JP7583536B2 - Polyol composition, foamable polyurethane composition, and polyurethane foam - Google Patents

Description

The present invention relates to a polyol composition, a foamable polyurethane composition, and a polyurethane foam.

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

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

Japanese Patent Application Publication No. 11-246754

As described above, in polyol compositions containing fillers, the filler settles over time during storage. Therefore, it is necessary to stir the polyol composition to disperse the filler before mixing with polyisocyanate to produce polyurethane foam. However, when stirring, the blowing agent contained in the polyol composition causes the liquid to boil and overflow from the container, which is problematic from the standpoint of operability and safety. In particular, the problem of liquid boiling (sudden rise in liquid level) occurs significantly during hot summer months and when a blowing agent with a low boiling point is used.

The present invention aims to provide a polyol composition that contains a polyol, a filler, and a foaming agent and that can suppress boiling during stirring.

As a result of intensive research into solving the above problems, the present inventors have found that the above problems can be solved by a polyol composition containing a polyol, a filler, a foaming agent, and a compatibilizer, in which ^Ra2 represented by formula (1) is a certain value or less, and have completed the present invention as described below.

The present invention relates to the following items [1] to [7].
[1] A polyol composition comprising a polyol, a filler, a foaming agent, and a compatibilizer, and having ^Ra2 represented by the following formula (1) of 200 J/ ^cm3 or less.
<Formula (1)>
Ra ² =4×(dD1-dD2) ² +(dP1-dP2) ² +(dH1-dH2) ²
In formula (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 ) ^1/2 ]: dispersion 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 bond term in the HSP of the blowing agent dH2 [(J/cm ³ ) ^1/2 ]: hydrogen bond term in the HSP of the compatibilizer [2] The polyol composition according to the above [1], 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 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 the above [4], wherein the phosphate ester compound does not contain chlorine.
[6] A foamable polyurethane composition comprising 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.

The present invention provides a polyol composition that can suppress the boiling of the liquid during stirring to disperse the filler.

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 ^Ra2 represented by formula (1) of 200 J/cm3 or ^less .
<Formula (1)>
Ra ² =4×(dD1-dD2) ² +(dP1-dP2) ² +(dH1-dH2) ²
In formula (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 ) ^1/2 ]: Dispersion 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 bond term in the HSP of the blowing agent dH2 [(J/cm ³ ) ^1/2 ]: Hydrogen bond term in the HSP of the compatibilizer

(Compatibilizer)
The polyol composition of the present invention contains a compatibilizer. The compatibilizer has Ra2 represented by the above formula (1), calculated between the ^{compatibilizer} and a blowing agent described later, of 200 J/ ^cm3 or less. If ^Ra2 exceeds 200 J/ ^cm3 , 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, ^Ra2 is preferably 150 or less, and more preferably 100 or less.

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 bond term in the HSP of the blowing agent, and dH2 represents the hydrogen bond term in the HSP of the compatibilizer.
Each of these parameters can be calculated based on a prediction method using a 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) may be calculated by averaging the volume fractions of the dispersion term, polarization term, and hydrogen bond term in the HSP of each compatibilizer and the blending amount of each compatibilizer. Similarly, when two or more components are used for the blowing agent described later, dD1, dP1, and dH1 in formula (1) may be calculated by averaging the volume fractions of the dispersion term, polarization term, and hydrogen bond value in the HSP of each blowing agent and the blending amount of each blowing agent.

The type of compatibilizer in the present invention is not particularly limited as long as it satisfies the above-mentioned ^Ra2 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), and in addition to these, for example, low molecular weight alcohols such as dipropylene glycol, carboxylic acid compounds such as 2-ethylhexanoic acid, imidazole compounds having an imidazole ring, etc. can also be used. The low molecular weight alcohol means 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, and more preferably contains a phosphate ester compound from the viewpoint of improving the flame retardancy of the polyurethane foam, which is the final product.

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

Examples of condensed phosphate esters include aromatic condensed phosphate esters such as trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate.

Among the above phosphoric acid ester compounds, trialkyl phosphates are preferred from the viewpoint of easily suppressing boiling during stirring, and at least one phosphoric acid ester compound selected from trimethyl phosphate and triethyl phosphate is particularly preferred.
In addition, 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 from the viewpoint of reducing the environmental load.

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 even more preferably 100% by mass.

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.

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 even more preferably 100% by mass.

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 even more preferably 5 parts by mass or more, per 100 parts by mass of polyol, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less. If the content of the compatibilizer is equal to or more than these lower limits, it becomes easier to suppress boiling during stirring, and if it is equal to or less than the upper limits, it is possible to suppress a decrease in the mechanical strength of the polyurethane foam.

<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.

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

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

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

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

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

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

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

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

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 during stirring of the polyol composition 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 is increased, thereby increasing the strength.
The hydroxyl value of the polyol can be measured in accordance with JIS K 1557-1:2007.

The content of polyol 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. If the content of polyol is equal to or greater than the lower limit, it is preferable because it makes it easier for the polyol to react with the polyisocyanate. On the other hand, if the content of polyol is equal to or less than the upper limit, it is preferable from the viewpoint of ease of handling because the viscosity of the polyol composition does not become too high.

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

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

The blowing agent is not particularly limited, but preferably contains a fluorocarbon-based blowing agent such as a fluorine compound, hydrochlorofluorocarbon, hydrofluorocarbon, or hydrofluoroolefin. Of these, the blowing agent is more preferably a hydrofluoroolefin, and more preferably consists of only hydrofluoroolefin, because the blowing agent is highly stable, its catalytic activity is less likely to decrease, and the environmental impact is also reduced.

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, chlorodifluoropropenes, chlorotrifluoropropenes, and chlorotetrafluoropropenes. More specifically, examples thereof 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 kinds.

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

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 polyol. When the amount of the blowing agent is equal to or greater than the lower limit, foaming is promoted, the foamability is improved, and the density of the resulting polyurethane foam can be reduced. On the other hand, when the amount of the blowing agent is equal to or less than the upper limit, excessive foaming can be prevented.

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

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

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

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

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

(Bromine-containing flame retardants)
The bromine-containing flame retardant is not particularly limited as long as it contains bromine in its molecular structure and is a solid at room temperature and pressure. Examples of the bromine-containing flame retardant include brominated aromatic ring-containing aromatic compounds.
Examples of the aromatic compounds containing a brominated aromatic ring include hexabrombenzene, pentabromtoluene, hexabromobiphenyl, decabromodiphenyl, decabromodiphenyl ether,
Examples of monomeric organic bromine compounds include octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene bis(pentabromophenyl), ethylene bis(tetrabromophthalimide), and tetrabromobisphenol A.

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

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

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

(Boron-containing flame retardants)
Examples of boron-containing flame retardants include borax, boron oxide, boric acid, borates, etc. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.
Borates include, for example, alkali metals, alkaline earth metals, and elements of Groups 4 and 12 of the periodic table.
Specific examples of the borate include alkali metal borate such as lithium borate, sodium borate, potassium borate, and cesium borate, alkaline earth metal borate 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.

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

<Inorganic fillers>
The polyol composition of the present invention may contain an inorganic filler other than the above-mentioned flame retardant, so long as the effect of the present invention is 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,
Examples of the inorganic filler include silica fiber and zirconia fiber. The inorganic filler is a solid component that becomes solid at room temperature and normal pressure.
The inorganic fillers may be used alone or in combination of two or more kinds.

The amount of 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, per 100 parts by mass of polyol.

<Catalyst>
The polyol composition of the present invention preferably contains a catalyst from the viewpoint of promoting the reaction between the polyol and the polyisocyanate, improving the flame retardancy of the polyurethane foam to be formed, etc. The catalyst contains a trimerization catalyst, a urethanization catalyst, etc., and more preferably contains both a trimerization catalyst and a urethanization catalyst.

(Trimerization Catalyst)
The trimerization catalyst is a catalyst that reacts isocyanate groups contained in a polyisocyanate, which will be described later, to perform trimerization and promote the formation of an isocyanurate ring. Examples of the trimerization catalyst 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 salts of carboxylic acids such as potassium acetate, potassium 2-ethylhexanoate, and potassium octylate; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt; and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium, tetraphenylammonium salt, and triethylmonomethylammonium salt. 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 carboxylates are preferred, and an embodiment in which both of these are used is also preferred.

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 polyol. If the amount of the trimerization catalyst is equal to or greater than these lower limits, trimerization of the polyisocyanate is more likely to occur, and the flame retardancy of the resulting polyurethane foam is improved. On the other hand, if the amount of the trimerization catalyst is equal to or less than the upper limit, the reaction is easier to control.

(Urethanization catalyst)
The urethanization catalyst is a catalyst that promotes the reaction between a polyol and a polyisocyanate. Examples of the urethanization catalyst include amine-based catalysts such as imidazole compounds and piperazine compounds, and metal-based catalysts.
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, 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. In addition, imidazole compounds in which the secondary amine in the imidazole ring is substituted with a cyanoethyl group may also be used.
Furthermore, examples of the piperazine compound include tertiary amines such as N-methyl-N'N'-dimethylaminoethylpiperazine and trimethylaminoethylpiperazine.
Further, 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.

Examples of the metal catalyst include metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc., and preferably organic acid metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. More preferably, 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 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 the group consisting of imidazole compounds and organic acid bismuth salts, and it is also preferable to use both of them.

The amount of the urethane catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of polyol. If the amount of the resinification catalyst is equal to or greater than these lower limits, urethane bonds are more easily formed and the reaction proceeds quickly. On the other hand, if the amount is equal to or less than these upper limits, the reaction rate is easier to control.

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. If it 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. If it is equal to or less than these upper limits, it becomes easier to control the urethane formation and trimerization reactions.

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

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

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

[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.

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

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

Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

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

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

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

<Method of manufacturing polyurethane foam>
There is no particular limitation on the method for producing the polyurethane foam, but it is preferable to foam and react the foamable polyurethane composition obtained by mixing the polyisocyanate and the polyol composition. Specifically, it is preferable to mix the polyisocyanate and the polyol composition by collision using a spray gun or the like, and 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.

<Applications of polyurethane foam>
The use of the polyurethane foam of the present invention is not particularly limited, but it can be suitably used in buildings such as walls, ceilings, roofs, floors, etc. 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 materials of buildings.

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

[Evaluation of boiling height]
The polyol compositions (total 300 g) prepared in each Example and Comparative Example were mixed and stirred, and 30 g was put into a 110 mL screw tube (manufactured by Maruemu Co., Ltd., product name: No. 8). After wrapping a sealing tape (made of polytetrafluoroethylene) around the screw 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 water bath at 29 ° C. for 30 minutes or more to keep the temperature constant, and then the stopper was opened and the stirrer was stirred at 1,500 rpm using a magnetic stirrer. The height of the highest point after stirring was measured, and the difference from the height before stirring was calculated and evaluated as the boiling height. The height of the highest point after stirring means the height from the bottom of the screw tube to the highest point of the liquid (polyol composition), and the height before stirring means the height from the bottom of the screw tube to the liquid (polyol composition) surface.
(judgement)
◎: Boiling height is 10mm or less. 〇: Boiling height is between 10mm and 20mm or less. ×: Boiling height is over 20mm.

The polyols, fillers, foaming agents, compatibilizers, urethane catalysts, and foam stabilizers used in each example and comparative example are shown in Tables 1 to 3.

[Examples 1 to 16, Comparative Examples 1 to 2 ]
The polyol, the filler, the foaming agent, the compatibilizer, the urethanization catalyst, and the foam stabilizer were mixed in the amounts shown in Table 4 to obtain polyol compositions, which were then evaluated for boiling height as described above. The results are shown in Table 4.

As is clear from the results of the above examples, the polyol composition of the present invention, which contains a polyol, a filler, a foaming agent, and a compatibilizer and has ^Ra2 of 200 J/ ^cm3 or less as represented by formula (1), has a low boiling height when stirred and is excellent in operability and safety. In contrast, as shown in Comparative Examples 1 and 2 , it was found that polyol compositions without a compatibilizer or with a compatibilizer but having ^Ra2 of more than 200 J/ ^cm3 have a high boiling height when stirred and are inferior in operability and safety.

Claims (7)

comprising a polyol, a filler, a foaming agent, and a compatibilizer;
the compatibilizer is at least one selected from the group consisting of triethyl phosphate, trimethyl phosphate, trixylenyl phosphate , methyl acetate, and propylene glycol methyl ether acetate;
A polyol composition (excluding those containing an alkylphosphinate compound) having ^Ra2 of 200 J/ ^cm3 or less, as represented by the following formula (1):
<Formula (1)>
Ra ² =4×(dD1-dD2) ² +(dP1-dP2) ² +(dH1-dH2) ²
In formula (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 ) ^1/2 ]: Dispersion 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 bond term in the HSP of the blowing agent dH2 [(J/cm ³ ) ^1/2 ]: Hydrogen bond term in the HSP of the compatibilizer The polyol composition of claim 1 further comprising a catalyst. The polyol composition according to claim 1 or 2, further comprising a foam stabilizer. The polyol composition according to any one of claims 1 to 3, wherein the polyol contains an aromatic polyester polyol. A foamable polyurethane composition comprising the polyol composition according to any one of claims 1 to 4 and a polyisocyanate. 6. The foamable polyurethane composition according to claim 5, which has an isocyanate index of 150 to 800. A polyurethane foam comprising the foamable polyurethane composition according to claim 5 or 6 .