Polyol composition, foaming 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 foaming polyurethane composition, and a polyurethane foam.

Background Art

[0002] Due to its excellent heat insulation and adhesiveness, polyurethane foam is used, for example, as a heat insulating material for buildings such as condominiums, single-family houses, various facilities in schools, and commercial buildings. Polyurethane foam is obtained by foaming a foaming polyurethane composition containing a polyol composition and a polyisocyanate.

[0003] The above polyol composition generally contains a polyol and a foaming agent, and further, fillers such as a flame retardant and an inorganic filler may be blended as necessary. These fillers are blended for the purpose of improving the flame retardancy of the obtained polyurethane foam, coloring, or improving mechanical strength. For example, Patent Document 1 describes an invention relating to a polyol composition obtained by blending a polyol and a specific flame retardant in a certain amount, and it is described that the composition is excellent in flame retardancy, low smoke generation, etc.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] 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.

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

[0007] As a result of intensive 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, the polyol composition having a Ra represented by the formula (1): 2 The present inventors have found that the above-mentioned problems can be solved by a polyol composition in which the molecular weight ratio is equal to or less than a certain value, and have completed the present invention as described below.

[0008] The present invention relates to the following items [1] to [7]. [1] A composition comprising a polyol, a filler, a foaming agent, and a compatibilizer, and having the following formula (1): 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 respectively represent the dispersion term, polarization term, and hydrogen bond term in the Hansen solubility parameter (HSP) as follows: dD1[(J / cm 3 ) 1 / 2Dispersion term in the HSP of the blowing agent dD2 [(J / cm 3 ) 1 / 2 Dispersion term in the HSP of the compatibilizer dP1 [(J / cm 3 ) 1 / 2 Polarization term in the HSP of the blowing agent dP2 [(J / cm 3 ) 1 / 2 Polarization term in the HSP of the compatibilizer dH1 [(J / cm 3 ) 1 / 2 Hydrogen bonding term in the HSP of the blowing agent dH2 [(J / cm 3 ) 1 / 2 Hydrogen bonding term in the HSP of the compatibilizer [2] The polyol composition according to [1] above, wherein the blowing agent contains a blowing agent having a boiling point of 40°C or lower. [3] The polyol composition according to [1] or [2] above, wherein the blowing agent contains a chlorofluorocarbon blowing agent. [4] The polyol composition according to any one of [1] to [3] above, wherein the compatibilizer contains a phosphate ester compound. [5] The polyol composition according to [4] above, wherein the phosphate ester compound does not contain chlorine. [6] A foaming polyurethane composition containing the polyol composition according to any one of [1] to [5] above and a polyisocyanate. [7] A polyurethane foam comprising the foaming polyurethane composition according to [6] above.

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a polyol composition capable of suppressing the boiling up of the liquid during stirring when dispersing the filler.

Modes for Carrying Out the Invention

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

[0011] (Compatibilizer) The polyol composition of the present invention contains a compatibilizer. The compatibilizer has Ra represented by the above formula (1) calculated with the foaming agent described below 2 is 200 J / cm 3 or less. When Ra 2 exceeds 200 J / cm 3 , it becomes difficult to effectively prevent the liquid from boiling up during stirring when dispersing the filler. From the viewpoint of effectively suppressing the boiling up 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 foaming agent, dD2 represents the dispersion term in the HSP of the compatibilizer, dP1 represents the polar term in the HSP of the foaming agent, dP2 represents the polar term in the HSP of the compatibilizer, dH1 represents the hydrogen bonding term in the HSP of the foaming agent, and dH2 represents the hydrogen bonding term in the HSP of the compatibilizer. Each of these parameters can be calculated based on a calculation method using the neutral network method called Y-MB in Hansen Solubility Parameter Software (HSPiP 5th Edition (ver.5.0.09)). The compatibilizer may be used alone as one component or in combination of two or more components. When using two or more components, dD2, dP2, and dH2 in formula (1) may be obtained by volume fraction averaging from the dispersion term, polar term, and hydrogen bonding term in the HSP of each individual compatibilizer and the blending amount of each individual compatibilizer. Similarly, when using two or more components for the foaming agent described later, dD1, dP1, and dH1 in formula (1) may be obtained by volume fraction averaging from the dispersion term, polar term, and hydrogen bonding value in the HSP of each individual foaming agent and the blending amount of each individual foaming agent.

[0013] The type of the compatibilizer in the present invention is not particularly limited as long as it satisfies the above-mentioned Ra 2 value, and examples thereof include phosphate ester compounds and ester compounds other than phosphate ester compounds (hereinafter also referred to as non-phosphate ester compounds). In addition to these, for example, low molecular alcohols such as dipropylene glycol, carboxylic acid compounds such as 2-ethylhexanoic acid, and imidazole compounds having an imidazole ring can also be used. The above-mentioned low molecular alcohol means an alcohol having a molecular weight of 200 or less. Among these, from the viewpoint of facilitating suppression of the boiling up of the liquid during stirring, the compatibilizer preferably contains at least one of a phosphate ester compound and a non-phosphate ester compound. Further, from the viewpoint of improving the flame retardancy of the polyurethane foam which is the final product, it is more preferable that the compatibilizer contains a phosphate ester compound.

[0014] Examples of the phosphate ester compound include monophosphate esters and condensed phosphate esters. A 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, cresyldiphenyl phosphate, and diphenyl(2-ethylhexyl) phosphate; and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate. In addition to the above, phosphite esters and the like may also be used as the phosphate ester compound. 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-described phosphate ester compounds, trialkyl phosphate is preferable from the viewpoint of easily suppressing boiling during stirring. In particular, at least one phosphate ester compound selected from trimethyl phosphate and triethyl phosphate is preferable. Further, from the viewpoints of easily suppressing boiling during stirring and reducing environmental load, a phosphate ester compound not containing chlorine in its structure is preferable as the phosphate ester compound.

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

[0018] Examples of the non-phosphate ester compound 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-propiolactone, γ-butyrolactone, and δ-valerolactone. Among them, ethyl acetate, ethylene glycol acetate, γ-butyrolactone, etc. are preferable.

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

[0020] The content of the compatibilizer in the present invention is not particularly limited, but is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more with respect to 100 parts by mass of the polyol, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less. When the content of the compatibilizer is equal to or more than these lower limit values, it becomes easy to suppress boiling during stirring, and when it is equal to or less than the upper limit value, 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, and examples thereof include polylactone polyol, polycarbonate polyol, polyester polyol, polyether polyol, polymer polyol, and the like.

[0022] Examples of the polylactone polyol include polypropionolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of the polycarbonate polyol include polyols obtained by a dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, or the like.

[0023] Examples of the polyester polyol include polymers obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, and condensates of hydroxycarboxylic acid and the polyhydric alcohol. Examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), and succinic acid. Examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, and neopentyl glycol. Examples of the hydroxycarboxylic acid include castor oil and reaction products of castor oil and ethylene glycol.

[0024] Examples of the polyether polyol 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 compound such as a low molecular weight active hydrogen compound having two or more active hydrogens. Examples of the low molecular weight active hydrogen compound 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 the polymer polyol include polymers obtained by graft polymerization of ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate onto aromatic polyols, alicyclic polyols, aliphatic polyols, and polyester polyols; polybutadiene polyols; and modified polyols of polyhydric alcohols or hydrogenated products thereof. Examples of the aromatic polyol used in the production of the polymer polyol include bisphenol A, bisphenol F, phenol novolak, and cresol novolak. Examples of the alicyclic polyol used in the production of the polymer polyol include cyclohexanediol, methylcyclohexanediol, isophorone diol, dicyclohexylmethane diol, and dimethyldicyclohexylmethane diol. Examples of the aliphatic polyol used in the production of the polymer polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

[0026] Examples of the modified polyol of the polyhydric alcohol include those obtained by modifying the raw material polyhydric alcohol by reacting it with an alkylene oxide. Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., sucrose, glucose, mannose, fructose, methyl glucoside and its derivatives, etc., tetra- to octahydric alcohols, phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene, etc., polyols, castor oil polyol, polyfunctional (for example, the number of functional groups is 2 to 100) polyols such as (co)polymers of hydroxyalkyl (meth)acrylate and polyvinyl alcohol, and condensates (novolac) of phenol and formaldehyde.

[0027] The method for 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 preferable, and PO and EO are more preferable. When using two or more kinds of AOs (for example, PO and EO), the addition method may be block addition, random addition, or a combination thereof.

[0028] As the polyol used in the present invention, it is preferably at least one selected from the group consisting of polyester polyol and polyether polyol. Also, a polyol having two hydroxyl groups is preferred. Among them, from the viewpoint of enhancing flame retardancy, an aromatic polyester polyol which is a polyester polyol having an aromatic ring is preferred. As the aromatic polyester polyol, those obtained by dehydration condensation of a polybasic acid having an aromatic ring such as isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), etc. and a dihydric alcohol such as bisphenol A, ethylene glycol, and 1,2-propylene glycol are more preferred.

[0029] The weight average molecular weight of the polyol is preferably more than 300, more preferably 400 or more, still more preferably 430 or more, and preferably 20000 or less, more preferably 10000 or less. The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0030] The hydroxyl value of the polyol is preferably 20 to 300 mgKOH / g, more preferably 40 to 280 mgKOH / g, still more preferably 100 to 250 mgKOH / g, and still more preferably 120 to 210 mgKOH / g. When the hydroxyl value of the polyol is below the upper limit value, it is easy to suppress the boiling up during stirring of the polyol composition, and the viscosity of the polyol composition is likely to decrease, which is preferable from the viewpoint of handleability and the like. On the other hand, when the hydroxyl value of the polyol is above the lower limit value, the crosslink density of the polyurethane foam increases, resulting in higher strength. In addition, the hydroxyl value of the polyol can be measured according to JIS K 1557-1:2007.

[0031] The content of the polyol in the polyol composition of the present invention is preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and still more preferably 30 to 70% by mass. When the content of the polyol is not less than the lower limit value, it is preferable because it becomes easier to react the polyol with the polyisocyanate. On the other hand, when the content of the polyol is not more than the upper limit value, it is preferable from the viewpoint of handleability because the viscosity of the polyol composition does not become too high.

[0032] <Blowing agent> The polyol composition of the present invention contains a blowing agent. By foaming the polyol composition containing the blowing agent and the foaming polyurethane composition containing the polyisocyanate, a polyurethane foam can be obtained.

[0033] From the viewpoint of improving the foamability when forming the polyurethane foam, the blowing agent preferably contains a blowing agent having a boiling point of 40°C or lower (hereinafter also referred to as a low-boiling blowing agent). Further, the boiling point of the low-boiling blowing agent is more preferably 20°C or lower. The boiling point means the boiling point at 1 atmospheric pressure. In addition, when the polyol composition contains such a low-boiling blowing agent, boiling due to stirring usually easily occurs. However, when a specific compatibilizer is contained as in the present invention, boiling can be suppressed. The content of the low-boiling blowing agent in the blowing agent is preferably 50% by mass or more, more preferably 80% by mass or more, and still 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 chlorofluorocarbon blowing agent such as a fluorine compound, hydrochlorofluorocarbon, hydrofluorocarbon, or hydrofluoroolefin. Among these, the blowing agent more preferably contains a hydrofluoroolefin because the blowing agent has high stability, is less likely to have its catalytic activity reduced, and further has a lower environmental load, and still more preferably consists only of a hydrofluoroolefin.

[0035] Examples of the hydrofluoroolefin include fluoroalkenes having about 3 to 6 carbon atoms. The hydrofluoroolefin may be a hydrochlorofluoroolefin having a chlorine atom, and thus may be a chlorofluoroalkene having about 3 to 6 carbon atoms. More specifically, examples include trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorotrifluoropropenes such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetrafluoropropene. More specifically, 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. Among these, HFO-1233zd is preferred. These hydrofluoroolefins may be used alone or in combination of two or more.

[0036] The content of the chlorofluorocarbon blowing agent contained in the blowing agent is preferably 80% by mass or more, more preferably 95% by mass or more, and still 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 the chlorofluorocarbon blowing agent. Examples of the blowing agent other than the chlorofluorocarbon blowing agent include water, nitrogen gas, oxygen gas, argon gas, carbon dioxide gas, and the like. Among these, from the viewpoint of handleability, water, oxygen gas, and carbon dioxide gas are preferred, and water is more preferred from the viewpoints of adjusting the isocyanate index and ease of handling. The content of the blowing agent other than the chlorofluorocarbon blowing agent contained in the blowing agent is preferably 20% by mass or less, more preferably 5% by mass or less, based on the total amount of the blowing agent.

[0037] The compounding amount of the blowing agent is preferably 10 to 80 parts by mass, more preferably 15 to 70 parts by mass, and still more preferably 20 to 60 parts by mass with respect to 100 parts by mass of the polyol. When the compounding amount of the blowing agent is at least the lower limit value, foaming is promoted, the foamability becomes good, and the density of the obtained polyurethane foam can be reduced. On the other hand, when the compounding amount of the blowing agent is at most the upper limit value, it is possible to suppress the excessive progress of foaming.

[0038] <Filler> The polyol composition of the present invention contains a filler. By containing the filler, characteristics according to the type of the filler can be imparted to the polyurethane foam, and for example, it becomes possible to improve the flame retardancy and mechanical strength, or to color the polyurethane foam. Examples of the filler 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 the flame retardant, the flame retardancy of the formed polyurethane foam can be effectively enhanced. Examples of the flame retardant include 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 solid flame retardants such as metal hydroxides.

[0040] (Red phosphorus-based flame retardant) The red phosphorus-based flame retardant may be composed of red phosphorus alone, or may be one in which red phosphorus is coated with a resin, metal hydroxide, metal oxide, etc., or may be one in which red phosphorus is mixed with a resin, metal hydroxide, metal oxide, etc. The resin coating red phosphorus or mixed with red phosphorus is not particularly limited, but phenolic resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, a ​Examples of the thermosetting resin include a nylon resin and a silicone resin. The coating or mixing From the viewpoint of flame retardancy, a metal hydroxide is preferable as the compound. The metal hydroxide may be appropriately selected from those described below and used.

[0041] (Phosphate-containing flame retardant) Examples of the phosphate-containing flame retardant include phosphates composed 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, and examples thereof include monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid. Examples of the 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, and piperazine. Examples of the aromatic amine include aniline, o-toluidine, 2,4,6-trimethylaniline, anisidine, and 3-(trifluoromethyl)aniline. Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, and melamine.

[0042] ​​​​​​​Specific examples of the phosphate-containing flame retardant include, for example, monophosphates, polyphosphates, etc. The monophosphate is not particularly limited, and examples thereof include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium salts such as sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium hypophosphite, sodium phosphite, sodium salts such as potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium hypophosphite, potassium phosphite, lithium salts such as lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium hypophosphite, lithium phosphite, barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, barium phosphate, barium hypophosphite, magnesium salts such as magnesium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, magnesium hypophosphite, calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite, zinc salts such as zinc phosphate, zinc phosphite, zinc hypophosphite, etc. Here, the polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, etc. The phosphate-containing flame retardant may be used alone or in combination of two or more thereof.

[0043] (Bromine-containing flame retardant) The bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure and being solid at normal temperature and pressure and examples thereof include aromatic compounds containing brominated aromatic rings. Examples of the aromatic compound containing brominated aromatic rings include hexabromobenzene, pentabromotoluene hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromo (Mophenoxy)ethane, ethylene bis(pentabromophenyl), ethylene bis(tetra bromophthalimide), monomeric organic bromine compounds such as tetrabromobisphenol A are mentioned.

[0044] Also, the brominated aromatic ring-containing aromatic compound may be a bromine compound polymer. Specifically there are polycarbonate oligomers produced from brominated bisphenol A, copolymers of such polycarbonate oligomers and bisphenol A, etc., brominated polycarbonates, diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin, etc. Further, brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, poly(brominated benzyl acrylate), condensates of brominated polyphenylene ether, brominated bisphenol A and chlorinated cyanuric acid, brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly( -methylstyrene), etc. are mentioned. Also, 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. These bromine-containing flame retardants may be used alone or in combination of two or more.

[0045] (Chlorine-containing flame retardant) Chlorine-containing flame retardants include those commonly used in flame-retardant resin compositions, for example, poly chlorinated naphthalene, chlorendic acid, dodecachlorododecahydrodimethanodibenzocyclooctene sold under the trade name "Dechlorane Plus", etc. are mentioned.

[0046] (Antimony-containing flame retardant) Examples of the antimony-containing flame retardant include antimony oxide, antimonate, pyroantimonate, etc. Examples of antimony oxide include antimony trioxide, antimony pentoxide, etc. Examples of antimonate include sodium antimonate, potassium antimonate, etc. Examples of pyroantimonate include sodium pyroantimonate, potassium pyroantimonate, etc. The antimony-containing flame retardant may be used alone or in combination of two or more kinds.

[0047] (Boron-containing flame retardant) Examples of the boron-containing flame retardant include borax, boron oxide, boric acid, borate, etc. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide, etc. Examples of borate include borates of alkali metals, alkaline earth metals, Group 4, Group 12, Group 13 elements of the periodic table, and ammonium. Specifically, alkali metal borates such as lithium borate, sodium borate, potassium borate, cesium borate, etc., alkaline earth metal borates such as magnesium borate, calcium borate, barium borate, etc., zirconium borate, zinc borate, aluminum borate, ammonium borate, etc. The boron-containing flame retardant may be used alone or in combination of two or more kinds.

[0048] (Metal hydroxide) ​​​​​​​​​Examples of the metal hydroxide include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide and the like. The metal hydroxide may be used alone or in combination of two or more thereof.

[0049] ≪Inorganic filler≫ The polyol composition of the present invention may contain an inorganic filler other than the above-mentioned flame retardant as long as the effects of the present invention are not impaired. Examples of the inorganic filler 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, sepiolite, imogolite, sericite, glass fiber, glass bead, 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 disulfide, silicon carbide, stainless fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber and the like. The inorganic filler is a solid component that becomes solid at normal temperature and normal pressure. The inorganic filler may be used alone or in combination of two or more thereof. 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 still more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the polyol.

[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 still more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the polyol.

[0051] <Catalyst> From the perspective of promoting the reaction between the polyol and the polyisocyanate, and improving the flame retardancy of the polyurethane foam to be formed, etc., the polyol composition of the present invention preferably contains a catalyst. The catalyst contains a trimerization catalyst, a urethanization catalyst, etc., and it is more preferable to contain both a trimerization catalyst and a urethanization catalyst.

[0052] (Trimerization catalyst) The trimerization catalyst is a catalyst that reacts with the isocyanate groups contained in the polyisocyanate described later to trimerize and promotes the formation of an isocyanurate ring. Examples of the trimerization catalyst include nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal carboxylates such as potassium acetate, potassium 2-ethylhexanoate, potassium octylate; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt; quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium, tetraphenylammonium salt, triethylmonomethylammonium salt, etc. Examples of the ammonium salt include ammonium salts of carboxylic acids such as 2,2-dimethylpropanoic acid, and more specifically, quaternary ammonium salts of carboxylic acids. 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 salts of carboxylic acids are preferable, and a mode of using both of these is also preferable.

[0053] The compounding amount of the trimerization catalyst is preferably 0.1 to 25 parts by mass, more preferably 0.3 to 20 parts by mass, and still more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the polyol. When the compounding amount of the trimerization catalyst is not less than these lower limit values, the trimerization of the polyisocyanate is likely to occur, and the flame retardancy of the obtained polyurethane foam is improved. On the other hand, when the compounding amount of the trimerization catalyst is not more than the upper limit value, the reaction is easier to control.

[0054] (Urethanization catalyst) The urethanization catalyst is a catalyst that promotes the reaction between the polyol and the polyisocyanate. Examples of the urethanization catalyst include amine-based catalysts such as imidazole compounds and piperazine compounds, and metal-based catalysts. Examples of the imidazole compound 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, etc. Specifically, N-methylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole, etc. may be mentioned. Further, an imidazole compound in which the secondary amine in the imidazole ring is substituted with a cyanoethyl group may also be used. Further, examples of the piperazine compound include tertiary amines such as N-methyl-N’N’-dimethylaminoethylpiper azine and trimethylaminoethylpiperazine. Further, examples of the amine-based catalyst include various tertiary amines such as pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinobis(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, etc., in addition to imidazole compounds and piperazine compounds.

[0055] Examples of the metal-based catalyst include those composed of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. Metal salts are mentioned, preferably metal organic salts composed of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. More preferably, they are dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatate, bismuth trioctoate, bismuth tris(2- ethylhexanoate), tin dioctylate, lead dioctylate, etc. Among them, metal bismuth organic 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 metal bismuth organic salts, and the mode of using both of them is also preferable.

[0056] The compounding 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 with respect to 100 parts by mass of the polyol. When the compounding amount of the resinification catalyst is at or above these lower limit values, urethane bonds are likely to be formed and the reaction proceeds rapidly. On the other hand, when it is at or below these upper limit values, the reaction rate is easy to control.

[0057] Also, 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. When it is at or above these lower limit values, the formation of urethane bonds and trimerization proceed appropriately, and the flame retardancy is likely to be good. Also, when it is at or below these upper limit values, the control of the urethanization and trimerization reactions becomes easy.

[0058] <Blowing agent> The polyol composition of the present invention may contain a blowing agent. The blowing agent improves the foamability of the foamable polyurethane composition containing the polyol composition and the 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 blending amount of the foam stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and still more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyol compound. When the blending amount of the foam stabilizer is not less than these lower limit values, it becomes easier to foam the polyurethane composition and it becomes easier to obtain a homogeneous polyurethane foam. Further, when the blending amount of the foam stabilizer is not more than these upper limit values, the balance between the production cost and the obtained effect becomes good.

[0059] <Other components> The polyol composition may contain one or more selected from antioxidants such as phenolic, amine-based, and sulfur-based antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, etc., as necessary within a range not impairing the object of the present invention.

[0060] <Method for producing polyol composition> There is no particular limitation on the method for producing the polyol composition of the present invention. For example, it can be produced by stirring each component at about 20 to 40 ° C for about 30 seconds to 20 minutes using a homodyne 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 these. The polyurethane foam of the present invention is composed of a foamable polyurethane composition, and specifically, it is a reaction product obtained by reacting and foaming the foamable polyurethane composition.

[0062] <Polyisocyanate> Examples of the polyisocyanate include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Examples of the aromatic polyisocyanate include phenylenediisocyanate, tolylenediisocyanate, xylylenediisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalenediisocyanate, polymethylene polyphenyl polyisocyanate, and the like.

[0063] Examples of the alicyclic polyisocyanate include cyclohexylenediisocyanate, methylcyclohexylenediisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate, and the like.

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

[0065] Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanate is preferable, and diphenylmethane diisocyanate is more preferable. The polyisocyanate may be used alone or in combination of two or more. Further, before mixing with the polyol composition, known additives to be compounded in the polyisocyanate may be appropriately compounded in the polyisocyanate.

[0066] <Isocyanate index> Although there is no particular limitation on the isocyanate index of the foaming polyurethane composition of the present invention, it is preferably 150 or more. When the isocyanate index is equal to or higher than the above lower limit value, the amount of polyisocyanate relative to the polyol becomes excessive, and an isocyanurate bond formed by a trimer of polyisocyanate is likely to be generated. As a result, the flame retardancy of the polyurethane foam is improved. Further, when the value is equal to or higher than the above lower limit value, combined with the above-described various catalysts used in combination, it is easy to produce a polyurethane foam having a sufficient isocyanurate bond, that is, a polyurethane foam having both high flame retardancy and heat insulation properties at a high level. From these viewpoints, the isocyanate index is more preferably 150 or more, still more preferably 200 or more, and even more preferably 250 or more. Also, the isocyanate index is preferably 800 or less, more preferably 600 or less, and still more preferably 400 or less. When the isocyanate index is equal to or lower than the above upper limit value, the balance between the flame retardancy and the production cost of the obtained polyurethane foam becomes good.

[0067] The isocyanate index can be calculated by the following method. Isocyanate index = Equivalent number of polyisocyanate ÷ (Equivalent number of polyol + Equivalent number 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 number of polyol = OHV × Amount of polyol used (g) ÷ Molecular weight of KOH (mmol) OHV is the hydroxyl value (mgKOH / g) of the polyol. · Equivalent number of water = Amount of water used (g) / Molecular weight of water (mol) × Number of OH groups of 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 of water is 2.

[0068] <Method for manufacturing polyurethane foam> The method for manufacturing the polyurethane foam is not particularly limited, but it is preferable to foam and react a foaming polyurethane composition obtained by mixing a polyisocyanate and a polyol composition. Specifically, it is preferable to collide and mix the polyisocyanate and the polyol composition using a spray gun or the like and perform spraying construction. Further, in the present invention, after mixing the polyisocyanate and the polyol composition, a polyurethane foam may be obtained by injecting the mixture into a container such as a mold or a frame material and curing it.

[0069] <Use of polyurethane foam> The use of the polyurethane foam of the present invention is not particularly limited, but it can be suitably used for buildings such as walls, ceilings, roofs, and floors of buildings. Further, it can also be suitably used as a member for filling any opening formed in a building, including joints and holes formed between structural materials of the building.

Examples

[0070] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

[0071] [Evaluation of boiling height] The polyol compositions (300 g in total) prepared in each example and comparative example were mixed and stirred, and 30 g thereof was put into a 110 mL screw tube (manufactured by Maruemu Co., Ltd., product name: No8). After winding a sealing tape (made of polytetrafluoroethylene) around the screw mouth, 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 hot water bath at 29 ° C. for 30 minutes or more to make 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 surface of the screw tube to the highest point of the liquid (polyol composition), and the height before stirring means the height from the bottom surface of the screw tube to the liquid surface (polyol composition). (Judgment) ◎ ··· The boiling height is 10 mm or less 〇 ··· The boiling height is more than 10 mm and 20 mm or less × ··· The boiling height is more than 20 mm

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

[0073]

Table 1

[0074]

Table 2

[0075]

Table 3

[0076] [Examples 1 to 16, Comparative Examples 1 to 3] The polyol, filler, blowing agent, compatibilizer, urethanization catalyst, and foam stabilizer were mixed in the amounts shown in Table 4 to obtain a polyol composition, and the above-described evaluation of the boiling height was performed. The results are shown in Table 4.

[0077]

Table 4

[0078] As is clear from the results of the above examples, the polyol composition of the present invention containing a polyol, a filler, a blowing agent, and a compatibilizer and having Ra represented by the formula (1) 2 of 200 J / cm 3 or less has a low boiling height during stirring and was found to be excellent in operability and safety. On the other hand, as shown in Comparative Examples 1 to 3, when no compatibilizer is used, or even when a compatibilizer is used and Ra 2 is 200 J / cm 3The polyol composition exceeding [a certain value] was found to have a high boiling height during stirring and be inferior in operability and safety.

Claims

1. A polyol composition containing a polyol, a filler, a blowing agent, and a compatibilizer, wherein the blowing agent contains a hydrofluoroolefin, the compatibilizer contains a phosphate ester compound, and the phosphate ester compound is one or more selected from the group consisting of triethyl phosphate, trimethyl phosphate, tris(β-chloropropyl) phosphate, and trixylenyl phosphate, the filler is one or more selected from the group consisting of ammonium polyphosphate, melamine polyphosphate, and calcium carbonate, and is used for forming a heat insulating material by spraying construction using a spray gun at a construction site.

2. The polyol composition according to claim 1, containing a catalyst.

3. The polyol composition according to claim 1 or 2, containing a foam stabilizer.

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

5. A polyurethane foam comprising the foaming polyurethane composition according to claim 4.

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