Polyol composition, flame-retardant urethane resin composition, and polyurethane foam

Abstract

To provide a polyol composition that can form a polyurethane foam less prone to reddening while maintaining high flame retardancy.SOLUTION: A polyol composition contains a polyol compound, a phosphorous solid flame retardant, a catalyst, and a foamer, the phosphorous solid flame retardant containing no red phosphorus.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyol composition, a flame-retardant urethane resin composition, and a polyurethane foam. [Background technology]

[0002] Taking advantage of their excellent heat insulating properties, polyurethane foams are used in practice for insulating and preventing condensation in building components such as ceilings, roofs, and walls of buildings such as apartment complexes, detached houses, commercial buildings, etc. Polyurethane foams are formed by spraying a flame-retardant urethane resin composition containing a polyol compound and a polyisocyanate compound onto the surface of each structure, followed by foaming and curing.

[0003] Although polyurethane foams are lightweight, they are organic and therefore flammable. To address this issue, polyurethane foams with high flame retardancy are needed. One method for improving the flame retardancy of polyurethane foams is to use red phosphorus in a foamable urethane resin composition, as disclosed in Patent Document 1, for example. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-172603 Summary of the Invention [Problem to be solved by the invention]

[0005] However, red phosphorus is a hazardous material under the Fire Service Act, and therefore must be handled with care when producing a foamable urethane resin composition. In addition, polyurethane foams formed from foamable urethane resin compositions using red phosphorus tend to turn red due to the red phosphorus, which can impair their design properties. Therefore, an object of the present invention is to provide a polyol composition capable of forming a polyurethane foam that is suppressed from turning red while maintaining good flame retardancy. [Means for solving the problem]

[0006] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a polyol composition containing a polyol compound, a phosphorus-based solid flame retardant, a catalyst, and a blowing agent, wherein the polyol composition does not contain red phosphorus, and have thus completed the present invention.

[0007] The present invention is summarized as follows [1] to

[15] . [1] A polyol composition comprising a polyol compound, a phosphorus-based solid flame retardant, a catalyst, and a blowing agent, wherein the phosphorus-based solid flame retardant does not contain red phosphorus. [2] The polyol composition according to [1], wherein the phosphorus concentration in the polyol composition is 2.5% by mass or more. [3] The polyol composition according to [1] or [2], wherein the phosphorus-based solid flame retardant is at least one selected from the group consisting of phosphates, phosphazene compounds, phosphoric acid ester compounds, and metal phosphinates. [4] The polyol composition according to [3], wherein the phosphorus-based solid flame retardant contains the phosphate, and the phosphate has a phosphorus concentration of 25 mass % or more. [5] The polyol composition according to [3] or [4], wherein the phosphorus-based solid flame retardant contains a polyphosphate. [6] The polyol composition according to [5], wherein the polyphosphate has an average particle size of 50 μm or less. [7] The polyol composition according to any one of [1] to [6], wherein the weighted average aromatic concentration of the polyol compound is 10% by mass or more. [8] The polyol composition according to any one of [1] to [7], wherein the catalyst comprises a trimerization catalyst. [9] The polyol composition according to any one of [1] to [8], wherein the catalyst comprises at least one selected from the group consisting of bismuth compounds and tin compounds.

[10] The polyol composition according to any one of [1] to [9], wherein the polyol composition contains a liquid flame retardant, and the content ratio of the liquid flame retardant to the phosphorus-based solid flame retardant is 0.2 to 3.

[11] The polyol composition according to any one of [1] to

[10] , wherein the content of halogen atoms derived from a flame retardant in the polyol composition is 20 mass % or less.

[12] A flame-retardant urethane resin composition comprising the polyol composition according to any one of [1] to

[11] and a polyisocyanate compound, wherein the flame-retardant urethane resin composition does not contain red phosphorus.

[13] Testing of polyurethane foam formed from a flame-retardant urethane resin composition in accordance with ISO-5660, with a radiant heat intensity of 50 kW / m 2 When heated for 10 minutes, the total calorific value is 8MJ / m 2 The flame-retardant urethane resin composition according to

[12] , which is:

[14] The flame-retardant urethane resin composition according to

[12] or

[13] , which is used for spray applications.

[15] A polyurethane foam formed from the flame-retardant urethane resin composition according to any one of

[12] to

[14] . [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a polyol composition capable of forming a polyurethane foam that is inhibited from turning red while maintaining good flame retardancy. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below. [Polyol composition] The polyol composition of the present invention is a polyol composition containing a polyol compound, a phosphorus-based solid flame retardant, a catalyst, and a blowing agent, wherein the phosphorus-based solid flame retardant does not contain red phosphorus.

[0010] The phosphorus-based solid flame retardant contained in the polyol composition of the present invention does not contain red phosphorus, which can prevent a polyurethane foam formed from the composition from turning red, thereby preventing the polyurethane foam from losing its design properties.

[0011] (Phosphorus-based solid flame retardant) The polyol composition of the present invention contains a phosphorus-based solid flame retardant other than the above-mentioned red phosphorus. The phosphorus-based solid flame retardant is a solid at room temperature (23°C) and normal pressure (1 atmosphere). By containing a phosphorus-based solid flame retardant other than red phosphorus, the flame retardancy of the polyurethane foam can be improved without containing red phosphorus. As the phosphorus-based solid flame retardant, it is preferable to use at least one selected from the group consisting of phosphates, phosphazene compounds, phosphoric acid ester compounds, and metal phosphinates.

[0012] <Phosphate> Specific examples of phosphates include monophosphates, polyphosphates, etc. The term "phosphates" as used herein includes not only orthophosphates but also phosphites, hypophosphites, etc. The same applies to polyphosphates. Examples of monophosphates 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 aluminum salts such as aluminum monophosphate, aluminum diphosphate, aluminum triphosphate, aluminum phosphite, and aluminum hypophosphite. Among these, ammonium phosphate and aluminum phosphite are preferred, and ammonium phosphate is more preferred. Examples of polyphosphates include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, etc., and among these, ammonium polyphosphate is preferred. There are various types of ammonium polyphosphate, such as type I and type II, depending on the crystal structure, but from the viewpoint of flame retardancy, at least one selected from the group consisting of type I ammonium polyphosphate and type II ammonium polyphosphate is preferred, and type II ammonium polyphosphate is more preferred.

[0013] <Intumescent flame retardant> As the phosphate, an intumescent flame retardant can also be used. Examples of intumescent flame retardants include phosphates containing a phosphorus-based component that promotes carbonization and a nitrogen-based component that promotes extinguishing and foaming. When combustion begins and heating occurs, intumescent flame retardants produce bubbles on the surface of the material, forming a foam-like, adiabatic expansion layer that prevents heat from the surface of the material from being transferred to the interior, and also inhibits thermal decomposition and oxidation reactions by blocking the supply of oxygen, thereby fulfilling their role as a flame retardant.

[0014] Examples of phosphorus-based components constituting intumescent flame retardants include polyphosphoric acids such as pyrophosphoric acid and triphosphoric acid, and monophosphoric acids such as orthophosphoric acid (normal phosphoric acid).

[0015] Examples of nitrogen-based components constituting the intumescent flame retardant include aliphatic diamines such as N,N,N',N'-tetramethyldiaminomethane, ethylenediamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane; piperazine; trans-2,5-dimethylpiperazine; 1,4-bis(2-aminoethyl)piperazine; 1,4-bis(2-aminoethyl)piperazine; Examples thereof include amine compounds containing a piperazine ring such as 4-bis(3-aminopropyl)piperazine, and amine compounds containing a triazine ring such as melamine, acetoguanamine, benzoguanamine, acrylguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3,5-triazine, and 2-amino-4,6-dimercapto-1,3,5-triazine.

[0016] The phosphorus-based component constituting the intumescent flame retardant preferably contains polyphosphoric acid, from the viewpoint of obtaining higher flame retardancy for the polyurethane foam.

[0017] The intumescent flame retardant is preferably at least one compound selected from the group consisting of melamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate. Among these, a mixture of a melamine salt selected from the group consisting of melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate, and a piperazine salt selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate, is more preferred. Furthermore, as the melamine salt, melamine pyrophosphate is more preferred from the viewpoint of flame retardancy, and as the piperazine salt, piperazine pyrophosphate is more preferred from the viewpoint of flame retardancy.

[0018] <Phosphazene compounds> A phosphazene compound is an organic compound in which phosphorus atoms and nitrogen atoms are alternately bonded. Examples of the phosphazene compound include cyclic phosphazene compounds, chain phosphazene compounds, and crosslinked phosphazene compounds crosslinked by a crosslinking group. Specific examples of the phosphazene compound include those containing a structural unit represented by the following general formula (1):

[0019] [ka] In the general formula (1), each X independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, an amino group, or a halogen atom. In the general formula (1), examples of the substituent on the aryl group include an alkyl group, an amino group, and a halogen atom. Each X is preferably independently any one of a phenyl group, a substituted phenyl group, a phenyloxy group, and a substituted phenyl group, and more preferably any one of a phenyl group and a phenyloxy group.

[0020] As the phosphazene compound contained in the polyol composition of the present invention, from the viewpoint of imparting better flame retardancy to the polyurethane foam, a cyclic phosphazene compound is preferred, and a cyclic phenoxyphosphazene compound is more preferred.

[0021] <Phosphate ester compounds> The phosphate ester compound is not particularly limited as long as it is solid at room temperature (23° C.), and examples thereof include monophosphate ester, condensed phosphate ester, etc. These phosphate ester compounds may be commercially available products. Examples of monophosphate esters include triphenyl phosphate and tris(tribromoneopentyl)phosphate. Commercially available monophosphate esters include "TPP," "CR-900," and "DAIGUARD-1000" (all manufactured by Daihachi Chemical Industry Co., Ltd.). The condensed phosphate ester may be a halogen-containing condensed phosphate ester, or a non-halogen condensed phosphate ester. More specifically, alkyl-substituted aromatic condensed phosphate esters such as 1,3-phenylenebis(di-2,6-xylenyl phosphate) may be used. Commercially available condensed phosphate esters may also be used. Specific examples include non-halogen condensed phosphate esters such as "DAIGUARD-850" and "PX200" (both manufactured by Daihachi Chemical Industry Co., Ltd.).

[0022] As the phosphate ester compound contained in the polyol composition of the present invention, tris(tribromoneopentyl)phosphate is preferably used from the viewpoint of imparting better flame retardancy to the polyurethane foam. Because tris(tribromoneopentyl)phosphate contains a halogen atom, using it as a phosphate ester compound can ensure a certain amount of halogen in the polyol composition and improve the flame retardancy of the polyurethane foam.

[0023] <Metal phosphinate> The metal phosphinate is a metal salt of an organic phosphinic acid. Specific examples of the metal phosphinate include aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, and titanium tetrakisdiphenylphosphinate. Among these, it is preferable to use aluminum trisdiethylphosphinate.

[0024] Furthermore, from the viewpoint of sufficiently increasing the flame retardancy of the polyurethane foam without using red phosphorus, the phosphorus concentration in the phosphorus-based solid flame retardant is preferably 10 mass% or more, more preferably 12 mass% or more, and even more preferably 25 mass% or more, based on the total amount of the phosphorus-based solid flame retardant.

[0025] From the viewpoint of enhancing the flame retardancy of the polyurethane foam, the polyol composition of the present invention preferably has a phosphorus concentration of 2.5% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. From the viewpoint of containing a certain amount of compounds other than flame retardants, such as polyol compounds, the phosphorus concentration is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less. The phosphorus concentration in the polyol composition can be calculated based on the phosphorus concentration of each component constituting the composition and the amount of each component mixed, but can also be measured by analyzing the polyol composition using X-ray fluorescence (XRF), inductively coupled plasma (ICP), atomic absorption spectroscopy (AAS), or the like.

[0026] Among the above-mentioned phosphorus-based solid flame retardants, phosphates are preferred, and phosphates having a phosphorus concentration of 25% by mass or more are more preferred. The phosphate is more preferably a polyphosphate, even more preferably ammonium polyphosphate, and even more preferably at least one selected from the group consisting of type I ammonium polyphosphate and type II ammonium polyphosphate, with type II ammonium polyphosphate being particularly preferred. In addition, the polyphosphate preferably has a small average particle size in order to reduce the load (wear and clogging) on ​​the machine when using the polyol composition, and specifically, an average particle size of 50 μm or less is preferred, and an average particle size of 40 μm or less is more preferred. The average particle size of the polyphosphate is not particularly limited, but is, for example, 1 μm or more. The average particle size can be measured using a particle size distribution measuring device or the like.

[0027] The phosphorus-based solid flame retardant may be used alone or in combination of two or more of the above-mentioned compounds.

[0028] In the polyol composition of the present invention, the content of the phosphorus-based solid flame retardant is preferably 10 to 120 parts by mass, more preferably 15 to 110 parts by mass, and even more preferably 25 to 100 parts by mass, per 100 parts by mass of the polyol compound. By ensuring that the content of the phosphorus-based solid flame retardant is equal to or greater than the above-mentioned lower limit, the flame retardancy of the polyurethane foam can be enhanced. On the other hand, by ensuring that the content of the phosphorus-based solid flame retardant is equal to or less than the above-mentioned upper limit, the viscosity of the polyol composition can be prevented from excessively increasing, ensuring good handleability when producing the flame-retardant urethane resin composition described below. Furthermore, the foamability and moldability of the urethane foam can be improved.

[0029] (Polyol compound) The flame-retardant urethane resin composition of the present invention contains a polyol compound as a raw material for polyurethane foam. Examples of the polyol compound used in the present invention include polylactone polyols, polycarbonate polyols, polyester polyols, polymer polyols, and polyether polyols.

[0030] Examples of polylactone polyols include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of polycarbonate polyols include polyols obtained by dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like.

[0031] Examples of polyester polyols include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, and condensates of hydroxycarboxylic acids and the above-mentioned polyhydric alcohols. Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), o-phthalic acid (phthalic acid), naphthalenedicarboxylic acid, and succinic acid. Examples of polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

[0032] Examples of polymer polyols include polymers obtained by graft polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, or methacrylate with an aromatic polyol, alicyclic polyol, aliphatic polyol, or polyester polyol, polybutadiene polyol, or hydrogenated products thereof.

[0033] Examples of polyether polyols include polymers obtained by ring-opening polymerization of an alkylene oxide having 2 to 6 carbon atoms, specifically at least one of ethylene oxide, propylene oxide, tetrahydrofuran, etc., in the presence of at least one low-molecular-weight active hydrogen compound having two or more active hydrogens, such as a polyhydric alcohol. Examples of the alkylene oxide include at least one of ethylene oxide and propylene oxide. Examples of low molecular weight active hydrogen compounds having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol; triols such as glycerin and trimethylolpropane; tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl glucoside, and derivatives thereof; phloroglucinol; and cresol. polyols such as pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene; polyfunctional (e.g., having 2 to 100 functional groups) polyols such as castor oil polyol, (co)polymers of hydroxyalkyl (meth)acrylate, and polyvinyl alcohol; condensates of phenol and formaldehyde (novolac), amines such as ethylenediamine, and butylenediamine.

[0034] The polyol compound used in the present invention is preferably a polyester polyol or a polyether polyol. Furthermore, a polyol compound having two hydroxyl groups is preferred. Among these, aromatic polyester polyols, which are polyester polyols having an aromatic ring, are preferred from the viewpoint of enhancing the flame retardancy of polyurethane foams. In this case, the weighted average aromatic concentration of the polyol compound is preferably 10% by mass or more, more preferably 12% by mass or more. Here, the aromatic concentration is obtained by the mass % of the total of carbon atoms and hydrogen atoms constituting the aromatic rings in the polyol compound, and the weighted average aromatic concentration is an aromatic concentration calculated by taking a weighted average of the respective contents of carbon atoms and hydrogen atoms in the aromatic rings. The aromatic polyester polyol is preferably a condensate of an aromatic dicarboxylic acid such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), or naphthalenedicarboxylic acid with a glycol. Among these, from the viewpoint of improving the flame retardancy, particularly the flame spread resistance, of the polyurethane foam, the aromatic polyester polyol more preferably contains a phthalic acid-based polyester polyol which is a condensate of phthalic acid and a glycol, and even more preferably contains at least one selected from p-phthalic acid-based polyester polyol which is a condensate of p-phthalic acid and a glycol, and o-phthalic acid-based polyester polyol which is a condensate of o-phthalic acid and a glycol.

[0035] When the polyol compound contains an aromatic polyester polyol, the content thereof is not particularly limited, but is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 100 parts by mass, per 100 parts by mass of the polyol compound in the flame-retardant urethane resin composition.

[0036] The weighted average hydroxyl value of the polyol compound is preferably 20 to 350 mgKOH / g, more preferably 30 to 300 mgKOH / g, and even more preferably 50 to 250 mgKOH / g. When the hydroxyl value of the polyol is equal to or less than the upper limit, the viscosity of the polyol composition tends to decrease, which is preferable from the viewpoint of handleability, etc. On the other hand, when the hydroxyl value of the polyol is equal to or more than the lower limit, the crosslink density of the polyurethane foam increases, thereby increasing the strength and improving the workability when sprayed. The hydroxyl value of the polyol compound can be measured in accordance with JIS K 1557-1:2007.

[0037] Here, the weighted average hydroxyl value of a polyol compound is calculated by multiplying the hydroxyl values ​​of the individual polyols constituting the polyol compound by the weight fraction of each polyol in the polyol compound. For example, when two types of polyol (d1) and polyol (d2) are used as the polyol compound, the weighted average hydroxyl value is expressed by the following formula, where X1 is the hydroxyl value of polyol (d1), m1 is the blending amount, and X2 is the hydroxyl value of polyol (d2), m2 is the blending amount. The blending amounts m1 and m2 are the parts by mass per 100 parts by mass of the polyol compound. Weighted average hydroxyl value (mgKOH / g)=X1×(m1 / (m1+m2))+X2×(m2 / (m1+m2))

[0038] (catalyst) The polyol composition of the present invention contains a catalyst, and the catalyst contained in the present invention preferably contains a trimerization catalyst.

[0039] <Trimerization catalyst> The trimerization catalyst is a catalyst that promotes trimerization to form an isocyanurate bond. By promoting trimerization in a flame-retardant urethane resin composition, the flame retardancy and flame spread resistance of the polyurethane foam are improved. Examples of trimerization catalysts that can be used include aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal salts such as potassium acetate, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium formate, potassium octoate, and sodium octoate; aziridines such as 2-ethylaziridine; lead compounds such as lead naphthenate and lead octoate; alcoholate compounds such as sodium methoxide; phenolate compounds such as potassium phenoxide; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt; and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt. Among these, quaternary ammonium salts are preferred. The use of quaternary ammonium salts maintains good catalytic activity, even when a hydrofluoroolefin compound such as a hydrochlorofluoroolefin is used as a blowing agent, resulting in appropriate trimerization and improved flame retardancy. The trimerization catalyst may be used alone or in combination of two or more, but from the viewpoint of sufficiently enhancing the flame retardancy of the polyurethane foam, it is preferable to use two or more in combination. When two or more are used in combination, it is preferable to use an alkali metal salt and a quaternary ammonium salt, and it is more preferable to use potassium 2-ethylhexanoate and a tetramethylammonium salt.

[0040] The content of the trimerization catalyst is not particularly limited, but is preferably in the range of 1 to 15 parts by mass, more preferably 1.5 to 13 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the polyol compound. By setting the content of the trimerization catalyst within the above range, isocyanurate bonds are formed appropriately, and flame retardancy is improved.

[0041] <Urethanization catalyst> The polyol composition of the present invention may contain a urethanization catalyst in addition to the trimerization catalyst described above. The urethanization catalyst is a catalyst that promotes the reaction between a polyol compound and a polyisocyanate compound. The urethanization catalyst preferably contains a metal catalyst such as a tin compound or a bismuth compound.

[0042] Examples of tin compounds include stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, etc. Examples of bismuth compounds include bismuth neodecanoate, bismuth octoate, etc.

[0043] From the viewpoint of initial activity, the polyol composition of the present invention preferably contains, as a metal catalyst, at least one selected from the group consisting of bismuth compounds and tin compounds. Furthermore, the content of the metal catalyst among the urethane-forming catalysts is preferably 0.05 to 18 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 1 to 13 parts by mass, per 100 parts by mass of the polyol compound. When the content of the metal catalyst is at least the above-mentioned lower limit, the initial activity of the flame-retardant urethane resin composition is improved, and accordingly, the foamability of the composition is also improved. On the other hand, when the content of the metal catalyst is at most the above-mentioned upper limit, it is possible to effectively prevent lateral foaming during foaming of the flame-retardant urethane resin composition.

[0044] The urethanization catalyst may contain, in addition to the above-mentioned metal catalyst, an amino compound, an acetylacetone metal salt, etc., with the amino compound being preferred. Examples of the amino compound include imidazole compounds such as 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group. Of the imidazole compounds, 1,2-dimethylimidazole is preferred.

[0045] When an amino compound is contained as the urethanization catalyst, the content of the amino compound is preferably 2 to 14 parts by mass, more preferably 3 to 10 parts by mass, and even more preferably 3.5 to 9 parts by mass, per 100 parts by mass of the polyol compound.

[0046] Examples of acetylacetone metal salts include acetylacetone aluminum, acetylacetone iron, acetylacetone copper, acetylacetone zinc, acetylacetone beryllium, acetylacetone chromium, acetylacetone indium, acetylacetone manganese, acetylacetone molybdenum, acetylacetone titanium, acetylacetone cobalt, acetylacetone vanadium, and acetylacetone zirconium.

[0047] The urethanization catalyst contained in the polyol composition of the present invention may be used alone or in combination of two or more. When a metal catalyst is contained as the urethanization catalyst, it is preferable to contain the above-mentioned bismuth compound from the viewpoint of improving the foamability when forming a polyurethane foam by spraying the flame-retardant urethane resin composition. Furthermore, when a urethanization catalyst other than a metal catalyst is contained in addition to the above-mentioned metal catalyst, it is preferable to use a bismuth compound and an amino compound in combination as the urethanization catalyst, and it is more preferable to use a bismuth compound and an imidazole compound in combination.

[0048] The content of the urethanization catalyst in the polyol composition of the present invention is, for example, 2 parts by mass or more, preferably 3 parts by mass or more, per 100 parts by mass of the polyol compound. By ensuring that the content is equal to or greater than the above lower limit, the reaction between the polyol compound and the polyisocyanate compound can be promoted at an appropriate reaction rate while improving foamability. Furthermore, in order to improve the reaction rate and make the composition suitable for spray applications, the content of the urethanization catalyst is more preferably 4 parts by mass or more, and even more preferably 5 parts by mass or more. Furthermore, from the viewpoint of obtaining foamability and reactivity commensurate with the catalyst content, the content of the urethanization catalyst is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and even more preferably 15 parts by mass or less.

[0049] (foaming agent) Specific examples of blowing agents include water, low-boiling hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, hydrofluoroolefins, etc. Further examples of 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 point hydrocarbon include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Examples of the chlorinated aliphatic hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Examples of the fluorine compound include CHF3, CH2F2, and CH3F. Examples of the hydrochlorofluorocarbon compounds include trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), and HCFC142b (1-chloro-1,1-difluoroethane)). Examples of the hydrofluorocarbon include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane). Examples of the ether compounds include diisopropyl ether. Examples of the hydrofluoroolefin include HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene), HFO-1234yf (2,3,3,3-tetrafluoro-1-propene), HFO-1336mzz(Z) (cis-1,1,1,4,4,4-hexafluorobut-2-ene), and HFO-1224yd(Z).

[0050] Among the above, hydrofluoroolefins, water, and the like are preferred as the blowing agent, and it is more preferred to use hydrofluoroolefins and water in combination. From the viewpoint of adjusting the density of the foam within a desired range, the content of the blowing agent is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the polyol compound.

[0051] The amount of hydrofluoroolefin used as a blowing agent is preferably 5 to 70 parts by mass, more preferably 8 to 60 parts by mass, and even more preferably 18 to 50 parts by mass, per 100 parts by mass of the polyol compound, from the viewpoint of achieving a polyurethane foam density within a desired range.

[0052] As the water used as a blowing agent, for example, ion-exchanged water, distilled water, etc. can be used as appropriate. Among these, it is preferable to use ion-exchanged water. The amount of water per 100 parts by mass of the polyol compound is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 5 parts by mass, and even more preferably 0.3 to 3 parts by mass. By setting the water content within the above range, a good balance between flame retardancy and foaming properties can be achieved.

[0053] (liquid flame retardant) The flame retardant contained in the polyol composition of the present invention may be a liquid flame retardant in addition to the above-mentioned phosphorus-based solid flame retardant. The liquid flame retardant is not particularly limited, but a phosphate ester-based flame retardant is preferred. Examples of the phosphate ester-based flame retardant include monophosphate ester and condensed phosphate ester. The monophosphate ester is not particularly limited, but examples thereof include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trischloroethyl phosphate, and tris(β-chloropropyl) phosphate. The condensed phosphate ester is not particularly limited, but examples thereof include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), and aromatic condensed phosphate ester (trade name CR747) (trade name ADEKA PFR). Among the above, monophosphate esters are preferred, and monophosphate esters having a halogen atom such as tris(β-chloropropyl)phosphate are more preferred. When a phosphate ester having a halogen atom is used as a liquid flame retardant, flame retardancy is easily improved. The content of the liquid flame retardant is preferably 20 to 150 parts by mass, more preferably 30 to 120 parts by mass, and even more preferably 45 to 85 parts by mass, relative to 100 parts by mass of the polyol compound.

[0054] When a liquid flame retardant is contained in the polyol composition of the present invention, the content ratio of the liquid flame retardant to the phosphorus-based solid flame retardant is preferably 0.2 to 3, more preferably 0.3 to 2.5, and even more preferably 0.4 to 2. By setting the content ratio of the liquid flame retardant to at least the above lower limit, the flame retardancy of the polyurethane foam can be improved, and the viscosity of the polyol composition can be adjusted to a desired value, resulting in excellent handleability of the composition. On the other hand, by setting the content ratio of the liquid flame retardant to at most the above upper limit, the amount of halogen atoms can be reduced.

[0055] The content of halogen atoms derived from the flame retardants contained in the polyol composition of the present invention, i.e., the phosphorus-based solid flame retardant and the liquid flame retardant, is preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 15% by mass or less, based on the total amount of the polyol composition, from the viewpoint of preventing the generation of toxic gases derived from halogen atoms in the event of a fire. The lower limit of the halogen atom content is not particularly limited, and it is preferably 0% by mass or more, but from the viewpoint of improving the flame retardancy of the polyurethane foam, it is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. Here, the content of halogen atoms is calculated by dividing the sum of the product of the content of the flame retardant and the halogen concentration of each flame retardant by the total amount of the polyol composition. For example, when two types of flame retardant (A1) and flame retardant (A2) are used as flame retardants, the halogen concentration of the flame retardant (A1) is a1 (mass%), the content is b1, the halogen concentration of the flame retardant (A2) is a2 (mass%), the content is b2, and the total amount of the polyol composition is M, the content of halogen atoms is expressed by the following formula. Note that the contents b1 and b2 and the total amount M are the number of parts by mass per 100 parts by mass of the polyol compound. Halogen atom content (mass%) = (a1 × b1 + a2 × b2) / M

[0056] (Foam stabilizer) The polyol composition of the present invention may contain a foam stabilizer. As the foam stabilizer, a compound having a polar portion and a non-polar portion in the molecule and having a surfactant effect can be suitably used. The foam stabilizer is not particularly limited, but examples thereof include surfactants such as polyoxyalkylene foam stabilizers (e.g., polyoxyalkylene alkyl ethers) and silicone foam stabilizers (e.g., organopolysiloxanes). Silicone foam stabilizers may also be graft copolymers of polyoxyalkylene glycols, which are polymers of ethylene oxide or propylene oxide, with polydimethylsiloxane. Commercially available products may also be used, including SH-193 (manufactured by Dow Corning Toray Co., Ltd.), S-824-02 (Nippon Unicar Co., Ltd.), SZ-1704 (Nippon Unicar Co., Ltd.), F501 (Shin-Etsu Chemical Co., Ltd.), and SF-2937F (manufactured by Dow Toray Co., Ltd.). The content of the foam stabilizer is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 12 parts by mass, and even more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the polyol compound.

[0057] (Other ingredients) The flame-retardant urethane resin composition may contain one or more selected from phenolic, amine, sulfur-based and other antioxidants, heat stabilizers, light stabilizers, metal inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, dyes, and the like, as needed, provided the object of the present invention is not impaired.

[0058] (Manufacturing method) The method for producing the polyol composition of the present invention is not particularly limited, and the polyol composition can be produced, for example, by stirring the components at about room temperature for about 30 seconds to 20 minutes using a homodisper or the like. In the present invention, the polyol composition does not contain red phosphorus, and therefore is easy to handle during production.

[0059] [Flame-retardant urethane resin composition] The flame-retardant urethane resin composition of the present invention contains the polyol composition and a polyisocyanate compound. The flame-retardant urethane resin composition is obtained by mixing the polyol composition and the polyisocyanate compound. Like the polyol composition, the flame-retardant urethane resin composition does not contain red phosphorus.

[0060] (Polyisocyanate compounds) The polyisocyanate compound contained in the flame-retardant urethane resin composition of the present invention can be any of various polyisocyanate compounds, such as aromatic, alicyclic, and aliphatic polyisocyanate compounds having two or more isocyanate groups. Liquid diphenylmethane diisocyanate (MDI) is preferred because of its ease of handling, rapid reaction, excellent physical properties of the resulting polyurethane foam, and low cost. Examples of liquid MDI include crude MDI (also known as polymeric MDI). Specific commercial liquid MDI products include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.) and "Millionate MR-200" (manufactured by Nippon Polyurethane Industry Co., Ltd.). Uretonimine-containing MDI (e.g., commercially available product "Millionate MTL" manufactured by Nippon Polyurethane Industry Co., Ltd.) may also be used. Furthermore, isocyanate compounds in which some of the isocyanate-active groups have been reacted with hydroxyl-containing compounds to enhance their affinity with polyols may also be used. In addition to liquid MDI, other polyisocyanate compounds may be used in combination, and as the polyisocyanate compounds to be used in combination, any polyisocyanate compounds known in the technical field of polyurethanes can be used without any limitations.

[0061] The isocyanate index of the flame-retardant urethane resin composition of the present invention is preferably not more than 600, more preferably not more than 550, and even more preferably not more than 500. When the isocyanate index is not more than these upper limit values, two-stage foaming during foam formation is more likely to be suppressed. The isocyanate index of the flame-retardant urethane resin composition is preferably 100 or more, more preferably 150 or more, and even more preferably 2000 or more, from the viewpoint of properly forming a polyurethane foam. The isocyanate index (INDEX) is calculated by the following method.

[0062] INDEX = number of equivalents of polyisocyanate compound ÷ (number of equivalents of polyol compound + number of equivalents of water) × 100 where: Equivalent weight of polyisocyanate compound = number of parts of polyisocyanate compound used x NCO content (%) x 100 / NCO molecular weight Equivalent weight of polyol compound = OHV × number of parts of polyol compound used ÷ molecular weight of KOH, where OHV is the hydroxyl value of polyol (mgKOH / g), Equivalents of water = parts of water used x number of OH groups in water / molecular weight of water In the above formula, the unit of parts used is weight (g), the molecular weight of the NCO group is 42, the NCO content is the proportion of NCO groups in the polyisocyanate compound expressed as mass %, and for the convenience of unit conversion in the above formula, the molecular weight of KOH is set to 56,100, the molecular weight of water is set to 18, and the number of OH groups in water is set to 2.

[0063] (Total heat generation) The polyurethane foam made from the foamable urethane resin composition of the present invention has a radiant heat intensity of 50 kW / m2 in accordance with the test method of ISO-5660. 2 When heated for 10 minutes, the total calorific value is 8MJ / m 2 The total calorific value is preferably 8MJ / m or less. 2 The polyurethane foam made from the foamable urethane resin composition of the present invention has a predetermined flame retardancy due to the following: From the viewpoint of further improving the flame retardancy of the foam, the total calorific value is set to 7.8 MJ / m 2 More preferably, it is 7MJ / m or less. 2 It is even more preferable that: Furthermore, the polyurethane foam made from the foamable urethane resin composition of the present invention has a total calorific value of 8 MJ / m when heated for 20 minutes in the same manner as above. 2 Even more preferably, it is 6MJ / m or less. 2 It is particularly preferred that:

[0064] (Maximum heat generation rate) The polyurethane foam made from the foamable urethane resin composition of the present invention was subjected to a test in accordance with ISO-5660 to measure a radiation heat intensity of 50 kW / m 2The maximum heat generation rate when heated for 10 minutes is 150kW / m 2 It is preferable that the maximum heat generation rate is 150 kW / m or less. 2 When the maximum heat release rate and total heat release amount are both adjusted as described above, the polyurethane foam made from the composition has a predetermined flame retardancy. In order to further improve the flame retardancy of polyurethane foam, the maximum heat release rate is set to 130 kW / m 2 More preferably, it is 110 kW / m or less. 2 It is even more preferable that:

[0065] The total calorific value and maximum heat release rate are measured by a cone calorimeter test, and specifically, can be measured by the method described in the Examples. In the above-mentioned cone calorimeter test, it is preferable that the polyurethane foam used in the test has a shape stability to such an extent that it does not come into contact with the spark igniter of the cone calorimeter.

[0066] [Polyurethane foam] The polyurethane foam formed from the flame-retardant urethane resin composition of the present invention is formed from the above-mentioned flame-retardant urethane resin composition, and specifically, is obtained by foaming and curing the flame-retardant urethane resin composition. The polyurethane foam of the present invention does not discolor to red because the flame-retardant urethane resin composition used to obtain the foam does not contain red phosphorus, resulting in excellent design. Furthermore, the polyurethane foam of the present invention is white or cream-colored, and the color tone can be easily changed by adding a colorant.

[0067] (Application) The flame-retardant urethane resin composition of the present invention and the polyurethane foam formed from the composition are not particularly limited in their applications, and they can be used to fill cavities in structures such as buildings, furniture, automobiles, trains, ships, etc., or to be sprayed onto such structures. Of these, spraying onto structures, i.e., spray applications, is preferred. Spraying can be carried out using a spraying device (e.g., GRACO's A-25) and a spray gun (e.g., Gasmar's D-gun). Spraying can be carried out by adjusting the temperature of the polyol composition and polyisocyanate composition contained in separate containers in the spraying device, causing them to collide and mix at the tip of the spray gun, and then turning the mixed liquid into a mist using air pressure. Spraying devices and spray guns are well known, and commercially available products can be used. Furthermore, the temperature settings and pressure of the raw liquid can be set according to general spraying conditions for polyurethane foam. [Example]

[0068] The present invention will be explained in more detail by way of examples, but the present invention is not limited to these examples in any way.

[0069] Details of each component used in each example and comparative example are as follows. (Polyol compound) Aromatic polyester polyol p-phthalic acid-based polyester polyol (Kawasaki Chemical Industries, Ltd., product name "Maximol RLK-087", aromatic concentration 8%, hydroxyl value = 200 mg KOH / g) Aromatic polyester polyol p-phthalic acid-based polyester polyol (Kawasaki Chemical Industries, Ltd., product name "Maximol RFK-505", aromatic concentration 22%, hydroxyl value = 250 mg KOH / g) (Foam stabilizer) Silicone foam stabilizer (manufactured by Dow Toray, product name "SH-193") (catalyst) (1) Trimerization catalyst Alkali metal salt: Potassium 2-ethylhexanoate (manufactured by Evonik, product name "DABCO K-15"), concentration 70-80% by mass Quaternary ammonium salt: 2,2-dimethylpropanoic acid tetramethylammonium salt (manufactured by Evonik, product name "DABCO TMR7"), concentration approximately 45% by mass (2) Urethane catalyst 1,2-Dimethylimidazole (amino compound: manufactured by Kao Corporation, product name: KL No. 390, concentration 65-75% by mass) Bismuth 2-ethylhexanoate (urethane metal catalyst: manufactured by Nitto Kasei Co., Ltd., product name: Bi28, concentration 81-90% by mass) (liquid flame retardant) Phosphate ester flame retardant: Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name "TMCPP", halogen atom content 32.5% by mass, phosphorus concentration 9.5%) (Phosphorus-based solid flame retardant) Red phosphorus (manufactured by Rinkagaku Kogyo Co., Ltd., product name "Nova Excel 140", halogen atom content 0% by mass, phosphorus concentration 100% by mass) Type II ammonium polyphosphate (manufactured by Taihei Chemical Industry Co., Ltd., product name "Taien C2", halogen atom content 0% by mass, phosphorus concentration 31% by mass, average particle size 17 μm) Type I ammonium polyphosphate (manufactured by Taihei Chemical Industry Co., Ltd., product name "Taien K," halogen atom content 0% by mass, phosphorus concentration 30% by mass, average particle size 23 μm) Ammonium phosphate (manufactured by Taihei Chemical Industry Co., Ltd., product name "Ammonium Phosphate C", halogen atom content 0% by mass, phosphorus concentration 27% by mass) Metal phosphinate (Clariant Japan, product name "OP930", halogen atom content 0% by mass, phosphorus concentration 23% by mass) Intumescent flame retardant (ADEKA Corporation, product name "FP-2200", a mixture of dimelamine pyrophosphate and piperazine pyrophosphate, halogen atom content 0% by mass, phosphorus concentration 18.5% by mass) Aluminum phosphite (manufactured by Taihei Chemical Industry Co., Ltd., product name "APA-100", halogen atom content 0% by mass, phosphorus concentration 29% by mass) Phosphazene compound (Fushimi Pharmaceutical Co., Ltd., product name "FP-110", halogen atom content 0% by mass, phosphorus concentration 14%) Phosphate ester compound (manufactured by Daihachi Chemical Industry Co., Ltd., product name "CR-900", tris(tribromoneopentyl)phosphate, halogen atom content 70.6% by mass, phosphorus concentration 3% by mass) (foaming agent) Ion-exchanged water HFO-1233zd (hydrofluoroolefin) (Honeywell, product name: Solstice LBA) (Polyisocyanate compounds) MDI (manufactured by Sumika Covestro Urethane Co., Ltd., product name: 44V-20)

[0070] The methods for measuring the physical properties and characteristics of the polyurethane foam are as follows. [Total heat generation, maximum heat generation rate] The total heat release amount and maximum heat release rate of the polyurethane foams produced in each of the Examples and Comparative Examples were evaluated by the following methods. The polyurethane foams with gypsum board as a base obtained in each Example and Comparative Example were cut into a length of 10 cm, a width of 10 cm and a thickness of 3.25 cm (within which the gypsum board was 12.5 mm) to prepare samples for cone calorimeter testing. The cone calorimeter test samples were subjected to a radiant heat intensity of 50 kW / m in accordance with the test method of ISO-5660. 2 The total heat release rate and maximum heat release rate were measured when the sample was heated at 40°C for 10 minutes.

[0071] The result of the 10-minute test was 6.0MJ / m 2 The following items were also tested for 20 minutes under the same conditions. The evaluation criteria for the total heat generation amount are as follows: ◎: 6.0MJ / m in 20-minute test 2 below ○: 8.0MJ / m in 10-minute test 2 below △: 9.0MJ / m in 10-minute test 2 below ×: 9.0 MJ / m in 10-minute test 2 Super

[0072] [Color tone] The appearance of the polyurethane foams produced in each of the Examples and Comparative Examples was visually inspected and the color tone was evaluated. The evaluation criteria were as follows: ◯: The foam did not turn red. ×: The foam turned red.

[0073] [Examples 1 to 10, Comparative Examples 1 to 3] A polyol composition obtained by mixing a polyol compound, a foam stabilizer, a catalyst, a liquid flame retardant, a phosphorus-based solid flame retardant, and a blowing agent according to the formulation shown in Table 1, and a polyisocyanate compound were stirred at 8000 rpm for 3 seconds at a liquid temperature of 10°C to give a total of 200 g, and the resulting liquid mixture was sprayed into a box measuring 180 mm x 180 mm and 100 mm deep. However, for the cone calorimeter test sample, a 12.5 mm thick gypsum board was set at the bottom of the box as a base and the sample was sprinkled on top of it.

[0074] The polyurethane foam thus obtained was subjected to the above-mentioned evaluations. The evaluation results for each item are shown in Table 1.

[0075] [Table 1]

[0076] The parts by mass of each catalyst are parts by mass of the product.

[0077] As described above, the polyurethane foams obtained from the flame-retardant urethane resin compositions produced in each Example maintained good flame retardancy and also had excellent color tone without discoloring to red. On the other hand, the flame-retardant urethane resin composition prepared in Comparative Example 1 did not contain a phosphorus-based solid flame retardant, and therefore the polyurethane foam obtained from this composition had impaired flame retardancy. Also, the flame-retardant urethane resin compositions prepared in Comparative Examples 2 and 3 contained red phosphorus, and therefore the polyurethane foams obtained from these compositions turned red, impairing their design properties.

Claims

1. A polyol composition containing a polyol compound, a phosphorus-based solid flame retardant, a catalyst, and a blowing agent, The polyol composition, wherein the phosphorus-based solid flame retardant does not contain red phosphorus.

2. The polyol composition according to claim 1 , wherein the phosphorus concentration in the polyol composition is 2.5% by mass or more.

3. 3. The polyol composition according to claim 1, wherein the phosphorus-based solid flame retardant is at least one selected from the group consisting of phosphates, phosphazene compounds, phosphoric acid ester compounds, and metal phosphinates.

4. The polyol composition according to claim 3 , wherein the phosphorus-based solid flame retardant contains the phosphate, and the phosphate has a phosphorus concentration of 25 mass % or more.

5. The polyol composition according to claim 3 or 4, wherein the phosphorus-based solid flame retardant comprises a polyphosphate.

6. The polyol composition according to claim 5, wherein the polyphosphate has an average particle size of 50 μm or less.

7. The polyol composition according to any one of claims 1 to 6, wherein the polyol compound has a weighted average aromatic concentration of 10% by mass or more.

8. The polyol composition of any one of claims 1 to 7, wherein the catalyst comprises a trimerization catalyst.

9. The polyol composition according to any one of claims 1 to 8, wherein the catalyst comprises at least one selected from the group consisting of bismuth compounds and tin compounds.

10. The polyol composition contains a liquid flame retardant, The polyol composition according to any one of claims 1 to 9, wherein the content ratio of the liquid flame retardant to the phosphorus-based solid flame retardant is 0.2 to 3.

11. The polyol composition according to any one of claims 1 to 10, wherein the content of halogen atoms derived from a flame retardant in the polyol composition is 20 mass% or less.

12. A flame-retardant urethane resin composition comprising the polyol composition according to any one of claims 1 to 11 and a polyisocyanate compound, The flame-retardant urethane resin composition does not contain red phosphorus.

13. In accordance with the ISO-5660 test method for polyurethane foam formed from a flame-retardant urethane resin composition, a radiant heat intensity of 50 kW / m ２ The total heat generated when heated for 10 minutes is 8MJ / m ２ The flame-retardant urethane resin composition according to claim 12, wherein:

14. The flame-retardant urethane resin composition according to claim 12 or 13, which is used for spray applications.

15. A polyurethane foam formed from the flame-retardant urethane resin composition according to any one of claims 12 to 14.

Images