Polyol composition, polyurethane foam-forming composition, and polyurethane foam

Abstract

To provide a polyol composition and a polyurethane foam-forming composition that contribute to the production of polyurethane foams having good flame retardancy. [Solution] A polyol composition comprising a polyol compound containing an orthophthalic acid-based polyester polyol and a terephthalic acid-based polyester polyol, and a solid flame retardant, The content of the bromine-containing polyol is 1% by mass or more and 29% by mass or less, relative to the sum of the content of the bromine-containing polyol and the content of the aromatic polyester polyol. A polyol composition in which the solid flame retardant is contained in an amount of 25 parts by mass or more per 100 parts by mass of the polyol compound.

Description

[Technical Field]

[0001] This disclosure relates to polyol compositions, polyurethane foam-forming compositions, and polyurethane foams. [Background technology]

[0002] Polyurethane foam is used in practical applications for insulation and condensation prevention in ceilings, roofs, and walls of buildings such as apartment buildings, detached houses, and commercial buildings, taking advantage of its excellent thermal insulation properties. Although lightweight, polyurethane foam is flammable because it is an organic material. To improve this, polyurethane foam with enhanced flame retardancy is used, incorporating flame retardants and other additives. Patent Document 1 describes a polyurethane foam containing a bromine-containing polyol, an aromatic polyester polyol, a solid flame retardant, a blowing agent, a catalyst, a foam stabilizer, a liquid flame retardant, and a polyisocyanate compound. Furthermore, Patent Documents 2 and 3 describe polyurethane foams that include a bromine-containing polyol, or an aromatic polyester polyol, and a bromine-containing polyol, and further include a blowing agent, a catalyst, a foam stabilizer, a liquid flame retardant, and a polyisocyanate compound. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2019-214651 [Patent Document 2] Japanese Patent Publication No. 2022-175950 [Patent Document 3] Japanese Patent Publication No. 2022-56074 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] According to Patent Document 1, the flexible polyurethane foam described in Patent Document 1 is said to have excellent appearance and uniform high flame retardancy. According to Patent Document 2, the polyurethane foam described in Patent Document 2 has improved flame retardancy and improved spray application properties. According to Patent Document 3, the polyurethane foam described in Patent Document 3 suppresses two-stage foaming and has excellent flame retardancy. However, the flame retardancy of these polyurethane foams was insufficient, and further improvements in flame retardancy were needed.

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

[0006] This disclosure provides the following aspects: [1] A polyol composition comprising a bromine-containing polyol and an aromatic polyester polyol, and a solid flame retardant, The content of the bromine-containing polyol is 1% by mass or more and 29% by mass or less, relative to the sum of the content of the bromine-containing polyol and the content of the aromatic polyester polyol. A polyol composition in which the solid flame retardant is contained in an amount of 25 parts by mass or more per 100 parts by mass of the polyol compound. [2] A polyol composition comprising a bromine-containing polyol and an aromatic polyester polyol, and a solid flame retardant, The content of the bromine-containing polyol is 1% by mass or more and 29% by mass or less, relative to the sum of the content of the bromine-containing polyol and the content of the aromatic polyester polyol. The solid flame retardant includes a solid phosphorus-containing flame retardant. A polyol composition, wherein the solid phosphorus-containing flame retardant comprises a phosphinic acid-based flame retardant or a phosphate-containing flame retardant. [3] The polyol composition according to [1] or [2], wherein the solid flame retardant comprises a solid phosphorus-containing flame retardant, and one or more selected from the group consisting of zinc borate and bromine-containing flame retardants. [4] The polyol composition according to any one of [1] to [3], wherein the solid flame retardant comprises a solid phosphorus-containing flame retardant, zinc borate, and a bromine-containing flame retardant. [5] The polyol composition according to any one of [1] to [4], wherein the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant. [6] A polyurethane foam, which is a foam of the polyurethane foam-formable composition according to any one of [1] to [5]. [7] The polyurethane foam according to [6], wherein the polyurethane foam complies with the test method of ISO-5660, and at a radiant heat intensity of 50kW / m 2 when heated, the total calorific value after 10 minutes is 8.0MJ / m 2 or less. [Effects of the Invention]

[0007] One aspect of the present disclosure can provide a polyol composition and a polyurethane foam-formable composition that contribute to the production of a polyurethane foam having good flame retardancy. Further, another aspect of the present disclosure can provide a polyurethane foam having good flame retardancy. [Modes for Carrying Out the Invention]

[0008] Exemplary embodiments for implementing each aspect of the present disclosure will be described in further detail. However, the present disclosure is not limited to the following embodiments. In the present specification, a numerical range indicated by using "~" represents a range including the numerical values stated before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the Examples. In addition, the individually stated upper limit values and lower limit values may be arbitrarily combined.

[0009] [Polyol Composition] A polyol composition according to one aspect of the present disclosure is a polyol composition comprising: a polyol compound including a bromine-containing polyol and an aromatic polyester polyol; and a solid flame retardant, wherein the content of the bromine-containing polyol is 1% by mass or more and 29% by mass or less with respect to the total sum of the content of the bromine-containing polyol and the content of the aromatic polyester polyol, and the content of the solid flame retardant is 25 parts by mass or more with respect to 100 parts by mass of the polyol compound. Further, a polyol composition according to another aspect of the present disclosure is a polyol composition comprising: a polyol compound including a bromine-containing polyol and an aromatic polyester polyol; and a solid flame retardant, wherein the content of the bromine-containing polyol is 1% by mass or more and 29% by mass or less with respect to the total sum of the content of the bromine-containing polyol and the content of the aromatic polyester polyol, the solid flame retardant includes a solid phosphorus-containing flame retardant, and the solid phosphorus-containing flame retardant includes a phosphinic acid-based flame retardant or a phosphate-containing flame retardant.

[0010] The polyol composition may further comprise one or more selected from the group consisting of polyol compounds other than the bromine-containing polyol and the aromatic polyester polyol, liquid flame retardants, foam stabilizers, blowing agents, catalysts, inorganic fillers, anti-settling agents, dispersion stabilizers, and other additives.

[0011] Here, the polyol composition forms a polyurethane foam by mixing it with the polyisocyanate composition. It is preferable to use the polyol composition as the first liquid of the polyurethane foam-forming composition. In other words, during distribution, it is desirable to use a two-component or multi-component form that combines a first liquid containing a polyol composition, a second liquid containing a polyisocyanate composition, and, in the case of a multi-component type, a third liquid (and fourth or more liquids) containing components other than the polyol composition and the polyisocyanate composition. When forming the foam, it is desirable to mix these first and second liquids, and in the case of a multi-component type, the third liquid (and fourth or more liquids). The polyol composition contains a polyol compound as an essential component.

[0012] The polyol composition, when containing a solid flame retardant, exhibits improved flame retardancy in the resulting polyurethane foam. Here, a solid flame retardant refers to a flame retardant that is solid at 23°C, and a liquid flame retardant refers to a flame retardant that is liquid at 23°C.

[0013] [Polyisocyanate composition] The polyisocyanate composition contains a polyisocyanate compound. The polyisocyanate composition may further contain one or more additives selected from the group consisting of solid flame retardants, liquid flame retardants, blowing agents, foam stabilizers, catalysts, inorganic fillers, settling inhibitors, dispersion stabilizers, and other additives.

[0014] [Polyurethane foam-forming composition] Other embodiments of the present disclosure include polyurethane foam-forming compositions comprising the polyol composition described above and a polyisocyanate composition. Furthermore, the polyurethane foam-forming composition includes a bromine-containing polyol, an aromatic polyester polyol, a polyisocyanate compound, and a solid flame retardant. In addition, the polyurethane foam-forming composition may also include one or more additives selected from the group consisting of polyol compounds other than bromine-containing polyols and aromatic polyester polyols, liquid flame retardants, foam stabilizers, blowing agents, catalysts, inorganic fillers, anti-settling agents, dispersion stabilizers, and other additives.

[0015] Here, the polyurethane foam-forming composition may be a two-component type or a multi-component type with two or more components. "Two-component type" means a form in which a first liquid containing a polyol composition and a second liquid containing a polyisocyanate composition are stored separately and mixed when foam is formed. "Multi-component type" means, for example, a form in which a first liquid containing a polyol composition, a second liquid containing a polyisocyanate composition, and a third liquid (and fourth or more liquids) containing components other than the polyol composition and polyisocyanate composition are stored separately and mixed when foam is formed. Note that the polyol composition contains a polyol compound, and the polyisocyanate composition contains a polyisocyanate compound.

[0016] [Polyurethane foam] A polyurethane foam in yet another aspect of this disclosure is a foam of the polyurethane foam-forming composition described above.

[0017] <Polyol compounds> Polyol compounds include bromine-containing polyols and aromatic polyester polyols.

[0018] [Bromine-containing polyols] Bromine-containing polyols have a skeleton in which one or more bromine atoms are bonded to aromatic and / or aliphatic carbon atoms, and examples include bromine-containing polyester polyols and bromine-containing polyether polyols.

[0019] Examples of bromine-containing polyester polyols include those obtained by the esterification reaction of a bromine-containing polycarboxylic acid, such as tetrabromophthalic acid, with a polyhydric alcohol.

[0020] Examples of bromine-containing polyether polyols include those obtained by addition polymerization of a bromine-containing polyhydric alcohol such as tetrabromobisphenol A with one or more alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide. Among these, aromatic bromine-containing polyether polyols, which are addition polymers of tetrabromobisphenol A and ethylene oxide and / or propylene oxide, are preferred.

[0021] The upper limit of the content ratio of ethylene oxide-derived structures in bromine-containing polyols may be 100% 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, 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, 5% by mass or less, or 0% by mass, relative to the sum of the content of ethylene oxide-derived structures in bromine-containing polyols and the content of propylene oxide-derived structures in bromine-containing polyols. The lower limit of the content ratio of ethylene oxide-derived structures in bromine-containing polyols may be 0% 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, 90% by mass or more, 95% by mass or more, or 100% by mass, relative to the sum of the content of ethylene oxide-derived structures in bromine-containing polyols and the content of propylene oxide-derived structures in bromine-containing polyols. The content ratio of ethylene oxide-derived structures in a bromine-containing polyol may be 0% to 100% by mass, 5% to 95% by mass, 10% to 90% by mass, 15% to 85% by mass, 20% to 80% by mass, 25% to 75% by mass, 30% to 70% by mass, 35% to 65% by mass, 40% to 60% by mass, or 45% to 55% by mass, relative to the sum of the content of ethylene oxide-derived structures and propylene oxide-derived structures in the bromine-containing polyol. When the content ratio of ethylene oxide-derived structures in a bromine-containing polyol is within the above range, it tends to be easier to obtain a bromine-containing polyol with reduced viscosity and a polyurethane foam with excellent flame retardancy. When the content ratio of ethylene oxide-derived structures in a bromine-containing polyol is below the aforementioned upper limit, it is particularly easy to obtain a bromine-containing polyol with excellent handling properties.When the content ratio of ethylene oxide-derived structures in bromine-containing polyols is above the aforementioned lower limit, polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0022] Furthermore, the content ratio of structures derived from ethylene oxide in bromine-containing polyols is 1 It can be calculated from the molecular weight obtained from H-NMR and GPC measurements.

[0023] The upper limit for the bromine atom content of a bromine-containing polyol may be 99% 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, 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, 5% by mass or less, or 1% by mass or less, relative to the mass of the bromine-containing polyol. The lower limit of the bromine atom content in a bromine-containing polyol may be 1% 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, 90% by mass or more, 95% by mass or more, or 99.00% by mass or more, relative to the mass of the bromine-containing polyol. The bromine atom content of the bromine-containing polyol may be 1% to 99% by mass, 5% to 95% by mass, 10% to 90% by mass, 15% to 85% by mass, 20% to 80% by mass, 25% to 75% by mass, 30% to 70% by mass, 35% to 65% by mass, 40% to 60% by mass, or 45% to 55% by mass, relative to the mass of the bromine-containing polyol. When the bromine atom content of the bromine-containing polyol is within the above range, it tends to be easier to obtain a bromine-containing polyol with excellent handling properties and a polyurethane foam with excellent flame retardancy. When the bromine atom content of the bromine-containing polyol is below the above upper limit, it tends to be easier to obtain a bromine-containing polyol with particularly excellent handling properties. When the bromine atom content of the bromine-containing polyol is above the above lower limit, it tends to be easier to obtain a polyurethane foam with particularly excellent flame retardancy.

[0024] The upper limit for the bromine-containing polyol content may be 29.0% by mass or less, 27.5% by mass or less, 26.0% by mass or less, 24.5% by mass or less, 23.0% by mass or less, 21.5% by mass or less, 20.0% by mass or less, 18.5% by mass or less, 17.0% by mass or less, 15.5% by mass or less, 14.0% by mass or less, 12.5% ​​by mass or less, 11.0% by mass or less, 9.5% by mass or less, 8.0% by mass or less, 6.5% by mass or less, 5.0% by mass or less, 3.5% by mass or less, 2.0% by mass or less, or 1.0% by mass or less, relative to the sum of the bromine-containing polyol content and the aromatic polyester polyol content. The lower limit of the bromine-containing polyol content may be 1.0% by mass or more, 2.0% by mass or more, 3.5% by mass or more, 5.0% by mass or more, 6.5% by mass or more, 8.0% by mass or more, 9.5% by mass or more, 11.0% by mass or more, 12.5% ​​by mass or more, 14.0% by mass or more, 15.5% by mass or more, 17.0% by mass or more, 18.5% by mass or more, 20.0% by mass or more, 21.5% by mass or more, 23.0% by mass or more, 24.5% by mass or more, 26.0% by mass or more, 27.5% by mass or more, or 29.0% by mass or more, relative to the sum of the bromine-containing polyol content and the aromatic polyester polyol content. The bromine-containing polyol content may be 1.0% to 29.0% by mass, 2.0% to 27.5% by mass, 3.5% to 26.0% by mass, 5.0% to 24.5% by mass, 6.5% to 23.0% by mass, 8.0% to 21.5% by mass, 9.5% to 20.0% by mass, 11.0% to 18.5% by mass, 12.5% ​​to 17.0% by mass, or 14.0% to 15.5% by mass, relative to the sum of the bromine-containing polyol content and the aromatic polyester polyol content. When the bromine-containing polyol content is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained.

[0025] The hydroxyl value of the bromine-containing polyol is preferably 50 to 450 mg KOH / g, more preferably 70 to 400 g KOH / g, even more preferably 80 to 350 g KOH / g, particularly preferably 90 to 350 g KOH / g, and most preferably 100 to 330 g KOH / g.

[0026] [Aromatic polyester polyols] Aromatic polyester polyols include one or more selected from the group consisting of terephthalic acid-based polyester polyols and orthophthalic acid-based polyester polyols. Terephthalic acid-based polyester polyols are obtained by polycondensation of terephthalic acid and glycol. Orthophthalic acid-based polyester polyols are obtained by polycondensation of orthophthalic acid and glycol. The glycol is not particularly limited, but it is preferable to use low molecular weight aliphatic glycols known as components of polyester polyols, such as ethylene glycol, propylene glycol, and diethylene glycol.

[0027] The upper limit for the content of orthophthalic acid-based polyester polyol may be 99.0 parts by mass or less, 95.0 parts by mass or less, 90.0 parts by mass or less, 85.0 parts by mass or less, 80.0 parts by mass or less, 75.0 parts by mass or less, 70.0 parts by mass or less, 65.0 parts by mass or less, 60.0 parts by mass or less, 55.0 parts by mass or less, 50.0 parts by mass or less, 45.0 parts by mass or less, 40.0 parts by mass or less, 35.0 parts by mass or less, 30.0 parts by mass or less, 25.0 parts by mass or less, 20.0 parts by mass or less, 15.0 parts by mass or less, 10.0 parts by mass or less, 5.0 parts by mass or less, or 1.0 part by mass or less, per 100 parts by mass of the polyol compound. The lower limit of the orthophthalic acid-based polyester polyol content may be 1.0 part by mass or more, 5.0 parts by mass or more, 10.0 parts by mass or more, 15.0 parts by mass or more, 20.0 parts by mass or more, 25.0 parts by mass or more, 30.0 parts by mass or more, 35.0 parts by mass or more, 40.0 parts by mass or more, 45.0 parts by mass or more, 50.0 parts by mass or more, 55.0 parts by mass or more, 60.0 parts by mass or more, 65.0 parts by mass or more, 70.0 parts by mass or more, 75.0 parts by mass or more, 80.0 parts by mass or more, 85.0 parts by mass or more, 90.0 parts by mass or more, 95.0 parts by mass or more, or 99.0 parts by mass or more, per 100 parts by mass of the polyol compound. The content of orthophthalic acid-based polyester polyol may be 1.0 to 99.0 parts by mass, 5.0 to 95.0 parts by mass, 10.0 to 90.0 parts by mass, 15.0 to 85.0 parts by mass, 20.0 to 80.0 parts by mass, 25.0 to 75.0 parts by mass, 30.0 to 70.0 parts by mass, 35.0 to 65.0 parts by mass, 40.0 to 60.0 parts by mass, or 45.0 to 55.0 parts by mass per 100 parts by mass of the polyol compound. When the content of orthophthalic acid-based polyester polyol is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained.

[0028] The upper limit for the content of terephthalic acid-based polyester polyol may be 99.0 parts by mass or less, 95.0 parts by mass or less, 90.0 parts by mass or less, 85.0 parts by mass or less, 80.0 parts by mass or less, 75.0 parts by mass or less, 70.0 parts by mass or less, 65.0 parts by mass or less, 60.0 parts by mass or less, 55.0 parts by mass or less, 50.0 parts by mass or less, 45.0 parts by mass or less, 40.0 parts by mass or less, 35.0 parts by mass or less, 30.0 parts by mass or less, 25.0 parts by mass or less, 20.0 parts by mass or less, 15.0 parts by mass or less, 10.0 parts by mass or less, 5.0 parts by mass or less, or 1.0 part by mass or less, per 100 parts by mass of the polyol compound. The lower limit of the terephthalic acid-based polyester polyol content may be 1.0 part by mass or more, 5.0 parts by mass or more, 10.0 parts by mass or more, 15.0 parts by mass or more, 20.0 parts by mass or more, 25.0 parts by mass or more, 30.0 parts by mass or more, 35.0 parts by mass or more, 40.0 parts by mass or more, 45.0 parts by mass or more, 50.0 parts by mass or more, 55.0 parts by mass or more, 60.0 parts by mass or more, 65.0 parts by mass or more, 70.0 parts by mass or more, 75.0 parts by mass or more, 80.0 parts by mass or more, 85.0 parts by mass or more, 90.0 parts by mass or more, 95.0 parts by mass or more, or 99.0 parts by mass or more, per 100 parts by mass of the polyol compound. The content of terephthalic acid-based polyester polyol may be 1.0 to 99.0 parts by mass, 5.0 to 95.0 parts by mass, 10.0 to 90.0 parts by mass, 15.0 to 85.0 parts by mass, 20.0 to 80.0 parts by mass, 25.0 to 75.0 parts by mass, 30.0 to 70.0 parts by mass, 35.0 to 65.0 parts by mass, 40.0 to 60.0 parts by mass, or 45.0 to 55.0 parts by mass per 100 parts by mass of the polyol compound. When the content of terephthalic acid-based polyester polyol is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained.

[0029] The upper limit of the content ratio of orthophthalic acid-based polyester polyol may be 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 orthophthalic acid-based polyester polyol and terephthalic acid-based polyester polyol. The lower limit of the content ratio of orthophthalic acid-based polyester polyol may be 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, 90% by mass or more, or 95% by mass or more, relative to the sum of the content of orthophthalic acid-based polyester polyol and terephthalic acid-based polyester polyol. The content ratio of orthophthalic acid-based polyester polyol may be 5% to 100% by mass, 10% to 95% by mass, 15% to 90% by mass, 20% to 85% by mass, 25% to 80% by mass, 30% to 75% by mass, 35% to 70% by mass, 40% to 65% by mass, 45% to 60% by mass, or 50% to 55% by mass, relative to the sum of the content of orthophthalic acid-based polyester polyol and terephthalic acid-based polyester polyol. When the content ratio of orthophthalic acid-based polyester polyol is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained.

[0030] (Other polyester polyols) Other polyester polyols may include naphthalenedicarboxylic acid-based polyester polyols and aliphatic polyester polyols. Naphthalenedicarboxylic acid-based polyester polyols are obtained by polycondensation of naphthalene dicarboxylic acid and glycol. Aliphatic polyester polyols are obtained by polycondensation of aliphatic dicarboxylic acid and glycol. The glycol is not particularly limited, but it is preferable to use low molecular weight aliphatic glycols known as components of polyester polyols, such as ethylene glycol, propylene glycol, and diethylene glycol.

[0031] The hydroxyl value of the polyester polyol is preferably 100 to 450 mg KOH / g, more preferably 150 to 400 g KOH / g, and even more preferably 180 to 350 g KOH / g.

[0032] (Polyether polyol) The polyol compound may include a polyether polyol. The polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide to an initiator having two or more active hydrogen atoms. Specific examples of initiators include aliphatic polyhydric alcohols, aliphatic amines, aromatic amines, and any combination of two or more of these. Examples of aliphatic polyhydric alcohols include glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, and cyclohexanedimethanol; triols such as trimethylolpropane and glycerin; and tetrafunctional alcohols such as pentaerythritol. Examples of aliphatic amines include alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine; and alkanolamines such as monoethanolamine and diethanolamine. Examples of aromatic amines include aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, and Mannich condensates.

[0033] As for polyether polyols, aromatic polyether polyols having an aromatic ring in the molecule are preferred from the viewpoint of improving the flame retardancy of polyurethane foams, and among these, amine-based polyether polyols such as tolylenediamine-based polyether polyols and Mannich-based polyether polyols are preferred, with Mannich-based polyether polyols being more preferred. The tolylenediamine-based polyether polyol mentioned above refers to a polyether polyol obtained using tolylenediamine as an initiator. The Mannich-based polyether polyol mentioned above refers to a polyether polyol produced using the Mannich reaction with phenols, primary or secondary amines, and aldehydes, such as a polyether polyol obtained using a Mannich condensate as an initiator.

[0034] The hydroxyl value of the polyether polyol is preferably 200 to 1000 mg KOH / g, and more preferably 300 to 600 mg KOH / g.

[0035] <Polyisocyanate compounds> As the polyisocyanate compound included in the polyisocyanate composition, various polyisocyanate compounds such as aromatic, alicyclic, and aliphatic compounds having two or more isocyanate groups can be used. Preferably, liquid diphenylmethane diisocyanate (MDI) is used due to its ease of handling, rapid reaction, excellent physical properties of the resulting polyurethane foam, and low cost. Examples of liquid MDI include crude MDI (also called polymeric MDI). Specific commercially available liquid MDI products include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.) and "Millionate MR200" (manufactured by Tosoh Corporation). Alternatively, uretonimine-containing MDI (for example, "Millionate MTL": manufactured by Tosoh Corporation, a commercially available product) may also be used. In addition to liquid MDI, other polyisocyanate compounds may be used in combination, and any polyisocyanate compound known in the field of polyurethanes can be used without limitation.

[0036] The upper limit of the isocyanate index may be 800 or less, 700 or less, 600 or less, 570 or less, 540 or less, 510 or less, 480 or less, 450 or less, 420 or less, 390 or less, 360 or less, 330 or less, or 300 or less. The lower limit of the isocyanate index may be 150 or more, 180 or more, 210 or more, 240 or more, 270 or more, 300 or more, 330 or more, 360 or more, 390 or more, 420 or more, 450 or more, 480 or more, or 510 or more. The isocyanate index content may be, for example, 150 to 800, 180 to 700, 210 to 610, 240 to 570, 270 to 540, 310 to 510, 340 to 470, 370 to 440, or 390 to 410. When the isocyanate index is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the isocyanate index is above the lower limit, the amount of isocyanate nurate groups produced increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. Furthermore, when the isocyanate index is below the upper limit, the rate of conversion from unreacted isocyanate groups to isocyanurate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0037] [Solid flame retardant] The polyol composition contains a solid flame retardant. The solid flame retardant may also contain a solid phosphorus-containing flame retardant. The solid flame retardant may contain one or more selected from the group consisting of a solid phosphorus-containing flame retardant, zinc borate, and a bromine-containing flame retardant. Alternatively, the solid flame retardant may contain a solid phosphorus-containing flame retardant, zinc borate, and a bromine-containing flame retardant. Both the polyisocyanate composition and the polyol composition may contain a solid flame retardant. Preferably, only the polyol composition contains a solid flame retardant.

[0038] (Solid phosphorus-containing flame retardant) Examples of solid phosphorus-containing flame retardants include red phosphorus, phosphinate-based flame retardants, and phosphate-containing flame retardants. Solid phosphorus-containing flame retardants may also contain phosphinate-based flame retardants or phosphate-containing flame retardants.

[0039] <Red Phosphorus> There are no restrictions on the type of red phosphorus used; for example, commercially available products can be selected and used as appropriate.

[0040] <Phosphinic acid-based flame retardant> As phosphinic acid-based flame retardants, one or more selected from phosphinic acid-based flame retardants represented by formula (A-1) or formula (A-2), and polymers thereof, are preferred.

[0041] [ka]

[0042] [ka]

[0043] In the formula, R 1 , R 2 R is either the same or different, and is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms; 3 is a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 20 carbon atoms, or an arylalkylene group having 7 to 20 carbon atoms; M is Na, Li, K, Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base; m is an integer selected from 1 to 4, n is an integer selected from 1 to 4, and x is an integer selected from 1 to 4.

[0044] R 1 , R 2are preferably the same or different, and each represent 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. R 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. The above M is preferably Mg, Ca, Al, Sn, Ti, Zn, Fe, or Zr.

[0045] Such phosphinic acid-based flame retardants can be obtained, for example, by reacting alkyl sulfonates and / or phosphinic acids and / or their alkali metal salts with olefins in the presence of a free radical initiator to obtain phosphinic acids and / or their alkali metal salts, and then further reacting them with a metal compound. Specifically, examples of phosphinate-based flame retardants include aluminum phosphinate, sodium phosphinate, calcium phosphinate, potassium phosphinate, aluminum tris(diethylphosphinate), potassium tris(diethylphosphinate), calcium tris(diethylphosphinate), sodium tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(butylethylphosphinate), aluminum tris(diphenylphosphinate), zinc bis(diethylphosphinate), zinc bis(methylethylphosphinate), zinc bis(diphenylphosphinate), titanyl bis(diethylphosphinate), titanium tetrakis(diethylphosphinate), titanyl bis(methylethylphosphinate), titanium tetrakis(methylethylphosphinate), titanyl bis(diphenylphosphinate), titanium tetrakis(diphenylphosphinate), etc., and any combination of two or more of these. Among these, aluminum phosphinate; sodium phosphinate; and tris(phosphinate)aluminum selected from tris(diethylphosphinate)aluminum, tris(methylethylphosphinate)aluminum, tris(butylethylphosphinate)aluminum, and tris(diphenylphosphinate)aluminum are particularly preferred.

[0046] [Phosphate-containing flame retardant] Examples of phosphate-containing flame retardants include phosphates consisting of a salt of phosphoric acid with at least one metal or compound selected from metals of groups IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. While there are no particular limitations on phosphoric acid, various types such as monophosphate, pyrophosphate, and polyphosphate are examples. Examples of metals of groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron(II), iron(III), and aluminum. Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, and any combination of two or more of these. Examples of aromatic amines include pyridine, triazine, and melamine. Furthermore, phosphate-containing flame retardants may be subjected to known water-resistance-improving treatments such as silane coupling agent treatment or coating with melamine resin.

[0047] Specific examples of phosphate-containing flame retardants include monophosphates, pyrophosphates, and polyphosphates.

[0048] The monophosphates are not particularly limited, but examples include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite; and any combination of two or more of these.

[0049] Polyphosphates are not particularly limited, but examples include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, aluminum polyphosphate, and any combination of two or more of these.

[0050] Among these, the use of polyphosphates is preferable because it improves the self-extinguishing properties of phosphate-containing flame retardants, and the use of ammonium polyphosphate is even more preferable.

[0051] The upper limit of the content of the solid phosphorus-containing flame retardant is 500.0 parts by mass or less, 250.0 parts by mass or less, 150.0 parts by mass or less, 100.0 parts by mass or less, 90.0 parts by mass or less, 80.0 parts by mass or less, 70.0 parts by mass or less, 60.0 parts by mass or less, 55.0 parts by mass or less, 45.8 parts by mass or less , 41.6 parts by mass or less, 37.4 parts by mass or less, 29.0 parts by mass or less, 20.6 parts by mass or less, 16.4 parts by mass or less, 12.2 parts by mass or less, 7.2 parts by mass or less, 6.4 parts by mass or less, 5.6 parts by mass or less, 4.8 parts by mass or less, 4.0 parts by mass or less, 2.4 parts by mass or less, 0.8 parts by mass or less, or 0.1 parts by mass or less. The lower limit of the content of the solid phosphorus-containing flame retardant may be 0.1 parts by mass or more, 0.8 parts by mass or more, 2.4 parts by mass or more, 4.0 parts by mass or more, 4.8 parts by mass or more, 5.6 parts by mass or more, 6.4 parts by mass or more, 7.2 parts by mass or more, 12.2 parts by mass or more, 16.4 parts by mass or more, 20.6 parts by mass or more, 29.0 parts by mass or more, 37.4 parts by mass or more, 41.6 parts by mass or more, 45.8 parts by mass or more, 55.0 parts by mass or more, 60.0 parts by mass or more, 70.0 parts by mass or more, 80.0 parts by mass or more, 90.0 parts by mass or more, 100.0 parts by mass or more, 150.0 parts by mass or more, 250.0 parts by mass or more, or 500.0 parts by mass or more, per 100 parts by mass of the polyol compound. The content of the solid phosphorus-containing flame retardant may be 0.1 parts by mass or more and 500.0 parts by mass or less, 0.8 parts by mass or more and 250.0 parts by mass or less, 2.4 parts by mass or more and 150.0 parts by mass or less, 4.0 parts by mass or more and 100.0 parts by mass or less, 4.8 parts by mass or more and 90.0 parts by mass or less, 5.6 parts by mass or more and 80.0 parts by mass or less, 6.4 parts by mass or more and 70.0 parts by mass or less, 7.2 parts by mass or more and 60.0 parts by mass or less, 12.2 parts by mass or more and 55.0 parts by mass or less, 16.4 parts by mass or more and 45.8 parts by mass or less, 20.6 parts by mass or more and 41.6 parts by mass or less, or 29.0 parts by mass or more and 37.4 parts by mass or less, per 100 parts by mass of the polyol compound. When the content of the solid phosphorus-containing flame retardant is within the above range, it tends to be easier to obtain a polyurethane foam with excellent flame retardancy. When the content of the solid phosphorus-containing flame retardant is below the aforementioned upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.When the content of the solid phosphorus-containing flame retardant is above the aforementioned lower limit, the flame retardant effect derived from the solid phosphorus-containing flame retardant is more easily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0052] (Bromine-containing flame retardant) The bromine-containing flame retardant may contain only one type or two or more types, but it is preferable to contain at least two types, consisting of a first bromine-containing flame retardant and a second bromine-containing flame retardant.

[0053] Bromine-containing flame retardants are not particularly limited as long as they are compounds that contain bromine atoms in their molecular structure. Examples include compounds containing aliphatic carbon-bromine atom bonds (aliphatic bromine-containing compounds), compounds that do not contain aliphatic carbon-bromine atom bonds but contain aromatic carbon-bromine atom bonds and have three or fewer aromatic rings (aromatic bromine-containing low molecular weight compounds), and compounds that contain aromatic carbon-bromine bonds and have an average of more than three aromatic rings within the molecule (aromatic bromine-containing high molecular weight compounds).

[0054] Here, the first bromine-containing flame retardant is one selected from the following three: (a) to (c): (a) Aliphatic bromine-containing compounds, (b) aromatic bromine-containing low molecular compound, (c) aromatic bromine-containing polymer compound; It is preferable that the second bromine-containing flame retardant is one selected from the other two, excluding the one selected from the three (a) to (c).

[0055] Using two bromine-containing flame retardants in combination, each with different carbon atom configurations and / or molecular weights to which bromine atoms are bonded, tends to yield polyurethane foams with even greater flame retardancy than using a single bromine-containing flame retardant. Furthermore, using three bromine-containing flame retardants in combination, each with different carbon atom configurations and / or molecular weights to which bromine atoms are bonded, tends to yield polyurethane foams with even greater flame retardancy than using two bromine-containing flame retardants. In particular, using two or more bromine-containing flame retardants selected from aliphatic bromine-containing compounds, aromatic bromine-containing low-molecular-weight compounds, and aromatic bromine-containing high-molecular-weight compounds tends to yield polyurethane foams with especially superior flame retardancy.

[0056] Examples of compounds containing aliphatic carbon-bromine atom bonds (aliphatic bromine-containing compounds) include low molecular weight organic bromine compounds such as 2,4,6-tris(2,4-dibromopropyl)-1,3,5-triazine (Piroguard SR-750), 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] (Piroguard SR-720), and 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2-methyl-2,3-dibromopropyloxy)benzene] (Piroguard SR-130). Among these, 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] is preferred.

[0057] Specific examples of low molecular weight organic bromine compounds that do not contain aliphatic carbon-bromine atom bonds, contain aromatic carbon-bromine atom bonds, and have three or fewer aromatic rings (aromatic bromine-containing low molecular weight compounds) include, for example, hexabromobenzene, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (Pyroguard SR-245), pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), tetrabromobisphenol A, and other low molecular weight organic bromine compounds. Among these, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine and ethylenebis(pentabromophenyl) are preferred.

[0058] Specific examples of compounds containing aromatic carbon-bromine atom bonds and having an average of more than three aromatic rings within the molecule (aromatic bromine-containing polymer compounds) include homopolymers derived from 2,6-dibromophenol or 2,4-dibromophenol (Piroguard SR-460B), polycarbonate oligomers produced using brominated bisphenol A as a raw material, brominated polycarbonates such as copolymers of the said polycarbonate oligomer and bisphenol A (FG-8500, FG-7500, FG-7000), and brominated polymers produced by the reaction of brominated bisphenol A with 1,2-dichloroethane. Examples include brominated epoxy compounds such as diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin, monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin, poly(brominated benzyl acrylate), brominated polyphenylene ether, cyanur chloride and condensates of brominated phenols, brominated polystyrenes such as brominated (polystyrene), poly(brominated styrene), and crosslinked brominated polystyrene, halogenated brominated compound polymers such as crosslinked or non-crosslinked brominated poly(α-methylstyrene), and any combination of two or more of these. Among these, brominated polycarbonates such as homopolymers derived from 2,6-dibromophenol or 2,4-dibromophenol, polycarbonate oligomers produced using brominated bisphenol A as a raw material, and copolymers of the said polycarbonate oligomer and bisphenol A are preferred.

[0059] The upper limit of the content of the bromine-containing flame retardant is 210.0 parts by mass or less, 105.0 parts by mass or less, 63.0 parts by mass or less, 42.0 parts by mass or less, 37.8 parts by mass or less, 33.6 parts by mass or less, 29.4 parts by mass or less, 25.2 parts by mass or less, 23.1 parts by mass or less, 19.2 parts by mass or less, based on 100 parts by mass of the polyol compound. Parts by weight or less, 17.4 parts by weight or less, 15.6 parts by weight or less, 12.0 parts by weight or less, 8.4 parts by weight or less, 6.6 parts by weight or less, 4.8 parts by weight or less, 2.7 parts by weight or less, 2.4 parts by weight or less, 2.1 parts by weight or less, 1.8 parts by weight or less, 1.5 parts by weight or less, 0.9 parts by weight or less, or 0.3 parts by weight or less. The lower limit of the bromine-containing flame retardant content 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, 4.8 parts by mass or more, 6.6 parts by mass or more, 8.4 parts by mass or more, 12.0 parts by mass or more, 15.6 parts by mass or more, 17.4 parts by mass or more, 19.2 parts by mass or more, 23.1 parts by mass or more, 25.2 parts by mass or more, 29.4 parts by mass or more, 33.6 parts by mass or more, 37.8 parts by mass or more, 42.0 parts by mass or more, 63.0 parts by mass or more, 105.0 parts by mass or more, or 210.0 parts by mass or more, per 100 parts by mass of the polyol compound. The content of the bromine-containing flame retardant may be 0.3 parts by mass or more and 210.0 parts by mass or less, 0.9 parts by mass or more and 105.0 parts by mass or less, 1.5 parts by mass or more and 63.0 parts by mass or less, 1.8 parts by mass or more and 42.0 parts by mass or less, 2.1 parts by mass or more and 37.8 parts by mass or less, 2.4 parts by mass or more and 33.6 parts by mass or less, 2.7 parts by mass or more and 29.4 parts by mass or less, 4.8 parts by mass or more and 25.2 parts by mass or less, 6.6 parts by mass or more and 23.1 parts by mass or less, 8.4 parts by mass or more and 19.2 parts by mass or less, or 12.0 parts by mass or more and 17.4 parts by mass or less, per 100 parts by mass of the polyol compound. When the content of the bromine-containing flame retardant is within the above range, it tends to be easier to obtain a polyurethane foam with excellent flame retardancy. When the content of the bromine-containing flame retardant is below the upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content of the bromine-containing flame retardant is above the lower limit, the flame retardant effect derived from the bromine-containing flame retardant is more easily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0060] The upper limit of the content of the aliphatic bromine-containing compound is 70.0 parts by mass or less, 35.0 parts by mass or less, 21.0 parts by mass or less, 14.0 parts by mass or less, 12.6 parts by mass or less, 11.2 parts by mass or less, 9.8 parts by mass or less, 8.4 parts by mass or less, 7.7 parts by mass or less, 6.4 parts by mass or less, based on 100 parts by mass of the polyol compound. Parts by weight or less, 5.8 parts by weight or less, 5.2 parts by weight or less, 4.0 parts by weight or less, 2.8 parts by weight or less, 2.2 parts by weight or less, 1.6 parts by weight or less, 0.9 parts by weight or less, 0.8 parts by weight or less, 0.7 parts by weight or less, 0.6 parts by weight or less, 0.5 parts by weight or less, 0.3 parts by weight or less, or 0.1 parts by weight or less. The lower limit of the content of aliphatic bromine-containing compounds may be 0.1 parts by mass or more, 0.3 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, 1.6 parts by mass or more, 2.2 parts by mass or more, 2.8 parts by mass or more, 4.0 parts by mass or more, 5.2 parts by mass or more, 5.8 parts by mass or more, 6.4 parts by mass or more, 7.7 parts by mass or more, 8.4 parts by mass or more, 9.8 parts by mass or more, 11.2 parts by mass or more, 12.6 parts by mass or more, 14.0 parts by mass or more, 21.0 parts by mass or more, 35.0 parts by mass or more, or 70.0 parts by mass or more, per 100 parts by mass of the polyol compound. The content of the aliphatic bromine-containing compound may be 0.1 parts by mass or more and 70.0 parts by mass or less, 0.3 parts by mass or more and 35.0 parts by mass or less, 0.5 parts by mass or more and 21.0 parts by mass or less, 0.6 parts by mass or more and 14.0 parts by mass or less, 0.7 parts by mass or more and 12.6 parts by mass or less, 0.8 parts by mass or more and 11.2 parts by mass or less, 0.9 parts by mass or more and 9.8 parts by mass or less, 1.6 parts by mass or more and 8.4 parts by mass or less, 2.2 parts by mass or more and 7.7 parts by mass or less, 2.8 parts by mass or more and 6.4 parts by mass or less, or 4.0 parts by mass or more and 5.8 parts by mass or less, per 100 parts by mass of the polyol compound. When the content of the aliphatic bromine-containing compound is within the above range, polyurethane foam with excellent flame retardancy tends to be obtained. When the content of the aliphatic bromine-containing compound is below the above upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foam with particularly excellent flame retardancy tends to be obtained. When the content of aliphatic bromine-containing compounds is above the aforementioned lower limit, the flame-retardant effect derived from the aliphatic bromine-containing compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0061] The upper limit of the content of the aromatic bromine-containing low molecular compound is 70.0 parts by mass or less, 35.0 parts by mass or less, 21.0 parts by mass or less, 14.0 parts by mass or less, 12.6 parts by mass or less, 11.2 parts by mass or less, 9.8 parts by mass or less, 8.4 parts by mass or less, 7.7 parts by mass or less, 6.4 parts by mass or less, based on 100 parts by mass of the polyol compound. The amount may be less than or equal to 5.8 parts by weight, less than or equal to 5.2 parts by weight, less than or equal to 4.0 parts by weight, less than or equal to 2.8 parts by weight, less than or equal to 2.2 parts by weight, less than or equal to 1.6 parts by weight, less than or equal to 0.9 parts by weight, less than or equal to 0.7 parts by weight, less than or equal to 0.6 parts by weight, less than or equal to 0.5 parts by weight, less than or equal to 0.3 parts by weight, or less than or equal to 0.1 parts by weight. The lower limit of the content of aromatic bromine-containing low molecular weight compounds may be 0.1 parts by mass or more, 0.3 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, 1.6 parts by mass or more, 2.2 parts by mass or more, 2.8 parts by mass or more, 4.0 parts by mass or more, 5.2 parts by mass or more, 5.8 parts by mass or more, 6.4 parts by mass or more, 7.7 parts by mass or more, 8.4 parts by mass or more, 9.8 parts by mass or more, 11.2 parts by mass or more, 12.6 parts by mass or more, 14.0 parts by mass or more, 21.0 parts by mass or more, 35.0 parts by mass or more, or 70.0 parts by mass or more, per 100 parts by mass of the polyol compound. The content of aromatic bromine-containing low molecular weight compounds may be 0.1 parts by mass or more and 70.0 parts by mass or less, 0.3 parts by mass or more and 35.0 parts by mass or less, 0.5 parts by mass or more and 21.0 parts by mass or less, 0.6 parts by mass or more and 14.0 parts by mass or less, 0.7 parts by mass or more and 12.6 parts by mass or less, 0.8 parts by mass or more and 11.2 parts by mass or less, 0.9 parts by mass or more and 9.8 parts by mass or less, 1.6 parts by mass or more and 8.4 parts by mass or less, 2.2 parts by mass or more and 7.7 parts by mass or less, 2.8 parts by mass or more and 6.4 parts by mass or less, or 4.0 parts by mass or more and 5.8 parts by mass or less, per 100 parts by mass of the polyol compound. When the content of aromatic bromine-containing low molecular weight compounds is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the content of aromatic bromine-containing low molecular weight compounds is below the aforementioned upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.When the content of aromatic bromine-containing low molecular weight compounds is above the aforementioned lower limit, the flame retardant effect derived from the aromatic bromine-containing low molecular weight compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0062] The upper limit of the content of the aromatic bromine-containing polymer compound is 70.0 parts by mass or less, 35.0 parts by mass or less, 21.0 parts by mass or less, 14.0 parts by mass or less, 12.6 parts by mass or less, 11.2 parts by mass or less, 9.8 parts by mass or less, 8.4 parts by mass or less, 7.7 parts by mass or less, 6.4 parts by mass or less, based on 100 parts by mass of the polyol compound. The amount may be less than or equal to 5.8 parts by weight, less than or equal to 5.2 parts by weight, less than or equal to 4.0 parts by weight, less than or equal to 2.8 parts by weight, less than or equal to 2.2 parts by weight, less than or equal to 1.6 parts by weight, less than or equal to 0.9 parts by weight, less than or equal to 0.7 parts by weight, less than or equal to 0.6 parts by weight, less than or equal to 0.5 parts by weight, less than or equal to 0.3 parts by weight, or less than or equal to 0.1 parts by weight. The lower limit of the content of aromatic bromine-containing polymer compounds may be 0.1 parts by mass or more, 0.3 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, 1.6 parts by mass or more, 2.2 parts by mass or more, 2.8 parts by mass or more, 4.0 parts by mass or more, 5.2 parts by mass or more, 5.8 parts by mass or more, 6.4 parts by mass or more, 7.7 parts by mass or more, 8.4 parts by mass or more, 9.8 parts by mass or more, 11.2 parts by mass or more, 12.6 parts by mass or more, 14.0 parts by mass or more, 21.0 parts by mass or more, 35.0 parts by mass or more, or 70.0 parts by mass or more, per 100 parts by mass of the polyol compound. The content of aromatic bromine-containing polymer compounds may be 0.1 parts by mass or more and 70.0 parts by mass or less, 0.3 parts by mass or more and 35.0 parts by mass or less, 0.5 parts by mass or more and 21.0 parts by mass or less, 0.6 parts by mass or more and 14.0 parts by mass or less, 0.7 parts by mass or more and 12.6 parts by mass or less, 0.8 parts by mass or more and 11.2 parts by mass or less, 0.9 parts by mass or more and 9.8 parts by mass or less, 1.6 parts by mass or more and 8.4 parts by mass or less, 2.2 parts by mass or more and 7.7 parts by mass or less, 2.8 parts by mass or more and 6.4 parts by mass or less, or 4.0 parts by mass or more and 5.8 parts by mass or less, per 100 parts by mass of polyol compound. When the content of aromatic bromine-containing polymer compounds is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the content of aromatic bromine-containing polymer compounds is below the aforementioned 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 aromatic bromine-containing polymer compounds is above the aforementioned lower limit, the flame retardant effect derived from the aromatic bromine-containing polymer compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0063] The content ratios of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing high molecular weight compounds in the polyol composition, polyurethane foam-forming composition, and polyurethane foam are, for example, within the following ranges. The lower limit of the content ratio of aliphatic bromine-containing compounds may be, for example, 1% or more by mass, 2% or more by mass, 3% or more by mass, 5% or more by mass, 10% or more by mass, 15% or more by mass, 20% or more by mass, 25% or more by mass, 30% or more by mass, 35% or more by mass, 40% or more by mass, or 45% or more by mass, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low-molecular-weight compounds, and aromatic bromine-containing high-molecular-weight compounds. The upper limit of the content ratio of aliphatic bromine-containing compounds may be, for example, 99% or less by mass, 96% or less by mass, 93% or less by mass, 90% or less by mass, 85% or less by mass, 80% or less by mass, 75% or less by mass, 70% or less by mass, 65% or less by mass, 60% or less by mass, 55% or less by mass, or 50% or less by mass, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low-molecular-weight compounds, and aromatic bromine-containing high-molecular-weight compounds. The content ratio of aliphatic bromine-containing compounds may be, for example, 1% to 99% by mass, 2% to 96% by mass, 3% to 93% by mass, 5% to 90% by mass, 10% to 85% by mass, 15% to 80% by mass, 20% to 75% by mass, 25% to 70% by mass, 30% to 65% by mass, 35% to 60% by mass, 40% to 55% by mass, or 45% to 50% by mass, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low-molecular-weight compounds, and aromatic bromine-containing polymer compounds. When the content ratio of aliphatic bromine-containing compounds is below the upper limit, the flame retardant effect derived from aromatic bromine-containing low molecular weight compounds and / or aromatic bromine-containing high molecular weight compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content ratio of aliphatic bromine-containing compounds is above the lower limit, the flame retardant effect derived from aliphatic bromine-containing compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0064] The lower limit of the content ratio of aromatic bromine-containing low molecular weight compounds may be, for example, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 4% by mass or more, 8% by mass or more, 12% by mass or more, 16% by mass or more, 20% by mass or more, 24% by mass or more, or 28% by mass or more, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing high molecular weight compounds. The upper limit of the content ratio of aromatic bromine-containing low molecular weight compounds may be, for example, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 52% by mass or less, 48% by mass or less, 44% by mass or less, 40% by mass or less, or 36% by mass or less, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing high molecular weight compounds. The content ratio of aromatic bromine-containing low molecular weight compounds may be, for example, 1% to 95% by mass, 1.5% to 90% by mass, 2% to 80% by mass, 4% to 70% by mass, 8% to 60% by mass, 12% to 52% by mass, 16% to 48% by mass, 20% to 44% by mass, 24% to 40% by mass, or 28% to 36% by mass, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing polymer compounds. When the content ratio of aromatic bromine-containing low molecular weight compounds is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained due to the synergistic effect of the flame retardant effects derived from aromatic bromine-containing low molecular weight compounds, aliphatic bromine-containing compounds, and / or aromatic bromine-containing polymer compounds. When the content ratio of aromatic bromine-containing low molecular weight compounds is below the upper limit, the flame retardant effect derived from aliphatic bromine-containing compounds and / or aromatic bromine-containing high molecular weight compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content ratio of aromatic bromine-containing low molecular weight compounds is above the lower limit, the flame retardant effect derived from aromatic bromine-containing low molecular weight compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0065] The lower limit of the content ratio of aromatic bromine-containing polymer compounds may be, for example, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 4% by mass or more, 8% by mass or more, 12% by mass or more, 16% by mass or more, 20% by mass or more, 24% by mass or more, or 28% by mass or more, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing polymer compounds. The upper limit of the content ratio of aromatic bromine-containing polymer compounds may be, for example, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 52% by mass or less, 48% by mass or less, 44% by mass or less, 40% by mass or less, or 36% by mass or less, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing polymer compounds. The content ratio of aromatic bromine-containing polymer compounds may be, for example, 1% to 95% by mass, 1.5% to 90% by mass, 2% to 80% by mass, 4% to 70% by mass, 8% to 60% by mass, 12% to 52% by mass, 16% to 48% by mass, 20% to 44% by mass, 24% to 40% by mass, or 28% to 36% by mass, relative to the sum of the content of aliphatic bromine-containing compounds, aromatic bromine-containing low molecular weight compounds, and aromatic bromine-containing polymer compounds. When the content ratio of aromatic bromine-containing polymer compounds is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained due to the synergistic effect of the flame retardant effects derived from aromatic bromine-containing polymer compounds, aliphatic bromine-containing compounds, and / or aromatic bromine-containing low molecular weight compounds. When the content ratio of aromatic bromine-containing polymer compounds is below the upper limit, the flame retardant effect derived from aliphatic bromine-containing compounds and / or aromatic bromine-containing low molecular weight compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content ratio of aromatic bromine-containing polymer compounds is above the lower limit, the flame retardant effect derived from aromatic bromine-containing polymer compounds is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0066] Using two bromine-containing flame retardants with different decomposition temperatures in combination tends to yield polyurethane foams with even better flame retardancy than using a single bromine-containing flame retardant. Furthermore, using three bromine-containing flame retardants with different decomposition temperatures in combination tends to yield polyurethane foams with even better flame retardancy than using two bromine-containing flame retardants.

[0067] In particular, using two or more bromine-containing flame retardants selected from among bromine-containing flame retardants with a decomposition temperature of less than 370°C, bromine-containing flame retardants with a decomposition temperature of 370°C to less than 450°C, and bromine-containing flame retardants with a decomposition temperature of 450°C or higher tends to yield polyurethane foams with particularly excellent flame retardancy. In other words, the first bromine-containing flame retardant is one selected from the following three: (i) to (iii): (i) Bromine-containing flame retardants with a decomposition temperature of less than 370°C (ii) Bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C, (iii) Bromine-containing flame retardants with a decomposition temperature of 450°C or higher; It is preferable that the second bromine-containing flame retardant is one selected from the other two, excluding the one selected from the three (i) to (iii). Here, the difference between the decomposition temperature of the first bromine-containing flame retardant and the decomposition temperature of the second bromine-containing flame retardant may be 15°C or higher, 20°C or higher, 25°C or higher, 30°C or higher, 35°C or higher, 40°C or higher, 45°C or higher, or 50°C or higher, and may be 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 90°C or lower, 80°C or lower, 70°C or lower, or 60°C or lower.

[0068] Examples of bromine-containing flame retardants with a decomposition temperature of less than 370°C include 2,4,6-tris(2,4-dibromopropyl)-1,3,5-triazine (Pyroguard SR-740N), 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] (Pyroguard SR-720), and 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2-methyl-2,3-dibromopropyloxy)benzene] (Pyroguard SR-130). Among these, 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] is preferred.

[0069] Examples of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C include 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (Pyroguard SR-245) and ethylenebis(pentabromophenyl).

[0070] Examples of bromine-containing flame retardants with 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).

[0071] The upper limit for the content of a bromine-containing flame retardant with a decomposition temperature of less than 370°C may be 70.0 parts by mass or less, 35.0 parts by mass or less, 21.0 parts by mass or less, 14.0 parts by mass or less, 12.6 parts by mass or less, 11.2 parts by mass or less, 9.8 parts by mass or less, 8.4 parts by mass or less, 7.7 parts by mass or less, 6.4 parts by mass or less, 5.8 parts by mass or less, 5.2 parts by mass or less, 4.0 parts by mass or less, 2.8 parts by mass or less, 2.2 parts by mass or less, 1.6 parts 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, 0.3 parts by mass or less, or 0.1 parts by mass or less, per 100 parts by mass of the polyol compound. The lower limit of the content of a bromine-containing flame retardant with a decomposition temperature of less than 370°C may be 0.1 parts by mass or more, 0.3 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, 1.6 parts by mass or more, 2.2 parts by mass or more, 2.8 parts by mass or more, 4.0 parts by mass or more, 5.2 parts by mass or more, 5.8 parts by mass or more, 6.4 parts by mass or more, 7.7 parts by mass or more, 8.4 parts by mass or more, 9.8 parts by mass or more, 11.2 parts by mass or more, 12.6 parts by mass or more, 14.0 parts by mass or more, 21.0 parts by mass or more, 35.0 parts by mass or more, or 70.0 parts by mass or more, per 100 parts by mass of the polyol compound. The content of bromine-containing flame retardants with a decomposition temperature of less than 370°C may be 0.1 parts by mass or more and 70.0 parts by mass or less, 0.3 parts by mass or more and 35.0 parts by mass or less, 0.5 parts by mass or more and 21.0 parts by mass or less, 0.6 parts by mass or more and 14.0 parts by mass or less, 0.7 parts by mass or more and 12.6 parts by mass or less, 0.8 parts by mass or more and 11.2 parts by mass or less, 0.9 parts by mass or more and 9.8 parts by mass or less, 1.6 parts by mass or more and 8.4 parts by mass or less, 2.2 parts by mass or more and 7.7 parts by mass or less, 2.8 parts by mass or more and 6.4 parts by mass or less, or 4.0 parts by mass or more and 5.8 parts by mass or less, per 100 parts by mass of the polyol compound. When the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the amount of bromine-containing flame retardant with a decomposition temperature of less than 370°C is below the aforementioned upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.When the amount of bromine-containing flame retardant with a decomposition temperature of less than 370°C is above the aforementioned lower limit, the flame retardant effect derived from the bromine-containing flame retardant with a decomposition temperature of less than 370°C is more likely to be exhibited, and polyurethane foam with particularly excellent flame retardancy tends to be obtained.

[0072] The upper limit for the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C may be 70.0 parts by mass or less, 35.0 parts by mass or less, 21.0 parts by mass or less, 14.0 parts by mass or less, 12.6 parts by mass or less, 11.2 parts by mass or less, 9.8 parts by mass or less, 8.4 parts by mass or less, 7.7 parts by mass or less, 6.4 parts by mass or less, 5.8 parts by mass or less, 5.2 parts by mass or less, 4.0 parts by mass or less, 2.8 parts by mass or less, 2.2 parts by mass or less, 1.6 parts 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, 0.3 parts by mass or less, or 0.1 parts by mass or less, per 100 parts by mass of the polyol compound. The lower limit of the content of a bromine-containing flame retardant with a decomposition temperature of 370°C or higher and less than 450°C may be 0.1 parts by mass or more, 0.3 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, 1.6 parts by mass or more, 2.2 parts by mass or more, 2.8 parts by mass or more, 4.0 parts by mass or more, 5.2 parts by mass or more, 5.8 parts by mass or more, 6.4 parts by mass or more, 7.7 parts by mass or more, 8.4 parts by mass or more, 9.8 parts by mass or more, 11.2 parts by mass or more, 12.6 parts by mass or more, 14.0 parts by mass or more, 21.0 parts by mass or more, 35.0 parts by mass or more, or 70.0 parts by mass or more, per 100 parts by mass of the polyol compound. The content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C may be 0.1 parts by mass or more and 70.0 parts by mass or less, 0.3 parts by mass or more and 35.0 parts by mass or less, 0.5 parts by mass or more and 21.0 parts by mass or less, 0.6 parts by mass or more and 14.0 parts by mass or less, 0.7 parts by mass or more and 12.6 parts by mass or less, 0.8 parts by mass or more and 11.2 parts by mass or less, 0.9 parts by mass or more and 9.8 parts by mass or less, 1.6 parts by mass or more and 8.4 parts by mass or less, 2.2 parts by mass or more and 7.7 parts by mass or less, 2.8 parts by mass or more and 6.4 parts by mass or less, or 4.0 parts by mass or more and 5.8 parts by mass or less, per 100 parts by mass of the polyol compound. When the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the content of bromine-containing flame retardants with a decomposition temperature of 370°C to less than 450°C is below the aforementioned upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.When the amount of bromine-containing flame retardant with a decomposition temperature of 370°C or higher but less than 450°C is above the aforementioned lower limit, the flame retardant effect derived from the bromine-containing flame retardant with a decomposition temperature of 370°C or higher but less than 450°C is more likely to be exhibited, and polyurethane foam with particularly excellent flame retardancy tends to be obtained.

[0073] The upper limit for the content of a bromine-containing flame retardant with a decomposition temperature of 450°C or higher may be 70.0 parts by mass or less, 35.0 parts by mass or less, 21.0 parts by mass or less, 14.0 parts by mass or less, 12.6 parts by mass or less, 11.2 parts by mass or less, 9.8 parts by mass or less, 8.4 parts by mass or less, 7.7 parts by mass or less, 6.4 parts by mass or less, 5.8 parts by mass or less, 5.2 parts by mass or less, 4.0 parts by mass or less, 2.8 parts by mass or less, 2.2 parts by mass or less, 1.6 parts 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, 0.3 parts by mass or less, or 0.1 parts by mass or less, per 100 parts by mass of the polyol compound. The lower limit of the content of a bromine-containing flame retardant with a decomposition temperature of 450°C or higher may be 0.1 parts by mass or more, 0.3 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, 1.6 parts by mass or more, 2.2 parts by mass or more, 2.8 parts by mass or more, 4.0 parts by mass or more, 5.2 parts by mass or more, 5.8 parts by mass or more, 6.4 parts by mass or more, 7.7 parts by mass or more, 8.4 parts by mass or more, 9.8 parts by mass or more, 11.2 parts by mass or more, 12.6 parts by mass or more, 14.0 parts by mass or more, 21.0 parts by mass or more, 35.0 parts by mass or more, or 70.0 parts by mass or more, per 100 parts by mass of the polyol compound. The content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher may be 0.1 parts by mass or more and 70.0 parts by mass or less, 0.3 parts by mass or more and 35.0 parts by mass or less, 0.5 parts by mass or more and 21.0 parts by mass or less, 0.6 parts by mass or more and 14.0 parts by mass or less, 0.7 parts by mass or more and 12.6 parts by mass or less, 0.8 parts by mass or more and 11.2 parts by mass or less, 0.9 parts by mass or more and 9.8 parts by mass or less, 1.6 parts by mass or more and 8.4 parts by mass or less, 2.2 parts by mass or more and 7.7 parts by mass or less, 2.8 parts by mass or more and 6.4 parts by mass or less, or 4.0 parts by mass or more and 5.8 parts by mass or less, per 100 parts by mass of the polyol compound. When the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is below the aforementioned upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.When the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is above the aforementioned lower limit, the flame retardant effect derived from the bromine-containing flame retardants with a decomposition temperature of 450°C or higher is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0074] The content ratios of bromine-containing flame retardants with a decomposition temperature of less than 370°C, bromine-containing flame retardants with a decomposition temperature of 370°C or more and less than 450°C, and bromine-containing flame retardants with a decomposition temperature of 450°C or more in the polyol composition, polyurethane foam-forming composition, and polyurethane foam are, for example, within the following ranges. The lower limit of the content ratio of bromine-containing flame retardants with a decomposition temperature of less than 370°C may be, for example, 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, or 45% by mass or more, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or more and less than 450°C, and the content of bromine-containing flame retardants with a decomposition temperature of 450°C or more. The upper limit for the content ratio of bromine-containing flame retardants with a decomposition temperature of less than 370°C may be, for example, 99% by mass or less, 96% by mass or less, 93% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or more and less The content ratio of bromine-containing flame retardants with a decomposition temperature of less than 370°C may be, for example, 1% to 99% by mass, 2% to 96% by mass, 3% to 93% by mass, 5% to 90% by mass, 10% to 85% by mass, 15% to 80% by mass, 20% to 75% by mass, 25% to 70% by mass, 30% to 65% by mass, 35% to 60% by mass, 40% to 55% by mass, or 45% to 50% by mass, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, bromine-containing flame retardants with a decomposition temperature of 370°C or more and less than 450°C, and bromine-containing flame retardants with a decomposition temperature of 450°C or more. When the content ratio of bromine-containing flame retardants with a decomposition temperature of less than 370°C is within the aforementioned range, a polyurethane foam with excellent flame retardancy tends to be obtained due to the synergistic effect of the flame retardant effects derived from the bromine-containing flame retardant with a decomposition temperature of less than 370°C, the bromine-containing flame retardant with a decomposition temperature of 370°C or more and less than 450°C, and / or the bromine-containing flame retardant with a decomposition temperature of 450°C or higher.When the content ratio of bromine-containing flame retardants with a decomposition temperature of less than 370°C is below the upper limit, the flame retardant effect derived from bromine-containing flame retardants with a decomposition temperature of 370°C or more and / or bromine-containing flame retardants with a decomposition temperature of 450°C or more tends to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content ratio of bromine-containing flame retardants with a decomposition temperature of less than 370°C is above the lower limit, the flame retardant effect derived from bromine-containing flame retardants with a decomposition temperature of less than 370°C tends to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0075] The lower limit of the content ratio of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C may be, for example, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 4% by mass or more, 8% by mass or more, 12% by mass or more, 16% by mass or more, 20% by mass or more, 24% by mass or more, or 28% by mass or more, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and less than 450°C, and the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher. The upper limit of the content ratio of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C may be, for example, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 52% by mass or less, 48% by mass or less, 44% by mass or less, 40% by mass or less, or 36% by mass or less, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C, and the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher. The content ratio of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C may be, for example, 1% by mass or more and 95% by mass or less, 1.5% by mass or more and 90% by mass or less, 2% by mass or more and 80% by mass or less, 4% by mass or more and 70% by mass or less, 8% by mass or more and 60% by mass or less, 12% by mass or more and 52% by mass or less, 16% by mass or more and 48% by mass or less, 20% by mass or more and 44% by mass or less, 24% by mass or more and 40% by mass or less, or 28% by mass or more and 36% by mass or less, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C, and the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher. When the content ratio of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C is within the aforementioned range, a polyurethane foam with excellent flame retardancy tends to be obtained due to the synergistic effect of the flame retardant effects derived from the bromine-containing flame retardant with a decomposition temperature of 370°C or higher but less than 450°C and the bromine-containing flame retardant with a decomposition temperature of less than 370°C and / or the bromine-containing flame retardant with a decomposition temperature of 450°C or higher.If the content ratio of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C is below the upper limit, the flame retardant effect derived from bromine-containing flame retardants with a decomposition temperature of less than 370°C and / or bromine-containing flame retardants with a decomposition temperature of 450°C or higher tends to be more readily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. If the content ratio of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C is above the lower limit, the flame retardant effect derived from bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C tends to be more readily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0076] The lower limit of the content ratio of bromine-containing flame retardants with a decomposition temperature of 450°C or higher may be, for example, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 4% by mass or more, 8% by mass or more, 12% by mass or more, 16% by mass or more, 20% by mass or more, 24% by mass or more, or 28% by mass or more, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher. The upper limit of the content ratio of bromine-containing flame retardants with a decomposition temperature of 450°C or higher may be, for example, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 52% by mass or less, 48% by mass or less, 44% by mass or less, 40% by mass or less, or 36% by mass or less, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, the content of bromine-containing flame retardants with a decomposition temperature of 370°C or higher and the content of bromine-containing flame retardants with a decomposition temperature of 450°C or higher. The content ratio of bromine-containing flame retardants with a decomposition temperature of 450°C or higher may be, for example, 1% to 95% by mass, 1.5% to 90% by mass, 2% to 80% by mass, 4% to 70% by mass, 8% to 60% by mass, 12% to 52% by mass, 16% to 48% by mass, 20% to 44% by mass, 24% to 40% by mass, or 28% to 36% by mass, relative to the sum of the content of bromine-containing flame retardants with a decomposition temperature of less than 370°C, bromine-containing flame retardants with a decomposition temperature of 370°C or higher or less than 450°C, and bromine-containing flame retardants with a decomposition temperature of 450°C or higher. When the content ratio of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is within the aforementioned range, a polyurethane foam with excellent flame retardancy tends to be obtained due to the synergistic effect of the flame retardant effects derived from the bromine-containing flame retardant with a decomposition temperature of 450°C or higher, the bromine-containing flame retardant with a decomposition temperature of less than 370°C, and / or the bromine-containing flame retardant with a decomposition temperature of 370°C or higher but less than 450°C. When the content ratio of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is below the aforementioned upper limit, the flame retardant effect derived from the bromine-containing flame retardant with a decomposition temperature of less than 370°C and / or the bromine-containing flame retardant with a decomposition temperature of 370°C or higher but less than 450°C becomes more readily apparent, and a polyurethane foam with particularly excellent flame retardancy tends to be obtained.When the content ratio of bromine-containing flame retardants with a decomposition temperature of 450°C or higher is above the aforementioned lower limit, the flame retardant effect derived from the bromine-containing flame retardants with a decomposition temperature of 450°C or higher is more likely to be exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0077] (Boron-containing flame retardant) Examples of boron-containing flame retardants include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate; alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate; zirconium borate, zinc borate, aluminum borate, and ammonium borate; and any combination of two or more of these. Among these, zinc borate is preferred.

[0078] The upper limit of the content of the boron-containing flame retardant is 303.0 parts by mass or less, 151.5 parts by mass or less, 90.9 parts by mass or less, 60.6 parts by mass or less, 54.5 parts by mass or less, 48.5 parts by mass or less, 42.4 parts by mass or less, 36.4 parts by mass or less, 33.3 parts by mass or less, 27.8 parts by mass or less, based on 100 parts by mass of the polyol compound. It may be 25.2 parts by mass or less, 22.7 parts by mass or less, 17.7 parts by mass or less, 12.6 parts by mass or less, 10.1 parts by mass or less, 7.5 parts by mass or less, 4.5 parts by mass or less, 4.0 parts by mass or less, 3.5 parts by mass or less, 3.0 parts by mass or less, 2.5 parts by mass or less, 1.5 parts by mass or less, 0.5 parts by mass or less, or 0.1 parts by mass or less. The lower limit of the boron-containing flame retardant content may be 0.1 parts by mass or more, 0.5 parts by mass or more, 1.5 parts by mass or more, 2.5 parts by mass or more, 3.0 parts by mass or more, 3.5 parts by mass or more, 4.0 parts by mass or more, 4.5 parts by mass or more, 7.5 parts by mass or more, 10.1 parts by mass or more, 12.6 parts by mass or more, 17.7 parts by mass or more, 22.7 parts by mass or more, 25.2 parts by mass or more, 27.8 parts by mass or more, 33.3 parts by mass or more, 36.4 parts by mass or more, 42.4 parts by mass or more, 48.5 parts by mass or more, 54.5 parts by mass or more, 60.6 parts by mass or more, 90.9 parts by mass or more, 151.5 parts by mass or more, or 303.0 parts by mass or more, per 100 parts by mass of the polyol compound. The content of the boron-containing flame retardant may be 0.1 parts by mass or more and 303.0 parts by mass or less, 0.5 parts by mass or more and 151.5 parts by mass or less, 1.5 parts by mass or more and 90.9 parts by mass or less, 2.5 parts by mass or more and 60.6 parts by mass or less, 3.0 parts by mass or more and 54.5 parts by mass or less, 3.5 parts by mass or more and 48.5 parts by mass or less, 4.0 parts by mass or more and 42.4 parts by mass or less, 4.5 parts by mass or more and 36.4 parts by mass or less, 7.5 parts by mass or more and 33.3 parts by mass or less, 10.1 parts by mass or more and 27.8 parts by mass or less, 12.6 parts by mass or more and 25.2 parts by mass or less, or 17.7 parts by mass or more and 22.7 parts by mass or less, per 100 parts by mass of the polyol compound. When the content of the boron-containing flame retardant is within the above range, it tends to be easier to obtain a polyurethane foam with excellent flame retardancy. When the content of the boron-containing flame retardant is below the aforementioned upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.When the content of the boron-containing flame retardant is above the aforementioned lower limit, the flame retardant effect derived from the boron-containing flame retardant is more easily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0079] The upper limit for the sum of the solid phosphorus-containing flame retardant, bromine-containing flame retardant, and boron-containing flame retardant content is 1000.0 parts by mass or less, 500.0 parts by mass or less, 300.0 parts by mass or less, 200.0 parts by mass or less, 180.0 parts by mass or less, 160.0 parts by mass or less, 140.0 parts by mass or less, 120.0 parts by mass or less, and 110 parts by mass per 100 parts by mass of the polyol compound. The amount may be 0.0 parts by mass or less, 91.6 parts by mass or less, 83.2 parts by mass or less, 74.8 parts by mass or less, 58.0 parts by mass or less, 41.2 parts by mass or less, 32.8 parts by mass or less, 24.4 parts by mass or less, 14.4 parts by mass or less, 12.8 parts by mass or less, 11.2 parts by mass or less, 9.6 parts by mass or less, 8.0 parts by mass or less, 4.8 parts by mass or less, 1.6 parts by mass or less, or 0.2 parts by mass or less. The lower limit of the sum of the content of solid phosphorus-containing flame retardant, bromine-containing flame retardant, and boron-containing flame retardant is 0.2 parts by mass or more, 1.6 parts by mass or more, 4.8 parts by mass or more, 8.0 parts by mass or more, 9.6 parts by mass or more, 11.2 parts by mass or more, 12.8 parts by mass or more, 14.4 parts by mass or more, 24.4 parts by mass or more, or 32.8 parts by mass or more per 100 parts by mass of the polyol compound. The above amounts may be 41.2 parts by mass or more, 58.0 parts by mass or more, 74.8 parts by mass or more, 83.2 parts by mass or more, 91.6 parts by mass or more, 110.0 parts by mass or more, 120.0 parts by mass or more, 140.0 parts by mass or more, 160.0 parts by mass or more, 180.0 parts by mass or more, 200.0 parts by mass or more, 300.0 parts by mass or more, 500.0 parts by mass or more, or 1000.0 parts by mass or more. The total amount of solid phosphorus-containing flame retardant, bromine-containing flame retardant, and boron-containing flame retardant may be 0.2 parts by mass or more and 1000.0 parts by mass or less, 1.6 parts by mass or more and 500.0 parts by mass or less, 4.8 parts by mass or more and 300.0 parts by mass or less, 8.0 parts by mass or more and 200.0 parts by mass or less, 9.6 parts by mass or more and 180.0 parts by mass or less, 11.2 parts by mass or more and 160.0 parts by mass or less, 12.8 parts by mass or more and 140.0 parts by mass or less, 14.4 parts by mass or more and 120.0 parts by mass or less, 24.4 parts by mass or more and 110.0 parts by mass or less, 32.8 parts by mass or more and 91.6 parts by mass or less, 41.2 parts by mass or more and 83.2 parts by mass or less, or 58.0 parts by mass or more and 74.8 parts by mass or less, per 100 parts by mass of the polyol compound. When the sum of the content of solid phosphorus-containing flame retardant, bromine-containing flame retardant, and boron-containing flame retardant is within the aforementioned range, a polyurethane foam with excellent flame retardancy tends to be obtained. When the sum of the content of solid phosphorus-containing flame retardant, bromine-containing flame retardant, and boron-containing flame retardant is below the aforementioned upper limit, the rate of formation of isocyanurate groups from unreacted isocyanate groups increases, and a polyurethane foam with particularly excellent flame retardancy tends to be obtained. When the sum of the content of solid phosphorus-containing flame retardant, bromine-containing flame retardant, and boron-containing flame retardant is above the aforementioned lower limit, the flame retardant effect derived from the flame retardant is more easily exhibited, and a polyurethane foam with particularly excellent flame retardancy tends to be obtained.

[0080] The content ratios of solid phosphorus-containing flame retardants, bromine-containing flame retardants, and boron-containing flame retardants in the polyol composition, polyurethane foam-forming composition, and polyurethane foam are, for example, within the following ranges. The lower limit of the content ratio of solid phosphorus-containing flame retardant may be, for example, 3% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, or 45% by mass or more, relative to the sum of the content of solid phosphorus-containing flame retardant, bromine-containing flame retardant, and boron-containing flame retardant. The upper limit of the content ratio of solid phosphorus-containing flame retardant may be, for example, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less, relative to the sum of the content of solid phosphorus-containing flame retardant, bromine-containing flame retardant, and boron-containing flame retardant. The content ratio of the solid phosphorus-containing flame retardant may be, for example, 3% to 95% by mass, 5% to 90% by mass, 10% to 85% by mass, 15% to 80% by mass, 20% to 75% by mass, 25% to 70% by mass, 30% to 65% by mass, 35% to 60% by mass, 40% to 55% by mass, or 45% to 50% by mass, relative to the sum of the solid phosphorus-containing flame retardant content, bromine-containing flame retardant content, and boron-containing flame retardant content. When the content ratio of the solid phosphorus-containing flame retardant is within the above range, a polyurethane foam with excellent flame retardancy tends to be obtained due to the synergistic effect of the flame retardant effects derived from the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and / or the boron-containing flame retardant. When the content ratio of the solid phosphorus-containing flame retardant is below the upper limit, the flame retardant effect derived from the bromine-containing flame retardant and / or boron-containing flame retardant tends to be more readily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content ratio of the solid phosphorus-containing flame retardant is above the lower limit, the flame retardant effect derived from the solid phosphorus-containing flame retardant tends to be more readily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0081] The lower limit of the bromine-containing flame retardant content ratio may be, for example, 3% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, or 45% by mass or more, relative to the sum of the solid phosphorus-containing flame retardant content, the bromine-containing flame retardant content, and the boron-containing flame retardant content. The upper limit of the bromine-containing flame retardant content ratio may be, for example, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less, relative to the sum of the solid phosphorus-containing flame retardant content, the bromine-containing flame retardant content, and the boron-containing flame retardant content. The content ratio of the bromine-containing flame retardant may be, for example, 3% to 95% by mass, 5% to 90% by mass, 10% to 85% by mass, 15% to 80% by mass, 20% to 75% by mass, 25% to 70% by mass, 30% to 65% by mass, 35% to 60% by mass, 40% to 55% by mass, or 45% to 50% by mass, relative to the sum of the content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. When the content ratio 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 retardant effects 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 below the upper limit, the flame retardant effect derived from the boron-containing flame retardant and / or solid phosphorus-containing flame retardant tends to be more readily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content ratio of the bromine-containing flame retardant is above the lower limit, the flame retardant effect derived from the bromine-containing flame retardant tends to be more readily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0082] The lower limit of the content ratio of the boron-containing flame retardant may be, for example, 2% by mass or more, 3% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, or 35% by mass or more, relative to the sum of the content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. The upper limit of the content ratio of the boron-containing flame retardant may be, for example, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less, relative to the sum of the content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. The content ratio of the boron-containing flame retardant may be, for example, 2% to 85% by mass, 3% to 80% by mass, 5% to 75% by mass, 7% to 70% by mass, 10% to 65% by mass, 15% to 60% by mass, 20% to 55% by mass, 25% to 50% by mass, 30% to 45% by mass, or 35% to 40% by mass, relative to the sum of the content of the solid phosphorus-containing flame retardant, the bromine-containing flame retardant, and the boron-containing flame retardant. When the content ratio 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 retardant effects 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 below the upper limit, the flame retardant effect derived from the bromine-containing flame retardant and / or solid phosphorus-containing flame retardant tends to be more readily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the content ratio of the boron-containing flame retardant is above the lower limit, the flame retardant effect derived from the boron-containing flame retardant tends to be more readily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0083] The polyol composition and the polyurethane foam-forming composition may contain solid flame retardants other than solid phosphorus-containing flame retardants, bromine-containing flame retardants, and boron-containing flame retardants. Either the polyisocyanate composition or the polyol composition may contain solid flame retardants other than solid phosphorus-containing flame retardants, bromine-containing flame retardants, and boron-containing flame retardants, or both may contain them. Examples of solid flame retardants other than solid phosphorus-containing flame retardants, bromine-containing flame retardants, and boron-containing flame retardants include antimony-containing flame retardants, metal hydroxide-based flame retardants, phosphazenes, silicone-based flame retardants, and organic sulfonate-based flame retardants. Two or more of these solid flame retardants may be used in combination.

[0084] [Antimony-containing flame retardant] Examples of antimony-containing flame retardants include antimony oxide, antimonate salts, pyroantimonate salts, and any combination of two or more of these. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonate salts include sodium antimonate and potassium antimonate, and any combination of two or more of these. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate, and any combination of two or more of these. Antimony-containing flame retardants are preferably antimony oxide.

[0085] [Metal hydroxide-based flame retardants] Examples of metal hydroxide-based flame retardants include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, and any combination of two or more of these.

[0086] The upper limit of the content of the solid flame retardant is 1000.0 parts by mass or less, 500.0 parts by mass or less, 300.0 parts by mass or less, 200.0 parts by mass or less, 180.0 parts by mass or less, 160.0 parts by mass or less, 140.0 parts by mass or less, 120.0 parts by mass or less, 110.0 parts by mass or less, 91.6 parts by mass or less, based on 100 parts by mass of the polyol compound. It may be 83.2 parts by mass or less, 74.8 parts by mass or less, 58.0 parts by mass or less, 41.2 parts by mass or less, 32.8 parts by mass or less, 24.4 parts by mass or less, 14.4 parts by mass or less, 12.8 parts by mass or less, 11.2 parts by mass or less, 9.6 parts by mass or less, 8.0 parts by mass or less, 4.8 parts by mass or less, 1.6 parts by mass or less, or 0.2 parts by mass or less. The lower limit of the solid flame retardant content may be 0.2 parts by mass or more, 1.6 parts by mass or more, 4.8 parts by mass or more, 8.0 parts by mass or more, 9.6 parts by mass or more, 11.2 parts by mass or more, 12.8 parts by mass or more, 14.4 parts by mass or more, 24.4 parts by mass or more, 25.0 parts by mass or more, 32.8 parts by mass or more, 41.2 parts by mass or more, 58.0 parts by mass or more, 74.8 parts by mass or more, 83.2 parts by mass or more, 91.6 parts by mass or more, 110.0 parts by mass or more, 120.0 parts by mass or more, 140.0 parts by mass or more, 160.0 parts by mass or more, 180.0 parts by mass or more, 200.0 parts by mass or more, 300.0 parts by mass or more, 500.0 parts by mass or more, or 1000.0 parts by mass or more, per 100 parts by mass of the polyol compound. The content of the solid flame retardant may be 0.2 parts by mass or more and 1000 parts by mass or less, 1.6 parts by mass or more and 500 parts by mass or less, 4.8 parts by mass or more and 300 parts by mass or less, 8.0 parts by mass or more and 200 parts by mass or less, 9.6 parts by mass or more and 180 parts by mass or less, 11.2 parts by mass or more and 160 parts by mass or less, 12.8 parts by mass or more and 140 parts by mass or less, 14.4 parts by mass or more and 120 parts by mass or less, 24.4 parts by mass or more and 110.0 parts by mass or less, 25.0 parts by mass or more and 110.0 parts by mass or less, 25.0 parts by mass or more and 91.6 parts by mass or less, 32.8 parts by mass or more and 91.6 parts by mass or less, 41.2 parts by mass or more and 83.2 parts by mass or less, or 58.0 parts by mass or more and 74.8 parts by mass or less, per 100 parts by mass of the polyol compound. When the content of the solid flame retardant is within the aforementioned range, it is easier to obtain a polyurethane foam with excellent flame retardancy.When the solid flame retardant content is below the upper limit, the rate of conversion from unreacted isocyanate groups to isocyanurate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the solid flame retardant content is above the lower limit, the flame retardant effect derived from the flame retardant is more easily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0087] (Inorganic filler) The polyol composition and the polyurethane foam-forming composition may contain inorganic fillers to the extent that they do not impair the effects of one aspect of the present disclosure. Either the polyisocyanate composition or the polyol composition may contain inorganic fillers, or both may contain them. Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salts such as calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica pulp, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon pulp, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum porate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, etc., and any combination of two or more of these.

[0088] From the viewpoint of foaming properties of polyurethane foam, the inorganic filler content is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, even more preferably 3 to 20% by mass, particularly preferably 4 to 15% by mass, and most preferably 5 to 10% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam forming composition.

[0089] [Liquid flame retardant] The polyol composition and the polyurethane foam-forming composition may contain a liquid flame retardant. Either the polyisocyanate composition or the polyol composition may contain a liquid flame retardant, or both may contain one. Examples of liquid flame retardants include phosphate ester-based flame retardants such as monophosphate esters and condensed phosphate esters. In particular, it is preferable to use phosphate ester-based flame retardants as the liquid flame retardant. Examples of monophosphate esters, though not particularly limited, include trimethyl phosphate, triethyl phosphate, tributoxyethyl phosphate, tributyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresylphenyl phosphate, dimethylmethyl phosphonate, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, tris(β-chloropropyl) phosphate, and any combination of two or more of these. The condensed phosphate esters are not particularly limited, but examples include resorcinol polyphenyl phosphate (product name CR-733S, manufactured by Daihachi Chemical Co., Ltd.), bisphenol A polycresyl phosphate (product name CR-741, manufactured by Daihachi Chemical Co., Ltd.), and aromatic condensed phosphate esters. Among these, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, and tris(β-chloropropyl) phosphate are preferred.

[0090] The upper limit of the content of liquid flame retardant is 1450.0 parts by mass or less, 725.0 parts by mass or less, 435.0 parts by mass or less, 290.0 parts by mass based on 100 parts by mass of the polyol compound. parts by mass or less, 261.0 parts by mass or less, 232.0 parts by mass or less, 203.0 parts by mass or less, 174.0 parts by mass or less, 159.5 parts by mass or less, 142.0 parts by mass or less, 139.0 parts by mass or less Parts by mass or less, 136.0 parts by mass or less, 130.0 parts by mass or less, 124.0 parts by mass or less, 121.0 parts by mass or less, 118.0 parts by mass or less, 103.5 parts by mass or less, 92. It may be 0 parts by weight or less, 80.5 parts by weight or less, 69.0 parts by weight or less, 57.5 parts by weight or less, 34.5 parts by weight or less, 11.5 parts by weight or less, or 1.2 parts by weight or less. The lower limit of the liquid flame retardant content may be 1.2 parts by mass or more, 11.5 parts by mass or more, 34.5 parts by mass or more, 57.5 parts by mass or more, 69.0 parts by mass or more, 80.5 parts by mass or more, 92.0 parts by mass or more, 103.5 parts by mass or more, 118.0 parts by mass or more, 121.0 parts by mass or more, 124.0 parts by mass or more, 130.0 parts by mass or more, 136.0 parts by mass or more, 139.0 parts by mass or more, 142.0 parts by mass or more, 159.5 parts by mass or more, 174.0 parts by mass or more, 203.0 parts by mass or more, 232.0 parts by mass or more, 261.0 parts by mass or more, 290.0 parts by mass or more, 435.0 parts by mass or more, 725.0 parts by mass or more, or 1450.0 parts by mass or more, per 100 parts by mass of the polyol compound. The liquid flame retardant content may be 1.2 parts by mass or more and 1450 parts by mass or less, 11.5 parts by mass or more and 725 parts by mass or less, 34.5 parts by mass or more and 435 parts by mass or less, 57.5 parts by mass or more and 290 parts by mass or less, 69.0 parts by mass or more and 261 parts by mass or less, 80.5 parts by mass or more and 232 parts by mass or less, 92.0 parts by mass or more and 203.0 parts by mass or less, 103.5 parts by mass or more and 174 parts by mass or less, 118.0 parts by mass or more and 159.5 parts by mass or less, 121.0 parts by mass or more and 142.0 parts by mass or less, 124.0 parts by mass or more and 139.0 parts by mass or less, or 130.0 parts by mass or more and 136.0 parts by mass or less, per 100 parts by mass of the polyol compound. When the liquid flame retardant content is within the above range, it tends to be easier to obtain a polyurethane foam with excellent flame retardancy.When the liquid flame retardant content is below the upper limit, the rate of conversion from unreacted isocyanate groups to isocyanurate groups increases, and polyurethane foams with particularly excellent flame retardancy tend to be obtained. When the liquid flame retardant content is above the lower limit, the flame retardant effect derived from the flame retardant is more easily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0091] The upper limit for the total content of solid and liquid flame retardants may be 2400 parts by mass or less, 1200 parts by mass or less, 720 parts by mass or less, 480 parts by mass or less, 432 parts by mass or less, 384 parts by mass or less, 336 parts by mass or less, 288 parts by mass or less, 264 parts by mass or less, 229 parts by mass or less, 218 parts by mass or less, 207 parts by mass or less, 185 parts by mass or less, 163 parts by mass or less, 152 parts by mass or less, 141 parts by mass or less, 117 parts by mass or less, 104 parts by mass or less, 91 parts by mass or less, 78 parts by mass or less, 65 parts by mass or less, 39 parts by mass or less, 13 parts by mass or less, or 1 part by mass or less, per 100 parts by mass of the polyol composition. The lower limit of the total content of solid and liquid flame retardants may be 1 part by mass or more, 13 parts by mass or more, 39 parts by mass or more, 65 parts by mass or more, 78 parts by mass or more, 91 parts by mass or more, 104 parts by mass or more, 117 parts by mass or more, 141 parts by mass or more, 152 parts by mass or more, 163 parts by mass or more, 185 parts by mass or more, 207 parts by mass or more, 218 parts by mass or more, 229 parts by mass or more, 264 parts by mass or more, 288 parts by mass or more, 336 parts by mass or more, 384 parts by mass or more, 432 parts by mass or more, 480.00 parts by mass or more, 720.00 parts by mass or more, 1200.00 parts by mass or more, or 2400.00 parts by mass or more, per 100 parts by mass of the polyol composition. The total content of solid and liquid flame retardants may be 1 to 2400 parts by mass, 13 to 1200 parts by mass, 39 to 720 parts by mass, 65 to 480 parts by mass, 78 to 432 parts by mass, 91 to 384 parts by mass, 104 to 336 parts by mass, 117 to 288 parts by mass, 141 to 264 parts by mass, 152 to 229 parts by mass, 163 to 218 parts by mass, or 185 to 207 parts by mass per 100 parts by mass of the polyol composition. When the total content of solid and liquid flame retardants is within the above range, polyurethane foams with excellent flame retardancy tend to be obtained. When the total content of solid and liquid flame retardants is below the aforementioned 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 total content of solid and liquid flame retardants is above the aforementioned lower limit, the flame retardant effect derived from the flame retardants is more easily exhibited, and polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0092] (Anti-settling agent) The polyol composition and the polyurethane foam-forming composition may contain a settling inhibitor. Either the polyisocyanate composition or the polyol composition may contain a settling inhibitor, or both may contain one. Examples of settling inhibitors include organic bentonite, aliphatic amide, hydrogenated castor oil wax, carbon black, silica powder, and any combination of two or more of these. Examples of aliphatic amides include ASA T-1700 (manufactured by Ito Oil Co., Ltd.), ASA T-1800 (manufactured by Ito Oil Co., Ltd.), ASA T-2800 (manufactured by Ito Oil Co., Ltd.), and Disparon 6100 (manufactured by Kusumoto Chemical Co., Ltd.). Among these, ASA T-1700 is preferred. By including a settling inhibitor, the settling of powder particles with a high specific gravity, such as solid flame retardants, in the polyurethane foam-forming composition can be suppressed.

[0093] The content of the settling inhibitor is preferably 0.1 to 3.0% by mass, more preferably 0.2 to 2.5% by mass, even more preferably 0.3 to 2.0% by mass, particularly preferably 0.4 to 1.5% by mass, and most preferably 0.5 to 1.0% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. When the content of the settling inhibitor is above the lower limit, it is easier to obtain a polyurethane foam-forming composition in which the settling of the solid flame retardant is suppressed. Conversely, when the content of the settling inhibitor is below the upper limit, it is easier to obtain a polyurethane foam with excellent flame retardancy.

[0094] (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 one. The dispersant is a material for improving the redispersibility of the solid flame retardant. Examples of dispersants include alkylammonium salts, organic ammonium salts, phosphate esters, and phosphate ester salts of acidic copolymers having hydroxyl groups. Examples of organic ammonium salts include alkylammonium salts, alkylol ammonium salts, and any combination of two or more of these. Examples of phosphate ester salts include lecithin. Among these, lecithin is preferred.

[0095] The dispersant content is preferably 0.01 to 3.0% by mass, more preferably 0.03 to 2.5% by mass, even more preferably 0.05 to 2.0% by mass, particularly preferably 0.07 to 1.5% by mass, and most preferably 0.09 to 1.0% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. When the dispersant content is above the lower limit, a polyurethane foam-forming composition with excellent dispersion stability tends to be obtained. Conversely, when the dispersant content is below the upper limit, a polyurethane foam with excellent flame retardancy tends to be obtained.

[0096] <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 surfactants such as polyoxyalkylene foam stabilizers like polyoxyalkylene alkyl ethers and silicone foam stabilizers like organopolysiloxanes, and any combination of two or more of these. Furthermore, the silicone foam stabilizer may include a graft copolymer of polydimethylsiloxane and polyethylene glycol.

[0097] The content of the foam stabilizer is not particularly limited, but is preferably 0.05 to 4.0% by mass, more preferably 0.1 to 3.0% by mass, even more preferably 0.15 to 2.5% by mass, particularly preferably 0.2 to 2.0% by mass, and most preferably 0.25 to 1.5% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam forming composition.

[0098] <Foaming 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 one. Preferably, only the polyol composition contains a blowing agent. Examples of blowing agents include water and / or physical blowing agents.

[0099] Specific examples of physical blowing agents include, for example, low-boiling-point hydrocarbon compounds, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbon compounds, ether compounds, and hydrofluoroolefin compounds. Furthermore, physical blowing agents include organic physical blowing agents such as mixtures of these compounds, and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Examples of the low-boiling hydrocarbon compounds mentioned above include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Examples of the above-mentioned chlorinated aliphatic hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Examples of the fluorine compounds mentioned above include CHF3, CH2F2, and CH3F. Examples of the above-mentioned hydrochlorofluorocarbon compounds include trichloromonofluoromethane, trichlorotrifluoroethane, and dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)). Examples of the above-mentioned hydrofluorocarbon compounds include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane). Examples of the ether compounds mentioned above include diisopropyl ether. Examples of the above hydrofluoroolefin compounds include HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene) and HFO-1234yf (2,3,3,3-tetrafluoro-1-propene). These physical blowing agents may be used individually or in any combination of two or more. Among these, hydrofluoroolefin compounds are preferred.

[0100] The upper limit of the content of the blowing agent is 550.0 parts by mass or less, 275.0 parts by mass or less, 165.0 parts by mass or less, 110.0 parts by mass or less, 99.0 parts by mass or less, 88.0 parts by mass or less, 77.0 parts by mass or less, 66.0 parts by mass or less, 60.5 parts by mass or less, 53.9 parts by mass or less, 52.8 parts by mass or less, based on 100 parts by mass of the polyol compound. Parts by weight or less, 51.7 parts by weight or less, 49.5 parts by weight or less, 47.3 parts by weight or less, 46.2 parts by weight or less, 45.1 parts by weight or less, 39.6 parts by weight or less, 35.2 parts by weight or less, 30.8 parts by weight or less, 26.4 parts by weight or less, 22.0 parts by weight or less, 13.2 parts by weight or less, 4.4 parts by weight or less, or 0.4 parts by weight or less. The lower limit of the foaming agent content may be 0.4 parts by mass or more, 4.4 parts by mass or more, 13.2 parts by mass or more, 22.0 parts by mass or more, 26.4 parts by mass or more, 30.8 parts by mass or more, 35.2 parts by mass or more, 39.6 parts by mass or more, 45.1 parts by mass or more, 46.2 parts by mass or more, 47.3 parts by mass or more, 49.5 parts by mass or more, 51.7 parts by mass or more, 52.8 parts by mass or more, 53.9 parts by mass or more, 60.5 parts by mass or more, 66.0 parts by mass or more, 77.0 parts by mass or more, 88.0 parts by mass or more, 99.0 parts by mass or more, 110.0 parts by mass or more, 165.0 parts by mass or more, 275.0 parts by mass or more, or 550.0 parts by mass or more, per 100 parts by mass of the polyol compound. The foaming agent content may be 0.4 parts by mass or more and 550.0 parts by mass or less, 4.4 parts by mass or more and 275.0 parts by mass or less, 13.2 parts by mass or more and 165.0 parts by mass or less, 22.0 parts by mass or more and 110.0 parts by mass or less, 26.4 parts by mass or more and 99.0 parts by mass or less, 30.8 parts by mass or more and 88.0 parts by mass or less, 35.2 parts by mass or more and 77.0 parts by mass or less, 39.6 parts by mass or more and 66.0 parts by mass or less, 45.1 parts by mass or more and 60.5 parts by mass or less, 46.2 parts by mass or more and 53.9 parts by mass or less, 47.3 parts by mass or more and 52.8 parts by mass or less, or 49.5 parts by mass or more and 51.7 parts by mass or less, per 100 parts by mass of the polyol compound. When the foaming agent content is within the above range, it tends to be easier to obtain polyurethane foam with reduced mechanical properties such as compressive strength, dimensional stability, and adhesion, as well as reduced raw material costs. When the foaming agent content is below the aforementioned upper limit, polyurethane foams with particularly excellent mechanical properties such as compressive strength, dimensional stability, and adhesiveness tend to be obtained.Furthermore, when the foaming agent content is above the aforementioned lower limit, polyurethane foams with particularly reduced raw material costs tend to be obtained.

[0101] The upper limit of water content is 7.0 parts by mass or less, 3.5 parts by mass or less, 2.1 parts by mass or less, 1.4 parts by mass or less, 1.3 parts by mass or less, 1.1 parts by mass or less, 1.0 parts by mass or less, 0.8 parts by mass or less, 0.8 parts by mass or less, 0.7 parts by mass or less, 0.7 parts by mass or less, based on 100 parts by mass of the polyol compound. 0.7 parts by mass or less, 0.7 parts by mass or less, 0.6 parts by mass or less, 0.6 parts by mass or less, 0.6 parts by mass or less, 0.5 parts by mass or less, 0.5 parts by mass or less, 0.4 parts by mass or less, 0.4 parts by mass or less, 0.3 parts by mass or less, 0.2 parts by mass or less, 0.1 parts by mass or less, or 0.0 parts by mass or less. The lower limit of the water content may be 0.0 parts by mass or more, 0.1 parts by mass or more, 0.2 parts by mass or more, 0.3 parts by mass or more, 0.4 parts by mass or more, 0.4 parts by mass or more, 0.5 parts by mass or more, 0.5 parts by mass or more, 0.6 parts by mass or more, 0.6 parts by mass or more, 0.6 parts by mass or more, 0.7 parts by mass or more, 0.7 parts by mass or more, 0.7 parts by mass or more, 0.7 parts by mass or more, 0.8 parts by mass or more, 0.8 parts by mass or more, 1.0 parts by mass or more, 1.1 parts by mass or more, 1.3 parts by mass or more, 1.4 parts by mass or more, 2.1 parts by mass or more, 3.5 parts by mass or more, or 7.0 parts by mass or more, per 100 parts by mass of the polyol compound. The water content may be 0.0 to 7.0 parts by mass, 0.1 to 3.5 parts by mass, 0.2 to 2.1 parts by mass, 0.3 to 1.4 parts by mass, 0.4 to 1.3 parts by mass, 0.4 to 1.1 parts by mass, 0.5 to 1.0 parts by mass, 0.5 to 0.8 parts by mass, 0.6 to 0.8 parts by mass, 0.6 to 0.7 parts by mass, 0.6 to 0.7 parts by mass, or 0.7 to 0.7 parts by mass, per 100 parts by mass of the polyol compound. When the water content is within the above range, polyurethane foams with excellent mechanical properties such as flame retardancy and compressive strength tend to be obtained. When the water content is below the above upper limit, polyurethane foams with particularly excellent flame retardancy tend to be obtained. Furthermore, when the water content is above the aforementioned lower limit, polyurethane resins with particularly excellent mechanical properties, such as compressive strength, tend to be obtained.

[0102] The upper limit of the content of the physical blowing agent is 550.0 parts by mass or less, 275.0 parts by mass or less, 165.0 parts by mass or less, 110.0 parts by mass or less, 99.0 parts by mass or less, 88.0 parts by mass or less, 77.0 parts by mass or less, 66.0 parts by mass or less, 60.5 parts by mass or less, 53.9 parts by mass or less, 52.8 parts by mass or less, based on 100 parts by mass of the polyol compound. The amount may be less than or equal to 51.7 parts by mass, 49.5 parts by mass or less, 47.3 parts by mass or less, 46.2 parts by mass or less, 45.1 parts by mass or less, 39.6 parts by mass or less, 35.2 parts by mass or less, 30.8 parts by mass or less, 26.4 parts by mass or less, 22.0 parts by mass or less, 13.2 parts by mass or less, 4.4 parts by mass or less, or 0.4 parts by mass or less. The lower limit of the physical blowing agent content may be 0.4 parts by mass or more, 4.4 parts by mass or more, 13.2 parts by mass or more, 22.0 parts by mass or more, 26.4 parts by mass or more, 30.8 parts by mass or more, 35.2 parts by mass or more, 39.6 parts by mass or more, 45.1 parts by mass or more, 46.2 parts by mass or more, 47.3 parts by mass or more, 49.5 parts by mass or more, 51.7 parts by mass or more, 52.8 parts by mass or more, 53.9 parts by mass or more, 60.5 parts by mass or more, 66.0 parts by mass or more, 77.0 parts by mass or more, 88.0 parts by mass or more, 99.0 parts by mass or more, 110.0 parts by mass or more, 165.0 parts by mass or more, 275.0 parts by mass or more, or 550.0 parts by mass or more, per 100 parts by mass of the polyol compound. The amount of physical blowing agent may be 0.4 parts by mass or more and 550.0 parts by mass or less, 4.4 parts by mass or more and 275.0 parts by mass or less, 13.2 parts by mass or more and 165.0 parts by mass or less, 22.0 parts by mass or more and 110.0 parts by mass or less, 26.4 parts by mass or more and 99.0 parts by mass or less, 30.8 parts by mass or more and 88.0 parts by mass or less, 35.2 parts by mass or more and 77.0 parts by mass or less, 39.6 parts by mass or more and 66.0 parts by mass or less, 45.1 parts by mass or more and 60.5 parts by mass or less, 46.2 parts by mass or more and 53.9 parts by mass or less, 47.3 parts by mass or more and 52.8 parts by mass or less, or 49.5 parts by mass or more and 51.7 parts by mass or less, per 100 parts by mass of the polyol compound. If the physical blowing agent contains chlorine atoms in its molecule, it also exhibits a flame retardant effect. When the content of the physical blowing agent is within the aforementioned range, polyurethane foams with excellent mechanical properties such as compressive strength, dimensional stability, and adhesion, as well as excellent flame retardancy, tend to be obtained.When the content of the physical blowing agent is below the upper limit, polyurethane foams with particularly excellent mechanical properties such as compressive strength, dimensional stability, and adhesiveness tend to be obtained. Conversely, when the content of the physical blowing agent is above the lower limit, polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0103] If the blowing agent contains water and a physical blowing agent, the lower limit of the physical blowing agent content may be 40 mol% or more, 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, 83 mol% or more, 85 mol% or more, or 87 mol% or more, relative to the sum of the water content and the physical blowing agent content. The upper limit of the physical blowing agent content may be, for example, 99 mol% or less, 98 mol% or less, 97 mol% or less, 96 mol% or less, 95 mol% or less, 94 mol% or less, 93 mol% or less, 92 mol% or less, 91 mol% or less, 90 mol% or less, or 89 mol% or less, relative to the sum of the water content and the physical blowing agent content. The content ratio of the physical blowing agent may be, for example, 40 mol% to 99 mol%, 50 mol% to 98 mol%, 55 mol% to 97 mol%, 60 mol% to 96 mol%, 65 mol% to 95 mol%, 70 mol% to 94 mol%, 75 mol% to 93 mol%, 80 mol% to 92 mol%, 83 mol% to 91 mol%, 85 mol% to 90 mol%, or 87 mol% to 89 mol% relative to the sum of the water content and the physical blowing agent content. If the physical blowing agent contains chlorine atoms in its molecule, it also exhibits a flame retardant effect. When the content ratio of the physical blowing agent is within the above range, it is easier to obtain a polyurethane foam with excellent flame retardancy and mechanical properties such as compressive strength. When the content ratio of the physical blowing agent is above the lower limit, it is easier to obtain a polyurethane foam with particularly excellent flame retardancy. When the physical blowing agent content is below the aforementioned upper limit, polyurethane foams with particularly excellent mechanical properties, such as compressive strength, tend to be obtained.

[0104] <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 one. It is preferable that only the polyol composition contains a catalyst. The catalyst may contain, for example, one or both of a urethane / urea conversion catalyst and a trimerization catalyst, and it is preferable that both are included.

[0105] Urethane / urea catalysts are catalysts that promote the reaction between polyol components and polyisocyanates. Specifically, these include amino compounds, tin compounds, bismuth compounds, and acetylacetone metal salts. Examples of amino compounds include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl) ether, bis(2-dimethylaminoethyl) ether, N,N,N',N”,N”-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl) ether, N-methyl-N',N'-dimethylaminoethylpiperazine, imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, 1-methylimidazole, trimethylaminoethylpiperazine, and tripropylamine. Examples of tin compounds include stannous octoate, dibutyltin diacetate, and dibutyltin dilaurate. Examples of bismuth compounds include bismuth neodecanoate and bismuth octoate. Examples of acetylacetone metal salts include aluminum acetylacetone, iron acetylacetone, copper acetylacetone, zinc acetylacetone, beryllium acetylacetone, chromium acetylacetone, indium acetylacetone, manganese acetylacetone, molybdenum acetylacetone, titanium acetylacetone, cobalt acetylacetone, vanadium acetylacetone, and zirconium acetylacetone. These urethane / urea catalysts may be used individually or in any combination of two or more types.

[0106] There are no particular limitations on the amount of urethane / urea-forming catalyst blended, but it is preferably 0.01 to 3.0% by mass, more preferably 0.03 to 2.0% by mass, even more preferably 0.05 to 1.5% by mass, particularly preferably 0.07 to 1.0% by mass, and most preferably 0.1 to 0.8% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. By keeping it within the above range, the reaction between the polyol component and the polyisocyanate component can be promoted at an appropriate reaction rate.

[0107] A trimerization catalyst is a catalyst that promotes the formation of isocyanurate bonds. In polyurethane foam-forming compositions, the flame retardancy of the resulting polyurethane foam is improved by promoting trimerization. Examples of trimerization catalysts include aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; aziridines such as potassium acetate, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium octoate, sodium octoate, and 2-ethylaziridine; lead compounds such as lead naphthenate and lead octoate; metal salts such as sodium methoxide and potassium phenoxide; tertiary or quaternary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt, tetramethylammonium salt, tetraethylammonium, and tetraphenylammonium salt; and any combination of two or more of these.

[0108] The content of the trimerizing catalyst is not particularly limited, but from the viewpoint of improving the curing speed of the polyurethane foam-forming composition and the flame retardancy of the polyurethane foam, it is preferably 0.5 to 6.0% by mass, more preferably 0.8 to 4.0% by mass, even more preferably 1.1 to 3.0% by mass, particularly preferably 1.3 to 2.5% by mass, and most preferably 1.5 to 2.0% by mass, relative to the mass of the polyurethane foam component of the polyurethane foam-forming composition. By keeping the content of the trimerizing catalyst within the above range, isocyanurate bonds are formed appropriately, improving flame retardancy.

[0109] Trimerization catalysts, when used in combination with a metal salt and a tertiary or quaternary ammonium salt, tend to produce polyurethane foams with excellent reactivity during foaming and flame retardancy.

[0110] The lower limit of the content of tertiary or quaternary ammonium salts may be, for example, 5.0% by mass or more, 15.0% by mass or more, 25.0% by mass or more, 35.0% by mass or more, 45.0% by mass or more, 55.0% by mass or more, or 65.0% by mass or more, relative to the content of the trimerization catalyst. The upper limit of the content of tertiary or quaternary ammonium salts may be, for example, 100% by mass or less, 95.0% by mass or less, 90.0% by mass or less, 85.0% by mass or less, 80.0% by mass or less, 75.0% by mass or less, or 70.0% by mass or less, relative to the content of the trimerization catalyst. The content of tertiary or quaternary ammonium salt may be, for example, 5.0% to 100% by mass, 15.0% to 95.0% by mass, 25.0% to 90.0% by mass, 35.0% to 85.0% by mass, 45.0% to 80.0% by mass, 55.0% to 75.0% by mass, or 65.0% to 70.0% by mass, relative to the content of the trimerizing catalyst. When the content of tertiary or quaternary ammonium salt is within the above range, polyurethane foams with excellent reactivity during foaming and flame retardancy tend to be obtained. When the content of tertiary or quaternary ammonium salt is above the lower limit, polyurethane foams with particularly high reactivity tend to be obtained, exhibiting particularly excellent effects for spray foaming applications. Furthermore, when the content of tertiary or quaternary ammonium salt is below the upper limit, polyurethane foams with particularly excellent flame retardancy tend to be obtained.

[0111] (Other additives) Polyol compositions and polyurethane foam-forming compositions may further contain other additives besides solid flame retardants, liquid flame retardants, polyol compounds, polyisocyanate compounds, foam stabilizers, blowing agents, catalysts, and inorganic fillers. Examples of other additives include antioxidants such as phenolic, amine, and sulfur-based agents, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifying resins, and tackifying agents (polybutene, petroleum resin, etc.).

[0112] (Manufacturing method) The method for producing polyurethane foam is not particularly limited, but examples include preparing a polyol composition and a polyisocyanate composition by kneading them in advance and then kneading the two, or kneading each component that makes up the polyurethane foam. However, it is usually produced by kneading the polyol composition and the polyisocyanate composition. The kneading can be carried out by known methods, for example, by kneading using known equipment such as a single-screw extruder, twin-screw extruder, Banbury mixer, kneader mixer, kneading roll, raika, or planetary agitator.

[0113] (Total heat generation) The polyurethane foam, a reaction product of a polyisocyanate composition and a polyol composition, was subjected to a radiant thermal intensity test of 50 kW / m² in accordance with the ISO-5660 test method. 2 When heated, the total heat output after 10 minutes was 10 MJ / m². 2 Preferably, the total heat output is 10 MJ / m³. 2 As a result of the following, a polyurethane foam according to one aspect of the present disclosure has a predetermined flame retardancy. From the viewpoint of further improving the flame retardancy of the polyurethane foam, the total heat generation is 9 MJ / m 2 Preferably, it is 8 MJ / m 2 It is more preferable that the following is true: 7 MJ / m 2 It is even more preferable that the following conditions are met: 6.5 MJ / m 2 It is particularly preferable that the following conditions are met: 6 MJ / m 2 The following is most preferable. The total calorific value is obtained by a cone calorimeter test and can be measured in detail by the method described in the examples. It is preferable that the polyurethane foam used in the cone calorimeter test has sufficient dimensional stability so that it does not come into contact with the spark igniter of the cone calorimeter.

[0114] (Application) The uses of the polyurethane foam formed from the polyurethane foam-forming composition are not particularly limited, but it can be used to fill cavities in structures such as buildings, furniture, automobiles, trains, and ships, or to spray onto such structures. In particular, it is preferable to use it for spraying onto structures, that is, as a polyurethane foam-forming composition for spraying. The structure is, for example, an object to which flame retardancy is to be imparted.

[0115] The solid flame retardant composition can be used for polyurethane foams. Furthermore, the solid flame retardant composition can be used for spray applications. In other words, the solid flame retardant composition can be used for spraying, where the solid flame retardant composition is sprayed onto an object to adhere it to the object.

[0116] Spraying can be carried out using a spraying device (e.g., GRACO A-25) and a spray gun (e.g., Gasmar D-gun). Spraying can be performed by adjusting the temperature of the polyol composition and polyisocyanate composition, which are in separate containers, in the spraying device, mixing them by collision at the tip of the spray gun, and atomizing the mixture with air pressure. Commercially available spraying devices and spray guns can be used.

[0117] The density of polyurethane foam is not particularly limited, but is typically between 20 and 200 kg / m³. 3 It is preferable that the density be within this range. 3 By doing the following, the polyurethane foam becomes lighter, improving its ease of application to structures. Also, 20 kg / m 3 By doing so, the desired flame retardancy is more easily achieved. From these perspectives, the density of the polyurethane foam should be 30-60 kg / m³. 3 It is more preferable that the range be 33-55 kg / m 3 It is even more preferable that the range be 33-52 kg / m 3 It is particularly preferable that the density be 35-50 kg / m 3This is the most preferable condition. The density of the polyurethane foam can be measured in accordance with JIS K7222.

[0118] <Calculation method for each composition> Amount of polyol composition (g) = Amount of polyol compound (g) + Additives * Amount of ingredient added (g) + Amount of foaming agent added (g) + Amount of foam stabilizer added (g) + Amount of catalyst added (g) *: Additives refer to solid flame retardants (solid phosphorus-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, and solid flame retardants other than these), liquid flame retardants, inorganic fillers, settling inhibitors, dispersion stabilizers, and other additives.

[0119] In this specification, "polyurethane foam components of a polyurethane foam-forming composition" means the components that make up the polyurethane foam. For example, among liquid flame retardants, solid flame retardants, polyol compounds, polyisocyanate compounds, foam stabilizers, blowing agents, catalysts, and other additives, the components that make up the polyurethane foam are considered "polyurethane foam components of a polyurethane foam-forming composition." Furthermore, the blowing agent is entirely or largely discharged from the system as bubbles and does not constitute the polyurethane foam. For example, of the water used as a blowing agent, the hydrogen atoms constitute part of the urea bonds in the polyurethane foam, but the oxygen atoms become CO2 and do not constitute the polyurethane foam itself. For this reason, in this specification, the blowing agent is not included in the "polyurethane foam components of the polyurethane foam-forming composition."

[0120] The mass (g) of the polyurethane foam component of the polyurethane foam-forming composition = amount of polyisocyanate compound (g) + amount of polyol compound (g) + additives * Preparation amount (g) *: Additives refer to solid flame retardants (solid phosphorus-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, and solid flame retardants other than these), liquid flame retardants, foam stabilizers, catalysts, inorganic fillers, settling inhibitors, dispersion stabilizers, and other additives.

[0121] Bromine-containing polyol content (mass%) = Amount of bromine-containing polyol added (g) / (Amount of bromine-containing polyol added (g) + Amount of aromatic polyester polyol added (g)) × 100

[0122] Bromine atom content (mass%) of bromine-containing polyol = Molecular weight of bromine atom (79.9) × Number of bromine atoms in bromine-containing polyhydric alcohol / (Number of functional groups in bromine-containing polyol × 56.11 × 1000 / Hydroxyl value of bromine-containing polyol) × 100

[0123] Orthophthalic acid-based polyester polyol content (parts by mass) = Amount of orthophthalic acid-based polyester polyol added (g) / Amount of polyol compound added (g) × 100

[0124] Terephthalic acid-based polyester polyol content (parts by mass) = Amount of terephthalic acid-based polyester polyol added (g) / Amount of polyol compound added (g) × 100

[0125] Orthophthalic acid-based polyester polyol content (mass%) = Amount of orthophthalic acid-based polyester polyol added (g) / (Amount of orthophthalic acid-based polyester polyol added (g) + Amount of orthophthalic acid-based polyester polyol added (g)) × 100

[0126] Isocyanate index = Equivalents of polyisocyanate ÷ (Equivalents of polyol + Equivalents of water) × 100 Here, the equivalent weight of polyisocyanate = number of parts of polyisocyanate used × NCO content (%) / 100 / molecular weight of NCO The equivalent number of polyols = OHV × number of polyols used ÷ molecular weight of KOH, where OHV is the hydroxyl value of the polyol (mgKOH / g), and the equivalent number of waters = number of waters used × number of OH groups in water / molecular weight of water. In the above formula, the unit of the number of parts used is mass (g), the molecular weight of the NCO group is 42, the NCO content is the percentage of NCO groups in the polyisocyanate compound expressed by mass%, and for the sake of unit conversion in the above formula, the molecular weight of KOH is assumed to be 56100, the molecular weight of water is assumed to be 18, and the number of OH groups in water is assumed to be 2.

[0127] Content of solid phosphorus-containing flame retardant (parts by mass) = Amount of solid phosphorus-containing flame retardant charged (g) / Amount of polyol compound charged (g) × 100

[0128] Bromine-containing flame retardant content (parts by mass) = Amount of bromine-containing flame retardant added (g) / Amount of polyol compound added (g) × 100

[0129] Content of aliphatic bromine-containing compounds (parts by mass) = Amount of aliphatic bromine-containing compounds added (g) / Amount of polyol compounds added (g) × 100

[0130] Content (parts by mass) of aromatic bromine-containing low molecular weight compound = Amount of aromatic bromine-containing low molecular weight compound charged (g) / Amount of polyol compound charged (g) × 100

[0131] Content of aromatic bromine-containing polymer compound (parts by mass) = Amount of aromatic bromine-containing polymer compound charged (g) / Amount of polyol compound charged (g) × 100

[0132] The percentage of aliphatic bromine-containing compounds (by mass) = Amount of aliphatic bromine-containing compounds added (g) / (Amount of aliphatic bromine-containing compounds added (g) + Amount of low molecular weight aromatic bromine-containing compounds added (g) + Amount of high molecular weight aromatic bromine-containing compounds added (g)) × 100

[0133] Content ratio (mass%) of aromatic bromine-containing low molecular weight compounds = Amount of aromatic bromine-containing low molecular weight compounds (g) / (Amount of aliphatic bromine-containing compounds (g) + Amount of aromatic bromine-containing low molecular weight compounds (g) + Amount of aromatic bromine-containing high molecular weight compounds (g)) × 100

[0134] Content ratio (mass%) of aromatic bromine-containing polymer compounds = Amount of aromatic bromine-containing polymer compounds added (g) / (Amount of aliphatic bromine-containing compounds added (g) + Amount of aromatic bromine-containing low molecular weight compounds added (g) + Amount of aromatic bromine-containing polymer compounds added (g)) × 100

[0135] Content (parts by mass) of bromine-containing flame retardant with a decomposition temperature of less than 370°C = Amount of bromine-containing flame retardant with a decomposition temperature of less than 370°C charged (g) / Amount of polyol compound charged (g) × 100

[0136] Content (parts by mass) of bromine-containing flame retardant with a decomposition temperature of 370°C or higher and less than 450°C = Amount of bromine-containing flame retardant with a decomposition temperature of 370°C or higher and less than 450°C charged (g) / Amount of polyol compound charged (g) × 100

[0137] Content (parts by mass) of bromine-containing flame retardant with a decomposition temperature of 450°C or higher = Amount of bromine-containing flame retardant with a decomposition temperature of 450°C or higher charged (g) / Amount of polyol compound charged (g) × 100

[0138] The percentage of bromine-containing flame retardants with a decomposition temperature below 370°C (mass %) = Amount of bromine-containing flame retardants with a decomposition temperature below 370°C (g) / (Amount of bromine-containing flame retardants with a decomposition temperature below 370°C (g) + Amount of bromine-containing flame retardants with a decomposition temperature between 370°C and 450°C (g) + Amount of bromine-containing flame retardants with a decomposition temperature of 450°C or higher (g)) × 100

[0139] The percentage of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C (mass %) = Amount of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C (g) / (Amount of bromine-containing flame retardants with a decomposition temperature of less than 370°C (g) + Amount of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C (g) + Amount of bromine-containing flame retardants with a decomposition temperature of 450°C or higher (g)) × 100

[0140] The percentage of bromine-containing flame retardants with a decomposition temperature of 450°C or higher (mass %) = Amount of bromine-containing flame retardants with a decomposition temperature of 450°C or higher (g) / (Amount of bromine-containing flame retardants with a decomposition temperature of less than 370°C (g) + Amount of bromine-containing flame retardants with a decomposition temperature of 370°C or higher but less than 450°C (g) + Amount of bromine-containing flame retardants with a decomposition temperature of 450°C or higher (g)) × 100

[0141] Boron-containing flame retardant content (parts by mass) = Amount of boron-containing flame retardant added (g) / Amount of polyol compound added (g) × 100

[0142] The percentage of solid phosphorus-containing flame retardant (mass %) = Amount of solid phosphorus-containing flame retardant added (g) / (Amount of solid phosphorus-containing flame retardant added (g) + Amount of bromine-containing flame retardant added (g) + Amount of boron-containing flame retardant added (g)) × 100

[0143] The percentage of bromine-containing flame retardant (mass %) = Amount of bromine-containing flame retardant added (g) / (Amount of solid phosphorus-containing flame retardant added (g) + Amount of bromine-containing flame retardant added (g) + Amount of boron-containing flame retardant added (g)) × 100

[0144] The percentage of boron-containing flame retardant (mass %) = Amount of boron-containing flame retardant added (g) / (Amount of solid phosphorus-containing flame retardant added (g) + Amount of bromine-containing flame retardant added (g) + Amount of boron-containing flame retardant added (g)) × 100

[0145] The sum of the amounts of solid phosphorus-containing flame retardant, bromine-containing flame retardant, and boron-containing flame retardant (parts by mass) = (Amount of solid phosphorus-containing flame retardant (g) + Amount of bromine-containing flame retardant (g) + Amount of boron-containing flame retardant (g)) / Amount of polyol compound (g) × 100

[0146] Solid flame retardant content (parts by mass) = Amount of solid flame retardant added (g) / Amount of polyol compound added (g) × 100

[0147] Liquid flame retardant content (parts by mass) = Amount of liquid flame retardant added (g) / Amount of polyol compound added (g) × 100

[0148] Total content (parts by mass) of solid and liquid flame retardants = Total flame retardants * Amount of compound added (g) / Amount of polyol compound added (g) × 100 *: All flame retardants are 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.

[0149] Inorganic filler content (mass %) = Amount of inorganic filler added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0150] Anti-settling agent content (mass %) = Amount of anti-settling agent added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0151] Dispersant content (mass %) = Amount of dispersant added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0152] Content of other additives (mass%) = Amount of other additives added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0153] Foam stabilizer content (mass %) = Amount of foam stabilizer added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0154] Foaming agent content (parts by mass) = Amount of foaming agent added (g) / Amount of polyol compound added (g) × 100

[0155] Water content (parts by mass) = Amount of water added (g) / Amount of polyol compound added (g) × 100

[0156] Physical blowing agent content (parts by mass) = Amount of physical blowing agent added (g) / Amount of polyol compound added (g) × 100

[0157] Physical blowing agent content ratio (mol%) = Amount of physical blowing agent added (mol) / (Amount of water added (mol) + Amount of physical blowing agent added (mol)) × 100

[0158] Urethane / urea catalyst content (mass%) = Amount of urethane / urea catalyst added (g) / Mass of polyurethane foam component of polyurethane foam-forming composition (g) × 100

[0159] Content of tertiary or quaternary ammonium salt (mass%) = Amount of tertiary or quaternary ammonium salt charged (g) / Amount of trimerization catalyst charged (g) × 100 [Examples]

[0160] One aspect of this disclosure will be described in more detail by reference to examples, but this aspect of the disclosure is not limited in any way by these examples.

[0161] Details of each component used in each example and comparative example are as follows. Note that some components are abbreviated in Tables 1 to 3, and these abbreviations are indicated in parentheses below. (1) Polyisocyanate compounds • "MR-200": Polymeric MDI (manufactured by Tosoh Corporation, product name: MR-200)

[0162] (2) Solid flame retardants • "Piroguard SR-720N": 4,4′-dimethylmethylenebis[2,6-dibromo-1-(2,3-dibromopropyloxy)benzene] (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Piroguard SR-720: aliphatic bromine-containing compound, decomposition temperature: 315℃) • "Piroguard SR-245": 2,4,6-Tris(2,4,6-tribromophenoxy)-1,3,5-triazine (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Piroguard SR-245: aromatic bromine-containing low molecular weight compound, decomposition temperature: 417℃) • "Fireguard 8500": A polycarbonate oligomer manufactured using brominated bisphenol A as a raw material (manufactured by Teijin Corporation, product name: Fireguard 8500: aromatic bromine-containing polymer compound, decomposition temperature: 474℃) • "AP-462": Ammonium polyphosphate (manufactured by Clariant Chemicals, product name: AP-462) • Zinc borate (manufactured by Kinsei Matec Co., Ltd.)

[0163] (3) Polyol compounds • "RFK-505": Terephthalic acid-based polyester polyol (manufactured by Air Water Performance Chemicals, product name: Maximol RFK-505, hydroxyl value = 250 mg KOH / g) • "RDK-133": Orthophthalic acid-based polyester polyol (manufactured by Air Water Performance Chemicals, product name: Maximol RDK-133, hydroxyl value = 315 mg KOH / g) • "Bromine-containing polyol": Hydroxyl value = 110 mg KOH / g, bromine atom content = approximately 30 wt%, bromine-containing polyether polyol initiated with tetrahydrobisphenol A.

[0164] (4) Liquid flame retardants • "TCPP": Phosphate ester-based flame retardant <Tris(β-chloropropyl) phosphate>, (manufactured by Yoke Chemicals and New Materials (Shanghai) Co., Ltd., product name: TCPP)

[0165] (5) Foam stabilizers • "SH-193": Polyalkylene glycol-based foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193)

[0166] (6) Catalyst (i) Urethane catalyst • "T-9": Tin compound (manufactured by Evonik, product name: DABCOT-9) (ii) Urea catalyst • "DT": Tertiary ammonium compound (manufactured by Tosoh Corporation, product name: TOYOCAT-DT) (iii) Trimerization catalyst • "TRV": Quaternary ammonium salt (manufactured by Tosoh Corporation, product name: TOYOCAT-TRV) • "K-15": Metal salt (manufactured by Tosoh Corporation, product name: DABCOK-15)

[0167] (7) Foaming agent ·water • HFO-1233zd <Hydrofluoroolefin> (Honeywell Corporation, product name: Solstice LBA)

[0168] The measurement methods for each physical property and characteristic are as follows.

[0169] [Decomposition temperature of bromine-containing flame retardants] The decomposition temperature of the bromine-containing flame retardant was calculated using TG-DTA. The bromine-containing flame retardant was heated in TG-DTA at 5°C / min up to 700°C, and the temperature at which the weight loss rate was 50% was defined as the decomposition temperature. The weight loss rate was calculated as: sample mass during measurement (mg) / sample mass before measurement (mg) × 100. The weight loss rate was measured under the following conditions.

[0170] [conditions] The following steps [1] to [3] were performed using the STA7200RV manufactured by Hitachi High-Tech Science Corporation. [1] 8.5 ± 0.5 mg of bromine-containing flame retardant was placed in a weighing device. [2] The airflow rate was set to 200 mL / min. [3] The temperature was increased from 25°C to 700°C at a rate of 5°C / min.

[0171] [Total heat generation] The total calorific value of the polyurethane foams produced in each example and comparative example was evaluated by the following method. A polyurethane foam-forming composition was obtained by mixing a polyol composition and a polyisocyanate compound in the formulations shown in Tables 1 and 2 in a polypropylene beaker and stirring the mixture with a labodiespar for 5 seconds. Immediately thereafter, the mixture was sprayed into a mold with dimensions of 150 mm x 150 mm x 150 mm to obtain a polyurethane foam. The polyurethane foam was cut into pieces 10 cm long, 10 cm wide, and 2.5 cm thick to prepare samples for cone calorimeter testing. Using the cone calorimeter test samples, the radiant heat intensity was measured to 50 kW / m² in accordance with the ISO-5660 test method. 2 The total calorific value after 10 minutes of heating was measured using a cone calorimeter. A CONE-III cone calorimeter (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used for the cone calorimeter test.

[0172] [Example 1] First, the polyol compound, blowing agent, catalyst, solid flame retardant, liquid flame retardant, and foam stabilizer were weighed into a 500 mL polypropylene beaker in the proportions shown in Table 1, and stirred with a hand mixer at 20°C for 10 minutes to obtain the polyol composition. Next, the polyisocyanate compound was weighed into a 500 mL polypropylene beaker to obtain the isocyanate composition. Then, the polyisocyanate composition, also heated to 10°C, was added to the polyol composition, which had been cooled to 10°C, to form a polyurethane foam-forming composition. This composition was then stirred with a labodiespar for 5 seconds to produce a polyurethane foam. The total calorific value described above was evaluated using this polyurethane foam. The various evaluation results are shown in Table 1.

[0173] [Examples 1-11, Comparative Examples 1-2] A polyurethane foam was obtained in the same manner as in Example 1, except that the formulation was changed as shown in Tables 1 and 2. The total calorific value was evaluated using the polyurethane foam according to the procedure described above. The various evaluation results are shown in Tables 1 and 2.

[0174] Table 1

[0175] Table 2

Claims

1. A polyol composition comprising a polyol compound containing a bromine-containing polyol and an aromatic polyester polyol, and a solid flame retardant, The content of the bromine-containing polyol is 1% by mass or more and 29% by mass or less, relative to the sum of the content of the bromine-containing polyol and the content of the aromatic polyester polyol. A polyol composition in which the solid flame retardant is contained in an amount of 25 parts by mass or more per 100 parts by mass of the polyol compound.

2. A polyol composition comprising a polyol compound containing a bromine-containing polyol and an aromatic polyester polyol, and a solid flame retardant, The content of the bromine-containing polyol is 1% by mass or more and 29% by mass or less, relative to the sum of the content of the bromine-containing polyol and the content of the aromatic polyester polyol. The solid flame retardant includes a solid phosphorus-containing flame retardant. A polyol composition wherein the solid phosphorus-containing flame retardant comprises a phosphinic acid-based flame retardant or a phosphate-containing flame retardant.

3. The solid flame retardant is Solid phosphorus-containing flame retardant, A polyol composition according to claim 1 or 2, comprising one or more selected from the group consisting of zinc borate and a bromine-containing flame retardant.

4. The polyol composition according to claim 1 or 2, wherein the solid flame retardant comprises a solid phosphorus-containing flame retardant, zinc borate, and a bromine-containing flame retardant.

5. The polyol composition according to claim 1 or 2, wherein the bromine-containing flame retardant comprises a first bromine-containing flame retardant and a second bromine-containing flame retardant.

6. A polyurethane foam, which is a foam of the polyurethane foam-forming composition according to claim 1 or 2.

7. The aforementioned polyurethane foam was tested in accordance with the ISO-5660 test method, and its radiant thermal intensity was 50 kW / m². ２ When heated, the total heat output after 10 minutes was 8.0 MJ / m³. ２ The polyurethane foam according to claim 6, which is as follows:

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