Polyurethane foam-forming composition and polyurethane foam

Abstract

To provide a polyurethane foam-forming composition that contributes to the production of polyurethane foams having good flame retardancy. A polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, The polyurethane foam-forming composition, wherein the solid flame retardant comprises two or more selected from the group consisting of a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, and a boron-containing flame retardant.

Description

[Technical Field]

[0001] The present disclosure relates to polyurethane foam-forming compositions and polyurethane foams. [Background technology]

[0002] Taking advantage of their excellent thermal insulation properties, polyurethane foams are used in ceilings, roofs, and walls of buildings such as apartment complexes, detached houses, and commercial buildings to insulate and prevent condensation. Although polyurethane foams are lightweight, they are organic and therefore highly flammable. To address this issue, polyurethane foams containing flame retardants or other additives to enhance their flame resistance are being used. 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, while Patent Document 2 describes a flame-retardant polyurethane foam obtained using a solid phosphorus-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 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-151524 Summary of the Invention [Problem to be solved by the invention]

[0004] The flame-retardant polyurethane foams described in Patent Documents 1 and 2 have excellent flame retardancy due to the incorporation of a large amount of a bromine-containing flame retardant or a solid phosphorus-containing flame retardant. However, in recent years, market demands for flame retardancy have become stronger, and the flame retardancy of these flame-retardant polyurethane foams is insufficient, so further improvement has been required.

[0005] Therefore, an object of one aspect of the present disclosure is to provide a polyurethane foam-forming composition that contributes to the production of polyurethane foams having good flame retardancy.An object of yet another aspect of the present disclosure is to provide polyurethane foams having good flame retardancy. [Means for solving the problem]

[0006] The present disclosure provides the following aspects. [1] A polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, The polyurethane foam-forming composition, wherein the solid flame retardant comprises two or more selected from the group consisting of a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, and a boron-containing flame retardant. [2] The polyurethane foam-forming composition according to [1], wherein the solid flame retardant comprises the solid phosphorus-containing flame retardant and the boron-containing flame retardant. [3] The polyurethane foam-forming composition according to [1], wherein the solid flame retardant comprises the solid phosphorus-containing flame retardant and the bromine-containing flame retardant. [4] The polyurethane foam-forming composition according to [3], wherein the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant. [5] The first bromine-containing flame retardant is one selected from the following three (i) to (iii): (i) Bromine-containing flame retardants having a decomposition temperature of less than 370°C; (ii) Bromine-containing flame retardants with a decomposition temperature of 370°C or higher but lower than 450°C; (iii) Bromine-containing flame retardants with a decomposition temperature of 450°C or higher; The polyurethane foam-forming composition according to [4], wherein the second bromine-containing flame retardant is one selected from two other than one selected from the three (i) to (iii). [6] 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 polyurethane foam-forming composition according to [4], wherein the second bromine-containing flame retardant is one selected from two other than one selected from the three (a) to (c). [7] The polyurethane foam-forming composition according to [1], wherein the solid flame retardant comprises the bromine-containing flame retardant and the boron-containing flame retardant. [8] The polyurethane foam-forming composition according to [7], wherein the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant. [9] The first bromine-containing flame retardant is one selected from the following three (i) to (iii): (i) Bromine-containing flame retardants having a decomposition temperature of less than 370°C; (ii) Bromine-containing flame retardants with a decomposition temperature of 370°C or higher but lower than 450°C; (iii) Bromine-containing flame retardants with a decomposition temperature of 450°C or higher; The polyurethane foam-forming composition according to [8], wherein the second bromine-containing flame retardant is one selected from two other than one selected from the three (i) to (iii).

[10] 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 polyurethane foam-forming composition according to [8], wherein the second bromine-containing flame retardant is one selected from two other than one selected from the three (a) to (c).

[11] The polyurethane foam-forming composition of [1], wherein the solid flame retardant comprises the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

[12] The polyurethane foam-forming composition according to

[11] , wherein the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant.

[13] The first bromine-containing flame retardant is one selected from the following three (i) to (iii): (i) Bromine-containing flame retardants having a decomposition temperature of less than 370°C; (ii) Bromine-containing flame retardants with a decomposition temperature of 370°C or higher but lower than 450°C; (iii) Bromine-containing flame retardants with a decomposition temperature of 450°C or higher; The polyurethane foam-forming composition according to

[12] , wherein the second bromine-containing flame retardant is one selected from two other than one selected from the three (i) to (iii).

[14] 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 polyurethane foam-forming composition according to

[12] , wherein the second bromine-containing flame retardant is one selected from two other than one selected from the three (a) to (c).

[15] The polyurethane foam-forming composition according to any one of [1] to

[14] , further comprising a polyol compound, a polyisocyanate compound, a foam stabilizer, a blowing agent, and a catalyst.

[16] The polyol compound includes an aromatic polyester polyol,

[15] The polyurethane foam-forming composition according to

[15] , wherein the content of the aromatic polyester polyol is 30% by mass or more based on the content of the polyol compound.

[17] The aromatic polyester polyol comprises a terephthalic acid-based polyester polyol;

[16] The polyurethane foam-forming composition according to

[16] , wherein the content of the terephthalic acid-based polyester polyol is 30% by mass or more, based on the content of the aromatic polyester polyol.

[18] The polyurethane foam-forming composition according to any one of [1] to

[17] , having an isocyanate index of 150 to 800.

[19] The blowing agent comprises water; The polyurethane foam-forming composition according to any one of

[15] to

[18] , wherein the water content is 0.55 mass% or less, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[20] The blowing agent comprises water and a physical blowing agent; The polyurethane foam-forming composition according to any one of

[15] to

[19] , wherein the content of the physical blowing agent is from 40 mol % to 99 mol % of the total content of water and physical blowing agent.

[21] The catalyst comprises a trimerization catalyst; the trimerization catalyst comprises a tertiary or quaternary ammonium salt; The polyurethane foam-forming composition according to any one of

[15] to

[20] , wherein the content of the tertiary or quaternary ammonium salt is from 5.0% by mass to 100% by mass, based on the content of the trimerization catalyst.

[22] The polyurethane foam-forming composition of any one of [1] to

[21] , wherein the content of the liquid flame retardant is 1% by mass or more and 36% by mass or less, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[23] The polyurethane foam-forming composition of any one of [1] to

[22] , wherein the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant is 1.0% by mass or more and 19.5% by mass or less, based on the mass of the polyurethane foam components of the polyurethane foam-forming composition.

[24] The solid flame retardant comprises a solid phosphorus-containing flame retardant; The polyurethane foam-forming composition according to any one of [1] to

[23] , wherein the content of the solid phosphorus-containing flame retardant is 0.5% by mass or more and 12.0% by mass or less, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[25] The solid flame retardant comprises a bromine-containing flame retardant; The polyurethane foam-forming composition according to any one of [1] to

[24] , wherein the content of the bromine-containing flame retardant is from 0.1 to 12.0 mass %, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[26] The solid flame retardant (i) comprises a bromine-containing flame retardant having a decomposition temperature of less than 370°C; The polyurethane foam-forming composition according to any one of [1] to

[25] , wherein the content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C is from 0.001% by mass to 12.0% by mass, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[27] The solid flame retardant (ii) comprises a bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C; The polyurethane foam-forming composition according to any one of [1] to

[26] , wherein the content of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°C is 0.001% by mass or higher and 12.0% by mass or lower, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[28] The solid flame retardant (iii) comprises a bromine-containing flame retardant having a decomposition temperature of 450°C or higher; The polyurethane foam-forming composition according to any one of [1] to

[27] , wherein the content of the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or higher is 0.001% by mass or more and 12.0% by mass or less, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[29] The solid flame retardant (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 but lower than 450°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or higher, The polyurethane foam-forming composition according to any one of [1] to

[28] , wherein the content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C is 1% by mass or more and 99% by mass or less of the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more but less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

[30] The solid flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) a bromine-containing flame retardant having a decomposition temperature of less than 370°C; and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; The polyurethane foam-forming composition according to any one of [1] to

[29] , wherein the content of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 1% by mass or more and 95% by mass or less of the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

[31] The solid flame retardant (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or higher; (i) a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or more but less than 450°C, The polyurethane foam-forming composition according to any one of [1] to

[30] , wherein the content of the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more is 1% by mass or more and 95% by mass or less of the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more but less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

[32] The solid flame retardant comprises: (a) an aliphatic bromine-containing compound; The polyurethane foam-forming composition according to any one of [1] to

[31] , wherein the content of the (a) aliphatic bromine-containing compound is 0.001% by mass or more and 12.0% by mass or less, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[33] The solid flame retardant comprises (b) an aromatic bromine-containing low molecular weight compound; The polyurethane foam-forming composition according to any one of [1] to

[31] , wherein the content of the (b) aromatic bromine-containing low molecular weight compound is 0.001% by mass or more and 12.0% by mass or less, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[34] The solid flame retardant comprises (c) an aromatic bromine-containing polymer compound; The polyurethane foam-forming composition according to any one of [1] to

[33] , wherein the content of the (c) aromatic bromine-containing polymeric compound is 0.001% by mass or more and 12.0% by mass or less, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[35] The solid flame retardant (a) an aliphatic bromine-containing compound; (b) an aromatic bromine-containing low molecular weight compound; and (c) an aromatic bromine-containing high molecular weight compound, The polyurethane foam-forming composition according to any one of [1] to

[34] , wherein the content ratio of the (a) aliphatic bromine-containing compound is 1% by mass or more and 99% by mass or less of the total content of the (a) aliphatic bromine-containing compound, the (b) aromatic bromine-containing low-molecular-weight compound, and the (c) aromatic bromine-containing high-molecular-weight compound.

[36] The solid flame retardant (b) an aromatic bromine-containing low molecular weight compound; (a) an aliphatic bromine-containing compound; and (c) an aromatic bromine-containing polymer compound. The polyurethane foam-forming composition according to any one of [1] to

[35] , wherein the content of the (b) aromatic bromine-containing low molecular weight compound is 1% by mass or more and 95% by mass or less of the total content of the (a) aliphatic bromine-containing compound, the (b) aromatic bromine-containing low molecular weight compound, and the (c) aromatic bromine-containing high molecular weight compound.

[37] The solid flame retardant (c) an aromatic bromine-containing polymer compound; (a) an aliphatic bromine-containing compound; and (b) an aromatic bromine-containing low molecular weight compound. The polyurethane foam-forming composition according to any one of [1] to

[36] , wherein the content of the (c) aromatic bromine-containing polymeric compound is 1% by mass or more and 95% by mass or less, based on the total content of the (a) aliphatic bromine-containing compound, the (b) aromatic bromine-containing low-molecular-weight compound, and the (c) aromatic bromine-containing polymeric compound.

[38] The solid flame retardant comprises the boron-containing flame retardant; The polyurethane foam-forming composition according to any one of [1] to

[37] , wherein the content of the boron-containing flame retardant is from 0.1% by mass to 12.0% by mass, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[39] The solid flame retardant comprises the solid phosphorus-containing flame retardant; The polyurethane foam-forming composition according to any one of [1] to

[38] , wherein the content of the solid phosphorus-containing flame retardant is 3% by mass or more and 95% by mass or less, based on the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

[40] The solid flame retardant comprises the bromine-containing flame retardant; The polyurethane foam-forming composition according to any one of [1] to

[39] , wherein the content of the bromine-containing flame retardant is 3% by mass or more and 95% by mass or less, based on the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

[41] The solid flame retardant comprises the boron-containing flame retardant; The polyurethane foam-forming composition according to any one of [1] to

[40] , wherein the content of the boron-containing flame retardant is 2% by mass or more and 85% by mass or less, based on the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

[42] The polyurethane foam-forming composition of any one of [1] to

[42] , wherein the total content of the solid flame retardant and the liquid flame retardant is 5% by mass or more and 57% by mass or less, based on the mass of the polyurethane foam components of the polyurethane foam-forming composition.

[43] A polyurethane foam, which is a foam of the polyurethane foam-forming composition according to any one of [1] to

[42] .

[44] The polyurethane foam is tested to a radiant heat intensity of 50 kW / m according to the ISO-5660 test method. 2 When heated at 10 minutes, the total heat generated is 8.0MJ / m 2

[43] The polyurethane foam according to

[43] , wherein: [Effects of the Invention]

[0007] One aspect of the present disclosure can provide a polyurethane foam-forming composition that contributes to the production of polyurethane foams with good flame retardancy. Further, yet another aspect of the present disclosure can provide polyurethane foams with good flame retardancy. DETAILED DESCRIPTION OF THE INVENTION

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

[0009] [Mechanism of flame retardancy derived from flame retardants] When polymeric materials are heated, they melt, decompose, and volatilize, releasing flammable gases that ignite in the presence of oxygen, initiating combustion. Flame retardants primarily exhibit flame-extinguishing effects through flame-retardant mechanisms in the gas or solid phase. It is known that the flame-retardant effect in the gas phase tends to increase with the amount of trapped OH radicals, which have a large combustion driving force and are generated when organic matter is burned. 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 presence of phosphorus in the carbonized layer leads to the formation of a multilayer structure, which tends to further improve flame retardancy.

[0010] In each aspect of the present disclosure, by using two or more of a bromine-containing flame retardant as an OH radical trap, a solid phosphorus-containing flame retardant as a phosphorus source necessary for forming a multilayer carbonized layer, and a boron-containing flame retardant as a carbonized layer formation aid, a polyurethane foam having superior flame retardancy compared to when each is used alone can be obtained. That is, the present inventors have found that when two or more of these flame retardants exhibit flame retardancy, they confer flame retardancy to the polyurethane foam through different actions, unlike when one is used alone, and therefore, the polyurethane foam exhibits unexpectedly excellent flame retardancy. Furthermore, by using three types of flame retardants, ie, a bromine-containing flame retardant, a solid phosphorus-containing flame retardant, and a boron-containing flame retardant in combination, a polyurethane foam having even better flame retardancy than when two types are used in combination can be obtained.

[0011] Furthermore, by using two bromine-containing flame retardants with different decomposition temperatures in combination, it becomes possible to trap OH radicals, which have a strong combustion traction force, over a wider temperature range than when a single bromine-containing flame retardant is used, resulting in a polyurethane foam with even better flame retardancy than when a single bromine-containing flame retardant is used.Furthermore, by using three bromine-containing flame retardants with different decomposition temperatures in combination, it becomes possible to trap OH radicals, which have a strong combustion traction force, over an even wider temperature range than when a two-bromine-containing flame retardant is used in combination, resulting in a polyurethane foam with even better flame retardancy than when a two-bromine-containing flame retardant is used in combination.

[0012] The decomposition temperature of a bromine-containing flame retardant depends on the shape of the carbon atom to which the bromine atom is bonded, and it is known that the decomposition temperature is higher for a carbon atom-bromine atom bond derived from an aromatic group than for a carbon atom-bromine atom bond derived from an aliphatic group. It is also known that the decomposition temperature is higher for a carbon atom-bromine atom bond derived from a polymer compound than for a carbon atom-bromine atom bond derived from a low molecular weight compound. Therefore, the decomposition temperature of a bromine-containing flame retardant depends on the shape and / or molecular weight of the carbon atom to which the bromine atom is bonded.

[0013] [Polyurethane foam-forming composition] A polyurethane foam-forming composition according to one embodiment of the present disclosure is a polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, The solid flame retardant includes two or more selected from the group consisting of a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, and a boron-containing flame retardant. The polyurethane foam-forming composition may further comprise a polyol compound, a polyisocyanate compound, a foam stabilizer, a blowing agent, and a catalyst.

[0014] Here, the polyurethane foam-forming composition may be a two-component type or a multi-component type consisting of two or more components. The term "two-component type" refers to a configuration in which a first component containing a polyol composition and a second component containing a polyisocyanate composition are stored separately and are mixed when foam is formed. The term "multi-component type" refers to a configuration in which, for example, a first component containing a polyol composition, a second component containing a polyisocyanate composition, and a third component (and a fourth or more components) containing components other than the polyol composition and the polyisocyanate composition are stored separately and are mixed when foam is formed. The polyol composition contains a polyol compound, and the polyisocyanate composition contains a polyisocyanate compound.

[0015] The polyurethane foam-forming composition contains a solid flame retardant and a liquid flame retardant, thereby improving the flame retardancy of the resulting polyurethane foam. Here, the solid flame retardant refers to a flame retardant that is solid at 23° C., and the liquid flame retardant refers to a flame retardant that is liquid at 23° C.

[0016] [Solid flame retardant] The polyurethane foam-forming composition includes a solid flame retardant. Either the polyisocyanate composition or the polyol composition may contain the solid flame retardant, or both may contain it, but preferably only the polyol composition contains the solid flame retardant. The solid flame retardant includes two or more selected from the group consisting of a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, and a boron-containing flame retardant. That is, the solid flame retardant may include two of a solid phosphorus-containing flame retardant and a bromine-containing flame retardant; a solid phosphorus-containing flame retardant and a boron-containing flame retardant; a bromine-containing flame retardant and a boron-containing flame retardant; or a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, and a boron-containing flame retardant.

[0017] (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.

[0018] <Red phosphorus> There is no limitation on the red phosphorus, and for example, commercially available products can be appropriately selected and used.

[0019] <Phosphinic acid flame retardants> The phosphinic acid flame retardant is preferably at least one selected from the phosphinate flame retardants represented by the following formula (A-1) or (A-2) and polymers thereof.

[0020] [ka]

[0021] [ka]

[0022] In the formula, R 1 , R 2 are the same or different and are a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms; R 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.

[0023] R 1 , R 2 are preferably the same or different and are methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl, or phenyl groups. 3is preferably a methylene group, an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, a t-butylene group, an n-pentylene group, an n-octylene group, an n-dodecylene group, a phenylene group, a naphthylene group, a methylphenylene group, an ethylphenylene group, a t-butylphenylene group, a methylnaphthylene group, an ethylnaphthylene group, a t-butylnaphthylene group, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenylbutylene group. The above M is preferably Mg, Ca, Al, Sn, Ti, Zn, Fe, or Zr.

[0024] Such phosphinic acid flame retardants can be obtained, for example, by reacting alkylsulfonic acid and / or phosphinic acid and / or alkali metal salts thereof with an olefin in the presence of a free radical initiator to obtain phosphinic acid and / or alkali metal salts thereof, which can then be reacted with a metal compound. Specific examples of the phosphinic acid flame retardant 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), and the like, as well as combinations of any two or more of these. Among these, aluminum phosphinate; sodium phosphinate; and aluminum tris(phosphinate) selected from aluminum tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(butylethylphosphinate), and aluminum tris(diphenylphosphinate) are particularly preferred.

[0025] [Phosphate-containing flame retardants] Examples of phosphate-containing flame retardants include phosphates formed from a salt of phosphoric acid and at least one metal or compound selected from metals of Groups IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. The phosphoric acid is not particularly limited, and examples include various phosphoric acids such as monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid. 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 the like, as well as combinations of any two or more of these. Examples of aromatic amines include pyridine, triazine, and melamine. The phosphate-containing flame retardant may be subjected to known water resistance-improving treatments such as silane coupling agent treatment and coating with melamine resin.

[0026] Specific examples of phosphate-containing flame retardants include monophosphates, pyrophosphates, and polyphosphates.

[0027] The monophosphate salt is not particularly limited, and examples thereof 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 combinations of any two or more thereof.

[0028] The polyphosphate is not particularly limited, but examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, and the like, as well as combinations of any two or more of these.

[0029] Among these, it is preferable to use polyphosphates, and it is more preferable to use ammonium polyphosphate, since this improves the self-extinguishing properties of the phosphate-containing flame retardant.

[0030] The lower limit of the content of the solid phosphorus-containing flame retardant, relative to the weight of the polyurethane foam component of the polyurethane foam-forming composition, may be, for example, 0.5% by weight or more, 1.0% by weight or more, 1.5% by weight or more, 2.0% by weight or more, 2.5% by weight or more, 3.0% by weight or more, 3.5% by weight or more, 4.0% by weight or more, 4.5% by weight or more, 5.0% by weight or more, 5.5% by weight or more, or 6.0% by weight or more. The upper limit of the content of the solid phosphorus-containing flame retardant, relative to the weight of the polyurethane foam component of the polyurethane foam-forming composition, may be, for example, 12.0% by weight or less, 11.5% by weight or less, 11.0% by weight or less, 10.5% by weight or less, 10.0% by weight or less, 9.5% by weight or less, 9.0% by weight or less, 8.5% by weight or less, 8.0% by weight or less, 7.5% by weight or less, 7.0% by weight or less, or 6.5% by weight or less. The content of the solid phosphorus-containing flame retardant, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, may be, for example, 0.5 to 12.0% 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. When the content of the solid phosphorus-containing flame retardant is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained. When the content of the solid phosphorus-containing flame retardant is equal to or less than the upper limit, the rate of conversion of unreacted isocyanate groups to isocyanurate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be easily obtained.When the content of the solid phosphorus-containing flame retardant is equal to or more than the lower limit, the flame retardancy effect derived from the solid phosphorus-containing flame retardant is easily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be easily obtained.

[0031] In one embodiment of the present disclosure, a polyurethane foam is produced under conditions in which, for example, isocyanate groups are in large excess relative to the active hydrogen-containing component (polyol compound, water). When producing a polyurethane foam under these conditions, a portion of the isocyanate groups react with the active hydrogen-containing component to form urethane or urea groups, while the remaining unreacted isocyanate groups are converted to isocyanurate groups. Because isocyanurate groups have a much higher decomposition temperature than urethane or urea groups, the more isocyanurate groups present, the better the flame retardancy of the resulting polyurethane foam. Meanwhile, unreacted isocyanate groups react with moisture in the air to form amino groups, which then react with carbonyl bonds in the polyurethane foam, resulting in decomposition of the polyurethane resin. Generally, the higher the molecular weight of a polyurethane resin, the better its flame retardancy tends to be. Therefore, the higher the conversion of unreacted isocyanate groups to isocyanurate groups, the better the flame retardancy of the resulting polyurethane foam.

[0032] In this specification, the term "polyurethane foam constituents of the polyurethane foam-forming composition" refers to the components that constitute the polyurethane foam. For example, the "polyurethane foam constituents of the polyurethane foam-forming composition" refers to the components that constitute the polyurethane foam, including liquid flame retardants, solid flame retardants, polyol compounds, polyisocyanate compounds, foam stabilizers, blowing agents, catalysts, and other additives. Note that all or most of the blowing agent turns into bubbles and is discharged outside the system, and does not constitute a polyurethane foam. For example, in the blowing agent water, the hydrogen atoms form 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 constituents of the polyurethane foam-forming composition."

[0033] (Bromine-containing flame retardants) The bromine-containing flame retardant may contain only one kind or two kinds, but it is preferable that the bromine-containing flame retardant contains at least two kinds consisting of a first bromine-containing flame retardant and a second bromine-containing flame retardant.

[0034] The bromine-containing flame retardant is not particularly limited as long as it is a compound containing a bromine atom in its molecular structure, and examples thereof include compounds containing an aliphatic carbon atom-bromine atom bond (aliphatic bromine-containing compound), compounds that do not contain an aliphatic carbon atom-bromine atom bond but contain an aromatic carbon atom-bromine atom bond and have three or less aromatic rings (aromatic bromine-containing low-molecular-weight compound), and compounds that contain an aromatic carbon atom-bromine atom bond and have an average of more than three aromatic rings in the molecule (aromatic bromine-containing high-molecular-weight compound).

[0035] wherein 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 is preferably one selected from two other than one selected from the three (a) to (c).

[0036] Using two bromine-containing flame retardants, each differing in the form of the carbon atom to which the bromine atom is bonded and / or in molecular weight, tends to produce polyurethane foams with even better flame retardancy than when a single bromine-containing flame retardant is used. Using three bromine-containing flame retardants, each differing in the form of the carbon atom to which the bromine atom is bonded and / or in molecular weight, tends to produce polyurethane foams with even better flame retardancy than when two bromine-containing flame retardants are used. In particular, using two or more bromine-containing flame retardants selected from aliphatic bromine-containing compounds, aromatic bromine-containing low-molecular-weight compounds, and aromatic bromine-containing high-molecular-weight compounds tends to produce polyurethane foams with especially excellent flame retardancy.

[0037] Examples of compounds containing a carbon atom-bromine atom bond of aliphatic origin (aliphatic bromine-containing compounds) include low-molecular-weight organic bromine compounds such as 2,4,6-tris(2,4-dibromopropyl)-1,3,5-triazine (Pyroguard SR-750), 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.

[0038] Specific examples of compounds (aromatic bromine-containing low-molecular-weight compounds) that do not contain an aliphatic carbon atom-bromine atom bond but contain an aromatic carbon atom-bromine atom bond and have three or less aromatic rings include low-molecular-weight organic bromine compounds such as 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), and tetrabromobisphenol A. Among these, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine and ethylenebis(pentabromophenyl) are preferred.

[0039] Specific examples of compounds (aromatic bromine-containing polymer compounds) that contain aromatic carbon atom-bromine atom bonds and have an average of more than three aromatic rings in the molecule include homopolymers derived from 2,6-(or 2,4-)dibromophenol (Pyroguard SR-460B), polycarbonate oligomers produced using brominated bisphenol A as a raw material, brominated polycarbonates such as copolymers of the polycarbonate oligomers and bisphenol A (FG-8500, FG-7500, FG-7000), brominated polymers produced by reacting brominated bisphenol A with 1,2-dichloroethane, and brominated bisphenol A copolymers. Examples of suitable brominated epoxy compounds include diepoxy compounds produced by reacting bisphenol A with epichlorohydrin, monoepoxy compounds obtained by reacting brominated phenols with epichlorohydrin, poly(brominated benzyl acrylate), brominated polyphenylene ether, condensates of cyanuric chloride and brominated phenol, brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, and halogenated bromine compound polymers such as crosslinked or non-crosslinked brominated poly(α-methylstyrene), as well as combinations of any two or more of these. Among these, preferred are brominated polycarbonates such as homopolymers derived from 2,6-(or 2,4-)dibromophenol, polycarbonate oligomers produced from brominated bisphenol A, and copolymers of the polycarbonate oligomers with bisphenol A.

[0040] The lower limit of the content of the bromine-containing flame retardant, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be, for example, 0.1 mass% or more, 0.3 mass% or more, 0.5 mass% or more, 1.0 mass% or more, 1.5 mass% or more, 2.0 mass% or more, 2.5 mass% or more, 3.0 mass% or more, 3.5 mass% or more, 4.0 mass% or more, 4.5 mass% or more, 5.0 mass% or more, 5.5 mass% or more, or 6.0 mass% or more. The upper limit of the content of the bromine-containing flame retardant, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be, for example, 12.0 mass% or less, 11.8 mass% or less, 11.7 mass% or less, 11.5 mass% or less, 11.0 mass% or less, 10.5 mass% or less, 10.0 mass% or less, 9.5 mass% or less, 9.0 mass% or less, 8.5 mass% or less, 8.0 mass% or less, 7.5 mass% or less, 7.0 mass% or less, or 6.5 mass% or less. The content of the bromine-containing flame retardant, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, 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. When the content of the bromine-containing flame retardant is within the above range, a polyurethane foam with excellent flame retardancy tends to be easily obtained. When the content of the bromine-containing flame retardant is equal to or less than the above upper limit, the rate of conversion of unreacted isocyanate groups to isocyanurate groups increases, and a polyurethane foam with particularly excellent flame retardancy tends to be easily obtained. When the content of the bromine-containing flame retardant is equal to or more than the above lower limit, the flame retardant effect derived from the bromine-containing flame retardant is easily exhibited, and a polyurethane foam with particularly excellent flame retardancy tends to be easily obtained.

[0041] The lower limit of the content of the aliphatic bromine-containing compound, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, 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, or 2.3% by mass or more. The upper limit of the content of the aliphatic bromine-containing compound, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, may be, for example, 12.0 mass% or less, 11.0 mass% or less, 10.0 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, or 2.5 mass% or less. The content of the aliphatic bromine-containing compound, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, is, for example, 0.001% by mass or more and 12.0% by mass or less, 0.01% by mass or more and 11.0% by mass or less, 0.03% by mass or more and 10.0% by mass or less, 0.05% by mass or more and 9.0% by mass or less, 0.07% by mass or more and 8.0% by mass or less, 0.09% by mass or more and 7.0% by mass or less, 0.1% by mass or more and 6.5% by mass or less, 0.3% by mass or more, % or more and 6.0% or less by mass, 0.5% or more and 5.5% or less by mass, 0.7% or more and 5.0% or less by mass, 0.9% or more and 4.5% or less by mass, 1.1% or more and 4.0% or less by mass, 1.3% or more and 3.5% or less by mass, 1.5% or more and 3.3% or less by mass, 1.7% or more and 3.1% or less by mass, 1.9% or more and 2.9% or less by mass, 2.1% or more and 2.7% or less by mass, or 2.3% or more and 2.5% or less by mass. When the content of the aliphatic bromine-containing compound is within the above range, a polyurethane foam with excellent flame retardancy tends to be easily obtained. When the content of the aliphatic bromine-containing compound is equal to or less than the above upper limit, the rate of conversion of unreacted isocyanate groups to isocyanurate groups increases, and a polyurethane foam with particularly excellent flame retardancy tends to be easily obtained.When the content of the aliphatic bromine-containing compound is at least the above lower limit, the flame retardant effect derived from the aliphatic bromine-containing compound is more likely to be exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be more easily obtained.

[0042] The lower limit of the aromatic bromine-containing low molecular weight compound, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, 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, or 2.3% by mass or more. The upper limit of the content of the aromatic bromine-containing low molecular weight compound, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, may be, for example, 12.0 mass% or less, 11.0 mass% or less, 10.0 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, or 2.5 mass% or less. The content of the aromatic bromine-containing low molecular weight compound, relative to the mass of the polyurethane foam constituent of the polyurethane foam-forming composition, is, for example, 0.001% by mass or more and 12.0% by mass or less, 0.01% by mass or more and 11.0% by mass or less, 0.03% by mass or more and 10.0% by mass or less, 0.05% by mass or more and 9.0% by mass or less, 0.07% by mass or more and 8.0% by mass or less, 0.09% by mass or more and 7.0% by mass or less, 0.1% by mass or more and 6.5% by mass or less, 0.3% by mass or more and 0.4% by mass or less The content of the aromatic bromine-containing low molecular weight compound may be from 0.5 to 5.5% by mass, from 0.7 to 5.0% by mass, from 0.9 to 4.5% by mass, from 1.1 to 4.0% by mass, from 1.3 to 3.5% by mass, from 1.5 to 3.3% by mass, from 1.7 to 3.1% by mass, from 1.9 to 2.9% by mass, from 2.1 to 2.7% by mass, or from 2.3 to 2.5% by mass. When the content of the aromatic bromine-containing low molecular weight compound is within the above range, a polyurethane foam having excellent flame retardancy tends to be obtained.When the content of the aromatic bromine-containing low molecular weight compound is equal to or less than the upper limit, the rate of conversion of unreacted isocyanate groups to isocyanurate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.When the content of the aromatic bromine-containing low molecular weight compound is equal to or more than the lower limit, the flame retardancy effect derived from the aromatic bromine-containing low molecular weight compound is more easily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0043] The lower limit of the aromatic bromine-containing polymeric compound, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, 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, or 2.3% by mass or more. The upper limit of the aromatic bromine-containing polymeric compound content, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, may be, for example, 12.0 mass% or less, 11.0 mass% or less, 10.0 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, or 2.5 mass% or less. The content of the aromatic bromine-containing polymer compound, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, is, for example, 0.001% by mass or more and 12.0% by mass or less, 0.01% by mass or more and 11.0% by mass or less, 0.03% by mass or more and 10.0% by mass or less, 0.05% by mass or more and 9.0% by mass or less, 0.07% by mass or more and 8.0% by mass or less, 0.09% by mass or more and 7.0% by mass or less, 0.1% by mass or more and 6.5% by mass or less, 0.3% by mass or more and 0.4% by mass or less The content of the aromatic bromine-containing polymer compound within the above range may be from 0.5% to 5.5% by mass, from 0.7% to 5.0% by mass, from 0.9% to 4.5% by mass, from 1.1% to 4.0% by mass, from 1.3% to 3.5% by mass, from 1.5% to 3.3% by mass, from 1.7% to 3.1% by mass, from 1.9% to 2.9% by mass, from 2.1% to 2.7% by mass, or from 2.3% to 2.5% by mass. When the content of the aromatic bromine-containing polymer compound is within the above range, a polyurethane foam having excellent flame retardancy tends to be easily obtained.When the content of the aromatic bromine-containing polymer compound is equal to or less than the upper limit, the rate of conversion of unreacted isocyanate groups to isocyanurate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.When the content of the aromatic bromine-containing polymer compound is equal to or more than the lower limit, the flame retardancy effect derived from the aromatic bromine-containing polymer compound is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0044] The lower limit of the content of the aliphatic bromine-containing compound 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, or 45% by mass or more, based on the total content of the aliphatic bromine-containing compound, the aromatic bromine-containing low molecular weight compound, and the aromatic bromine-containing polymer compound. The upper limit of the content of the aliphatic bromine-containing compound 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, or 50% by mass or less, based on the total content of the aliphatic bromine-containing compound, the aromatic bromine-containing low molecular weight compound, and the aromatic bromine-containing polymer compound. The content of the aliphatic bromine-containing compound may be, for example, 1% by mass to 99% by mass, 2% by mass to 96% by mass, 3% by mass to 93% by mass, 5% by mass to 90% by mass, 10% by mass to 85% by mass, 15% by mass to 80% by mass, 20% by mass to 75% by mass, 25% by mass to 70% by mass, 30% by mass to 65% by mass, 35% by mass to 60% by mass, 40% by mass to 55% by mass, or 45% by mass to 50% by mass. When the content of the aliphatic bromine-containing compound is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained due to the synergistic effect of the flame retardancy derived from the aliphatic bromine-containing compound and the aromatic bromine-containing low molecular weight compound and / or the aromatic bromine-containing polymer compound. When the content ratio of the aliphatic bromine-containing compound is equal to or less than the upper limit, the flame retardant effect derived from the aromatic bromine-containing low molecular weight compound and / or the aromatic bromine-containing high molecular weight compound is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.When the content ratio of the aliphatic bromine-containing compound is equal to or more than the lower limit, the flame retardant effect derived from the aliphatic bromine-containing compound is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.

[0045] The lower limit of the content of the aromatic bromine-containing low molecular weight compound 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, or 28% by mass or more, based on the total content of the aliphatic bromine-containing compound, the aromatic bromine-containing low molecular weight compound, and the aromatic bromine-containing polymer compound. The upper limit of the content of the aromatic bromine-containing low molecular weight compound 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, or 36% by mass or less, based on the total content of the aliphatic bromine-containing compound, the aromatic bromine-containing low molecular weight compound, and the aromatic bromine-containing polymer compound. The content of the aromatic bromine-containing low molecular weight compound may be, for example, 1% by mass to 95% by mass, 1.5% by mass to 90% by mass, 2% by mass to 80% by mass, 4% by mass to 70% by mass, 8% by mass to 60% by mass, 12% by mass to 52% by mass, 16% by mass to 48% by mass, 20% by mass to 44% by mass, 24% by mass to 40% by mass, or 28% by mass to 36% by mass, based on the total content of the aliphatic bromine-containing compound, the aromatic bromine-containing low molecular weight compound, and the aromatic bromine-containing polymer compound. When the content of the aromatic bromine-containing low molecular weight compound is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained due to the synergistic effect of the flame retardancy derived from the aromatic bromine-containing low molecular weight compound and the aliphatic bromine-containing compound and / or the aromatic bromine-containing polymer compound. When the content ratio of the aromatic bromine-containing low molecular weight compound is equal to or less than the upper limit, the flame retardant effect derived from the aliphatic bromine-containing compound and / or the aromatic bromine-containing polymer compound is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.When the content ratio of the aromatic bromine-containing low molecular weight compound is equal to or more than the lower limit, the flame retardant effect derived from the aromatic bromine-containing low molecular weight compound is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.

[0046] The lower limit of the content of the aromatic bromine-containing polymeric compound 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, or 28% by mass or more, based on the total content of the aliphatic bromine-containing compound, the aromatic bromine-containing low molecular weight compound, and the aromatic bromine-containing polymeric compound. The upper limit of the content of the aromatic bromine-containing polymeric compound 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, or 36% by mass or less, based on the total content of the aliphatic bromine-containing compound, the aromatic bromine-containing low molecular weight compound, and the aromatic bromine-containing polymeric compound. The content of the aromatic bromine-containing polymeric compound may be, for example, 1% by mass to 95% by mass, 1.5% by mass to 90% by mass, 2% by mass to 80% by mass, 4% by mass to 70% by mass, 8% by mass to 60% by mass, 12% by mass to 52% by mass, 16% by mass to 48% by mass, 20% by mass to 44% by mass, 24% by mass to 40% by mass, or 28% by mass to 36% by mass, based on the total content of the aliphatic bromine-containing compound, the aromatic bromine-containing low molecular weight compound, and the aromatic bromine-containing polymeric compound. When the content of the aromatic bromine-containing polymeric compound is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained due to the synergistic effect of the flame retardancy derived from the aromatic bromine-containing polymeric compound and the aliphatic bromine-containing compound and / or the aromatic bromine-containing low molecular weight compound. When the content ratio of the aromatic bromine-containing polymer compound is equal to or less than the upper limit, the flame retardant effect derived from the aliphatic bromine-containing compound and / or the aromatic bromine-containing low molecular weight compound is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.When the content ratio of the aromatic bromine-containing polymer compound is equal to or more than the lower limit, the flame retardant effect derived from the aromatic bromine-containing polymer compound is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.

[0047] When two bromine-containing flame retardants with different decomposition temperatures are used in combination, polyurethane foams with even better flame retardancy tend to be obtained than when a single bromine-containing flame retardant is used. Furthermore, when three bromine-containing flame retardants with different decomposition temperatures are used in combination, polyurethane foams with even better flame retardancy tend to be obtained than when two bromine-containing flame retardants are used.

[0048] In particular, by using 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, and bromine-containing flame retardants with a decomposition temperature of 450°C or more, polyurethane foams with particularly excellent flame retardancy tend to be obtained. That is, the first bromine-containing flame retardant is one selected from the following three (i) to (iii): (i) Bromine-containing flame retardants having a decomposition temperature of less than 370°C; (ii) Bromine-containing flame retardants with a decomposition temperature of 370°C or higher but lower than 450°C; (iii) Bromine-containing flame retardants with a decomposition temperature of 450°C or higher; The second bromine-containing flame retardant is preferably one selected from two other than one selected from the three (i) to (iii). 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 more, 20°C or more, 25°C or more, 30°C or more, 35°C or more, 40°C or more, 45°C or more, or 50°C or more, and may be 130°C or less, 120°C or less, 110°C or less, 100°C or less, 90°C or less, 80°C or less, 70°C or less, or 60°C or less.

[0049] 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). Of these, 4,4'-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] is preferred.

[0050] Bromine-containing flame retardants with a decomposition temperature of 370° C. or higher and lower than 450° C. include 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (Pyroguard SR-245) and ethylenebis(pentabromophenyl).

[0051] Bromine-containing flame retardants with a decomposition temperature of 450°C or higher include homopolymers derived from 2,6-(or 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).

[0052] The lower limit of the bromine-containing flame retardant having a decomposition temperature of less than 370°C 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, or 2.3% by mass or more, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition. The upper limit of the content of the bromine-containing flame retardant having 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, or 2.5% by mass or less, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition. The content of the bromine-containing flame retardant having a decomposition temperature of less than 370°C, relative to the mass of the polyurethane foam constituent of the polyurethane foam-forming composition, is, for example, 0.001% by mass or more and 12.0% by mass or less, 0.01% by mass or more and 11.0% by mass or less, 0.03% by mass or more and 10.0% by mass or less, 0.05% by mass or more and 9.0% by mass or less, 0.07% by mass or more and 8.0% by mass or less, 0.09% by mass or more and 7.0% by mass or less, 0.1% by mass or more and 6.5% by mass or less, The content of the bromine-containing flame retardant having a decomposition temperature of less than 370°C within the above range may be 0.3% to 6.0% by mass, 0.5% to 5.5% by mass, 0.7% to 5.0% by mass, 0.9% to 4.5% by mass, 1.1% to 4.0% by mass, 1.3% to 3.5% by mass, 1.5% to 3.3% by mass, 1.7% to 3.1% by mass, 1.9% to 2.9% by mass, 2.1% to 2.7% by mass, or 2.3% to 2.5% by mass. When the content of the bromine-containing flame retardant having a decomposition temperature of less than 370°C is within the above range, a polyurethane foam having excellent flame retardancy tends to be obtained.When the content of the bromine-containing flame retardant having a decomposition temperature of less than 370°C is equal to or less than the upper limit, the rate of conversion of unreacted isocyanate groups to isocyanurate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.When the content of the bromine-containing flame retardant having a decomposition temperature of less than 370°C is equal to or greater than the lower limit, the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of less than 370°C is more likely to be exerted, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0053] The lower limit of the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C 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, or 2.3% by mass or more, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition. The upper limit of the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°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, or 2.5% by mass or less, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition. The content of the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, relative to the mass of the polyurethane foam constituent of the polyurethane foam-forming composition, is, for example, 0.001% by mass or more and 12.0% by mass or less, 0.01% by mass or more and 11.0% by mass or less, 0.03% by mass or more and 10.0% by mass or less, 0.05% by mass or more and 9.0% by mass or less, 0.07% by mass or more and 8.0% by mass or less, 0.09% by mass or more and 7.0% by mass or less, 0.1% by mass or more and 6.5% by mass or less In the above range, the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°C may be 0.3% by mass or higher and 6.0% by mass or lower, 0.5% by mass or higher and 5.5% by mass or lower, 0.7% by mass or higher and 5.0% by mass or lower, 0.9% by mass or higher and 4.5% by mass or lower, 1.1% by mass or higher and 4.0% by mass or lower, 1.3% by mass or higher and 3.5% by mass or lower, 1.5% by mass or higher and 3.3% by mass or lower, 1.7% by mass or higher and 3.1% by mass or lower, 1.9% by mass or higher and 2.9% by mass or lower, 2.1% by mass or higher and 2.7% by mass or lower, or 2.3% by mass or higher and 2.5% by mass or lower. When the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°C is within the above range, a polyurethane foam having excellent flame retardancy tends to be easily obtained.When the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C is equal to or lower than the upper limit, the rate of conversion of unreacted isocyanurate groups to isocyanurate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.When the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C is equal to or higher than the lower limit, the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C tends to be more easily exerted, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0054] The lower limit of the bromine-containing flame retardant having a decomposition temperature of 450°C or higher, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, 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, or 2.3% by mass or more. The upper limit of the content of the bromine-containing flame retardant having a decomposition temperature of 450°C or higher, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, 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, or 2.5% by mass or less. The content of the bromine-containing flame retardant having a decomposition temperature of 450°C or higher, relative to the mass of the polyurethane foam constituent of the polyurethane foam-forming composition, is, for example, 0.001% by mass or more and 12.0% by mass or less, 0.01% by mass or more and 11.0% by mass or less, 0.03% by mass or more and 10.0% by mass or less, 0.05% by mass or more and 9.0% by mass or less, 0.07% by mass or more and 8.0% by mass or less, 0.09% by mass or more and 7.0% by mass or less, 0.1% by mass or more and 6.5% by mass or less, The content of the bromine-containing flame retardant having a decomposition temperature of 450°C or higher within the above range may be 0.3% to 6.0% by mass, 0.5% to 5.5% by mass, 0.7% to 5.0% by mass, 0.9% to 4.5% by mass, 1.1% to 4.0% by mass, 1.3% to 3.5% by mass, 1.5% to 3.3% by mass, 1.7% to 3.1% by mass, 1.9% to 2.9% by mass, 2.1% to 2.7% by mass, or 2.3% to 2.5% by mass. When the content of the bromine-containing flame retardant having a decomposition temperature of 450°C or higher is within the above range, a polyurethane foam having excellent flame retardancy tends to be obtained.When the content of the bromine-containing flame retardant having a decomposition temperature of 450°C or higher is equal to or lower than the upper limit, the rate of conversion of unreacted isocyanate groups to isocyanurate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.When the content of the bromine-containing flame retardant having a decomposition temperature of 450°C or higher is equal to or higher than the lower limit, the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of 450°C or higher is more likely to be exerted, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0055] The lower limit of the content ratio of the bromine-containing flame retardant having 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, or 45% by mass or more relative to the sum of the content of the bromine-containing flame retardant having a decomposition temperature of less than 370°C, the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or more but less than 450°C, and the content of the bromine-containing flame retardant having a decomposition temperature of 450°C or more. The upper limit of the content ratio of bromine-containing flame retardants having 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, or 50% by mass or less, relative to the sum of the content of bromine-containing flame retardants having a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants having a decomposition temperature of 370°C or more but less than 450°C, and the content of bromine-containing flame retardants having a decomposition temperature of 450°C or more. The content ratio of the bromine-containing flame retardant having a decomposition temperature of less than 370°C may be, for example, 1% by mass or more and 99% by mass or less, 2% by mass or more and 96% by mass or less, 3% by mass or more and 93% by mass or less, 5% by mass or more and 90% by mass or less, 10% by mass or more and 85% by mass or less, 15% by mass or more and 80% by mass or less, 20% by mass or more and 75% by mass or less, 25% by mass or more and 70% by mass or less, 30% by mass or more and 65% by mass or less, 35% by mass or more and 60% by mass or less, 40% by mass or more and 55% by mass or less, or 45% by mass or more and 50% by mass or less, relative to the sum of the content of the bromine-containing flame retardant having a decomposition temperature of less than 370°C, the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, When the content ratio of the bromine-containing flame retardant having a decomposition temperature of less than 370°C is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained more easily due to the synergistic effect of the flame retardant effects derived from the bromine-containing flame retardant having a decomposition temperature of less than 370°C and the bromine-containing flame retardant having a decomposition temperature of 370°C or more but less than 450°C and / or the bromine-containing flame retardant having a decomposition temperature of 450°C or more.When the content ratio of the bromine-containing flame retardant having a decomposition temperature of less than 370°C is equal to or less than the upper limit, the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of 370°C or more but less than 450°C and / or the bromine-containing flame retardant having a decomposition temperature of 450°C or more is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained. When the content ratio of the bromine-containing flame retardant having a decomposition temperature of less than 370°C is equal to or more than the lower limit, the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of less than 370°C is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.

[0056] The lower limit of the content ratio of bromine-containing flame retardants having a decomposition temperature of 370°C or more and less than 450°C may be, for example, 1 mass% or more, 1.5 mass% or more, 2 mass% or more, 4 mass% or more, 8 mass% or more, 12 mass% or more, 16 mass% or more, 20 mass% or more, 24 mass% or more, or 28 mass% or more relative to the sum of the content of bromine-containing flame retardants having a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants having a decomposition temperature of 370°C or more and less than 450°C, and the content of bromine-containing flame retardants having a decomposition temperature of 450°C or more. The upper limit of the content ratio of bromine-containing flame retardants having a decomposition temperature of 370°C or more and 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, or 36% by mass or less of the total content of bromine-containing flame retardants having a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants having a decomposition temperature of 370°C or more and less than 450°C, and the content of bromine-containing flame retardants having a decomposition temperature of 450°C or more. The content ratio of the bromine-containing flame retardant having a decomposition temperature of 370°C or more and 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 the bromine-containing flame retardant having a decomposition temperature of less than 370°C, the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the content of the bromine-containing flame retardant having a decomposition temperature of 450°C or more. When the content ratio of the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained more easily due to the synergistic effect of the flame retardant effects derived from the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the bromine-containing flame retardant having a decomposition temperature of less than 370°C and / or the bromine-containing flame retardant having a decomposition temperature of 450°C or more.When the content ratio of the bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C is equal to or lower than the upper limit, the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of less than 370°C and / or the bromine-containing flame retardant having a decomposition temperature of 450°C or higher is more likely to be exhibited, and a polyurethane foam with particularly excellent flame retardancy tends to be easily obtained. When the content ratio of the bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C is equal to or higher than the lower limit, the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C is more likely to be exhibited, and a polyurethane foam with particularly excellent flame retardancy tends to be easily obtained.

[0057] The lower limit of the content ratio of the bromine-containing flame retardant having a decomposition temperature of 450°C or more 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, or 28% by mass or more relative to the sum of the content of the bromine-containing flame retardant having a decomposition temperature of less than 370°C, the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or more but less than 450°C, and the content of the bromine-containing flame retardant having a decomposition temperature of 450°C or more. The upper limit of the content ratio of bromine-containing flame retardants having 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, or 36% by mass or less of the total content of bromine-containing flame retardants having a decomposition temperature of less than 370°C, bromine-containing flame retardants having a decomposition temperature of 370°C or more but less than 450°C, and bromine-containing flame retardants having a decomposition temperature of 450°C or higher. The content ratio of the bromine-containing flame retardant having a decomposition temperature of 450°C or higher 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 the bromine-containing flame retardant having a decomposition temperature of less than 370°C, the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the content of the bromine-containing flame retardant having a decomposition temperature of 450°C or more. When the content ratio of the bromine-containing flame retardant having a decomposition temperature of 450° C. or higher is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained more easily due to the synergistic effect of the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of 450° C. or higher and the bromine-containing flame retardant having a decomposition temperature of less than 370° C. and / or the bromine-containing flame retardant having a decomposition temperature of 370° C. or higher but less than 450° C. When the content ratio of the bromine-containing flame retardant having a decomposition temperature of 450° C. or higher is equal to or lower than the above upper limit, the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of less than 370° C. and / or the bromine-containing flame retardant having a decomposition temperature of 370° C. or higher but less than 450° C. is more easily exhibited, and a polyurethane foam with particularly excellent flame retardancy tends to be obtained more easily.When the content ratio of the bromine-containing flame retardant having a decomposition temperature of 450°C or higher is equal to or higher than the above lower limit, the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of 450°C or higher is more easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be more easily obtained.

[0058] (Boron-containing flame retardants) Specific 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, and ammonium borate, and combinations of any two or more of these. Of these, zinc borate is preferred.

[0059] The lower limit of the content of the boron-containing flame retardant, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be, for example, 0.1 mass% or more, 0.2 mass% or more, 0.3 mass% or more, 0.4 mass% or more, 0.8 mass% or more, 1.2 mass% or more, 1.6 mass% or more, 2.0 mass% or more, 2.4 mass% or more, 2.8 mass% or more, 3.2 mass% or more, 3.6 mass% or more, 4.0 mass% or more, 4.4 mass% or more, or 4.8 mass% or more. The upper limit of the content of the boron-containing flame retardant, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be, for example, 12.0 mass% or less, 11.0 mass% or less, 10.0 mass% or less, 9.6 mass% or less, 9.2 mass% or less, 8.8 mass% or less, 8.4 mass% or less, 8.0 mass% or less, 7.6 mass% or less, 7.2 mass% or less, 6.8 mass% or less, 6.4 mass% or less, 6.0 mass% or less, 5.6 mass% or less, or 5.2 mass% or less. The content of the boron-containing flame retardant, relative to the mass of the polyurethane foam constituent of the polyurethane foam-forming composition, may be, for example, 0.1 to 12.0% by mass, 0.2 to 11.0% by mass, 0.3 to 10.0% by mass, 0.4 to 9.6% by mass, 0.8 to 9.2% by mass, 1.2 to 8.8% by mass, 1.6 to 8.4% by mass, 2.0 to 8.0% by mass, 2.4 to 7.6% by mass, 2.8 to 7.2% by mass, 3.2 to 6.8% by mass, 3.6 to 6.4% by mass, 4.0 to 6.0% by mass, 4.4 to 5.6% by mass, or 4.8 to 5.2% by mass. When the content of the boron-containing flame retardant is within the above range, polyurethane foams with excellent flame retardancy tend to be easily obtained. When the content of the boron-containing flame retardant is equal to or less than the above upper limit, the rate of conversion of unreacted isocyanate groups to isocyanurate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be easily obtained. When the content of the boron-containing flame retardant is equal to or more than the above lower limit, the flame retardant effect derived from the boron-containing flame retardant is easily exerted, and polyurethane foams with particularly excellent flame retardancy tend to be easily obtained.

[0060] The lower limit of the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, may be, for example, 1.0 mass% or more, 2.0 mass% or more, 2.5 mass% or more, 3.5 mass% or more, 4.0 mass% or more, 4.5 mass% or more, 5.0 mass% or more, 5.5 mass% or more, 6.0 mass% or more, 6.5 mass% or more, 7.5 mass% or more, or 8.5 mass% or more. The upper limit of the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, may be, for example, 19.5 mass% or less, 18.5 mass% or less, 17.5 mass% or less, 16.5 mass% or less, 15.5 mass% or less, 14.5 mass% or less, 13.5 mass% or less, 12.5 mass% or less, 11.5 mass% or less, 10.5 mass% or less, or 9.5 mass% or less. The sum of the content of the solid phosphorus-containing flame retardant, the content of the bromine-containing flame retardant, and the content of the boron-containing flame retardant, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, may be, for example, 1.0 to 19.5% by mass, 2.0 to 18.5% by mass, 2.5 to 17.5% by mass, 3.5 to 16.5% by mass, 4.0 to 15.5% by mass, 4.5 to 14.5% by mass, 5.5 to 13.5% by mass, 6.0 to 12.5% by mass, 6.5 to 11.5% by mass, 7.5 to 10.5% by mass, or 8.5 to 9.5% by mass. When the sum of the contents of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained. When the sum of the contents of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant is equal to or less than the above upper limit, the rate of conversion of unreacted isocyanate groups to isocyanurate groups increases, and a polyurethane foam with particularly excellent flame retardancy tends to be obtained.When the sum of the content of the solid phosphorus-containing flame retardant, the content of the bromine-containing flame retardant, and the content of the boron-containing flame retardant is equal to or greater than the above lower limit, the flame retardant effect derived from the flame retardant is more easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be more easily obtained.

[0061] The lower limit of the content of the solid phosphorus-containing flame retardant may be, for example, 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, or 45% by mass or more, based on the sum of the contents of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. The upper limit of the content of the solid phosphorus-containing flame retardant may be, for example, 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, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less, based on the sum of the contents of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. The content of the solid phosphorus-containing flame retardant may be, for example, 3% by mass to 95% by mass, 5% by mass to 90% by mass, 10% by mass to 85% by mass, 15% by mass to 80% by mass, 20% by mass to 75% by mass, 25% by mass to 70% by mass, 30% by mass to 65% by mass, 35% by mass to 60% by mass, 40% by mass to 55% by mass, or 45% by mass to 50% by mass, based on the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. When the content of the solid phosphorus-containing flame retardant is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained due to the synergistic effect of the flame retardancy derived from the solid phosphorus-containing flame retardant and the bromine-containing flame retardant and / or the boron-containing flame retardant. When the content ratio of the solid phosphorus-containing flame retardant is equal to or less than the upper limit, the flame retardant effect derived from the bromine-containing flame retardant and / or boron-containing flame retardant is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.When the content ratio of the solid phosphorus-containing flame retardant is equal to or more than the lower limit, the flame retardant effect derived from the solid phosphorus-containing flame retardant is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.

[0062] The lower limit of the bromine-containing flame retardant content may be, for example, 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, or 45% by mass or more, based on the sum of the solid phosphorus-containing flame retardant content, the bromine-containing flame retardant content, and the boron-containing flame retardant content. The upper limit of the bromine-containing flame retardant content may be, for example, 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, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less, based on the sum of the solid phosphorus-containing flame retardant content, the bromine-containing flame retardant content, and the boron-containing flame retardant content. The content of the bromine-containing flame retardant may be, for example, 3% by mass to 95% by mass, 5% by mass to 90% by mass, 10% by mass to 85% by mass, 15% by mass to 80% by mass, 20% by mass to 75% by mass, 25% by mass to 70% by mass, 30% by mass to 65% by mass, 35% by mass to 60% by mass, 40% by mass to 55% by mass, or 45% by mass to 50% by mass, based on the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. When the content of the bromine-containing flame retardant is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained due to the synergistic effect of the flame retardancy derived from the bromine-containing flame retardant and the solid phosphorus-containing flame retardant and / or the boron-containing flame retardant. When the content ratio of the bromine-containing flame retardant is equal to or less than the upper limit, the flame retardant effect derived from the boron-containing flame retardant and / or the solid phosphorus-containing flame retardant is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.When the content ratio of the bromine-containing flame retardant is equal to or more than the lower limit, the flame retardant effect derived from the bromine-containing flame retardant is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.

[0063] The lower limit of the content of the boron-containing flame retardant may be, for example, 2% by mass or more, 3% by mass or more, 5% by mass or more, 7% 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, or 35% by mass or more, based on the sum of the contents of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. The upper limit of the content of the boron-containing flame retardant may be, for example, 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, or 40% by mass or less, based on the sum of the contents of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. The content of the boron-containing flame retardant may be, for example, 2% by mass to 85% by mass, 3% by mass to 80% by mass, 5% by mass to 75% by mass, 7% by mass to 70% by mass, 10% by mass to 65% by mass, 15% by mass to 60% by mass, 20% by mass to 55% by mass, 25% by mass to 50% by mass, 30% by mass to 45% by mass, or 35% by mass to 40% by mass, based on the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. When the content of the boron-containing flame retardant is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained due to the synergistic effect of the flame retardancy derived from the boron-containing flame retardant and the solid phosphorus-containing flame retardant and / or the bromine-containing flame retardant. When the content ratio of the boron-containing flame retardant is equal to or less than the upper limit, the flame retardant effect derived from the bromine-containing flame retardant and / or the solid phosphorus-containing flame retardant is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.When the content ratio of the boron-containing flame retardant is equal to or more than the lower limit, the flame retardant effect derived from the boron-containing flame retardant is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.

[0064] The polyurethane foam-forming composition may contain a solid flame retardant other than a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, or a boron-containing flame retardant. Either the polyisocyanate composition or the polyol composition may contain a solid flame retardant other than a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, or a boron-containing flame retardant, or both may contain such a solid flame retardant. Examples of solid flame retardants other than solid phosphorus-containing flame retardants, bromine-containing flame retardants, and boron-containing flame retardants include antimony-containing flame retardants, metal hydroxide-based flame retardants, phosphazenes, silicone-based flame retardants, and organic sulfonate-based flame retardants. Two or more of these solid flame retardants may be used in combination.

[0065] [Antimony-containing flame retardants] Examples of antimony-containing flame retardants include antimony oxide, antimony salts, pyroantimony salts, etc., and combinations of any two or more of these. Examples of antimony oxides include antimony trioxide and antimony pentoxide. Examples of antimony salts include sodium antimonate, potassium antimonate, etc., and combinations of any two or more of these. Examples of pyroantimonate salts include sodium pyroantimonate, potassium pyroantimonate, etc., and combinations of any two or more of these. The antimony-containing flame retardant is preferably antimony oxide.

[0066] [Metal hydroxide flame retardants] Examples of metal hydroxide 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 combinations of any two or more of these.

[0067] [Liquid flame retardant] The polyurethane foam-forming composition includes a liquid flame retardant. Either the polyisocyanate composition or the polyol composition may include the liquid flame retardant, or both may include the liquid flame retardant. Examples of the liquid flame retardant 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 include, but are not limited to, trimethyl phosphate, triethyl phosphate, tributoxyethyl phosphate, tributyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl phenyl phosphate, dimethyl methyl phosphonate, tris(chloroethyl)phosphate, tris(dichloropropyl)phosphate, tris(β-chloropropyl)phosphate, and the like, as well as combinations of any two or more of these. The condensed phosphate ester is not particularly limited, but examples thereof 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.), aromatic condensed phosphate ester, etc. Among these, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, and tris(β-chloropropyl) phosphate are preferred.

[0068] The lower limit of the liquid flame retardant content, relative to the weight of the polyurethane foam component of the polyurethane foam-forming composition, may be, for example, 1% by weight or more, 2% by weight or more, 4% by weight or more, 5% by weight or more, 6% by weight or more, 7% by weight or more, 8% by weight or more, 9% by weight or more, 10% by weight or more, 11% by weight or more, 12% by weight or more, 13% by weight or more, 14% by weight or more, 15% by weight or more, or 16% by weight or more. The upper limit of the liquid flame retardant content, relative to the weight of the polyurethane foam component of the polyurethane foam-forming composition, may be, for example, 36% by weight or less, 34% by weight or less, 32% by weight or less, 30% by weight or less, 28% by weight or less, 26% by weight or less, 25% by weight or less, 24% by weight or less, 23% by weight or less, 22% by weight or less, 21% by weight or less, 20% by weight or less, 19% by weight or less, 18% by weight or less, or 17% by weight or less. The content of the liquid flame retardant, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, may be, for example, 1% by mass to 36% by mass, 2% by mass to 34% by mass, 4% by mass to 32% by mass, 5% by mass to 30% by mass, 6% by mass to 28% by mass, 7% by mass to 26% by mass, 8% by mass to 25% by mass, 9% by mass to 24% by mass, 10% by mass to 23% by mass, 11% by mass to 22% by mass, 12% by mass to 21% by mass, 13% by mass to 20% by mass, 14% by mass to 19% by mass, 15% by mass to 18% by mass, or 16% by mass to 17% by mass. When the content of the liquid flame retardant is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained. When the content of the liquid flame retardant is equal to or less than the upper limit, the rate of conversion of unreacted isocyanate groups to isocyanurate groups increases, and a polyurethane foam having particularly excellent flame retardancy tends to be obtained.When the content of the liquid flame retardant is equal to or more than the lower limit, the flame retardant effect derived from the flame retardant is easily exerted, and a polyurethane foam having particularly excellent flame retardancy tends to be obtained.

[0069] The lower limit of the total content of the solid flame retardant and the liquid, relative to the weight of the polyurethane foam component of the polyurethane foam-forming composition, may be, for example, 5% by weight or more, 7% by weight or more, 10% by weight or more, 12% by weight or more, 14% by weight or more, 16% by weight or more, 18% by weight or more, 20% by weight or more, 22% by weight or more, 24% by weight or more, or 26% by weight or more. The upper limit of the total content of the liquid flame retardant and the solid flame retardant, relative to the weight of the polyurethane foam component of the polyurethane foam-forming composition, may be, for example, 57% by weight or less, 54% by weight or less, 51% by weight or less, 48% by weight or less, 45% by weight or less, 42% by weight or less, 39% by weight or less, 36% by weight or less, 33% by weight or less, 30% by weight or less, or 28% by weight or less. The total content of the liquid flame retardant and the solid flame retardant, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, may be, for example, 5% by mass to 57% by mass, 7% by mass to 54% by mass, 10% by mass to 51% by mass, 12% by mass to 48% by mass, 14% by mass to 45% by mass, 16% by mass to 42% by mass, 18% by mass to 39% by mass, 20% by mass to 36% by mass, 22% by mass to 33% by mass, 24% by mass to 30% by mass, or 26% by mass to 28% by mass. When the total content of the liquid flame retardant and the solid flame retardant is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained. When the total content of the flame retardants is equal to or less than the above upper limit, the rate of conversion of unreacted isocyanate groups to isocyanurate groups increases, and a polyurethane foam with particularly excellent flame retardancy tends to be obtained. When the total content of the liquid flame retardant and the solid flame retardant is at least the above lower limit, the flame retardant effect derived from the flame retardant is easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.

[0070] [Polyurethane foam] The polyurethane foam of another embodiment of the present disclosure is a foam of the polyurethane foam-forming composition described above.

[0071] [Polyol composition] The polyol composition forms a polyurethane foam by mixing with the polyisocyanate composition, and the polyol composition is desirably used as the first liquid of the polyurethane foam-forming composition. That is, during distribution, it is desirable to prepare a two-component or multi-component product by combining a first component containing a polyol composition, a second component containing a polyisocyanate composition, and, in the case of a multi-component product, a third component (and a fourth or more components) containing components other than the polyol composition and the polyisocyanate composition, and then, during foam formation, mix these first and second components, or, in the case of a multi-component product, the third component (and a fourth or more components). The polyol composition contains a polyol compound as an essential component.

[0072] <Polyol compounds> The polyol compound contained in the polyol composition is not particularly limited, but preferably contains a polyether polyol or a polyester polyol. Among these, from the viewpoint of enhancing the flame retardancy of the resulting polyurethane foam, it is preferable to contain an aromatic polyol such as an aromatic polyether polyol or an aromatic polyester polyol, as described below. Furthermore, from the viewpoint of enhancing the flame retardancy of the resulting polyurethane foam, it is particularly preferable to contain a terephthalic acid-based polyester polyol, as described below.

[0073] (Polyether polyol) Polyether polyols are polyoxyalkylene polyols obtained by ring-opening addition polymerization of alkylene oxides with an initiator having two or more active hydrogen atoms. Specific examples of initiators include aliphatic polyhydric alcohols, aliphatic amines, aromatic amines, and combinations of any 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 condensation products.

[0074] From the viewpoint of enhancing the flame retardancy of polyurethane foams, the polyether polyol is preferably an aromatic polyether polyol having an aromatic ring in the molecule, 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 is a polyether polyol obtained using tolylenediamine as an initiator. The Mannich-based polyether polyol is a polyether polyol produced by utilizing the Mannich reaction of phenols, primary or secondary amines, and aldehydes, such as polyether polyols obtained using a Mannich condensate as an initiator.

[0075] The hydroxyl value of the polyether polyol is preferably 200 to 1000 mgKOH / g, more preferably 300 to 600 mgKOH / g. The hydroxyl value is a value measured in accordance with JIS K1557-1:2007.

[0076] (polyester polyol) Examples of polyester polyols include aromatic polyester polyols and aliphatic polyester polyols. However, considering the flame retardancy of the resulting polyurethane foam, aromatic polyester polyols are preferred. The aromatic polyester polyol is preferably a condensate of an aromatic dicarboxylic acid, such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), or naphthalenedicarboxylic acid, with a 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 a glycol, are preferred, and p-phthalic acid-based polyester polyols, which are condensates of p-phthalic acid with a glycol, are more preferred. The glycol is not particularly limited, but it is preferable to use low molecular weight aliphatic glycols known as constituent components of polyester polyols, such as ethylene glycol, propylene glycol, and diethylene glycol.

[0077] Among the above-mentioned polyol compounds, from the viewpoint of enhancing the flame retardancy of the polyurethane foam, it is preferable to contain an aromatic polyester polyol, 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.

[0078] The hydroxyl value of the polyester polyol is preferably from 100 to 400 mgKOH / g, and more preferably from 150 to 350 mgKOH / g.

[0079] 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 the aromatic polyester polyol, relative to the content of the polyol compound, may be, for example, 50% by mass to 100% by mass, 55% by mass to 99% by mass, 60% by mass to 98% by mass, 65% by mass to 96% by mass, 70% by mass to 94% by mass, 75% by mass to 92% by mass, 80% by mass to 90% by mass, or 85% by mass to 88% by mass. When the content of the aromatic polyester polyol is within the above range, a polyurethane foam-forming composition with excellent handleability due to reduced viscosity and a polyurethane foam with excellent flame retardancy tend to be readily obtained. When the content of the aromatic polyester polyol is equal to or less than the above upper limit, a polyurethane foam-forming composition with excellent handleability due to reduced viscosity tend to be readily obtained. Furthermore, when the content of the aromatic polyester polyol is equal to or greater than the above lower limit, a polyurethane foam with excellent flame retardancy tend to be readily obtained.

[0080] The lower limit of the content of the terephthalic acid-based polyester polyol relative to the content of the polyol compound 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. The upper limit of the content of the terephthalic acid-based polyester polyol relative to the content of the polyol compound 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. The amount of the terephthalic acid-based polyester polyol relative to the total amount of the polyol compound may be, for example, 30% by mass to 100% by mass, 35% by mass to 98% by mass, 40% by mass to 95% by mass, 45% by mass to 90% by mass, 50% by mass to 85% by mass, 55% by mass to 80% by mass, 60% by mass to 75% by mass, or 65% by mass to 70% by mass. When the amount of the terephthalic acid-based polyester polyol is within the above range, the viscosity is reduced, which tends to facilitate the production of a polyurethane foam-forming composition with excellent handleability and a polyurethane foam with excellent flame retardancy. When the amount of the terephthalic acid-based polyester polyol is equal to or less than the above upper limit, the viscosity is reduced, which tends to facilitate the production of a polyurethane foam-forming composition with excellent handleability. Furthermore, when the amount of the terephthalic acid-based polyester polyol is equal to or greater than the above lower limit, the polyurethane foam with excellent flame retardancy tends to be readily produced.

[0081] [Polyisocyanate composition] The polyisocyanate composition can be mixed with a polyol composition to form a polyurethane foam. The polyisocyanate composition is preferably used as the second component of a two-component or multi-component polyurethane foam-forming composition. That is, during distribution, the composition is prepared in the form of a two-component or multi-component combination of a first component containing a polyol composition, a second component containing a polyisocyanate composition, and, in the case of a multi-component composition, a third component (and / or fourth component) containing components other than the polyol composition and the polyisocyanate composition. During foam formation, the first component and the second component, or in the case of a multi-component composition, the third component (and / or fourth component) are preferably mixed and used. The polyisocyanate composition contains a polyisocyanate compound as an essential component.

[0082] <Polyisocyanate compounds> The polyisocyanate compound contained in the polyisocyanate composition can be any of various polyisocyanate compounds, such as aromatic, alicyclic, and aliphatic polyisocyanate compounds having two or more isocyanate groups. Liquid diphenylmethane diisocyanate (MDI) is preferably used because of 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 known as polymeric MDI). Specific commercial liquid MDI products include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.) and "Millionate MR200" (manufactured by Tosoh Corporation). Uretonimine-containing MDI (e.g., commercially available product "Millionate MTL" manufactured by Tosoh Corporation) may also be used. In addition to liquid MDI, other polyisocyanate compounds may be used in combination, and as the polyisocyanate compounds to be used in combination, any polyisocyanate compounds known in the technical field of polyurethanes can be used without any limitations.

[0083] The lower limit of the isocyanate index (NCO INDEX) is not particularly limited, and may be 150 or more, 180 or more, 210 or more, 240 or more, 270 or more, 310 or more, 340 or more, 370 or more, or 390 or more. The upper limit of the isocyanate index may be, for example, 800 or less, 700 or less, 610 or less, 570 or less, 540 or less, 510 or less, 470 or less, 440 or less, or 410 or less. The isocyanate index content may be, for example, 150 or more and 800 or less, 180 or more and 700 or less, 210 or more and 610 or less, 240 or more and 570 or less, 270 or more and 540 or less, 310 or more and 510 or less, 340 or more and 470 or less, 370 or more and 440 or less, or 390 or more and 410 or less. When the isocyanate index is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained. When the isocyanate index is equal to or greater than the above lower limit, the amount of isocyanate nurate groups produced increases, and a polyurethane foam with particularly excellent flame retardancy tends to be obtained. On the other hand, when the isocyanate index is equal to or less than the above upper limit, the rate of conversion of unreacted isocyanate groups to isocyanurate groups increases, and a polyurethane foam with particularly excellent flame retardancy tends to be obtained.

[0084] (Inorganic filler) The polyurethane foam-forming composition may contain an inorganic filler, as long as the effect of one embodiment of the present disclosure is not impaired. Either the polyisocyanate composition or the polyol composition may contain an inorganic filler, or both may contain an inorganic filler. 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 of calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica palan, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon palan, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, and the like, and combinations of any two or more of these.

[0085] From the viewpoint of the foamability of the polyurethane foam, the content of the inorganic filler is preferably 1 to 30 mass %, more preferably 2 to 25 mass %, even more preferably 3 to 20 mass %, particularly preferably 4 to 15 mass %, and most preferably 5 to 10 mass %, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[0086] (Anti-settling agent) The polyurethane foam-forming composition may contain an anti-settling agent. Either the polyisocyanate composition or the polyol composition may contain the anti-settling agent, or both may contain the anti-settling agent. Examples of anti-settling agents include organic bentonite, aliphatic amides, hydrogenated castor oil wax, carbon black, silica powder, etc., and combinations of any two or more of these. Examples of aliphatic amides include ASA T-1700 (manufactured by Ito Oil Mills), ASA T-1800 (manufactured by Ito Oil Mills), ASA T-2800 (manufactured by Ito Oil Mills), and Disparlon 6100 (manufactured by Kusumoto Chemicals). Among these, ASA T-1700 is preferred. The inclusion of an anti-settling agent can suppress the settling of powder particles with a high specific gravity, such as solid flame retardants, in the polyurethane foam-forming composition.

[0087] The content of the anti-settling agent 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, based on the mass of the polyurethane foam components in the polyurethane foam-forming composition. When the content of the anti-settling agent is at least as high as the lower limit, a polyurethane foam-forming composition in which settling of the solid flame retardant is suppressed tends to be obtained. On the other hand, when the content of the anti-settling agent is at most as high as the upper limit, a polyurethane foam with excellent flame retardancy tends to be obtained.

[0088] (dispersant) The polyurethane foam-forming 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 of acidic copolymers having hydroxyl groups, organic ammonium salts, phosphate esters, and phosphate ester salts. Examples of organic ammonium salts include alkylammonium salts, alkylolammonium salts, and combinations of any two or more of these. Examples of phosphate ester salts include lecithin. Among these, lecithin is preferred.

[0089] The content of the dispersant 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, based on the mass of the polyurethane foam components in the polyurethane foam-forming composition. When the content of the dispersant is at least as large as the lower limit, a polyurethane foam-forming composition with excellent dispersion stability tends to be obtained. On the other hand, when the content of the dispersant is at most as large as the upper limit, a polyurethane foam with excellent flame retardancy tends to be obtained.

[0090] <Foam stabilizer> The polyurethane foam-forming composition may contain a foam stabilizer. Either the polyisocyanate composition or the polyol composition may contain a foam stabilizer, or both may contain a foam stabilizer. Examples of foam stabilizers include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, surfactants such as silicone foam stabilizers such as organopolysiloxanes, and combinations of any two or more of these. Furthermore, the silicone foam stabilizer may contain a graft copolymer of polydimethylsiloxane and polyethylene glycol.

[0091] The content of the foam stabilizer is not particularly limited, but is preferably 0.05 to 2.0 mass %, more preferably 0.1 to 1.7 mass %, even more preferably 0.15 to 1.4 mass %, particularly preferably 0.2 to 1.1 mass %, and most preferably 0.25 to 0.80 mass %, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[0092] <Foaming agent> The polyurethane foam-forming composition may contain a blowing agent. Either the polyisocyanate composition or the polyol composition may contain the blowing agent, or both may contain the blowing agent. Preferably, only the polyol composition contains the blowing agent. The blowing agent may be water and / or a physical blowing agent.

[0093] Specific examples of physical blowing agents include low-boiling hydrocarbon compounds, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbon compounds, ether compounds, hydrofluoroolefin compounds, etc. Further examples of 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 compound include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Examples of the chlorinated aliphatic hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Examples of the fluorine compound include CHF3, CH2F2, and CH3F. Examples of the hydrochlorofluorocarbon compounds include trichloromonofluoromethane, trichlorotrifluoroethane, and dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), and HCFC142b (1-chloro-1,1-difluoroethane)). Examples of the hydrofluorocarbon compound include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane). Examples of the ether compounds include diisopropyl ether. Examples of the hydrofluoroolefin compound include HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene) and HFO-1234yf (2,3,3,3-tetrafluoro-1-propene). These physical foaming agents may be used alone or in any combination of two or more. Among these, hydrofluoroolefin compounds are preferred.

[0094] The lower limit of the blowing agent content, relative to the mass of the polyurethane foam constituent of the polyurethane foam-forming composition, may be, for example, 1.0 mass% or more, 2.0 mass% or more, 3.0 mass% or more, 4.0 mass% or more, 5.0 mass% or more, 6.0 mass% or more, 7.0 mass% or more, 8.0 mass% or more, or 9.0 mass% or more. The upper limit of the blowing agent content, relative to the mass of the polyurethane foam constituent of the polyurethane foam-forming composition, may be, for example, 18.0 mass% or less, 17.0 mass% or less, 16.0 mass% or less, 15.0 mass% or less, 14.0 mass% or less, 13.0 mass% or less, 12.0 mass% or less, 11.0 mass% or less, or 10.0 mass% or less. The content of the blowing agent, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, may be, for example, 1.0% by mass to 18.0% by mass, 2.0% by mass to 17.0% by mass, 3.0% by mass to 16.0% by mass, 4.0% by mass to 15.0% by mass, 5.0% by mass to 14.0% by mass, 6.0% by mass to 13.0% by mass, 7.0% by mass to 12.0% by mass, 8.0% by mass to 11.0% by mass, or 9.0% by mass to 10.0% by mass. A blowing agent content within this range tends to facilitate the production of polyurethane foams with improved mechanical properties, such as compressive strength, dimensional stability, and adhesiveness, and with reduced raw material costs. A blowing agent content below the upper limit tends to facilitate the production of polyurethane foams with excellent mechanical properties, particularly compressive strength, dimensional stability, and adhesiveness. Furthermore, when the content of the blowing agent is equal to or greater than the lower limit, a polyurethane foam tends to be obtained, particularly with reduced raw material costs.

[0095] The lower limit of the water content, relative to the weight of the polyurethane foam component of the polyurethane foam-forming composition, may be, for example, 0.01% by weight or more, 0.02% by weight or more, 0.03% by weight or more, 0.04% by weight or more, 0.05% by weight or more, 0.07% by weight or more, 0.09% by weight or more, 0.11% by weight or more, or 0.13% by weight or more. The upper limit of the water content, relative to the weight of the polyurethane foam component of the polyurethane foam-forming composition, may be, for example, 0.55% by weight or less, 0.50% by weight or less, 0.45% by weight or less, 0.40% by weight or less, 0.35% by weight or less, 0.30% by weight or less, 0.25% by weight or less, 0.20% by weight or less, or 0.15% by weight or less. The water content, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, may be, for example, 0.01% by mass to 0.55% by mass, 0.02% by mass to 0.50% by mass, 0.03% by mass to 0.45% by mass, 0.04% by mass to 0.40% by mass, 0.05% by mass to 0.35% by mass, 0.07% by mass to 0.30% by mass, 0.09% by mass to 0.25% by mass, 0.11% by mass to 0.20% by mass, or 0.13% by mass to 0.15% by mass. A water content within this range tends to facilitate the production of polyurethane foams with excellent mechanical properties, such as flame retardancy and compressive strength. A water content of up to the upper limit tends to facilitate the production of polyurethane foams with particularly excellent flame retardancy. A water content of up to the lower limit tends to facilitate the production of polyurethane resins with particularly excellent mechanical properties, such as compressive strength.

[0096] The lower limit of the content of the physical blowing agent 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, or 9.0% by mass or more, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition. The upper limit of the content of the physical blowing agent 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, or 10.0% by mass or less, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition. The content of the physical blowing agent, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition, may be, for example, 1.0% by mass to 18.0% by mass, 2.0% by mass to 17.0% by mass, 3.0% by mass to 16.0% by mass, 4.0% by mass to 15.0% by mass, 5.0% by mass to 14.0% by mass, 6.0% by mass to 13.0% by mass, 7.0% by mass to 12.0% by mass, 8.0% by mass to 11.0% by mass, or 9.0% by mass to 10.0% by mass. Because the physical blowing agent contains chlorine in its molecule, it also exhibits flame retardancy. A physical blowing agent content within the above ranges tends to provide polyurethane foams with excellent mechanical properties, such as compressive strength, dimensional stability, and adhesiveness, as well as excellent flame retardancy. A physical blowing agent content below the above upper limit tends to provide polyurethane foams with excellent mechanical properties, particularly compressive strength, dimensional stability, and adhesiveness. Furthermore, when the content of the physical blowing agent is equal to or greater than the lower limit, a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.

[0097] When the blowing agent contains water and a physical blowing agent, the lower limit of the content of the physical blowing agent 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, or 87 mol% or more, based on the total content of the water and the physical blowing agent. The upper limit of the content of the physical blowing agent 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, or 89 mol% or less, based on the total content of the water and the physical blowing agent. The content of the physical blowing agent relative to the total content of water and 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%. Because the physical blowing agent contains chlorine in its molecule, it also exhibits flame retardancy. A content of the physical blowing agent within the above range tends to facilitate the production of polyurethane foams with excellent flame retardancy and mechanical properties such as compressive strength. A content of the physical blowing agent equal to or greater than the above lower limit tends to facilitate the production of polyurethane foams with particularly excellent flame retardancy. When the content of the physical blowing agent is equal to or less than the upper limit, a polyurethane foam having excellent mechanical properties, particularly compressive strength, tends to be obtained.

[0098] <Catalyst> The polyurethane foam-forming composition may contain a catalyst. Either the polyisocyanate composition or the polyol composition may contain a catalyst, or both may contain a catalyst. Preferably, only the polyol composition contains a catalyst. The catalyst may include, for example, one or both of a urethane / urea catalyst and a trimerization catalyst, preferably both.

[0099] The urethane / urea catalyst is a catalyst that accelerates the reaction between the polyol component and the polyisocyanate. Specific examples include amino compounds, tin compounds, bismuth compounds, and metal acetylacetone salts. Examples of the amino compound 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 the bismuth compound include bismuth neodecanoate and bismuth octoate. Examples of acetylacetone metal salts include acetylacetone aluminum, acetylacetone iron, acetylacetone copper, acetylacetone zinc, acetylacetone beryllium, acetylacetone chromium, acetylacetone indium, acetylacetone manganese, acetylacetone molybdenum, acetylacetone titanium, acetylacetone cobalt, acetylacetone vanadium, and acetylacetone zirconium. These urethane / urea catalysts may be used alone or in any combination of two or more.

[0100] The amount of the urethane / urea catalyst is not particularly limited, but 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, based on the mass of the polyurethane foam components in the polyurethane foam-forming composition. By ensuring that the amount is within the above range, the reaction between the polyol component and the polyisocyanate component can be promoted at an appropriate reaction rate.

[0101] The trimerization catalyst is a catalyst that promotes the formation of an isocyanurate bond. By promoting trimerization in the polyurethane foam-forming composition, the flame retardancy of the resulting polyurethane foam is improved. 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 octylate, sodium octylate, and 2-ethylaziridine; lead compounds such as lead naphthenate and lead octylate; 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 combinations of any two or more of these.

[0102] The content of the trimerization catalyst is not particularly limited, but from the viewpoint of improving the curing rate of the polyurethane foam-forming composition and the flame retardancy of the polyurethane foam, it is preferably 0.5 to 6.0 mass %, more preferably 0.8 to 4.0 mass %, even more preferably 1.1 to 3.0 mass %, particularly preferably 1.3 to 2.5 mass %, and most preferably 1.5 to 2.0 mass %, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition. By keeping the content of the trimerization catalyst within the above range, an appropriate amount of isocyanurate bonds are formed, improving flame retardancy.

[0103] The trimerization catalyst tends to provide polyurethane foams that are excellent in reactivity during foaming and in flame retardancy by using a metal salt in combination with a tertiary or quaternary ammonium salt.

[0104] The lower limit of the content of the tertiary or quaternary ammonium salt, relative to the content of the trimerization catalyst, may be, for example, 5.0 mass% or more, 15.0 mass% or more, 25.0 mass% or more, 35.0 mass% or more, 45.0 mass% or more, 55.0 mass% or more, or 65.0 mass% or more. The upper limit of the content of the tertiary or quaternary ammonium salt, relative to the content of the trimerization catalyst, may be, for example, 100 mass% or less, 95.0 mass% or less, 90.0 mass% or less, 85.0 mass% or less, 80.0 mass% or less, 75.0 mass% or less, or 70.0 mass% or less. The content of the tertiary or quaternary ammonium salt, relative to the content of the trimerization catalyst, may be, for example, 5.0% by mass to 100% by mass, 15.0% by mass to 95.0% by mass, 25.0% by mass to 90.0% by mass, 35.0% by mass to 85.0% by mass, 45.0% by mass to 80.0% by mass, 55.0% by mass to 75.0% by mass, or 65.0% by mass to 70.0% by mass. When the content of the tertiary or quaternary ammonium salt is within the above range, a polyurethane foam having excellent reactivity during foaming and excellent flame retardancy tends to be obtained. When the content of the tertiary or quaternary ammonium salt is equal to or greater than the above lower limit, a polyurethane foam having particularly high reactivity tends to be obtained, which is particularly effective for spray foaming applications. When the content of the tertiary or quaternary ammonium salt is equal to or less than the above upper limit, a polyurethane foam having particularly excellent flame retardancy tends to be obtained.

[0105] (Other additives) The polyurethane foam-forming composition may further contain additives other than the solid flame retardant, liquid flame retardant, polyol compound, polyisocyanate compound, foam stabilizer, blowing agent, catalyst, and inorganic filler. Examples of the additives include phenolic, amine, and sulfur-based antioxidants, heat stabilizers, metal inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifying resins, and tackifiers (such as polybutene and petroleum resins).

[0106] (Manufacturing method) The method for producing a polyurethane foam is not particularly limited, and examples thereof include a method in which a polyol composition and a polyisocyanate composition are previously prepared by kneading them, and a method in which the components constituting the polyurethane foam are kneaded together. However, the polyurethane foam is usually produced by kneading a polyol composition and a polyisocyanate composition. The kneading can be carried out by a known method, and the polyurethane foam can be obtained by kneading using a known device such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a Raikai mixer, or a planetary mixer.

[0107] (Total heat generation) Polyurethane foam, which is a reaction product of a polyisocyanate composition and a polyol composition, was subjected to a radiant heat intensity of 50 kW / m in accordance with the ISO-5660 test method. 2 When heated at 10 minutes, the total heat generated is 10MJ / m 2 The total calorific value is preferably 10 MJ / m or less. 2 In order to further improve the flame retardancy of the polyurethane foam, the total calorific value is set to 9 MJ / m or less. 2 Preferably, it is 8MJ / m or less. 2 More preferably, it is 7MJ / m or less. 2 More preferably, it is 6.5 MJ / m or less. 2 It is particularly preferable that the concentration is 6 MJ / m or less. 2It is most preferable that the gross calorific value is equal to or less than 100%. The gross calorific value can be 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 used in the test has shape stability to such an extent that it does not come into contact with the spark igniter of the cone calorimeter.

[0108] (Application) The uses of the polyurethane foam, which is a foam of the polyurethane foam-forming composition, are not particularly limited, but it can be used to fill cavities in structures such as buildings, furniture, automobiles, trains, and ships, or to spray onto such structures. Among these, the use of the polyurethane foam for spraying onto structures, i.e., as a polyurethane foam for spraying, is preferred. Spraying can be carried out using a spraying device (e.g., A-25 manufactured by GRACO) and a spray gun (e.g., D-gun manufactured by Gasmar). Spraying can be carried out by adjusting the temperature of a polyol composition and a polyisocyanate composition contained in separate containers in the spraying device, causing them to collide and mix at the tip of the spray gun, and then atomizing the mixture using air pressure. Spraying devices and spray guns are well known, and commercially available products can be used.

[0109] The density of the polyurethane foam is not particularly limited, but is preferably 20 to 200 kg / m 3 The density is preferably in the range of 200 kg / m 3 By setting the weight below 20 kg / m, the polyurethane foam becomes lighter and easier to apply to structures. 3 From these viewpoints, the density of the polyurethane foam is set to 25 to 100 kg / m or more, so that the desired flame retardancy can be easily exhibited. 3 More preferably, it is in the range of 25 to 80 kg / m 3 It is more preferable that the density of the polyurethane foam is in the range of

[0045] The density of the polyurethane foam can be measured in accordance with JIS K7222.

[0110] <Calculation method for each composition> Mass (g) of polyurethane foam constituents of polyurethane foam-forming composition = charged amount (g) of polyisocyanate compound + charged amount (g) of polyol compound + additives * Charge amount (g) + Charge amount of foam stabilizer (g) + Charge amount of catalyst (g) *Additives include 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, inorganic fillers, anti-settling agents, dispersion stabilizers, and other additives.

[0111] Aromatic polyester polyol compound content (mass%) = (amount of aromatic polyester polyol compound charged (g) + amount of aromatic / aliphatic polyester polyol compound charged (g) × aromatic content ratio (%) of aromatic / aliphatic polyester polyol compound * ) / mass of polyol compound (g) x 100 *: Aromatic content ratio (%) of aromatic / aliphatic polyester polyol compound = content (mol) derived from aromatic dicarboxylic acid / (content (mol) derived from aromatic dicarboxylic acid + content (mol) derived from aliphatic dicarboxylic acid) × 100

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

[0113] Isocyanate index = polyisocyanate equivalents ÷ (polyol equivalents + water equivalents) × 100 Here, the equivalent weight of polyisocyanate = the number of parts of polyisocyanate used × NCO content (%) × 100 / NCO molecular weight Polyol equivalents = OHV × number of parts of polyol used ÷ molecular weight of KOH, OHV is the hydroxyl value of the polyol (mgKOH / g), and water equivalents = number of parts of water used × number of OH groups in water / molecular weight of water. Note that in the above formula, the unit of parts used is weight (g), the molecular weight of the NCO group is 42, and the NCO content is the proportion of NCO groups in the polyisocyanate compound expressed in mass %. For convenience of unit conversion in the above formula, the molecular weight of KOH is set to 56,100, the molecular weight of water to 18, and the number of OH groups in water to 2.

[0114] Content (mass%) of solid phosphorus-containing flame retardant = Charged amount (g) of solid phosphorus-containing flame retardant / Mass (g) of polyurethane foam component of polyurethane foam-forming composition × 100

[0115] Bromine-containing flame retardant content (mass%) = Bromine-containing flame retardant charge (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0116] Content of aliphatic bromine-containing compound (% by mass) = Amount of aliphatic bromine-containing compound charged (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

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

[0118] Aromatic bromine-containing polymer compound content (% by mass) = Amount of aromatic bromine-containing polymer compound charged (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

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

[0120] Content ratio (mass%) of aromatic bromine-containing low molecular weight compound = charge amount (g) of aromatic bromine-containing low molecular weight compound / (charge amount (g) of aliphatic bromine-containing compound + charge amount (g) of aromatic bromine-containing low molecular weight compound + charge amount (g) of aromatic bromine-containing high molecular weight compound) × 100

[0121] Content ratio of aromatic bromine-containing polymer compound (mass%) = Amount of aromatic bromine-containing polymer compound charged (g) / (Amount of aliphatic bromine-containing compound charged (g) + Amount of aromatic bromine-containing low molecular weight compound charged (g) + Amount of aromatic bromine-containing polymer compound charged (g)) × 100

[0122] Content (mass%) of bromine-containing flame retardant having a decomposition temperature of less than 370°C = Charged amount (g) of bromine-containing flame retardant having a decomposition temperature of less than 370°C / Mass (g) of polyurethane foam constituent of polyurethane foam-forming composition × 100

[0123] Content (mass%) of bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C = Charge amount (g) of bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C / Mass (g) of polyurethane foam constituent of polyurethane foam-forming composition × 100

[0124] Content (mass%) of bromine-containing flame retardant having a decomposition temperature of 450°C or higher = Charged amount (g) of bromine-containing flame retardant having a decomposition temperature of 450°C or higher / Mass (g) of polyurethane foam component of polyurethane foam-forming composition × 100

[0125] Content ratio (mass%) of bromine-containing flame retardants with a decomposition temperature of less than 370°C = Charge amount (g) of bromine-containing flame retardants with a decomposition temperature of less than 370°C / (Charge amount (g) of bromine-containing flame retardants with a decomposition temperature of less than 370°C + Charge amount (g) of bromine-containing flame retardants with a decomposition temperature of 370°C or more but less than 450°C + Charge amount (g) of bromine-containing flame retardants with a decomposition temperature of 450°C or more) x 100

[0126] Content ratio (mass%) of bromine-containing flame retardants with a decomposition temperature of 370°C or more and less than 450°C = Charge amount (g) of bromine-containing flame retardants with a decomposition temperature of 370°C or more and less than 450°C / (Charge amount (g) of bromine-containing flame retardants with a decomposition temperature of less than 370°C + Charge amount (g) of bromine-containing flame retardants with a decomposition temperature of 370°C or more and less than 450°C + Charge amount (g) of bromine-containing flame retardants with a decomposition temperature of 450°C or more) x 100

[0127] Content ratio (mass%) of bromine-containing flame retardants with a decomposition temperature of 450°C or more but less than 450°C = Charge amount (g) of bromine-containing flame retardants with a decomposition temperature of 450°C or more but less than 450°C / (Charge amount (g) of bromine-containing flame retardants with a decomposition temperature of less than 370°C + Charge amount (g) of bromine-containing flame retardants with a decomposition temperature of 370°C or more but less than 450°C + Charge amount (g) of bromine-containing flame retardants with a decomposition temperature of 450°C or more) x 100

[0128] Content of boron-containing flame retardant (mass%) = Amount of boron-containing flame retardant charged (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0129] Content ratio of solid phosphorus-containing flame retardant (mass%) = charge amount of solid phosphorus-containing flame retardant (g) / (charge amount of solid phosphorus-containing flame retardant (g) + charge amount of bromine-containing flame retardant (g) + charge amount of boron-containing flame retardant (g)) × 100

[0130] Bromine-containing flame retardant content (mass%) = Bromine-containing flame retardant charge (g) / (Solid phosphorus-containing flame retardant charge (g) + Bromine-containing flame retardant charge (g) + Boron-containing flame retardant charge (g)) × 100

[0131] Content ratio of boron-containing flame retardant (mass%) = amount of boron-containing flame retardant (g) / (amount of solid phosphorus-containing flame retardant (g) + amount of bromine-containing flame retardant (g) + amount of boron-containing flame retardant (g)) × 100

[0132] Sum (mass %) of the content of the solid phosphorus-containing flame retardant, the content of the bromine-containing flame retardant, and the content of the boron-containing flame retardant = (charge amount (g) of the solid phosphorus-containing flame retardant + charge amount (g) of the bromine-containing flame retardant + charge amount (g) of the boron-containing flame retardant) / mass (g) of the polyurethane foam constituent of the polyurethane foam-forming composition × 100

[0133] Liquid flame retardant content (mass%) = liquid flame retardant charge (g) / mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0134] Total content (mass%) of solid and liquid flame retardants = Total flame retardants * Charge amount (g) / mass (g) of polyurethane foam constituent of polyurethane foam-forming composition×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.

[0135] Content of inorganic filler (% by mass) = Amount of inorganic filler charged (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0136] Anti-settling agent content (mass%) = anti-settling agent charged (g) / mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0137] Dispersant content (mass%) = Amount of dispersant charged (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0138] Content of other additives (% by mass) = Amount of other additives charged (g) / Mass of polyurethane foam constituent of polyurethane foam-forming composition (g) × 100

[0139] Foam stabilizer content (mass%) = foam stabilizer charge (g) / mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0140] Blowing agent content (mass%) = foaming agent charge (g) / mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0141] Water content (mass%) = water amount (g) / mass (g) of polyurethane foam component of polyurethane foam-forming composition × 100

[0142] Content of physical blowing agent (% by mass) = Amount of physical blowing agent charged (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0143] Physical blowing agent content (mol%) = amount of physical blowing agent (mol) / (amount of water (mol) + amount of physical blowing agent (mol)) x 100

[0144] Urethane / urea catalyst content (mass%) = amount of urethane / urea catalyst charged (g) / mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0145] Tertiary or quaternary ammonium salt content (mass%) = tertiary or quaternary ammonium salt charge (g) / trimerization catalyst charge (g) × 100 [Example]

[0146] An embodiment of the present disclosure will be described in more detail with reference to examples, but the embodiment of the present disclosure is not limited to these examples. 8~16、22~25 is a test example for reference that does not fall within the scope of the present invention.

[0147] Details of each component used in each example and comparative example are as follows: In Tables 1-1 to 15-1, some components are shown by abbreviations, and these abbreviations are written in parentheses below. (1) Polyisocyanate compounds "MR-200": MDI (manufactured by Tosoh Corporation, product name: MR-200)

[0148] (2) Solid flame retardants "Pyroguard SR-720N": 4,4'-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Pyroguard SR-720: aliphatic bromine-containing compound, decomposition temperature: 315°C) "Pyroguard SR-750": 2,4,6-tris(2,4-dibromopropyl)-1,3,5-triazine (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Pyroguard SR-750: aliphatic bromine-containing compound, decomposition temperature: 324°C) Pyroguard SR-245: 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Pyroguard SR-245: aromatic bromine-containing low molecular weight compound, decomposition temperature: 417°C) Ethylenebispentabromophenyl (Tokyo Chemical Industry Co., Ltd., aromatic bromine-containing low molecular weight compound, decomposition temperature: 428°C) "Pyroguard SR-460B": Homopolymer derived from 2,6-(or 2,4-)dibromophenol (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Pyroguard SR-460B: aromatic bromine-containing polymer compound, decomposition temperature: 515°C) Fireguard 8500: Polycarbonate oligomer made from brominated bisphenol A (manufactured by Teijin, product name: Fireguard 8500: aromatic bromine-containing polymer compound, decomposition temperature: 474°C) Fireguard 7500: Polycarbonate oligomer made from brominated bisphenol A (manufactured by Teijin, product name: Fireguard 7500: aromatic bromine-containing polymer compound, decomposition temperature: 470°C) AP-462: Ammonium polyphosphate (Clariant Chemical Company, product name: AP-462) "PHOSMEL (registered trademark)-100" melamine polyphosphate (manufactured by Nissan Chemical Industries, Ltd., product name: PHOSMEL (registered trademark)-100) Diammonium phosphate (manufactured by Taihei Chemical Industry Co., Ltd.) Monoammonium phosphate (Tokyo Chemical Industry Co., Ltd.) Aluminum phosphate (Sigma-Aldrich) Sodium phosphate (Tokyo Chemical Industry Co., Ltd.) Zinc borate (Kinseimatec)

[0149] (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 polyester polyol (manufactured by Air Water Performance Chemicals, product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g) RDK-133: Orthophthalic acid polyester polyol (manufactured by Air Water Performance Chemicals, product name: Maximol RDK-133, hydroxyl value = 315 mg KOH / g)

[0150] (4) Liquid flame retardants TCPP: Phosphate ester flame retardant, tris(β-chloropropyl)phosphate (manufactured by Yoke Chemicals and New Materials (Shanghai) Co., Ltd., product name: TCPP)

[0151] (5) Foam stabilizer "SH-193": Polyalkylene glycol foam stabilizer (manufactured by Toray Dow Corning Co., Ltd., product name: SH-193)

[0152] (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)

[0153] (7) Foaming agent ·water HFO-1233zd (hydrofluoroolefin) (Honeywell, product name: Solstice LBA)

[0154] The methods for measuring the various physical properties and characteristics are as follows.

[0155] [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 to 700°C at 5°C / min using TG-DTA, and the temperature at which the weight loss rate reached 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 measurement was performed under the following conditions.

[0156] [conditions] The following steps [1] to [3] were carried out 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 air flow 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.

[0157] [Total heat generation, maximum heat generation rate, weight retention rate] The gross 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 prepared by mixing a polyol composition and a polyisocyanate compound in the formulations shown in Tables 1-1 to 15-1 in a polypropylene beaker, and the mixture was stirred for 5 seconds with a laboratory spar. The composition was then immediately dispersed into a mold measuring 150 mm high x 150 mm deep x 150 mm wide to obtain a polyurethane foam. The polyurethane foam was cut into a length of 10 cm, width of 10 cm, and thickness of 2.5 cm to prepare a cone calorimeter test sample. The cone calorimeter test sample was used to measure the heat intensity of 50 kW / m2 in accordance with the test method of ISO-5660-1. 2 The total heat release rate and maximum heat release rate after 10 minutes were measured using a cone calorimeter test when the sample was heated at 400°C for 10 minutes. The weight retention rate was calculated from the difference between the sample mass before and after the cone calorimeter test. The cone calorimeter test was performed using a CONE-III (manufactured by Toyo Seiki Seisakusho, Ltd.).

[0158] [Example 1] First, the polyol compound, blowing agent, catalyst, solid flame retardant, liquid flame retardant, and foam stabilizer were weighed into a 500 mL polypropylene beaker in the proportions shown in Table 1 and stirred with a hand mixer at 20°C for 10 minutes to obtain a polyol composition. A polyisocyanate compound was also weighed into a 500 mL polypropylene beaker to obtain an isocyanate composition. The polyol composition was then cooled to 10°C, and the polyisocyanate composition, also kept at 10°C, was added to obtain a polyurethane foam-forming composition. The composition was then stirred for 5 seconds with a laboratory spar to produce a polyurethane foam. The polyurethane foam was then evaluated for total heat release, maximum heat release rate, and weight retention. The results of these evaluations are shown in Table 1-1.

[0159] [Examples 2 to 104, Comparative Examples 1 to 3] Polyurethane foams were obtained in the same manner as in Example 1, except that the formulations were changed as shown in Tables 1-1 to 15-1. The total heat release value, maximum heat release rate, and weight retention rate of the polyurethane foams were evaluated according to the procedures described above. The results of the evaluations are shown in Tables 1-2 to 15-2.

[0160] [Table 1-1]

[0161] [Table 1-2]

[0162] [Table 2-1]

[0163] [Table 2-2]

[0164] [Table 3-1]

[0165] [Table 3-2]

[0166] [Table 4-1]

[0167] [Table 4-2]

[0168] [Table 5-1]

[0169]

Table 5-2

[0170]

Table 6-1

[0171]

Table 6-2

[0172]

Table 7-1

[0173]

Table 7-2

[0174]

Table 8-1

[0175]

Table 8-2

[0176]

Table 9-1

[0177]

Table 9-2

[0178]

Table 10-1

[0179]

Table 10-2

[0180]

Table 11-1

[0181]

Table 11-2

[0182]

Table 12-1

[0183]

Table 12-2

[0184]

Table 13-1

[0185]

Table 13-2

[0186]

Table 14-1

[0187]

Table 14-2

[0188]

Table 15-1

[0189]

Table 15-2

Claims

1. 1. A polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, the solid flame retardant comprises a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, and a boron-containing flame retardant; the solid phosphorus-containing flame retardant comprises a phosphinic acid-based flame retardant or a phosphate-containing flame retardant; the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant; The bromine-containing flame retardant includes a bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°C, a polyurethane foam-forming composition, wherein the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°C is 3.5 mass% or less, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition.

2. 1. A polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, the solid flame retardant comprises a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, and a boron-containing flame retardant; the solid phosphorus-containing flame retardant comprises a phosphinic acid-based flame retardant or a phosphate-containing flame retardant; The bromine-containing flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) one or more selected from the group consisting of a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; a content ratio of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 52 mass% or less of the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

3. The polyurethane foam-forming composition according to claim 1 or 2, further comprising a polyol compound, a polyisocyanate compound, a foam stabilizer, a blowing agent, and a catalyst.

4. A polyurethane foam, which is a foam of the polyurethane foam-forming composition according to claim 3.

5. The polyurethane foam has a radiant heat intensity of 50 kW / m according to the test method of ISO-5660. ２ When heated at 10 minutes, the total heat generated was 8.0 MJ / m ２ 5. The polyurethane foam of claim 4, wherein:

6. 1. A solid flame retardant composition comprising a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, and a boron-containing flame retardant, the solid phosphorus-containing flame retardant comprises a phosphinic acid-based flame retardant or a phosphate-containing flame retardant; The bromine-containing flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) one or more selected from the group consisting of a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; a content ratio of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 52 mass% or less relative to the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

7. The solid flame retardant composition of claim 6 for use in a polyurethane foam-forming composition.

8. The solid flame retardant composition according to claim 6, which is for use in polyurethane foam.

9. The solid flame retardant composition according to claim 8, which is sprayable.

10. 1. A polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, the solid flame retardant comprises a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, and a boron-containing flame retardant; the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant; the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant; The bromine-containing flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) one or more selected from the group consisting of a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; a content ratio of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 52 mass% or less of the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

11. 1. A polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, the solid flame retardant comprises a solid phosphorus-containing flame retardant and a bromine-containing flame retardant; the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant; the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant; The bromine-containing flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) one or more selected from the group consisting of a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; a content ratio of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 52 mass% or less of the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

12. 1. A polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, the solid flame retardant comprises a solid phosphorus-containing flame retardant and a bromine-containing flame retardant; the solid phosphorus-containing flame retardant comprises a phosphinic acid-based flame retardant or a phosphate-containing flame retardant; the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant; The bromine-containing flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) one or more selected from the group consisting of a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; a content ratio of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 52 mass% or less of the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

13. 1. A polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, the solid flame retardant comprises a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, and a boron-containing flame retardant; the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant; The bromine-containing flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) one or more selected from the group consisting of a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; a content ratio of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 52 mass% or less of the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

14. 1. A polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, the solid flame retardant comprises a solid phosphorus-containing flame retardant and a bromine-containing flame retardant; the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant; The bromine-containing flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) one or more selected from the group consisting of a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; a content ratio of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 52 mass% or less of the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

15. 1. A solid flame retardant composition comprising a bromine-containing flame retardant, a solid phosphorus-containing flame retardant, and a boron-containing flame retardant, the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant; the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant; The bromine-containing flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) one or more selected from the group consisting of a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; a content ratio of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 52 mass% or less relative to the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

16. A solid flame retardant composition comprising a bromine-containing flame retardant and a solid phosphorus-containing flame retardant, the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant; The bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant; The bromine-containing flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) one or more selected from the group consisting of a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; a content ratio of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 52 mass% or less relative to the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

17. A solid flame retardant composition comprising a bromine-containing flame retardant and a solid phosphorus-containing flame retardant, the solid phosphorus-containing flame retardant comprises a phosphinic acid-based flame retardant or a phosphate-containing flame retardant; the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant; The bromine-containing flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) one or more selected from the group consisting of a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; a content ratio of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 52 mass% or less relative to the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

18. 1. A solid flame retardant composition comprising a bromine-containing flame retardant, a solid phosphorus-containing flame retardant, and a boron-containing flame retardant, the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant; The bromine-containing flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) one or more selected from the group consisting of a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; a content ratio of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 52 mass% or less relative to the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

19. A solid flame retardant composition comprising a bromine-containing flame retardant and a solid phosphorus-containing flame retardant, the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant; The bromine-containing flame retardant (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C; (i) one or more selected from the group consisting of a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; a content ratio of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 52 mass% or less relative to the total content of the (i) bromine-containing flame retardant having a decomposition temperature of less than 370°C, the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more.

20. 1. A solid flame retardant composition for use in a polyurethane foam-forming composition, comprising a solid phosphorus-containing flame retardant and a bromine-containing flame retardant, the solid phosphorus flame retardant comprises a phosphate-containing flame retardant; the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant; The bromine-containing flame retardant includes a bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°C, A cone calorimeter test sample prepared under the following preparation conditions from a polyurethane foam-forming composition containing the solid flame retardant composition, the liquid flame retardant, the polyol compound, the polyisocyanate compound, the foam stabilizer, the blowing agent, and the catalyst was measured at a radiant heat intensity of 50 kW / m in accordance with the test method of ISO-5660. ２ When heated at 10 minutes, the total heat generated was 8.0 MJ / m ２ 1. A solid flame retardant composition, wherein: (However, this does not include solid flame retardant compositions containing red phosphorus.) [Conditions for preparing samples for cone calorimeter testing] (1): The polyurethane foam-forming composition is stirred for 5 seconds with a lab-di-spar. (2): Immediately after (1), the mixture is sprayed into a mold having a height x depth x width of 150 mm x 150 mm x 150 mm to obtain a polyurethane foam. (3): The polyurethane foam is cut into a piece 10 cm long, 10 cm wide and 2.5 cm thick to obtain a sample for cone calorimeter testing.

21. 1. A solid flame retardant composition for use in a polyurethane foam-forming composition, comprising a solid phosphorus-containing flame retardant and a bromine-containing flame retardant, the solid phosphorus flame retardant comprises a phosphinic acid flame retardant or a phosphate-containing flame retardant; the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant; The bromine-containing flame retardant includes a bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°C, A cone calorimeter test sample prepared under the following preparation conditions from a polyurethane foam-forming composition containing the solid flame retardant composition, the liquid flame retardant, the polyol compound, the polyisocyanate compound, the foam stabilizer, the blowing agent, and the catalyst was measured at a radiant heat intensity of 50 kW / m in accordance with the test method of ISO-5660. ２ When heated at 10 minutes, the total heat generated was 8.0 MJ / m ２ 1. A solid flame retardant composition, wherein: (However, this does not include solid flame retardant compositions containing red phosphorus.) [Conditions for preparing samples for cone calorimeter testing] (1): The polyurethane foam-forming composition is stirred for 5 seconds with a lab-di-spar. (2): Immediately after (1), the mixture is sprayed into a mold having a height x depth x width of 150 mm x 150 mm x 150 mm to obtain a polyurethane foam. (3): The polyurethane foam is cut into a piece 10 cm long, 10 cm wide and 2.5 cm thick to obtain a sample for cone calorimeter testing.

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