JP2024023753A - Polyol composition, foamable polyurethane composition and polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: 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

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to polyol compositions, expandable polyurethane compositions, and polyurethane foams.

Due to its excellent heat insulating properties and adhesive properties, polyurethane foam is used as a heat insulating material in buildings such as apartment complexes such as condominiums, 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 above polyol composition generally contains a polyol and a blowing 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 formed by blending a polyol and a certain amount of a specific flame retardant, and describes that the composition has excellent flame retardancy, low smoke generation, and the like.

Japanese Patent Application Publication No. 11-246754

As described above, in a 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 it with polyisocyanate to produce polyurethane foam. However, when stirring, the foaming agent contained in the polyol composition causes the liquid to boil and overflow from the container, resulting in problems from the viewpoint of operability and safety. In particular, the problem of liquid boiling (rapid rise in liquid level) has occurred particularly in the summer when the temperature is high or when a blowing agent with a low boiling point is used.

Therefore, an object of the present invention is to provide a polyol composition containing a polyol, a filler, and a blowing agent that can suppress boiling up during stirring.

As a result of extensive studies to solve the above problems, the present inventors have developed a polyol composition containing a polyol, a filler, a blowing agent, and a compatibilizer, which has Ra ² represented by formula (1). The inventors have discovered that the above-mentioned problems can be solved by using a polyol composition that has a certain value or less, and have completed the present invention as described below.

The gist of the present invention is the following [1] to [7].
[1] A polyol composition containing a polyol, a filler, a blowing agent, and a compatibilizer, and having an Ra ² represented by the following formula (1) of 200 J/cm ³ or less.
<Formula (1)>
Ra ² =4×(dD1-dD2) ² +(dP1-dP2) ² +(dH1-dH2) ²
dD, dP, and dH in Equation (1) represent the dispersion term, polarization term, and hydrogen bond term in the Hansen solubility parameter (HSP), respectively, as shown below.
dD1 [(J/cm ³ ) ^1/2 ]: Dispersion term in HSP of blowing agent dD2 [(J/cm ³ ) ^1/2 ]: Dispersion term in HSP of 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 ]: Polarization term in the HSP of the blowing agent Hydrogen bond term dH2 [(J/cm ³ ) ^1/2 ]: Hydrogen bond term in HSP of compatibilizer [2] The polyol according to [1] above, wherein the blowing agent includes a blowing agent with a boiling point of 40° C. or lower Composition.
[3] The polyol composition according to [1] or [2] above, wherein the blowing agent contains a fluorocarbon foaming agent.
[4] The polyol composition according to any one of [1] to [3] above, wherein the compatibilizing agent contains a phosphoric acid ester compound.
[5] The polyol composition according to [4] above, wherein the phosphoric acid ester compound does not contain chlorine.
[6] A foamable polyurethane composition containing the polyol composition according to any one of [1] to [5] above and a polyisocyanate.
[7] A polyurethane foam made of the foamable polyurethane composition described in [6] above.

According to the present invention, it is possible to provide a polyol composition that can suppress the boiling up of a liquid during stirring when dispersing a filler.

The present invention will be explained in detail below.
[Polyol composition]
The polyol composition of the present invention contains a polyol, a filler, a blowing agent, and a compatibilizer, and has an Ra ² represented by formula (1) of 200 J/cm ³ or less.
<Formula (1)>
Ra ² =4×(dD1-dD2) ² +(dP1-dP2) ² +(dH1-dH2) ²
dD, dP, and dH in Equation (1) represent the dispersion term, polarization term, and hydrogen bond term in the Hansen solubility parameter (HSP), respectively, as shown below.
dD1 [(J/cm ³ ) ^1/2 ]: Dispersion term in HSP of blowing agent dD2 [(J/cm ³ ) ^1/2 ]: Dispersion term in HSP of 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 ]: Polarization term in the HSP of the blowing agent Hydrogen bond term dH2 [(J/cm ³ ) ^1/2 ]: Hydrogen bond term in HSP of compatibilizer

(Compatibilizer)
The polyol composition of the present invention contains a compatibilizer. The compatibilizer has an Ra ² of 200 J/cm ³ or less, which is calculated with the foaming agent described below and is expressed by the above formula (1). 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 ² is preferably 150 or less, more preferably 100 or less.

In the above formula (1), dD1 is the dispersion term in the Hansen solubility parameter (HSP) of the blowing agent, dD2 is the dispersion term in the HSP of the compatibilizer, dP1 is the polarization term in the HSP of the blowing agent, and dP2 is 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 an estimation method using a neutral network method called Y-MB in Hansen Solubility Parameter Software (HSPiP 5th Edition (ver. 5.0.09)).
One component of the compatibilizing agent may be used alone, or two or more components may be used in combination. When two or more components are used, dD2, dP2, and dH2 in formula (1) are determined by the volume from the dispersion term, polarization term, and hydrogen bond term in the HSP of each compatibilizer and the blended amount of each compatibilizer. It can be calculated by averaging the fractions. Similarly, when using two or more components of the blowing agent described later, dD1, dP1, and dH1 in formula (1) are the dispersion term, polarization term, and hydrogen bond value in the HSP of each blowing agent, and the individual It can be determined by averaging the volume fraction from the amount of foaming agent blended.

The type of compatibilizing agent in the present invention is not particularly limited as long as it satisfies the above Ra ² value, but examples include phosphoric ester compounds and ester compounds other than phosphoric ester compounds (hereinafter also referred to as non-phosphoric 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. Note that the above-mentioned low molecular weight alcohol means alcohol having a molecular weight of 200 or less.
Among these, the compatibilizing agent preferably contains at least one of a phosphate ester compound and a non-phosphate ester compound, from the viewpoint of easily suppressing the boiling up of the liquid during stirring. Furthermore, from the viewpoint of improving the flame retardance of the polyurethane foam that is the final product, it is more preferable that the compatibilizer contains a phosphate ester compound.

Examples of the phosphoric acid ester compound include monophosphoric acid ester, condensed phosphoric acid ester, and the like. A monophosphoric acid ester is a phosphoric acid ester having one phosphorus atom in the molecule. Examples of monophosphates 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, and tributoxyethyl phosphate. Aromatic ring-containing phosphate esters such as trialkoxy phosphate, tricresyl phosphate, tricylenyl phosphate, tris(isopropylphenyl) phosphate, cresyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, monoisodecyl phosphate, diisodecyl Examples include acidic phosphoric acid esters such as phosphate. In addition to the above-mentioned phosphoric acid ester compounds, phosphorous acid esters and the like may also be used.
Examples of the phosphite include triphenyl phosphite, tricresyl phosphite, trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and the like.

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

Among the above-mentioned phosphoric acid ester compounds, trialkyl phosphates are preferred from the viewpoint of easily suppressing boiling up during stirring. Particularly preferred is at least one phosphoric acid ester compound selected from trimethyl phosphate and triethyl phosphate.
Further, the phosphoric ester compound is preferably a phosphoric ester compound that does not contain chlorine in its structure, from the viewpoint of easily suppressing boiling up during stirring and from the viewpoint of reducing environmental load.

When the compatibilizing agent contains a phosphoric ester compound, the content of the phosphoric ester compound based on the total amount of the compatibilizing agent is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass or more. 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, α-acetolactone, β-propion lactone, Examples include cyclic ester compounds such as γ-butyrolactone and δ-valerolactone, among which ethyl acetate, ethylene glycol acetate, and γ-butyrolactone are 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 Preferably it is 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, still more preferably 5 parts by mass or more, and preferably is 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less. When the content of the compatibilizing agent is at least the lower limit, boiling up during stirring can be easily suppressed, and when the content is at most the upper limit, the decrease in mechanical strength of the polyurethane foam can be suppressed.

<Polyol>
The polyol composition of the present invention contains a polyol as a raw material for polyurethane foam.
Polyols used in the present invention include, but are not particularly limited to, polylactone polyols, polycarbonate polyols, polyester polyols, polyether polyols, polymer polyols, and the like.

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

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

As the polyether polyol, for example, at least one alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran is ring-opened in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens. Examples include polymers obtained by polymerization. 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, and triols such as glycerin and trimethylolpropane. , ethylene diamine, and butylene diamine.

Examples of polymer polyols include polymers obtained by graft polymerizing ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate to aromatic polyols, alicyclic polyols, aliphatic polyols, and polyester polyols. , polybutadiene polyol, modified polyol of polyhydric alcohol, or hydrogenated products thereof.
Examples of aromatic polyols used in the production of polymer polyols include bisphenol A, bisphenol F, phenol novolak, and cresol novolak.
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 polyhydric alcohols as raw materials with alkylene oxide to modify them.
Examples of polyhydric alcohols include trihydric alcohols such as glycerin and trimethylolpropane, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl glucoside, and Tetra- to octavalent alcohols such as derivatives thereof, phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4 , 5,8-tetrahydroxyanthracene, etc., castor oil polyol, (co)polymer of hydroxyalkyl (meth)acrylate, polyfunctional (for example, functional group number 2 to 100) polyol such as polyvinyl alcohol, condensation of phenol and formaldehyde. (novolak).

The method for modifying the polyhydric alcohol is not particularly limited, but a method of adding alkylene oxide (hereinafter also referred to as "AO") is preferably used. Examples of AO include AO 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-propyleoxide, Examples include 1,2-butylene oxide and 1,4-butylene oxide.
Among these, from the viewpoint of properties and reactivity, PO, EO and 1,2-butylene oxide are preferred, and PO and EO are more preferred. When two or more types of AO are used (for example, PO and EO), the addition method may be block addition, random addition, or a combination of these.

The polyol used in the present invention is preferably at least one selected from the group consisting of polyester polyols and polyether polyols. Moreover, a polyol having two hydroxyl groups is preferable. Among these, aromatic polyester polyols, which are polyester polyols having an aromatic ring, are preferred from the viewpoint of improving flame retardancy. Aromatic polyester polyols include polybasic acids having an aromatic ring such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), bisphenol A, ethylene glycol, and 1,2-propylene glycol. More preferred is one obtained by dehydration condensation with a dihydric alcohol.

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 preferably 20,000 or less, more preferably 10,000 or less.
The weight average molecular weight is a polystyrene equivalent weight average molecular weight 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, even more preferably 120 to 210 mgKOH/g. When the hydroxyl value of the polyol is less than or equal to the above upper limit, boiling of the polyol composition during stirring can be easily suppressed, and the viscosity of the polyol composition can be easily lowered, which is preferable from the viewpoint of ease of handling. On the other hand, when the hydroxyl value of the polyol is greater than or equal to the lower limit, the crosslinking density of the polyurethane foam increases, thereby increasing the strength.
Note that the hydroxyl value of the polyol can be measured according to JIS K 1557-1:2007.

The content of polyol in the polyol composition of the present invention is preferably 20 to 90% by weight, more preferably 25 to 80% by weight, and still more preferably 30 to 70% by weight. It is preferable that the content of the polyol is equal to or higher than the lower limit because it facilitates the reaction between the polyol and the polyisocyanate. On the other hand, when the polyol content is below the above upper limit, the viscosity of the polyol composition does not become too high, which is preferable from the viewpoint of handleability.

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

The blowing agent preferably includes a blowing agent having a boiling point of 40° C. or lower (hereinafter also referred to as a low-boiling point blowing agent) from the viewpoint of improving foamability when forming a polyurethane foam. Furthermore, it is more preferable that the boiling point of the low boiling point blowing agent is 20°C or less. The boiling point means the boiling point at 1 atmosphere.
Note that when the polyol composition contains such a low boiling point blowing agent, boiling is likely to occur due to stirring, but when it contains a specific compatibilizer as in the present invention, , it is possible to suppress boiling.
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 still more preferably 100% by mass, based on the total amount of the blowing agent.

The blowing agent is not particularly limited, but preferably includes a fluorocarbon blowing agent such as a fluorine compound, hydrochlorofluorocarbon, hydrofluorocarbon, or hydrofluoroolefin. Among these, it is more preferable that the blowing agent contains hydrofluoroolefins, and it is even more preferable that the blowing agent contains only hydrofluoroolefins, because the blowing agent has high stability, does not easily reduce catalyst activity, and has a low environmental impact. preferable.

Examples of the hydrofluoroolefins include fluoroalkenes having about 3 to 6 carbon atoms. The hydrofluoroolefin may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having about 3 to 6 carbon atoms.
More specifically, trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorotrifluoropropene such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetra Examples include fluoropropene. 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.

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

The amount of the blowing agent to be blended is preferably 10 to 80 parts by weight, more preferably 15 to 70 parts by weight, and even more preferably 20 to 60 parts by weight, based on 100 parts by weight of the polyol. When the amount of the blowing agent is at least the lower limit, foaming is promoted, the foamability becomes good, and the density of the resulting polyurethane foam can be reduced. On the other hand, if the amount of the foaming agent is less than or equal to the upper limit, excessive foaming can be prevented.

<Filler>
The polyol composition of the present invention contains a filler. By containing a filler, properties depending on the type of filler can be imparted to the polyurethane foam, such as improving flame retardancy and mechanical strength, or adding color. Examples of fillers include flame retardants and inorganic fillers other than flame retardants.

≪Flame retardant≫
The polyol composition of the present invention may contain a flame retardant. By containing a flame retardant, the flame retardancy of the polyurethane foam to be formed can be effectively increased. Examples of flame retardants include red phosphorus 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. It will be done.

(Red phosphorus flame retardant)
The red phosphorus flame retardant may be made of red phosphorus alone, or may be made by coating red phosphorus with a resin, metal hydroxide, metal oxide, etc., or by coating red phosphorus with a resin, metal hydroxide, metal oxide, etc. A mixture of oxides or the like may also be used. Examples of resins coated with red phosphorus or mixed with red phosphorus include, but are not limited to, thermosetting resins such as phenol resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. It will be done. From the viewpoint of flame retardancy, metal hydroxides are preferred as the coating or compound to be mixed. As the metal hydroxide, those described below may be appropriately selected and used.

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

Specific examples of phosphate-containing flame retardants include monophosphates, polyphosphates, and the like. Monophosphates are not particularly limited, but include, for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and ammonium hydrogen phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, and phosphorous acid. Sodium salts such as monosodium, disodium phosphite, sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, hypophosphorous acid Potassium salts such as potassium, monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, lithium hypophosphite, etc., barium dihydrogen phosphate, phosphorus Barium salts such as barium oxyhydrogen, tribarium phosphate, barium hypophosphite, magnesium salts such as monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium hypophosphite, calcium dihydrogen phosphate , calcium salts such as 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 includes, for example, ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, and the like.
The phosphate-containing flame retardants may be used singly or in combination of two or more of the above-mentioned flame retardants.

(bromine-containing flame retardant)
The bromine-containing flame retardant is not particularly limited as long as it is a compound that contains bromine in its molecular structure and becomes solid at normal temperature and pressure, and examples thereof include aromatic compounds containing brominated aromatic rings.
Brominated aromatic ring-containing aromatic compounds include hexabromobenzene, pentabromotoluene, hexabromo biphenyl, decabromo biphenyl, decabromodiphenyl ether,
Examples include monomeric organic bromine compounds such as octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

Further, the brominated aromatic ring-containing aromatic compound may be a bromine compound polymer. Specifically, polycarbonate oligomers produced using brominated bisphenol A as a raw material, brominated polycarbonates such as copolymers of this polycarbonate oligomer and bisphenol A, and diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin. Examples include. Furthermore, brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, poly(brominated benzyl acrylate), brominated phenols of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, etc. Brominated polystyrene such as condensation products, brominated (polystyrene), poly(brominated styrene), crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly(
-methylstyrene), etc.
Moreover, 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 retardant)
Examples of chlorine-containing flame retardants include those commonly used in flame-retardant resin compositions, such as polychlorinated naphthalene, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclo, which is sold under the trade name "Dechlorane Plus." Examples include octene.

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

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

≪Inorganic filler≫
The polyol composition of the present invention may contain inorganic fillers other than the flame retardant described above, as long as the effects of the present invention are not impaired.
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, hydrotal. site,
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 fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber , alumina fiber,
Examples include silica fibers and zirconia fibers. The inorganic filler is a solid component that becomes solid at normal temperature and pressure.
The inorganic fillers may be used alone or in combination of two or more.

The content of the filler in the polyol composition is not particularly limited, but is preferably 1 to 150 parts by weight, more preferably 10 to 120 parts by weight, and even more preferably 30 to 80 parts by weight, based on 100 parts by weight of the polyol. .

<Catalyst>
The polyol composition of the present invention preferably contains a catalyst from the viewpoint of promoting the reaction between the polyol and polyisocyanate, and from the viewpoint of improving the flame retardance of the polyurethane foam to be formed. 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 causes the isocyanate groups contained in the polyisocyanate described below to react and trimerize, thereby promoting the production of isocyanurate rings. Trimerization catalysts 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 carboxylates such as potassium acetate, potassium 2-ethylhexanoate, potassium octylate, tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt, tetramethylammonium salt, tetraethylammonium, tetra Quaternary ammonium salts such as phenylammonium salts and triethylmonomethylammonium salts can be used. Examples of ammonium salts 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 embodiments in which both of these are used are also preferred.

The amount of the trimerization catalyst to be blended is preferably 0.1 to 25 parts by weight, more preferably 0.3 to 20 parts by weight, and even more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the polyol. If the amount of the trimerization catalyst is equal to or higher than these lower limits, trimerization of the polyisocyanate will easily occur, and the flame retardance of the resulting polyurethane foam will improve. On the other hand, when the amount of the trimerization catalyst is below the upper limit, the reaction can be easily controlled.

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

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

The amount of the urethanization catalyst is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 15 parts by weight, and even more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyol. When the amount of the resin-forming catalyst is equal to or higher than these lower limits, urethane bonds are likely to be formed and the reaction will proceed rapidly. On the other hand, when it is below these upper limits, the reaction rate becomes easier to control.

Further, the total amount of catalyst in the polyol composition is not particularly limited, but is preferably 0.2 to 30 parts by weight, more preferably 0.6 to 20 parts by weight, and even more preferably 1 to 10 parts by weight. When it is above these lower limits, formation of urethane bonds and trimerization proceed appropriately, and flame retardancy tends to be good. Moreover, when the content is below these upper limit values, the urethanization and trimerization reactions can be easily controlled.

<Foam stabilizer>
The polyol composition of the present invention may contain a foam stabilizer. A foam stabilizer improves the foamability of a foamable polyurethane composition containing a polyol composition and a polyisocyanate.
Examples of the foam stabilizer include surfactants such as polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ether, and silicone foam stabilizers such as organopolysiloxane. 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 weight, more preferably 0.5 to 8 parts by weight, and even more preferably 1 to 5 parts by weight, based on 100 parts by weight of the polyol compound. When the amount of the foam stabilizer is equal to or higher than these lower limits, it becomes easier to foam the polyurethane composition, and it becomes easier to obtain a homogeneous polyurethane foam. Moreover, when the amount of the foam stabilizer is below these upper limits, the balance between manufacturing cost and the effect obtained will be good.

<Other ingredients>
The polyol composition may contain antioxidants such as phenol-based, amine-based, and sulfur-based antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, and crosslinking agents, as necessary, within a range that does not impair the purpose of the present invention. It can contain one or more selected from agents, lubricants, softeners, pigments, and the like.

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

[Expansible 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 made of a foamable polyurethane composition, and specifically is a reaction product obtained by reacting and foaming a foamable polyurethane composition.

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

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

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

Among these, from the viewpoint of ease of use and availability, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred. One type of polyisocyanate may be used alone, or two or more types may be used in combination.
In addition, known additives that are blended into polyisocyanate may be appropriately blended with the polyisocyanate before mixing 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. When the isocyanate index is greater than or equal to the lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, and isocyanurate bonds due to trimerization of polyisocyanate are likely to be formed, resulting in improved flame retardancy of the polyurethane foam. Furthermore, when the above lower limit value is exceeded, the combination of using the various catalysts mentioned above also makes it possible to produce a polyurethane foam that has sufficient isocyanurate bonds, that is, a polyurethane foam that has both flame retardancy and heat insulation properties at a high level. Easy to manufacture. From these viewpoints, the isocyanate index is more preferably 150 or more, further preferably 200 or more, and even more preferably 250 or more.
Moreover, the isocyanate index is preferably 800 or less, more preferably 600 or less, and even more preferably 400 or less. When the isocyanate index is less than or equal to the above upper limit, the resulting polyurethane foam has a good balance between flame retardancy and manufacturing cost.

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

<Production method of polyurethane foam>
Although there are no particular limitations on the method for producing polyurethane foam, it is preferable to foam and react a foamable polyurethane composition obtained by mixing a polyisocyanate and a polyol composition. Specifically, it is preferable to impact-mix the polyisocyanate and the polyol composition using a spray gun or the like, and then spray the mixture.
Further, in the present invention, a polyurethane foam may be obtained by mixing a polyisocyanate and a polyol composition, and then injecting the mixture into a container such as a mold or a frame material 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 for building walls, ceilings, roofs, floors, etc. of buildings. It can also be suitably used as a member to fill any openings that occur in buildings, including joints and holes that occur between structural members of buildings.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[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 was put into a 110 mL screw tube (manufactured by Maruem Co., Ltd., product name: No. 8), and the sealing tape (polytetrafluorocarbon After winding the container with a stirrer (made of ethylene), a stirrer (diameter 14 mm) was put in and the lid was closed. Thereafter, the screw tube into which the polyol composition was introduced was placed in a 29°C water bath for 30 minutes or more to keep the temperature constant, and then the cap was opened and stirred using a magnetic stirrer at 1,500 rpm. . 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 highest point of the liquid (polyol composition). (object) means the height to the surface.
(judgement)
◎... Boiling height is 10 mm or less 〇... Boiling height is over 10 mm and 20 mm or less ×... Boiling height is over 20 mm

Tables 1 to 3 show the polyols, fillers, blowing agents, compatibilizers, urethanization catalysts, and foam stabilizers used in each Example and Comparative Example.

[Examples 1 to 16, Comparative Examples 1 to 3]
A polyol, a filler, a blowing agent, a compatibilizer, a urethanization catalyst, and a foam stabilizer were mixed in the amounts shown in Table 4 to obtain a polyol composition, and the boiling height was evaluated 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 contains a polyol, a filler, a blowing agent, and a compatibilizer, and has an Ra ² represented by formula (1) of 200 J/cm ³ or less. It was found that the boiling height during stirring was low and that it was excellent in operability and safety. On the other hand, as shown in Comparative Examples 1 to 3, when a compatibilizer is not used, or even when a compatibilizer is used, polyol compositions with Ra ² exceeding 200 J/cm ³ have a boiling point of 200 J/cm 3 during stirring. It was found that the operating conditions were high, and the operability and safety were poor.

Claims (7)

A polyol composition containing a polyol, a filler, a blowing agent, and a compatibilizer, and having an Ra ² represented by the following formula (1) of 200 J/cm ³ or less.
<Formula (1)>
Ra ² =4×(dD1-dD2) ² +(dP1-dP2) ² +(dH1-dH2) ²
dD, dP, and dH in Equation (1) represent the dispersion term, polarization term, and hydrogen bond term in the Hansen solubility parameter (HSP), respectively, as shown below.
dD1 [(J/cm ³ ) ^1/2 ]: Dispersion term in HSP of blowing agent dD2 [(J/cm ³ ) ^1/2 ]: Dispersion term in HSP of 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 ]: Polarization term in the HSP of the blowing agent Hydrogen bond term dH2 [(J/cm ³ ) ^1/2 ]: Hydrogen bond term in HSP of compatibilizer The polyol composition according to claim 1, wherein the blowing agent has a boiling point of 40°C or less. The polyol composition according to claim 1 or 2, wherein the blowing agent contains a fluorocarbon blowing agent. The polyol composition according to any one of claims 1 to 3, wherein the compatibilizer comprises a phosphate ester compound. The polyol composition according to claim 4, wherein the phosphoric acid ester compound is chlorine-free. A foamable polyurethane composition comprising the polyol composition according to any one of claims 1 to 5 and a polyisocyanate. A polyurethane foam comprising the expandable polyurethane composition according to claim 6.