Polyol composition for polyurethane foam raw material and polyurethane foam

Abstract

Provided is a polyol composition for use as a raw material for polyurethane foam, which produces polyurethane foam exhibiting excellent flame retardancy and strength properties. [Solution] The polyol composition is a raw material for polyurethane foam, containing particles consisting of a reaction product (C) of a compound (A) having two primary amino groups and one or more polyalkyleneoxy chains (a) in the molecule with a polyisocyanate (B), and a polyol, wherein the polyisocyanate (B) contains an isocyanurate of an aliphatic diisocyanate, aromatic diisocyanate, and / or alicyclic diisocyanate having 6 to 16 carbon atoms.

Description

[Technical Field]

[0001] The present invention relates to a polyol composition for use as a raw material for polyurethane foam and a polyurethane foam. [Background technology]

[0002] Polymer polyols containing various resins are known as polyols that can increase the resin strength of polyurethane foams. For example, Patent Document 1 discloses a polyurethane foam having high resin strength and flame retardancy obtained by dispersing a urea resin in a polyol. However, the resin strength and flame retardancy are not sufficient and there is room for improvement. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2020 / 040117 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a polyol composition for use as a raw material for polyurethane foam, which can be reacted with a polyisocyanate to produce a polyurethane foam that exhibits excellent flame retardancy and strength properties. [Means for solving the problem]

[0005] The present inventors have made extensive studies and arrived at the present invention. The present invention provides a polyol composition for use as a raw material for polyurethane foam, which contains particles formed from a reaction product (C) of a compound (A) having two primary amino groups and one or more polyalkyleneoxy chains (a) in the molecule with a polyisocyanate (B), and a polyol, wherein the polyisocyanate (B) contains an isocyanurate of an aliphatic diisocyanate, aromatic diisocyanate, and / or alicyclic diisocyanate having 6 to 16 carbon atoms; and a polyurethane foam obtained by reacting a polyol component (G) containing the polyol composition with a polyisocyanate component (H). [Effects of the Invention]

[0006] The use of the polyol composition for polyurethane foam raw material of the present invention as a polyol component has the effect of producing a polyurethane foam having high strength and high flame retardancy. DETAILED DESCRIPTION OF THE INVENTION

[0007] The polyol composition for polyurethane foam raw materials of the present invention (also simply referred to as polyol composition or polyol composition (D)) contains particles of a reaction product (C) between a compound (A) having two primary amino groups and one or more polyalkyleneoxy chains (a) in the molecule and a polyisocyanate (B), and a polyol. In a preferred embodiment, the polyol composition for polyurethane foam raw materials of the present invention is a polyol composition in which particles of the reaction product (C) are dispersed in a continuous phase made of a polyol.

[0008] The compound (A) contains two primary amino groups and one or more polyalkyleneoxy chains (a) in the molecule. The two primary amino groups in compound (A) react with polyisocyanate (B) to generate urea groups, which contribute to the flame retardancy and strength of polyurethane foams. If compound (A) does not contain a primary amino group, no urea groups are generated, resulting in insufficient flame retardancy and strength of polyurethane foams. If compound (A) contains one primary amino group, the reaction product with polyisocyanate (B) contains only one urea group per primary amino group, resulting in insufficient flame retardancy and strength of polyurethane foams. On the other hand, if compound (A) contains three or more primary amino groups, the number of urea groups is sufficient, but the reaction product becomes three-dimensionally crosslinked, resulting in an extremely large molecular weight, high viscosity, and difficulty in granulation.

[0009] The polyalkyleneoxy chain (a) of the compound (A) is derived from an addition reaction of an alkylene oxide having 2 to 4 carbon atoms (i.e., an addition chain). The alkylene oxide having 2 to 4 carbon atoms may be one or more selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being preferred. These may be used alone or in combination of two or more. The polyalkyleneoxy chain (a) preferably has a terminal hydroxyl group.

[0010] The compound (A) is preferably a primary amino group-containing alkylene oxide adduct (A1) represented by the following general formula (1).

[0011] [ka]

[0012] In general formula (1), R 1 and R 2 and R 3 are each independently a linear or branched alkylene group having 1 to 4 carbon atoms, and R 2When there are multiple R 3 When there are multiple n1, they may be the same or different. n1 is an integer of 1 to 5, and n2 is an integer of 0 to 5. AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and m represents the number of moles of alkylene oxide added to each of the n1 nitrogen atoms, and each of the n1 m's is independently a number of 1 to 100.

[0013] R 1 and R 2 and R 3 Examples of the groups include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, and the like, with an ethylene group being preferred.

[0014] n1 is an integer of 1 to 5, and from the viewpoint of viscosity, is preferably an integer of 1 to 3, and more preferably 1 or 2. n2 is an integer of 0 to 5, and from the viewpoint of dispersion stability, is preferably an integer of 0 to 3, and more preferably 0.

[0015] The primary amino group-containing alkylene oxide adduct (A1) is obtained by adding an alkylene oxide to a polyamine compound. Examples of the polyamine compound include dialkylene triamine, trialkylene tetramine, and tetraalkylene pentamine. Specific examples include diethylene triamine, dipropylene triamine (norspermidine), dibutylene triamine (spermidine), triethylene tetramine, tetraethylene pentamine, and tributylene tetramine (spermine). Diethylene triamine and triethylene tetramine are preferred, and diethylene triamine is particularly preferred.

[0016] Examples of the alkyleneoxy group having 2 to 4 carbon atoms in AO in general formula (1) include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group, and preferably an ethyleneoxy group or a propyleneoxy group, which may be used alone or in combination of two or more.

[0017] The n1 m's each independently represent a number from 1 to 100, preferably 1 to 50, and more preferably 1 to 40.

[0018] The reaction between the active hydrogen of the amino group of the polyamine and the alkylene oxide can occur with all amino groups in the molecule. Therefore, the primary amino group-containing alkylene oxide adduct (A1) must be produced via a ketimine compound in which the primary amino group moiety is ketiminated and blocked, so that the alkylene oxide can react selectively with only the secondary amino groups in the molecular chain, rather than with the terminal primary amino groups. Specific production methods for the primary amino group-containing alkylene oxide adduct (A1) include, for example, the method described in JP-A-1-249748.

[0019] The compound (A) preferably has a hydroxyl group at the end of the polyalkyleneoxy chain (a), and the reaction product (C) preferably has at least two hydroxyl groups.

[0020] The polyisocyanate (B) contains an isocyanurate of an aliphatic diisocyanate, aromatic diisocyanate and / or alicyclic diisocyanate having 6 to 16 carbon atoms. Preferred isocyanurates include isocyanurates of aliphatic diisocyanates having 6 to 16 carbon atoms, isocyanurates of aromatic diisocyanates having 6 to 16 carbon atoms, and isocyanurates of alicyclic diisocyanates having 6 to 16 carbon atoms. Specific examples include isocyanurates of 1,6-hexamethylene diisocyanate, isocyanurates of 2,4- and / or 2,6-tolylene diisocyanate (TDI), isocyanurates of 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), and isocyanurates of isophorone diisocyanate (IPDI).

[0021] As the polyisocyanate (B), in addition to the above-mentioned isocyanurates, one or more polyisocyanates selected from the group consisting of aromatic polyisocyanates (B1), aliphatic polyisocyanates (B2), alicyclic polyisocyanates (B3), and araliphatic polyisocyanates (B4) may be used in combination.

[0022] Examples of the aromatic polyisocyanate (B1) include aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbon atoms in NCO groups; the same applies to the number of carbon atoms in the polyisocyanate (B) below), aromatic triisocyanates having 6 to 20 carbon atoms, crude products of these isocyanates, and mixtures of these isocyanates. Specific examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MDI or polymeric MDI), and mixtures of TDI and polymeric MDI.

[0023] Examples of the aliphatic polyisocyanate (B2) include aliphatic diisocyanates having 6 to 16 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate and lysine diisocyanate.

[0024] Examples of the alicyclic polyisocyanate (B3) include alicyclic diisocyanates having 6 to 16 carbon atoms. Specific examples include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate, and norbornane diisocyanate.

[0025] Examples of the araliphatic polyisocyanate (B4) include araliphatic diisocyanates having a carbon number of 8 to 12. Specific examples include xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate.

[0026] The content of isocyanate groups in the polyisocyanate (B) is preferably 10 to 40% by weight based on the weight of the polyisocyanate (B) from the viewpoint of the viscosity of the polyol composition. Furthermore, from the viewpoint of the flame retardancy and strength of the polyurethane foam, the total content of isocyanurates is preferably 50% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, and most preferably 100% by weight, based on the weight of the polyisocyanate (B).

[0027] The reaction product (C) of the compound (A) and the polyisocyanate (B) may contain, in addition to the compound (A), a compound having a hydroxyl group or an amino group capable of reacting with the polyisocyanate (B), as long as it does not adversely affect the reaction between the compound (A) and the polyisocyanate (B). Examples of the compound having an amino group include a compound having two primary amino groups in the molecule but not having a polyalkyleneoxy chain (a). Examples of the compound having a hydroxyl group include the polyol (E) not having a urea group, which will be described later.

[0028] The volume-based median diameter of the particles comprising the reaction product (C) of the compound (A) and the polyisocyanate (B) in the polyol composition is preferably 10 to 500 μm, more preferably 10 to 100 μm, and even more preferably 10 to 50 μm, from the viewpoints of resin strength and dispersion stability. The volume-based median diameter of the particles made of the reaction product (C) can be controlled by adjusting the molecular weight of the reaction product (C), the shear rate, and the reaction temperature. The volume-based median diameter can be measured using a polyol composition as a sample with a particle size distribution analyzer (trade name "LA-960", manufactured by Horiba, Ltd.) according to JIS Z 8825 particle size analysis - laser diffraction and scattering method.

[0029] The polyol composition for use as a polyurethane foam raw material of the present invention contains particles of the reaction product (C) of the compound (A) and polyisocyanate (B) and a polyol. The polyol is a polyol that constitutes the continuous phase in a polyol composition for use as a polyurethane foam raw material, which has a dispersed phase of particles made of reaction product (C), and when reaction product (C) is a polyol having at least two hydroxyl groups, the polyol is a polyol other than reaction product (C).

[0030] The polyol is not particularly limited, but it is preferable to contain a polyol (E) that does not have a urea group from the viewpoint of handling properties and dispersibility of particles made of the reaction product (C).Furthermore, it is preferable to contain the polyol (E) when reacting the compound (A) with the polyisocyanate (B), because this further improves the dispersion stability of particles made of the reaction product (C) by reacting a part of the polyol (E) with the polyisocyanate (B).

[0031] Examples of the polyol (E) having no urea group in the present invention include a polyoxyalkylene polyol (E1) having no urea group, a polyester polyol (E2), and a polymer polyol (E3) having no urea group. In the polyol (E) having no urea group, no urea group is detected by analysis.

[0032] The polyoxyalkylene polyol (E1) not having a urea group is a compound obtained by adding an alkylene oxide (hereinafter sometimes abbreviated as AO) to a polyhydric alcohol such as ethylene glycol, glycerin, propylene glycol, pentaerythritol, sorbitol, trimethylolpropane, or sucrose; a polyhydric phenol such as bisphenol A or bisphenol F; or a mixture thereof. The AO to be added preferably has 2 to 4 carbon atoms, such as propylene oxide (hereinafter sometimes abbreviated as PO), ethylene oxide (hereinafter sometimes abbreviated as EO), or butylene oxide, and two or more of them may be used together. PO alone, EO alone, or a mixture of PO and EO are preferred. When two or more of them are used together, the addition form may be block or random.

[0033] Examples of the polyester polyol (E2) include polyhydric alcohols [dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol; the above-mentioned polyoxyalkylene polyols (E1) (particularly dihydric polyether polyols); or mixtures of these with trihydric or higher polyhydric alcohols such as glycerin and trimethylolpropane] and polycarboxylic acids such as adipic acid and sebacic acid, or esters thereof. Examples of suitable polyols include polyester polyols obtained by polymerization of polymerizable derivatives (such as acid anhydrides like maleic anhydride and phthalic anhydride, and lower alkyl (alkyl group carbon number: 1 to 4) esters like dimethyl terephthalate); condensation products of the above-mentioned carboxylic acid anhydrides with AO; AO (EO, PO, etc.) adducts of these condensation products; polylactone polyols obtained by ring-opening polymerization of lactones (such as ε-caprolactone) using polyhydric alcohols as an initiator; and polycarbonate polyols obtained by reaction of polyhydric alcohols with alkylene carbonates.

[0034] Further, examples of polyester polyols (E2) that are naturally derived include those containing castor oil, castor oil derivatives, and mixtures thereof.

[0035] Examples of the polymer polyol (E3) not containing a urea group include a styrene / acrylonitrile-based polymer polyol obtained by polymerizing styrene / acrylonitrile in a polyol, a PIPA polyol obtained by performing a urethane reaction in a polyol, and a melamine polyol obtained by polycondensing melamine and formaldehyde in a polyol.

[0036] The hydroxyl value (unit: mgKOH / g) of the polyol (E) having no urea group is preferably 20 to 2,000, more preferably 20 to 1,500, and even more preferably 20 to 1,000, from the viewpoint of the strength and foamability of the polyurethane foam. The hydroxyl value in the present invention is measured by the method specified in JIS K 0070 (1995 edition). When two or more polyols are used, the hydroxyl value is the arithmetic mean value by weight of the hydroxyl values ​​of the individual polyols.

[0037] The content of urea groups in the polyol composition is preferably 0.01 to 2.0 mmol / g, more preferably 0.02 to 1.5 mmol / g, and even more preferably 0.05 to 1.2 mmol / g, based on the weight of the polyol composition, from the viewpoint of the flame retardancy and strength of the foam.

[0038] <Method for measuring urea group content> The content of the polyol composition (or polyurethane resin obtained from the composition) is calculated from the nitrogen atom content determined using a nitrogen analyzer [ANTEK7000 (manufactured by Antec)] and the ratio of urethane groups to urea groups determined by H-NMR. NMR measurements are performed according to the method described in "Structural Studies of Polyurethane Resins by NMR: Takeda Research Institute Bulletin 34(2), 224-323 (1975)." Specifically, H-NMR is measured, and when an aliphatic isocyanate is used, the weight ratio of urea groups to urethane groups is determined from the ratio of the integral amount of hydrogen derived from urea groups at a chemical shift of approximately 6 ppm to the integral amount of hydrogen derived from urethane groups at a chemical shift of approximately 7 ppm. The urea group content is calculated from this weight ratio and the above-mentioned N atom content. When an aromatic isocyanate is used, the weight ratio of urea groups to urethane groups is calculated from the ratio of the integral amount of hydrogen derived from urea groups at a chemical shift of approximately 8 ppm to the integral amount of hydrogen derived from urethane groups at a chemical shift of approximately 9 ppm. The urea group content is calculated from this weight ratio and the above-mentioned N atom content.

[0039] The content of the reaction product (C) of the compound (A) and the polyisocyanate (B) is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, and particularly preferably 40 to 50% by weight, based on the weight of the polyol composition, from the viewpoints of the concentration of the reactants in the polyurethane foam and handling.

[0040] A method for producing a polyol composition for use as a raw material for polyurethane foam will now be described. A preferred example of a method for producing the polyol composition of the present invention includes a step of reacting a compound (A) having two primary amino groups and one or more polyalkyleneoxy chains (a) in the molecule with a polyisocyanate (B) in a polyol to obtain a polyol composition containing particles made of a reaction product (C).

[0041] The polyurethane foam of the present invention is obtained by reacting a polyol component (G) containing a polyol composition with a polyisocyanate component (H). The polyurethane foam can be obtained, for example, by placing the above-mentioned polyol component (G), polyisocyanate component (H), and, if necessary, a urethane catalyst (J), a foam stabilizer (I) described below, and a blowing agent (K) in a container, mixing them, and curing them by a urethane reaction.

[0042] As the polyisocyanate component (H) for obtaining polyurethane foam, the same polyisocyanates as the above-mentioned polyisocyanate (B) can be used.

[0043] The polyol component (G) for obtaining the polyurethane foam includes the polyol composition and other polyols used as needed, such as the above-mentioned polyol (E) having no urea group.

[0044] When the ratio of the polyol component (G) to the polyisocyanate component (H) is expressed as an isocyanate index [(NCO group / OH group equivalent ratio) × 100], the index can be varied in various ways, but is preferably 80 to 140, more preferably 85 to 120, and particularly preferably 90 to 115.

[0045] The reaction method of the polyol component (G) and the polyisocyanate component (H) may be a one-shot method, or a prepolymer method in which a part of the mixture of (G) is reacted with (H) in advance to form an NCO-terminated prepolymer, which is then reacted with the remaining (G), or a prepolymer method in which a part of the polyol component (G) is reacted with (H) in advance to form an OH-terminated prepolymer, which is then reacted with the remaining (H).

[0046] As the urethanization catalyst (J) that can be used when the polyol component (G) and the polyisocyanate component (H) are subjected to a curing reaction, any of the usual urethanization catalysts that promote the urethanization reaction can be used, and examples thereof include tertiary amines and their carboxylates, such as PO adducts of triethylenediamine, bis(N,N-dimethylamino-2-ethyl) ether, N,N,N',N'-tetramethylhexamethylenediamine, and N,N-dimethylaminopropylamine; metal carboxylates, such as potassium acetate, potassium octoate, and stannous octoate; and organometallic compounds, such as dibutyltin dilaurate.

[0047] As the foam stabilizer (I) that can be used in the curing reaction of the polyol component (G) and the polyisocyanate component (H), any foam stabilizer that is used in the production of ordinary polyurethane foams can be used. Specific examples include dimethylsiloxane-based foam stabilizers (such as "SRX-253" and "PRX-607" manufactured by Dow Corning Toray Co., Ltd.) and polyether-modified dimethylsiloxane-based foam stabilizers (such as "SZ-1142," "SRX-294A," "SH-193," "SZ-1720," "SZ-1675t," "SF-2936F," "SZ-1346," "SF-2962," and "SZ-1327" manufactured by Dow Corning Toray Co., Ltd.; "B8715LF2," "B8738LF2," "B8737," "B8742," and "B4900" manufactured by Degussa Japan Co., Ltd.; and "L-540," "L-595," "L-3601," "L-3640," and "L-5309" manufactured by Momentive Performance Materials, LLC). The amount of foam stabilizer used is preferably 0.1 to 5.0 parts by weight, more preferably 0.5 to 2.0 parts by weight, per 100 parts by weight of the polyol component (G), from the viewpoints of mechanical properties, changes in mechanical properties over time, and discoloration of the foam.

[0048] Examples of the blowing agent (K) that can be used in the curing reaction of the polyol component (G) and the polyisocyanate component (H) include water, hydrogen atom-containing halogenated hydrocarbons, low-boiling hydrocarbons, and liquefied carbon dioxide. Two or more of these may be used in combination. When water is used alone as the blowing agent (K), the amount of water used is preferably 1.0 to 7.0 parts by weight, more preferably 2.0 to 5.5 parts by weight, per 100 parts by weight of the polyol component (G), from the viewpoints of the moldability and mechanical properties of the polyurethane foam. When water is used in combination with other blowing agents, the amount of water used is preferably 1.0 to 5.5 parts by weight, more preferably 2.0 to 4.0 parts by weight, per 100 parts by weight of the polyol component (G), from the viewpoints of the moldability and mechanical properties of the foam.

[0049] Examples of hydrogen atom-containing halogenated hydrocarbons include HCFC (hydrochlorofluorocarbon) types (e.g., HCFC-123, HCFC-141b, HCFC-22, and HCFC-142b); HFC (hydrofluorocarbon) types (e.g., HFC-134a, HFC-152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, and HFC-365mfc); and HFO (hydrofluoroolefin) types (e.g., HFO-1233zd(E), HFO-1336mzz(Z)). Of these, preferred from the viewpoint of foam flammability are HCFC-141b, HFC-134a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, HFC-365mfc, HFO-1233zd(E), HFO-1336mzz(Z), and mixtures of two or more of these.

[0050] When a hydrogen atom-containing halogenated hydrocarbon is used, the amount used is preferably 50 parts by weight or less, more preferably 5 to 45 parts by weight, per 100 parts by weight of the polyol component (G), from the viewpoint of foam moldability and mechanical properties.

[0051] The low-boiling hydrocarbons are hydrocarbons having a boiling point of -5 to 50°C, and specific examples thereof include butane, pentane, cyclopentane, and mixtures thereof. When a low-boiling hydrocarbon is used, the amount used is preferably 40 parts by weight or less, more preferably 5 to 30 parts by weight, per 100 parts by weight of the polyol component (G), from the viewpoint of foam moldability and mechanical properties.

[0052] When liquefied carbon dioxide gas is used, the amount used is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, per 100 parts by weight of the polyol component (G) from the viewpoint of foam moldability and mechanical properties.

[0053] The polyurethane foam of the present invention may contain various additives (L) as needed, provided that the effects of the present invention are not impaired. Examples of additives include dehydrating agents, lubricants, plasticizers, thixotropic agents, fillers, UV absorbers, antioxidants, antioxidants, colorants, flame retardants, mildew inhibitors, antibacterial agents, dispersants (anti-settling agents), antifoaming agents, inorganic fillers, organic fillers, and microballoons. The amount of each additive added is preferably 30% by weight or less, more preferably 20% by weight or less, based on the total weight of the polyol component (G) and the polyisocyanate component (H). [Example]

[0054] The present invention will be further explained below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, % means % by weight and parts means parts by weight.

[0055] [Production of Polyol Composition (D) for Polyurethane Foam Raw Material] Example 1 A container equipped with a stirrer was charged with 437.8 parts of a primary amino group-containing alkylene oxide adduct (A-1), 62.2 parts of a polyisocyanate (B-1) [Duranate TLA-100 manufactured by Asahi Kasei Corporation], and 500.0 parts of a polyol (E-1) [SANNICS GP-3050NS manufactured by Sanyo Chemical Industries, Ltd.], and the mixture was stirred at a liquid temperature of 25°C and a rotation speed of 150 rpm for 15 minutes to complete the urea reaction, thereby obtaining 1,000 parts of a polyol composition (D-1) containing particles consisting of a reaction product (C-1) of a compound (A-1) having two primary amino groups and one or more polyalkyleneoxy chains (a) in the molecule and the polyisocyanate (B-1).

[0056] <Examples 2 to 11> The same procedure as in Example 1 was carried out using the parts listed in Table 1, to obtain polyol compositions (D-2) to (D-11) of Examples 2 to 11, each containing particles made of reaction products (C-2) to (C-11).

[0057] <Comparative Example 1> The same operation as in Example 1 was carried out using the parts listed in Table 1, but the operation was interrupted due to the formation of a gel, and a polyol composition (D'-1) of Comparative Example 1 containing a reaction product (C'-1) of a primary amino group-containing compound (A'-1) and a polyisocyanate (B-1) was obtained.

[0058] The volume-based median diameter (μm), hydroxyl value (mgKOH / g), and viscosity (mPa·s) of the polyol compositions (D-1) to (D-11) of Examples 1 to 11 are shown in Table 1. The polyol composition (D'-1) was not evaluated. Table 1 also shows the visual appearance at 25°C immediately after production and the appearance after storage at 25°C for 30 days.

[0059] The compounds listed in Table 1 are as follows: Primary amino group-containing alkylene oxide adduct (A-1): San-Amil TAP-40 [manufactured by Sanyo Chemical Industries, Ltd.], R 1 and R 2 is an ethylene group, n1 is 1, n2 is 0, AO is PO, m is 37 Primary amino group-containing alkylene oxide adduct (A-2): San-Amil TAP-10 [manufactured by Sanyo Chemical Industries, Ltd.], R 1 and R 2 is an ethylene group, n1 is 1, n2 is 0, AO is PO, m is 10 Primary amino group-containing compound (A'-1): Diethylenetriamine Polyol (E-1): Sannix GP-3050NS [manufactured by Sanyo Chemical Industries, Ltd., glycerin PO / EO adduct, hydroxyl value 56] Polyol (E-2): Sannix GP-3030 [manufactured by Sanyo Chemical Industries, Ltd., glycerin PO, EO adduct, hydroxyl value 55] Polyol (E-3): Sannix GP-3000R [manufactured by Sanyo Chemical Industries, Ltd., glycerin PO adduct, hydroxyl value 56] Polyol (E-4): Sannix FA-703 [manufactured by Sanyo Chemical Industries, Ltd., glycerin PO, EO adduct, hydroxyl value 33] Polyol (E-5): Sannix FA-974 [manufactured by Sanyo Chemical Industries, Ltd., glycerin PO, EO adduct, hydroxyl value 28] Polyisocyanate (B-1): Duranate TLA-100 [manufactured by Asahi Kasei Corporation, isocyanurate of hexamethylene diisocyanate, isocyanate group content 23.5% by weight] Polyisocyanate (B-2): Duranate TPA-100 [manufactured by Asahi Kasei Corporation, isocyanurate of hexamethylene diisocyanate, isocyanate group content 23.1% by weight]

[0060] [Table 1]

[0061] As shown in Table 1, all of the polyol compositions of Examples 1 to 11 were uniform both immediately after production and after 30 days, but (D'-1) of Comparative Example 1 formed a gel-like substance immediately after production.

[0062] [Production of polyurethane foam (F) with a flexible foam formulation] Example 12 The polyol composition (D-1) prepared in Example 1, polyol (E-3), foam stabilizer (I-1) [NIAX* SILICONE L-580 manufactured by Momentive Performance Materials Japan, LLC], urethanization catalyst (J-1) [DABCO-33LV manufactured by Air Products Japan, Inc.], urethanization catalyst (J-2) [Neostan U-28 manufactured by Nitto Kasei Co., Ltd.], water as a blowing agent (K-1), and flame retardant (L-1) [TEP manufactured by Daihachi Chemical Industry Co., Ltd.] were placed in a 1-L cup in the amounts shown in Table 2 and stirred at 3,000 RPM for 30 seconds to mix uniformly. Polyisocyanate (H-1) was added to the resulting mixture, which was then immediately stirred for 6 seconds at 3000 RPM using a mixer. The mixture was then placed in a 30 cm x 30 cm x 20 cm container and cured for 10 minutes to obtain polyurethane foam (F-1).

[0063] <Examples 13 to 24 and Comparative Examples 2 and 3> Using the quantities shown in Table 2, polyurethane foams (F-2) to (F-13) of Examples 13 to 24 and polyurethane foams (F'-1) to (F'-2) of Comparative Examples 2 and 3 were obtained in the same manner as in Example 12.

[0064] The compounds listed in Table 2 but not listed in Table 1 are as follows: Polyisocyanate (H-1): Coronate T-80 [2,4-toluene diisocyanate: 2,6-toluene diisocyanate = 8:2 mixture, manufactured by Tosoh Corporation, isocyanate group content 48% by weight] Polyol (E-3): Sannix GP-3000R [manufactured by Sanyo Chemical Industries, Ltd., glycerin PO adduct, hydroxyl value 56] Polyol (E-6): Sharpflow FS-7305 [Sanyo Chemical Industries, Ltd., styrene / acrylonitrile polymer polyol, polymer concentration 44% by weight, hydroxyl value 31] Foam stabilizer (I-1): NIAX* SILICONE L-580 manufactured by Momentive Performance Materials Japan, LLC Urethane catalyst (J-1): "DABCO-33LV" (33% by weight solution of triethylenediamine in dipropylene glycol) manufactured by Air Products Japan Co., Ltd. Urethane catalyst (J-2): "Neostan U-28" manufactured by Nitto Kasei Co., Ltd. Foaming agent (K-1): Water Flame retardant (L-1): Daihachi Chemical Industry Co., Ltd. [TEP (triethyl phosphate)]

[0065] The foam density, air permeability, compressive strength, and flame retardancy of the polyurethane foams (F-1) to (F-13) and (F'-1) to (F'-2) prepared in Examples 12 to 24 and Comparative Examples 2 and 3 were measured by the following methods. The results are shown in Table 2.

[0066] <Foam density> Foam density (kg / m) according to JIS K 6400 3 ) was measured.

[0067] <Breathability> Air permeability (CC / cm) according to JIS K 6400 2 ·s) was measured.

[0068] <Compression strength> 40% compressive strength (N / mm 2 ) was measured.

[0069] <Flame retardancy (combustion test)> Flame retardancy was evaluated in accordance with the following FMVSS302.

[0070] FMVSS302 Combustion Test Method This is a combustion test for automotive interior materials and is known as the US Federal Motor Vehicle Safety Standard. In summary, a burner flame is applied 38 mm from the right end for 15 seconds, and the burning distance and burning rate are measured over a 254 mm length from the right end mark A to the left end mark B.

[0071] [Table 2]

[0072] As is clear from Table 2, the low-density polyurethane foams of Examples 12 to 24, which were produced using the polyol composition of the present invention according to a flexible foam production recipe, had high compressive strength and demonstrated high flame retardancy in the FMVSS 302 combustion test. On the other hand, the polyurethane foam (F'-1) of Comparative Example 2, which did not use the polyol composition (D) of the present invention but used a general polyol, and the polyurethane foam (F'-2) of Comparative Example 3, which used a styrene / acrylonitrile polymer polyol, demonstrated poor flame retardancy. [Industrial Applicability]

[0073] The polyol composition of the present invention has excellent handleability and dispersibility, and therefore can be suitably used as a raw material for general-purpose polyurethane foams. Furthermore, polyurethane foams using the polyol composition of the present invention have high strength and contain a high concentration of the reaction product (C) having urea groups, which has excellent flame retardancy, and are therefore particularly suitable for applications requiring high flame retardancy and physical properties, such as urethane resin engine covers, urethane seat cushions for railway vehicles, urethane seat cushions for public transport vehicles, and insulating urethane boards for building materials.

Claims

1. The polyol composition is a raw material for polyurethane foam, and contains particles of a reaction product (C) of a compound (A) having two primary amino groups and one or more polyalkyleneoxy chains (a) in the molecule with a polyisocyanate (B), and a polyol, wherein the polyisocyanate (B) contains an isocyanurate of an aliphatic diisocyanate, aromatic diisocyanate, and / or alicyclic diisocyanate having 6 to 16 carbon atoms.

2. 2. The polyol composition according to claim 1, wherein the compound (A) is a primary amino group-containing alkylene oxide adduct (A1) represented by the following general formula (1): 【Chemistry 1】 [In general formula (1), R １ and R ２ and R ３ are each independently a linear or branched alkylene group having 1 to 4 carbon atoms, and R ２ and R ３ When there are a plurality of n, they may be the same or different. １ is an integer from 1 to 5, and n ２ is an integer of 0 to 5. AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and m is n １ represents the number of moles of alkylene oxide added to each of the nitrogen atoms, １ Each m is independently a number from 1 to 100.

3. The polyol composition according to claim 1, wherein the particles of the reaction product (C) have a volume-based median diameter of 10 to 500 μm.

4. The polyol composition according to claim 1, further comprising a polyol (E) having no urea group as the polyol.

5. A polyurethane foam obtained by reacting a polyol component (G) containing the polyol composition according to any one of claims 1 to 4 with a polyisocyanate component (H).

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