Polyol Composition

Abstract

To provide a polyol composition that can be prevented from bumping during storage even though it contains a fluorine-based foaming agent.SOLUTION: A polyol composition contains a polyol compound, a fluorine-based foaming agent, and a nonionic surfactant.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyol composition containing a fluorine-containing blowing agent. [Background technology]

[0002] BACKGROUND ART Polyurethane foams, taking advantage of their excellent heat insulating properties, are used in practical applications for insulating and preventing condensation on ceilings, roofs, walls, and the like of buildings such as apartment complexes, detached houses, and commercial buildings. Polyurethane foams are obtained by mixing a polyol composition containing a polyol compound, a filler, a blowing agent, etc. with a polyisocyanate compound, followed by foaming. The polyol composition and the polyisocyanate compound are typically stored separately and then mixed and used at the construction site. Therefore, the storage stability of the polyol composition, in particular, can be poor due to the mixture of various components, and there is a need for an improvement in storage stability.

[0003] For example, Patent Document 1 describes an invention relating to a polyol composition comprising a polyol compound, a foaming agent, a filler, and metal oxide fine particles, wherein the foaming agent is a hydrofluoroolefin and the surfaces of the metal oxide fine particles have been hydrophobized, and indicates that the polyol composition can be used well even after long-term storage of one month or more. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-178096 Summary of the Invention [Problem to be solved by the invention]

[0005] However, polyol compositions containing a fluorine-based blowing agent such as hydrofluoroolefin have the problem of being prone to bumping during transportation and application at the site, and this problem is particularly noticeable in the summer when temperatures are high. Therefore, an object of the present invention is to provide a polyol composition that can prevent bumping during storage even when the polyol composition contains a fluorine-based blowing agent. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by a polyol composition containing a polyol compound, a blowing agent including a fluorine-containing blowing agent, and a nonionic surfactant, and have completed the present invention. That is, the present invention provides the following [1] to

[11] . [1] A polyol composition containing a polyol compound, a fluorine-based blowing agent, and a nonionic surfactant. [2] The polyol composition according to the above [1], wherein the nonionic surfactant is a surfactant containing a hydrocarbon group X having 6 or more carbon atoms. [3] The polyol composition according to [1] or [2] above, wherein the nonionic surfactant is at least one selected from the group consisting of fatty acid esters, polyoxyalkylene alkyl ethers, and higher alcohols. [4] The polyol composition according to any one of the above [1] to [3], wherein the fluorine-based blowing agent is a hydrofluoroolefin. [5] The polyol composition according to any one of the above [1] to [4], wherein the boiling point of the fluorine-based blowing agent is 45°C or lower. [6] The polyol composition according to any one of the above [1] to [5], wherein the polyol compound contains at least one of a polyester polyol and a polyether polyol. [7] The polyol composition according to [6] above, wherein the polyester polyol is a phthalic acid-based polyester polyol. [8] The polyol composition according to any one of the above [1] to [7], further comprising water as a blowing agent. [9] The polyol composition according to any one of the above [1] to [8], further comprising a foam stabilizer.

[10] The polyol composition according to any one of the above [1] to [9], further comprising a catalyst.

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

[10] , further comprising a flame retardant. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a polyol composition that can prevent bumping during storage even when the polyol composition contains a fluorine-based blowing agent. DETAILED DESCRIPTION OF THE INVENTION

[0008] [Polyol composition] The polyol composition of the present invention is a polyol composition containing a polyol compound, a fluorine-based blowing agent, and a nonionic surfactant. A polyurethane foam can be formed using the polyol composition and a polyisocyanate compound described below as raw materials. Each component contained in the polyol composition of the present invention will be described in detail below.

[0009] (nonionic surfactant) The polyol compound of the present invention contains a nonionic surfactant, which can suppress bumping of the polyol composition containing a fluorine-containing blowing agent. From the viewpoint of easily preventing bumping of the polyol composition, the nonionic surfactant preferably contains a hydrocarbon group X having 6 or more carbon atoms. The hydrocarbon group X preferably has 8 or more carbon atoms, more preferably 12 or more carbon atoms, and even more preferably 16 or more carbon atoms, and preferably has 30 or less carbon atoms, more preferably 20 or less carbon atoms. The hydrocarbon group X may be a saturated or unsaturated hydrocarbon group.

[0010] The type of nonionic surfactant is not particularly limited, but is preferably one containing at least one group selected from an ether group, an ester group, and an alcohol group, and the above-mentioned hydrocarbon group X. Specifically, the nonionic surfactant is preferably at least one selected from the group consisting of fatty acid esters, polyoxyalkylene alkyl ethers, and higher alcohols. The fatty acid ester may be a saturated fatty acid ester or an unsaturated fatty acid ester. The fatty acid ester is preferably a compound represented by the following formula (1). [ka] In the above formula (1), R1 is a hydrocarbon group, which may be a saturated or unsaturated hydrocarbon group. Of these, R1 is preferably the hydrocarbon group X described above. R2 is a hydrocarbon group, which may be a saturated or unsaturated hydrocarbon group, but is preferably a saturated hydrocarbon group. Of these, R2 is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, even more preferably a hydrocarbon group having 1 to 2 carbon atoms, and even more preferably a methyl group. Suitable fatty acid esters include, for example, saturated fatty acid esters such as methyl octanoate, ethyl octanoate, methyl nonanoate, ethyl nonanoate, methyl decanoate, ethyl decanoate, methyl undecanoate, ethyl undecanoate, methyl laurate, ethyl laurate, methyl tridecanoate, methyl myristate, ethyl myristate, methyl pentadecanoate, ethyl pentadecanoate, methyl palmitate, ethyl palmitate, methyl heptadecanoate, ethyl heptadecanoate, methyl stearate, ethyl stearate, methyl nonadecanoate, and ethyl nonadecanoate; methyl octenoate, ethyl octenoate; Examples of unsaturated fatty acid esters include methyl nonenoate, ethyl nonenoate, methyl decenoate, ethyl decenoate, methyl undecenoate, ethyl undecenoate, methyl dodecenoate, ethyl dodecenoate, methyl tridecenoate, ethyl tridecenoate, methyl tetradecenoate, ethyl tetradecenoate, methyl pentadecenoate, ethyl pentadecenoate, methyl hexadecenoate, ethyl hexadecenoate, methyl heptadecenoate, ethyl heptadecenoate, methyl oleate, ethyl oleate, methyl linoleate, ethyl linoleate, methyl linolenate, ethyl linolenate, methyl nonadecenoate, and ethyl nonadecenoate. Among these, methyl stearate, methyl oleate, and methyl linoleate are more preferred. The fatty acid ester may be used alone or in combination of two or more.

[0011] The polyoxyalkylene alkyl ether is preferably a compound represented by the following formula (2). [ka] R3 is an alkyl group, and the alkyl group preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, even more preferably 12 or more carbon atoms, and even more preferably 16 or more carbon atoms, and preferably has 30 or less carbon atoms, more preferably 20 or less carbon atoms. Examples of R3 include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a lauryl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a palmityl group, a heptadecyl group, a stearyl group, a nonadecyl group, and an icosyl group. Among these, an undecyl group, a lauryl group, and a tridecyl group are preferred, and a lauryl group is more preferred.

[0012] The repeating unit AO is an oxyalkylene group, preferably an oxyalkylene group having 2 to 6 carbon atoms, and more preferably an oxyethylene group or an oxypropylene group. Here, the oxyethylene group is a group derived from ethylene oxide, and the oxypropylene group is a group derived from propylene oxide. Although n is not particularly limited, it is preferably an integer of 1 to 30, more preferably an integer of 3 to 20, and even more preferably an integer of 5 to 10.

[0013] Among the polyoxyalkylene alkyl ethers of the above formula (2), polyoxyethylene alkyl ethers, polyoxyethylene propylene alkyl ethers, etc. are preferred from the viewpoint of easily preventing bumping of the polyol composition, and polyoxyethylene propylene alkyl ethers are more preferred. Note that polyoxyethylene propylene alkyl ethers are polyoxyethylene alkyl ethers in which some of the oxyethylene groups, which are repeating units, are substituted with oxypropylene groups.

[0014] In the polyoxyalkylene alkyl ether of the present invention, from the viewpoint of easily preventing bumping of the polyol composition, the terminal hydrogen atom in the above formula (2) is preferably substituted with R4. R4 is preferably an organic group having 1 to 10 carbon atoms, and more preferably an organic group having 1 to 5 carbon atoms. The organic group may have a group such as an ester group, an ether group, an amide group, a hydroxyl group, or a carboxyl group, and preferably has an ether group.

[0015] Particularly preferred polyoxyalkylene alkyl ether compounds include polyoxyethylene lauryl ether and polyoxyethylene propylene lauryl ether.

[0016] The higher alcohol is preferably an alcohol having 6 or more carbon atoms and containing the above-mentioned hydrocarbon group X. Specific examples include hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, palmityl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, and icosyl alcohol. Among these, preferred higher alcohols are octyl alcohol, nonyl alcohol, and decyl alcohol, with octyl alcohol and decyl alcohol being more preferred.

[0017] The content of the nonionic surfactant is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the polyol compound. When the content of the nonionic surfactant is equal to or greater than these lower limits, bumping of the polyol composition is easily prevented, and when it is equal to or less than these upper limits, an effect corresponding to the blending amount is easily obtained.

[0018] (Fluorine-based blowing agent) The blowing agent in the present invention contains a fluorine-based blowing agent. The fluorine-based blowing agent is a blowing agent containing fluorine atoms, and examples thereof include fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, and hydrofluoroolefins. Among these, hydrofluoroolefins are preferred because they are less likely to have adverse effects on the environment, such as destruction of the ozone layer and global warming. Examples of the fluorine compound include CHF3, CH2F2, and CH3F. Examples of the hydrochlorofluorocarbon compounds include trichloromonofluoromethane, trichlorotrifluoroethane, and dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), and HCFC142b (1-chloro-1,1-difluoroethane)). Examples of the hydrofluorocarbon include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane). Examples of the hydrofluoroolefin include HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene) and HFO-1234yf (2,3,3,3-tetrafluoro-1-propene).

[0019] The boiling point of the fluorine-based blowing agent is preferably 45°C or lower, more preferably 35°C or lower, and even more preferably 25°C or lower, from the viewpoint of increasing the foaming efficiency. Generally, polyol compositions containing a fluorine-based blowing agent having a boiling point within the above range are prone to bumping at high temperatures. However, the polyol composition of the present invention can prevent bumping and also improve foaming efficiency, even when it contains a fluorine-based blowing agent having a boiling point within the above range.

[0020] The amount of the fluorine-based blowing agent relative to 100 parts by mass of the polyol compound is not particularly limited, but is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less. When the amount of the fluorine-based blowing agent is equal to or greater than the lower limit, the foaming property is increased, whereas when the amount is equal to or less than the upper limit, the dimensional stability of the resulting foam is likely to be improved.

[0021] The polyol composition of the present invention preferably contains water as a blowing agent other than the above-mentioned fluorine-based blowing agent. That is, it is preferable to use a fluorine-based blowing agent and water in combination as the blowing agent. As the water, for example, ion-exchanged water, distilled water, etc. can be appropriately used. The amount of water per 100 parts by mass of the polyol compound is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less. When the amount of water is equal to or greater than the lower limit, the foaming property is enhanced, whereas when the amount of water is equal to or less than the upper limit, the dimensional stability of the resulting polyurethane foam is likely to be improved.

[0022] (Polyol compound) The polyol compound contained in the polyol composition of the present invention is not particularly limited, but preferably contains at least one of a polyester polyol and a polyether polyol, and more preferably contains both a polyester polyol and a polyether polyol.

[0023] <Polyether polyol> Polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of alkylene oxide to an initiator having two or more active hydrogen atoms. Specific examples of the initiator include aliphatic polyhydric alcohols (e.g., glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, and cyclohexanedimethanol; triols such as trimethylolpropane and glycerin; tetrafunctional alcohols such as pentaerythritol; and sugars such as sucrose and sorbitol), aliphatic amines (e.g., alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine; alkanolamines such as monoethanolamine and diethanolamine), and aromatic amines (e.g., aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, and Mannich condensation products). These may be used alone or in combination of two or more.

[0024] As the polyether polyol, Mannich-based polyether polyols and ethylenediamine-based polyether polyols are preferred from the viewpoint of improving moldability during injection during urethane foaming and workability during spraying. The content of the polyether polyol is preferably 5 to 90 mass %, more preferably 10 to 70 mass %, based on the total amount of the polyol compounds.

[0025] The Mannich polyether polyol is a polyether polyol obtained by utilizing the Mannich reaction, which is a Mannich condensation product having two or more hydroxyl groups in the molecule, or a polyether polyol obtained by adding an alkylene oxide to such a Mannich condensation product. More specifically, it is a Mannich condensation product obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde, and alkanolamine, or a polyether polyol obtained by ring-opening addition polymerization of this compound with at least one of ethylene oxide and propylene oxide. The ethylenediamine-based polyether polyol is a polyether polyol obtained by using ethylenediamine as an initiator.

[0026] The hydroxyl value of the polyether polyol is preferably 200 to 2000 mgKOH / g, more preferably 300 to 1000 mgKOH / g. The hydroxyl value is a value measured in accordance with JIS K1557-1:2007.

[0027] <Polyester polyol> Examples of polyester polyols include aromatic polyester polyols and aliphatic polyester polyols. However, when the flame retardancy of the resulting polyurethane foam is taken into consideration, it is preferable to use an aromatic polyester polyol. The aromatic polyester polyol is preferably a condensate of an aromatic dicarboxylic acid, such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), or naphthalenedicarboxylic acid, with a glycol. In particular, from the viewpoint of improving the flame retardancy of the polyurethane foam, the polyester polyol is preferably a phthalic acid-based polyester polyol, which is a condensate of phthalic acid and a glycol, and more preferably includes a p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid and a glycol. The glycol is not particularly limited, but it is preferable to use low molecular weight aliphatic glycols known as constituent components of polyester polyols, such as ethylene glycol, propylene glycol, and diethylene glycol. The content of the polyester polyol is preferably 5 to 90 mass %, more preferably 10 to 70 mass %, based on the total amount of the polyol compounds.

[0028] The hydroxyl value of the polyester polyol is preferably from 100 to 500 mgKOH / g, and more preferably from 150 to 450 mgKOH / g.

[0029] (Foam stabilizer) The foamable urethane resin composition contains a foam stabilizer. Examples of the foam stabilizer include silicone foam stabilizers such as organopolysiloxane. The silicone foam stabilizer may also include a graft copolymer of polydimethylsiloxane and polyethylene glycol. The content of the foam stabilizer is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the polyol compound. One type of foam stabilizer may be used alone, or two or more types may be used.

[0030] (catalyst) The polyol composition of the present invention preferably contains a catalyst. The catalyst may contain, for example, one or both of a urethanization catalyst and a trimerization catalyst, and preferably contains both.

[0031] The urethanization catalyst is a catalyst that promotes the reaction between a polyol compound and a polyisocyanate compound. Specific examples include amino compounds, tin compounds, bismuth compounds, and metal salts of acetylacetone. Examples of the amino compound include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl) ether, bis(2-dimethylaminoethyl) ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl) ether, N-methyl-N',N'-dimethylaminoethylpiperazine, an imidazole compound in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, 1-methylimidazole, trimethylaminoethylpiperazine, and tripropylamine. Examples of tin compounds include stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, etc. Examples of bismuth compounds include bismuth neodecanoate, bismuth octoate, etc. Examples of acetylacetone metal salts include acetylacetone aluminum, acetylacetone iron, acetylacetone copper, acetylacetone zinc, acetylacetone beryllium, acetylacetone chromium, acetylacetone indium, acetylacetone manganese, acetylacetone molybdenum, acetylacetone titanium, acetylacetone cobalt, acetylacetone vanadium, and acetylacetone zirconium. The urethane resin curing catalyst may be used alone or in combination of two or more.

[0032] The amount of the urethane catalyst in the polyol composition is not particularly limited, but is preferably in the range of 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 3 to 15 parts by mass, relative to 100 parts by mass of the polyol compound. By adjusting the amount within the above range, the reaction between the polyol compound and the polyisocyanate compound can be promoted at an appropriate reaction rate.

[0033] The trimerization catalyst promotes the trimerization that forms isocyanurate bonds, which improves the flame retardancy of polyurethane foams. Examples of trimerization catalysts that can be used include aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal salts such as potassium acetate, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium octylate, and sodium octylate; aziridines such as 2-ethylaziridine; lead compounds such as lead naphthenate and lead octylate; alcoholate compounds such as sodium methoxide; phenolate compounds such as potassium phenoxide; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt; and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium, and tetraphenylammonium salt. The trimerization catalyst may be used alone or in combination of two or more.

[0034] The amount of the trimerization catalyst is not particularly limited, but is preferably in the range of 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the polyol compound. By setting the amount of the trimerization catalyst within the above range, an appropriate amount of isocyanurate bond is formed, improving flame retardancy. The total amount of catalyst is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, and even more preferably 2 to 20 parts by mass, per 100 parts by mass of the urethane resin, from the viewpoint of improving the curing speed and flame retardancy of the urethane.

[0035] (Flame retardant) The polyol composition of the present invention preferably contains a flame retardant from the viewpoint of improving flame retardancy. The flame retardant may be a liquid flame retardant or a solid flame retardant, but a liquid flame retardant is preferred because it is less likely to produce precipitates during storage, is easy to handle, and can suppress wear on equipment used during use. Here, the liquid flame retardant is a flame retardant that is liquid at 23°C, and the solid flame retardant is a flame retardant that is solid at 23°C. Examples of liquid flame retardants include phosphate ester-based flame retardants such as monophosphate esters and condensed phosphate esters. The monophosphate ester is not particularly limited, but includes trimethyl phosphate, triethyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tris(β-chloropropyl) phosphate, and the like. The condensed phosphate ester is not particularly limited, but examples thereof include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), and aromatic condensed phosphate ester (trade name CR747).

[0036] Examples of solid flame retardants include antimony-containing flame retardants such as antimony oxide, antimonates, and pyroantimonates; metal hydroxide-based flame retardants such as magnesium hydroxide, calcium hydroxide, and aluminum hydroxide; boron-containing flame retardants such as lithium borate and sodium borate; phosphinic acid-based flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, and red phosphorus.

[0037] The content of the flame retardant is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and even more preferably 15 to 70 parts by mass, relative to 100 parts by mass of the polyol compound.

[0038] (inorganic filler) The polyol composition of the present invention may contain an inorganic filler, but the inorganic filler does not include the above-mentioned solid flame retardant. Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salts of calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica palan, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon palan, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, and the like.

[0039] The polyol composition may contain other additives, such as phenolic, amine, or sulfur-based antioxidants, heat stabilizers, metal inhibitors, antistatic agents, crosslinking agents, lubricants, softeners, pigments, and tackifying resins, within the scope of not impairing the effects of the present invention.

[0040] (Polyisocyanate compounds) A foamable urethane resin composition is prepared by mixing the polyol composition of the present invention with a polyisocyanate composition containing a polyisocyanate compound, and the composition is foamed and cured to form a polyurethane foam. The polyol composition of the present invention is resistant to bumping, and therefore has excellent storage stability even at high temperatures such as in summer. This improves workability when mixing with the polyisocyanate composition, facilitating the formation of a polyurethane foam. As the polyisocyanate compound, various polyisocyanate compounds having two or more isocyanate groups, such as aromatic, alicyclic, and aliphatic polyisocyanate compounds, can be used. Liquid diphenylmethane diisocyanate (MDI) is preferred because of its ease of handling, rapid reaction, excellent physical properties of the resulting polyurethane foam, and low cost. Examples of liquid MDI include crude MDI (also known as polymeric MDI). Specific commercial liquid MDI products include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.) and "Millionate MR-200" (manufactured by Nippon Polyurethane Industry Co., Ltd.). Uretonimine-containing MDI (e.g., commercially available product "Millionate MTL" manufactured by Nippon Polyurethane Industry Co., Ltd.) may also be used. Liquid MDI may be used in combination with other polyisocyanate compounds, and any polyisocyanate compound known in the polyurethane technical field can be used without limitation.

[0041] The above-mentioned flame retardant, foam stabilizer, catalyst, and other additives may be contained in the polyol composition, may be contained in the polyisocyanate composition, or may be provided separately from the polyol composition and the polyisocyanate composition, but are preferably contained in the polyol composition.

[0042] The method for producing the foamable urethane resin composition is not particularly limited, and examples thereof include a method in which a polyol composition and a polyisocyanate composition are prepared by kneading them in advance and then kneading them together, and a method in which the components constituting the foamable urethane resin composition are kneaded together, but the foamable urethane resin composition is usually produced by kneading a polyol composition and a polyisocyanate composition. Kneading can be carried out by a known method, for example, by using a known device such as a high-pressure foaming machine, a low-pressure foaming machine, a spray foaming machine, or a hand mixer.

[0043] (Application) The uses of the polyol composition of the present invention and the foamable urethane resin composition described above are not particularly limited, and they can be used to fill cavities in structures such as buildings, furniture, automobiles, trains, ships, etc., or to spray onto such structures. Among these, the use of spraying onto structures, i.e., spraying, is preferred. Spraying can be carried out using a spraying device (e.g., A-25 manufactured by GRACO) and a spray gun (e.g., D-gun manufactured by Gasmar). Spraying can be carried out by adjusting the temperature of the polyol composition and the polyisocyanate composition contained in separate containers in the spraying device, causing them to collide and mix at the tip of the spray gun, and turning the mixed liquid into a mist using air pressure. Spraying devices and spray guns are known, and commercially available products can be used. [Example]

[0044] The present invention will be explained in more detail by way of examples, but the present invention is not limited to these examples in any way.

[0045] Details of each component used in each example and comparative example are as follows. (1) Polyol compounds (i) Polyester polyol o-Phthalic acid-based polyester polyol (Kawasaki Chemical Industries, Ltd., product name: RDK133, hydroxyl value = 315 mg KOH / g) (ii) Polyether polyol Mannich polyether polyol (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: DK3776, hydroxyl value = 350 mg KOH / g) Ethylenediamine-based polyether polyol (AGC Corporation, product name: Exenol 750ED, hydroxyl value = 760 mg KOH / g) (2) Liquid flame retardants Phosphate ester flame retardant <tris(β-chloropropyl)phosphate> (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP) (3) Foam stabilizer Silicone foam stabilizer (Toray Dow Corning, product name: SH-193) (4) Catalyst (i) Trimerization catalyst Quaternary ammonium salt (manufactured by Evonik Japan, product name: TMR-7) (ii) urethanization catalyst Imidazole compound (Kao Corporation, product name: KL No. 390) Bismuth compounds (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600) (5) Foaming agent ·water HFO-1233zd (hydrofluoroolefin) (Honeywell, product name: Solstice LBA) (6) Nonionic surfactants Surfactant A: Lion Corporation's "Pastel M182" fatty acid esters Surfactant B: Sanyo Chemical Industries, Ltd. "Emulmin FL-80" Polyoxyethylene Propylene Lauryl Ether Surfactant C: Emulgen 103 manufactured by Kao Corporation Polyoxyethylene lauryl ether Surfactant D "Kalcol 0898" manufactured by Kao Corporation Octyl alcohol Surfactant E "Kalcol 1098" manufactured by Kao Corporation Decyl alcohol

[0046] [Evaluation of bumping (boiling evaluation)] The polyol compositions prepared in each of the Examples and Comparative Examples were evaluated for bumping property as follows. 30 g of the polyol composition of each Example and Comparative Example was placed in a 110 cc cylindrical screw tube (12 cm long) containing a stirrer and heated to 30°C. The mixture was then stirred for 1 minute at a rotation speed of 100 rpm using a magnetic stirrer, and the maximum liquid level during the 1 minute of stirring was measured. The liquid level is the height of the liquid surface relative to the bottom of the screw tube. The bumping tendency was evaluated according to the following criteria. A lower maximum liquid level means that bumping is less likely to occur and indicates a superior effect of the present invention. <Evaluation criteria> ◎ Maximum liquid level is 50mm or less ○ Maximum liquid level is over 50mm and 60mm or less △ Maximum liquid level is over 60mm and 70mm or less × Maximum liquid level is over 70mm

[0047] [Example 1] According to the formulation in Table 1, a polyol compound, a flame retardant, a foam stabilizer, a catalyst, a blowing agent, and a surfactant were weighed into a 1000 mL polypropylene beaker and stirred with a hand mixer at 20°C for 10 seconds to prepare a polyol composition. The polyol composition was evaluated for bumping tendency. The results are shown in Table 1.

[0048] [Examples 2 to 5, Comparative Examples 1 to 3] A polyol composition was prepared in the same manner as in Example 1, except that the formulation was changed as shown in Table 1.

[0049] [Table 1]

[0050] As shown in each example, it was found that the polyol composition of the present invention containing a nonionic surfactant had a low maximum liquid level and was less likely to cause bumping even when a fluorine-containing blowing agent was used. In contrast, it was found that the polyol compositions of each comparative example not containing a nonionic surfactant had a high maximum liquid level and were more likely to cause bumping.

Claims

1. Contains a polyol compound, a fluorine-based foaming agent, and a nonionic surfactant (excluding silicone foam stabilizers), the polyol compound contains a polyester polyol and a polyether polyol, the fluorine-based blowing agent is trans-1-chloro-3,3,3-trifluoropropene or 2,3,3,3-tetrafluoro-1-propene; The polyol composition, wherein the nonionic surfactant is a fatty acid ester.

2. The polyol composition according to claim 1, wherein the nonionic surfactant is a surfactant containing a hydrocarbon group X having 6 or more carbon atoms.

3. The polyol composition according to claim 1 or 2, wherein the polyester polyol is a phthalic acid-based polyester polyol.

4. The polyol composition according to any one of claims 1 to 3, further comprising water as a blowing agent.

5. The polyol composition according to any one of claims 1 to 4, further comprising a foam stabilizer.

6. The polyol composition according to any one of claims 1 to 5, further comprising a catalyst.

7. The polyol composition according to any one of claims 1 to 6, further comprising a flame retardant.

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