Polyol composition, foamable polyurethane composition, and polyurethane foam

Abstract

To provide a polyol composition which can suppress the boiling-up of a liquid during stirring when dispersing a filler, and can suppress the generation of an odor when forming a polyurethane foam.SOLUTION: The present invention discloses a polyol composition for on-site spraying, containing a polyol, a foaming agent, a filler, a catalyst, and a phosphate compound.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Due to its excellent heat insulating properties and adhesive properties, polyurethane foam is used as a heat insulating material for buildings such as apartment complexes, detached houses, various school facilities, commercial buildings, etc. Polyurethane foam is obtained by foaming a foamable polyurethane composition containing a polyol composition and a polyisocyanate.

[0003] The polyol composition generally contains a polyol and a foaming agent, and may further contain fillers such as a flame retardant and an inorganic filler, if necessary. These fillers are added for the purpose of improving the flame retardancy, coloring, or mechanical strength of the resulting polyurethane foam. For example, Patent Document 1 describes an invention relating to a polyol composition obtained by blending a polyol with a fixed amount of a specific flame retardant, and describes that the polyol composition has excellent flame retardancy, low smoke generation, and the like.

[0004] In addition, as a method for applying polyurethane foam, for example, a method is adopted in which a polyol composition and a polyisocyanate are mixed at the application site, reacted, foamed, and sprayed, as described in Patent Document 2. Therefore, the polyol composition and the polyisocyanate are mixed immediately before application. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 11-246754 [Patent Document 2] JP 2016-145360 A Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, in the polyol composition containing a filler, the filler settles over time during storage. Therefore, it is necessary to stir the polyol composition to disperse the filler before mixing with a polyisocyanate to produce a polyurethane foam. However, when stirring, there are problems from the viewpoint of operability and safety, such as the liquid boiling up and overflowing from the container due to the blowing agent contained in the polyol composition. In particular, the problem of the liquid boiling up (rapid rise in the liquid level) has been prominent during the summer when the temperature is high or when a blowing agent with a low boiling point is used. Furthermore, during on-site construction, odors may be generated during the formation of polyurethane foam, which can cause problems in terms of the working environment.

[0007] Therefore, an object of the present invention is to provide a polyol composition containing a polyol, a foaming agent, and a filler, which can suppress boiling during stirring and can suppress the generation of odor during polyurethane foam formation. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems, and as a result have found that the above problems can be solved by a polyol composition containing a polyol, a foaming agent, a filler, a catalyst, and a phosphate ester compound, and have completed the present invention as described below.

[0009] The present invention relates to the following items [1] to [9]. [1] A spray-in-place polyol composition comprising a polyol, a blowing agent, a filler, a catalyst, and a phosphate ester compound. [2] The polyol composition according to the above [1], wherein the blowing agent contains a hydrofluoroolefin having a boiling point of 40°C or less. [3] The polyol composition according to the above [1] or [2], wherein the phosphate ester compound comprises at least one selected from a condensed phosphate ester and a monophosphate ester. [4] The polyol composition according to any one of the above [1] to [3], wherein the phosphate ester compound contains a phosphate ester not containing an aromatic ring. [5] The polyol composition according to any one of the above [1] to [4], wherein the phosphate ester compound contains a chlorine-free phosphate ester. [6] The polyol composition according to any one of the above [1] to [5], wherein the phosphate ester compound is a mixture of two or more kinds of phosphate esters. [7] The polyol composition according to any one of the above [1] to [6], wherein the phosphate ester compound comprises at least one selected from the group consisting of trimethyl phosphate and triethyl phosphate. [8] A foamable polyurethane composition comprising the polyol composition according to any one of the above [1] to [7] and a polyisocyanate. [9] A polyurethane foam comprising the foamable polyurethane composition according to [8] above. Effect of the Invention

[0010] According to the present invention, it is possible to provide a polyol composition which can suppress the boiling of the liquid during stirring for dispersing a filler and can suppress odors during spray application on site. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described in detail below. [Polyol composition] The polyol composition of the present invention comprises a polyol, a blowing agent, a filler, a catalyst, and a phosphate ester compound.

[0012] <Phosphate ester compounds> The polyol composition of the present invention is characterized by containing a phosphoric acid ester compound. By containing the phosphoric acid ester compound, the solubility of the blowing agent in the polyol is improved, so that the boiling of the liquid during stirring can be easily suppressed. In other words, the phosphoric acid ester compound functions as a compatibilizer between the polyol and the blowing agent. Furthermore, by containing a phosphate ester compound, odors generated during the formation of polyurethane foam can be suppressed, which in turn suppresses unpleasant odors during on-site spraying work, improving the working environment. Furthermore, the incorporation of a phosphate ester compound can improve the flame retardancy of the polyurethane foam.

[0013] Examples of the phosphate ester compound include monophosphate ester and condensed phosphate ester. The monophosphate ester is a phosphate ester having one phosphorus atom in the molecule. Examples of the monophosphate ester include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl)phosphate, halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate, trialkoxy phosphates such as tributoxyethyl phosphate, aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)phosphate, cresyl diphenyl phosphate, and diphenyl(2-ethylhexyl)phosphate, and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate. In addition to the above, phosphite esters may also be used as the phosphate ester compound. Examples of the phosphite include triphenyl phosphite, tricresyl phosphite, trisnonylphenyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite. The monophosphate esters may be used alone or in combination of two or more.

[0014] Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate. The condensed phosphate ester may be used alone or in combination of two or more kinds. Also, the condensed phosphate ester and the monophosphate ester may be used in combination.

[0015] In addition, the phosphoric acid ester compound preferably contains a phosphoric acid ester compound that does not contain chlorine in its structure from the viewpoint of easily suppressing boiling during stirring and reducing the environmental load, etc. Furthermore, in terms of easily suppressing boiling during stirring and suppressing odor during spraying work, etc., it preferably contains a phosphoric acid ester compound that does not contain an aromatic ring in its structure.

[0016] Among the above phosphoric acid ester compounds, trialkyl phosphates are preferred from the viewpoint of easily suppressing boiling during stirring and easily suppressing odor during operation. In particular, at least one phosphoric acid ester compound selected from trimethyl phosphate and triethyl phosphate is preferred. Moreover, as the halogen-containing phosphate ester, tris(β-chloropropyl) phosphate is preferred. When two or more phosphoric acid ester compounds are used, it is preferable to use a trialkyl phosphate in combination with a halogen-containing phosphoric acid ester. Therefore, it is more preferable to use, as the phosphoric acid ester, tris(β-chloropropyl)phosphate in combination with at least one selected from trimethyl phosphate and triethyl phosphate.

[0017] The polyol composition of the present invention may contain a compatibilizer other than the phosphoric acid ester, but from the viewpoint of preventing bad odor, the content of the phosphoric acid ester compound based on the total amount of the compatibilizer is preferably 50 mass% or more, more preferably 80 mass% or more, and even more preferably 100 mass%. Therefore, it is more preferable that the polyol composition does not contain a compatibilizer other than the phosphoric acid ester.

[0018] Examples of compatibilizers other than phosphate esters include ester compounds other than phosphate ester compounds (hereinafter also referred to as non-phosphate ester compounds), and in addition to these, for example, low molecular weight alcohols such as dipropylene glycol, carboxylic acid compounds such as 2-ethylhexanoic acid, imidazole compounds having an imidazole ring, etc. can also be used. The low molecular weight alcohol refers to alcohols having a molecular weight of 200 or less. Examples of non-phosphate ester compounds include chain ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, and ethylene glycol acetate, and cyclic ester compounds such as α-acetolactone, β-propionolactone, γ-butyrolactone, and δ-valerolactone.

[0019] The content of the phosphoric acid ester in the polyol composition of the present invention is not particularly limited, but is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 40 parts by mass or more, and preferably 80 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, based on 100 parts by mass of the polyol. If the content of the phosphoric acid ester is equal to or more than these lower limits, it becomes easier to suppress boiling during stirring, and odor can be suppressed. Also, if it is equal to or less than the upper limits, a decrease in the mechanical strength of the polyurethane foam can be suppressed.

[0020] <Polyol> The polyol composition of the present invention contains a polyol as a raw material for polyurethane foam. The polyol used in the present invention is not particularly limited, but examples thereof include polylactone polyols, polycarbonate polyols, polyester polyols, polyether polyols, and polymer polyols.

[0021] Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of polycarbonate polyols include polyols obtained by dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like.

[0022] Examples of polyester polyols include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, and condensates of hydroxycarboxylic acids and the above-mentioned polyhydric alcohols. Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), and succinic acid, etc. Examples of polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol, etc. Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

[0023] Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one alkylene oxide, such as ethylene oxide, propylene oxide, and tetrahydrofuran, in the presence of at least one low-molecular-weight active hydrogen compound having two or more active hydrogens. Examples of low-molecular-weight active hydrogen compounds having two or more active hydrogens include diols, such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol; triols, such as glycerin and trimethylolpropane; and amines, such as ethylenediamine and butylenediamine.

[0024] Examples of polymer polyols include polymers obtained by graft polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, or methacrylate with an aromatic polyol, an alicyclic polyol, an aliphatic polyol, or a polyester polyol, polybutadiene polyol, or a modified polyol of a polyhydric alcohol, or a hydrogenated product thereof. Examples of aromatic polyols used in the production of polymer polyols include bisphenol A, bisphenol F, phenol novolac, and cresol novolac. Examples of alicyclic polyols used in the production of polymer polyols include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol. Examples of aliphatic polyols used in the production of polymer polyols include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

[0025] Examples of modified polyols of polyhydric alcohols include those obtained by reacting a raw material polyhydric alcohol with an alkylene oxide to modify it. Examples of polyhydric alcohols include trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, and dipentaerythritol; sucrose, glucose, mannose, fructose, methyl glucoside, and derivatives thereof; polyols such as phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene; polyfunctional polyols (e.g., having 2 to 100 functional groups) such as castor oil polyol, (co)polymers of hydroxyalkyl (meth)acrylate, and polyvinyl alcohol; and condensates of phenol and formaldehyde (novolaks).

[0026] The method of modifying the polyhydric alcohol is not particularly limited, but a method of adding an alkylene oxide (hereinafter also referred to as "AO") is preferably used. Examples of the AO include AOs having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter also referred to as "EO"), 1,2-propylene oxide (hereinafter also referred to as "PO"), 1,3-propylene oxide, 1,2-butylene oxide, and 1,4-butylene oxide. Among these, from the viewpoints of properties and reactivity, PO, EO and 1,2-butylene oxide are preferred, and PO and EO are more preferred. When two or more AOs are used (for example, PO and EO), the addition method may be block addition or random addition, or a combination of these may be used.

[0027] The polyol used in the present invention is preferably at least one selected from the group consisting of polyester polyols and polyether polyols. Also, polyols having two hydroxyl groups are preferred. Among them, aromatic polyester polyols, which are polyester polyols having aromatic rings, are preferred from the viewpoint of enhancing flame retardancy. As the aromatic polyester polyol, those obtained by dehydration condensation of polybasic acids having aromatic rings such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid) with dihydric alcohols such as bisphenol A, ethylene glycol, and 1,2-propylene glycol are more preferred.

[0028] The weight average molecular weight of the polyol is preferably more than 300, more preferably 400 or more, even more preferably 430 or more, and is preferably 20,000 or less, more preferably 10,000 or less. The weight average molecular weight is a weight average molecular weight calculated as polystyrene, measured by gel permeation chromatography (GPC).

[0029] The hydroxyl value of the polyol is preferably 20 to 300 mgKOH / g, more preferably 40 to 280 mgKOH / g, further preferably 100 to 250 mgKOH / g, and particularly preferably 120 to 210 mgKOH / g. When the hydroxyl value of the polyol is equal to or less than the upper limit, the polyol composition is easily prevented from boiling during stirring, and the viscosity of the polyol composition is easily reduced, which is preferable from the viewpoint of ease of handling. On the other hand, when the hydroxyl value of the polyol is equal to or more than the lower limit, the crosslink density of the polyurethane foam is increased, thereby increasing the strength. The hydroxyl value of the polyol can be measured in accordance with JIS K 1557-1:2007.

[0030] The content of the polyol in the polyol composition of the present invention is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass. When the content of the polyol is equal to or more than the lower limit, it is preferable because the polyol and the polyisocyanate are easily reacted. On the other hand, when the content of the polyol is equal to or less than the upper limit, it is preferable from the viewpoint of handleability because the viscosity of the polyol composition does not become too high.

[0031] <Foaming agent> The polyol composition of the present invention contains a foaming agent. A polyurethane foam can be obtained by foaming the polyol composition containing the foaming agent and a foamable polyurethane composition containing a polyisocyanate.

[0032] From the viewpoint of improving the foaming property when forming a polyurethane foam, the foaming agent preferably contains a foaming agent having a boiling point of 40° C. or less (hereinafter also referred to as a low-boiling point foaming agent). Furthermore, the boiling point of the low-boiling point foaming agent is more preferably 20° C. or less. The boiling point means the boiling point at 1 atmospheric pressure. In addition, when the polyol composition contains such a low-boiling point blowing agent, boiling is usually likely to occur due to stirring. However, when a phosphoric acid ester is contained as in the present invention, boiling can be suppressed. The content of the low-boiling point blowing agent in the blowing agent is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass, based on the total amount of the blowing agent.

[0033] The blowing agent is not particularly limited, but preferably contains a fluorocarbon-based blowing agent such as a fluorine compound, hydrochlorofluorocarbon, hydrofluorocarbon, hydrofluoroolefin, etc. Among these, the blowing agent is more preferably a hydrofluoroolefin (hereinafter sometimes referred to as "HFO"), and further preferably consists of only hydrofluoroolefin, because the blowing agent has high stability, is less likely to lose catalytic activity, and has a low environmental impact.

[0034] The HFO, which is a suitable blowing agent, is not particularly limited as long as it has a boiling point of 40° C. or less, and examples thereof include fluoroalkenes having about 3 to 6 carbon atoms. Furthermore, the HFO may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having about 3 to 6 carbon atoms.

[0035] Examples of HFOs having a boiling point of 40° C. or lower include trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorodifluoropropene, chlorotrifluoropropenes such as HFO-1233, and chlorotetrafluoropropene. More specifically, 3,3,3-trifluoropropene (HFO-1243zf, boiling point: -18°C), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), boiling point: -19°C), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z), boiling point: 10°C), 2,3,3,3-tetrafluoropropene (HFO-1234yf, boiling point: -29°C), 1,1,3,3-tetrafluoropropene (boiling point: 4°C), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E), boiling point: -10°C), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z), boiling point : -19 ° C), 1,1,3,3,3-pentafluoropropene (HFO-1225zc, boiling point: -21 ° C), 1,1,2,3,3-pentafluoropropene (HFO-1225yc, boiling point: 2 ° C), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd (E), boiling point: 18 ° C), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z), boiling point: 39 ° C), (Z)-1,1,1,4,4,4-hexafluorobutan-2-ene (HFO-1336mzz (z), boiling point: 33 ° C), (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HFO-1224yd (Z), boiling point 14 ° C), and the like. Of these, HFO-1233zd(E), HFO-1336mzz(z) and HFO-1224yd(Z) are preferred, and HFO-1233zd(E) is more preferred. These HFOs may be used alone or in combination of two or more.

[0036] The lower limit of the boiling point of the HFO is not particularly limited, but is preferably 0° C. or higher from the viewpoint of easy handling. Therefore, the boiling point of the HFO according to the present invention is preferably 0 to 40° C. Furthermore, from the viewpoints of suppressing boiling of the polyol composition and achieving good handleability, the boiling point of the HFO is more preferably in the range of 10 to 20° C.

[0037] The content of the fluorocarbon blowing agent in the blowing agent is preferably 80% by mass or more, more preferably 95% by mass or more, and even more preferably 100% by mass, based on the total amount of the blowing agent. The polyol composition of the present invention may contain a blowing agent other than a fluorocarbon blowing agent. Examples of the blowing agent other than a fluorocarbon blowing agent include water, nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Among these, water, oxygen gas, and carbon dioxide gas are preferred from the viewpoint of handling, and water is more preferred from the viewpoint of adjusting the isocyanate index and from the viewpoint of ease of handling. The content of the blowing agent other than the fluorocarbon-based blowing agent in the blowing agent is preferably 20% by mass or less, and more preferably 5% by mass or less, based on the total amount of the blowing agents.

[0038] The amount of the foaming agent is preferably 10 to 80 parts by mass, more preferably 15 to 70 parts by mass, and even more preferably 20 to 60 parts by mass, based on 100 parts by mass of the polyol. When the amount of the foaming agent is equal to or more than the lower limit, foaming is promoted, the foamability is improved, and the density of the resulting polyurethane foam can be reduced. On the other hand, when the amount of the foaming agent is equal to or less than the upper limit, excessive foaming can be suppressed.

[0039] <Filler> The polyol composition of the present invention contains a filler. By containing a filler, it is possible to impart properties to the polyurethane foam according to the type of filler, for example, to improve flame retardancy and mechanical strength, and to color the polyurethane foam. Examples of the filler include a flame retardant and an inorganic filler other than a flame retardant.

[0040] <Flame retardants> The polyol composition of the present invention may contain a flame retardant as a filler. By containing a flame retardant, the flame retardancy of the polyurethane foam formed can be effectively improved. Examples of the flame retardant include solid flame retardants such as red phosphorus-based flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, chlorine-containing flame retardants, antimony-containing flame retardants, boron-containing flame retardants, and metal hydroxides.

[0041] (Red phosphorus flame retardant) The red phosphorus-based flame retardant may be made of red phosphorus alone, may be red phosphorus coated with a resin, a metal hydroxide, a metal oxide, or may be red phosphorus mixed with a resin, a metal hydroxide, a metal oxide, or the like. The resin that coats the red phosphorus or is mixed with the red phosphorus is not particularly limited, but examples thereof include thermosetting resins such as phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. From the viewpoint of flame retardancy, metal hydroxides are preferred as the compound to be coated or mixed. The metal hydroxide to be used may be appropriately selected from those described below.

[0042] (Phosphate-containing flame retardants) Examples of the phosphate-containing flame retardant include phosphates consisting of salts of various phosphoric acids and at least one metal or compound selected from metals in Groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. The phosphoric acid is not particularly limited, but examples thereof include monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid. Examples of metals in Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum. Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, etc. Examples of the aromatic amine include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, 3-(trifluoromethyl)aniline, etc. Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine, etc.

[0043] Specific examples of the phosphate-containing flame retardant include monophosphates, polyphosphates, etc. Examples of the monophosphates include, but are not limited to, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as monohydrogen magnesium phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; and zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite. Here, the polyphosphate is not particularly limited, but examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate. The phosphate-containing flame retardants may be used alone or in combination of two or more of the above-mentioned compounds.

[0044] (Bromine-containing flame retardants) The bromine-containing flame retardant is not particularly limited as long as it contains bromine in its molecular structure and is a solid at room temperature and normal pressure, and examples thereof include brominated aromatic ring-containing aromatic compounds, etc. Examples of brominated aromatic ring-containing aromatic compounds include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0045] In addition, the brominated aromatic ring-containing aromatic compound may be a bromine compound polymer.Specific examples include brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A as a raw material, copolymers of this polycarbonate oligomer and bisphenol A, and diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin.Furthermore, examples include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, poly(brominated benzyl acrylate), brominated phenol condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, brominated (polystyrene), poly(brominated styrene), brominated polystyrene such as crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly(-methylstyrene), and the like. In addition, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may be used. These bromine-containing flame retardants may be used alone or in combination of two or more.

[0046] (Chlorine-containing flame retardants) Chlorine-containing flame retardants include those commonly used in flame-retardant resin compositions, such as polychlorinated naphthalenes, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene sold under the trade name "Dechlorane Plus."

[0047] (Antimony-containing flame retardants) Examples of antimony-containing flame retardants include antimony oxide, antimony salts, and pyroantimony salts. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimony salts include sodium antimonate and potassium antimonate. Examples of pyroantimonate include sodium pyroantimonate and potassium pyroantimonate. The antimony-containing flame retardants may be used alone or in combination of two or more.

[0048] (Boron-containing flame retardants) Examples of boron-containing flame retardants include borax, boron oxide, boric acid, borates, etc. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide. Examples of borates include borates of alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the periodic table, and ammonium. Specific examples include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate, alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate. The boron-containing flame retardants may be used alone or in combination of two or more kinds.

[0049] (metal hydroxide) Examples of metal hydroxides include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, etc. The metal hydroxides may be used alone or in combination of two or more kinds.

[0050] <Inorganic fillers> The polyol composition of the present invention may contain an inorganic filler other than the above-mentioned flame retardants as a filler. Examples of inorganic fillers include needle-shaped fillers such as potassium titanate whiskers, aluminum borate whiskers, magnesium-containing whiskers, silicon-containing whiskers, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fibers, carbon fibers, graphite fibers, metal fibers, slag fibers, gypsum fibers, silica fibers, alumina fibers, silica alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, and stainless steel fibers; carbon black, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferric oxide, and the like. Lights, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, seviolite, imogolite, sericite, glass beads, silica balloon, aluminum nitride, boron nitride, silicon nitride, graphite, carbon balloon, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash, etc. Inorganic fillers are solid components that become solid at normal temperature and pressure. Among these, needle-like fillers such as wollastonite and other silicon-based needle-like fillers, carbon black, calcium carbonate, and the like are preferable. The inorganic filler may be used alone or in combination of two or more kinds.

[0051] The content of the filler in the polyol composition is not particularly limited, but is preferably 1 to 150 parts by mass, more preferably 10 to 120 parts by mass, and further preferably 30 to 80 parts by mass, relative to 100 parts by mass of the polyol.

[0052] <Catalyst> The polyol composition of the present invention preferably contains a catalyst from the viewpoint of promoting the reaction between the polyol and the polyisocyanate, improving the flame retardancy of the polyurethane foam to be formed, etc. The catalyst contains a trimerization catalyst, a urethanization catalyst, etc., and it is also preferable to contain both a trimerization catalyst and a urethanization catalyst.

[0053] (trimerization catalyst) The trimerization catalyst is a catalyst that reacts the isocyanate group contained in the polyisocyanate described below to trimerize it and promote the formation of an isocyanurate ring. As the trimerization catalyst, nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate, and potassium octylate, tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt, and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, and triethylmonomethylammonium salt can be used. As the ammonium salt, ammonium salts of carboxylic acids such as 2,2-dimethylpropanoic acid can be mentioned, and more specifically, quaternary ammonium salts of carboxylic acids can be mentioned. These may be used alone or in combination of two or more. Of these, one or more selected from alkali metal carboxylates and quaternary ammonium carboxylates are preferred, and an embodiment in which both of these are used is also preferred.

[0054] The amount of the trimerization catalyst is preferably 0.1 to 25 parts by mass, more preferably 0.3 to 20 parts by mass, and even more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the polyol. When the amount of the trimerization catalyst is equal to or greater than these lower limits, the trimerization of the polyisocyanate is more likely to occur, and the flame retardancy of the resulting polyurethane foam is improved. On the other hand, when the amount of the trimerization catalyst is equal to or less than the upper limit, the reaction is easier to control.

[0055] (Urethanization catalyst) The urethanization catalyst is a catalyst that promotes the reaction between a polyol and a polyisocyanate. Examples of the urethanization catalyst include amine-based catalysts such as imidazole compounds and piperazine compounds, and metal-based catalysts. The imidazole compound may be a tertiary amine in which the secondary amine at the 1-position of the imidazole ring is substituted with an alkyl group, an alkenyl group, or the like. Specific examples include N-methylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Also usable are imidazole compounds in which the secondary amine in the imidazole ring is substituted with a cyanoethyl group. Furthermore, examples of the piperazine compound include tertiary amines such as N-methyl-N'N'-dimethylaminoethylpiperazine and trimethylaminoethylpiperazine. In addition to imidazole compounds and piperazine compounds, examples of the amine catalyst include various tertiary amines such as pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinebis(2-dimethylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, and tripropylamine.

[0056] Examples of the metal catalyst include metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc., and preferably organic acid metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. More preferred are dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatate, bismuth trioctate, bismuth tris(2-ethylhexanoate), tin dioctylate, lead dioctylate, etc., and among these, organic acid bismuth salts are even more preferred. The urethanization catalyst may be used alone or in combination of two or more. Among the above, it is preferable to use one or more selected from imidazole compounds and organic acid bismuth salts, and an embodiment in which both of these are used is also preferable.

[0057] The amount of the urethane catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the polyol. When the amount of the resinification catalyst is equal to or greater than these lower limits, urethane bonds are easily formed and the reaction proceeds quickly. On the other hand, when the amount is equal to or less than these upper limits, the reaction rate is easily controlled.

[0058] The total amount of the catalyst in the polyol composition is not particularly limited, but is preferably 0.2 to 30 parts by mass, more preferably 0.6 to 20 parts by mass, and even more preferably 1 to 10 parts by mass. If it is equal to or more than these lower limits, the formation of urethane bonds and trimerization proceed appropriately, and flame retardancy tends to be good. If it is equal to or less than these upper limits, it becomes easy to control the urethane formation and trimerization reactions.

[0059] <Foam stabilizer> The polyol composition of the present invention may contain a foam stabilizer. The foam stabilizer improves the foamability of a foamable polyurethane composition containing the polyol composition and a polyisocyanate. Examples of the foam stabilizer include surfactants such as polyoxyalkylene-based foam stabilizers such as polyoxyalkylene alkyl ethers, and silicone-based foam stabilizers such as organopolysiloxanes. These foam stabilizers may be used alone or in combination of two or more. The amount of the foam stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 5 parts by mass, based on 100 parts by mass of the polyol compound. When the amount of the foam stabilizer is equal to or greater than these lower limits, the polyurethane composition is easily foamed, and a homogeneous polyurethane foam is easily obtained. When the amount of the foam stabilizer is equal to or less than these upper limits, the balance between the production cost and the obtained effect is good.

[0060] <Other ingredients> The polyol composition may contain, as necessary, one or more selected from phenol-based, amine-based, sulfur-based and other antioxidants, heat stabilizers, metal inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, and the like, within the scope of the object of the present invention.

[0061] <Method of producing polyol composition> The method for producing the polyol composition of the present invention is not particularly limited, and the composition can be produced, for example, by stirring each component at about 20 to 40° C. for about 30 seconds to 20 minutes using a homodisper or the like.

[0062] [Foamable polyurethane composition and polyurethane foam] The foamable polyurethane composition of the present invention contains the polyol composition of the present invention and a polyisocyanate, and is obtained by mixing them. The polyurethane foam of the present invention is made of the foamable polyurethane composition, and specifically, is a reaction product obtained by reacting and foaming the foamable polyurethane composition.

[0063] <Polyisocyanate> Examples of the polyisocyanate include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

[0064] Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0065] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0066] Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred. The polyisocyanates may be used alone or in combination of two or more. Furthermore, the polyisocyanate may be appropriately mixed with known additives that are mixed with polyisocyanates before being mixed with the polyol composition.

[0067] <Isocyanate Index> The isocyanate index of the foamable polyurethane composition of the present invention is not particularly limited, but is preferably 150 or more. If the isocyanate index is equal to or more than the lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, and isocyanurate bonds due to the trimer of polyisocyanate are easily formed, resulting in improved flame retardancy of the polyurethane foam. Furthermore, if the isocyanate index is equal to or more than the lower limit, combined with the use of the various catalysts described above, it is easy to produce a polyurethane foam having sufficient isocyanurate bonds, that is, a polyurethane foam having both high levels of flame retardancy and heat insulation. From these viewpoints, the isocyanate index is preferably 150 or more, more preferably 200 or more, and even more preferably 250 or more. The isocyanate index is preferably not more than 800, more preferably not more than 600, and even more preferably not more than 400. When the isocyanate index is not more than the upper limit, the resulting polyurethane foam has a good balance between flame retardancy and production costs.

[0068] The isocyanate index can be calculated by the following method. Isocyanate Index = equivalents of polyisocyanate ÷ (equivalents of polyol + equivalents of water) × 100 Here, each equivalent number can be calculated as follows: Equivalent number of polyisocyanate = Amount of polyisocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (mol) × 100 Equivalent weight of polyol = OHV × amount of polyol used (g) ÷ molecular weight of KOH (mmol) OHV is the hydroxyl value of the polyol (mg KOH / g). Equivalents of water = amount of water used (g) / molecular weight of water (mol) × number of OH groups in water In the above formulas, the molecular weight of NCO is 42 (mol), the molecular weight of KOH is 56,100 (mmol), the molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

[0069] The polyol composition of the present invention is used for on-site spraying, which may involve mixing the polyol composition with a polyisocyanate at the work site and spraying the mixture onto a surface to be sprayed to form a polyurethane foam on the surface to be sprayed. More specifically, the polyol composition and the isocyanate filled in a container or the like brought to the work site are sent to a foaming machine, the polyol composition and the isocyanate are mixed in the foaming machine, and the mixture (foamable polyurethane composition) is sprayed onto the surface to be sprayed. The spraying may be performed using a spray gun or the like attached to the foaming machine. The surface to be sprayed is not particularly limited, but is preferably a building such as a wall, ceiling, roof, floor, etc. The polyol composition filled in a container or the like may be stirred at the work site before being mixed with the isocyanate.

[0070] In the present invention, since the boiling of the liquid during stirring of the polyol composition can be suppressed, the polyol composition can be prevented from overflowing from a container during stirring even when the outside air temperature is relatively high in summer, etc. Furthermore, since a phosphoric acid ester compound is used as a compatibilizer, the generation of a foul odor can be prevented even when the polyol composition is stirred at a construction site, delivered, and further mixed with a polyisocyanate. EXAMPLES

[0071] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these.

[0072] [Boiling height evaluation] Each Example 、Reference example The polyol composition prepared in the comparative example (total 300 g) was mixed and stirred, and 30 g was put into a 110 mL screw tube (manufactured by Maruemu Co., Ltd., product name: No. 8). After wrapping a sealing tape (made of polytetrafluoroethylene) around the screw, a stirrer (diameter 14 mm) was put in and the lid was closed. Then, the screw tube into which the polyol composition was introduced was put into a water bath at 29 ° C. for 30 minutes or more to keep the temperature constant, and then the stopper was opened and the stirrer was stirred at 1,500 rpm using a magnetic stirrer. The height of the highest point after stirring was measured, and the difference from the height before stirring was calculated and evaluated as the boiling height. The height of the highest point after stirring means the height from the bottom of the screw tube to the highest point of the liquid (polyol composition), and the height before stirring means the height from the bottom of the screw tube to the liquid (polyol composition) surface. (judgement) ○ Boiling height is less than 15mm × Boiling height is 15mm or more

[0073] [Odor evaluation] Each Example 、Reference example A polyol composition (total 300 g) was prepared by mixing and stirring the components described in the Comparative Example and Comparative Example, and the polyol composition immediately after preparation was sniffed for 5 seconds from a height of 15 cm, and the unpleasant odor felt was evaluated according to the 6-level odor intensity rating method. The evaluation criteria and judgment were as follows. (Evaluation Criteria) 0. Odorless 1. The odor that can just be detected (detection threshold) 2. Weak odors that can be identified (cognitive threshold) 3. Easily detectable odors 4. Strong odor 5. Strong odor (judgement) ○ 3 or less × 4 or more

[0074] Example 1 ~2,4,6 ~18, Reference examples 3, 5, Comparative Examples 1 to 3 Each Example 、Reference example The polyols, fillers, foaming agents, phosphate esters, urethane catalysts, and foam stabilizers used in the comparative examples are shown in Table 1. In the comparative examples, compatibilizers used in place of the phosphate esters are listed as other compatibilizers. The polyol, filler, foaming agent, phosphate ester (other compatibilizer), urethanization catalyst, and foam stabilizer were mixed in the amounts shown in Table 2 to obtain a polyol composition, which was then evaluated for boiling height and odor as described above. The results are shown in Table 2.

[0075] [Table 1]

[0076] [Table 2]

[0077] As is clear from the results of the above examples, the polyol composition of the present invention, which contains a polyol, a foaming agent, a filler, a catalyst, and a phosphoric acid ester, has a low boiling height when stirred, and is excellent in operability and safety. In addition, the odor evaluation showed a low odor intensity and good results. In contrast, it was found that a polyol composition containing neither a phosphoric ester nor a compatibilizer had a high boiling point during stirring, and was inferior in operability and safety, as shown in Comparative Example 1. Moreover, it was found that a polyol composition using a compatibilizer other than a phosphoric ester had a strong odor and was unsuitable for use as a field spray, as shown in Comparative Examples 2 and 3.

Claims

1. The composition includes a polyol, a foaming agent, a filler, a catalyst, and a phosphoric acid ester compound, The blowing agent contains a hydrofluoroolefin having a boiling point of 40° C. or less, The polyol composition for field spraying, wherein the phosphoric acid ester compound comprises at least one selected from the group consisting of triethyl phosphate, trimethyl phosphate, tricresyl phosphate, and a halogen-containing condensed phosphoric acid ester.

2. The field spray polyol composition of claim 1, wherein the polyol comprises an aromatic polyester polyol.

3. A polyol composition for field spraying as described in claim 1 or 2, further comprising a foam stabilizer.

4. A foamable polyurethane composition comprising the polyol composition according to any one of claims 1 to 3 and a polyisocyanate.

5. A polyurethane foam formed from the foamable polyurethane composition according to claim 4.

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