Polyol composition, foamable polyurethane composition and polyurethane foam

Abstract

To provide a polyol composition that can suppress boiling up of liquid at stirring when dispersing a filler.SOLUTION: A polyol composition has a polyol, a filler, a foaming agent, and a compatibilizer, and Ra2 represented by the formula (1) is 200 J / cm3 or less. The formula (1) is represented by Ra2=4×(dD1-dD2)2+(dP1-dP2)2+(dH1-dH2)2. In the formula (1), dD1 is a dispersion term of the foaming agent in a Hansen solubility parameter (HSP), dD2 is a dispersion term of the compatibilizer in the HSP, dP1 is a polarization term of the foaming agent in the HSP, dP2 is a polarization term of the compatibilizer in the HSP, dH1 is a hydrogen bond term of the foaming agent in the HSP, and dH2 is a hydrogen bond term of the compatibilizer in the HSP.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 blowing agent, and may further contain fillers such as a flame retardant and an inorganic filler, as needed. These fillers are added for the purposes 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 specific amount of a flame retardant, and describes that the polyol composition has excellent flame retardancy, low smoke generation, and the like. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 11-246754 Summary of the Invention [Problem to be solved by the invention]

[0005] As described above, in polyol compositions containing a filler, the filler settles over time during storage. Therefore, the polyol composition must be stirred to disperse the filler before mixing with a polyisocyanate to produce a polyurethane foam. However, during stirring, the blowing agent contained in the polyol composition can cause the liquid to boil and overflow from the container, creating problems in terms of operability and safety. This problem of liquid boiling (rapid rise in the liquid level) is particularly pronounced during hot summer months or when a blowing agent with a low boiling point is used.

[0006] Therefore, an object of the present invention is to provide a polyol composition containing a polyol, a filler, and a foaming agent, which can suppress boiling during stirring. [Means for solving the problem]

[0007] As a result of extensive research into solving the above problems, the present inventors have discovered a polyol composition comprising a polyol, a filler, a foaming agent, and a compatibilizer, wherein the polyol composition is a polyol having a viscosity of 1000 psig, and the viscosity of the polyol is ... 2 The present inventors have found that the above-mentioned problems can be solved by a polyol composition in which the value of β-glutamic acid is equal to or less than a certain value, and have completed the present invention as described below.

[0008] The present invention is summarized as follows [1] to [7]. [1] A composition comprising a polyol, a filler, a foaming agent, and a compatibilizer, and having a formula (1) represented by Ra 2 is 200J / cm 3 A polyol composition which is: <Formula (1)> Ra 2 =4×(dD1-dD2) 2 +(dP1-dP2) 2 +(dH1-dH2) 2 In equation (1), dD, dP, and dH represent the dispersion term, polarization term, and hydrogen bond term in the Hansen solubility parameter (HSP), respectively, as follows: dD1[(J / cm 3 ) 1 / 2]: Dispersion term in HSP of foaming agent dD2[(J / cm 3 ) 1 / 2 ]: Dispersion term in the HSP of the compatibilizer dP1[(J / cm 3 ) 1 / 2 ]: Polarization term in HSP of foaming agent dP2[(J / cm 3 ) 1 / 2 ]: Polarization term in the HSP of the compatibilizer dH1[(J / cm 3 ) 1 / 2 ]: Hydrogen bond term in HSP of foaming agents dH2[(J / cm 3 ) 1 / 2 ]: Hydrogen bond term in the HSP of the compatibilizer [2] The polyol composition according to [1] above, wherein the blowing agent comprises a blowing agent having a boiling point of 40°C or less. [3] The polyol composition according to the above [1] or [2], wherein the blowing agent comprises a fluorocarbon-based blowing agent. [4] The polyol composition according to any one of the above [1] to [3], wherein the compatibilizer comprises a phosphate ester compound. [5] The polyol composition according to [4] above, wherein the phosphate ester compound does not contain chlorine. [6] A foamable polyurethane composition containing the polyol composition according to any one of [1] to [5] above and a polyisocyanate. [7] A polyurethane foam comprising the foamable polyurethane composition according to [6] above. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a polyol composition that can suppress boiling of the liquid during stirring when dispersing a filler. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. [Polyol composition] The polyol composition of the present invention contains a polyol, a filler, a foaming agent, and a compatibilizer, and has a Ra represented by formula (1) 2 is 200J / cm 3 The following is the result. <Formula (1)> Ra 2 =4×(dD1-dD2) 2 +(dP1-dP2) 2 +(dH1-dH2) 2 In equation (1), dD, dP, and dH represent the dispersion term, polarization term, and hydrogen bond term in the Hansen solubility parameter (HSP), respectively, as follows: dD1[(J / cm 3 ) 1 / 2 ]: Dispersion term in HSP of foaming agent dD2[(J / cm 3 ) 1 / 2 ]: Dispersion term in the HSP of the compatibilizer dP1[(J / cm 3 ) 1 / 2 ]: Polarization term in HSP of foaming agent dP2[(J / cm 3 ) 1 / 2 ]: Polarization term in the HSP of the compatibilizer dH1[(J / cm 3 ) 1 / 2 ]: Hydrogen bond term in HSP of foaming agents dH2[(J / cm 3 ) 1 / 2 ]: Hydrogen bond term in the HSP of the compatibilizer

[0011] (Compatibilizer) The polyol composition of the present invention contains a compatibilizer. The compatibilizer has a Ra represented by the above formula (1) calculated between the compatibilizer and a blowing agent described later. 2 is 200J / cm 3 The result is as follows: Ra 2 is 200J / cm 3 If the temperature exceeds this range, it becomes difficult to effectively prevent the liquid from boiling up during stirring to disperse the filler. From the viewpoint of effectively suppressing boiling of the liquid during stirring, Ra 2is preferably 150 or less, more preferably 100 or less.

[0012] In the above formula (1), dD1 represents the dispersion term in the Hansen solubility parameter (HSP) of the blowing agent, dD2 represents the dispersion term in the HSP of the compatibilizer, dP1 represents the polarization term in the HSP of the blowing agent, dP2 represents the polarization term in the HSP of the compatibilizer, dH1 represents the hydrogen bonding term in the HSP of the blowing agent, and dH2 represents the hydrogen bonding term in the HSP of the compatibilizer. These parameters can be calculated based on the estimation method using the neural network method called Y-MB in the Hansen Solubility Parameter software (HSPiP 5th Edition (ver.5.0.09)). The compatibilizer may be used alone or in combination with two or more components. When two or more components are used, dD2, dP2, and dH2 in formula (1) can be calculated by averaging the volume fractions of the dispersion term, polarization term, and hydrogen bonding term in the HSP of each compatibilizer and the blend amount of each compatibilizer. Similarly, when two or more blowing agents, which will be described later, are used, dD1, dP1, and dH1 in formula (1) can be calculated by averaging the volume fractions of the dispersion term, polarization term, and hydrogen bonding value in the HSP of each blowing agent and the blend amount of each blowing agent.

[0013] The type of the compatibilizer in the present invention is the above-mentioned Ra 2 Examples of the compound include phosphate ester compounds and ester compounds other than phosphate ester compounds (hereinafter also referred to as non-phosphate ester compounds), and other compounds that can be used include low-molecular-weight alcohols such as dipropylene glycol, carboxylic acid compounds such as 2-ethylhexanoic acid, and imidazole compounds having an imidazole ring. The low-molecular-weight alcohol refers to an alcohol having a molecular weight of 200 or less. Among these, from the viewpoint of easily suppressing boiling of the liquid during stirring, the compatibilizer preferably contains at least one of a phosphate ester compound and a non-phosphate ester compound. Furthermore, from the viewpoint of improving the flame retardancy of the polyurethane foam, which is the final product, the compatibilizer more preferably contains a phosphate ester compound.

[0014] Examples of phosphate ester compounds include monophosphate esters and condensed phosphate esters. Monophosphate esters are phosphate esters having one phosphorus atom in the molecule. Examples of monophosphate esters 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, phosphites and the like may also be used as the phosphate ester compounds. Examples of the phosphite ester include triphenyl phosphite, tricresyl phosphite, trisnonylphenyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite.

[0015] 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.

[0016] Among the above-mentioned phosphate ester compounds, trialkyl phosphate is preferred from the viewpoint of easily suppressing boiling during stirring, and at least one phosphate ester compound selected from trimethyl phosphate and triethyl phosphate is particularly preferred. Furthermore, the phosphate ester compound is preferably a phosphate ester compound that does not contain chlorine in its structure, from the viewpoint of easily suppressing boiling during stirring and reducing the environmental load.

[0017] When the compatibilizer contains a phosphate ester compound, the content of the phosphate ester compound relative to the total amount of the compatibilizer is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass.

[0018] 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, with ethyl acetate, ethylene glycol acetate, and γ-butyrolactone being preferred.

[0019] When the compatibilizer contains a non-phosphate ester compound, the content of the non-phosphate ester compound relative to the total amount of the compatibilizer is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass.

[0020] The content of the compatibilizer in the present invention is not particularly limited, but is preferably at least 1 part by mass, more preferably at least 3 parts by mass, and even more preferably at least 5 parts by mass, per 100 parts by mass of polyol, and is preferably not more than 30 parts by mass, more preferably not more than 20 parts by mass, and even more preferably not more than 15 parts by mass. If the content of the compatibilizer is at least these lower limits, boiling during stirring can be easily suppressed, and if it is at most these upper limits, a decrease in the mechanical strength of the polyurethane foam can be suppressed.

[0021] <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.

[0022] Examples of polylactone polyols 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.

[0023] 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. 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. Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

[0024] Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one alkylene oxide, such as ethylene oxide, propylene oxide, or 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.

[0025] 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; and modified polyols of polyhydric alcohols or hydrogenated products 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.

[0026] Examples of modified polyols of polyhydric alcohols include those obtained by modifying raw material polyhydric alcohols by reacting them with alkylene oxides. 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 (novolak).

[0027] Although the method for modifying the polyhydric alcohol is not particularly limited, a method of adding alkylene oxide (hereinafter also referred to as "AO") is preferably used. Examples of 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, PO, EO, and 1,2-butylene oxide are preferred from the viewpoints of properties and reactivity, 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, random addition, or a combination of these.

[0028] The polyol used in the present invention is preferably at least one selected from the group consisting of polyester polyols and polyether polyols. Furthermore, polyols having two hydroxyl groups are preferred. Among these, aromatic polyester polyols, which are polyester polyols having aromatic rings, are preferred from the viewpoint of enhancing flame retardancy. More preferred aromatic polyester polyols are 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.

[0029] 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 measured by gel permeation chromatography (GPC) and converted into polystyrene.

[0030] The hydroxyl value of the polyol is preferably 20 to 300 mgKOH / g, more preferably 40 to 280 mgKOH / g, even more preferably 100 to 250 mgKOH / g, and even more preferably 120 to 210 mgKOH / g. When the hydroxyl value of the polyol is equal to or less than the upper limit, boiling of the polyol composition during stirring is easily suppressed, and the viscosity of the polyol composition is easily reduced, which is preferable from the viewpoint of handleability, etc. 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 increases, thereby increasing its strength. The hydroxyl value of the polyol can be measured in accordance with JIS K 1557-1:2007.

[0031] The polyol content in the polyol composition of the present invention is preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and even more preferably 30 to 70% by mass. A polyol content of at least the lower limit is preferred because it facilitates the reaction between the polyol and the polyisocyanate. On the other hand, a polyol content of at most the upper limit is preferred from the viewpoint of ease of handling because the viscosity of the polyol composition does not become too high.

[0032] <Foaming agent> The polyol composition of the present invention contains a blowing agent. A polyurethane foam can be obtained by foaming the polyol composition containing the blowing agent and a foamable polyurethane composition containing a polyisocyanate.

[0033] From the viewpoint of achieving good foaming properties when forming a polyurethane foam, the blowing agent preferably contains a blowing agent having a boiling point of 40° C. or less (hereinafter also referred to as a low-boiling-point blowing agent). Furthermore, the boiling point of the low-boiling-point blowing agent is more preferably 20° C. or less. The boiling point means the boiling point at 1 atmosphere. When the polyol composition contains such a low-boiling-point blowing agent, boiling is usually likely to occur due to stirring. However, when the polyol composition contains a specific compatibilizer 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.

[0034] 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 more preferably contains a hydrofluoroolefin, and even more preferably consists of only a hydrofluoroolefin, because the blowing agent has high stability, is less likely to lose catalytic activity, and further has a low environmental impact.

[0035] Examples of hydrofluoroolefins include fluoroalkenes having about 3 to 6 carbon atoms. The hydrofluoroolefins may be hydrochlorofluoroolefins having chlorine atoms, and therefore may be chlorofluoroalkenes having about 3 to 6 carbon atoms. More specific examples include trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorotrifluoropropenes such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetrafluoropropene. More specific examples include 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3,3,3-hexafluorobut-2-ene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yez), 1-chloro-3,3,3-trifluoropropene (HFO-1233zd), and 1,1,1,4,4,4-hexafluorobut-2-ene. Of these, HFO-1233zd is preferred. These hydrofluoroolefins may be used alone or in combination of two or more.

[0036] 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-based blowing agent. Examples of blowing agents other than a fluorocarbon-based 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 ease of handling, and water is more preferred from the viewpoint of adjusting the isocyanate index and ease of handling. The content of blowing agents other than fluorocarbon-based blowing agents in the blowing agent is preferably 20% by mass or less, more preferably 5% by mass or less, based on the total amount of blowing agents.

[0037] The amount of the blowing 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, per 100 parts by mass of the polyol. When the amount of the blowing agent is equal to or greater than the lower limit, foaming is promoted, resulting in good foamability and a reduced density of the resulting polyurethane foam. On the other hand, when the amount of the blowing agent is equal to or less than the upper limit, excessive foaming can be prevented.

[0038] <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 depending on the type of filler, such as improving flame retardancy and mechanical strength, or coloring. Examples of fillers include flame retardants and inorganic fillers other than flame retardants.

[0039] <Flame retardant> The polyol composition of the present invention may contain a flame retardant. By containing a flame retardant, the flame retardancy of the resulting polyurethane foam 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.

[0040] (Red phosphorus flame retardant) The red phosphorus-based flame retardant may consist of red phosphorus alone, or may be red phosphorus coated with a resin, metal hydroxide, metal oxide, or the like, or may be red phosphorus mixed with a resin, metal hydroxide, 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 phenolic 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.

[0041] (phosphate-containing flame retardants) Examples of phosphate-containing flame retardants include phosphates formed from salts of various phosphoric acids with at least one metal or compound selected from metals of 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-toliidine, 2,4,6-trimethylaniline, anisidine, 3-(trifluoromethyl)aniline, etc. Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine, etc.

[0042] Specific examples of phosphate-containing flame retardants include monophosphates, polyphosphates, etc. The monophosphates are not particularly limited, and examples thereof include 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 magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; 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 singly or in combination of two or more of the above.

[0043] (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 compound that is solid at room temperature and normal pressure, and examples thereof include brominated aromatic ring-containing aromatic compounds. Examples of the brominated aromatic ring-containing aromatic compound include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0044] The brominated aromatic ring-containing aromatic compound may also be a bromine compound polymer. Specific examples include brominated polycarbonates such as polycarbonate oligomers produced using brominated bisphenol A as a raw material, copolymers of the polycarbonate oligomers with bisphenol A, and diepoxy compounds produced by reacting brominated bisphenol A with epichlorohydrin. Further examples include brominated epoxy compounds such as monoepoxy compounds obtained by reacting brominated phenols with epichlorohydrin, poly(brominated benzyl acrylate), brominated phenol condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, and crosslinked or non-crosslinked brominated poly(methylstyrene). Furthermore, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may also be used. These bromine-containing flame retardants may be used alone or in combination of two or more.

[0045] (Chlorine-containing flame retardants) Chlorine-containing flame retardants include those commonly used in flame-retardant resin compositions, such as polychlorinated naphthalene, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene, which is sold under the trade name "Dechlorane Plus."

[0046] (Antimony-containing flame retardant) 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 salts include sodium pyroantimonate and potassium pyroantimonate. The antimony-containing flame retardants may be used alone or in combination of two or more.

[0047] (Boron-containing flame retardants) Examples of boron-containing flame retardants include borax, boron oxide, boric acid, borate salts, 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.

[0048] (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.

[0049] <Inorganic fillers> The polyol composition of the present invention may contain inorganic fillers other than the above-mentioned flame retardants, as long as the effects of the present invention are not impaired. Examples of inorganic fillers include alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, seviolite, imogolite, sericite, glass fiber, glass beads, silica balloon, aluminum nitride, boron nitride, silicon nitride, graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, etc. Inorganic fillers are solid components that become solid at room temperature and normal pressure. The inorganic fillers may be used alone or in combination of two or more.

[0050] 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 even more preferably 30 to 80 parts by mass, relative to 100 parts by mass of the polyol.

[0051] <Catalyst> The polyol composition of the present invention preferably contains a catalyst from the viewpoint of accelerating 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 more preferably contains both a trimerization catalyst and a urethanization catalyst.

[0052] (trimerization catalyst) The trimerization catalyst promotes the trimerization of isocyanate groups contained in the polyisocyanate (described below) by reacting them with each other, thereby promoting the formation of isocyanurate rings. Examples of trimerization catalysts that can be used include nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal carboxylic acid salts such as potassium acetate, potassium 2-ethylhexanoate, and potassium octoate; 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. Examples of ammonium salts include ammonium salts of carboxylic acids such as 2,2-dimethylpropanoic acid, and more specifically, quaternary ammonium carboxylic acid salts. These may be used alone or in combination of two or more. Among 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.

[0053] 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, per 100 parts by mass of the polyol. When the amount of the trimerization catalyst is equal to or greater than these lower limits, trimerization of the polyisocyanate occurs more easily, improving the flame retardancy of the resulting polyurethane foam. On the other hand, when the amount of the trimerization catalyst is equal to or less than the upper limit, the reaction can be more easily controlled.

[0054] (Urethanization catalyst) The urethanization catalyst is a catalyst that promotes the reaction between polyol and polyisocyanate. Examples of the urethanization catalyst include amine-based catalysts such as imidazole compounds and piperazine compounds, and metal-based catalysts. Examples of imidazole compounds include tertiary amines 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 suitable 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. Furthermore, examples of the amine catalyst include, in addition to imidazole compounds and piperazine compounds, 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.

[0055] Examples of metal catalysts 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.

[0056] The amount of the urethanization 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, per 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.

[0057] The total amount of 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. When the amount is equal to or greater than these lower limits, the formation of urethane bonds and trimerization proceed appropriately, and flame retardancy tends to be good. When the amount is equal to or less than these upper limits, control of the urethane formation and trimerization reactions becomes easier.

[0058] <Foam stabilizer> The polyol composition of the present invention may contain a foam stabilizer, which 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, per 100 parts by mass of the polyol compound. When the amount of the foam stabilizer is at least these lower limits, the polyurethane composition is easily foamed, making it easier to obtain a homogeneous polyurethane foam. When the amount of the foam stabilizer is at most these upper limits, a good balance between production costs and the obtained effects is achieved.

[0059] <Other ingredients> The polyol composition may contain 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, as needed, within the scope of the object of the present invention.

[0060] <Method of producing polyol composition> There are no particular limitations on the method for producing the polyol composition of the present invention, and it can be produced, for example, by stirring each component at about 20 to 40° C. for about 30 seconds to 20 minutes using a homodisper or the like.

[0061] [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.

[0062] <Polyisocyanate> Examples of polyisocyanates 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.

[0063] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0064] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0065] Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred. One type of polyisocyanate may be used alone, or two or more types may be used in combination. Furthermore, known additives that are typically added to polyisocyanates may be appropriately added to the polyisocyanate before it is mixed with the polyol composition.

[0066] <Isocyanate Index> The isocyanate index of the foamable polyurethane composition of the present invention is not particularly limited, but is preferably 150 or higher. If the isocyanate index is equal to or higher than the lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, facilitating the formation of isocyanurate bonds due to the trimerization of the polyisocyanate, resulting in improved flame retardancy of the polyurethane foam. Furthermore, if the isocyanate index is equal to or higher than the lower limit, combined with the use of the various catalysts described above, it becomes easier to produce a polyurethane foam having sufficient isocyanurate bonds, i.e., a polyurethane foam that combines high levels of flame retardancy and thermal insulation. From these perspectives, the isocyanate index is more preferably 150 or higher, even more preferably 200 or higher, and even more preferably 250 or higher. 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 will have a good balance between flame retardancy and production costs.

[0067] The isocyanate index can be calculated by the following method. Isocyanate Index = number of equivalents of polyisocyanate ÷ (number of equivalents of polyol + number of equivalents of water) × 100 Here, each equivalent number can be calculated as follows: Polyisocyanate equivalent number = 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 (moles) × Number of OH groups in water In the above formulas, the molecular weight of NCO is 42 (mol), the molecular weight of KOH is 56,100 (mmol), the molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

[0068] <Method of manufacturing polyurethane foam> Although there are no particular limitations on the method for producing the polyurethane foam, it is preferable to foam and react a foamable polyurethane composition obtained by mixing a polyisocyanate and a polyol composition. Specifically, it is preferable to mix the polyisocyanate and the polyol composition by collision mixing using a spray gun or the like, and then spray the mixture. In the present invention, the polyurethane foam may be obtained by mixing the polyisocyanate and the polyol composition, pouring the mixture into a container such as a mold or a frame, and curing the mixture.

[0069] <Applications of polyurethane foam> The polyurethane foam of the present invention is not particularly limited in its application, but can be suitably used in buildings such as walls, ceilings, roofs, and floors of buildings. It can also be suitably used as a member for filling any openings that occur in buildings, including joints and holes that occur between structural members of buildings. [Example]

[0070] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0071] [Boiling height evaluation] The polyol compositions (300 g in total) prepared in each example and comparative example were mixed and stirred, and 30 g was placed in a 110 mL screw tube (Maruem Co., Ltd., product name: No. 8). Sealing tape (made of polytetrafluoroethylene) was wrapped around the screw cap, and a stirrer (14 mm in diameter) was placed in and the lid was closed. The screw tube containing the polyol composition was then placed in a 29 ° C. water bath for 30 minutes or more to maintain a constant temperature, after which the cap 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 10mm or less ○ Boiling height is over 10mm and less than 20mm × Boiling height exceeds 20mm

[0072] Tables 1 to 3 show the polyols, fillers, blowing agents, compatibilizers, urethanization catalysts, and foam stabilizers used in the examples and comparative examples.

[0073] [Table 1]

[0074] [Table 2]

[0075] [Table 3]

[0076] [Examples 1 to 16, Comparative Examples 1 to 3] Polyol compositions were obtained by mixing polyol, filler, blowing agent, compatibilizer, urethanization catalyst, and foam stabilizer in the amounts shown in Table 4, and the boiling height was evaluated as described above. The results are shown in Table 4.

[0077] [Table 4]

[0078] As is clear from the results of the above examples, the composition of the present invention is a composition containing a polyol, a filler, a foaming agent, and a compatibilizer, and having Ra represented by formula (1). 2 is 200J / cm 3 It was found that the polyol composition of the present invention, which is below the boiling point, has a low boiling point when stirred, and is excellent in operability and safety. In contrast, as shown in Comparative Examples 1 to 3, when no compatibilizer was used or when a compatibilizer was used, the Ra 2 is 200J / cm 3 It was found that polyol compositions exceeding this value had a high boiling point when stirred, and were inferior in operability and safety.

Claims

1. The composition contains a polyol, a filler, a foaming agent, and a compatibilizer, and has Ra represented by the following formula (1): ２ is 200 J / cm ３ A polyol composition which is: <Formula (1)> Ra ２ =4×(dD1-dD2) ２ +(dP1-dP2) ２ +(dH1-dH2) ２ In equation (1), dD, dP, and dH represent the dispersion term, polarization term, and hydrogen bond term in the Hansen solubility parameter (HSP), respectively, as follows: dD1 [(J / cm ３ ) １／２ ]: dispersion term in HSP of foaming agent dD2 [(J / cm ３ ) １／２ ]: dispersion term in HSP of the compatibilizer dP1 [(J / cm ３ ) １／２ ]: Polarization term in the HSP of the foaming agent dP2 [(J / cm ３ ) １／２ ]: Polarization term in the HSP of the compatibilizer dH1 [(J / cm ３ ) １／２ ]: hydrogen bond term in the HSP of the foaming agent dH2 [(J / cm ３ ) １／２ ]: hydrogen bond term in the HSP of the compatibilizer

2. The polyol composition of claim 1 , wherein the blowing agent comprises a blowing agent having a boiling point of 40° C. or less.

3. The polyol composition according to claim 1 or 2, wherein the blowing agent comprises a fluorocarbon-based blowing agent.

4. The polyol composition according to any one of claims 1 to 3, wherein the compatibilizer comprises a phosphate ester compound.

5. The polyol composition of claim 4, wherein the phosphate ester compound is chlorine-free.

6. A foamable polyurethane composition comprising the polyol composition according to any one of claims 1 to 5 and a polyisocyanate.

7. A polyurethane foam comprising the foamable polyurethane composition according to claim 6.

Images