Polyurethane-foam-forming composition, polyol composition, solid flame retardant composition, flame retardant composition, and polyurethane foam

Abstract

Provided is a polyurethane-foam-forming composition containing a liquid flame retardant and a solid flame retardant, wherein the solid flame retardant contains two or more selected from the group consisting of solid phosphorus-containing flame retardants, bromine-containing flame retardants, and boron-containing flame retardants.

Description

Polyurethane foam-forming composition, polyol composition, solid flame retardant composition, flame retardant composition, and polyurethane foam

[0001] The present disclosure relates to polyurethane foam-forming compositions, polyol compositions, solid flame retardant compositions, flame retardant compositions, and polyurethane foams.

[0002] Taking advantage of their excellent insulating properties, polyurethane foams are used in practical applications for insulating ceilings, roofs, walls, and the like of buildings such as apartment complexes, detached houses, and commercial buildings, as well as for preventing condensation. Although polyurethane foams are lightweight, they are organic and therefore flammable. To address this issue, polyurethane foams containing flame retardants or the like to enhance their flame retardancy have been 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. Patent Document 2 also 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.

[0003] JP 03-140363 A JP 2015-151524 A

[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 polyol composition, a polyurethane foam-forming composition, a solid flame retardant composition, and a flame retardant composition that contribute to the production of a polyurethane foam having good flame retardancy. Another object of the present disclosure is to provide a polyurethane foam having good flame retardancy.

[0006] The present disclosure provides the following aspects. [1] A polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, 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 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. [3] The polyurethane foam-forming composition of [1] or [2], wherein the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant or a phosphinic acid flame retardant. [4] First Aspect: The polyurethane foam-forming composition of any one of [1] to [3], wherein the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant. Second Aspect The polyurethane foam-forming composition according to any one of [1] to [3], wherein the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant, and the first bromine-containing flame retardant is one selected from the following three (i) to (iii): (i) a bromine-containing flame retardant having a decomposition temperature of less than 370°C, (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or higher but lower than 450°C, or (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or higher; and the second bromine-containing flame retardant is one selected from two other than the one selected from the three (i) to (iii). (c) an aromatic bromine-containing polymeric compound; and the second bromine-containing flame retardant is one selected from two other than the one selected from (a) to (c). [5] The polyurethane foam-forming composition of any one of (1) to (4), wherein the solid phosphorus-containing flame retardant comprises red phosphorus, and the content of the red phosphorus is 3.0 mass% or less, based on the mass of the polyurethane foam components of the polyurethane foam-forming composition.[6] The polyurethane foam-forming composition of any one of [1] to [5], wherein the solid phosphorus-containing flame retardant comprises a phosphinic acid flame retardant, and the amount of the phosphinic acid flame retardant is 3.0 mass% or less, based on the mass of the polyurethane foam component of the polyurethane foam-forming composition. [7] The polyurethane foam-forming composition of any one of [1] to [6], wherein the bromine-containing flame retardant comprises (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the amount of the bromine-containing flame retardant (ii) having a decomposition temperature of 370°C or more and less than 450°C is 3.5 mass% or less, based on the mass of the polyurethane foam component of the polyurethane foam-forming composition. [8] The polyurethane foam-forming composition of any one of [1] to [7], wherein the bromine-containing flame retardant comprises one or more selected from the group consisting of (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or more but less than 450°C, and (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, wherein the content of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more but 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 but less than 450°C, and the (iii) bromine-containing flame retardant having a decomposition temperature of 450°C or more. [9] First Aspect: The polyurethane foam-forming composition according to any one of [1] to [8], further comprising a polyol compound, a polyisocyanate compound, a foam stabilizer, a blowing agent, and a catalyst. Second Aspect: A cone calorimeter test sample prepared from the polyurethane foam-forming composition comprising a polyol compound, the liquid flame retardant, the solid flame retardant, a polyisocyanate compound, a foam stabilizer, a blowing agent, and a catalyst under the following preparation conditions exhibited 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 ２The polyurethane foam-forming composition of any one of [1] to [8], which is as follows. [Conditions for Preparing Samples for Cone Calorimeter Test] (1): The polyurethane foam-forming composition is stirred for 5 seconds with a laboratory spar. (2): Immediately after (1), the composition is sprayed into a mold having dimensions of 150 mm (height) x 150 mm (depth) x 150 mm (width) to obtain a polyurethane foam. (3): The polyurethane foam is cut into a length of 10 cm, width of 10 cm, and thickness of 2.5 cm to obtain a sample for cone calorimeter test.

[10] The polyurethane foam-forming composition of [9], wherein the polyol compound comprises an aromatic polyester polyol, and the content of the aromatic polyester polyol is 30% by mass or more relative to the content of the polyol compound.

[11] The polyurethane foam-forming composition of

[10] , wherein the aromatic polyester polyol comprises a terephthalic acid-based polyester polyol, and the content of the terephthalic acid-based polyester polyol is 30% by mass or more relative to the content of the aromatic polyester polyol.

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

[11] , having an Isocyanate Index of 150 to 800.

[13] The polyurethane foam-forming composition of any one of [9] to

[12] , wherein the blowing agent comprises water, and the content of the water is 0.55 mass% or less, based on the mass of the polyurethane foam components of the polyurethane foam-forming composition.

[14] The polyurethane foam-forming composition of any one of [9] to

[13] , wherein the blowing agent comprises water and a physical blowing agent, and the content of the physical blowing agent is 40 mol% or more and 99 mol% or less, based on the total content of the water and the physical blowing agent.

[15] The polyurethane foam-forming composition of any one of [9] to

[14] , wherein the catalyst comprises a trimerization catalyst, the trimerization catalyst comprises a tertiary or quaternary ammonium salt, and the content of the tertiary or quaternary ammonium salt is 5.0% by mass or more and 100% by mass or less, based on the content of the trimerization catalyst.

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

[15] , wherein the content of the liquid flame retardant is 1 to 36% by mass, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition.

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

[16] , wherein 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 1.0 to 19.5% by mass, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition.

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

[17] , wherein the solid flame retardant comprises a solid phosphorus-containing flame retardant, and the content of the solid phosphorus-containing flame retardant is 0.5 to 12.0% by mass, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition.

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

[18] , wherein the solid flame retardant comprises a bromine-containing flame retardant, and the amount of the bromine-containing flame retardant is 0.1% by mass or more and 12.0% by mass or less, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition.

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

[19] , wherein the solid flame retardant comprises (i) a bromine-containing flame retardant having a decomposition temperature of less than 370°C, and the amount of the bromine-containing flame retardant (i) having a decomposition temperature of less than 370°C is 0.001% by mass or more and 12.0% by mass or less, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition.

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

[20] , wherein the solid flame retardant comprises (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and the content of the (ii) bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C 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.

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

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

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

[22] , wherein the solid flame retardant comprises one or more selected from the group consisting of: (i) a bromine-containing flame retardant having a decomposition temperature of less than 370°C; (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or more but less than 450°C; and (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; and wherein the content of the bromine-containing flame retardant (i) having a decomposition temperature of less than 370°C is 1% by mass or more but less than 99% by mass of the total content of the bromine-containing flame retardant (i) having a decomposition temperature of less than 370°C, the bromine-containing flame retardant (ii) having a decomposition temperature of 370°C or more but less than 450°C, and the bromine-containing flame retardant (iii) having a decomposition temperature of 450°C or more.

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

[23] , wherein the solid flame retardant comprises one or more selected from the group consisting of (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C, and (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, 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.

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

[24] , wherein the solid flame retardant comprises one or more selected from the group consisting of (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more, and (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, 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 but 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.

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

[25] , wherein the solid flame retardant comprises (a) an aliphatic bromine-containing compound, and 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 constituent of the polyurethane foam-forming composition.

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

[26] , wherein the solid flame retardant comprises (b) an aromatic bromine-containing low molecular weight compound, and 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 constituent of the polyurethane foam-forming composition.

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

[27] , wherein the solid flame retardant comprises (c) an aromatic bromine-containing polymeric compound, and 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.

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

[28] , wherein the solid flame retardant comprises one or more selected from the group consisting of: (a) an aliphatic bromine-containing compound; (b) an aromatic bromine-containing low molecular weight compound; and (c) an aromatic bromine-containing polymeric compound; and the content of the (a) aliphatic bromine-containing compound is from 1% by mass to 99% by mass 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.

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

[29] , wherein the solid flame retardant comprises: (b) an aromatic bromine-containing low molecular weight compound; and one or more compounds selected from the group consisting of (a) an aliphatic bromine-containing compound and (c) an aromatic bromine-containing polymeric compound; and 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 polymeric compound.

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

[30] , wherein the solid flame retardant comprises: (c) an aromatic bromine-containing polymeric compound, and one or more selected from the group consisting of: (a) an aliphatic bromine-containing compound, and (b) an aromatic bromine-containing low molecular weight compound, and 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.

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

[31] , wherein the solid flame retardant comprises the boron-containing flame retardant, and the content of the boron-containing flame retardant is 0.1% by mass or more and 12.0% by mass or less, based on the mass of the polyurethane foam components of the polyurethane foam-forming composition.

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

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

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

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

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

[34] , wherein the solid flame retardant comprises the boron-containing flame retardant, and 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.

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

[35] , 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.

[37] A polyurethane foam that is a foam of the polyurethane foam-forming composition of any one of [1] to

[36] .

[38] The polyurethane foam is characterized by a radiant heat intensity of 50 kW / m2 in accordance with the ISO-5660 test method. ２ When heated at 10 minutes, the total heat generated was 8.0 MJ / m ２ The polyurethane foam according to

[37] , which is:

[0007]

[99] A polyol composition comprising a liquid flame retardant, a solid flame retardant, and a polyol compound, wherein the solid flame retardant comprises: a bromine-containing flame retardant; and one or more selected from the group consisting of a solid phosphorus-containing flame retardant and a boron-containing flame retardant, wherein if the solid phosphorus-containing flame retardant contains red phosphorus, the content of the red phosphorus is 15 parts by mass or less per 100 parts by mass of the polyol compound, and if the solid phosphorus-containing flame retardant does not contain red phosphorus, the liquid flame retardant comprises a phosphate ester flame retardant.

[100] A polyol composition comprising a polyol compound, a liquid flame retardant, and a solid flame retardant, 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.

[101] The polyol composition according to

[99] or

[100] , wherein the solid flame retardant comprises the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

[102] The polyol composition according to any one of

[99] to

[101] , wherein the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant or a phosphinic acid-based flame retardant.

[103] The polyol composition according to any one of

[99] to

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

[104] The polyol composition according to any one of

[99] to

[103] , wherein the solid phosphorus-containing flame retardant comprises red phosphorus, and the content of the red phosphorus is 15 parts by mass or less per 100 parts by mass of the polyol compound.

[105] The polyol composition according to any one of

[99] to

[104] , wherein the solid phosphorus-containing flame retardant comprises a phosphinic acid flame retardant, and the content of the phosphinic acid flame retardant is 15 parts by mass or less per 100 parts by mass of the polyol compound.

[106] A cone calorimeter test sample prepared from a polyurethane foam-forming composition comprising the polyol composition, a polyisocyanate compound, a foam stabilizer, a blowing agent, and a catalyst under the following preparation conditions has a radiant heat intensity of 50 kW / m2 in accordance with the test method of ISO-5660. ２ When heated at 10 minutes, the total heat generated was 8.0 MJ / m ２The polyol composition according to any one of

[99] to

[105] , wherein the composition is as follows: [Conditions for Preparing a Sample for Cone Calorimeter Test] (1): The polyurethane foam-forming composition is stirred for 5 seconds with a laboratory spar; (2): Immediately after (1), the composition is sprayed into a mold having dimensions of 150 mm (height) x 150 mm (depth) x 150 mm (width) to obtain a polyurethane foam; (3): The polyurethane foam is cut into a 10 cm (length) x 10 cm (width) x 2.5 cm (thickness) sample for cone calorimeter test.

[107] The polyol composition according to any one of

[99] to

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

[108] The polyol composition according to any one of

[99] to

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

[109] The polyol composition according to any one of

[99] to

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

[110] The polyol composition according to any one of

[99] to

[109] , wherein the bromine-containing flame retardant comprises (c) an aromatic bromine-containing polymer compound.

[111] A polyurethane foam-forming composition comprising the polyol composition according to any one of

[99] to

[110] , a polyisocyanate compound, a foam stabilizer, a blowing agent, and a catalyst, wherein, when the solid phosphorus-containing flame retardant comprises red phosphorus, the content of the red phosphorus is 3.0 mass% or less, based on the mass of the polyurethane foam components of the polyurethane foam-forming composition, and when the solid phosphorus-containing flame retardant does not comprise red phosphorus, the liquid flame retardant comprises a phosphate ester flame retardant.

[112] A cone calorimeter test sample prepared from the polyurethane foam-forming composition under the following preparation conditions was tested in accordance with the ISO-5660 test method at a radiant heat intensity of 50 kW / m ２ When heated at 10 minutes, the total heat generated was 8.0 MJ / m ２The polyurethane foam-forming composition according to

[111] , which is as follows. [Conditions for preparing a sample for cone calorimeter test] (1): The polyurethane foam-forming composition is stirred for 5 seconds with a laboratory spar. (2): Immediately after (1), the composition is sprayed into a mold having dimensions of 150 mm height x 150 mm width to obtain a polyurethane foam. (3): The polyurethane foam is cut into a sample having a length of 10 cm, a width of 10 cm and a thickness of 2.5 cm to obtain a sample for cone calorimeter test.

[113] A polyurethane foam, which is a foam of the polyurethane foam-forming composition according to

[111] or

[112] .

[114] The polyurethane foam is subjected to a test using a radiant heat intensity of 50 kW / m2 in accordance with the ISO-5660 test method. ２ When heated at 10 minutes, the total heat generated was 8.0 MJ / m ２ The polyurethane foam according to

[113] , which is:

[0008]

[116] A solid flame retardant composition comprising a bromine-containing flame retardant and one or more selected from the group consisting of a solid phosphorus-containing flame retardant and a boron-containing flame retardant, wherein when the solid phosphorus-containing flame retardant contains red phosphorus, the content of the red phosphorus is 15% by mass or less relative to the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant, and when the solid phosphorus-containing flame retardant does not contain red phosphorus, the content of bromine atoms in the solid flame retardant composition is 0.1 to 99% by mass relative to the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

[117] A solid flame retardant composition comprising 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.

[118] The solid flame retardant composition according to

[116] or

[117] , comprising the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

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

[116] to

[118] , wherein the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant or a phosphinic acid-based flame retardant.

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

[116] to

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

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

[116] to

[120] , wherein the solid phosphorus-containing flame retardant contains red phosphorus, and the content of the red phosphorus is 15 mass% or less relative to the sum of the contents of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

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

[116] to

[121] , wherein the solid phosphorus-containing flame retardant contains a phosphinic acid-based flame retardant, and the content of the phosphinic acid-based flame retardant is 35 mass% or less relative to the sum of the contents of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

[123] A cone calorimeter test sample prepared under the following preparation conditions from a polyurethane foam-forming composition containing the solid flame retardant composition, a liquid flame retardant, a polyol compound, a polyisocyanate compound, a foam stabilizer, a blowing agent, and a catalyst was tested in accordance with the ISO-5660 test method at a radiant heat intensity of 50 kW / m. ２ When heated at 10 minutes, the total heat generated was 8.0 MJ / m ２The solid flame retardant composition according to any one of

[116] to

[122] , which is the following. [Conditions for Preparing a Sample for Cone Calorimeter Test] (1): The polyurethane foam-forming composition is stirred for 5 seconds with a laboratory spar. (2): Immediately after (1), the composition is sprayed into a mold having dimensions of 150 mm (height) x 150 mm (depth) x 150 mm (width) to obtain a polyurethane foam. (3): The polyurethane foam is cut into a size of 10 cm (length) x 10 cm (width) x 2.5 cm (thickness) to obtain a sample for cone calorimeter test.

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

[116] to

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

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

[116] to

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

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

[116] to

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

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

[116] to

[126] , wherein the bromine-containing flame retardant comprises (c) an aromatic bromine-containing polymeric compound.

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

[116] to

[127] , wherein the solid flame retardant comprises the solid phosphorus-containing flame retardant and the boron-containing flame retardant.

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

[116] to

[128] , which is for use in a polyurethane foam-forming composition.

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

[116] to

[128] , which is for use in a polyurethane foam.

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

[116] to

[128] , which is for spraying to adhere the solid flame retardant composition to an object by spraying it.

[132] A flame retardant composition comprising the solid flame retardant composition according to any one of

[116] to

[131] and a liquid flame retardant.

[0009] One aspect of the present disclosure can provide a polyol composition, a polyurethane foam-forming composition, a solid flame retardant composition, and a flame retardant composition that are useful for producing a polyurethane foam having good flame retardancy. Another aspect of the present disclosure can provide a polyurethane foam having good flame retardancy.

[0010] Exemplary embodiments for carrying out each aspect of the present disclosure will be described in further detail. However, 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 limits individually described can be combined in any combination.

[0011] [Mechanism of Flame Retardancy Derived from Flame Retardants] Polymeric materials melt, decompose, and volatilize when heated, resulting in flammable gases that ignite in the presence of oxygen, initiating combustion. Flame retardants primarily exhibit flame-retardant effects through flame-retardant mechanisms in the gas or solid phase. The flame-retardant effect in the gas phase tends to be higher the more OH radicals, which have a strong combustion traction force and are generated during organic combustion, are trapped. On the other hand, the flame-retardant effect in the solid phase tends to be higher the more highly flame-retardant graphite-like carbon layers (carbonized layers) are produced. Furthermore, the carbonized layers form a multilayer structure due to the presence of phosphorus, which tends to further improve flame retardancy.

[0012] In each aspect of the present disclosure, the present inventors speculate that the use of 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 the formation of a multilayer carbonized layer, and a boron-containing flame retardant as a carbonized layer formation aid will result in a polyurethane foam with superior flame retardancy compared to the use of each agent alone. That is, the present inventors speculate that when two or more of these flame retardants exhibit flame retardancy, they confer flame retardancy to the polyurethane foam through different mechanisms, unlike the use of a single agent alone, resulting in unexpectedly excellent flame retardancy. Furthermore, the combined use of a bromine-containing flame retardant, a solid phosphorus-containing flame retardant, and a boron-containing flame retardant will result in a polyurethane foam with even superior flame retardancy compared to the use of two or more of these flame retardants in combination.

[0013] Furthermore, by using two bromine-containing flame retardants with different decomposition temperatures in combination, it becomes possible to trap OH radicals, which have a large combustion traction force, over a wider temperature range than when a single bromine-containing flame retardant is used, thereby obtaining 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 large combustion traction force, over a wider temperature range than when a two-bromine-containing flame retardant is used in combination, thereby obtaining a polyurethane foam with even better flame retardancy than when a two-bromine-containing flame retardant is used in combination.

[0014] 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 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. Also, 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 of the carbon atom to which the bromine atom is bonded and / or the molecular weight.

[0015] [Polyol Composition] The polyol composition forms a polyurethane foam by mixing with a polyisocyanate composition. The polyol composition contains a polyol compound as an essential component and may contain a solid flame retardant and a liquid flame retardant. A polyol composition according to one embodiment of the present disclosure is a polyol composition containing a liquid flame retardant, a solid flame retardant, and a polyol compound, wherein 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.

[0016] The polyol composition may further contain one or more selected from the group consisting of a foam stabilizer, a blowing agent, a catalyst, an inorganic filler, an anti-settling agent, a dispersion stabilizer, and other additives.

[0017] The polyol composition is preferably used as the first liquid of the polyurethane foam-forming composition. That is, during distribution, the composition is preferably in the form of a two-component or multi-component type that combines a first liquid containing the polyol composition, a second liquid containing the polyisocyanate composition, and, in the case of a multi-component type, a third liquid (and fourth or more liquids) containing components other than the polyol composition and the polyisocyanate composition, and the first liquid and the second liquid, or, in the case of a multi-component type, the third liquid (and fourth or more liquids), are preferably mixed together during foam formation.

[0018] The polyol composition contains a solid flame retardant and a liquid flame retardant, and the resulting polyurethane foam has improved flame retardancy. 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.

[0019] [Polyurethane Foam-Forming Composition] The polyurethane foam-forming composition of one embodiment of the present disclosure is a polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, wherein the solid flame retardant comprises two or more selected from the group consisting of solid phosphorus-containing flame retardants, bromine-containing flame retardants, and boron-containing flame retardants.

[0020] The polyurethane foam-forming composition may further include a polyol compound, a polyisocyanate compound, a solid flame retardant, or a liquid flame retardant. The polyurethane foam-forming composition may further include one or more additives selected from the group consisting of a foam stabilizer, a blowing agent, a catalyst, an inorganic filler, an anti-settling agent, a dispersion stabilizer, and other additives.

[0021] The polyurethane foam-forming composition may include a polyol composition containing a polyol compound. The polyol composition may be the polyol composition described above. The polyurethane foam-forming composition may include a polyisocyanate composition containing a polyisocyanate compound. The polyisocyanate composition may further include one or more additives selected from the group consisting of a solid flame retardant, a liquid flame retardant, a blowing agent, a foam stabilizer, a catalyst, an inorganic filler, an anti-settling agent, a dispersion stabilizer, and other additives.

[0022] 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 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 component or more) containing components other than the polyol composition and the polyisocyanate composition are stored separately and mixed when foam is formed. The polyol composition contains a polyol compound, and the polyisocyanate composition contains a polyisocyanate compound.

[0023] 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.

[0024] [Polyurethane Foam] The polyurethane foam of yet another embodiment of the present disclosure is a foam of the polyurethane foam-forming composition described above.

[0025] [Solid Flame Retardant Composition] The solid flame retardant composition of another embodiment of the present disclosure contains two or more members selected from the group consisting of solid phosphorus-containing flame retardants, bromine-containing flame retardants, and boron-containing flame retardants.

[0026] The solid flame retardant composition may further contain a solid flame retardant such as an antimony-containing flame retardant or a metal hydroxide-based flame retardant.

[0027] [Flame Retardant Composition] A flame retardant composition according to another embodiment of the present disclosure includes the solid flame retardant composition and a liquid flame retardant.

[0028] [Solid Flame Retardant] The polyol composition, polyurethane foam-forming composition, flame retardant composition, and solid flame retardant composition each contain a solid flame retardant. The polyisocyanate composition may contain a solid flame retardant, or both the polyol composition and the polyisocyanate composition may contain a solid flame retardant. Preferably, only the polyol composition contains a solid flame retardant. The solid flame retardant contains 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 contain two types of flame retardants: a solid phosphorus-containing flame retardant and a bromine-containing flame retardant; a solid phosphorus-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.

[0029] (Solid phosphorus-containing flame retardant) Examples of the solid phosphorus-containing flame retardant include red phosphorus, phosphinic acid-based flame retardants, phosphate-containing flame retardants, etc. Among these, from the viewpoint of further suppressing coloration of the polyurethane foam, the solid phosphorus-containing flame retardant may be one or more selected from the group consisting of phosphinic acid-based flame retardants and phosphate-containing flame retardants.

[0030] <Red Phosphorus> There is no limitation on the red phosphorus, and for example, commercially available products can be appropriately selected and used.

[0031] From the viewpoint of further suppressing discoloration of the polyurethane foam, the content of red phosphorus is preferably 15.0 parts by mass or less per 100 parts by mass of the polyol compound, or 3.00% by mass or less, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[0032] The upper limit of the content of red phosphorus may be 15.0 parts by mass or less, 14.0 parts by mass or less, 13.0 parts by mass or less, 12.0 parts by mass or less, 11.0 parts by mass or less, 10.0 parts by mass or less, 9.0 parts by mass or less, 8.0 parts by mass or less, 7.0 parts by mass or less, 6.0 parts by mass or less, 5.0 parts by mass or less, 4.0 parts by mass or less, 3.0 parts by mass or less, 2.0 parts by mass or less, 1.0 parts by mass or less, 0.1 parts by mass or less, 0.01 parts by mass or less, 0.001 parts by mass or less, or 0.0001 parts by mass or less, relative to 100 parts by mass of the polyol compound. The lower limit of the content of red phosphorus may be 0.0001 parts by mass or more, 0.001 parts by mass or more, 0.01 parts by mass or more, 0.1 parts by mass or more, 1.0 parts by mass or more, 2.0 parts by mass or more, 3.0 parts by mass or more, 4.0 parts by mass or more, 5.0 parts by mass or more, 6.0 parts by mass or more, 7.0 parts by mass or more, 8.0 parts by mass or more, 9.0 parts by mass or more, 10.0 parts by mass or more, 11.0 parts by mass or more, 12.0 parts by mass or more, 13.0 parts by mass or more, 14.0 parts by mass or more, or 15.0 parts by mass or more, relative to 100 parts by mass of the polyol compound. The content of red phosphorus may be from 0.0001 to 15.0 parts by mass, from 0.001 to 14.0 parts by mass, from 0.01 to 13.0 parts by mass, from 0.1 to 12.0 parts by mass, from 1.0 to 11.0 parts by mass, from 2.0 to 10.0 parts by mass, from 3.0 to 9.0 parts by mass, from 4.0 to 8.0 parts by mass, or from 5.0 to 7.0 parts by mass, relative to 100 parts by mass of the polyol compound. The upper limit of the red phosphorus content may be 3.00% by mass or less, 2.80% by mass or less, 2.60% by mass or less, 2.40% by mass or less, 2.20% by mass or less, 2.00% by mass or less, 1.80% by mass or less, 1.60% by mass or less, 1.40% by mass or less, 1.20% by mass or less, 1.00% by mass or less, 0.80% by mass or less, 0.60% by mass or less, 0.40% by mass or less, 0.20% by mass or less, 0.10% by mass or less, 0.01% by mass or less, 0.001% by mass or less, 0.0001% by mass or less, or 0.00001% by mass or less, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.The lower limit of the content of red phosphorus may be 0.00001% by mass or more, 0.0001% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.10% by mass or more, 0.20% by mass or more, 0.40% by mass or more, 0.60% by mass or more, 0.80% by mass or more, 1.00% by mass or more, 1.20% by mass or more, 1.40% by mass or more, 1.60% by mass or more, 1.80% by mass or more, 2.00% by mass or more, 2.20% by mass or more, 2.40% by mass or more, 2.60% by mass or more, 2.80% by mass or more, or 3.00% by mass or more, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition. The content of red phosphorus may be from 0.00001 to 3.00% by mass, from 0.0001 to 2.80% by mass, from 0.0001 to 2.60% by mass, from 0.01 to 2.40% by mass, from 0.10 to 2.20% by mass, from 0.20 to 2.00% by mass, from 0.40 to 1.80% by mass, from 0.60 to 1.60% by mass, from 0.80 to 1.40% by mass, or from 1.00 to 1.20% by mass, based on the mass of the polyurethane foam components of the polyurethane foam-forming composition. When the content of red phosphorus is within the above range, a polyurethane foam having excellent flame retardancy and further suppressed coloration, and a polyol composition and a polyurethane foam-forming composition having even better storage stability with respect to reactivity, tend to be obtained. When the content of red phosphorus is equal to or less than the upper limit, it is particularly likely that a polyurethane foam with further reduced coloration and a polyol composition and a polyurethane foam-forming composition with even better storage stability in terms of reactivity can be obtained.When the content of red phosphorus is equal to or more than the lower limit, it is particularly likely that a polyurethane foam with excellent flame retardancy and a polyol composition and a polyurethane foam-forming composition with even better storage stability in terms of reactivity can be obtained.

[0033] <Phosphinic Acid Flame Retardant> The phosphinic acid flame retardant is preferably one or more selected from the phosphinate flame retardants represented by formula (A-1) or formula (A-2) and polymers thereof.

[0034]

[0035]

[0036] 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.

[0037] R １ , R ２ are preferably the same or different and are a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, or a phenyl group. ３ is 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. M is preferably Mg, Ca, Al, Sn, Ti, Zn, Fe, or Zr.

[0038] 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 thereof. 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.

[0039] From the viewpoint of improving the storage stability with respect to the reactivity of the polyol composition and the polyurethane foam-forming composition, the content of the phosphinic acid flame retardant is preferably 15.0 parts by mass or less relative to the polyol composition, or 3.00% by mass or less relative to the mass of the polyurethane foam constituent of the polyurethane foam-forming composition.

[0040] The upper limit of the content of the phosphinic acid flame retardant may be 15.0 parts by mass or less, 14.0 parts by mass or less, 13.0 parts by mass or less, 12.0 parts by mass or less, 11.0 parts by mass or less, 10.0 parts by mass or less, 9.0 parts by mass or less, 8.0 parts by mass or less, 7.0 parts by mass or less, 6.0 parts by mass or less, 5.0 parts by mass or less, 4.0 parts by mass or less, 3.0 parts by mass or less, 2.0 parts by mass or less, 1.0 parts by mass or less, 0.8 parts by mass or less, 0.5 parts by mass or less, 0.1 parts by mass or less, 0.05 parts by mass or less, or 0.0 parts by mass, relative to 100 parts by mass of the polyol compound. The lower limit of the content of the phosphinic acid flame retardant may be 0.0 part by mass or more, 0.01 part by mass or more, 0.05 part by mass or more, 0.1 part by mass or more, 0.5 part by mass or more, 1.0 part by mass or more, 2.0 parts by mass or more, 3.0 parts by mass or more, 4.0 parts by mass or more, 5.0 parts by mass or more, 6.0 parts by mass or more, 7.0 parts by mass or more, 8.0 parts by mass or more, 9.0 parts by mass or more, 10.0 parts by mass or more, 11.0 parts by mass or more, 12.0 parts by mass or more, 13.0 parts by mass or more, 14.0 parts by mass or more, or 15.0 parts by mass or more, relative to 100 parts by mass of the polyol compound. The content of the phosphinic acid flame retardant may be, relative to 100 parts by mass of the polyol compound, 0.0 parts by mass to 15.0 parts by mass, 0.01 parts by mass to 14.0 parts by mass, 0.05 parts by mass to 13.0 parts by mass, 0.1 parts by mass to 12.0 parts by mass, 0.5 parts by mass to 11.0 parts by mass, 1.0 parts by mass to 10.0 parts by mass, 2.0 parts by mass to 9.0 parts by mass, 3.0 parts by mass to 8.0 parts by mass, 4.0 parts by mass to 7.0 parts by mass, or 5.0 parts by mass to 6.0 parts by mass. The upper limit of the content of the phosphinic acid flame retardant may be 3.00% by mass or less, 2.80% by mass or less, 2.60% by mass or less, 2.40% by mass or less, 2.20% by mass or less, 2.00% by mass or less, 1.80% by mass or less, 1.60% by mass or less, 1.40% by mass or less, 1.20% by mass or less, 1.00% by mass or less, 0.80% by mass or less, 0.60% by mass or less, 0.40% by mass or less, 0.20% by mass or less, 0.10% by mass or less, 0.08% by mass or less, 0.05% by mass or less, 0.01% by mass or less, or 0.00% by mass, relative to the mass of the polyurethane foam constituent of the polyurethane foam-forming composition.The lower limit of the content of the phosphinic acid flame retardant may be 0.00% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.08% by mass or more, 0.10% by mass or more, 0.20% by mass or more, 0.40% by mass or more, 0.60% by mass or more, 0.80% by mass or more, 1.00% by mass or more, 1.20% by mass or more, 1.40% by mass or more, 1.60% by mass or more, 1.80% by mass or more, 2.00% by mass or more, 2.20% by mass or more, 2.40% by mass or more, 2.60% by mass or more, 2.80% by mass or more, or 3.00% by mass or more, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition. The content of the phosphinic acid flame retardant may be from 0.00 to 3.00% by mass, from 0.01 to 2.80% by mass, from 0.05 to 2.60% by mass, from 0.08 to 2.40% by mass, from 0.10 to 2.20% by mass, from 0.20 to 2.00% by mass, from 0.40 to 1.80% by mass, from 0.60 to 1.60% by mass, from 0.80 to 1.40% by mass, or from 1.00 to 1.20% by mass, relative to the mass of the polyurethane foam components of the polyurethane foam-forming composition. When the content of the phosphinic acid flame retardant is within the above range, a polyurethane foam with excellent flame retardancy and further reduced discoloration, and a polyol composition and a polyurethane foam-forming composition with even better storage stability in terms of reactivity, tend to be obtained. When the content of the phosphinic acid flame retardant is equal to or less than the upper limit, a polyol composition and a polyurethane foam-forming composition having even better storage stability, particularly with respect to reactivity, tend to be easily obtained.When the content of the phosphinic acid flame retardant is equal to or more than the lower limit, a polyurethane foam having especially excellent flame retardancy and further suppressed coloration tends to be easily obtained.

[0041] [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. Among these, lithium, calcium, barium, iron(II), iron(III), and aluminum are preferred from the viewpoint of improving flame retardancy.

[0042] Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, etc., and combinations of any two or more of these. Examples of aromatic amines include pyridine, triazine, melamine, etc. The phosphate-containing flame retardant may be subjected to a known water resistance improving treatment, such as treatment with a silane coupling agent or coating with a melamine resin.

[0043] Specific examples of phosphate-containing flame retardants include monophosphates, pyrophosphates, and polyphosphates.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] The upper limit of the content of the phosphate-containing flame retardant is 380.0 parts by mass or less, 190.0 parts by mass or less, 114.0 parts by mass or less, 76.0 parts by mass or less, 68.4 parts by mass or less, 60.8 parts by mass or less, 53.2 parts by mass or less, 45.6 parts by mass or less, 41.8 parts by mass or less, 34.8 parts by mass or less , 31.6 parts by mass or less, 28.4 parts by mass or less, 22.0 parts by mass or less, 15.6 parts by mass or less, 12.4 parts by mass or less, 9.2 parts by mass or less, 5.4 parts by mass or less, 4.8 parts by mass or less, 4.2 parts by mass or less, 3.6 parts by mass or less, 3.0 parts by mass or less, 1.8 parts by mass or less, 0.6 parts by mass or less, or 0.1 parts by mass or less. The lower limit of the content of the phosphate-containing flame retardant may be 0.1 parts by mass or more, 0.6 parts by mass or more, 1.8 parts by mass or more, 3.0 parts by mass or more, 3.6 parts by mass or more, 4.2 parts by mass or more, 4.8 parts by mass or more, 5.4 parts by mass or more, 9.2 parts by mass or more, 12.4 parts by mass or more, 15.6 parts by mass or more, 22.0 parts by mass or more, 28.4 parts by mass or more, 31.6 parts by mass or more, 34.8 parts by mass or more, 41.8 parts by mass or more, 45.6 parts by mass or more, 53.2 parts by mass or more, 60.8 parts by mass or more, 68.4 parts by mass or more, 76.0 parts by mass or more, 114.0 parts by mass or more, 190.0 parts by mass or more, or 380.0 parts by mass or more, relative to 100 parts by mass of the polyol compound. The content of the phosphate-containing flame retardant may be 0.1 parts by mass or more and 380.0 parts by mass or less, 0.6 parts by mass or more and 190.0 parts by mass or less, 1.8 parts by mass or more and 114.0 parts by mass or less, 3.0 parts by mass or more and 76.0 parts by mass or less, 3.6 parts by mass or more and 68.4 parts by mass or less, 4.2 parts by mass or more and 60.8 parts by mass or less, 4.8 parts by mass or more and 53.2 parts by mass or less, 5.4 parts by mass or more and 45.6 parts by mass or less, 9.2 parts by mass or more and 41.8 parts by mass or less, 12.4 parts by mass or more and 34.8 parts by mass or less, 15.6 parts by mass or more and 31.6 parts by mass or less, or 22.0 parts by mass or more and 28.4 parts by mass or less, relative to 100 parts by mass of the polyol compound.The upper limit of the content of the phosphate-containing flame retardant may be 75.00% by mass or less, 45.00% by mass or less, 30.00% by mass or less, 27.00% by mass or less, 24.00% by mass or less, 21.00% by mass or less, 18.00% by mass or less, 16.50% by mass or less, 13.80% by mass or less, 12.60% by mass or less, 11.40% by mass or less, 9.00% by mass or less, 6.60% by mass or less, 5.40% by mass or less, 4.20% by mass or less, 2.70% by mass or less, 2.40% by mass or less, 2.10% by mass or less, 1.80% by mass or less, 1.50% by mass or less, 0.90% by mass or less, 0.30% by mass or less, or 0.03% by mass or less, relative to the mass of the polyurethane foam constituent of the polyurethane foam-forming composition. The lower limit of the content of the phosphate-containing flame retardant may be 0.03% by mass or more, 0.30% by mass or more, 0.90% by mass or more, 1.50% by mass or more, 1.80% by mass or more, 2.10% by mass or more, 2.40% by mass or more, 2.70% by mass or more, 4.20% by mass or more, 5.40% by mass or more, 6.60% by mass or more, 9.00% by mass or more, 11.40% by mass or more, 12.60% by mass or more, 13.80% by mass or more, 16.50% by mass or more, 18.00% by mass or more, 21.00% by mass or more, 24.00% by mass or more, 27.00% by mass or more, 30.00% by mass or more, 45.00% by mass or more, or 75.00% by mass or more, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition. The content of the phosphate-containing flame retardant may be 0.03% by mass or more and 75.00% by mass or less, 0.30% by mass or more and 45.00% by mass or less, 0.90% by mass or more and 30.00% by mass or less, 1.50% by mass or more and 27.00% by mass or less, 1.80% by mass or more and 24.00% by mass or less, 2.10% by mass or more and 21.00% by mass or less, 2.40% by mass or more and 18.00% by mass or less, 2.70% by mass or more and 16.50% by mass or less, 4.20% by mass or more and 13.80% by mass or less, 5.40% by mass or more and 12.60% by mass or less, or 6.60% by mass or more and 11.40% by mass or less, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition.When the content of the phosphate-containing flame retardant is within the above range, it is likely that a polyurethane foam with excellent flame retardancy and further reduced discoloration, and a polyol composition and a polyurethane foam-forming composition with even better storage stability in terms of reactivity, are obtained. When the content of the phosphate-containing flame retardant is equal to or less than the above upper limit, it is likely that a polyurethane foam with excellent flame retardancy and further reduced discoloration, and a polyol composition and a polyurethane foam-forming composition with even better storage stability in terms of reactivity are obtained. When the content of the phosphate-containing flame retardant is equal to or greater than the above lower limit, it is likely that a polyurethane foam with excellent flame retardancy and further reduced discoloration, and a polyol composition and a polyurethane foam-forming composition with even better storage stability in terms of reactivity are obtained.

[0048] The upper limit of the content of the solid phosphorus-containing flame retardant may be 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 67 parts by mass or less, 64 parts by mass or less, 61 parts by mass or less, 58 parts by mass or less, 55 parts by mass or less, 52 parts by mass or less, 49 parts by mass or less, 46 parts by mass or less, 43 parts by mass or less, 40 parts by mass or less, 37 parts by mass or less, 34 parts by mass or less, 31 parts by mass or less, 28 parts by mass or less, 25 parts by mass or less, 22 parts by mass or less, 20 parts by mass or less, 19 parts by mass or less, 18 parts by mass or less, 17 parts by mass or less, 16 parts by mass or less, 15 parts by mass or less, 14 parts by mass or less, 13 parts by mass or less, 12 parts by mass or less, 11 parts by mass or less, or 10 parts by mass or less, based on 100 parts by mass of the polyol compound. The lower limit of the content of the solid phosphorus-containing flame retardant may be 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, 5 parts by mass or more, 6 parts by mass or more, 7 parts by mass or more, 8 parts by mass or more, 9 parts by mass or more, 10 parts by mass or more, 11 parts by mass or more, 12 parts by mass or more, 13 parts by mass or more, 14 parts by mass or more, 15 parts by mass or more, 16 parts by mass or more, 17 parts by mass or more, 18 parts by mass or more, 19 parts by mass or more, 20 parts by mass or more, 22 parts by mass or more, 25 parts by mass or more, 28 parts by mass or more, 31 parts by mass or more, 34 parts by mass or more, 37 parts by mass or more, 40 parts by mass or more, 43 parts by mass or more, 46 parts by mass or more, 49 parts by mass or more, or 52 parts by mass or more, based on 100 parts by mass of the polyol compound. The content of the solid phosphorus-containing flame retardant may be 1 part by mass or more and 100 parts by mass or less, 2 parts by mass or more and 90 parts by mass or less, 3 parts by mass or more and 80 parts by mass or less, 4 parts by mass or more and 70 parts by mass or less, 5 parts by mass or more and 67 parts by mass or less, 6 parts by mass or more and 64 parts by mass or less, 7 parts by mass or more and 61 parts by mass or less, 8 parts by mass or more and 58 parts by mass or less, 9 parts by mass or more and 55 parts by mass or less, 10 parts by mass or more and 52 parts by mass or less, 11 parts by mass or more and 49 parts by mass or less, 12 parts by mass or more and 46 parts by mass or less, 13 parts by mass or more and 43 parts by mass or less, 14 parts by mass or more and 40 parts by mass or less, 15 parts by mass or more and 37 parts by mass or less, 16 parts by mass or more and 34 parts by mass or less, 17 parts by mass or more and 31 parts by mass or less, 18 parts by mass or more and 28 parts by mass or less, 19 parts by mass or more and 25 parts by mass or less, or 20 parts by mass or more and 22 parts by mass or less, based on 100 parts by mass of the polyol compound.The lower limit of the content of the solid phosphorus-containing flame retardant, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be, for example, 0.5% by mass or more, 1.0% by mass or more, 1.5% by mass or more, 2.0% by mass or more, 2.5% by mass or more, 3.0% by mass or more, 3.5% by mass or more, 4.0% by mass or more, 4.5% by mass or more, 5.0% by mass or more, 5.5% by mass or more, 6.0% by mass or more, 6.5% by mass or more, 7.0% by mass or more, 7.5% by mass or more, 8.0% by mass or more, 8.5% by mass or more, 9.0% by mass or more, 9.5% by mass or more, 10.0% by mass or more, 10.5% by mass or more, 11.0% by mass or more, or 11.5% by mass or more. The upper limit of the content of the solid phosphorus-containing flame retardant, 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, 11.5% by mass or less, 11.0% by mass or less, 10.5% by mass or less, 10.0% by mass or less, 9.5% by mass or less, 9.0% by mass or less, 8.5% by mass or less, 8.0% by mass or less, 7.5% by mass or less, 7.0% by mass or less, 6.5% by mass or less, 6.0% by mass or less, 5.5% by mass or less, 5.0% by mass or less, 4.5% by mass or less, 4.0% by mass or less, 3.5% by mass or less, 3.0% by mass or less, 2.5% by mass or less, 2.0% by mass or less, 1.5% by mass or less, or 1.0% by mass or less. 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% by mass to 12.0% by mass, 1.0% by mass to 11.5% by mass, 1.5% by mass to 11.0% by mass, 2.0% by mass to 10.5% by mass, 2.5% by mass to 10.0% by mass, 3.0% by mass to 9.5% by mass, 3.5% by mass to 9.0% by mass, 4.0% by mass to 8.5% by mass, 4.5% by mass to 8.0% by mass, 5.0% by mass to 7.5% by mass, 5.5% by mass to 7.0% by mass, or 6.0% by mass to 6.5% by mass. When the content of the solid phosphorus-containing flame retardant is within the above range, a polyurethane foam having 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 a polyurethane foam having particularly excellent flame retardancy tends to be obtained.When the content of the solid phosphorus-containing flame retardant is at least as high as 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.

[0049] In yet another embodiment of the polyurethane foam of the present disclosure, for example, the polyurethane foam is produced under conditions in which isocyanate groups are in large excess relative to the active hydrogen-containing component (polyol compound, water). When producing the 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 the polyurethane resin, the better the flame retardancy. Therefore, the higher the rate of isocyanurate groups produced from unreacted isocyanate groups, the better the flame retardancy of the resulting polyurethane foam.

[0050] In this specification, "polyurethane foam constituents of a polyurethane foam-forming composition" refers to components that constitute a polyurethane foam. For example, the components that constitute a polyurethane foam, among liquid flame retardants, solid flame retardants, polyol compounds, polyisocyanate compounds, foam stabilizers, blowing agents, catalysts, and other additives, are "polyurethane foam constituents of a polyurethane foam-forming composition." Note that all or most of the blowing agent is discharged to the outside of the system as bubbles and does not constitute a polyurethane foam. For example, in the case of water used as a blowing agent, hydrogen atoms constitute part of the urea bonds in the polyurethane foam, but oxygen atoms form CO ２ Therefore, in this specification, the blowing agent is not included in the "polyurethane foam constituent component of the polyurethane foam-forming composition."

[0051] (Bromine-containing flame retardant) 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.

[0052] 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 which 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 which 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).

[0053] Here, it is preferred that the first bromine-containing flame retardant is one selected from the following three (a) to (c): (a) an aliphatic bromine-containing compound, (b) an aromatic bromine-containing low molecular weight compound, or (c) an aromatic bromine-containing high molecular weight compound; and the second bromine-containing flame retardant is one selected from two other than the one selected from the three (a) to (c).

[0054] The use of 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. Furthermore, the use of 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 a single bromine-containing flame retardant is used. In particular, the use of two or more bromine-containing flame retardants selected from (a) aliphatic bromine-containing compounds, (b) aromatic bromine-containing low-molecular-weight compounds, and (c) aromatic bromine-containing high-molecular-weight compounds tends to produce polyurethane foams with especially excellent flame retardancy.

[0055] Examples of compounds containing an aliphatic carbon atom-bromine atom bond (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, aliphatic bromine-containing compounds containing an aliphatic carbon atom-bromine atom bond and an aromatic carbon atom-bromine atom bond are preferred, with 4,4'-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] being particularly preferred.

[0056] 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. Of these, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine and ethylenebis(pentabromophenyl) are preferred.

[0057] Specific examples of compounds containing aromatic carbon atom-bromine atom bonds and having an average of more than three aromatic rings in the molecule (aromatic bromine-containing polymer compounds) include homopolymers derived from 2,6-dibromophenol 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), and brominated polymers produced by reacting brominated bisphenol A with 1,2-dichloroethane. brominated epoxy compounds such as diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin and monoepoxy compounds obtained by the reaction of 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, halogenated bromine compound polymers such as crosslinked or non-crosslinked brominated poly(α-methylstyrene), and combinations of any two or more of these. Among these, brominated polycarbonates such as homopolymers derived from 2,6-dibromophenol or 2,4-dibromophenol, polycarbonate oligomers produced using brominated bisphenol A as a raw material, and copolymers of the polycarbonate oligomers with bisphenol A are preferred.

[0058] The upper limit of the content of the bromine-containing flame retardant may be 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 67 parts by mass or less, 64 parts by mass or less, 61 parts by mass or less, 58 parts by mass or less, 55 parts by mass or less, 52 parts by mass or less, 49 parts by mass or less, 46 parts by mass or less, 43 parts by mass or less, 40 parts by mass or less, 37 parts by mass or less, 34 parts by mass or less, 31 parts by mass or less, 28 parts by mass or less, 25 parts by mass or less, 22 parts by mass or less, 19 parts by mass or less, 15 parts by mass or less, 14.5 parts by mass or less, 14 parts by mass or less, 13.5 parts by mass or less, 13 parts by mass or less, 12.5 parts by mass or less, 12 parts by mass or less, 11.5 parts by mass or less, 11 parts by mass or less, or 10.5 parts by mass or less, based on 100 parts by mass of the polyol compound. The lower limit of the content of the bromine-containing flame retardant may be 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, 5 parts by mass or more, 6 parts by mass or more, 7 parts by mass or more, 8 parts by mass or more, 9 parts by mass or more, 9.5 parts by mass or more, 10 parts by mass or more, 10.5 parts by mass or more, 11 parts by mass or more, 11.5 parts by mass or more, 12 parts by mass or more, 12.5 parts by mass or more, 13 parts by mass or more, 13.5 parts by mass or more, 14 parts by mass or more, 14.5 parts by mass or more, 15 parts by mass or more, 19 parts by mass or more, 22 parts by mass or more, 25 parts by mass or more, 28 parts by mass or more, 31 parts by mass or more, 34 parts by mass or more, 37 parts by mass or more, 40 parts by mass or more, 43 parts by mass or more, or 46 parts by mass or more, based on 100 parts by mass of the polyol compound. The content of the bromine-containing flame retardant may be 1 part by mass or more and 100 parts by mass or less, 2 parts by mass or more and 90 parts by mass or less, 3 parts by mass or more and 80 parts by mass or less, 4 parts by mass or more and 70 parts by mass or less, 5 parts by mass or more and 67 parts by mass or less, 6 parts by mass or more and 64 parts by mass or less, 7 parts by mass or more and 61 parts by mass or less, 8 parts by mass or more and 58 parts by mass or less, 9 parts by mass or more and 55 parts by mass or less, 9.5 parts by mass or more and 52 parts by mass or less, 10 parts by mass or more and 49 parts by mass or less, 10.5 parts by mass or more and 46 parts by mass or less, 11 parts by mass or more and 43 parts by mass or less, 11.5 parts by mass or more and 40 parts by mass or less, 12 parts by mass or more and 37 parts by mass or less, 12.5 parts by mass or more and 34 parts by mass or less, 13 parts by mass or more and 31 parts by mass or less, 13.5 parts by mass or more and 28 parts by mass or less, 14 parts by mass or more and 25 parts by mass or less, 14.5 parts by mass or more and 22 parts by mass or less, or 15 parts by mass or more and 19 parts by mass or less, based on 100 parts by mass of the polyol compound.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% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 1.0% by mass or more, 1.5% by mass or more, 2.0% by mass or more, 2.5% by mass or more, 3.0% by mass or more, 3.5% by mass or more, 4.0% by mass or more, 4.5% by mass or more, 5.0% by mass or more, 5.5% by mass or more, 6.0% by mass or more, 6.5% by mass or more, 7.0% by mass or more, 7.5% by mass or more, 8.0% by mass or more, 8.5% by mass or more, 9.0% by mass or more, 9.5% by mass or more, 10.0% by mass or more, 10.5% by mass or more, 11.0% by mass or more, or 11.5% by mass or more. 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% by mass or less, 11.8% by mass or less, 11.7% by mass or less, 11.5% by mass or less, 11.0% by mass or less, 10.5% by mass or less, 10.0% by mass or less, 9.5% by mass or less, 9.0% by mass or less, 8.5% by mass or less, 8.0% by mass or less, 7.5% by mass or less, 7.0% by mass or less, 6.5% by mass or less, 6.0% by mass or less, 5.5% by mass or less, 5.0% by mass or less, 4.5% by mass or less, 4.0% by mass or less, 3.5% by mass or less, 3.0% by mass or less, 2.5% by mass or less, 2.0% by mass or less, 1.5% by mass or less, or 1.0% by mass or less. 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% by mass to 12.0% by mass, 0.3% by mass to 11.8% by mass, 0.5% by mass to 11.7% by mass, 1.0% by mass to 11.5% by mass, 1.5% by mass to 11.0% by mass, 2.0% by mass to 10.5% by mass, 2.5% by mass to 10.0% by mass, 3.0% by mass to 9.5% by mass, 3.5% by mass to 9.0% by mass, 4.0% by mass to 8.5% by mass, 4.5% by mass to 8.0% by mass, 5.0% by mass to 7.5% by mass, 5.5% by mass to 7.0% by mass, or 6.0% by mass to 6.5% by mass. When the content of the bromine-containing flame retardant 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 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 is equal to or more than the lower limit, the flame retardant effect derived from the bromine-containing flame retardant is easily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0059] The upper limit of the content of bromine atoms in the polyol composition may be 300.0 parts by mass or less, 150.0 parts by mass or less, 90.0 parts by mass or less, 60.0 parts by mass or less, 54.0 parts by mass or less, 48.0 parts by mass or less, 42.0 parts by mass or less, 36.0 parts by mass or less, 33.0 parts by mass or less, 27.3 parts by mass or less, 24.6 parts by mass or less, 21.9 parts by mass or less, 16.5 parts by mass or less, 11.1 parts by mass or less, 8.4 parts by mass or less, 5.7 parts by mass or less, 2.7 parts by mass or less, 2.4 parts by mass or less, 2.1 parts by mass or less, 1.8 parts by mass or less, 1.5 parts by mass or less, 0.9 parts by mass or less, or 0.3 parts by mass or less, relative to 100 parts by mass of the polyol compound. The lower limit of the content of bromine atoms in the polyol composition may be 0.3 parts by mass or more, 0.9 parts by mass or more, 1.5 parts by mass or more, 1.8 parts by mass or more, 2.1 parts by mass or more, 2.4 parts by mass or more, 2.7 parts by mass or more, 5.7 parts by mass or more, 8.4 parts by mass or more, 11.1 parts by mass or more, 16.5 parts by mass or more, 21.9 parts by mass or more, 24.6 parts by mass or more, 27.3 parts by mass or more, 33.0 parts by mass or more, 36.0 parts by mass or more, 42.0 parts by mass or more, 48.0 parts by mass or more, 54.0 parts by mass or more, 60.0 parts by mass or more, 90.0 parts by mass or more, 150.0 parts by mass or more, or 300.0 parts by mass or more, relative to 100 parts by mass of the polyol compound. The content of bromine atoms in the polyol composition may be, relative to 100 parts by mass of the polyol compound, 0.3 parts by mass to 300.0 parts by mass, 0.9 parts by mass to 150.0 parts by mass, 1.5 parts by mass to 90.0 parts by mass, 1.8 parts by mass to 60.0 parts by mass, 2.1 parts by mass to 54.0 parts by mass, 2.4 parts by mass to 48.0 parts by mass, 2.7 parts by mass to 42.0 parts by mass, 5.7 parts by mass to 36.0 parts by mass, 8.4 parts by mass to 33.0 parts by mass, 11.1 parts by mass to 27.3 parts by mass, or 16.5 parts by mass to 24.6 parts by mass. When the content of bromine atoms in the polyol composition is within the above range, a polyurethane foam having excellent flame retardancy tends to be obtained more easily due to the synergistic effect of the flame retardancy resulting from the bromine-containing flame retardant and the solid phosphorus-containing flame retardant and / or the boron-containing flame retardant.When the content of bromine atoms in the polyol composition 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 of bromine atoms in the polyol composition 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.

[0060] The upper limit of the bromine atom content in the polyurethane foam-forming composition may be 60.00% by mass or less, 30.00% by mass or less, 18.00% by mass or less, 12.00% by mass or less, 10.80% by mass or less, 9.60% by mass or less, 8.40% by mass or less, 7.20% by mass or less, 6.60% by mass or less, 5.46% by mass or less, 4.92% by mass or less, 4.38% by mass or less, 3.30% by mass or less, 2.22% by mass or less, 1.68% by mass or less, 1.14% by mass or less, 0.54% by mass or less, 0.48% by mass or less, 0.42% by mass or less, 0.36% by mass or less, 0.30% by mass or less, 0.18% by mass or less, 0.06% by mass or less, or 0.01% by mass or less, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition. The lower limit of the bromine atom content in the polyurethane foam-forming composition may be 0.01% by mass or more, 0.06% by mass or more, 0.18% by mass or more, 0.30% by mass or more, 0.36% by mass or more, 0.42% by mass or more, 0.48% by mass or more, 0.54% by mass or more, 1.14% by mass or more, 1.68% by mass or more, 2.22% by mass or more, 3.30% by mass or more, 4.38% by mass or more, 4.92% by mass or more, 5.46% by mass or more, 6.60% by mass or more, 7.20% by mass or more, 8.40% by mass or more, 9.60% by mass or more, 10.80% by mass or more, 12.00% by mass or more, 18.00% by mass or more, 30.00% by mass or more, or 60.00% by mass or more, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition. The content of bromine atoms in the polyurethane foam-forming composition may be 0.01% by mass or more and 60.00% by mass or less, 0.06% by mass or more and 30.00% by mass or less, 0.18% by mass or more and 18.00% by mass or less, 0.30% by mass or more and 12.00% by mass or less, 0.36% by mass or more and 10.80% by mass or less, 0.42% by mass or more and 9.60% by mass or less, 0.48% by mass or more and 8.40% by mass or less, 0.54% by mass or more and 7.20% by mass or less, 1.14% by mass or more and 6.60% by mass or less, 1.68% by mass or more and 5.46% by mass or less, 2.22% by mass or more and 4.92% by mass or less, or 3.30% by mass or more and 4.38% by mass or less, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition.When the content of bromine atoms in the polyurethane foam-forming composition 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 retardancy derived from the bromine-containing flame retardant and the solid phosphorus-containing flame retardant and / or boron-containing flame retardant. When the content of bromine atoms in the polyurethane foam-forming composition is equal to or less than the above upper limit, the flame retardancy derived from the boron-containing flame retardant and / or solid phosphorus-containing flame retardant tends to be more easily exhibited, and polyurethane foam with particularly excellent flame retardancy tends to be more easily obtained. When the content of bromine atoms in the polyurethane foam-forming composition is equal to or greater than the above lower limit, the flame retardancy derived from the bromine-containing flame retardant tends to be more easily exhibited, and polyurethane foam with particularly excellent flame retardancy tends to be more easily obtained.

[0061] The upper limit of the bromine atom content in the solid flame retardant composition may be 99.0% by mass or less, 75.0% by mass or less, 45.0% by mass or less, 30.0% by mass or less, 27.0% by mass or less, 24.0% by mass or less, 21.0% by mass or less, 18.0% by mass or less, 16.5% by mass or less, 13.6% by mass or less, 12.2% by mass or less, 10.8% by mass or less, 8.0% by mass or less, 5.2% by mass or less, 3.8% by mass or less, 2.4% by mass or less, 0.9% by mass or less, 0.8% by mass or less, 0.7% by mass or less, 0.6% by mass or less, 0.5% by mass or less, 0.3% by mass or less, or 0.1% 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 lower limit of the bromine atom content in the solid flame retardant composition may be 0.1 mass% or more, 0.3 mass% or more, 0.5 mass% or more, 0.6 mass% or more, 0.7 mass% or more, 0.8 mass% or more, 0.9 mass% or more, 2.4 mass% or more, 3.8 mass% or more, 5.2 mass% or more, 8.0 mass% or more, 10.8 mass% or more, 12.2 mass% or more, 13.6 mass% or more, 16.5 mass% or more, 18.0 mass% or more, 21.0 mass% or more, 24.0 mass% or more, 27.0 mass% or more, 30.0 mass% or more, 45.0 mass% or more, 75.0 mass% or more, or 99.0 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 content of bromine atoms in the solid flame retardant composition may be 0.1% by mass or more and 99.0% by mass or less, 0.3% by mass or more and 75.0% by mass or less, 0.5% by mass or more and 45.0% by mass or less, 0.6% by mass or more and 30.0% by mass or less, 0.7% by mass or more and 27.0% by mass or less, 0.8% by mass or more and 24.0% by mass or less, 0.9% by mass or more and 21.0% by mass or less, 2.4% by mass or more and 18.0% by mass or less, 3.8% by mass or more and 16.5% by mass or less, 5.2% by mass or more and 13.6% by mass or less, or 8.0% by mass or more and 12.2% 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. When the content of bromine atoms in the solid flame retardant composition 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 retardancy resulting from the bromine-containing flame retardant and the solid phosphorus-containing flame retardant and / or boron-containing flame retardant.When the content of bromine atoms in the solid flame retardant composition 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 of bromine atoms in the solid flame retardant composition 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.

[0062] The upper limit of the content of aliphatic odor compounds is defined as follows: below 100% of the mass fraction of aliphatic compounds, below 90% of the mass fraction, below 80% of the mass fraction, below 70% of the mass fraction, below 63% of the mass fraction, below 60% of the mass fraction, below 57% of the mass fraction, below 54% of the mass fraction, below 51% of the mass fraction, below 48% of the mass fraction, below 45% of the mass fraction, below 42% of the mass fraction, below 39% of the mass fraction, and below 36% of the mass fraction. Below the quantity section, below the quality section of 33, below the quality section of 30, below the quality section of 27, below the quality section of 24, below the quality section of 21, below the quality section of 18, below the quality section of 15, below the quality section of 12, below the quality section of 8, below the quality section of 7.6, below the quality section of 7.2, below the quality section of 6.8, below the quality section of 6.4, below the quality section of 6, below the quality section of 5.6, below the quality section of 5.2, below the quality section of 5.2, de àtte yoi. The lower limit of the content of aliphatic odor compounds is defined as follows: 0.01% or more, 0.1% or more, 0.4% or more, 0.8% or more, 1.2% or more, 1.6% or more, 2% or more, 2.4% or more, 2.8% or more, 3.2% or more, 3.6% or more, 4% or more, 4.4% or more. 、4.8 or above, 5.2 or above, 5.6 or above, 6 or above, 6.4 or above, 6.8 or above, 7.2 or above, 7.6 or above, 8 or above, 12 or above, 15 or above, 18 or above, 21 or above, 24 or above, 27 or above, 30 or above, and also 33 or above. The content of aliphatic odorant compounds is defined as follows: 0.01% to 100%; 0.1% to 90%; 0.4% to 80%; 0.8% to 70%; 1.2% to 63%; 1.6% to 60%; 2% to 57%; 2.4% to 54%; 2.8% to 51%; 3.2% to 48% 3.6 Quality Department or above 45 Quality Department or below, 4 Quality Department or above 42 Quality Department or below, 4.4 Quality Department or above 39 Quality Department or below, 4.8 Quality Department or above 36 Quality Department or below, 5.2 Quality Department or above 33 Quality Department or below, 5.6 Quality Department or above 30 Quality Department or below, 6 Quality Department or above 27 Quality Department or below, 6.4 Quality Department or above 24 Quality Department or below, 6.8 Quality Department or above 21 Quality Department or below, 7.2 Quality Department or above 18 Quality Department or below, 7.6 Quality Department or above 15 Quality Department or below, and also 8 Quality Department or above 12 Quality Department or below.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, 2.3% by mass or more, 2.5% by mass or more, 2.7% by mass or more, 2.9% by mass or more, 3.2% by mass or more, 3.5% by mass or more, 3.8% by mass or more, 4.3% by mass or more, 4.8% by mass or more, 5.3% by mass or more, 5.8% by mass or more, or 7.0% by mass or more. The upper limit of the content of the aliphatic bromine-containing compound is, for example, 12.0% by mass or less, 11.0% by mass or less, 10.0% by mass or less, based on the mass of the polyurethane foam component of the polyurethane foam-forming composition. 0 mass% or less, 9.0 mass% or less, 8.0 mass% or less, 7.0 mass% or less, 6.5 mass% or less, 6.0 mass% or less, 5.5 mass% or less, 5.0 mass% or less, 4.5 mass% or less, 4.0 quality % by mass or less, 3.5% by mass or less, 3.3% by mass or less, 3.1% by mass or less, 2.9% by mass or less, 2.7% by mass or less, 2.5% by mass or less, 2.3% by mass or less, 2.1% by mass or less, 1.9% by mass The content may be 1.7% by mass or less, 1.5% by mass or less, 1.3% by mass or less, 1.2% by mass or less, 1.0% by mass or less, 0.8% by mass or less, 0.6% by mass or less, or 0.4% by mass or less.The content of 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 to 12.0% by mass, 0.01% by mass to 11.0% by mass, 0.03% by mass to 10.0% by mass, 0.05% by mass to 9.0% by mass, 0.07% by mass to 8.0% by mass, 0.09% by mass to 7.0% by mass, 0.1% by mass to 6.5% by mass, 0.3% by mass to 10.0% by mass, or % 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 having 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 having 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.

[0063] The upper limit of the content of low molecular weight compounds in aromatic odorants is defined as follows: below 100%, below 90%, below 80%, below 70%, below 63%, below 60%, below 57%, below 54%, below 51%, below 48%, below 45%, below 42%, below 39%, and below 3%. 6 quality department and below, 33 quality department and below, 30 quality department and below, 27 quality department and below, 24 quality department and below, 21 quality department and below, 18 quality department and below, 15 quality department and below, 12 quality department and below, 8 quality department and below, 7.6 quality department and below, 7.2 quality department and below, 6.8 quality department and below, 6.4 quality department and below, 6 quality department and below, 5.6 quality department and below, also 5.2 quality department and below, de àtte yoi. The lower limit of the content of low molecular weight compounds in aromatic odorants is defined as follows: 0.01% or more, 0.1% or more, 0.4% or more, 0.8% or more, 1.2% or more, 1.6% or more, 2% or more, 2.4% or more, 2.8% or more, 3.2% or more, 3.6% or more, 4% or more, 4.4% or more. Above, 4.8 quality department and above, 5.2 quality department and above, 5.6 quality department and above, 6 quality department and above, 6.4 quality department and above, 6.8 quality department and above, 7.2 quality department and above, 7.6 quality department and above, 8 quality department and above, 12 quality department and above, 15 quality department and above, 18 quality department and above, 21 quality department and above, 24 quality department and above, 27 quality department and above, 30 quality department and above, also 33 quality department and above, de àtte yoi. The content of low molecular weight compounds in aromatic odorants is defined as follows: 0.01% to 100%; 0.1% to 90%; 0.4% to 80%; 0.8% to 70%; 1.2% to 63%; 1.6% to 60%; 2% to 57%; 2.4% to 54%; 2.8% to 51%; 3.2% to 48% and below. Below, 3.6 quality department and above 45 quality department and below, 4 quality department and above 42 quality department and below, 4.4 quality department and above 39 quality department and below, 4.8 quality department and above 36 quality department and below, 5.2 quality department and above 33 quality department and below, 5.6 quality department and above 30 quality department and below, 6 quality department and above 27 quality department and below, 6.4 quality department and above 24 quality department and below, 6.8 quality department and above 21 quality department and below, 7.2 quality department and above 18 quality department and below, 7.6 quality department and above 15 quality department and below, also 8 quality department and above 12 quality department and below, de àtte yoi.The lower limit of the aromatic bromine-containing low molecular weight compound may be, for example, 0.001% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, 0.9% by mass or more, 1.1% by mass or more, 1.3% by mass or more, 1.5% by mass or more, 1.7% by mass or more, 1.9% by mass or more, 2.1% by mass or more, 2.3% by mass or more, 2.5% by mass or more, 2.7% by mass or more, 2.9% by mass or more, 3.2% by mass or more, 3.5% by mass or more, 3.8% by mass or more, 4.3% by mass or more, 4.8% by mass or more, 5.3% by mass or more, 5.8% by mass or more, or 7.0% by mass or more, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition. The upper limit of the content of the aromatic bromine-containing low-molecular compound is, for example, 12.0% by mass or less, 11.0% by mass or less, 1% by mass or less, based on the mass of the polyurethane foam component of the polyurethane foam-forming composition. 0.0 mass% or less, 9.0 mass% or less, 8.0 mass% or less, 7.0 mass% or less, 6.5 mass% or less, 6.0 mass% or less, 5.5 mass% or less, 5.0 mass% or less, 4.5 mass% or less, 4.0 Mass% or less, 3.5 mass% or less, 3.3 mass% or less, 3.1 mass% or less, 2.9 mass% or less, 2.7 mass% or less, 2.5 mass% or less, 2.3 mass% or less, 2.1 mass% or less, 1.9 mass% % or less, 1.7% by weight or less, 1.5% by weight or less, 1.3% by weight or less, 1.2% by weight or less, 1.0% by weight or less, 0.8% by weight or less, 0.6% by weight or less, or 0.4% by weight or less.The content of the aromatic bromine-containing low molecular weight compound, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, is, for example, 0.001% by mass to 12.0% by mass, 0.01% by mass to 11.0% by mass, 0.03% by mass to 10.0% by mass, 0.05% by mass to 9.0% by mass, 0.07% by mass to 8.0% by mass, 0.09% by mass to 7.0% by mass, 0.1% by mass to 6.5% by mass, 0.3% by mass to 10.0% by mass, and the like.

[0033] The content of the aromatic bromine-containing low molecular weight compound may be from 0.5 to 6.0% by mass, 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 easily obtained. When the content of the aromatic bromine-containing low molecular weight compound is below the above 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 easily obtained. When the content of the aromatic bromine-containing low molecular weight compound is at least as high as the lower limit, the flame retardant effect derived from the aromatic bromine-containing low molecular weight compound is more easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be more easily obtained.

[0064] The upper limit of the content of aromatic odor compounds containing high molecular weight compounds is defined as follows: below 100%, below 90%, below 80%, below 70%, below 63%, below 60%, below 57%, below 54%, below 51%, below 48%, below 45%, below 42%, below 39%, and below 36%. Below, 33 below the quality department, 30 below the quality department, 27 below the quality department, 24 below the quality department, 21 below the quality department, 18 below the quality department, 15 below the quality department, 12 below the quality department, 8 below the quality department, 7.6 below the quality department, 7.2 below the quality department, 6.8 below the quality department, 6.4 below the quality department, 6 below the quality department, 5.6 below the quality department, 5.2 below the quality department, also 4.8 below the quality department, de àtte yoi. The lower limit of the content of aromatic odor compounds containing high molecular weight compounds is defined as follows: 0.01% or more, 0.1% or more, 0.4% or more, 0.8% or more, 1.2% or more, 1.6% or more, 2% or more, 2.4% or more, 2.8% or more, 3.2% or more, 3.6% or more, 4% or more, 4.4% or more, 4% or more. . 8 quality department or above, 5.2 quality department or above, 5.6 quality department or above, 6 quality department or above, 6.4 quality department or above, 6.8 quality department or above, 7.2 quality department or above, 7.6 quality department or above, 8 quality department or above, 12 quality department or above, 15 quality department or above, 18 quality department or above, 21 quality department or above, 24 quality department or above, 27 quality department or above, 30 quality department or above, 33 quality department or above, and also 36 quality department or above.The content of the aromatic bromine-containing polymer compound is 0.01 parts by mass or more and 100 parts by mass or less, 0.1 parts by mass or more and 90 parts by mass or less, 0.4 parts by mass or more and 80 parts by mass or less, and 0.8 parts by mass or more and 70 parts by mass, based on 100 parts by mass of the polyol compound. Parts by mass or less, 1.2 parts by mass or more and 63 parts by mass or less, 1.6 parts by mass or more and 60 parts by mass or less, 2 parts by mass or more and 57 parts by mass or less, 2.4 parts by mass or more and 54 parts by mass or less, 2.8 parts by mass or more and 51 parts by mass or less, 3.2 parts by mass or more and 48 parts by mass or less Lower, 3.6 parts by mass to 45 parts by mass, 4 parts by mass to 42 parts by mass, 4.4 parts by mass to 39 parts by mass, 4.8 parts by mass to 36 parts by mass, 5.2 parts by mass to 33 parts by mass, 5.6 parts by mass to 30 parts by mass, 6 parts Parts by weight or more and 27 parts by weight or less, 6.4 parts by weight or more and 24 parts by weight or less, 6.8 parts by weight or more and 21 parts by weight or less, 7.2 parts by weight or more and 18 parts by weight or less, 7.6 parts by weight or more and 15 parts by weight or less, or 8 parts by weight or more and 12 parts by weight or less. The lower limit of the aromatic bromine-containing polymeric compound may be, for example, 0.001% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, 0.9% by mass or more, 1.1% by mass or more, 1.3% by mass or more, 1.5% by mass or more, 1.7% by mass or more, 1.9% by mass or more, 2.1% by mass or more, 2.3% by mass or more, 2.5% by mass or more, 2.7% by mass or more, 2.9% by mass or more, 3.2% by mass or more, 3.5% by mass or more, 3.8% by mass or more, 4.3% by mass or more, 4.8% by mass or more, 5.3% by mass or more, 5.8% by mass or more, or 7.0% by mass or more, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.The upper limit of the content of the aromatic bromine-containing polymer compound is, for example, 12.0% by mass or less, 11.0% by mass or less, 1% by mass or less, based on the mass of the polyurethane foam component of the polyurethane foam-forming composition. 0.0 mass% or less, 9.0 mass% or less, 8.0 mass% or less, 7.0 mass% or less, 6.5 mass% or less, 6.0 mass% or less, 5.5 mass% or less, 5.0 mass% or less, 4.5 mass% or less, 4.0 Mass% or less, 3.5 mass% or less, 3.3 mass% or less, 3.1 mass% or less, 2.9 mass% or less, 2.7 mass% or less, 2.5 mass% or less, 2.3 mass% or less, 2.1 mass% or less, 1.9 mass% % or less, 1.7% by weight or less, 1.5% by weight or less, 1.3% by weight or less, 1.2% by weight or less, 1.0% by weight or less, 0.8% by weight or less, 0.6% by weight or less, or 0.4% by weight or less. The content of the aromatic bromine-containing polymeric 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

[0033] The content of the aromatic bromine-containing polymer compound may be from 0.5 to 6.0% by mass, 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 below the above 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 easily obtained. When the content of the aromatic bromine-containing polymer compound is at least the above lower limit, the flame retardant effect derived from the aromatic bromine-containing polymer compound is more easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be more easily obtained.

[0065] The content ratios of the aliphatic bromine-containing compound, aromatic bromine-containing low molecular weight compound, and aromatic bromine-containing high molecular weight compound in the polyol composition, polyurethane foam-forming composition, polyurethane foam, flame retardant composition, and solid flame retardant composition are, for example, in the following ranges.

[0066] The lower limit of the content ratio 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, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more, based on the total content of the aliphatic bromine-containing compound, the content of the aromatic bromine-containing low molecular weight compound, and the content of the aromatic bromine-containing high molecular weight compound. The upper limit of the content ratio of the aliphatic bromine-containing compound relative to the total content of the aliphatic bromine-containing compound, the content of the aromatic bromine-containing low molecular weight compound, and the content of the aromatic bromine-containing high molecular weight 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, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less. The content ratio of the aliphatic bromine-containing compound relative to the sum of the contents of the aliphatic bromine-containing compound, the aromatic bromine-containing low molecular weight compound, and the aromatic bromine-containing high molecular weight 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 ratio of the aliphatic bromine-containing compound is within the above range, a polyurethane foam with excellent flame retardancy tends to be easily 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 high molecular weight 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.

[0067] The lower limit of the content ratio of the aromatic bromine-containing low molecular weight compound relative to the sum of the content of the aliphatic bromine-containing compound, the content of the aromatic bromine-containing low molecular weight compound, and the content of the aromatic bromine-containing high 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, 28% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more. The upper limit of the content ratio of the aromatic bromine-containing low molecular weight compound relative to the total content of the aliphatic bromine-containing compound, the aromatic bromine-containing low molecular weight compound, and the aromatic bromine-containing high 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, 36% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less. 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 high molecular weight compound is more 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 at least the above lower limit, the flame retardant effect derived from the aromatic bromine-containing low molecular weight compound is more easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained.

[0068] The lower limit of the content ratio of the aromatic bromine-containing polymer 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, 28% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more, 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 ratio of the aromatic bromine-containing polymer 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, 36% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, 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 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 more easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be more easily obtained.When the content ratio of the aromatic bromine-containing polymer compound is at least the above 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.

[0069] The combined use of two bromine-containing flame retardants with different decomposition temperatures tends to make it easier to obtain polyurethane foams with even better flame retardancy than when a single bromine-containing flame retardant is used. Furthermore, the combined use of three bromine-containing flame retardants with different decomposition temperatures tends to make it easier to obtain polyurethane foams with even better flame retardancy than when two bromine-containing flame retardants are used.

[0070] That is, the first bromine-containing flame retardant is one selected from the following three (i) to (iii): (i) a bromine-containing flame retardant having a decomposition temperature of less than 370°C, (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or more but less than 450°C, or (iii) a bromine-containing flame retardant having a decomposition temperature of 450°C or more; and it is preferable that the second bromine-containing flame retardant is one selected from two other than one selected from the three (i) to (iii).

[0071] In particular, polyurethane foams with particularly excellent flame retardancy tend to be obtained more easily by using two or more bromine-containing flame retardants selected from (i) bromine-containing flame retardants having a decomposition temperature of less than 370° C., (ii) bromine-containing flame retardants having a decomposition temperature of 370° C. or more but less than 450° C., and (iii) bromine-containing flame retardants having a decomposition temperature of 450° C. or more in combination. That is, the bromine-containing flame retardant preferably comprises one or more selected from (ii) bromine-containing flame retardants having a decomposition temperature of 370° C. or more but less than 450° C., (i) bromine-containing flame retardants having a decomposition temperature of less than 370° C., and (iii) bromine-containing flame retardants having a decomposition temperature of 450° C. or more.

[0072] 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.

[0073] Examples of bromine-containing flame retardants having 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.

[0074] Examples of bromine-containing flame retardants having 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).

[0075] Examples of bromine-containing flame retardants having a decomposition temperature of 450°C or higher include homopolymers derived from 2,6-dibromophenol 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).

[0076] The upper limit of the content of the bromine-containing flame retardant with a decomposition temperature of less than 370°C is 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, based on 100 parts by mass of the polyol compound. , 63 parts by mass or less, 60 parts by mass or less, 57 parts by mass or less, 54 parts by mass or less, 51 parts by mass or less, 48 ​​parts by mass or less, 45 parts by mass or less, 42 parts by mass or less, 39 parts by mass or less, 36 parts by mass or less , 33 parts by mass or less, 30 parts by mass or less, 27 parts by mass or less, 24 parts by mass or less, 21 parts by mass or less, 18 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 8 parts by mass or less, 7.6 parts by mass or less , 7.2 parts by weight or less, 6.8 parts by weight or less, 6.4 parts by weight or less, 6 parts by weight or less, 5.6 parts by weight or less, 5.2 parts by weight or less, 4.8 parts by weight or less, or 4.4 parts by weight or less. The lower limit of the content of the bromine-containing flame retardant having a decomposition temperature of less than 370°C may be 0.01 parts by mass or more, 0.1 parts by mass or more, 0.4 parts by mass or more, 0.8 parts by mass or more, 1.2 parts by mass or more, 1.6 parts by mass or more, 2 parts by mass or more, 2.4 parts by mass or more, 2.8 parts by mass or more, 3.2 parts by mass or more, 3.6 parts by mass or more, 4 parts by mass or more, 4.4 parts by mass or more, 4.8 parts by mass or more, 5.2 parts by mass or more, 5.6 parts by mass or more, 6 parts by mass or more, 6.4 parts by mass or more, 6.8 parts by mass or more, 7.2 parts by mass or more, 7.6 parts by mass or more, 8 parts by mass or more, 12 parts by mass or more, 15 parts by mass or more, 18 parts by mass or more, 21 parts by mass or more, 24 parts by mass or more, 27 parts by mass or more, 30 parts by mass or more, 33 parts by mass or more, or 36 parts by mass or more, relative to 100 parts by mass of the polyol compound.The content of the bromine-containing flame retardant having a decomposition temperature of less than 370°C is, relative to 100 parts by mass of the polyol compound, 0.01 parts by mass to 100 parts by mass, 0.1 parts by mass to 90 parts by mass, 0.4 parts by mass to 80 parts by mass, 0.8 parts by mass to 70 parts by mass, 1.2 parts by mass to 63 parts by mass, 1.6 parts by mass to 60 parts by mass, 2 parts by mass to 57 parts by mass, 2.4 parts by mass to 54 parts by mass, 2.8 parts by mass to 51 parts by mass, 3.2 parts by mass to 48 parts by mass. Parts by weight or less, 3.6 parts by weight or more and 45 parts by weight or less, 4 parts by weight or more and 42 parts by weight or less, 4.4 parts by weight or more and 39 parts by weight or less, 4.8 parts by weight or more and 36 parts by weight or less, 5.2 parts by weight or more and 33 parts by weight or less, 5.6 parts by weight or more and 30 parts by weight or less, 6 It may be at least 6.4 parts by mass and at most 24 parts by mass, at least 6.8 parts by mass and at most 21 parts by mass, at least 7.2 parts by mass and at most 18 parts by mass, at least 7.6 parts by mass and at most 15 parts by mass, or at least 8 parts by mass and at most 12 parts by mass. The lower limit of the bromine-containing flame retardant having a decomposition temperature of less than 370°C, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, is, for example, 0.001 mass% or more, 0.01 mass% or more, 0.03 mass% or more, 0.05 mass% or more, 0.07 mass% or more, 0.09 mass% or more, 0.1 mass% or more, 0.3 mass% or more, 0.5 mass% or more, 0.7 mass% or more, 0.9 mass% or more. Above, 1.1% by mass or more, 1.3% by mass or more, 1.5% by mass or more, 1.7% by mass or more, 1.9% by mass or more, 2.1% by mass or more, 2.3% by mass or more, 2.5% by mass or more, 2.7% by mass or more, 2.9 It may be at least 3.2 mass%, at least 3.5 mass%, at least 3.8 mass%, at least 4.3 mass%, at least 4.8 mass%, at least 5.3 mass%, at least 5.8 mass%, or at least 7.0 mass%.The upper limit of 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 constituents of the polyurethane foam-forming composition, is, 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, 2.5 mass% or less, 2.3 mass% or less, 2.1 mass% or less, 1.9 quality % or less, 1.7% by weight or less, 1.5% by weight or less, 1.3% by weight or less, 1.2% by weight or less, 1.0% by weight or less, 0.8% by weight or less, 0.6% by weight or less, or 0.4% by weight or less. 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 bromine-containing flame retardant content may be 3% by mass or more and 6.0% by mass or less, 0.5% by mass or more and 5.5% by mass or less, 0.7% by mass or more and 5.0% by mass or less, 0.9% by mass or more and 4.5% by mass or less, 1.1% by mass or more and 4.0% by mass or less, 1.3% by mass or more and 3.5% by mass or less, 1.5% by mass or more and 3.3% by mass or less, 1.7% by mass or more and 3.1% by mass or less, 1.9% by mass or more and 2.9% by mass or less, 2.1% by mass or more and 2.7% by mass or less, or 2.3% by mass or more and 2.5% by mass or less. When the content of 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 easily 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 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 having a decomposition temperature of less than 370°C is equal to or greater than the above lower limit, the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of less than 370°C is more easily exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be more easily obtained.

[0077] The upper limit of the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 63 parts by mass or less, 60 parts by mass or less, 57 parts by mass or less, 54 parts by mass or less, 51 parts by mass or less, 48 ​​parts by mass or less, 45 parts by mass or less, 42 parts by mass or less, 39 parts by mass or less Parts by weight or less, 36 parts by weight or less, 33 parts by weight or less, 30 parts by weight or less, 27 parts by weight or less, 24 parts by weight or less, 21 parts by weight or less, 18 parts by weight or less, 15 parts by weight or less, 12 parts by weight or less, 8 parts by weight or less, 7.6 parts by weight or less, 7.2 parts by weight or less, 6.8 parts by weight or less, 6.4 parts by weight or less, 6 parts by weight or less, 5.6 parts by weight or less, or 5.2 parts by weight or less. The lower limit of the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C may be 0.01 parts by mass or more, 0.1 parts by mass or more, 0.4 parts by mass or more, 0.8 parts by mass or more, 1.2 parts by mass or more, 1.6 parts by mass or more, 2 parts by mass or more, 2.4 parts by mass or more, 2.8 parts by mass or more, 3.2 parts by mass or more, 3.6 parts by mass or more, 4 parts by mass or more, 4.4 parts by mass or more, 4.8 parts by mass or more, 5.2 parts by mass or more, 5.6 parts by mass or more, 6 parts by mass or more, 6.4 parts by mass or more, 6.8 parts by mass or more, 7.2 parts by mass or more, 7.6 parts by mass or more, 8 parts by mass or more, 12 parts by mass or more, 15 parts by mass or more, 18 parts by mass or more, 21 parts by mass or more, 24 parts by mass or more, 27 parts by mass or more, 30 parts by mass or more, or 33 parts by mass or more, relative to 100 parts by mass of the polyol compound.The content of the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is, relative to 100 parts by mass of the polyol compound, 0.01 parts by mass or more and 100 parts by mass or less, 0.1 parts by mass or more and 90 parts by mass or less, 0.4 parts by mass or more and 80 parts by mass or less, 0.8 parts by mass or more and 70 parts by mass or less, 1.2 parts by mass or more and 63 parts by mass or less, 1.6 parts by mass or more and 60 parts by mass or less, 2 parts by mass or more and 57 parts by mass or less, 2.4 parts by mass or more and 54 parts by mass or less, 2.8 parts by mass or more and 51 parts by mass or less, 3.2 parts by mass or more 48 parts by mass or less, 3.6 parts by mass or more and 45 parts by mass or less, 4 parts by mass or more and 42 parts by mass or less, 4.4 parts by mass or more and 39 parts by mass or less, 4.8 parts by mass or more and 36 parts by mass or less, 5.2 parts by mass or more and 33 parts by mass or less, 5.6 parts by mass or more and 30 parts by mass or less , 6 parts by mass to 27 parts by mass, 6.4 parts by mass to 24 parts by mass, 6.8 parts by mass to 21 parts by mass, 7.2 parts by mass to 18 parts by mass, 7.6 parts by mass to 15 parts by mass, or 8 parts by mass to 12 parts by mass. The lower limit of the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is, for example, 0.001% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.09% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, 0.9% by mass or more, or % by mass or more, 1.1% by mass or more, 1.3% by mass or more, 1.5% by mass or more, 1.7% by mass or more, 1.9% by mass or more, 2.1% by mass or more, 2.3% by mass or more, 2.5% by mass or more, 2.7% by mass or more, 2 .9 mass% or more, 3.2 mass% or more, 3.5 mass% or more, 3.8 mass% or more, 4.3 mass% or more, 4.8 mass% or more, 5.3 mass% or more, 5.8 mass% or more, or 7.0 mass% or more.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, relative to the mass of the polyurethane foam constituent of the polyurethane foam-forming composition, is, 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% by mass or less, 3.5% by mass or less, 3.3% by mass or less, 3.1% by mass or less, 2.9% by mass or less, 2.7% by mass or less, 2.5% by mass or less, 2.3% by mass or less, 2.1% by mass or less, 1. It may be 9% by weight or less, 1.7% by weight or less, 1.5% by weight or less, 1.3% by weight or less, 1.2% by weight or less, 1.0% by weight or less, 0.8% by weight or less, 0.6% by weight or less, or 0.4% by weight or less. 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 isocyanate groups to isocyanurate groups increases, and a polyurethane foam having particularly excellent flame retardancy tends to be obtained.When the content of the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is equal to or more than the above lower limit, the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is more likely to be exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be more easily obtained.

[0078] The upper limit of the content of the bromine-containing flame retardant having a decomposition temperature of 450° C. or higher is 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 63 parts by mass or less, 60 parts by mass or less, 57 parts by mass or less, 54 parts by mass or less, 51 parts by mass or less, 48 ​​parts by mass or less, 45 parts by mass or less, 42 parts by mass or less, 39 parts by mass or less, 36 parts by mass or less Parts by weight or less, 33 parts by weight or less, 30 parts by weight or less, 27 parts by weight or less, 24 parts by weight or less, 21 parts by weight or less, 18 parts by weight or less, 15 parts by weight or less, 12 parts by weight or less, 8 parts by weight or less, 7 .6 parts by weight or less, 7.2 parts by weight or less, 6.8 parts by weight or less, 6.4 parts by weight or less, 6 parts by weight or less, 5.6 parts by weight or less, 5.2 parts by weight or less, or 4.8 parts by weight or less. The lower limit of the content of the bromine-containing flame retardant having a decomposition temperature of 450°C or higher may be 0.01 parts by mass or more, 0.1 parts by mass or more, 0.4 parts by mass or more, 0.8 parts by mass or more, 1.2 parts by mass or more, 1.6 parts by mass or more, 2 parts by mass or more, 2.4 parts by mass or more, 2.8 parts by mass or more, 3.2 parts by mass or more, 3.6 parts by mass or more, 4 parts by mass or more, 4.4 parts by mass or more, 4.8 parts by mass or more, 5.2 parts by mass or more, 5.6 parts by mass or more, 6 parts by mass or more, 6.4 parts by mass or more, 6.8 parts by mass or more, 7.2 parts by mass or more, 7.6 parts by mass or more, 8 parts by mass or more, 12 parts by mass or more, 15 parts by mass or more, 18 parts by mass or more, 21 parts by mass or more, 24 parts by mass or more, 27 parts by mass or more, 30 parts by mass or more, 33 parts by mass or more, or 36 parts by mass or more, relative to 100 parts by mass of the polyol compound.The content of the bromine-containing flame retardant having a decomposition temperature of 450°C or higher is, relative to 100 parts by mass of the polyol compound, 0.01 parts by mass to 100 parts by mass, 0.1 parts by mass to 90 parts by mass, 0.4 parts by mass to 80 parts by mass, 0.8 parts by mass to 70 parts by mass, 1.2 parts by mass to 63 parts by mass, 1.6 parts by mass to 60 parts by mass, 2 parts by mass to 57 parts by mass, 2.4 parts by mass to 54 parts by mass, 2.8 parts by mass to 51 parts by mass, 3.2 parts by mass to 48 parts by mass. Parts by weight or less, 3.6 parts by weight or more and 45 parts by weight or less, 4 parts by weight or more and 42 parts by weight or less, 4.4 parts by weight or more and 39 parts by weight or less, 4.8 parts by weight or more and 36 parts by weight or less, 5.2 parts by weight or more and 33 parts by weight or less, 5.6 parts by weight or more and 30 parts by weight or less, 6 It may be at least 6.4 parts by mass and at most 24 parts by mass, at least 6.8 parts by mass and at most 21 parts by mass, at least 7.2 parts by mass and at most 18 parts by mass, at least 7.6 parts by mass and at most 15 parts by mass, or at least 8 parts by mass and at most 12 parts by mass. 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, is, for example, 0.001 mass% or more, 0.01 mass% or more, 0.03 mass% or more, 0.05 mass% or more, 0.07 mass% or more, 0.09 mass% or more, 0.1 mass% or more, 0.3 mass% or more, 0.5 mass% or more, 0.7 mass% or more, 0.9 mass% or more. Above, 1.1% by mass or more, 1.3% by mass or more, 1.5% by mass or more, 1.7% by mass or more, 1.9% by mass or more, 2.1% by mass or more, 2.3% by mass or more, 2.5% by mass or more, 2.7% by mass or more, 2.9 It may be at least 3.2 mass%, at least 3.5 mass%, at least 3.8 mass%, at least 4.3 mass%, at least 4.8 mass%, at least 5.3 mass%, at least 5.8 mass%, or at least 7.0 mass%.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, is, for example, 12.0% by mass or less, 11.0% by mass or less, 10.0% by mass or less, 9.0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.5% by mass or less, 6.0% by mass or less, 5.5% by mass or less, 5.0% by mass or less, 4.5% by mass or less, 4.0 mass% or less, 3.5 mass% or less, 3.3 mass% or less, 3.1 mass% or less, 2.9 mass% or less, 2.7 mass% or less, 2.5 mass% or less, 2.3 mass% or less, 2.1 mass% or less, 1.9 quality % or less, 1.7% by weight or less, 1.5% by weight or less, 1.3% by weight or less, 1.2% by weight or less, 1.0% by weight or less, 0.8% by weight or less, 0.6% by weight or less, or 0.4% by weight 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 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, The flame retardant content may be 3% by mass or more and 6.0% by mass or less, 0.5% by mass or more and 5.5% by mass or less, 0.7% by mass or more and 5.0% by mass or less, 0.9% by mass or more and 4.5% by mass or less, 1.1% by mass or more and 4.0% by mass or less, 1.3% by mass or more and 3.5% by mass or less, 1.5% by mass or more and 3.3% by mass or less, 1.7% by mass or more and 3.1% by mass or less, 1.9% by mass or more and 2.9% by mass or less, 2.1% by mass or more and 2.7% by mass or less, or 2.3% by mass or more and 2.5% by mass or less. When the content of the bromine-containing flame retardant having a decomposition temperature of 450°C or more 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 having a decomposition temperature of 450°C or more is below 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 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.

[0079] The content ratios of the bromine-containing flame retardant having a decomposition temperature of less than 370°C, the bromine-containing flame retardant having a decomposition temperature of 370°C or more but less than 450°C, and the bromine-containing flame retardant having a decomposition temperature of 450°C or more in the polyol composition, the polyurethane foam-forming composition, the polyurethane foam, the flame retardant composition, and the solid flame retardant composition are, for example, in the following ranges.

[0080] 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, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more relative to the sum of the content of 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. The upper limit of the content ratio of the bromine-containing flame retardant 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, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the sum of the content of 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 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 effect 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 higher but less than 450°C and / or the bromine-containing flame retardant having a decomposition temperature of 450°C or higher. When the content ratio of the bromine-containing flame retardant having a decomposition temperature of less than 370°C 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 370°C or higher but less than 450°C and / or the bromine-containing flame retardant having a decomposition temperature of 450°C or higher 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 less than 370°C 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 less than 370°C is more easily exhibited, and a polyurethane foam with particularly excellent flame retardancy tends to be obtained more easily.

[0081] The lower limit of 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, 1.5% by mass or more, 2% by mass or more, 4% by mass or more, 8% by mass or more, 12% by mass or more, 16% by mass or more, 20% by mass or more, 24% by mass or more, 28% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more relative to the sum of the content of 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 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 the bromine-containing flame retardant 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, 36% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the sum of the content of 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. 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 effect 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 more and less than 450° C. is equal to or less 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 450° C. or more 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 370°C or more and less than 450°C is equal to or more than the above lower limit, the flame retardant effect derived from the bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C is more likely to be exhibited, and a polyurethane foam having particularly excellent flame retardancy tends to be more easily obtained.

[0082] 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, 28% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more relative to the sum of the content of 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 the bromine-containing flame retardant 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, 36% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the sum of the content of 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 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 effects 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 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 lower than 450° C. is more likely to be exhibited, and a polyurethane foam having particularly excellent flame retardancy is more likely to be obtained. 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 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 exhibited, and a polyurethane foam having particularly excellent flame retardancy is more likely to be obtained.

[0083] (Boron-containing flame retardant) Specific examples of the boron-containing flame retardant 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. Among these, zinc borate is preferred.

[0084] The upper limit of the content of the boron-containing flame retardant may be 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 63 parts by mass or less, 60 parts by mass or less, 57 parts by mass or less, 54 parts by mass or less, 51 parts by mass or less, 48 parts by mass or less, 45 parts by mass or less, 42 parts by mass or less, 39 parts by mass or less, 36 parts by mass or less, 33 parts by mass or less, 30 parts by mass or less, 27 parts by mass or less, 24 parts by mass or less, 21 parts by mass or less, 18 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 8 parts by mass or less, 7.6 parts by mass or less, 7.2 parts by mass or less, 6.8 parts by mass or less, 6.4 parts by mass or less, 6 parts by mass or less, 5.6 parts by mass or less, 5.2 parts by mass or less, or 4.8 parts by mass or less, based on 100 parts by mass of the polyol compound. The lower limit of the content of the boron-containing flame retardant may be 0.01 part by mass or more, 0.1 part by mass or more, 0.4 part by mass or more, 0.8 part by mass or more, 1.2 parts by mass or more, 1.6 parts by mass or more, 2 parts by mass or more, 2.4 parts by mass or more, 2.8 parts by mass or more, 3.2 parts by mass or more, 3.6 parts by mass or more, 4 parts by mass or more, 4.4 parts by mass or more, 4.8 parts by mass or more, 5.2 parts by mass or more, 5.6 parts by mass or more, 6 parts by mass or more, 6.4 parts by mass or more, 6.8 parts by mass or more, 7.2 parts by mass or more, 7.6 parts by mass or more, 8 parts by mass or more, 12 parts by mass or more, 15 parts by mass or more, 18 parts by mass or more, 21 parts by mass or more, 24 parts by mass or more, 27 parts by mass or more, 30 parts by mass or more, 33 parts by mass or more, or 36 parts by mass or more, based on 100 parts by mass of the polyol compound. The content of the boron-containing flame retardant may be 0.01 part by mass or more and 100 parts by mass or less, 0.1 part by mass or more and 90 parts by mass or less, 0.4 part by mass or more and 80 parts by mass or less, 0.8 part by mass or more and 70 parts by mass or less, 1.2 parts by mass or more and 63 parts by mass or less, 1.6 parts by mass or more and 60 parts by mass or less, 2 parts by mass or more and 57 parts by mass or less, 2.4 parts by mass or more and 54 parts by mass or less, 2.8 parts by mass or more and 51 parts by mass or less, 3.2 parts by mass or more and 48 parts by mass or less, 3.6 parts by mass or more and 45 parts by mass or less, 4 parts by mass or more and 42 parts by mass or less, 4.4 parts by mass or more and 39 parts by mass or less, 4.8 parts by mass or more and 36 parts by mass or less, 5.2 parts by mass or more and 33 parts by mass or less, 5.6 parts by mass or more and 30 parts by mass or less, 6 parts by mass or more and 27 parts by mass or less, 6.4 parts by mass or more and 24 parts by mass or less, 6.8 parts by mass or more and 21 parts by mass or less, 7.2 parts by mass or more and 18 parts by mass or less, 7.6 parts by mass or more and 15 parts by mass or less, or 8 parts by mass or more and 12 parts by mass or less, based on 100 parts by mass of the polyol compound.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% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, 0.8% by mass or more, 1.2% by mass or more, 1.6% by mass or more, 2.0% by mass or more, 2.4% by mass or more, 2.8% by mass or more, 3.2% by mass or more, 3.6% by mass or more, 4.0% by mass or more, 4.4% by mass or more, 4.8% by mass or more, 5.5% by mass or more, 6.0% by mass or more, 6.5% by mass or more, 7.0% by mass or more, 7.5% by mass or more, 8.0% by mass or more, 8.5% by mass or more, 9.0% by mass or more, 9.5% by mass or more, 10.0% by mass or more, 10.5% by mass or more, 11.0% by mass or more, or 11.5% by mass or more. The upper limit of 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, 12.0% by mass or less, 11.0% by mass or less, 10.0% by mass or less, 9.6% by mass or less, 9.2% by mass or less, 8.8% by mass or less, 8.4% by mass or less, 8.0% by mass or less, 7.6% by mass or less, 7.2% by mass or less, 6.8% by mass or less, 6.4% by mass or less, 6.0% by mass or less, 5.6% by mass or less, 5.2% by mass or less, 5.0% by mass or less, 4.5% by mass or less, 4.0% by mass or less, 3.5% by mass or less, 3.0% by mass or less, 2.5% by mass or less, 2.0% by mass or less, 1.5% by mass or less, or 1.0% by mass or less. 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% by mass to 12.0% by mass, 0.2% by mass to 11.0% by mass, 0.3% by mass to 10.0% by mass, 0.4% by mass to 9.6% by mass, 0.8% by mass to 9.2% by mass, 1.2% by mass to 8.8% by mass, 1.6% by mass to 8.4% by mass, 2.0% by mass to 8.0% by mass, 2.4% by mass to 7.6% by mass, 2.8% by mass to 7.2% by mass, 3.2% by mass to 6.8% by mass, 3.6% by mass to 6.4% by mass, 4.0% by mass to 6.0% by mass, 4.4% by mass to 5.6% by mass, or 4.8% by mass to 5.2% by mass. When the content of the boron-containing flame retardant is within the above range, a polyurethane foam having excellent flame retardancy tends to be easily obtained.When the content of the boron-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 obtained.When the content 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 polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0085] 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 is 200 parts by mass or less, 190 parts by mass or less, 180 parts by mass or less, 170 parts by mass or less, 160 parts by mass or less, 150 parts by mass or less, 140 parts by mass or less, 130 parts by mass or less, 120 parts by mass or less, 110 parts by mass or less, 100 parts by mass or less, 90 parts by mass or less, or 100 parts by mass or less, based on 100 parts by mass of the polyol compound. 0 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 67 parts by mass or less, 64 parts by mass or less, 61 parts by mass or less, 58 parts by mass or less, 55 parts by mass or less, 52 parts by mass or less, 49 parts by mass or less, 41 parts by mass The following may be 39 parts by mass or less, 37 parts by mass or less, 35 parts by mass or less, 33 parts by mass or less, 31 parts by mass or less, 29 parts by mass or less, 27 parts by mass or less, 25 parts by mass or less, or 23 parts by mass or less. 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 may be 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 7 parts by mass or more, 9 parts by mass or more, 11 parts by mass or more, 13 parts by mass or more, 15 parts by mass or more, 17 parts by mass or more, 19 parts by mass or more, 21 parts by mass or more, 23 parts by mass or more, 25 parts by mass or more, 27 parts by mass or more, 29 parts by mass or more, 31 parts by mass or more, 33 parts by mass or more, 35 parts by mass or more, 37 parts by mass or more, 39 parts by mass or more, 41 parts by mass or more, 49 parts by mass or more, 52 parts by mass or more, 55 parts by mass or more, 58 parts by mass or more, 61 parts by mass or more, 64 parts by mass or more, 67 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, or 90 parts by mass or more, relative to 100 parts by mass of the polyol compound.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, relative to 100 parts by mass of the polyol compound, 1 part by mass to 200 parts by mass, 3 parts by mass to 190 parts by mass, 5 parts by mass to 180 parts by mass, 7 parts by mass to 170 parts by mass, 9 parts by mass to 160 parts by mass, 11 parts by mass to 150 parts by mass, 13 parts by mass to 140 parts by mass, 15 parts by mass to 130 parts by mass, 17 parts by mass to 120 parts by mass, 0 parts by weight or less, 19 parts by weight or more and 110 parts by weight or less, 21 parts by weight or more and 100 parts by weight or less, 23 parts by weight or more and 90 parts by weight or less, 25 parts by weight or more and 80 parts by weight or less, 27 parts by weight or more and 70 parts by weight or less, 29 parts by weight or more and 67 parts by weight, It may be from 31 parts by mass to 64 parts by mass, from 33 parts by mass to 61 parts by mass, from 35 parts by mass to 58 parts by mass, from 37 parts by mass to 55 parts by mass, from 39 parts by mass to 52 parts by mass, or from 41 parts by mass to 49 parts by mass. 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, 8.5 mass% or more, 9.0 mass% or more, 9.5 mass% or more, 10.0 mass% or more, 10.5 mass% or more, 11.0 mass% or more, 12.0 mass% or more, 12.5 mass% or more, 13.0 mass% or more, or 13.5 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% by mass or less, 18.5% by mass or less, 17.5% by mass or less, 16.5% by mass or less, 15.5% by mass or less, 14.5% by mass or less, 13.5% by mass or less, 12.5% ​​by mass or less, 11.5% by mass or less, 10.5% by mass or less, 9.5% by mass or less, 9.0% by mass or less, 8.5% by mass or less, 8.0% by mass or less, 7.5% by mass or less, 7.0% by mass or less, 6.5% by mass or less, 6.0% by mass or less, 5.5% by mass or less, 5.0% by mass or less, 4.5% by mass or less, or 3.0% by 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% by mass or more and 19.5% by mass or less, 2.0% by mass or more and 18.5% by mass or less, 2.5% by mass or more and 17.5% by mass or less, 3.5% by mass or more and 16.5% by mass or less, 4.0% by mass or more and 15.5% by mass or less, 4.5% by mass or more and 14.5% by mass or less, 5.5% by mass or more and 13.5% by mass or less, 6.0% by mass or more and 12.5% ​​by mass or less, 6.5% by mass or more and 11.5% by mass or less, 7.5% by mass or more and 10.5% by mass or less, or 8.5% by mass or more and 9.5% by mass or less. 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, polyurethane foams with excellent flame retardancy tend 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 polyurethane foams with particularly excellent flame retardancy tend 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 greater than the above lower limit, the flame retardant effect derived from the flame retardant is easily exerted, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0086] The content ratios of the red phosphorus, solid phosphorus-containing flame retardant, bromine-containing flame retardant, and boron-containing flame retardant in the polyol composition, polyurethane foam-forming composition, polyurethane foam, flame retardant composition, and solid flame retardant composition are, for example, in the following ranges.

[0087] From the viewpoint of further suppressing discoloration of the polyurethane foam, the content of red phosphorus is preferably 15.0 mass% or less relative to the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

[0088] The upper limit of the content of red phosphorus may be 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, 10.0 mass % or less, 9.0 mass % or less, 8.0 mass % or less, 7.0 mass % or less, 6.0 mass % or less, 5.0 mass % or less, 4.0 mass % or less, 3.0 mass % or less, 2.0 mass % or less, 1.0 mass % or less, 0.1 mass % or less, 0.01 mass % or less, 0.001 mass % or less, or 0.0001 mass % or less, relative to the sum of the contents of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. The lower limit of the content of red phosphorus may be 0.0001% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 1.0% by mass or more, 2.0% by mass or more, 3.0% by mass or more, 4.0% by mass or more, 5.0% by mass or more, 6.0% by mass or more, 7.0% by mass or more, 8.0% by mass or more, 9.0% by mass or more, 10.0% by mass or more, 11.0% by mass or more, 12.0% by mass or more, 13.0% by mass or more, 14.0% by mass or more, or 15.0% by mass or more, relative to 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 red phosphorus may be 0.0001% by mass to 15.0% by mass, 0.001% by mass to 14.0% by mass, 0.01% by mass to 13.0% by mass, 0.1% by mass to 12.0% by mass, 1.0% by mass to 11.0% by mass, 2.0% by mass to 10.0% by mass, 3.0% by mass to 9.0% by mass, 4.0% by mass to 8.0% by mass, or 5.0% by mass to 7.0% by mass, relative to the sum of the contents of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. When the content of red phosphorus is within the above range, a polyurethane foam having excellent flame retardancy and further suppressed coloration, and a polyol composition and a polyurethane foam-forming composition having even better storage stability with respect to reactivity, tend to be obtained. When the content of red phosphorus is equal to or less than the upper limit, a polyurethane foam with further suppressed coloration, and a polyol composition and a polyurethane foam-forming composition with even better storage stability with respect to reactivity tend to be easily obtained.When the content of red phosphorus is at least as much as the above lower limit, a polyurethane foam having excellent flame retardancy, and a polyol composition and a polyurethane foam-forming composition having even better storage stability with respect to reactivity tend to be easily obtained.

[0089] From the viewpoint of improving the storage stability with respect to the reactivity of the polyol composition and the polyurethane foam-forming composition, the content ratio of the phosphinic acid flame retardant is preferably 35.0 mass% or less relative to the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

[0090] The upper limit of the content of the phosphinic acid flame retardant may be 35.0 mass% or less, 33.0 mass% or less, 31.0 mass% or less, 29.0 mass% or less, 27.0 mass% or less, 25.0 mass% or less, 23.0 mass% or less, 21.0 mass% or less, 19.0 mass% or less, 17.0 mass% or less, 15.0 mass% or less, 13.0 mass% or less, 11.0 mass% or less, 9.0 mass% or less, 7.0 mass% or less, 5.0 mass% or less, 3.0 mass% or less, 1.0 mass% or less, 0.5 mass% or less, 0.3 mass% or less, 0.1 mass% or less, or 0.0 mass% relative to 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. The lower limit of the content ratio of the phosphinic acid flame retardant may be 0.0 mass% or more, 0.1 mass% or more, 0.3 mass% or more, 0.5 mass% or more, 1.0 mass% or more, 3.0 mass% or more, 5.0 mass% or more, 7.0 mass% or more, 9.0 mass% or more, 11.0 mass% or more, 13.0 mass% or more, 15.0 mass% or more, 17.0 mass% or more, 19.0 mass% or more, 21.0 mass% or more, 23.0 mass% or more, 25.0 mass% or more, 27.0 mass% or more, 29.0 mass% or more, 31.0 mass% or more, 33.0 mass% or more, or 35.0 mass% or more, relative to 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. The content ratio of the phosphinic acid flame retardant may be 0.0 mass% or more and 35.0 mass% or less, 0.1 mass% or more and 33.0 mass% or less, 0.3 mass% or more and 31.0 mass% or less, 0.5 mass% or more and 29.0 mass% or less, 1.0 mass% or more and 27.0 mass% or less, 3.0 mass% or more and 25.0 mass% or less, 5.0 mass% or more and 23.0 mass% or less, 7.0 mass% or more and 21.0 mass% or less, 9.0 mass% or more and 19.0 mass% or less, 11.0 mass% or more and 17.0 mass% or less, or 13.0 mass% or more and 15.0 mass% or less, relative to 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. When the content ratio of the phosphinic acid flame retardant is within the above range, a polyurethane foam having excellent flame retardancy and further suppressed coloration, and a polyol composition and a polyurethane foam-forming composition having even better storage stability with respect to reactivity tend to be readily obtained.When the content of the phosphinic acid flame retardant is equal to or less than the upper limit, a polyol composition and a polyurethane foam-forming composition having even better storage stability, particularly with respect to reactivity, tend to be obtained.When the content of the phosphinic acid flame retardant is equal to or more than the lower limit, a polyurethane foam having especially excellent flame retardancy and further suppressed discoloration tends to be obtained.

[0091] The upper limit of the content of the phosphate-containing flame retardant may be 100.0 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, 70.0 mass% or less, 65.0 mass% or less, 60.0 mass% or less, 55.0 mass% or less, 50.0 mass% or less, 45.0 mass% or less, 40.0 mass% or less, 35.0 mass% or less, 30.0 mass% or less, 25.0 mass% or less, 20.0 mass% or less, 15.0 mass% or less, 10.0 mass% or less, 5.0 mass% or less, or 0.0 mass% with respect to 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. The lower limit of the content ratio of the phosphate-containing flame retardant may be 0.0 mass% or more, 5.0 mass% or more, 10.0 mass% or more, 15.0 mass% or more, 20.0 mass% or more, 25.0 mass% or more, 30.0 mass% or more, 35.0 mass% or more, 40.0 mass% or more, 45.0 mass% or more, 50.0 mass% or more, 55.0 mass% or more, 60.0 mass% or more, 65.0 mass% or more, 70.0 mass% or more, 75.0 mass% or more, 80.0 mass% or more, 85.0 mass% or more, 90.0 mass% or more, 95.0 mass% or more, or 100.0 mass% with respect to 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. The content ratio of the phosphate-containing flame retardant may be 0.0 mass% or more and 100.0 mass% or less, 5.0 mass% or more and 95.0 mass% or less, 10.0 mass% or more and 90.0 mass% or less, 15.0 mass% or more and 85.0 mass% or less, 20.0 mass% or more and 80.0 mass% or less, 25.0 mass% or more and 75.0 mass% or less, 30.0 mass% or more and 70.0 mass% or less, 35.0 mass% or more and 65.0 mass% or less, 40.0 mass% or more and 60.0 mass% or less, or 45.0 mass% or more and 55.0 mass% or less, relative to 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. When the content ratio of the phosphate-containing flame retardant is within the above range, a polyurethane foam having excellent flame retardancy and further suppressed coloration, and a polyol composition and a polyurethane foam-forming composition having even better storage stability with respect to reactivity tend to be readily obtained.When the content of the phosphate-containing flame retardant is equal to or less than the upper limit, a polyurethane foam having excellent flame retardancy and further suppressed discoloration, and a polyol composition and a polyurethane foam-forming composition having even better storage stability in terms of reactivity, tend to be readily obtained.When the content of the phosphate-containing flame retardant is equal to or more than the lower limit, a polyurethane foam having excellent flame retardancy and further suppressed discoloration, and a polyol composition and a polyurethane foam-forming composition having even better storage stability in terms of reactivity, tend to be readily obtained.

[0092] The lower limit of the content ratio of the solid phosphorus-containing flame retardant may be, for example, 3 mass% or more, 5 mass% or more, 10 mass% or more, 15 mass% or more, 20 mass% or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, 40 mass% or more, 45 mass% or more, 50 mass% or more, 55 mass% or more, 60 mass% or more, 65 mass% or more, 70 mass% or more, 75 mass% or more, 80 mass% or more, 85 mass% or more, or 90 mass% or more, based on 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. 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, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, based on the total content 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 sum of the contents 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 easily 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 the 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.

[0093] The lower limit of the content ratio of the bromine-containing flame retardant may be, for example, 3 mass% or more, 5 mass% or more, 10 mass% or more, 15 mass% or more, 20 mass% or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, 40 mass% or more, 45 mass% or more, 50 mass% or more, 55 mass% or more, 60 mass% or more, 65 mass% or more, 70 mass% or more, 75 mass% or more, 80 mass% or more, 85 mass% or more, or 90 mass% or more, relative to 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. The upper limit of the content of the bromine-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, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the sum of the content of the solid phosphorus-containing flame retardant, the content of the bromine-containing flame retardant, and the content of the boron-containing flame retardant. 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 sum of the contents 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.

[0094] The lower limit of the content ratio of the boron-containing flame retardant may be, for example, 2 mass% or more, 3 mass% or more, 5 mass% or more, 7 mass% or more, 10 mass% or more, 15 mass% or more, 20 mass% or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, 40 mass% or more, 45 mass% or more, 50 mass% or more, 55 mass% or more, 60 mass% or more, 65 mass% or more, 70 mass% or more, 75 mass% or more, 80 mass% or more, 85 mass% or more, or 90 mass% or more, relative to 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. 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, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the sum of the content of the solid phosphorus-containing flame retardant, the content of the bromine-containing flame retardant, and the content of 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, relative to the sum of the contents 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.

[0095] The polyol composition, polyurethane foam-forming composition, flame retardant composition, and solid flame retardant 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. One of the polyisocyanate composition and 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 a solid phosphorus-containing flame retardant, a bromine-containing flame retardant, or a boron-containing flame retardant 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.

[0096] [Antimony-Containing Flame Retardant] 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 oxide 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.

[0097] [Metal hydroxide-based flame retardant] Examples of metal hydroxide-based flame retardants include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, and the like, and combinations of any two or more of these.

[0098] [Liquid Flame Retardant] The polyol composition and the polyurethane foam-forming composition contain a liquid flame retardant. Either the polyisocyanate composition or the polyol composition may contain the liquid flame retardant, or both may contain the liquid flame retardant. Examples of liquid flame retardants include phosphate ester-based flame retardants such as monophosphate esters and condensed phosphate esters. In particular, it is preferable to use phosphate ester-based flame retardants as the liquid flame retardant. Examples of monophosphate esters 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, etc., and 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.

[0099] The upper limit of the content of the liquid flame retardant is 300 parts by mass or less, 280 parts by mass or less, 260 parts by mass or less, 240 parts by mass or less, 220 parts by mass or less, 200 parts by mass or less, 180 parts by mass or less, 160 parts by mass or less, 140 parts by mass or less, 135 parts by mass or less, 130 parts by mass or less, 125 parts by mass or less, 120 parts by mass or less Parts by weight or less, 115 parts by weight or less, 110 parts by weight or less, 105 parts by weight or less, 100 parts by weight or less, 95 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 77 parts by weight or less, 74 parts by weight or less, 71 parts by weight or less, 68 parts by weight or less, 65 parts by weight or less, 60 parts by weight or less, 55 parts by weight or less, 50 parts by weight or less, or 45 parts by weight or less. The lower limit of the content of the liquid flame retardant may be 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, 55 parts by mass or more, 60 parts by mass or more, 65 parts by mass or more, 68 parts by mass or more, 71 parts by mass or more, 74 parts by mass or more, 77 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, 95 parts by mass or more, 100 parts by mass or more, 105 parts by mass or more, 110 parts by mass or more, 115 parts by mass or more, 120 parts by mass or more, 125 parts by mass or more, 130 parts by mass or more, or 135 parts by mass or more, relative to 100 parts by mass of the polyol compound. The content of the liquid flame retardant relative to 100 parts by mass of the polyol compound is 1 part by mass or more and 300 parts by mass or less, 5 parts by mass or more and 280 parts by mass or less, 10 parts by mass or more and 260 parts by mass or less, 15 parts by mass or more and 240 parts by mass or less, 20 parts by mass or more and 220 parts by mass or less, 25 parts by mass or more and 200 parts by mass or less, 30 parts by mass or more and 180 parts by mass or less, 35 parts by mass or more and 160 parts by mass or less, or 40 parts by mass or more and 140 parts by mass 45 parts by mass or more and 135 parts by mass or less, 50 parts by mass or more and 130 parts by mass or less, 55 parts by mass or more and 125 parts by mass or less, 60 parts by mass or more and 120 parts by mass or less, 65 parts by mass or more and 115 parts by mass or less, 68 It may be at least 71 parts by mass and at most 105 parts by mass, at least 74 parts by mass and at most 100 parts by mass, at least 77 parts by mass and at most 95 parts by mass, or at least 80 parts by mass and at most 90 parts by mass.The lower limit of the content of the liquid flame retardant, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be, for example, 1% by mass or more, 2% by mass or more, 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 8% by mass or more, 9% by mass or more, 10% by mass or more, 11% by mass or more, 12% by mass or more, 13% by mass or more, 14% by mass or more, 15% by mass or more, 16% by mass or more, 17% by mass or more, 18% by mass or more, 19% by mass or more, 20% by mass or more, 22% by mass or more, 24% by mass or more, 26% by mass or more, 28% by mass or more, or 30% by mass or more. The upper limit of the content of the liquid flame retardant, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be, for example, 36% by mass or less, 34% by mass or less, 32% by mass or less, 30% by mass or less, 28% by mass or less, 26% by mass or less, 25% by mass or less, 24% by mass or less, 23% by mass or less, 22% by mass or less, 21% by mass or less, 20% by mass or less, 19% by mass or less, 18% by mass or less, 17% by mass or less, 16% by mass or less, 15% by mass or less, 14% by mass or less, 13% by mass or less, 12% by mass or less, 11% by mass or less, 9% by mass or less, 7% by mass or less, or 5% by mass or less. 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.

[0100] The upper limit of the total content of solid flame retardant and liquid flame retardant is 400 parts by mass or less, 380 parts by mass or less, 360 parts by mass or less, 340 parts by mass or less, 320 parts by mass or less, 300 parts by mass or less, 280 parts by mass or less, 260 parts by mass or less, 240 parts by mass or less, 220 parts by mass or less, 200 parts by mass or less, 1 It may be 90 parts by weight or less, 180 parts by weight or less, 170 parts by weight or less, 160 parts by weight or less, 150 parts by weight or less, 140 parts by weight or less, 130 parts by weight or less, 125 parts by weight or less, 120 parts by weight or less, 115 parts by weight or less, 110 parts by weight or less, 105 parts by weight or less, 100 parts by weight or less, 90 parts by weight or less, or 80 parts by weight or less. The lower limit of the total content of the solid flame retardant and the liquid flame retardant may be 1 part by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, 100 parts by mass or more, 105 parts by mass or more, 110 parts by mass or more, 115 parts by mass or more, 120 parts by mass or more, 125 parts by mass or more, 130 parts by mass or more, 140 parts by mass or more, 150 parts by mass or more, 160 parts by mass or more, 170 parts by mass or more, 180 parts by mass or more, 190 parts by mass or more, 200 parts by mass or more, 220 parts by mass or more, or 240 parts by mass or more, relative to 100 parts by mass of the polyol compound. The total content of the solid flame retardant and the liquid flame retardant, relative to 100 parts by mass of the polyol compound, may be 1 part by mass or more and 400 parts by mass or less, 10 parts by mass or more and 380 parts by mass or less, 20 parts by mass or more and 360 parts by mass or less, 30 parts by mass or more and 340 parts by mass or less, 40 parts by mass or more and 320 parts by mass or less, 50 parts by mass or more and 300 parts by mass or less, 60 parts by mass or more and 280 parts by mass or less, 70 parts by mass or more and 260 parts by mass or less, 80 parts by mass or more and 240 parts by mass or less, 90 parts by mass or more and 220 parts by mass or less, 100 parts by mass or more and 200 parts by mass or less, 105 parts by mass or more and 190 parts by mass or less, 110 parts by mass or more and 180 parts by mass or less, 115 parts by mass or more and 170 parts by mass or less, 120 parts by mass or more and 160 parts by mass or less, 125 parts by mass or more and 150 parts by mass or less, or 130 parts by mass or more and 140 parts by mass or less.The lower limit of the total content of the solid flame retardant and the liquid flame retardant, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be, for example, 5% by mass or more, 7% by mass or more, 10% by mass or more, 12% by mass or more, 14% by mass or more, 16% by mass or more, 18% by mass or more, 20% by mass or more, 22% by mass or more, 24% by mass or more, 26% by mass or more, 28% by mass or more, 30% by mass or more, 32% by mass or more, 34% by mass or more, 37% by mass or more, 40% by mass or more, 43% by mass or more, 46% by mass or more, 49% by mass or more, or 52% by mass or more. The upper limit of the total content of the solid flame retardant and the liquid flame retardant, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be, for example, 57% by mass or less, 54% by mass or less, 51% by mass or less, 48% by mass or less, 45% by mass or less, 42% by mass or less, 39% by mass or less, 36% by mass or less, 33% by mass or less, 30% by mass or less, 28% by mass or less, 26% by mass or less, 24% by mass or less, 22% by mass or less, 20% by mass or less, 18% by mass or less, 16% by mass or less, 14% by mass or less, 12% by mass or less, or 10% by mass or less. The total content of the solid flame retardant and the liquid 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 solid flame retardant and the liquid flame retardant is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained. When the total content of the solid flame retardant and the liquid 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 total content of the solid flame retardant and the liquid 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.

[0101] <Polyol Compound> The polyol composition contains a polyol compound. The polyurethane foam-forming composition may contain a polyol compound or a polyol composition. The polyol compound is not particularly limited, but preferably contains a polyether polyol or a polyester polyol. Among these, from the viewpoint of enhancing the flame retardancy, etc. of the resulting polyurethane foam, it is preferable to contain an aromatic polyol such as an aromatic polyether polyol or an aromatic polyester polyol. Furthermore, from the viewpoint of enhancing the flame retardancy, etc. of the resulting polyurethane foam, it is particularly preferable to contain a terephthalic acid-based polyester polyol.

[0102] (Polyether Polyol) Polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide with an initiator having two or more active hydrogen atoms. Specific examples of initiators include aliphatic polyhydric alcohols, aliphatic amines, aromatic amines, and the like, as well as 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.

[0103] 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 a polyether polyol obtained using a Mannich condensate as an initiator.

[0104] The hydroxyl value of the polyether polyol is preferably 200 to 1000 mgKOH / g, more preferably 300 to 600 mgKOH / g, as measured in accordance with JIS K1557-1:2007.

[0105] (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 enhancing 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 preferred to use low-molecular-weight aliphatic glycols known as constituent components of polyester polyols, such as ethylene glycol, propylene glycol, and diethylene glycol.

[0106] 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.

[0107] The hydroxyl value of the polyester polyol is preferably from 100 to 400 mgKOH / g, and more preferably from 150 to 350 mgKOH / g.

[0108] 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 content of the polyol compound. 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 content of the polyol compound. 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 tends 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 tends to be readily obtained.

[0109] 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, a polyurethane foam-forming composition with excellent handleability and a polyurethane foam with excellent flame retardancy tend to be obtained due to a decrease in viscosity. When the amount of the terephthalic acid-based polyester polyol is equal to or less than the above upper limit, a polyurethane foam-forming composition with excellent handleability tend to be obtained due to a decrease in viscosity. Furthermore, when the amount of the terephthalic acid-based polyester polyol is equal to or greater than the above lower limit, a polyurethane foam with excellent flame retardancy tends to be obtained.

[0110] [Polyisocyanate Composition, Polyisocyanate Compound] The polyisocyanate composition contains a polyisocyanate compound. The polyisocyanate composition may consist solely of a polyisocyanate compound. As the polyisocyanate compound, various polyisocyanate compounds having two or more isocyanate groups, such as aromatic, alicyclic, and aliphatic polyisocyanate compounds, can be used. 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 commercially available liquid MDI products include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.), and "Millionate MR200" (manufactured by Tosoh Corporation). Alternatively, uretonimine-containing MDI (for example, a commercially available product such as "Millionate MTL" manufactured by Tosoh Corporation) may be used. In addition to liquid MDI, other polyisocyanate compounds may be used in combination, and any polyisocyanate compounds known in the technical field of polyurethanes may be used without limitation.

[0111] 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, 390 or more, 420 or more, 450 or more, 480 or more, 510 or more, 540 or more, 570 or more, or 600 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, 410 or less, 390 or less, 360 or less, 330 or less, 300 or less, 270 or less, 240 or less, or 210 or less. The isocyanate index 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 easily 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 easily 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 easily obtained.

[0112] (Inorganic Filler) The polyol composition and the polyurethane foam-forming composition may contain an inorganic filler, as long as the effects of each aspect of the present disclosure are 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 thereof.

[0113] From the viewpoint of the foamability of the polyurethane foam, the content of the inorganic filler is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, even more preferably 3 to 20% by mass, particularly preferably 4 to 15% by mass, and most preferably 5 to 10% by mass, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[0114] (Anti-settling Agent) The polyol composition and the polyurethane foam-forming composition may contain an anti-settling agent. Either the polyisocyanate composition or the polyol composition may contain an anti-settling agent, or both may contain an 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 A-S-A T-1700 (manufactured by Ito Oil Mills, Ltd.), A-S-A T-1800 (manufactured by Ito Oil Mills, Ltd.), A-S-A T-2800 (manufactured by Ito Oil Mills, Ltd.), and Disparlon 6100 (manufactured by Kusumoto Chemicals Co., Ltd.). Among these, A-S-A 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.

[0115] 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 of the polyurethane foam-forming composition. When the content of the anti-settling agent is at least as high as the aforementioned 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 aforementioned upper limit, a polyurethane foam with excellent flame retardancy tends to be obtained.

[0116] (Dispersant) The polyol composition and 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 a dispersant. 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.

[0117] 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 of the polyurethane foam-forming composition. When the content of the dispersant is at least the above-mentioned 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 the above-mentioned upper limit, a polyurethane foam with excellent flame retardancy tends to be obtained.

[0118] <Foam stabilizer> The polyol composition and 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 one. 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.

[0119] 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. The content of the foam stabilizer is also not particularly limited, but is preferably 0.05 to 4.0 mass %, more preferably 0.1 to 3.0 mass %, even more preferably 0.15 to 2.5 mass %, particularly preferably 0.2 to 2.0 mass %, and most preferably 0.25 to 1.5 mass %, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

[0120] <Blowing Agent> The polyol composition and the polyurethane foam-forming composition may contain a blowing agent. Either the polyisocyanate composition or the polyol composition may contain a blowing agent, or both may contain a blowing agent. It is preferred that only the polyol composition contains a blowing agent. Examples of the blowing agent include water and / or a physical blowing agent.

[0121] Specific examples of physical blowing agents include low-boiling hydrocarbon compounds, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbon compounds, ether compounds, and hydrofluoroolefin compounds. 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 compounds 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 compounds include CHF ３ , C.H. ２ F ２ , C.H. ３F, etc. Examples of the hydrochlorofluorocarbon compounds include trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)), etc. Examples of the hydrofluorocarbon compounds include HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane), etc. Examples of the ether compounds include diisopropyl ether, etc. 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 blowing agents may be used alone or in any combination of two or more. Among these, hydrofluoroolefin compounds are preferred.

[0122] The upper limit of the content of the blowing agent may be 100 parts by mass or less, 95 parts by mass or less, 90 parts by mass or less, 85 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, 45 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less, relative to 100 parts by mass of the polyol compound. The lower limit of the content of the blowing agent may be 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 60 parts by mass or more, 65 parts by mass or more, 70 parts by mass or more, 75 parts by mass or more, or 80 parts by mass or more, relative to 100 parts by mass of the polyol compound. The content of the blowing agent may be 5 parts by mass or more and 100 parts by mass or less, 10 parts by mass or more and 95 parts by mass or less, 15 parts by mass or more and 90 parts by mass or less, 20 parts by mass or more and 85 parts by mass or less, 25 parts by mass or more and 80 parts by mass or less, 30 parts by mass or more and 75 parts by mass or less, 35 parts by mass or more and 70 parts by mass or less, 40 parts by mass or more and 65 parts by mass or less, or 45 parts by mass or more and 60 parts by mass or less, relative to 100 parts by mass of the polyol compound. The lower limit of the blowing agent content, relative to the mass of the polyurethane foam constituents 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, 9.0 mass% or more, 10.0 mass% or more, 11.0 mass% or more, 12.0 mass% or more, 13.0 mass% or more, or 14.0 mass% or more. The upper limit of the blowing agent content, relative to the mass of the polyurethane foam constituents 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, 10.0 mass% or less, 9.0 mass% or less, 8.0 mass% or less, 7.0 mass% or less, 6.0 mass% or less, or 5.0 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. When the content of the blowing agent is within the above range, a polyurethane foam having excellent mechanical properties such as compressive strength, dimensional stability, and adhesiveness, and reduced raw material costs, tends to be obtained. When the content of the blowing agent is equal to or less than the above upper limit, a polyurethane foam having excellent mechanical properties, particularly compressive strength, dimensional stability, and adhesiveness, tends to be obtained. 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.

[0123] The upper limit of the water content is 10 parts by mass or less, 9 parts by mass or less, 8 parts by mass or less, 7 parts by mass or less, 6 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1 part by mass or less, 0.9 parts by mass or less, 0.8 parts by mass or less , 0.7 parts by mass or less, 0.6 parts by mass or less, 0.5 parts by mass or less, 0.29 parts by mass or less, 0.27 parts by mass or less, 0.25 parts by mass or less, 0.23 parts by mass or less, 0.21 parts by mass or less, 0.19 parts by mass or less, 0.17 parts by mass or less, or 0.15 parts by mass or less. The lower limit of the water content may be 0.01 parts by mass or more, 0.03 parts by mass or more, 0.05 parts by mass or more, 0.07 parts by mass or more, 0.09 parts by mass or more, 0.11 parts by mass or more, 0.13 parts by mass or more, 0.15 parts by mass or more, 0.17 parts by mass or more, 0.19 parts by mass or more, 0.21 parts by mass or more, 0.23 parts by mass or more, 0.25 parts by mass or more, 0.27 parts by mass or more, 0.29 parts by mass or more, 0.5 parts by mass or more, 0.6 parts by mass or more, 0.7 parts by mass or more, 0.8 parts by mass or more, 0.9 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass or more, relative to 100 parts by mass of the polyol compound. The content of water is 0.01 parts by mass or more and 10 parts by mass or less, 0.03 parts by mass or more and 9 parts by mass or less, 0.05 parts by mass or more and 8 parts by mass or less, 0.07 parts by mass or more and 7 parts by mass or less, 0.09 parts by mass or more and 6 parts by mass or less, 0.11 parts by mass or more and 5 parts by mass or less, 0.13 parts by mass or more and 4 parts by mass or less, and 0.15 parts by mass or more, with respect to 100 parts by mass of the polyol compound. It may be at least 0.17 parts by mass and at most 2 parts by mass, at least 0.19 parts by mass and at most 1 part by mass, at least 0.21 parts by mass and at most 0.9 parts by mass, at least 0.23 parts by mass and at most 0.8 parts by mass, at least 0.25 parts by mass and at most 0.6 parts by mass, or at least 0.29 parts by mass and at most 0.5 parts by mass.The lower limit of the water content, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be, for example, 0.01 mass% or more, 0.02 mass% or more, 0.03 mass% or more, 0.04 mass% or more, 0.05 mass% or more, 0.07 mass% or more, 0.09 mass% or more, 0.11 mass% or more, 0.13 mass% or more, 0.16 mass% or more, 0.19 mass% or more, 0.22 mass% or more, 0.25 mass% or more, 0.28 mass% or more, 0.31 mass% or more, 0.34 mass% or more, or 0.37 mass% or more. The upper limit of the water content, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be, for example, 0.55% by mass or less, 0.50% by mass or less, 0.45% by mass or less, 0.40% by mass or less, 0.35% by mass or less, 0.30% by mass or less, 0.25% by mass or less, 0.20% by mass or less, 0.15% by mass or less, 0.13% by mass or less, 0.11% by mass or less, 0.09% by mass or less, 0.07% by mass or less, 0.05% by mass or less, or 0.03% by mass or less. 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. When the water content is within the above range, a polyurethane foam having excellent mechanical properties such as flame retardancy and compressive strength tends to be easily obtained. When the water content is equal to or less than the above upper limit, a polyurethane foam having particularly excellent flame retardancy tends to be easily obtained. Furthermore, when the water content is equal to or greater than the above lower limit, a polyurethane resin having particularly excellent mechanical properties such as compressive strength tends to be easily obtained.

[0124] The upper limit of the content of the physical blowing agent may be 100 parts by mass or less, 95 parts by mass or less, 90 parts by mass or less, 85 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, 45 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less, relative to 100 parts by mass of the polyol compound. The lower limit of the content of the physical blowing agent may be 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 60 parts by mass or more, 65 parts by mass or more, 70 parts by mass or more, 75 parts by mass or more, or 80 parts by mass or more, relative to 100 parts by mass of the polyol compound. The content of the physical foaming agent may be 5 parts by mass or more and 100 parts by mass or less, 10 parts by mass or more and 95 parts by mass or less, 15 parts by mass or more and 90 parts by mass or less, 20 parts by mass or more and 85 parts by mass or less, 25 parts by mass or more and 80 parts by mass or less, 30 parts by mass or more and 75 parts by mass or less, 35 parts by mass or more and 70 parts by mass or less, 40 parts by mass or more and 65 parts by mass or less, or 45 parts by mass or more and 60 parts by mass or less, relative to 100 parts by mass of the polyol compound. The lower limit of the content of the physical blowing agent, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be 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, 9.0 mass% or more, 10.0 mass% or more, 11.0 mass% or more, 12.0 mass% or more, 13.0 mass% or more, or 14.0 mass% or more. The upper limit of the content of the physical blowing agent, relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition, may be, for example, 18.0% by mass or less, 17.0% by mass or less, 16.0% by mass or less, 15.0% by mass or less, 14.0% by mass or less, 13.0% by mass or less, 12.0% by mass or less, 11.0% by mass or less, 10.0% by mass or less, 9.0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.0% by mass or less, or 5.0% by mass or less.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. When the content of the physical blowing agent is within the above range, polyurethane foams tend to be obtained that are excellent in mechanical properties such as compressive strength, dimensional stability, and adhesiveness, as well as in flame retardancy. When the content of the physical blowing agent is equal to or less than the above upper limit, polyurethane foams tend to be obtained that are excellent in 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.

[0125] 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, 87 mol% or more, 89 mol% or more, 91 mol% or more, 93 mol% or more, 95 mol% or more, 97 mol% or more, or 99 mol% or more, based on the total content of the water and the physical blowing agent. The upper limit of the content of the physical blowing agent relative to the total content of water and 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, 89 mol% or less, 86 mol% or less, 83 mol% or less, 80 mol% or less, 77 mol% or less, 74 mol% or less, or 71 mol% or less. The content of the physical blowing agent, relative to the sum of the water content and the physical blowing agent content, 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%. When the physical blowing agent contains a chlorine atom in its molecule, it also exhibits flame retardancy. When the content of the physical blowing agent is within the above range, polyurethane foams with excellent flame retardancy and mechanical properties such as compressive strength tend to be easily obtained. When the content of the physical blowing agent is equal to or greater than the above lower limit, polyurethane foams with particularly excellent flame retardancy tend to be easily obtained. 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.

[0126] <Catalyst> The polyol composition and 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. It is preferred that only the polyol composition contains a catalyst. The catalyst may contain, for example, one or both of a urethane / urea formation catalyst and a trimerization catalyst, and it is preferred that both are contained.

[0127] The urethane / urea catalyst is a catalyst that promotes the reaction between a polyol component and a polyisocyanate. Specific examples include amino compounds, tin compounds, bismuth compounds, and metal acetylacetone salts. Examples of amino compounds include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl) ether, bis(2-dimethylaminoethyl) ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl) ether, N-methyl-N',N'-dimethylaminoethylpiperazine, imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, 1-methylimidazole, trimethylaminoethylpiperazine, and tripropylamine. Examples of tin compounds include stannous octoate, dibutyltin diacetate, and dibutyltin dilaurate. Examples of bismuth compounds include bismuth neodecanoate and bismuth octoate. Examples of acetylacetone metal salts include aluminum acetylacetone, iron acetylacetone, copper acetylacetone, zinc acetylacetone, beryllium acetylacetone, chromium acetylacetone, indium acetylacetone, manganese acetylacetone, molybdenum acetylacetone, titanium acetylacetone, cobalt acetylacetone, vanadium acetylacetone, and zirconium acetylacetone. These urethane / urea catalysts may be used alone or in any combination of two or more.

[0128] The amount of the urethane / urea catalyst is not particularly limited, but is preferably 0.01 to 3.0 mass %, more preferably 0.03 to 2.0 mass %, even more preferably 0.05 to 1.5 mass %, particularly preferably 0.07 to 1.0 mass %, and most preferably 0.1 to 0.8 mass %, based on the mass of the polyurethane foam constituents of 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.

[0129] The trimerization catalyst is a catalyst that promotes the formation of isocyanurate bonds. 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 octoate, sodium octoate, and 2-ethylaziridine; lead compounds such as lead naphthenate and lead octoate; metal salts such as sodium methoxide and potassium phenoxide; tertiary or quaternary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt, tetramethylammonium salt, tetraethylammonium, and tetraphenylammonium salt; and combinations of any two or more thereof.

[0130] 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.

[0131] The trimerization catalyst tends to provide a polyurethane foam that is excellent in reactivity during foaming and in flame retardancy by using a metal salt in combination with a tertiary or quaternary ammonium salt.

[0132] The lower limit of the content of the tertiary or quaternary ammonium salt 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, relative to the content of the trimerization catalyst. The upper limit of the content of the tertiary or quaternary ammonium salt 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, relative to the content of the trimerization catalyst. 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. Furthermore, 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.

[0133] (Other Additives) The polyol composition and 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 other additives include phenolic, amine, and sulfur-based antioxidants, heat stabilizers, metal inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifying resins, and tackifiers (polybutene, petroleum resins, etc.).

[0134] (Production 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 and then kneading the two, 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.

[0135] (Total heat generation) The polyurethane foam, which is a foam of the polyurethane foam-forming composition (a reaction product of a polyisocyanate composition and a polyol composition), is a cone calorimeter test sample prepared under the following preparation conditions from a polyurethane foam-forming composition containing a polyol compound, a liquid flame retardant, a solid flame retardant, a polyisocyanate compound, a foam stabilizer, a blowing agent, and a catalyst, and has a radiant heat intensity of 50 kW / m2 or more, as measured in accordance with the test method of ISO-5660. ２ When heated at 10 minutes, the total heat generated is 10 MJ / 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 9 MJ / m or less. ２ Preferably, it is 8 MJ / m or less. ２ More preferably, it is 7 MJ / 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 1000 kJ / min. The gross calorific value can be obtained by a cone calorimeter test, and in detail, 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 sufficient shape stability to avoid contact with the spark igniter of the cone calorimeter. [Conditions for preparing a sample for cone calorimeter test] (1): The polyurethane foam-forming composition is stirred for 5 seconds with a laboratory spar. (2): Immediately after (1), the composition is spread into a mold having dimensions of 150 mm height x 150 mm depth x 150 mm width to obtain a polyurethane foam. (3): The polyurethane foam is cut into a length of 10 cm, width of 10 cm, and thickness of 2.5 cm to obtain a sample for cone calorimeter test.

[0136] (Applications) The applications of the polyurethane foam, which is a foam of the polyurethane foam-forming composition (a reaction product of a polyisocyanate composition and a polyol composition), are not particularly limited, and the polyurethane foam can be used to fill cavities in structures such as buildings, furniture, automobiles, trains, and ships, or to be sprayed onto such structures. Among these, it is preferable to use the polyurethane foam-forming composition for spraying onto structures, i.e., for spraying. The structure is, for example, an object to which flame retardancy is to be imparted.

[0137] The solid flame retardant composition can be used for polyurethane foam. The solid flame retardant composition can also be used for spraying. In other words, the solid flame retardant composition can be used for spraying, in which the solid flame retardant composition is sprayed onto an object to adhere the solid flame retardant composition to the object.

[0138] 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 the polyol composition and the polyisocyanate composition contained in separate containers in the spraying device, causing them to collide and mix at the tip of the spray gun, and turning the mixed liquid into a mist using air pressure. Commercially available spraying devices and spray guns can be used.

[0139] The density of the polyurethane foam is not particularly limited, but is preferably 20 to 200 kg / m ３ It is preferable that the density is in the range of 200 kg / m ３ By setting the density to 20 kg / m or less, the polyurethane foam becomes lightweight and the workability to structures is improved. ３ From these viewpoints, the density of the polyurethane foam is set to 25 to 100 kg / m or more, which makes it easier to exhibit the desired flame retardancy. ３ More preferably, it is in the range of 25 to 80 kg / m ３ More preferably, it is in the range of 30 to 60 kg / m ３ More preferably, it is in the range of 35 to 50 kg / m ３ The density of the polyurethane foam can be measured in accordance with JIS K7222.

[0140] <Method of calculating each composition> The composition of each component in the polyol compound (e.g., the content relative to 100 parts by mass of the polyol compound) can be calculated using the following formula. Furthermore, the composition of each component in the polyurethane foam-forming composition (e.g., the content relative to the mass of the polyurethane foam constituents of the polyurethane foam-forming composition) can be calculated using the following formula. Mass (g) of polyurethane foam constituents of polyurethane foam-forming composition = charged amount (g) of polyisocyanate compound + charged amount (g) of polyol compound + additives ＊ *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 solid flame retardants), liquid flame retardants, foam stabilizers, catalysts, inorganic fillers, anti-settling agents, dispersion stabilizers, and other additives.

[0141] Aromatic polyester polyol compound content (mass%) = (amount of aromatic polyester polyol compound charged (g) + amount of aromatic and aliphatic polyester polyol compounds charged (g) × aromatic content ratio (%) of aromatic and aliphatic polyester polyol compounds ＊) / mass (g) of polyol compound × 100 *: Aromatic content ratio (%) of aromatic and aliphatic polyester polyol compounds = content (mol) derived from aromatic dicarboxylic acid / (content (mol) derived from aromatic dicarboxylic acid + content (mol) derived from aliphatic dicarboxylic acid) × 100

[0142] Content (mass%) of terephthalic acid-based polyester polyol compound=charge amount (g) of terephthalic acid-based polyester polyol compound / mass (g) of polyol compound×100

[0143] Isocyanate index = number of equivalents of polyisocyanate ÷ (number of equivalents of polyol + number of equivalents of water) × 100, where, number of equivalents of polyisocyanate = number of parts of polyisocyanate used × NCO content (%) / 100 / NCO molecular weight, number of equivalents of polyol = OHV × number of parts of polyol used ÷ molecular weight of KOH, OHV is the hydroxyl value of polyol (mg KOH / g), number of equivalents of water = number of parts of water used × number of OH groups in water / molecular weight of water. In the above formula, the unit of number of parts used is mass (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%, and for convenience of unit conversion in the above formula, the molecular weight of KOH is set to 56,100, the molecular weight of water is 18, and the number of OH groups in water is 2.

[0144] Content of solid phosphorus-containing flame retardant (parts by mass) = charge amount of solid phosphorus-containing flame retardant (g) / charge amount of polyol compound (g) × 100 Content of solid phosphorus-containing flame retardant (% by mass) = charge amount of solid phosphorus-containing flame retardant (g) / mass of polyurethane foam constituent of polyurethane foam-forming composition (g) × 100

[0145] Red phosphorus content (parts by mass) = charged amount of red phosphorus (g) / charged amount of polyol compound (g) × 100 Red phosphorus content (% by mass) = charged amount of red phosphorus (g) / mass of polyurethane foam constituent of polyurethane foam-forming composition (g) × 100

[0146] Phosphinic acid flame retardant content (parts by mass) = charged amount of phosphinic acid flame retardant (g) / charged amount of polyol compound (g) × 100 Phosphinic acid flame retardant content (% by mass) = charged amount of phosphinic acid flame retardant (g) / mass of polyurethane foam constituent of polyurethane foam-forming composition (g) × 100

[0147] Content of phosphate-containing flame retardant (parts by mass) = charged amount of phosphate-containing flame retardant (g) / charged amount of polyol compound (g) × 100 Content of phosphate-containing flame retardant (% by mass) = charged amount of phosphate-containing flame retardant (g) / mass of polyurethane foam constituent of polyurethane foam-forming composition (g) × 100

[0148] Bromine-containing flame retardant content (parts by mass) = bromine-containing flame retardant charge (g) / polyol compound charge (g) × 100 Bromine-containing flame retardant content (% by mass) = bromine-containing flame retardant charge (g) / polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0149] Content of bromine atoms (parts by mass) in polyol composition = amount of bromine-containing flame retardant charged (g) x molecular weight of bromine atom (79.9 g / mol) x number of bromine atoms in bromine-containing flame retardant / molecular weight of bromine-containing flame retardant (g / mol) / amount of polyol compound charged (g) x 100 Content of bromine atoms (% by mass) in polyurethane foam-forming composition = amount of bromine-containing flame retardant charged (g) x molecular weight of bromine atom (79.9 g / mol) x number of bromine atoms in bromine-containing flame retardant / molecular weight of bromine-containing flame retardant (g / mol) / mass of polyurethane foam constituent of polyurethane foam-forming composition (g) x 100 Content of bromine atoms in solid flame retardant composition (mass%) = Amount of bromine-containing flame retardant charged (g) × Molecular weight of bromine atom (79.9 g / mol) × Number of bromine atoms in bromine-containing flame retardant / Molecular weight of bromine-containing flame retardant (g / mol) / (Amount of solid phosphorus-containing flame retardant charged (g) + Amount of bromine-containing flame retardant charged (g) + Amount of boron-containing flame retardant charged (g)) × 100

[0150] Content of aliphatic bromine-containing compound (parts by mass) = charged amount of aliphatic bromine-containing compound (g) / charged amount of polyol compound (g) × 100 Content of aliphatic bromine-containing compound (% by mass) = charged amount of aliphatic bromine-containing compound (g) / mass of polyurethane foam constituent of polyurethane foam-forming composition (g) × 100

[0151] Content of aromatic bromine-containing low molecular weight compound (parts by mass) = charged amount of aromatic bromine-containing low molecular weight compound (g) / charged amount of polyol compound (g) × 100 Content of aromatic bromine-containing low molecular weight compound (% by mass) = charged amount of aromatic bromine-containing low molecular weight compound (g) / mass of polyurethane foam constituent of polyurethane foam-forming composition (g) × 100

[0152] Aromatic bromine-containing polymer compound content (parts by mass) = Amount of aromatic bromine-containing polymer compound charged (g) / Amount of polyol compound charged (g) × 100 Aromatic bromine-containing polymer compound content (% by mass) = Amount of aromatic bromine-containing polymer compound charged (g) / Mass of polyurethane foam constituent of polyurethane foam-forming composition (g) × 100

[0153] Content ratio (mass%) of aliphatic bromine-containing compound=charge amount (g) of aliphatic bromine-containing 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

[0154] 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

[0155] Content ratio (mass%) of aromatic bromine-containing polymer compound=charge amount (g) of aromatic bromine-containing polymer 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 polymer compound)×100

[0156] Content (parts by 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 / charged amount (g) of polyol compound × 100 Content (% by 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

[0157] Content (parts by mass) of bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°C = charged amount (g) of bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°C / charged amount (g) of polyol compound × 100 Content (% by mass) of bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°C = charged amount (g) of bromine-containing flame retardant having a decomposition temperature of 370°C or higher and lower than 450°C / mass (g) of polyurethane foam constituent of polyurethane foam-forming composition × 100

[0158] Content (parts by 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 / charged amount (g) of polyol compound × 100 Content (% by 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 constituent of polyurethane foam-forming composition × 100

[0159] Content ratio (mass%) of bromine-containing flame retardant having a decomposition temperature of less than 370°C = (feed amount (g) of bromine-containing flame retardant having a decomposition temperature of less than 370°C) / (feed amount (g) of bromine-containing flame retardant having a decomposition temperature of less than 370°C + (g) of bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C + (g) of bromine-containing flame retardant having a decomposition temperature of 450°C or more) × 100

[0160] Content ratio (mass%) of bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C = (feed amount (g) of bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C) / (feed amount (g) of bromine-containing flame retardant having a decomposition temperature of less than 370°C + (g) of bromine-containing flame retardant having a decomposition temperature of 370°C or more and less than 450°C + (g) of bromine-containing flame retardant having a decomposition temperature of 450°C or more) × 100

[0161] Content ratio (mass%) of bromine-containing flame retardant having a decomposition temperature of 450°C or more = (charge amount (g) of bromine-containing flame retardant having a decomposition temperature of 450°C or more) / (charge amount (g) of bromine-containing flame retardant having a decomposition temperature of less than 370°C + charge amount (g) of bromine-containing flame retardant having a decomposition temperature of 370°C or more but less than 450°C + charge amount (g) of bromine-containing flame retardant having a decomposition temperature of 450°C or more) × 100

[0162] Content of boron-containing flame retardant (parts by mass) = charged amount of boron-containing flame retardant (g) / charged amount of polyol compound (g) × 100 Content of boron-containing flame retardant (% by mass) = charged amount of boron-containing flame retardant (g) / mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0163] Content ratio (mass%) of solid phosphorus-containing flame retardant = charge amount (g) of solid phosphorus-containing flame retardant / (charge amount (g) of solid phosphorus-containing flame retardant + charge amount (g) of bromine-containing flame retardant + charge amount (g) of boron-containing flame retardant) × 100

[0164] 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

[0165] Content ratio of boron-containing flame retardant (mass%)=charge amount of boron-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

[0166] Red phosphorus content (mass%)=(amount of red phosphorus (g)) / (amount of solid phosphorus-containing flame retardant (g)+amount of bromine-containing flame retardant (g)+amount of boron-containing flame retardant (g))×100

[0167] Phosphinic acid flame retardant content (mass%) = amount of phosphinic acid 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

[0168] Content ratio (mass%) of phosphate-containing flame retardant = charge amount (g) of phosphate-containing flame retardant / (charge amount (g) of solid phosphorus-containing flame retardant + charge amount (g) of bromine-containing flame retardant + charge amount (g) of boron-containing flame retardant) × 100

[0169] Sum (parts by mass) of the solid phosphorus-containing flame retardant content, the bromine-containing flame retardant content, and the boron-containing flame retardant content=(charged amount (g) of solid phosphorus-containing flame retardant+charged amount (g) of bromine-containing flame retardant+charged amount (g) of boron-containing flame retardant) / charged amount (g) of polyol compound×100 Sum (% by mass) of the solid phosphorus-containing flame retardant content, the bromine-containing flame retardant content, and the boron-containing flame retardant content=(charged amount (g) of solid phosphorus-containing flame retardant+charged amount (g) of bromine-containing flame retardant+charged amount (g) of boron-containing flame retardant) / mass (g) of polyurethane foam constituents of polyurethane foam-forming composition×100

[0170] Liquid flame retardant content (parts by mass) = charged amount of liquid flame retardant (g) / charged amount of polyol compound (g) × 100 Liquid flame retardant content (% by mass) = charged amount of liquid flame retardant (g) / mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0171] Total content (parts by mass) of solid and liquid flame retardants = Total flame retardants ＊ Charge amount (g) / Charge amount (g) of polyol compound × 100 Total content (mass%) of solid flame retardant and liquid flame retardant = Total flame retardant ＊ Charged 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.

[0172] Inorganic filler content (mass %)=(amount of inorganic filler charged (g)) / (mass of polyurethane foam constituent of polyurethane foam-forming composition (g))×100

[0173] Anti-settling agent content (mass %)=anti-settling agent charged (g) / mass of polyurethane foam component of polyurethane foam-forming composition (g)×100

[0174] Dispersant content (mass %)=dispersant charge (g) / mass of polyurethane foam component of polyurethane foam-forming composition (g)×100

[0175] Content of other additives (% by mass) = Amount of other additives charged (g) / Mass of polyurethane foam constituents of polyurethane foam-forming composition (g) × 100

[0176] Foam stabilizer content (mass %)=amount of foam stabilizer charged (g) / mass of polyurethane foam constituent of polyurethane foam-forming composition (g)×100

[0177] Blowing agent content (parts by mass) = foaming agent charge (g) / polyol compound charge (g) × 100 Blowing agent content (% by mass) = foaming agent charge (g) / mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0178] Water content (parts by mass) = water charge (g) / polyol compound charge (g) × 100 Water content (% by mass) = water charge (g) / mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0179] Physical blowing agent content (parts by mass) = physical blowing agent charge (g) / polyol compound charge (g) × 100 Physical blowing agent content (% by mass) = physical blowing agent charge (g) / mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0180] Content ratio of physical blowing agent (mol %)=charged amount of physical blowing agent (mol) / (charged amount of water (mol)+charged amount of physical blowing agent (mol))×100

[0181] Urethane / urea catalyst content (mass %)=urethane / urea catalyst charged (g) / mass of polyurethane foam constituent of polyurethane foam-forming composition (g)×100

[0182] Content of tertiary or quaternary ammonium salt (mass%) = Amount of tertiary or quaternary ammonium salt charged (g) / Amount of trimerization catalyst charged (g) × 100

[0183] The above content and content ratio can also be calculated by replacing "charge amount" with "content."

[0184] Each aspect of the present disclosure will be described in more detail using examples, but each aspect of the present disclosure is not limited to these examples in any way.

[0185] Details of each component used in each example and comparative example are as follows. In Tables 1-1 to 20-1, some components are shown by abbreviations, and these abbreviations are written in parentheses below. (1) Polyisocyanate compound "MR-200": Polymeric MDI (manufactured by Tosoh Corporation, product name: MR-200)

[0186] (2) Solid flame retardants "Pyroguard SR-720N": 4,4'-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name: Pyroguard SR-720: aliphatic bromine-containing compound, decomposition temperature: 315°C) "Pyroguard SR-245": 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name: Pyroguard SR-245: aromatic bromine-containing low molecular weight compound, decomposition temperature: 417°C) Ethylenebispentabromophenyl (manufactured by 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 Dai-ichi Kogyo Seiyaku Co., Ltd., product name: Pyroguard SR-460B: aromatic bromine-containing polymer compound, decomposition temperature: 515°C) ・"Fireguard 8500": Polycarbonate oligomer produced from brominated bisphenol A (manufactured by Teijin Limited, product name: Fireguard 8500: aromatic bromine-containing polymer compound, decomposition temperature: 474°C) ・"Fireguard 7500": Polycarbonate oligomer produced from brominated bisphenol A (manufactured by Teijin Limited, product name: Fireguard 7500: aromatic bromine-containing polymer compound, decomposition temperature: 470°C) ・"AP-462": Ammonium polyphosphate (manufactured by Clariant Chemical Co., Ltd., 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 (manufactured by Tokyo Chemical Industry Co., Ltd.) Aluminum phosphate (manufactured by Sigma-Aldrich) Zinc borate (manufactured by Kinseimatec Co., Ltd.) Red phosphorus (manufactured by Rinkagaku Kogyo Co., Ltd., product name: NovaExcel 140) Aluminum phosphinate (manufactured by Hubei Hongjia Chemical Industry Co., Ltd.) "OP930": aluminum diethylphosphinate (manufactured by Clariant Chemical Co., Ltd., product name: OP930)

[0187] (3) Polyol Compounds "RFK-505": terephthalic acid-based polyester polyol (manufactured by Air Water Performance Chemicals, Inc., product name: Maximol RFK-505, hydroxyl value = 250 mg KOH / g) "RLK-087": terephthalic acid / adipic acid-based polyester polyol (manufactured by Air Water Performance Chemicals, Inc., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g) "RDK-133": orthophthalic acid-based polyester polyol (manufactured by Air Water Performance Chemicals, Inc., product name: Maximol RDK-133, hydroxyl value = 315 mg KOH / g)

[0188] (4) Liquid Flame Retardant "TCPP": Phosphate ester flame retardant (tris(β-chloropropyl)phosphate), (manufactured by Yoke Chemicals and New Materials (Shanghai) Co., Ltd., product name: TCPP)

[0189] (5) Foam stabilizer "SH-193": Polyalkylene glycol-based foam stabilizer (manufactured by Toray Dow Corning Co., Ltd., product name: SH-193)

[0190] (6) Catalysts (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)

[0191] (7) Blowing agent: Water; HFO-1233zd (hydrofluoroolefin) (manufactured by Honeywell, product name: Solstice LBA)

[0192] The methods for evaluating the appearance and measuring the various physical properties and characteristics are as follows.

[0193] [Decomposition temperature of bromine-containing flame retardant] The decomposition temperature of the bromine-containing flame retardant was calculated by 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 taken as the decomposition temperature. The weight loss rate was calculated as sample mass during measurement (mg) / sample mass before measurement (mg) × 100. The weight loss rate was measured under the following conditions.

[0194] [Conditions] The following steps [1] to [3] were carried out using a Hitachi High-Tech Science STA7200RV. [1] 8.5±0.5 mg of bromine-containing flame retardant was placed in the measuring 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.

[0195] [Total Heat Release, Maximum Heat Release Rate, Weight Retention Rate] The total heat release rate of the polyurethane foams produced in each of the Examples and Comparative Examples was evaluated by the following method. A polyurethane foam-forming composition was obtained by mixing a polyol composition and a polyisocyanate compound in the formulations shown in Tables 1-1 to 20-1 in a polypropylene beaker, and the mixture was stirred for 5 seconds with a laboratory spar. The composition was then immediately sprayed 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 sample for cone calorimeter testing. Using the cone calorimeter test sample, a test was conducted in accordance with the ISO-5660 test method, with a radiant heat intensity of 50 kW / m ２ The total heat release rate and maximum heat release rate after 10 minutes were measured by 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 the cone calorimeter test and the sample mass after the cone calorimeter test. The cone calorimeter test was performed using a CONE-III (manufactured by Toyo Seiki Seisakusho, Ltd.).

[0196] [Appearance of Polyurethane Foam] The appearance of the obtained polyurethane foam was evaluated visually. The degree of coloration of the polyurethane foam was evaluated as A, B, C, or D (A: no coloration, B: very slight coloration, C: slight coloration, D: coloration). The evaluation results are shown in Tables 1-2 to 20-2.

[0197] [Gel Time] The gel times (seconds) of the polyol and polyisocyanate compositions prepared in each Example and Comparative Example immediately after preparation (initial) and two weeks after preparation at 25°C were measured by measuring the time from the start of mixing the polyol and polyisocyanate compositions, which had been cooled to 0°C, to the start of stringing of the foaming liquid concentrate composition when a thin glass or metal rod was lightly inserted into the top of the foaming foaming liquid concentrate composition and then quickly pulled out, as gelation progressed, in an atmosphere at 23°C. The reaction delay time was calculated by subtracting the gel time immediately after preparation of the polyol and polyisocyanate compositions from the gel time two weeks after preparation at 25°C. The results of various evaluations are shown in Tables 1-2, 2-2, 4-2 to 7-2, and 17-2 to 20-2.

[0198] Example 1 First, a polyol compound, a blowing agent, a catalyst, a solid flame retardant, a liquid flame retardant, and a foam stabilizer were weighed into a 500 mL polypropylene beaker in the proportions shown in Table 1-1 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. Subsequently, a polyurethane foam-forming composition was prepared by adding a polyisocyanate composition, also cooled to 10°C, to the polyol 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 appearance, total heat release, maximum heat release rate, and weight retention. The results of the various evaluations are shown in Table 1-2.

[0199] Examples 2 to 121, Comparative Examples 1 to 11 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 20-1. Using the polyurethane foams, the appearance, total heat generation, maximum heat generation rate, and weight retention of the polyurethane foams were evaluated according to the procedures described above. The results of the various evaluations are shown in Tables 1-2 to 20-2. In addition, the gel time (seconds) and reaction delay time were determined according to the procedures described above immediately after preparation of the polyol composition and polyisocyanate composition (initial period) and two weeks after preparation of the polyol composition and polyisocyanate composition at 25°C. The results of the various evaluations are shown in Tables 1-2, 2-2, 4-2 to 7-2, and 17-2 to 20-2.

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Claims

1. A polyurethane foam-forming composition comprising a liquid flame retardant and a solid flame retardant, wherein the solid flame retardant comprises two or more selected from the group consisting of solid phosphorus-containing flame retardants, bromine-containing flame retardants, and boron-containing flame retardants.

2. The polyurethane foam-forming composition of claim 1, wherein said solid flame retardant comprises said solid phosphorus-containing flame retardant, said bromine-containing flame retardant, and said boron-containing flame retardant.

3. The polyurethane foam-forming composition of claim 1 or 2, wherein the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant or a phosphinic acid-based flame retardant.

4. The polyurethane foam-forming composition according to any one of claims 1 to 3, wherein the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant.

5. The polyurethane foam-forming composition according to any one of claims 1 to 4, wherein the solid phosphorus-containing flame retardant comprises red phosphorus, and the content of the red phosphorus is 3.0 mass% or less, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition.

6. The polyurethane foam-forming composition according to any one of claims 1 to 5, wherein the solid phosphorus-containing flame retardant comprises a phosphinic acid flame retardant, and the content of the phosphinic acid flame retardant is 3.0 mass% or less, based on the mass of the polyurethane foam constituent of the polyurethane foam-forming composition.

7. The polyurethane foam-forming composition according to any one of claims 1 to 6, wherein the bromine-containing flame retardant (ii) has a decomposition temperature of 370°C or higher but lower than 450°C, and the content of the bromine-containing flame retardant (ii) having a decomposition temperature of 370°C or higher but lower than 450°C is 3.5 mass% or less, based on the mass of the polyurethane foam constituents of the polyurethane foam-forming composition.

8. The polyurethane foam-forming composition according to any one of claims 1 to 7, wherein the bromine-containing flame retardant comprises one or more selected from the group consisting of: (ii) a bromine-containing flame retardant having a decomposition temperature of 370°C or more and less 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; and the content 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.

9. A cone calorimeter test sample prepared under the following preparation conditions from the polyurethane foam-forming composition containing a polyol compound, the liquid flame retardant, the solid flame retardant, a polyisocyanate compound, a foam stabilizer, a blowing agent, and a 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 The polyurethane foam-forming composition according to any one of claims 1 to 8, which is as follows: [Conditions for preparing a sample for cone calorimeter testing] (1): The polyurethane foam-forming composition is stirred for 5 seconds in a laboratory spar. (2): Immediately after (1), the composition is sprayed into a mold having dimensions of 150 mm height x 150 mm depth x 150 mm width 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.

10. A polyol composition comprising a polyol compound, a liquid flame retardant, and a solid flame retardant, wherein the solid flame retardant comprises two or more selected from the group consisting of solid phosphorus-containing flame retardants, bromine-containing flame retardants, and boron-containing flame retardants.

11. The polyol composition of claim 10, wherein said solid flame retardant comprises said solid phosphorus-containing flame retardant, said bromine-containing flame retardant, and said boron-containing flame retardant.

12. The polyol composition according to claim 10 or 11, wherein the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant or a phosphinic acid-based flame retardant.

13. The polyol composition according to any one of claims 10 to 12, wherein the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant.

14. The polyol composition according to any one of claims 10 to 13, wherein the solid phosphorus-containing flame retardant contains red phosphorus, and the content of the red phosphorus is 15 parts by mass or less per 100 parts by mass of the polyol compound.

15. The polyol composition according to any one of claims 10 to 14, wherein the solid phosphorus-containing flame retardant comprises a phosphinic acid flame retardant, and the content of the phosphinic acid flame retardant is 15 parts by mass or less per 100 parts by mass of the polyol compound.

16. A cone calorimeter test sample prepared under the following preparation conditions from the polyurethane foam-forming composition containing the polyol composition, polyisocyanate compound, foam stabilizer, blowing agent, and 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 The polyol composition according to any one of claims 10 to 15, wherein the polyol composition is as follows: [Conditions for preparing a sample for cone calorimeter testing] (1): The polyurethane foam-forming composition is stirred for 5 seconds with a laboratory spar. (2): Immediately after (1), the composition is sprayed into a mold having dimensions of 150 mm height x 150 mm depth x 150 mm width 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.

17. A solid flame retardant composition comprising two or more members selected from the group consisting of solid phosphorus-containing flame retardants, bromine-containing flame retardants, and boron-containing flame retardants.

18. The solid flame retardant composition of claim 17, comprising said solid phosphorus-containing flame retardant, said bromine-containing flame retardant, and said boron-containing flame retardant.

19. The solid flame retardant composition according to claim 17 or 18, wherein the solid phosphorus-containing flame retardant comprises a phosphate-containing flame retardant or a phosphinic acid-based flame retardant.

20. The solid flame retardant composition of any one of claims 17 to 19, wherein the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant.

21. The solid flame retardant composition according to any one of claims 17 to 20, wherein the solid phosphorus-containing flame retardant contains red phosphorus, and the content of the red phosphorus is 15 mass% or less of the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

22. A solid flame retardant composition according to any one of claims 17 to 21, wherein the solid phosphorus-containing flame retardant comprises a phosphinic acid flame retardant, and the content of the phosphinic acid flame retardant is 35 mass% or less of the total content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant.

23. A cone calorimeter test sample prepared under the following preparation conditions from a polyurethane foam-forming composition containing the solid flame retardant composition, liquid flame retardant, polyol compound, polyisocyanate compound, foam stabilizer, blowing agent, and catalyst was measured at a radiant heat intensity of 50 kW / m2 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 The solid flame retardant composition according to any one of claims 17 to 22, wherein the composition is as follows: [Conditions for preparing a sample for cone calorimeter testing] (1): The polyurethane foam-forming composition is stirred for 5 seconds with a laboratory spar. (2): Immediately after (1), the composition is sprayed into a mold having dimensions of 150 mm height x 150 mm depth x 150 mm width 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.

24. A flame retardant composition comprising the solid flame retardant composition according to any one of claims 17 to 23 and a liquid flame retardant.

25. A polyurethane foam, which is a foam of the polyurethane foam-forming composition according to any one of claims 1 to 9.

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