Polyol composition, polyurethane resin composition, and polyurethane foam

Abstract

To provide a polyol composition that can form a polyurethane foam having flame retardancy, and also has high storage stability.SOLUTION: A polyol composition contains a polyol, a flame retardant, a foaming agent, a catalyst, and a nucleophilic inhibitor.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Due to its excellent heat insulating properties and adhesiveness, polyurethane foam is used as a heat insulating material in buildings such as apartment complexes, detached houses, various school facilities, and commercial buildings. Polyurethane foam is obtained by mixing a polyol composition and an isocyanate, foaming the mixture, and spraying the mixture onto objects such as ceilings, walls, and roofs using a spray device. Since such polyurethane foam is used in buildings, it is natural that it must be flame retardant to prevent the fire from spreading to the polyurethane foam in the event of a fire.

[0003] As a polyol composition for obtaining the above-mentioned polyurethane foam, for example, a polyol composition containing an HFO-based blowing agent, a catalyst, and a flame retardant, as described in Patent Document 1, is known. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-172650 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in such conventional polyol compositions, the flame retardant may react with the catalyst, resulting in a loss of catalyst activity. This problem tends to be particularly pronounced when the flame retardant contains a metal component, since the metal component and the catalyst undergo a chelation reaction. Even if the flame retardant does not contain a metal component and does not react with the catalyst, the blowing agent may react with the catalyst to produce a different compound, which also results in a loss of catalyst activity. In particular, when an amine compound is used as the catalyst, the above-mentioned series of problems tend to become more pronounced. When the activity of the catalyst in the polyol composition is impaired in this way, the storage stability of the polyol composition decreases, making it impossible to store the polyol composition in a stable state, which results in a decrease in the reaction rate with isocyanate, making it impossible to form a high-quality polyurethane foam.

[0006] Therefore, an object of the present invention is to provide a polyol composition that can form a flame-retardant polyurethane foam and has excellent storage stability. [Means for solving the problem]

[0007] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by a polyol composition containing a polyol, a flame retardant, a blowing agent, a catalyst, and a nucleophilic inhibitor, and have thus completed the present invention.

[0008] The present invention is summarized as follows [1] to [7]. [1] A polyol composition comprising a polyol, a flame retardant, a blowing agent, a catalyst, and a nucleophilic inhibitor. [2] The polyol composition according to [1], wherein the flame retardant comprises a metal-based flame retardant. [3] The polyol composition according to [1] or [2], wherein the nucleophilic inhibitor is at least one selected from the group consisting of alkali metal compounds and alkaline earth metal compounds. [4] The polyol composition according to any one of [1] to [3], wherein the blowing agent comprises a hydrofluoroolefin (HFO). [5] The polyol composition according to any one of [1] to [4], wherein the catalyst comprises an amine catalyst. [6] A polyurethane resin composition comprising the polyol composition according to any one of [1] to [5] and an isocyanate. [7] A polyurethane foam obtained by reacting and foaming the polyurethane resin composition according to [6]. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a polyol composition which can form a flame-retardant polyurethane foam and has excellent storage stability. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Polyol composition] The polyol composition of the present invention contains a polyol, a flame retardant, a blowing agent, a catalyst, and a nucleophilic inhibitor.

[0011] <Nucleophilic inhibitors> The polyol composition of the present invention contains a nucleophilic inhibitor. The electrophilic nucleophilic inhibitor acts on the catalyst in the polyol composition preferentially over the flame retardant or blowing agent, and acts gently on the catalyst to such an extent that the catalyst's activity is not impaired, thereby suppressing the reaction between the flame retardant and the catalyst, or between the blowing agent and the catalyst. Therefore, by including a nucleophilic inhibitor in the polyol composition, the reaction between the flame retardant, particularly a metal-based flame retardant, and the catalyst, or between the blowing agent and the catalyst, can be suppressed, thereby maintaining the storage stability of the polyol composition. Nucleophilic inhibitors used in the present invention include alkali metal compounds, alkaline earth metal compounds, transition metal compounds, and the like. Examples of alkali metal compounds used as nucleophilic inhibitors include hydroxides, carbonates, acetates, etc. of alkali metals. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. Examples of alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, etc. Examples of alkali metal carboxylates include acetates of alkali metals such as lithium acetate, sodium acetate, potassium acetate, etc.

[0012] Examples of alkaline earth metal compounds include hydroxides, carbonates, sulfates, etc. of alkaline earth metals. Examples of alkaline earth metal hydroxides include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, etc. Examples of alkaline earth metal carbonates include beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, etc. Examples of alkaline earth metal sulfates include beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, etc. Examples of transition metal compounds include hydroxides of transition metals, such as manganese(II) hydroxide, iron(II) hydroxide, iron(III) hydroxide, nickel(II) hydroxide, copper(II) hydroxide, zinc hydroxide, vanadium hydroxide, and chromium(III) hydroxide.

[0013] The nucleophilic inhibitors used in the present invention may be used alone or in combination of two or more, but it is preferable to use one alone. The nucleophilic inhibitor used in the present invention is preferably at least one selected from the group consisting of alkali metal compounds and alkaline earth metal compounds. Among these, alkaline earth metal compounds are more preferred, and alkaline earth metal hydroxides are even more preferred, as they are more likely to exhibit the effects of the nucleophilic inhibitor. Specific preferred compounds include magnesium hydroxide, lithium hydroxide, sodium acetate, potassium carbonate, calcium carbonate, barium sulfate, and copper (II) hydroxide, with magnesium hydroxide being particularly preferred.

[0014] The content of the nucleophilic inhibitor in the polyol composition of the present invention is preferably 0.2 to 87 parts by mass, more preferably 0.5 to 60 parts by mass, even more preferably 1 to 30 parts by mass, and particularly preferably 2 to 10 parts by mass, per 100 parts by mass of the polyol described below. When the content of the nucleophilic inhibitor is equal to or greater than the lower limit, catalyst deactivation is reliably suppressed. On the other hand, when the content of the nucleophilic inhibitor is equal to or less than the upper limit, catalyst activity can be appropriately maintained.

[0015] <Polyol> The polyol is not particularly limited, but examples thereof include polyether polyols and polyester polyols. From the viewpoint of improving the flame retardancy of the polyurethane foam, the polyol preferably includes a polyester polyol. Also, from the viewpoint of improving the flame retardancy, it is preferable to use a halogen-containing polyol or a phosphorus-containing polyol. From this viewpoint, for every 100 parts by mass of polyol, it is preferable to use polyester polyol in an amount of 20 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 80 parts by mass or more, and particularly preferably 100 parts by mass.

[0016] The average hydroxyl value of the polyol used in the present invention is preferably from 100 to 500 mgKOH / g, more preferably from 150 to 450 mgKOH / g, and even more preferably from 200 to 400 mgKOH / g, from the viewpoint of improving the flame retardancy of the polyurethane foam.

[0017] When one type of polyol is used, the average hydroxyl value refers to the hydroxyl value of that polyol. When two or more types of polyols are used, the average hydroxyl value is the weighted average value of the hydroxyl groups in accordance with the blending ratio of the two or more types of polyols. For example, when two types of polyols, polyol (d1) and polyol (d2), are used as polyols, the hydroxyl value of polyol (d1) is X1, the blending ratio is m1, and the hydroxyl value of polyol (d2) is X2, the blending ratio is m2, the average hydroxyl value is expressed by the following formula: Note that the blending ratio is based on mass. Average hydroxyl value (mgKOH / g)=X1×(m1 / (m1+m2))+X2×(m2 / (m1+m2)) The hydroxyl value is a value measured in accordance with JIS K1557-1:2007.

[0018] (polyester polyol) The polyester polyol may be a polyester polyol having an aromatic ring or an aliphatic polyester polyol, but when the flame retardancy of the resulting polyurethane foam is taken into consideration, it is preferable to use a polyester polyol having an aromatic ring. The polyester polyol having an aromatic ring 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. In particular, from the viewpoint of improving the flame retardancy of the polyurethane foam, it is preferable that the polyol contains a phthalic acid-based polyester polyol, which is a condensate of phthalic acid and a glycol, and more preferably a p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid and a glycol. The glycol is not particularly limited, but it is preferable to use low molecular weight aliphatic glycols known as constituent components of polyester polyols, such as ethylene glycol, propylene glycol, and diethylene glycol.

[0019] The hydroxyl value of the polyester polyol is preferably from 100 to 500 mgKOH / g, more preferably from 150 to 450 mgKOH / g, and even more preferably from 200 to 400 mgKOH / g.

[0020] (Polyether polyol) Polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of alkylene oxide to an initiator having two or more active hydrogen atoms. Specific examples of the initiator include aliphatic polyhydric alcohols (e.g., 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; tetrafunctional alcohols such as pentaerythritol; and highly functional alcohols such as sucrose and sorbitol), aliphatic amines (e.g., alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine; alkanolamines such as monoethanolamine and diethanolamine), and aromatic amines (e.g., aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, and Mannich condensation products). The polyether polyol preferably has an aromatic ring.Among the above, the polyether polyol produced using an initiator having an aromatic ring is the polyether polyol having an aromatic ring, for example, the polyether polyol produced using an aromatic amine as an initiator is the polyether polyol having an aromatic ring.Among the polyether polyols having an aromatic ring, tolylenediamine-based polyether polyols, Mannich-based polyether polyols, etc. can be preferably used.

[0021] The tolylenediamine-based polyether polyol is a tolylenediamine-based polyether polyol produced using tolylenediamine as an initiator. The Mannich polyether polyol is a polyether polyol obtained by utilizing the Mannich reaction, which is a Mannich condensation product having two or more hydroxyl groups in the molecule, or a polyether polyol obtained by adding an alkylene oxide to such a Mannich condensation product. More specifically, it is a Mannich condensation product obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde, and alkanolamine, or a polyether polyol obtained by ring-opening addition polymerization of this compound with at least one of ethylene oxide and propylene oxide.

[0022] The hydroxyl value of the polyether polyol is preferably from 200 to 2000 mgKOH / g, and more preferably from 300 to 1000 mgKOH / g.

[0023] <Flame retardant> The flame retardant contained in the polyol composition of the present invention is not particularly limited, but preferably contains a metallic flame retardant. As described above, metallic flame retardants cause relatively large catalyst deactivation, but in the present invention, the use of a nucleophilic inhibitor can improve flame retardancy while suppressing catalyst deactivation. Examples of metal flame retardants include metal borates, metal phosphates, stannates, sulfides, halides, sulfates, etc., and among these, metal borates and metal phosphates are preferred. Note that the metal salts mentioned above as nucleophilic inhibitors are not included in the metal flame retardants. Examples of metal borates include borates of alkali metals, alkaline earth metals, and elements of Groups 4, 12, and 13 of the periodic table. Specific examples 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. Of these, zinc borate is preferred. Examples of metal phosphates include 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, aluminum salts are preferred, and aluminum phosphite is more preferred.

[0024] The flame retardant contained in the polyol composition of the present invention may contain a flame retardant other than the above-mentioned metallic flame retardants, i.e., a non-metallic flame retardant. Non-metallic flame retardants are not particularly limited, but from the viewpoint of obtaining good flame retardancy, examples thereof include phosphate ester-based flame retardants, red phosphorus-based flame retardants, bromine-based flame retardants, and chlorine-based flame retardants. Among these, it is preferable to contain a phosphate ester-based flame retardant. It is more preferable to contain at least one of a bromine-based flame retardant and a red phosphorus-based flame retardant together with the phosphate ester-based flame retardant, and it is even more preferable to use at least a phosphate ester-based flame retardant and a red phosphorus-based flame retardant in combination. In addition, from the viewpoint of further improving flame retardancy, it is also preferable to use the non-metallic flame retardant in combination with a metallic flame retardant.

[0025] Examples of phosphate ester-based flame retardants include tricresyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, and octyl diphenyl phosphate. Furthermore, halogenated phosphate ester-based flame retardants such as tri(chloroethyl)phosphate, tris(dichloropropyl)phosphate, and tris(β-chloropropyl)phosphate may also be used. Among these, at least one selected from the group consisting of tris(β-chloropropyl)phosphate and triphenylphosphate is preferred, with tris(β-chloropropyl)phosphate being more preferred.

[0026] The red phosphorus-based flame retardant may be composed of red phosphorus alone, or may be red phosphorus coated with a resin, metal hydroxide, metal oxide, etc., or may be a powder obtained by mixing red phosphorus with a resin, metal hydroxide, metal oxide, etc. Note that when a metal hydroxide is used as a coating of red phosphorus or as a powder mixed with red phosphorus, it is used separately from the nucleophilic inhibitor. As the red phosphorus-based flame retardant, commercially available products such as Novaled 120 and Novaexcel 140 (both manufactured by Rinkagaku Kogyo Co., Ltd.) and Hishiguard (manufactured by Nippon Chemical Industry Co., Ltd.) can be used as they are.

[0027] The bromine-containing flame retardant is not particularly limited as long as it contains bromine in its molecular structure and is a solid at room temperature (23°C) and normal pressure (1 atmosphere), and examples thereof include brominated aromatic ring-containing aromatic compounds. Examples of the brominated aromatic ring-containing aromatic compound include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0028] The brominated aromatic ring-containing aromatic compound may be a bromine compound polymer. Specific examples include brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A as a raw material, copolymers of the polycarbonate oligomers with bisphenol A, and diepoxy compounds produced by reacting brominated bisphenol A with epichlorohydrin. Further examples include brominated epoxy compounds such as monoepoxy compounds obtained by reacting brominated phenols with epichlorohydrin, brominated phenol condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, and uncrosslinked or crosslinked brominated polystyrene. Furthermore, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may also be used. When the polyol composition of the present invention contains a brominated flame retardant, it is preferable that the brominated flame retardant contains ethylene bis(pentabromophenyl).

[0029] Examples of chlorine-based flame retardants include chlorinated paraffin, chlorinated polyethylene, dodecachloropentacyclooctadeca-7,15-diene (Dechlorane Plus 25 (registered trademark) (manufactured by Occidental Chemical)), and PEG anhydride.

[0030] The flame retardant may be contained alone or in combination of two or more. When two or more types are used in combination, one or more metallic flame retardants and one or more non-metallic flame retardants may be used in combination, two or more metallic flame retardants may be used in combination, or two or more non-metallic flame retardants may be used in combination. Therefore, the combination of flame retardants is not particularly limited, but from the viewpoint of improving the flame retardancy of the polyurethane foam, the flame retardant contained in the polyol composition of the present invention preferably contains a metallic flame retardant, more preferably contains zinc borate, and even more preferably contains a combination of zinc borate and one or more non-metallic flame retardants.

[0031] The content of the flame retardant in the polyol composition of the present invention is preferably 45 to 160 parts by mass, more preferably 55 to 150 parts by mass, and even more preferably 65 to 140 parts by mass, relative to 100 parts by mass of the polyol. The content of the metallic flame retardant is preferably 5 to 40 parts by mass, more preferably 10 to 35 parts by mass, and even more preferably 18 to 30 parts by mass, relative to 100 parts by mass of the polyol. The content of the non-metallic flame retardant is preferably 40 to 120 parts by mass, more preferably 45 to 115 parts by mass, and even more preferably 47 to 110 parts by mass, relative to 100 parts by mass of the polyol.

[0032] <Foaming agent> The blowing agent promotes foaming of the foamable polyurethane composition described below. Examples of the blowing agent include organic physical blowing agents such as low-boiling hydrocarbons such as water, propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane, chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride, ether compounds such as hydrofluoroolefins (hereinafter sometimes referred to as "HFO") and diisopropyl ether, and mixtures of these compounds, and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. The blowing agent contained in the polyol composition of the present invention is preferably at least one selected from the group consisting of water, cyclopentane, and HFO, among the above, and more preferably contains HFO, which has high stability as a blowing agent, is less likely to decrease in catalytic activity, and also has a low environmental impact. Furthermore, from the viewpoint of foaming ability, the blowing agent preferably contains a blowing agent having a boiling point of 40°C or less, and more preferably contains HFO, which has a boiling point of 40°C or less.

[0033] Examples of suitable HFO blowing agents include fluoroalkenes having about 3 to 6 carbon atoms. The HFO may also be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having about 3 to 6 carbon atoms. Examples of HFOs include trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorodifluoropropene, chlorotrifluoropropenes such as HFO-1233, and chlorotetrafluoropropene. More specifically, 3,3,3-trifluoropropene (HFO-1243zf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,1,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), trans-1,2,3,3,3-pentafluoropropene (HFO-1234ze(Z)), Examples of suitable fluoropropenes include fluoropropene (HFO-1225ye(E)), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,1,2,3,3-pentafluoropropene (HFO-1225yc), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), and 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz). Among these, at least one selected from the group consisting of HFO-1233zd(E) and HFO-1336mzz is preferred, with HFO-1233zd(E) being more preferred.

[0034] The content of the blowing agent is not particularly limited, and is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 35 to 60 parts by mass, per 100 parts by mass of the polyol. When the content of the blowing agent is equal to or greater than the lower limit, foaming is promoted, resulting in good foamability and a reduced density of the polyurethane foam. On the other hand, when the content of the blowing agent is equal to or less than the upper limit, excessive foaming can be prevented.

[0035] The above-mentioned blowing agents may be used alone or in combination of two or more. In the foamable polyurethane composition of the present invention, it is preferable to use the above-mentioned HFO in combination with another blowing agent. For example, HFO or cyclopentane may be used in combination with water, oxygen gas, or carbon dioxide gas, which are easy to handle. Water is particularly preferable from the viewpoints of adjusting the isocyanate index and ease of handling.

[0036] The content of HFO is not particularly limited, and is preferably 19 to 75 parts by mass, more preferably 29 to 67 parts by mass, and even more preferably 34 to 58 parts by mass, per 100 parts by mass of polyol. When the content of the blowing agent is equal to or greater than the lower limit, foaming is promoted, resulting in good foamability and enabling a reduction in the density of the polyurethane foam. On the other hand, when the content of the blowing agent is equal to or less than the upper limit, excessive foaming can be suppressed.

[0037] The content of cyclopentane is not particularly limited, and is preferably 19 to 75 parts by mass, more preferably 29 to 67 parts by mass, and even more preferably 34 to 58 parts by mass, per 100 parts by mass of polyol. When the content of the blowing agent is equal to or greater than the lower limit, foaming is promoted, foamability is improved, and the density of the polyurethane foam can be reduced. On the other hand, when the content of the blowing agent is equal to or less than the upper limit, excessive foaming can be suppressed.

[0038] The water content is not particularly limited, and is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and even more preferably 0.3 to 2 parts by mass, per 100 parts by mass of polyol. When the content of the blowing agent is equal to or greater than the lower limit, foaming is promoted, resulting in good foamability and a reduced density of the polyurethane foam. On the other hand, when the content of the blowing agent is equal to or less than the upper limit, excessive foaming can be prevented.

[0039] <Catalyst> (resinification catalyst) The catalyst contained in the polyol composition of the present invention is preferably an amine-based catalyst as a resinification catalyst, which sufficiently promotes the reaction between the polyol and the isocyanate, thereby producing a high-quality polyurethane foam. The amine catalyst contained in the polyol composition of the present invention is preferably at least one selected from the group consisting of imidazole compounds and tertiary amines other than imidazole compounds. These compounds are less susceptible to deactivation by blowing agents and flame retardants when acted upon by a nucleophilic inhibitor, thereby improving the storage stability of the polyol composition. The imidazole compound is preferably an imidazole substituted at the 1st and 2nd positions with an alkyl group having 8 or less carbon atoms, and the alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms. A specific example of a suitable imidazole compound is represented by the following general formula (1).

[0040] [ka] (In general formula (1), R 1 and R 2 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.

[0041] R in general formula (1) 1 and R 2each independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. The alkyl group and the alkenyl group may each be linear or have a branched structure. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a hexyl group, a heptyl group, and an octyl group. Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. R 1 and R 2 When the number of carbon atoms in the alkyl group or alkenyl group in R is equal to or greater than the lower limit, steric hindrance increases, making the polymer less susceptible to the influence of blowing agents such as hydrofluoroolefins, which is preferable. 1 and R 2 When the number of carbon atoms in the alkyl group is equal to or less than the upper limit, the steric hindrance is not extremely large, so that the reaction between the polyol and the isocyanate can proceed quickly, and the foaming property is also good. From these perspectives, R 1 and R 2 are each independently preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group.

[0042] Examples of the imidazole derivative represented by the general formula (1) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole.

[0043] Examples of tertiary amines other than imidazole compounds include morpholine compounds such as bis(2-morpholinoethyl)ether, 4,4'-carbonyldimorpholine, 4-[2-(ethoxycarbonyl)ethyl]morpholine, and 4-(p-tolyl)morpholine, diazabicycloundecene, triethylamine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol incorporated into a poly(p-vinylphenol) matrix, triethylenediamine, and N,N-dimethylpiperidine.

[0044] The amine catalyst contained as a resinification catalyst in the polyol composition of the present invention is preferably an imidazole compound. Among them, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are more preferred from the viewpoint of improving the activity of the catalyst in the presence of hydrofluoroolefin and from the viewpoint of rapidly progressing the reaction. Furthermore, 1,2-dimethylimidazole is even more preferred from the viewpoint of further improving stability.

[0045] The content of the amine catalyst in the polyol composition is preferably 1.5 to 20 parts by mass, more preferably 2 to 15 parts by mass, even more preferably 2.5 to 12 parts by mass, and particularly preferably 3 to 10 parts by mass, relative to 100 parts by mass of the polyol. When the content of the amine catalyst is equal to or greater than the lower limit, urethane bond formation is facilitated, the reaction proceeds rapidly, and foaming properties are improved. On the other hand, when the content of the amine catalyst is equal to or less than the upper limit, the reaction rate can be easily controlled, which is preferable.

[0046] (Foaming catalyst) The polyol composition of the present invention may contain a foaming catalyst. The foaming catalyst preferably contains a metal catalyst. In the present invention, the inclusion of a metal catalyst as the foaming catalyst promotes the reaction between the polyol and the isocyanate, thereby increasing the initial reaction rate in particular. Furthermore, the inclusion of a certain amount or more of a solid flame retardant, such as the red phosphorus-based flame retardant, tends to inhibit the reactivity of the polyurethane foam and reduce its foamability. However, the inclusion of a metal catalyst makes it easier to maintain good foamability of the polyurethane foam. From the viewpoint of foamability, the metal catalyst preferably contains bismuth or tin, and more preferably contains bismuth.

[0047] The metal catalyst is preferably a metal salt selected from bismuth and tin, more preferably a bismuth salt. The metal salt is preferably an organic acid metal salt, more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. When the carboxylic acid has 5 or more carbon atoms, stability to a blowing agent, particularly a hydrofluoroolefin, is improved. Furthermore, from the viewpoint of catalytic activity, the number of carbon atoms of the carboxylic acid is preferably 18 or less, more preferably 12 or less. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or may have a branched structure, but preferably has a branched structure. Specific examples of carboxylic acids include octylic acid, lauric acid, versatic acid, pentanoic acid, and acetic acid, among which octylic acid is preferred. That is, the transition metal salt is preferably a metal salt of octylic acid. These carboxylic acids may be linear as described above, but may also have a branched structure. An example of an octylic acid having a branched structure is 2-ethylhexanoic acid. As the metal salt of carboxylic acid, bismuth salt of carboxylic acid and tin salt of carboxylic acid are preferred, and among them, bismuth salt of octylic acid is preferred. Furthermore, the metal salt of carboxylic acid may be a carboxylate of an alkyl metal. For example, the tin carboxylate may be a dialkyltin carboxylate, and preferably a dioctyltin carboxylate. Specific examples of metal salts of carboxylic acids include bismuth trioctate, dioctyltin versatate, dibutyltin dilaurate, dioctyltin dilaurate, and tin dioctylate, with bismuth trioctate and dioctyltin versatate being preferred, and bismuth trioctate being more preferred.

[0048] The content of the foaming catalyst in the polyol composition is not particularly limited, but from the viewpoint of reacting the polyol and the isocyanate at an appropriate rate, it is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 1 to 8 parts by mass, and even more preferably 1.5 to 5 parts by mass, per 100 parts by mass of the polyol.

[0049] (trimerization catalyst) The polyol composition of the present invention may further contain a trimerization catalyst. The trimerization catalyst is a catalyst that reacts isocyanate groups contained in isocyanate to trimerize them and promote the formation of isocyanurate rings. The inclusion of a trimerization catalyst has the advantage of completing the reaction of unreacted isocyanate groups, thereby producing a good polyurethane foam. Examples of trimerization catalysts include metal catalysts and ammonium salts. Examples of metal catalysts used as trimerization catalysts (trimerization metal catalysts) include potassium organic acids, and preferred are potassium carboxylates having 2 to 8 carbon atoms, such as potassium octylate, such as potassium 2-ethylhexanoate, potassium acetate, potassium propionate, potassium butanoate, and potassium benzoate. Examples of ammonium salts that can be used include tertiary ammonium salts such as triethylammonium salts and triphenylammonium salts, and quaternary ammonium salts such as tetramethylammonium salts, tetraethylammonium salts and tetraphenylammonium salts, with quaternary ammonium salts being preferred. The ammonium salt is, for example, an ammonium salt of a carboxylic acid. Examples of the carboxylic acid in the ammonium salt include saturated fatty acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms. The saturated fatty acid may have a hydrocarbon group that is either linear or branched, with branched being preferred. Specific examples of carboxylic acids include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid, with 2,2-dimethylpropanoic acid being preferred. The trimerization catalyst may be used alone or in combination of two or more. When two or more types are used in combination, it is preferred to use a quaternary ammonium salt in combination with a metal catalyst.

[0050] The content of the trimerization catalyst in the polyol composition is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, even more preferably 2 to 20 parts by mass, and even more preferably 3 to 10 parts by mass, per 100 parts by mass of the polyol. When the content of the trimerization catalyst is at or above the lower limit, there is no significant difference in activity between resinification and trimerization, and two-stage foaming can be suppressed, resulting in good foamability. On the other hand, when the content of the trimerization catalyst is at or below the upper limit, the resinification reaction proceeds actively, and the heat from the resinification reaction can help activate the trimerization, resulting in good foamability and allowing the formation of a good polyurethane foam.

[0051] <Filler> The polyol composition of the present invention may contain a filler other than the above-mentioned nucleophilic inhibitor and flame retardant. The filler is contained as a solid component in the polyol composition and is generally present in the form of particles or powder in the polyol composition. In the present invention, the inclusion of a filler makes it easier to improve various physical properties of the polyurethane foam, such as flame retardancy and mechanical properties.

[0052] The filler may be any component that is solid at room temperature (23°C) and normal pressure (1 atmosphere) and does not dissolve in the polyol composition. From the viewpoint of reducing the water absorption rate of the polyurethane foam, the filler is preferably one that is neither hygroscopic nor deliquescent. Note that the above-mentioned catalysts are not included in the filler.

[0053] Examples of the filler include acicular fillers, such as potassium titanate whiskers, aluminum borate whiskers, magnesium-containing whiskers, silicon-containing whiskers, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fibers, carbon fibers, graphite fibers, metal fibers, slag fibers, gypsum fibers, silica fibers, alumina fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, and stainless steel fibers. The aspect ratio (length / diameter) of the needle-like filler used in the present invention is preferably in the range of 5 to 50, more preferably in the range of 10 to 40. The aspect ratio can be determined by observing the needle-like filler with a scanning electron microscope and measuring its length and width. These fillers may be used alone or in combination of two or more.

[0054] The content of the filler in the polyol composition is not particularly limited, but is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass, and even more preferably 20 to 40 parts by mass, per 100 parts by mass of the polyol.

[0055] <Foam stabilizer> The polyol composition of the present invention may contain a foam stabilizer. The foam stabilizer can improve the foaming properties of the polyurethane foam, and can promote foaming when reacting with isocyanate during spraying, for example. Specific examples of the foam stabilizer include surfactants, more specifically, nonionic surfactants, cationic surfactants, anionic surfactants, etc. Specific examples of nonionic surfactants include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and silicone foam stabilizers such as organopolysiloxanes. The foam stabilizer used in the present invention is not particularly limited, but silicone foam stabilizers are preferred from the viewpoint of foaming properties. One type of foam stabilizer may be used alone, or two or more types may be used in combination.

[0056] The content of the foam stabilizer in the polyol composition of the present invention is preferably 0.1 to 12 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 8 parts by mass, per 100 parts by mass of the polyol. When the content of the foam stabilizer is equal to or greater than the lower limit, the mixture of the polyol composition and the isocyanate is easily foamed, making it possible to obtain a homogeneous polyurethane foam. When the content of the foam stabilizer is equal to or less than the upper limit, the balance between production costs and the obtained effects is optimal.

[0057] <Other ingredients> The polyol composition may contain, as needed, one or more additives selected from phenolic, sulfur-based, and other antioxidants, heat stabilizers, metal inhibitors (metal deactivators), antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, plasticizers, tackifying resins, and tackifiers such as polybutene and petroleum resins, within the scope of the present invention.

[0058] <Method of producing polyol composition> There are no particular limitations on the method for producing the polyol composition of the present invention, and it can be produced, for example, by stirring each component at about 20 to 40° C. for about 30 seconds to 20 minutes using a homodisper or the like.

[0059] [Polyurethane resin composition and polyurethane foam] The present invention also provides a polyurethane resin composition, which contains an isocyanate in addition to the polyol composition of the present invention. The polyurethane resin composition may also contain fillers other than the red phosphorus-based flame retardant, liquid flame retardants such as phosphoric acid esters, a foam stabilizer, and other components. The details of each component contained in the polyurethane resin composition are as described above, and therefore, description thereof will be omitted.

[0060] The polyurethane resin composition of the present invention preferably contains the polyol composition and an isocyanate, and is obtained by mixing them. The polyurethane foam of the present invention is a reaction product obtained by reacting and foaming the polyurethane resin composition.

[0061] <Isocyanate> In the present invention, examples of the isocyanate include aromatic isocyanates, alicyclic isocyanates, and aliphatic isocyanates. Examples of aromatic isocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenylisocyanate (polymeric MDI).

[0062] Examples of alicyclic isocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0063] Examples of the aliphatic isocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0064] Among these, from the viewpoints of ease of use and availability, aromatic isocyanates are preferred, diphenylmethane diisocyanate, polymeric MDI, or a mixture thereof is more preferred, and diphenylmethane diisocyanate is even more preferred, with 4,4'-diphenylmethane diisocyanate being particularly preferred. One type of isocyanate may be used alone, or two or more types may be used in combination. Furthermore, known additives that are typically added to isocyanates may be appropriately added to the isocyanates before they are mixed with the polyol composition.

[0065] When the polyurethane resin composition is formed by mixing the polyol composition and the isocyanate, the mass ratio of the isocyanate to the polyol composition is preferably 0.1 to 1.0, more preferably 0.15 to 0.8, and even more preferably 0.2 to 0.5.

[0066] <Isocyanate Index> The isocyanate index of the polyurethane resin composition of the present invention is not particularly limited, but is preferably 200 or higher. If the isocyanate index is equal to or higher than the lower limit, the amount of isocyanate relative to the polyol becomes excessive, facilitating the formation of isocyanurate bonds due to isocyanate trimerization, resulting in improved flame retardancy of the polyurethane foam. It also becomes possible to impart flame retardancy. Furthermore, if the isocyanate index is equal to or higher than the lower limit, combined with the use of the various catalysts described above, it becomes easier to produce a polyurethane foam having sufficient isocyanurate bonds, i.e., a polyurethane foam that combines high levels of flame retardancy and thermal insulation. From these viewpoints, the isocyanate index is more preferably 250 or higher, and even more preferably 300 or higher. The isocyanate index is preferably not more than 1,000, more preferably not more than 800, and even more preferably not more than 600. When the isocyanate index is not more than the upper limit, flame retardancy that is sufficiently commensurate with the production cost can be obtained.

[0067] The isocyanate index can be calculated by the following method. Isocyanate Index = number of equivalents of isocyanate ÷ (number of equivalents of polyol + number of equivalents of water) × 100 Here, each equivalent number can be calculated as follows: Isocyanate equivalent number = Amount of isocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (mol) × 100 Equivalent weight of polyol = OHV × amount of polyol used (g) ÷ molecular weight of KOH (mmol) OHV is the hydroxyl value of the polyol (mg KOH / g). Equivalents of water = Amount of water used (g) / Molecular weight of water (moles) × Number of OH groups in water In the above formulas, the molecular weight of NCO is 42 (mol), the molecular weight of KOH is 56,100 (mmol), the molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

[0068] <Total heat generation> The polyurethane foam made from the polyurethane resin composition of the present invention has a radiant heat intensity of 50 kW / m2 according to the test method of ISO-5660. 2 When heated for 10 minutes, the total calorific value is 15MJ / m 2 The total calorific value is preferably 10 MJ / m or less. 2 The polyurethane foam made from the polyurethane 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 8 MJ / m 2 More preferably, it is 5MJ / m or less. 2 It is even more preferable that:

[0069] The gross calorific value can be measured by a cone calorimeter test, specifically 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.

[0070] <Method of manufacturing polyurethane foam> Although there are no particular limitations on the method for producing polyurethane foam, it is preferable to produce polyurethane foam by mixing a polyol composition with an isocyanate in a foaming machine or the like, and reacting and foaming the resulting mixed liquid (polyurethane resin composition). As the foaming machine, it is preferable to use a spray device having a spray gun or the like. The polyol composition is preferably fed to a foaming machine and mixed by collision inside the foaming machine with an isocyanate fed from another container, etc. The mixed liquid (polyurethane resin composition) is then discharged from a discharge port of a spray gun, etc., and a polyurethane foam is formed from the discharged polyurethane resin composition.

[0071] The present production method is preferably applicable to spray applications, and the mixed liquid discharged from the foaming machine is sprayed onto a target surface at a certain discharge pressure to cause foaming, thereby forming a polyurethane foam on the target surface.

[0072] <Applications of polyurethane foam> The uses of the polyurethane foam of the present invention are not particularly limited, but because it has excellent flame retardancy and heat insulation properties, it can be suitably used in buildings such as walls, ceilings, roofs, and floors, and it is advisable to mold the polyurethane foam onto walls, ceilings, roofs, floors, etc. as the target surfaces to be sprayed. [Example]

[0073] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0074] [Materials used] <Polyol composition> (Polyol) p-Phthalic acid polyester polyol (Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g)

[0075] (Metallic flame retardants) Zinc borate (Hayakawa Shoji Co., Ltd., product name: Firebrake ZB) Aluminum phosphite (manufactured by Taihei Chemical Industry Co., Ltd., product name: APA-100) (Non-metallic flame retardant) Phosphate ester flame retardant (1) Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP) Phosphate ester flame retardant (2) Triphenyl phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TPP) Brominated flame retardant: Ethylenebis(pentabromophenyl) (manufactured by Albemarle Japan, product name: SAYTEX 8010) Red phosphorus flame retardant (Rinkagaku Kogyo Co., Ltd., product name: NovaExcel 140)

[0076] (foaming agent) HFO-1233zd (Honeywell, product name: Solstice LBA, boiling point: 19°C) ·water HFO-1336mzz (Chemours, product name: Opteon 1100, boiling point: 33°C) Cyclopentane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: Cyclopentane)

[0077] (nucleophilic inhibitors) Magnesium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: magnesium hydroxide) Lithium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: Lithium hydroxide) Sodium acetate (Fujifilm Wako Pure Chemical Industries, Ltd., product name: sodium acetate) Potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: potassium carbonate) Calcium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: calcium carbonate) Barium sulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: barium sulfate) Copper(II) hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: Copper(II) hydroxide)

[0078] (non-nucleophilic inhibitors) Diisopropylamine (Fujifilm Wako Pure Chemical Industries, Ltd., product name: diisopropylamine)

[0079] (catalyst) 1. Resinification catalyst Amine catalyst (1) 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT DM70) concentration 65 to 75 mass% Amine catalyst (2) Diazabicycloundecene (manufactured by San-Apro Co., Ltd., product name: DBU) concentration 98% by mass Amine catalyst (3): Bis(2-morpholinoethyl) ether (Mitsui Fine Chemicals, product name: DMDEE), concentration 85% by mass or more

[0080] 2. Foaming catalyst Metal catalyst: Bismuth trioctate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600) concentration: 55-58% by mass

[0081] 3.Trimerization catalyst Ammonium salt: 2,2-dimethylpropanoic acid tetramethylammonium salt (manufactured by Air Products, product name: DABCO (registered trademark) TMR-7) concentration: 45 to 55% by mass

[0082] <Isocyanate> 4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (Manka Chemical Japan Co., Ltd., product name: PM200)

[0083] [Examples 1 to 18, Comparative Examples 1 to 5] <Inactivation evaluation> A polyol composition and a polyurethane resin composition were prepared according to the following procedures (1) to (13). (1) Two pressure-resistant bottles (Buerkle aluminum bottles, UN standard compliant, 1200 ml capacity) were prepared, and 130 g of a solution consisting of a polyol composition prepared in the proportions shown in Table 1 was placed in each bottle. One bottle was used for deactivation promotion (hereinafter referred to as "Bottle A"), and the other bottle was used for benchmarking (hereinafter referred to as "Bottle B"). Here, the polyol composition in bottle A is referred to as "polyol composition A," and the polyol composition in bottle B is referred to as "polyol composition B." (2) Bottle A was stored at 45°C for 20 hours, and bottle B was simultaneously stored in a refrigerator at 10°C for 20 hours. (3) Bottle A was cooled to below 30°C and the lid was opened. (4) 260 g of TMCPP for dilution was added to each of bottles A and B, and the lids were immediately closed after addition. This TMCPP was added separately from the TMCPP contained as the non-metallic flame retardant. (5) Bottles A and B were each shaken 50 times by hand at a speed of about twice per second at intervals of about 30 cm to agitate the contents. (6) After stirring, 120 g of each of the polyol compositions A and B was placed in a 1 L plastic cup. Here, the plastic cup containing polyol composition A is referred to as "cup A," and the plastic cup containing polyol composition B is referred to as "cup B." (7) The temperatures of the polyol compositions A and B in the plastic cups were adjusted to 15°C ± 1°C, respectively. (8) The isocyanate was placed in a 1 L plastic cup separate from the cups A and B, and the temperature was adjusted to 15°C ± 1°C. (9) 120 g of isocyanate was added to each of the cups A and B, and the polyol composition and the isocyanate were mixed in each of the cups A and B to obtain a polyurethane resin composition. Here, the polyurethane resin composition obtained by adding isocyanate to cup A is referred to as "polyurethane resin composition A," and the polyurethane resin composition obtained by adding isocyanate to cup B is referred to as "polyurethane resin composition B." (10) Seven seconds after mixing in (9) above, polyurethane resin compositions A and B were stirred with a homodisper. (11) 12 seconds after the mixing in (9) above, stirring was stopped. (12) The polyurethane resin compositions A and B were allowed to stand. (13) Tweezers were pierced into the polyurethane resin compositions A and B obtained by the above method, and the time when stirring stopped was set to 0 seconds, and the number of seconds when resistance began to be felt (when curing began) was recorded. The difference in the number of seconds between polyurethane resin compositions A and B was evaluated according to the following evaluation criteria. Note that the numerical values ​​for each number of seconds were rounded to the nearest whole number, and the difference in the number of seconds was then calculated. ◎: 6 seconds or less 〇: 7 seconds or more and 9 seconds or less △: 10 seconds or more and 12 seconds or less ×: 13 seconds or more

[0084] <Flame retardancy> According to the formulation in Table 1, each component constituting the polyol composition was weighed into a 1 L polypropylene beaker and stirred by hand at 25°C for 1 minute to obtain a polyol composition. To the obtained polyol composition, isocyanate was added according to the formulation in Table 1, and the mixture was stirred with a hand mixer for approximately 10 seconds to produce a polyurethane foam. The obtained polyurethane foam was cut into a length of 10 cm, width of 10 cm, and thickness of 5 cm to prepare a sample for cone calorimeter testing. The cone calorimeter test sample was subjected to a test at a radiant heat intensity of 50 kW / m in accordance with the test method of ISO-5660. 2 The total heat release amount when heated for 10 minutes was measured and the flame retardancy was evaluated. The flame retardancy evaluation criteria are as follows: ◎: 4MJ / m 2 below 〇: 4.1MJ / m 2 More than 8.5MJ / m 2 below △:8.6MJ / m 2 More than 13MJ / m 2 below ×:13.1MJ / m 2 End

[0085] [Table 1] Each catalyst content is the content as a product.

[0086] As is clear from the above examples, the polyol composition of the present invention, which contains a nucleophilic inhibitor, maintains catalytic activity and exhibits excellent storage stability. Furthermore, polyurethane foams formed from the composition exhibit good flame retardancy. On the other hand, for the polyol compositions prepared in the comparative examples, the flame retardancy of the polyurethane foams formed from the compositions was comparable to that of the examples, but because the compositions did not contain a nucleophilic inhibitor, the catalyst activity could not be maintained, and as a result, the storage stability of the polyol compositions was impaired.

Claims

1. Contains a polyol, a flame retardant, a blowing agent, a catalyst, and a nucleophilic inhibitor; The blowing agent contains a hydrofluoroolefin, the catalyst comprises an amine-based catalyst; the nucleophilic inhibitor is at least one selected from the group consisting of magnesium hydroxide, lithium hydroxide, sodium acetate, potassium carbonate, calcium carbonate, barium sulfate, and copper (II) hydroxide, and the content of the nucleophilic inhibitor is 0.2 to 87 parts by mass relative to 100 parts by mass of the polyol; Polyol compositions (excluding those containing red phosphorus and metal stannates).

2. The polyol composition of claim 1 , wherein the flame retardant comprises a metal-based flame retardant (excluding the nucleophilic inhibitor).

3. Contains a polyol, a flame retardant, a blowing agent, a catalyst, and a nucleophilic inhibitor; The blowing agent contains a hydrofluoroolefin, the catalyst comprises an amine-based catalyst; the nucleophilic inhibitor is at least one selected from the group consisting of magnesium hydroxide, lithium hydroxide, sodium acetate, potassium carbonate, calcium carbonate, barium sulfate, and copper (II) hydroxide, and the content of the nucleophilic inhibitor is 0.2 to 87 parts by mass relative to 100 parts by mass of the polyol; The flame retardant includes a metal-based flame retardant, and the metal-based flame retardant is at least one selected from the group consisting of a metal borate and a metal phosphate. Polyol compositions (excluding those containing red phosphorus and metal stannates).

4. A polyurethane resin composition comprising the polyol composition according to any one of claims 1 to 3 and an isocyanate.

5. A polyurethane foam obtained by reacting and foaming the polyurethane resin composition according to claim 4.

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