% or less, 95 mol% or less, 94 mol% or less, 93 mol% or less, 92 mol% or less, 91 mol% or less, 90 mol% or less, 89 mol% or less, 86 mol% or less, 83 mol% or less, 80 mol% or less, 77 mol% or less, 74 mol% or less, or 71 mol% or less, relative to the sum of the water content and the physical blowing agent content. The content ratio of the physical blowing agent may be, for example, 40 mol% to 99 mol%, 50 mol% to 98 mol%, 55 mol% to 97 mol%, 60 mol% to 96 mol%, 65 mol% to 95 mol%, 70 mol% to 94 mol%, 75 mol% to 93 mol%, 80 mol% to 92 mol%, 83 mol% to 91 mol%, 85 mol% to 90 mol%, or 87 mol% to 89 mol% relative to the sum of the water content and the physical blowing agent content. If the physical blowing agent contains chlorine atoms in its molecule, it also exhibits a flame retardant effect. When the content ratio of the physical blowing agent is within the above range, it is easier to obtain polyurethane foams with excellent flame retardancy and mechanical properties such as compressive strength. When the content ratio of the physical blowing agent is above the lower limit, it is easier to obtain polyurethane foams with particularly excellent flame retardancy. When the physical blowing agent content is below the aforementioned upper limit, polyurethane foams with particularly excellent mechanical properties, such as compressive strength, tend to be obtained.

[0096] <Catalyst> The polyol composition may contain a catalyst. Either the polyisocyanate composition or the polyol composition may contain a catalyst, or both may contain one. It is preferable that only the polyol composition contains a catalyst. The catalyst may contain, for example, one or both of a urethane / urea conversion catalyst and a trimerization catalyst, and it is preferable that both are included.

[0097] Urethane / urea catalysts are catalysts that promote the reaction between polyol components and polyisocyanates. Specifically, these include amino compounds, tin compounds, bismuth compounds, and acetylacetone metal salts. Examples of amino compounds include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl) ether, bis(2-dimethylaminoethyl) ether, N,N,N',N”,N”-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl) ether, N-methyl-N',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, trimethylaminoethylpiperazine, and tripropylamine. 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. These urethane / urea catalysts may be used individually or in any combination of two or more types.

[0098] There are no particular limitations on the amount of urethane / urea-forming catalyst blended, but it is preferably 0.01 to 3.0% by mass, more preferably 0.03 to 2.0% by mass, even more preferably 0.05 to 1.5% by mass, particularly preferably 0.07 to 1.0% by mass, and most preferably 0.1 to 0.8% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. By keeping it within the above range, the reaction between the polyol component and the polyisocyanate component can be promoted at an appropriate reaction rate.

[0099] A trimerization catalyst is a catalyst that promotes the formation of isocyanurate bonds. In polyurethane foam-forming compositions, the flame retardancy of the resulting polyurethane foam is improved by promoting trimerization. Examples of trimerization catalysts include aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; aziridines such as potassium acetate, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium octoate, sodium octoate, and 2-ethylaziridine; lead compounds such as lead naphthenate and lead octoate; metal salts such as sodium methoxide and potassium phenoxide; tertiary or quaternary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt, tetramethylammonium salt, tetraethylammonium, and tetraphenylammonium salt; and any combination of two or more of these.

[0100] The content of the trimerizing catalyst is not particularly limited, but from the viewpoint of improving the curing speed of the polyurethane foam-forming composition and the flame retardancy of the polyurethane foam, it is preferably 0.5 to 6.0% by mass, more preferably 0.8 to 4.0% by mass, even more preferably 1.1 to 3.0% by mass, particularly preferably 1.3 to 2.5% by mass, and most preferably 1.5 to 2.0% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. By keeping the content of the trimerizing catalyst within the above range, isocyanurate bonds are formed appropriately, improving flame retardancy.

[0101] Trimerization catalysts, when used in combination with a metal salt and a tertiary or quaternary ammonium salt, tend to produce polyurethane foams with excellent reactivity during foaming and flame retardancy.

[0102] The lower limit of the content of tertiary or quaternary ammonium salts may be, for example, 5.0% by mass or more, 15.0% by mass or more, 25.0% by mass or more, 35.0% by mass or more, 45.0% by mass or more, 55.0% by mass or more, or 65.0% by mass or more, relative to the content of the trimerization catalyst. The upper limit of the content of tertiary or quaternary ammonium salts may be, for example, 100% by mass or less, 95.0% by mass or less, 90.0% by mass or less, 85.0% by mass or less, 80.0% by mass or less, 75.0% by mass or less, or 70.0% by mass or less, relative to the content of the trimerization catalyst. The content of tertiary or quaternary ammonium salt may be, for example, 5.0% to 100% by mass, 15.0% to 95.0% by mass, 25.0% to 90.0% by mass, 35.0% to 85.0% by mass, 45.0% to 80.0% by mass, 55.0% to 75.0% by mass, or 65.0% to 70.0% by mass, relative to the content of the trimerizing catalyst. When the content of tertiary or quaternary ammonium salt is within the above range, polyurethane foams with excellent reactivity during foaming and flame retardancy tend to be obtained. When the content of tertiary or quaternary ammonium salt is above the lower limit, polyurethane foams with particularly high reactivity tend to be obtained, exhibiting particularly excellent effects for spray foaming applications. Furthermore, when the content of tertiary or quaternary ammonium salt is below the upper limit, polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0103] (Other additives) The polyol composition may further contain other additives besides solid flame retardants, liquid flame retardants, polyol compounds, polyisocyanate compounds, foam stabilizers, blowing agents, catalysts, and inorganic fillers. Examples of other additives include antioxidants such as phenolic, amine, and sulfur-based agents, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifying resins, and tackifiers (polybutene, petroleum resin, etc.).

[0104] (Manufacturing method) The method for producing the polyurethane foam is not particularly limited, and examples thereof include a method of preparing a polyol composition and a polyisocyanate composition that are prepared by kneading in advance and then kneading the two, and a method of kneading each component constituting the polyurethane foam, and the polyurethane foam is usually produced by kneading the polyol composition and the polyisocyanate composition. The kneading can be carried out by a known method, for example, by using a known apparatus such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a planetary mixer, and a planetary stirring machine to perform the kneading.

[0105] (Total calorific value) The polyurethane foam, which is a foam of the polyurethane foam-forming composition (the reaction product of the polyisocyanate composition and the polyol composition), is subjected to a test in accordance with the test method of ISO-5660 at a radiant heat intensity of 50 kW / m 2 When heated at , the total calorific value after 10 minutes is preferably 10 MJ / m 2 or less. When the total calorific value is 10 MJ / m 2 or less, the polyurethane foam according to one aspect of the present disclosure has predetermined flame retardancy. From the viewpoint of further improving the flame retardancy of the polyurethane foam, the total calorific value is preferably 9 MJ / m 2 or less, more preferably 8 MJ / m 2 or less, still more preferably 7 MJ / m 2 or less, particularly preferably 6.5 MJ / m 2 or less, and most preferably 6 MJ / m 2 or less. The total calorific value is obtained by a cone calorimeter test, and specifically can be measured by the method described in the Examples. In the 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.

[0106] (Application) The polyurethane foam, which is a foam produced from a polyurethane foam-forming composition (a reaction product of a polyisocyanate composition and a polyol composition), has no particular use, but 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 it for spraying onto structures, that is, as a polyurethane foam-forming composition for spraying. The structure is, for example, an object to which flame retardancy is to be imparted.

[0107] The solid flame retardant composition can be used for polyurethane foams. Furthermore, the solid flame retardant composition can be used for spray applications. In other words, the solid flame retardant composition can be used for spraying, where the solid flame retardant composition is sprayed onto an object to adhere it to the object.

[0108] Spraying can be carried out using a spraying device (e.g., GRACO A-25) and a spray gun (e.g., Gasmar D-gun). Spraying can be performed by adjusting the temperature of the polyol composition and polyisocyanate composition, which are in separate containers, in the spraying device, mixing them by collision at the tip of the spray gun, and atomizing the mixture with air pressure. Commercially available spraying devices and spray guns can be used.

[0109] 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 25-100 kg / m³. 3 It is more preferable that the range be 25-80 kg / m 3 It is even more preferable that the range be 30-60 kg / m 3It is even more preferable that the range be 35-50 kg / m 3 It is particularly preferable that the density be within this range. The density of the polyurethane foam can be measured in accordance with JIS K7222.

[0110] <Calculation method for each composition> The composition of each component in a polyol compound (e.g., content per 100 parts by mass of the polyol compound) can be determined by the following formula. Furthermore, the composition of each component in a polyurethane foam-forming composition (e.g., content per mass of the polyurethane foam component of the polyurethane foam-forming composition) can be determined by the following formula. The mass (g) of the polyurethane foam component of the polyurethane foam-forming composition = amount of polyisocyanate compound (g) + amount of polyol compound (g) + additives * Preparation amount (g) *: Additives refer to solid flame retardants (solid phosphorus-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, and solid flame retardants other than these), liquid flame retardants, foam stabilizers, catalysts, inorganic fillers, settling inhibitors, dispersion stabilizers, and other additives.

[0111] Aromatic polyester polyol compound content (mass%) = (Amount of aromatic polyester polyol compound charged (g) + Amount of aromatic and aliphatic polyester polyol compound charged (g) × Aromatic content ratio of aromatic and aliphatic polyester polyol compounds (%) * ) / Mass of polyol compound (g) × 100 *: Aromatic content ratio (%) of aromatic and aliphatic polyester polyol compounds = Aromatic dicarboxylic acid content (mol) / (Aromatic dicarboxylic acid content (mol) + Aliphatic dicarboxylic acid content (mol)) × 100

[0112] Content of terephthalic acid-based polyester polyol compound (mass%) = Amount of terephthalic acid-based polyester polyol compound added (g) / Mass of polyol compound (g) × 100

[0113] Isocyanate index = Equivalents of polyisocyanate ÷ (Equivalents of polyol + Equivalents of water) × 100 Here, the equivalent weight of polyisocyanate = number of parts of polyisocyanate used × NCO content (%) / 100 / molecular weight of NCO The equivalent number of polyols = OHV × number of polyols used ÷ molecular weight of KOH, where OHV is the hydroxyl value of the polyol (mgKOH / g), and the equivalent number of waters = number of waters used × number of OH groups in water / molecular weight of water. In the above formula, the unit of the number of parts used is mass (g), the molecular weight of the NCO group is 42, the NCO content is the percentage of NCO groups in the polyisocyanate compound expressed by 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.

[0114] Bromine-containing flame retardant content (parts by mass) = Amount of bromine-containing flame retardant added (g) / Amount of polyol compound added (g) × 100 Bromine-containing flame retardant content (mass %) = Amount of bromine-containing flame retardant added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0115] Content of aliphatic bromine-containing compounds (parts by mass) = Amount of aliphatic bromine-containing compounds added (g) / Amount of polyol compounds added (g) × 100 Aliphatic bromine-containing compound content (mass%) = Amount of aliphatic bromine-containing compound added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0116] Content (parts by mass) of aromatic bromine-containing low molecular weight compound = Amount of aromatic bromine-containing low molecular weight compound charged (g) / Amount of polyol compound charged (g) × 100 Content of aromatic bromine-containing low molecular weight compounds (mass%) = Amount of aromatic bromine-containing low molecular weight compounds added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0117] Content of aromatic bromine-containing polymer compound (parts by mass) = Amount of aromatic bromine-containing polymer compound charged (g) / Amount of polyol compound charged (g) × 100 Content of aromatic bromine-containing polymer compound (mass%) = Amount of aromatic bromine-containing polymer compound added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0118] The percentage of aliphatic bromine-containing compounds (by mass) = Amount of aliphatic bromine-containing compounds added (g) / (Amount of aliphatic bromine-containing compounds added (g) + Amount of low molecular weight aromatic bromine-containing compounds added (g) + Amount of high molecular weight aromatic bromine-containing compounds added (g)) × 100

[0119] Content ratio (mass%) of aromatic bromine-containing low molecular weight compounds = Amount of aromatic bromine-containing low molecular weight compounds (g) / (Amount of aliphatic bromine-containing compounds (g) + Amount of aromatic bromine-containing low molecular weight compounds (g) + Amount of aromatic bromine-containing high molecular weight compounds (g)) × 100

[0120] Content ratio (mass%) of aromatic bromine-containing polymer compounds = Amount of aromatic bromine-containing polymer compounds added (g) / (Amount of aliphatic bromine-containing compounds added (g) + Amount of aromatic bromine-containing low molecular weight compounds added (g) + Amount of aromatic bromine-containing polymer compounds added (g)) × 100

[0121] Content (parts by mass) of bromine-containing flame retardant with a decomposition temperature of less than 370°C = Amount of bromine-containing flame retardant with a decomposition temperature of less than 370°C charged (g) / Amount of polyol compound charged (g) × 100 Content (mass%) of bromine-containing flame retardant with a decomposition temperature of less than 370°C = Amount of bromine-containing flame retardant with a decomposition temperature of less than 370°C (g) / Mass (g) of polyurethane foam component of the polyurethane foam-forming composition × 100

[0122] Content (parts by mass) of bromine-containing flame retardant with a decomposition temperature of 370°C or higher and less than 450°C = Amount of bromine-containing flame retardant with a decomposition temperature of 370°C or higher and less than 450°C charged (g) / Amount of polyol compound charged (g) × 100 Content (mass%) of bromine-containing flame retardant with a decomposition temperature of 370°C or higher and less than 450°C = Amount of bromine-containing flame retardant with a decomposition temperature of 370°C or higher and less than 450°C added (g) / Mass (g) of polyurethane foam component of the polyurethane foam-forming composition × 100

[0123] Content (parts by mass) of bromine-containing flame retardant with a decomposition temperature of 450°C or higher = Amount of bromine-containing flame retardant with a decomposition temperature of 450°C or higher charged (g) / Amount of polyol compound charged (g) × 100 Content (mass%) of bromine-containing flame retardant with a decomposition temperature of 450°C or higher = Amount of bromine-containing flame retardant with a decomposition temperature of 450°C or higher added (g) / Mass (g) of polyurethane foam component of the polyurethane foam-forming composition × 100

[0124] The percentage of bromine-containing flame retardants with a decomposition temperature below 370°C (mass %) = Amount of bromine-containing flame retardants with a decomposition temperature below 370°C (g) / (Amount of bromine-containing flame retardants with a decomposition temperature below 370°C (g) + Amount of bromine-containing flame retardants with a decomposition temperature between 370°C and 450°C (g) + Amount of bromine-containing flame retardants with a decomposition temperature of 450°C or higher (g)) × 100

[0125] The percentage of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C (mass %) = Amount of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C (g) / (Amount of bromine-containing flame retardants with a decomposition temperature of less than 370°C (g) + Amount of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C (g) + Amount of bromine-containing flame retardants with a decomposition temperature of 450°C or higher (g)) × 100

[0126] The percentage of bromine-containing flame retardants with a decomposition temperature of 450°C or higher (mass %) = Amount of bromine-containing flame retardants with a decomposition temperature of 450°C or higher (g) / (Amount of bromine-containing flame retardants with a decomposition temperature of less than 370°C (g) + Amount of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C (g) + Amount of bromine-containing flame retardants with a decomposition temperature of 450°C or higher (g)) × 100

[0127] The percentage of bromine-containing flame retardant (mass %) = Amount of bromine-containing flame retardant added (g) / (Amount of solid phosphorus-containing flame retardant added (g) + Amount of bromine-containing flame retardant added (g) + Amount of boron-containing flame retardant added (g)) × 100

[0128] Liquid flame retardant content (parts by mass) = Amount of liquid flame retardant added (g) / Amount of polyol compound added (g) × 100 Liquid flame retardant content (mass %) = Amount of liquid flame retardant added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0129] Total content (parts by mass) of solid and liquid flame retardants = Total flame retardants * Amount of preparation (g) / Amount of polyol compound prepared (g) × 100 Total content (mass%) of solid and liquid flame retardants = Total flame retardants * Amount of preparation (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100 *: All flame retardants refer to solid flame retardants (solid phosphorus-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, and solid flame retardants other than these solid flame retardants) and liquid flame retardants.

[0130] Inorganic filler content (mass %) = Amount of inorganic filler added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0131] Anti-settling agent content (mass %) = Amount of anti-settling agent added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0132] Dispersant content (mass %) = Amount of dispersant added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0133] Content of other additives (mass%) = Amount of other additives added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0134] Foam stabilizer content (mass %) = Amount of foam stabilizer added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0135] Foaming agent content (parts by mass) = Amount of foaming agent added (g) / Amount of polyol compound added (g) × 100 Foaming agent content (mass %) = Amount of foaming agent added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0136] Water content (parts by mass) = Amount of water added (g) / Amount of polyol compound added (g) × 100 Water content (mass %) = Amount of water added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0137] Physical blowing agent content (parts by mass) = Amount of physical blowing agent added (g) / Amount of polyol compound added (g) × 100 Physical blowing agent content (mass %) = Amount of physical blowing agent added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0138] Physical blowing agent content ratio (mol%) = Amount of physical blowing agent added (mol) / (Amount of water added (mol) + Amount of physical blowing agent added (mol)) × 100

[0139] Urethane / urea catalyst content (mass%) = Amount of urethane / urea catalyst added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0140] Content of tertiary or quaternary ammonium salt (mass%) = Amount of tertiary or quaternary ammonium salt charged (g) / Amount of trimerization catalyst charged (g) × 100

[0141] The above amounts and percentages can also be calculated by replacing "amount prepared" with "amount contained". [Examples]

[0142] Each aspect of this disclosure will be described in further detail by reference to examples, but the aspects of this disclosure are not limited in any way by these examples.

[0143] Details of the components used in each example and comparative example are as follows. Note that some components are abbreviated in Tables 1-1 to 7-1, and these abbreviations are indicated in parentheses below. (1) Polyisocyanate compounds • "MR-200": Polymeric MDI (manufactured by Tosoh Corporation, product name: MR-200)

[0144] (2) Solid flame retardants • "Piroguard SR-720N": 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Piroguard SR-720: aliphatic bromine-containing compound, decomposition temperature: 315℃) • "Piroguard SR-245": 2,4,6-Tris(2,4,6-tribromophenoxy)-1,3,5-triazine (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Piroguard SR-245: aromatic bromine-containing low molecular weight compound, decomposition temperature: 417℃) • "Fireguard 8500": A polycarbonate oligomer manufactured using brominated bisphenol A as a raw material (manufactured by Teijin Corporation, product name: Fireguard 8500: aromatic bromine-containing polymer compound, decomposition temperature: 474℃)

[0145] (3) Polyol compounds • "RFK-505": Terephthalic acid-based polyester polyol (manufactured by Air Water Performance Chemicals, product name: Maximol RFK-505, hydroxyl value = 250 mg KOH / g) • "RLK-087": Terephthalic acid / adipic acid-based polyester polyol (manufactured by Air Water Performance Chemicals, product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g) • "RDK-133": Orthophthalic acid-based polyester polyol (manufactured by Air Water Performance Chemicals, product name: Maximol RDK-133, hydroxyl value = 315 mg KOH / g)

[0146] (4) Liquid flame retardants • "TCPP": Phosphate ester-based flame retardant <Tris(β-chloropropyl) phosphate>, (manufactured by Yoke Chemicals and New Materials (Shanghai) Co., Ltd., product name: TCPP)

[0147] (5) Foam stabilizers • "SH-193": Polyalkylene glycol-based foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193)

[0148] (6) Catalyst (i) Urethane catalyst • "T-9": Tin compound (manufactured by Evonik, product name: DABCOT-9) (ii) Urea catalyst • "DT": Tertiary ammonium compound (manufactured by Tosoh Corporation, product name: TOYOCAT-DT) (iii) Trimerization catalyst • "TRV": Quaternary ammonium salt (manufactured by Tosoh Corporation, product name: TOYOCAT-TRV) • "K-15": Metal salt (manufactured by Tosoh Corporation, product name: DABCOK-15)

[0149] (7) Foaming agent ·water • HFO-1233zd <Hydrofluoroolefin> (Honeywell Corporation, product name: Solstice LBA)

[0150] The measurement methods for each physical property and characteristic are as follows.

[0151] [Decomposition temperature of bromine-containing flame retardants] The decomposition temperature of the bromine-containing flame retardant was calculated using TG-DTA. The bromine-containing flame retardant was heated in TG-DTA at 5°C / min up to 700°C, and the temperature at which the weight loss rate was 50% was defined as the decomposition temperature. The weight loss rate was calculated as: sample mass during measurement (mg) / sample mass before measurement (mg) × 100. The weight loss rate was measured under the following conditions.

[0152] [conditions] The following steps [1] to [3] were performed using the STA7200RV manufactured by Hitachi High-Tech Science Corporation. [1] 8.5 ± 0.5 mg of bromine-containing flame retardant was placed in a weighing device. [2] The airflow rate was set to 200 mL / min. [3] The temperature was increased from 25°C to 700°C at a rate of 5°C / min.

[0153] [Emissions from polyol compositions] The redispersibility of the polyol compositions prepared in each example and comparative example was evaluated by the following method. Polyol compositions were prepared and mixed in 200 mL glass bottles according to the formulations shown in Tables 1-1 to 7-1. After standing at 23°C for one week, the 200 mL glass bottles containing the polyol compositions were shaken by hand for 3 seconds, and immediately after, the glass bottles were inverted for 3 seconds. The amount of polyol composition discharged from the 200 mL bottle was measured and used as an indicator of the redispersibility of the polyol composition. A higher discharge amount of polyol composition indicates better redispersibility of the polyol composition.

[0154] [Total heat output, heating rate after 10 minutes, maximum heating rate, weight retention rate] The total calorific value of the polyurethane foams produced in each example and comparative example was evaluated by the following method. A polyurethane foam-forming composition was obtained by mixing a polyol composition and a polyisocyanate compound in the formulations shown in Tables 1-1 to 7-1 in a polypropylene beaker and stirring the mixture with a labodiespar for 5 seconds. Immediately thereafter, the mixture was sprayed into a mold with dimensions of 150 mm x 150 mm x 150 mm to obtain a polyurethane foam. The polyurethane foam was cut into pieces 10 cm long, 10 cm wide, and 2.5 cm thick to prepare samples for cone calorimeter testing. Using the cone calorimeter test samples, the radiant heat intensity was measured to 50 kW / m² in accordance with the ISO-5660 test method. 2 The heat generation rate, total heat generation, and maximum heat generation rate after 10 minutes of heating were measured using a cone calorimeter. Furthermore, the weight retention rate was determined from the difference between the sample mass before and after the cone calorimeter test. A CONE-III cone calorimeter (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used for the cone calorimeter test.

[0155] [Example 1] First, polyol compounds, blowing agents, catalysts, solid flame retardants, liquid flame retardants, and foam stabilizers were weighed into 500 mL polypropylene beakers according to the mixing ratios shown in Table 1-1, and stirred with a hand mixer at 20°C for 10 minutes to obtain a polyol composition. Similarly, polyisocyanate compounds were weighed into 500 mL polypropylene beakers to obtain an isocyanate composition. Then, the polyisocyanate composition, also heated to 10°C, was added to the polyol composition cooled to 10°C to form a polyurethane foam-forming composition. This composition was then stirred with a labodiespar for 5 seconds to produce a polyurethane foam. Using this polyurethane foam, the exothermic rate after 10 minutes, total exothermic rate, maximum exothermic rate, and weight retention rate were evaluated. The results of the various evaluations are shown in Table 1-2.

[0156] [Examples 2-35, Comparative Examples 1-2] A polyurethane foam was obtained in the same manner as in Example 1, except that the formulation was changed as shown in Tables 1-1 to 7-1. Using this polyurethane foam, the heat generation rate, total heat generation amount, maximum heat generation rate, and weight retention rate after 10 minutes were evaluated using the procedure described above. The results of each evaluation are shown in Tables 1-2 to 7-2.

[0157] [Table 1-1]

[0158] [Table 1-2]

[0159] [Table 2-1]

[0160] [Table 2-2]

[0161] [Table 3-1]

[0162] [Table 3-2]

[0163] Table 4-1

[0164] Table 4-2

[0165] Table 5-1

[0166] Table 5-2

[0167] Table 6-1

[0168] Table 6-2

[0169] Table 7-1

[0170] Table 7-2

Claims

1. A polyol composition comprising a solid flame retardant, a liquid flame retardant, and a polyol compound, The solid flame retardant includes a bromine-containing flame retardant. The bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant. The first bromine-containing flame retardant is one selected from the following three: (a) to (c): (a) Aliphatic bromine-containing compounds, (b) aromatic bromine-containing low molecular compound, (c) aromatic bromine-containing polymer compound; A polyol composition wherein the second bromine-containing flame retardant comprises one selected from the other two, excluding one selected from the three (a) to (c).

2. The polyol composition according to claim 1, wherein the first bromine-containing flame retardant comprises the (c) aromatic bromine-containing polymer compound.

3. The polyol composition according to claim 2, wherein the second bromine-containing flame retardant comprises the aliphatic bromine-containing compound (a).

4. A polyol composition comprising a solid flame retardant, a liquid flame retardant, and a polyol compound, The solid flame retardant includes a bromine-containing flame retardant. The bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant. The first bromine-containing flame retardant is one selected from the following three: (i) to (iii): (i) Bromine-containing flame retardants with a decomposition temperature of less than 370°C (ii) Bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C. (iii) Bromine-containing flame retardants with a decomposition temperature of 450°C or higher; A polyol composition wherein the second bromine-containing flame retardant comprises one selected from two other than the one selected from the three (i) to (iii).

5. The polyol composition according to claim 4, wherein the first bromine-containing flame retardant comprises the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or higher.

6. The polyol composition according to claim 5, wherein the second bromine-containing flame retardant comprises (i) a bromine-containing flame retardant having a decomposition temperature of less than 370°C.

7. A polyol composition according to any one of claims 1 to 6, further comprising a polyol compound, a foam stabilizer, a blowing agent, and a catalyst.

8. A polyurethane foam-forming composition comprising the polyol composition described in claim 7.

9. A sample for cone calorimeter testing, prepared from the polyurethane foam-forming composition under the following conditions, was tested in accordance with the ISO-5660 test method, with a radiant thermal intensity of 50 kW / m². ２ When heated, the total heat output after 10 minutes was 8.0 MJ / m³. ２ The polyurethane foam-forming composition according to claim 8, which is as follows: [Conditions for preparing samples for corn calorimeter testing] (1) The polyurethane foam-forming composition is stirred in a laboside spar for 5 seconds. (2) Immediately after (1), the material is sprayed into a mold with dimensions of 150 mm x 150 mm x 150 mm to obtain polyurethane foam. (3) The polyurethane foam is cut into pieces measuring 10 cm in length, 10 cm in width, and 2.5 cm in thickness to obtain samples for the cone calorimeter test.

10. A polyurethane foam, which is a foam of the polyurethane foam-forming composition described in claim 8.

11. A first bromine-containing flame retardant and a second bromine-containing flame retardant are included. The first bromine-containing flame retardant is one selected from the following three: (a) to (c): (a) Aliphatic bromine-containing compounds, (b) aromatic bromine-containing low molecular compound, (c) aromatic bromine-containing polymer compound; A solid flame retardant composition wherein the second bromine-containing flame retardant comprises one selected from the other two selected from the three (a) to (c).

12. The solid flame retardant composition according to claim 11, wherein the first bromine-containing flame retardant comprises the (c) aromatic bromine-containing polymer compound.

13. The solid flame retardant composition according to claim 12, wherein the second bromine-containing flame retardant comprises the aliphatic bromine-containing compound (a) as described above.

14. A first bromine-containing flame retardant and a second bromine-containing flame retardant are included. The first bromine-containing flame retardant is one selected from the following three: (i) to (iii): (i) Bromine-containing flame retardants with a decomposition temperature of less than 370°C (ii) Bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C. (iii) Bromine-containing flame retardants with a decomposition temperature of 450°C or higher; A solid flame retardant composition wherein the second bromine-containing flame retardant comprises one selected from two other than the one selected from the three (i) to (iii).

15. The solid flame retardant composition according to claim 14, wherein the first bromine-containing flame retardant comprises the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or higher.

16. The solid flame retardant composition according to claim 15, wherein the second bromine-containing flame retardant comprises (i) a bromine-containing flame retardant having a decomposition temperature of less than 370°C.

17. A solid flame retardant composition according to any one of claims 11 to 16, for use in polyurethane foam-forming compositions.

18. A solid flame retardant composition according to any one of claims 11 to 16, for use with polyurethane foam.

19. The solid flame retardant composition according to any one of claims 11 to 16, which is for spraying to adhere the solid flame retardant composition to an object.

20. A flame retardant composition comprising a solid flame retardant composition according to any one of claims 11 to 16 and a liquid flame retardant.

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