Polyol composition for polyurethane foam

Abstract

To provide a polyol composition for a polyurethane foam, enabling production of a polyurethane foam which reduces an addition amount of a chlorine-containing polyol (A) and has excellent flame retardancy while maintaining foam physical properties.SOLUTION: A polyol composition for a polyurethane foam comprises: a chlorine-containing polyol (A) having a number average molecular weight of 400-5,000 represented by formula (1); a polyalkylene oxide (B) having monomer units of ethylene oxide and propylene oxide and having an ethylene oxide content of 0-25 wt.%; and a polyether polyol (C) having an ethylene oxide content of 50 wt.% or more. [H-Q-]mR1...(1) (wherein, Q represents a polymer component comprising a structural unit [I]; m represents an integer of 2 to 3; and R1 represents an active hydrogen-containing compound residue).SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to polyol compositions for polyurethane foams. [Background technology]

[0002] Polyurethane foam is manufactured by mixing polyether polyols and / or polyester polyols with isocyanate compounds and blowing agents, and then reacting and foaming them.

[0003] Traditionally, flame retardants have been added to polyurethane foam to make it flame-retardant. These flame retardants have primarily been liquid at room temperature, such as phosphate ester monomers.

[0004] Generally, when liquid phosphate ester monomers at room temperature are used as flame retardants in polyurethane foam, they have a plasticizing effect, which can easily lead to a decrease in the moldability of the polyurethane foam as the amount of flame retardant used increases.

[0005] To solve the above problem, a method has been proposed using a chlorine-containing polyether polyol obtained by adding a chlorine-containing alkylene oxide to a bifunctional or more active hydrogen compound to a predetermined molecular weight using a Lewis acid catalyst or a complex metal cyanide catalyst (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2020-180169 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, when such a chlorine-containing polyol (A) is used, the amount of the chlorine-containing polyol (A) required to produce a polyurethane foam having excellent flame retardancy increases, the polyurethane foam becomes denser, the durability deteriorates, and furthermore, the hardness decreases, which has been a problem. Therefore, one aspect of the present invention is directed to providing a polyol composition for a polyurethane foam that can produce a polyurethane foam having excellent flame retardancy while reducing the amount of the chlorine-containing polyol (A) added and maintaining the foam physical properties.

Means for Solving the Problems

[0008] Each aspect of the present invention is as follows [1] to [5]. [1] A composition containing a chlorine-containing polyol (A), a polyalkylene oxide (B), and a polyether polyol (C), wherein the chlorine-containing polyol (A) is a chlorine-containing polyol having a number average molecular weight of 400 to 5,000 represented by the following formula (1), the polyalkylene oxide (B) has monomer units of ethylene oxide and propylene oxide and is a polyalkylene oxide having an ethylene oxide content of 0 to 25% by weight, and the polyether polyol (C) is a polyether polyol having an ethylene oxide content of 50% by weight or more. A polyol composition for a polyurethane foam.

[0009]

Chemical formula

[0010] (In the above formula (1), Q represents a polymer component containing a structural unit [I], m is an integer of 2 to 3, and R ,

[0011] , , , , , ,

[0012] , represents a residue of an active hydrogen-containing compound.)

[0011]

Chemical formula

[0012] [2] The polyol composition for polyurethane foam according to [1], wherein, with a total amount of the polyol composition being 100% by weight, the chlorine-containing polyol (A) is 3 to 45% by weight, the polyalkylene oxide (B) is 35 to 95% by weight, and the polyether polyol (C) is 2 to 20% by weight. [3] A polyurethane foam composition comprising the polyol composition for polyurethane foam described in [1] or [2], an isocyanate compound, a blowing agent, and a catalyst. [4] [3] A polyurethane foam obtained from the polyurethane foam composition described above. [5] A method for producing polyurethane foam by reacting and foaming the polyurethane foam composition described in [3]. <Polyol composition for polyurethane foam> A polyol composition for polyurethane foam according to one aspect of the present invention contains a chlorine-containing polyol (A), a polyalkylene oxide (B) having monomer units of ethylene oxide and propylene oxide with an ethylene oxide content of 0 to 25% by weight, and a polyether polyol (C) with an ethylene oxide content of 50% by weight or more. <<Chlorine-containing polyol (A)>> Chlorine-containing polyol (A) is represented by formula (1) and has a number-average molecular weight of 400 to 5000.

[0013] In formula (1), R 1 The active hydrogen-containing compound residues represented by are not particularly limited, but examples include hydroxyl residues, amine residues, carboxylic acid residues, thiol residues, etc.

[0014] Examples of hydroxyl residues include residues derived from hydroxyl compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, 1,9-nonanediol, 2,5-hexanediol, 1,3-cyclohexanediol, 2-methylpentane-2,4-diol, 2,5-dimethyl-2,5-hexanediol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, sucrose, glucose, 2-naphthol, bisphenol, polyether polyol, polyester polyol, and polycarbonate polyol.

[0015] Examples of amine residues include residues derived from amino compounds such as ethylenediamine, 1,3-propylenediamine, and 1,4- or 1,2-butylenediamine.

[0016] Examples of carboxylic acid residues include residues derived from carboxylic acid compounds such as phthalic acid and adipic acid.

[0017] Examples of thiol residues include residues derived from thiol compounds such as ethanedithiol and butanedithiol.

[0018] Since it is possible to improve flame retardancy, active hydrogen-containing compound residues with a molecular weight of 200 to 1,000 are preferred, and among these active hydrogen-containing compound residues, residues of polycarbonate polyols with a molecular weight of 200 to 1,000 and residues of polyester polyols with a molecular weight of 200 to 1,000 are preferred, and polyester polyol residues with a molecular weight of 200 to 1,000 are particularly preferred. Polycarbonate polyols are not particularly limited, but examples include those obtained by reacting at least one polyhydric alcohol such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, or diethylene glycol with diethylene carbonate, dimethyl carbonate, diethyl carbonate, etc.

[0019] Polyester polyols are not particularly limited, but examples include those produced by esterifying an aromatic and / or aliphatic polybasic acid or acid anhydride with a compound having two or three hydroxyl groups using a known method. From the viewpoint of improving flame retardancy, it is preferable to use an aromatic polybasic acid alone or a combination of two or more aromatic and aliphatic polybasic acids. Aromatic polybasic acids are not particularly limited, but examples include orthophthalic acid, isophthalic acid, and terephthalic acid.

[0020] Compounds having two or three hydroxyl groups (polyhydric alcohols) are not particularly limited, but include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, bis Examples include short-chain diols such as phenol A; and short-chain triols such as glycerin, hexanetriol, and trimethylolpropane. Due to the high versatility of the polyester polyols produced, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and 3-methyl-1,5-pentanediol are preferred, with 1,6-hexanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and 3-methyl-1,5-pentanediol being particularly preferred. These can be used individually or in combination of two or more.

[0021] The number average molecular weight of the chlorine-containing polyol (A) is 400 to 5,000, and it is preferable that the number average molecular weight be 400 to 4,000 or less, and particularly preferable that it be 600 to 3,000, as this results in excellent handling and polyurethane production efficiency.

[0022] The content of chlorine-containing polyol (A) is preferably 3 to 45% by weight, more preferably 5 to 40% by weight, and particularly preferably 10 to 25% by weight, based on 100% by weight of the total amount of the polyol composition, from the viewpoint of improving flame retardancy. The chlorine-containing polyol (A) is not particularly limited and can be produced by conventionally known production methods. For example, it can be obtained by ring-opening polymerization of a chlorine-containing alkylene oxide alone or a chlorine-containing alkylene oxide and an alkylene oxide, using the active hydrogen-containing compound as an initiator in the presence of a composition containing an onium salt, a Lewis acid, and an active hydrogen-containing compound.

[0023] Epichlorohydrin is preferred as the chlorine-containing alkylene oxide because it is readily available and the resulting polyalkylene oxide has high industrial value.

[0024] Chlorine-containing alkylene oxides can be used alone or in combination of two or more types.

[0025] Examples of alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide. Ethylene oxide and propylene oxide are preferred because they provide good handling of the chlorine-containing polyol (A).

[0026] Alkylene oxides can be used alone or in combination of two or more types.

[0027] While not specifically limited, examples of onium salts include phosphazenium salts, ammonium salts, and phosphonium salts.

[0028] The structure of the phosphazenium salt is not particularly limited, but can be represented, for example, by the following formula (2).

[0029] [ka]

[0030] In equation (2) above, R 2 and R 3 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 A ring structure in which these are bonded to each other, R 2 Mutual or R3 It may be a ring structure in which the members are bonded to each other. Z - represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, a chlorine anion, a bromine anion, an iodine anion or a hydrogen carbonate anion.

[0031] R 2 and R 3 Although not particularly limited, examples of the hydrocarbon group having 1 to 20 carbon atoms represented by, for example, a methyl group, an ethyl group, a vinyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an allyl group, an n-butyl group, an isobutyl group, a t-butyl group, a cyclobutyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenyl group, a heptyl group, a cycloheptyl group, an octyl group, a cyclooctyl group, a nonyl group, a cyclononyl group, a decyl group, a cyclodecyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, etc.

[0032] R 2 and R 3 Examples of the case where R forms a ring structure by bonding to each other include a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indolyl group, an isoindolyl group, etc.

[0033] R 2 each other or R 3 Although not particularly limited, examples of the ring structure in which the members are bonded to each other include a ring structure in which one substituent is an alkylene group such as an ethylene group, a propylene group, a butylene group and the other substituent is bonded to each other.

[0034] Among these, R 2 and R 3 are preferably a methyl group, an ethyl group or an isopropyl group from the viewpoint of being an alkylene oxide polymerization catalyst having particularly excellent catalytic activity and easy availability of raw materials.

[0035] Also, Z in equation (2) above - These are hydroxy anions, alkoxy anions with 1 to 4 carbon atoms, carboxy anions, alkyl carboxy anions with 2 to 5 carbon atoms, or bicarbonate anions.

[0036] While there are no particular limitations on the alkoxy anions having 1 to 4 carbon atoms, examples include methoxy anions, ethoxy anions, n-propoxy anions, isopropoxy anions, n-butoxy anions, isobutoxy anions, and t-butoxy anions.

[0037] The alkyl carboxyanions having 2 to 5 carbon atoms are not particularly limited, but examples include acetoxyanion, ethyl carboxyanion, n-propyl carboxyanion, isopropyl carboxyanion, n-butyl carboxyanion, isobutyl carboxyanion, t-butyl carboxyanion, and the like.

[0038] Among these, Z - As such, hydroxy anions and bicarbonate anions are particularly preferred because they serve as chlorine-containing alkylene oxide polymerization catalysts with excellent catalytic activity.

[0039] The phosphazenium salt represented by formula (2) above is not particularly limited, but specifically includes tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraethylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium hydroxide, tetrakis( 1,1,3,3-Tetra(n-butyl)guanidino)phosphonium hydroxide, Tetrakis(1,1,3,3-tetraphenylguanidino)phosphonium hydroxide, Tetrakis(1,1,3,3-tetrabenzylguanidino)phosphonium hydroxide, Tetrakis(1,3-dimethylimidazolidine-2-imino)phosphonium hydroxide, Tetrakis(1,1,3, 3-Tetramethylguanidino)phosphonium hydrogen carbonate, Tetrakis(1,1,3,3-tetraethylguanidino)phosphonium hydrogen carbonate, Tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium hydrogen carbonate, Tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium hydrogen carbonate, Tetrakis(1,1,3,3-tetra(n-butyl)guanidino)phosphonium Examples include phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetraphenylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetrabenzylguanidino)phosphonium hydrogen carbonate, tetrakis(1,3-dimethylimidazolidined-2-imino)phosphonium hydrogen carbonate, and tetrakis(1,3-dimethylimidazolidined-2-imino)phosphonium hydrogen carbonate.

[0040] Also, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium hydroxide, 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis(tris(dimethylamino)phosphoranylideneamino)-2λ5,4λ5-catenadi(phosphazene), tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(di-n-butylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(1,3-dimethylimidazolidin-2-imino)phosphoranylidene Examples include [mino]phosphonium hydroxide, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(di-n-butylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, and tetrakis[tris(1,3-dimethylimidazolidined-2-imino)phosphoranylideneamino]phosphonium hydrogen carbonate.

[0041] Among these, tetrakis(1,1,3,3-tetramethylguanidino)phosphazenium hydroxide, tetrakis(1,1,3,3-tetramethylguanidino)phosphazenium hydrogen carbonate, and tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide are particularly preferred because they serve as catalysts for producing chlorine-containing polyols (A) with excellent catalytic performance.

[0042] The structure of an ammonium salt or phosphonium salt can be represented, for example, by the following formula (3).

[0043] [ka]

[0044] In formula (3) above, D represents a nitrogen atom or a phosphorus atom, and R 4 , R 5 , R 6 and R 7 Each of these independently represents an alkyl group, aryl group, alkoxy group, dialkylamino group, halogen atom, or hydrogen atom having 1 to 20 carbon atoms, which may contain heteroatoms, and E represents a counterion consisting of an inorganic or organic group. 4 ~R 7 Two to four of these atoms may bond together to form a cyclic structure, and this cyclic structure may also contain heteroatoms.

[0045] R 4 , R 5 , R 6 and R 7Examples of alkyl or aryl groups having 1 to 20 carbon atoms represented by are not particularly limited, but include methyl, ethyl, vinyl, n-propyl, isopropyl, cyclopropyl, allyl, n-butyl, isobutyl, t-butyl, cyclobutyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl, heptyl, cycloheptyl, benzyl, tolyl, octyl, cyclooctyl, xylyl, etc. Examples of alkoxy groups include methoxy, ethoxy, vinyloxy, n-propoxy, isopropoxy, cyclopropyl Examples of dialkylamino groups include ropoxy group, allyloxy group, n-butoxy group, isobutoxy group, t-butoxy group, cyclobutoxy group, n-pentyloxy group, neopentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, phenoxy group, heptyloxy group, cycloheptyloxy group, octyloxy group, benzyloxy group, tolyloxy group, cyclooctyloxy group, and xylyloxy group. Examples of dialkylamino groups include dimethylamino group, diethylamino group, pyrrolidino group, piperidino group, di-n-propylamino group, diisopropylamino group, and dicyclopropylamino group.

[0046] Since it is a catalyst for producing chlorine-containing polyol (A) with excellent catalytic activity, R 4 , R 5 , R 6 and R 7 Each of these groups is preferably an alkyl or aryl group having 1 to 10 carbon atoms, which may contain heteroatoms, and is particularly preferably a methyl group, an ethyl group, a n-butyl group, a n-octyl group, or a phenyl group.

[0047] R 4 ~R 7 Examples of ammonium salt structures in which two or three of these are bonded to form a cyclic structure include pyridinium salts and imidazolium salts. Imidazolium salts are preferred because they serve as catalysts for producing chlorine-containing polyols (A) with excellent catalytic activity.

[0048] In formula (3) above, E is either an inorganic or organic group.

[0049] Among these, while not particularly limited, examples include halogen atoms, hydroxyl groups, alkoxyl groups, amino groups, carboxyl groups, sulfonic acid groups, boron hydride groups, and hexafluorophosphate groups. Since these serve as catalysts for producing chlorine-containing polyols (A) with excellent catalytic activity, it is preferable that they be bromine atoms, chlorine atoms, iodine atoms, or hexafluorophosphate groups.

[0050] The ammonium salt or phosphonium salt represented by formula (3) above is not particularly limited, but specifically includes tetramethylammonium bromide, tetraethylammonium bromide, tetran-propylammonium bromide, tetran-butylammonium bromide, tetran-pentylammonium bromide, tetran-hexylammonium bromide, tetran-heptylammonium bromide, tetran-octylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetran-propylammonium chloride, tetran-butylammonium chloride, tetran-pentylammonium chloride, tetran-hexylammonium chloride, tetran-heptylammonium chloride, tetran-octylammonium chloride, 1-butyl-3-methylimidazolium chloride, 1-butyl-2,3- Examples include dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetran-propylphosphonium bromide, tetran-butylphosphonium bromide, tetran-pentylphosphonium bromide, tetran-hexylphosphonium bromide, tetran-heptylphosphonium bromide, tetran-octylphosphonium bromide, tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetran-propylphosphonium chloride, tetran-butylphosphonium chloride, tetran-pentylphosphonium chloride, tetran-hexylphosphonium chloride, tetran-heptylphosphonium chloride, tetran-octylphosphonium chloride, bromotris(dimethylamino)phosphonium hexafluorophosphate, and others.

[0051] Among these, tetran-octylammonium chloride, tetran-octylammonium bromide, and tetran-butylphosphonium bromide are preferred because they serve as catalysts for producing chlorine-containing polyols (A) with excellent catalytic activity.

[0052] In a method for producing a chlorine-containing polyol (A), examples of Lewis acids include aluminum compounds, zinc compounds, boron compounds, and the like.

[0053] Examples of aluminum compounds include organoaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trin-normalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, and monophenyldiisobutylaluminum; aluminoxanes such as methylaluminoxane, isobutylaluminoxane, and methyl-isobutylaluminoxane; and inorganic aluminum such as aluminum chloride, aluminum hydroxide, and aluminum oxide.

[0054] Examples of zinc compounds include organozincs such as dimethylzinc, diethylzinc, and diphenylzinc; and inorganic zincs such as zinc chloride and zinc oxide.

[0055] Examples of boron compounds include triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris(pentafluorophenyl)borane, and trifluoroborane.

[0056] Among these, organoaluminum, aluminoxane, and organozinc are preferred, with organoaluminum being particularly preferred, as they serve as catalysts for producing chlorine-containing polyols (A) with excellent catalytic performance.

[0057] In the method for producing chlorine-containing polyol (A), it is possible to efficiently produce chlorine-containing polyol (A), so the amount of onium salt is preferably 0.001 to 0.1 moles, and particularly preferably 0.001 to 0.05 moles, per mole of hydroxyl groups in the active hydrogen-containing compound.

[0058] Furthermore, since it becomes possible to efficiently produce chlorine-containing polyol (A), the amount of Lewis acid is preferably 0.002 to 0.2 moles, and particularly preferably 0.002 to 0.1 moles, per mole of hydroxyl groups of the active hydrogen-containing compound.

[0059] In the method for producing chlorine-containing polyol (A), the polymerization pressure is in the range of atmospheric pressure to 1.0 MPa, preferably in the range of atmospheric pressure to 0.5 MPa. In the method for producing chlorine-containing polyol (A), the polymerization temperature is in the range of 0 to 180°C, and more preferably in the range of 50 to 130°C.

[0060] In the method for producing chlorine-containing polyol (A), the polymerization reaction can be carried out without a solvent or in a solvent. When using a solvent, examples of solvents include benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, and 1,2-dimethoxyethane. <<Polyalkylene oxide (B)>> Polyalkylene oxide (B) has monomer units of ethylene oxide and propylene oxide, and is a polyalkylene oxide with an ethylene oxide content of 0 to 25% by weight. From the viewpoint of moldability and foam properties, an ethylene oxide content of 0 to 20% by weight is preferred.

[0061] The polymerization form of polyalkylene oxide (B) is not particularly limited and may be a random copolymer or a block copolymer.

[0062] The number of functional groups in polyalkylene oxide (B) is not particularly limited, but from the viewpoint of moldability and foam properties, it is preferably 2 to 8, and particularly preferably 2 to 4.

[0063] The hydroxyl value of polyalkylene oxide (B) is not particularly limited, but from the viewpoint of moldability and foam properties, it is preferably 15 to 120 (mgKOH / g), and particularly preferably 20 to 80 (mgKOH / g).

[0064] Polyalkylene oxide (B) can be used alone or in combination of two or more types.

[0065] The content of polyalkylene oxide (B) in the polyol composition is not particularly limited, but it is preferably 35 to 95% by weight, more preferably 40 to 92% by weight, and particularly preferably 65 to 85% by weight, based on 100% by weight of the total amount of the polyol composition, as this provides excellent handling and polyurethane production efficiency. <<Polyether Polyol (C)>> Polyether polyol (C) is a polyether polyol with an ethylene oxide content of 50% by weight or more, and from the viewpoint of improving flame retardancy, the ethylene oxide content is preferably 70 to 100% by weight.

[0066] The polyether polyol (C) is not particularly limited, but specifically includes, for example, polyethylene oxide, propylene oxide-ethylene oxide random or block copolymers.

[0067] From the viewpoint of improving flame retardancy, the polyether polyol (C) preferably has 1 to 8 functional groups and a number-average molecular weight of 600 to 10,000.

[0068] From the viewpoint of improving flame retardancy, the content of polyether polyol (C) is preferably 2 to 20% by weight, more preferably 3 to 20% by weight, and particularly preferably 5 to 15% by weight, based on 100% by weight of the total amount of the polyol composition. <Composition for polyurethane foam> A polyurethane foam composition according to one aspect of the present invention comprises the above-mentioned polyurethane foam polyol composition, an isocyanate compound, a blowing agent, and a catalyst.

[0069] It may also contain a foam stabilizer. <<Isocyanate compounds>> The isocyanate compound included in the polyurethane foam composition is not particularly limited, and any compound having at least two isocyanate groups can be used. Examples include aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds, and polyisocyanate derivatives thereof.

[0070] Among these, aromatic isocyanate compounds include, for example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixture thereof) (TDI), phenylene diisocyanate (m-,p-phenylene diisocyanate or mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4' or 2,2'-diphenylmethane diisocyanate or mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), and 4,4'-diphenyl ether diisocyanate. Xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixture thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- or 1,4-tetramethyl xylylene diisocyanate or mixture thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate Examples include polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate. Aliphatic isocyanate compounds include, for example, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene Examples include diisocyanates (1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capeate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, etc.Examples of monocyclic alicyclic isocyanate compounds include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate or these) Examples include mixtures (hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanate methyl)cyclohexane (1,3- or 1,4-bis(isocyanate methyl)cyclohexane or mixtures thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI), etc.

[0071] Examples of cross-linked cyclic alicyclic isocyanate compounds include norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl)tricyclodecane.

[0072] The above-mentioned isocyanate compounds or their derivatives may be used individually or in combination of two or more. <<Foaming agent>> As the blowing agent included in the polyurethane foam composition, commercially available physical and / or chemical blowing agents can be used. While not particularly limited, examples of physical blowing agents include chlorofluorocarbons, hydrochlorofluoroolefins, hydrochlorofluorocarbons, hydrofluoroolefins, hydrofluorocarbons, perfluorocarbons, low-boiling halogenated hydrocarbons such as methylene chloride, hydrocarbons such as pentane and cyclopentane, and gases or low-temperature liquids such as air, nitrogen, and carbon dioxide. Examples of chemical blowing agents include water, organic acids, inorganic acids such as boric acid, alkali carbonates, cyclic carbonates, and dialkyl carbonates, as well as those that react with polyurethane raw materials or decompose by heat to generate gas.

[0073] In particular, hydrochlorofluoroolefins such as HCFO-1233zd, its trans isomer, HCFO-1233xf, and dichlorofluoropropene, and hydrochlorofluorocarbons such as HCFC-141b have low ozone depletion potential (ODP) and low global warming potential (GWP). HFO-1234zf, E-HFO-1234ze, Z-HFO-1234ze, and HFO-1234y have zero ODP and low GWP. Hydrofluoroolefins such as f, E-HFO-1255ye, Z-HFO-125ye, E-HFO-1336mzz, Z-HFO-1336mzz, HFO-1438mzz, hydrofluorocarbons such as HFC-134a, HFC-245, HFC-236, HFC-356, HFC-365mfc, HFC-227ea, hydrocarbons such as propane, butane, pentane, hexane, cyclopentane, etc., or water are preferred. <<Foam stabilizer>> The polyurethane foam composition preferably contains a foam stabilizer. By using a foam stabilizer, the size of the bubbles in the polyurethane foam can be controlled. Generally, polyether / siloxane-type organosilicon surfactants having linear, branched, or pendant structures are used. For example, polydimethylolsiloxane-polyalkylene oxide block copolymers and vinylsilane-polyalkyl polyol polymers can be used. The amount of foam stabilizer added is preferably in the range of 0.1 to 5 parts by weight per 100 parts by weight of the polyol composition, as this helps to stabilize the bubble structure and size. <<Catalyst>> As the catalyst included in the polyurethane foam composition, known catalysts can be used. Examples include tertiary amine compounds and organometallic compounds.

[0074] Examples of tertiary amine compounds are not particularly limited, but include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, and diazabicycloundecene. Commercially available products can be used, and for example, triethylenediamine (TEDA-L33) and bis(dimethylaminoethyl) ether (TOYOCAT-ET) are preferably used.

[0075] Examples of organometallic compounds include, but are not limited to, tin-based compounds and non-tin-based compounds. Examples of tin-based compounds are not particularly limited, but include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, dioctyltin dilaurine (also known as DOTDL), and tin 2-ethylhexanoate.

[0076] Non-tin compounds are not particularly limited, but examples include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyltitanate, and butoxytitanium trichloride; lead-based compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium naphthenate.

[0077] Among the urethane catalysts mentioned above, dibutyltin dilaurate (also known as DBTDL), dioctyltin dilaurate (also known as DOTDL), and tin 2-ethylhexanoate are preferred in terms of reactivity and hygiene.

[0078] The catalysts mentioned above, such as tertiary amine compounds and organometallic compounds, can be used individually, but two or more can also be used in combination. <Preparation of compositions for polyurethane foam> The method for preparing the polyurethane foam composition is not particularly limited, but a preferred method is to prepare a mixture (polyol premix) consisting of the remaining components excluding the isocyanate compound, which is then mixed with the isocyanate compound, as this method offers excellent handling and polyurethane production efficiency.

[0079] The preparation of the polyol premix involves adding a catalyst to a polyol composition for polyurethane foam, followed by the addition of a foam stabilizer and a blowing agent. <Polyurethane foam> A polyurethane foam according to one aspect of the present invention is obtained by reacting and foaming the polyurethane foam composition (hereinafter sometimes referred to as the foaming stock). For example, it can be produced by reacting and foaming a polyol composition for polyurethane foam according to one aspect of the present invention with an isocyanate compound in the presence of a foaming agent, a foam stabilizer, a catalyst, etc.

[0080] Polyurethane foams are broadly classified into flexible and rigid types, but when obtaining polyurethane foam using a polyol composition for polyurethane foam according to one aspect of the present invention, conventionally known manufacturing methods can be applied to both flexible and rigid foams. For example, to obtain a flexible foam, either a conventionally known method (slab foaming) in which the foaming liquid is discharged onto a belt conveyor and foamed at atmospheric pressure and room temperature, or a conventionally known method (mold foaming) in which the foaming liquid is injected into a mold and foamed and molded can be employed.

[0081] From the viewpoint of preventing the separation of each component of the foaming concentrate, it is preferable to prepare the foaming concentrate in advance immediately before discharging or injecting it onto the belt conveyor or into the mold. In this case, the temperature of the foaming concentrate is preferably 10 to 50°C, more preferably 20 to 45°C, and even more preferably 20 to 40°C.

[0082] In the case of slab foaming, foaming and curing are carried out on a belt conveyor belt under atmospheric pressure and at room temperature. As the foaming machine exits, it is cut into large blocks to produce flexible polyurethane foam. In mold foaming, the foaming liquid is injected into the mold under atmospheric pressure, then foamed and cured inside the mold, demolded, and obtained as a flexible polyurethane foam. The mold temperature is preferably 40 to 80°C, more preferably 50 to 70°C.

[0083] The polyurethane foam according to one aspect of the present invention is not subject to any special limitations on its use. Due to the characteristics of the polyurethane foam made from the reaction products of the composition according to one aspect of the present invention, it can be used in applications where soft polyurethane foam is typically applied, such as seats and pillows for automobiles and vehicles, furniture and interiors, bedding, shoe soles, sponges, various cushions, tennis balls, landing mats, etc. Furthermore, the polyurethane foam made from the reaction products of the composition of the present invention can be used in applications where rigid polyurethane foam is typically applied, such as heat insulation and cooling materials, vibration damping and sound absorbing materials, cushioning materials, and buoyancy materials. For example, it can be used for marine applications such as insulation for fishing boats, large vessels, refrigerated cargo ships, LNG carriers, LPG carriers, liquefied gas carriers, and containers, as well as core materials for FRP boats and buoyancy materials for large vessels, lifeboats, buoys, and floats; for automotive applications such as insulation for refrigerated trucks, insulated trucks, railway containers, tank trucks, and roof insulation for vehicles and trucks; for plant applications such as insulation for chemical industry equipment tanks and piping, heat insulation for heavy oil tanks and piping, insulation for LPG and LNG low-temperature liquefied gas refrigeration and piping, insulation covers, and tank lids; for refrigerators and freezers, insulation components for air conditioners, and insulation for various insulated equipment such as showcases, storage units, vending machines, water heaters, and hot water storage tanks; and furthermore, for residential use. Applications include insulation for residential and office buildings (walls, underfloors, ceilings, under roofs, etc.), insulating building materials (laminated boards, composite panels, siding materials, etc.), insulation for bathtubs (stainless steel, FRP, enamel), insulation for cold storage warehouses, agricultural warehouses, livestock barns, etc., void filling (insulated sashes), insulation for constant temperature rooms and district heating and cooling systems, civil engineering applications such as road floor insulation and vibration damping materials, and other applications such as chair cores, door panels, decorative crafts, recreational equipment (cooler boxes, water bottles), educational materials (3D maps, etc.), molds and jigs, surfboard cores, RIM method products (ski cores, racket cores, housings, etc.), and packaging materials. [Examples]

[0084] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited in any way by these examples. 1. Polyol composition: <<Chlorine-containing polyol (A)>> 1-1. Chlorine-containing polyol (A-1): By thoroughly dehydrating and desolvating an aromatic polyester polyol (Kuraray Co., Ltd., product name: Kuraray Polyol P-520) with a molecular weight of 500 (manufactured by Kuraray Co., Ltd., trade name: Kuraray Polyol P-520) using tetran-butylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and triisopropoxyaluminum, epichlorohydrin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to prepare a bifunctional, chlorine-containing polyol (A-1) with a molecular weight of 1,000. 1-2. Chlorine-containing polyols (A-2): A bifunctional, chlorine-containing polyol (A-2) with a molecular weight of 1,000 was prepared by mixing an aliphatic polyester polyol with a molecular weight of 500 (Kuraray Co., Ltd., product name: Kuraray Polyol P-510) with tetran-butylammonium bromide (Fujifilm Wako Pure Chemical Industries, Ltd.) and triisopropoxyaluminum, thoroughly dehydrating and desolvating the mixture, and then adding epichlorohydrin (Fujifilm Wako Pure Chemical Industries, Ltd.). 1-3. Chlorine-containing polyols (A-3): A polyether polyol with a molecular weight of 600 (manufactured by Sanyo Chemical Industries, Ltd., product name: Sannix PP-600) was mixed with tetran-butylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and triisopropoxyaluminum, and after thorough dehydration and solvent removal, epichlorohydrin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to prepare a bifunctional, chlorine-containing polyol (A-3) with a molecular weight of 1,000. 1-4. Chlorine-containing polyols (A-4): A polycarbonate polyol with a molecular weight of 500 (manufactured by Kuraray Co., Ltd., product name: Kuraray Polyol C-590) was mixed with tetran-butylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and triisopropoxyaluminum, and after thorough dehydration and solvent removal, epichlorohydrin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to prepare a bifunctional, chlorine-containing polyol (A-4) with a molecular weight of 1,000. <<Polyalkylene oxide (B)>> 1-5. Polyalkylene oxide (B-1): Molecular weight 3,000, number of functional groups 3, ethylene oxide content 13% by weight, propylene oxide content 87% by weight: Sanyo Chemical Industries, Ltd. "Sannix GP-3050V" 1-6. Polyalkylene oxide (B-2): Molecular weight 3,000, number of functional groups 3, ethylene oxide content 0% by weight, propylene oxide content 100% by weight: Sanyo Chemical Industries, Ltd. "Sannix GP-3000" <<Polyether Polyol (C)>> 1-7. Polyether polyol (C-1): Molecular weight 8,000, number of functional groups 4, ethylene oxide content 80% by weight, propylene oxide content 20% by weight, hydroxyl value 28 mgKOH / g: Tosoh Corporation "NEF-024" 1-8. Polyether polyol (C-2): Molecular weight 2,000, number of functional groups 2, ethylene oxide content 45% by weight, propylene oxide content 55% by weight, hydroxyl value 56 mgKOH / g: AGC "EL-540" 1-9. Polyether polyol (C-3): Molecular weight 3,300, number of functional groups 3, ethylene oxide content 70% by weight, propylene oxide content 30% by weight, hydroxyl value 50 mgKOH / g: Sanyo Chemical Industries, Ltd. "FA-103" 1-10. Polyether polyol (C-4): Molecular weight 600, number of functional groups 2, ethylene oxide content 100% by weight, hydroxyl value 187 mgKOH / g: "Polyethylene Glycol 600" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. 2. Isocyanate compound: Toluene diisocyanate: "Coronate T-80" manufactured by Tosoh Corporation 3. Foaming agent: Ion-exchanged water 4. Foam stabilizer: Silicone-based foam stabilizer: Dow Toray "SRX-280A" 5. Catalyst: 5-1. Amine catalyst: Tosoh Corporation "TEDA-L33" 5-2. Tin catalyst: "Nikka Octic Tin" manufactured by Nippon Chemical Industries Co., Ltd. <Foam molding> Predetermined amounts of chlorine-containing polyol (A), polyalkylene oxide (B), and polyether polyol (C) as shown in Tables 1-5, 4.1 parts by weight of water, 1 part by weight of the foam stabilizer "SRX-280A", and 0.24 parts by weight and 0.23 parts by weight of the catalyst "TEDA-L33" and "tin octylate", respectively, were measured into a polypropylene cup (1L) and mixed at 1400 rpm for 20 minutes at room temperature (25°C) using a small high-speed stirrer (PRIMIX, manufactured by Primix) to obtain a polyol premix. Isocyanate "Coronate T-80" was added to the polyol premix so that the index below was 100, and mixed at 3800 rpm for 10 seconds using a small high-speed stirrer (PRIMIX, manufactured by Primix) to prepare a foaming stock solution. Immediately after preparing the foaming stock solution, it was transferred from a polypropylene cup (1L) to an acrylic box (250mm x 250mm x 250mm) and heated in a 70°C oven for 30 minutes to obtain a flexible slab foam. After curing at room temperature under atmospheric pressure for one week, it was cut to an appropriate sample size and evaluated using the evaluation method described below.

[0085] Unless otherwise specified, the amounts of each component in Tables 1 to 5 represent the weight ratio relative to 100 parts by weight of the polyol composition.

[0086] Note that the "Isocyanate component (index)" in Tables 1 to 5 refers to the following formula. In the following formula, the equivalent isocyanate parts refer to the amount of isocyanate required for the active hydrogen to react completely.

[0087] "Index" = "Actual amount of isocyanate used" / "Equivalent amount of isocyanate" × 100 <Evaluation Method> density: The density of the flexible polyurethane foam is the apparent density of the entire foam (unit: kg / m³) measured in accordance with JIS K-6400 (2004). 3The following was obtained: The weight (W) of a rectangular prism of flexible polyurethane foam (200 mm long x 200 mm wide x 100 mm thick) was measured, and then the volume (V) was determined from the length, width, and thickness of the rectangular prism, and the density (ρ) was calculated.

[0088] Hardness (25%ILD): The hardness (25% ILD) of the flexible polyurethane foam conforms to JIS K6400. The load (N) was measured as the result of compressing a flexible polyurethane foam (70mm x 70mm x 50mm) by 25% using a pressure plate. The measurements were taken in an environment of 23°C and 50% relative humidity. The target hardness value obtained from this test is 80N or higher, more preferably 100N or higher. A (good hardness): 25%ILD 100N or more B (Good hardness): 25% ILD 80N or higher, less than 100N C (Poor Hardness): 25% ILD less than 80N Compression residual strain: The compression set of flexible polyurethane foam was measured according to the method conforming to JIS K6400. Flexible polyurethane foam (50 mm long x 50 mm wide x 30 mm thick) was compressed to 50% of its original thickness (d0) using two flat plates, and then held at 70°C for 22 hours. After release, it was placed on the surface of a material with low thermal conductivity, such as wood, and allowed to recover for 30 minutes in an environment of 23°C and 50% relative humidity, after which the thickness (dr) after the test was measured. The compression set (Cs) was calculated using the following formula.

[0089] Cs(%) = (d0 - dr) / d0 × 100 The target value for the compressive residual strain obtained from this test is 5% or less, more preferably 3% or less. A (Good compression residual strain): Cs 3% or less B (Good compression residual strain): Cs greater than 3% and less than or equal to 5%. C (Compression Residual Stress Defect): Cs greater than 5% Flame retardant: Regarding the flame retardancy of the flexible polyurethane foam, following the method of the FMVSS No. 302 flammability test, a flexible polyurethane foam (100 mm long x 200 mm wide x 10 mm thick) was held horizontally, and a 38 mm flame was applied indirectly for 15 seconds. The combustion behavior between mark A (38 mm from the left edge) and mark B (165 mm from the left edge) was observed (N=10). (Self-extinguishing rate): The percentage of samples that self-extinguished before or within 51 mm of mark A and within 60 seconds. The target flame retardancy value obtained by this test method is a self-extinguishing rate of 80% or higher, more preferably 100%. A (Flame retardancy approved): Self-extinguishing rate 100% B (Flame retardancy compliant): Self-extinguishing rate of 80% or more, less than 100% C (Flames retardancy failure): Self-extinguishing rate less than 80% <Example 1> According to the foaming molding method described above, the polyurethane foam produced by blending 20 parts by weight of chlorine-containing polyol (A-3), 78 parts by weight of polyalkylene oxide (B-1), and 2 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0090] <Example 2> According to the foaming molding method described above, the polyurethane foam produced by blending 20 parts by weight of chlorine-containing polyol (A-3), 75 parts by weight of polyalkylene oxide (B-1), and 5 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0091] <Example 3> According to the foaming molding method described above, the polyurethane foam produced by blending 20 parts by weight of chlorine-containing polyol (A-3), 70 parts by weight of polyalkylene oxide (B-1), and 10 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0092] <Example 4> According to the foaming molding method described above, the polyurethane foam produced by blending 20 parts by weight of chlorine-containing polyol (A-3), 55 parts by weight of polyalkylene oxide (B-1), and 25 parts by weight of polyether polyol (C-1) was a polyurethane foam with excellent hardness, compression set, and extremely high flame retardancy.

[0093] <Example 5> According to the foaming molding method described above, the polyurethane foam produced by blending 3 parts by weight of chlorine-containing polyol (A-3), 87 parts by weight of polyalkylene oxide (B-1), and 10 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0094] <Example 6> According to the foaming molding method described above, the polyurethane foam produced by blending 45 parts by weight of chlorine-containing polyol (A-3), 45 parts by weight of polyalkylene oxide (B-1), and 10 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, flame retardancy, and compression set.

[0095] <Example 7> According to the foaming molding method described above, the polyurethane foam produced by blending 41 parts by weight of chlorine-containing polyol (A-3), 39 parts by weight of polyalkylene oxide (B-1), and 20 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, flame retardancy, and compression set.

[0096] <Example 8> According to the foaming molding method described above, the polyurethane foam produced by blending 4 parts by weight of chlorine-containing polyol (A-3), 93 parts by weight of polyalkylene oxide (B-1), and 3 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0097] <Example 9> According to the foaming molding method described above, the polyurethane foam produced by blending 10 parts by weight of chlorine-containing polyol (A-2), 80 parts by weight of polyalkylene oxide (B-1), and 10 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0098] <Example 10> According to the foaming molding method described above, the polyurethane foam produced by blending 20 parts by weight of chlorine-containing polyol (A-2), 70 parts by weight of polyalkylene oxide (B-1), and 10 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, flame retardancy, and compression set.

[0099] <Example 11> According to the foaming molding method described above, the polyurethane foam produced by blending 10 parts by weight of chlorine-containing polyol (A-1), 80 parts by weight of polyalkylene oxide (B-1), and 10 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0100] <Example 12> According to the foaming molding method described above, the polyurethane foam produced by blending 20 parts by weight of chlorine-containing polyol (A-1), 70 parts by weight of polyalkylene oxide (B-1), and 10 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0101] <Example 13> According to the foaming molding method described above, the polyurethane foam produced by blending 10 parts by weight of chlorine-containing polyol (A-4), 80 parts by weight of polyalkylene oxide (B-1), and 10 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0102] <Example 14> According to the foaming molding method described above, the polyurethane foam produced by blending 20 parts by weight of chlorine-containing polyol (A-4), 70 parts by weight of polyalkylene oxide (B-1), and 10 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, flame retardancy, and compression set.

[0103] <Example 15> According to the foaming molding method described above, the polyurethane foam produced by blending 20 parts by weight of chlorine-containing polyol (A-3), 75 parts by weight of polyalkylene oxide (B-1), and 5 parts by weight of polyether polyol (C-3) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0104] <Example 16> According to the foaming molding method described above, the polyurethane foam produced by blending 20 parts by weight of chlorine-containing polyol (A-3), 70 parts by weight of polyalkylene oxide (B-1), and 10 parts by weight of polyether polyol (C-3) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0105] <Example 17> According to the foaming molding method described above, the polyurethane foam produced by blending 20 parts by weight of chlorine-containing polyol (A-3), 75 parts by weight of polyalkylene oxide (B-1), and 5 parts by weight of polyether polyol (C-4) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0106] <Example 18> According to the foaming molding method described above, the polyurethane foam produced by blending 20 parts by weight of chlorine-containing polyol (A-3), 70 parts by weight of polyalkylene oxide (B-1), and 10 parts by weight of polyether polyol (C-4) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0107] <Example 19> According to the foaming molding method described above, the polyurethane foam produced by blending 20 parts by weight of chlorine-containing polyol (A-3), 70 parts by weight of polyalkylene oxide (B-2), and 10 parts by weight of polyether polyol (C-1) was a polyurethane foam with extremely excellent hardness, compression set, and flame retardancy.

[0108] <Comparative Example 1> According to the foaming molding method described above, a polyurethane foam was prepared by blending 20 parts by weight of chlorine-containing polyol (A-1) and 80 parts by weight of polyalkylene oxide (B-1), without blending polyether polyol. This polyurethane foam exhibited excellent hardness and compression set, but lacked flame retardancy.

[0109] <Comparative Example 2> According to the foaming molding method described above, a polyurethane foam was prepared by blending 20 parts by weight of chlorine-containing polyol (A-2) and 80 parts by weight of polyalkylene oxide (B-2), without blending polyether polyol. This polyurethane foam exhibited excellent hardness and compression set, but lacked flame retardancy.

[0110] <Comparative Example 3> According to the foaming molding method described above, a polyurethane foam was prepared by blending 20 parts by weight of chlorine-containing polyol (A-3) and 80 parts by weight of polyalkylene oxide (B-1), without blending polyether polyol. This polyurethane foam exhibited excellent hardness and compression set, but lacked flame retardancy.

[0111] <Comparative Example 4> According to the foaming molding method described above, a polyurethane foam was prepared by blending 20 parts by weight of chlorine-containing polyol (A-4) and 80 parts by weight of polyalkylene oxide (B-1), without blending polyether polyol. This polyurethane foam exhibited excellent hardness and compression set, but lacked flame retardancy.

[0112] <Comparative Example 5> According to the foaming molding method described above, a polyurethane foam was prepared by blending 20 parts by weight of chlorine-containing polyol (A-3), 70 parts by weight of polyalkylene oxide (B-1), and 10 parts by weight of polyether polyol (C-2). This polyurethane foam exhibited excellent hardness and compression set, but lacked flame retardancy.

[0113] [Table 1]

[0114] [Table 2]

[0115] [Table 3]

[0116] [Table 4]

[0117] [Table 5]

Claims

1. A composition containing a chlorine-containing polyol (A), a polyalkylene oxide (B), and a polyether polyol (C), wherein the chlorine-containing polyol (A) is a chlorine-containing polyol (A) represented by the following formula (1) with a number average molecular weight of 400 to 5,000, the polyalkylene oxide (B) is a polyalkylene oxide having monomer units of ethylene oxide and propylene oxide, with an ethylene oxide content of 0 to 25% by weight, and the polyether polyol (C) is a polyether polyol with an ethylene oxide content of 50% by weight or more. A polyol composition for polyurethane foam, wherein, with a total amount of polyol composition of 100% by weight, the chlorine-containing polyol (A) is 3 to 45% by weight, the polyalkylene oxide (B) is 35 to 92% by weight, and the polyether polyol (C) is 5 to 20% by weight. 【Chemistry 1】 (In the above formula (1), Q represents a polymer component containing the following structural unit [I], m is an integer from 2 to 3, R １ (This represents a compound residue containing active hydrogen.) 【Chemistry 2】

2. A polyurethane foam composition comprising the polyol composition for polyurethane foam described in claim 1, an isocyanate compound, a blowing agent, and a catalyst.

3. A polyurethane foam obtained from the polyurethane foam composition described in claim 2.

4. A method for producing polyurethane foam by reacting and foaming the polyurethane foam composition described in claim 2.

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