JP2024023087A - Polyol composition, polyurethane composition, and polyurethane foam - Google Patents

Abstract

To provide a polyol composition for aerosol with superior incombustibility.SOLUTION: A polyol composition includes a polyol compound, red phosphorus, and a gas component with a boiling point of 10°C or lower.SELECTED DRAWING: None

Description

The present invention relates to a polyol composition, a polyurethane composition comprising the polyol composition and a polyisocyanate composition, and a polyurethane foam formed from the polyurethane composition.

Conventionally, polyurethane foam has been used as a heat insulating material in vehicles such as automobiles, railroad cars, and ships, and in buildings. Two-component polyurethane, in which a polyol composition and a polyisocyanate composition filled in separate containers are mixed to form a foam, is widely used as a polyurethane foam.
Two-component polyurethane is sometimes used in aerosol containers, such as those disclosed in Patent Documents 1 to 5, in which each liquid can be discharged from the container and mixed with a relatively simple configuration. When a two-component polyurethane is used in an aerosol container, one container is filled with a polyol compound and a low boiling point compound, and the other container is filled with a polyisocyanate compound and a low boiling point compound. A polyol liquid agent and a polyisocyanate liquid agent are respectively discharged from each container by the vapor pressure of the low-boiling point compound, and are mixed to form a polyurethane foam.
Polyol compositions used in such aerosol containers are often suitably used as polyol compositions for aerosols to replenish defects that occur during construction of polyurethane foams.

International Publication No. 2020/067139 JP 2021-155506 Publication International Publication No. 2021/193871 International Publication No. 2021/193872 International Publication No. 2012/034492

However, while conventional polyol compositions for aerosols have excellent discharge properties, the polyurethane foam formed from the compositions has insufficient nonflammability and is easily flammable. For this reason, polyol compositions for aerosols are required to have performance that improves the nonflammability of polyurethane foams.
Therefore, an object of the present invention is to provide an aerosol polyol composition that can form a polyurethane foam with excellent nonflammability.

As a result of extensive studies, the present inventors have found that the above problem can be solved by having the following configuration, and have completed the present invention.
The present invention provides the following [1] to [8].
[1] A polyol composition for aerosol containing a polyol compound, a red phosphorus flame retardant, and a low boiling point compound having a boiling point of 10°C or less.
[2] The polyol composition for aerosol according to [1], which contains HFO as the low-boiling compound.
[3] The polyol composition for aerosol according to [1] or [2], further comprising a catalyst having a morpholine skeleton.
[4] The polyol composition for aerosol according to any one of [1] to [3], further comprising a phosphoric acid ester.
[5] The polyol composition for aerosol according to any one of [1] to [4], further comprising a flame retardant other than a red phosphorus flame retardant and a phosphoric acid ester.
[6] An aerosol container filled with the polyol composition for aerosol according to any one of [1] to [5].
[7] A polyurethane composition comprising the aerosol polyol composition according to any one of [1] to [5] and a polyisocyanate composition containing a polyisocyanate compound.
[8] A polyurethane foam formed from the polyurethane composition according to [7].

According to the present invention, it is possible to provide an aerosol polyol composition that can form a polyurethane foam with excellent nonflammability.

FIG. 1 is a schematic diagram illustrating one embodiment of a mixing system. FIG. 3 is a schematic diagram showing another embodiment of a mixing system.

[Polyol composition]
The polyol composition of the present invention is a polyol composition for aerosol, and contains a polyol compound, a red phosphorus flame retardant, and a low boiling point compound having a boiling point of 10° C. or less. The polyol composition of the present invention is mixed with a polyisocyanate composition containing a polyisonate compound to produce a polyurethane foam, as described below.
This will be explained in more detail below.

<Red phosphorus flame retardant>
The polyol composition of the present invention contains a red phosphorus flame retardant. Red phosphorus flame retardants are included as fillers in polyol compositions. The filler is contained as a solid flame retardant in the polyol composition, and is a component generally present in the polyol composition in the form of granules or powder. In the present invention, by including a red phosphorus flame retardant as a filler, the nonflammability of a polyurethane foam formed by spraying from a container such as an aerosol container can be improved.

The red phosphorus-based flame retardant may be composed of red phosphorus alone, or may be composed of red phosphorus coated with a resin, metal hydroxide, metal oxide, etc., or red phosphorus coated with a resin, metal hydroxide, metal oxide, etc. A mixture of oxides or the like may also be used. The resin coated with red phosphorus or mixed with red phosphorus is not particularly limited, but thermosetting resins such as phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin can be used. Can be mentioned. The compound to be coated or mixed is preferably a metal hydroxide from the viewpoint of nonflammability. As the metal hydroxide, those described below may be appropriately selected and used.

The content of the red phosphorus flame retardant in the polyol composition is preferably 1 to 70 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, based on 100 parts by mass of the polyol compound. 15 to 35 parts by mass is even more preferred. When the content of the red phosphorus flame retardant is at least the above lower limit, it is possible to impart good nonflammability to the polyurethane foam. Further, by setting the amount to be equal to or less than the above upper limit value, handling properties when discharging the polyol composition are improved.

<Phosphoric acid ester>
It is preferable that the polyol composition in the present invention contains a phosphoric acid ester.
Phosphate ester functions as a flame retardant, and when used in combination with a red phosphorus flame retardant, it becomes easy to improve the nonflammability of the polyurethane foam without substantially reducing the discharge flow rate, mixability, etc. Phosphate esters are generally liquid flame retardants. Note that a liquid flame retardant is a flame retardant that becomes a liquid at normal temperature (23° C.) and normal pressure (1 atmosphere).

As the phosphoric acid ester, monophosphoric acid ester, condensed phosphoric acid ester, etc. can be used. A monophosphoric acid ester is a phosphoric acid ester having one phosphorus atom in the molecule. Examples of monophosphate esters include, but are not limited to, trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl) phosphate, and 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, tricylenyl phosphate, tris (isopropylphenyl) phosphate, cresyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, mono Examples include acidic phosphoric acid esters such as isodecyl phosphate and diisodecyl phosphate.

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.
Commercial products of condensed phosphate esters include, for example, "CR-733S", "CR-741", and "CR747" manufactured by Daihachi Kagaku Kogyo Co., Ltd., and "ADEK STAB PFR" and "FP-600" manufactured by ADEKA. etc.

The phosphoric acid esters listed above may be used alone or in combination of two or more. Among these, monophosphoric acid esters are preferable from the viewpoint of easily adjusting the viscosity of the polyol compound and improving the nonflammability of the polyurethane foam, and halogen-containing phosphoric acid esters such as tris(β-chloropropyl) phosphate are preferable. More preferred.

When the polyol composition contains a phosphoric ester, the content of the phosphoric ester is preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight, and 20 to 70 parts by weight, based on 100 parts by weight of the polyol compound. is more preferred, and 35 to 65 parts by mass is even more preferred. By setting the content of the phosphoric ester to be equal to or higher than these lower limits, the effect of containing the phosphoric ester can be easily exhibited. Furthermore, by setting the amount to be below the upper limit, the foaming of the polyurethane foam will not be inhibited by the phosphoric acid ester.

<Other flame retardants>
The present invention may contain flame retardants other than red phosphorus flame retardants and phosphoric acid esters (hereinafter also referred to as "other flame retardants"). Such flame retardants are preferably solid flame retardants, and specifically include phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, chlorine-containing flame retardants, metal hydroxides, Examples include acicular fillers. These solid flame retardants may be used alone or in combination of two or more. Note that the solid flame retardant is a flame retardant that becomes solid at normal temperature (23° C.) and normal pressure (1 atm), and is included as a filler like the red phosphorus flame retardant.

(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 one type of metal or compound. Note that the term "various phosphoric acids" is a concept that includes not only phosphoric acid but also phosphorous acid, hypophosphorous 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 aliphatic amines 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 contains bromine in its molecular structure and is solid at room temperature (23°C) and normal pressure (1 atm), but for example, brominated aromatic ring-containing aromatic Examples include compounds.
Brominated aromatic ring-containing aromatic compounds include hexabromobenzene, pentabromotoluene, hexabromo biphenyl, decabromo biphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene bis( Examples include monomeric organic bromine compounds such as 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. etc. Furthermore, brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, brominated phenol condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, uncrosslinked or crosslinked Examples include brominated polystyrene.
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.

(Boron-containing flame retardant)
Examples of the boron-containing flame retardant used in the present invention 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 borates of alkali metals, alkaline earth metals, elements of Group 4, Group 12, and Group 13 of the periodic table, 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.
One type of boron-containing flame retardant may be used alone, or two or more types may be used in combination.
The boron-containing flame retardant used in the present invention is preferably a borate, more preferably zinc borate.

(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.
The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

(Chlorine-containing flame retardant)
Examples of chlorine-containing flame retardants include those commonly used in polyurethane foams, such as polychlorinated naphthalene, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene sold under the trade name "Dechlorane Plus". Can be mentioned.

(metal hydroxide)
Examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, Examples include vanadium hydroxide and tin hydroxide. The metal hydroxides may be used alone or in combination of two or more. As the metal hydroxide, aluminum hydroxide is preferred.

(acicular filler)
Examples of acicular fillers include potassium titanate whiskers, aluminum borate whiskers, magnesium-containing whiskers, silicon-containing whiskers, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fibers, carbon fibers, and graphite fibers. , metal fibers, slag fibers, gypsum fibers, silica fibers, alumina fibers, silica alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, stainless steel fibers, and the like. The use of acicular fillers can effectively improve the mechanical properties of polyurethane foams.
These acicular fillers can be used alone or in combination of two or more.
The aspect ratio (length/diameter) of the acicular filler used in the present invention is preferably in the range of 5 to 50, more preferably in the range of 10 to 40. Note that the aspect ratio can be determined by observing the acicular filler with a scanning electron microscope and measuring its length and width.

When the polyol composition contains other flame retardants, the total content of the other flame retardants in the polyol composition is preferably 5 to 80 parts by mass, and 10 to 70 parts by mass, based on 100 parts by mass of the polyol compound. It is more preferably 15 to 60 parts by weight, even more preferably 35 to 50 parts by weight. When the total content of other flame retardants is at least the above lower limit, good nonflammability can be easily imparted to the polyurethane foam. Further, by setting the amount to be equal to or less than the above upper limit value, handling properties when discharging the polyol composition are improved.

Moreover, the polyol composition may contain fillers other than the solid flame retardant described above, and examples of such fillers include anti-settling agents.
By using an anti-settling agent, it is possible to prevent the solid flame retardant etc. dispersed in the polyol composition from settling, making it easier to discharge the solid flame retardant etc., making it easier to form a highly nonflammable polyurethane foam. Furthermore, the use of an anti-settling agent makes it easier to uniformly disperse fillers such as red phosphorus flame retardants.

The anti-settling agent is not particularly limited, but for example, it is preferable to use one or more selected from carbon black, powdered silica, organic clay, etc. Among these, powdered silica is more preferable. .
The carbon black used in the antisettling agent can be produced by a furnace method, a channel method, a thermal method, or the like. As carbon black, a commercially available product may be appropriately selected and used.
Further, as the powdered silica, fumed silica, colloidal silica, silica gel, etc. can be used. Among these, fumed silica is preferred. As the fumed silica, Aerosil (registered trademark) manufactured by Nippon Aerosil Co., Ltd., etc. can be used.

The content of the antisettling agent in the polyol composition is preferably 1 to 60 parts by weight, more preferably 3 to 50 parts by weight, even more preferably 10 to 40 parts by weight, and even more preferably 15 to 40 parts by weight, based on 100 parts by weight of the polyol compound. 35 parts by mass is even more preferred. When the content of the antisettling agent is at least the above lower limit, fillers such as red phosphorus flame retardants are prevented from precipitating within the polyol composition, and the dischargeability of the polyol composition is improved. Moreover, since the viscosity of a polyol composition does not become it high that the content of an anti-settling agent is below the said upper limit excessively, it becomes easy to improve discharge property.

The polyol composition may contain fillers other than solid flame retardants and anti-settling agents, for example, may contain inorganic fillers other than those mentioned above. Inorganic fillers include alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, sulfuric acid. Calcium, barium sulfate, calcium silicate, talc, mica, montmorillonite, bentonite, activated clay, imogolite, sericite, glass beads, aluminum nitride, boron nitride, silicon nitride, various metal powders, magnesium sulfate, lead zirconate titanate, Molybdenum sulfide, silicon carbide, various magnetic powders, fly ash, etc. can be used as appropriate. These inorganic fillers may be used alone or in combination of two or more.

The total content of fillers in the polyol composition is preferably 20 to 150 parts by weight, more preferably 25 to 130 parts by weight, and even more preferably 30 to 120 parts by weight, based on 100 parts by weight of the polyol compound. When the content of the filler is at least the above lower limit, it is possible to impart good nonflammability and good mechanical properties to the polyurethane foam. On the other hand, when the content of the filler is below the above upper limit, the handling properties when discharging the polyol composition are improved.

<Low boiling point compound>
The polyol composition of the present invention includes a low boiling point compound. The low boiling point compound causes the polyol composition to be discharged from the aerosol container due to its vapor pressure, and is vaporized when the polyol composition is discharged, thereby foaming the polyol composition and the polyurethane composition described below. The low boiling point compound has a boiling point at 1 atm (hereinafter also simply referred to as "boiling point") of 10° C. or lower, from the viewpoint of increasing the discharge amount of the polyol composition. If the boiling point of the low-boiling point compound exceeds 10°C, for example, when the polyol composition is filled into an aerosol container, the vapor pressure inside the container cannot be sufficiently increased, and the composition cannot be sufficiently discharged. It becomes difficult. From the viewpoint of such dischargeability, the low boiling point compound preferably has a boiling point of 0°C or lower, more preferably -10°C or lower, and even more preferably -15°C or lower. Here, the boiling point of the low-boiling compound means the boiling point of the low-boiling compound alone, and does not mean the azeotropic boiling point of the low-boiling compound, for example, when the low-boiling compound azeotropes with another compound.

The type of low boiling point compound is not particularly limited as long as the polyol composition can be discharged by its vapor pressure, and examples include hydrofluorocarbons (HFC), hydrochlorofluorocarbons (HCFC), hydrofluoroolefins (HFO), and hydrocarbons. , ether compounds, inorganic gases, etc. can be used. Among these, hydrofluoroolefins (HFO), hydrocarbons, ether compounds, inorganic gases, etc. can be suitably used from the viewpoint of reducing environmental impact and improving discharge performance and mixing properties. Among these, it is preferable to include hydrofluoroolefin (HFO) as a low boiling point compound. HFO may be used alone as a low boiling point compound, or may be used in combination with a low boiling point compound other than HFO such as an inorganic gas. In the polyol composition, the content of HFO among the low-boiling compounds is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass.

As mentioned above, the low boiling point compound HFO preferably has a boiling point of 0°C or lower, more preferably -10°C or lower, and even more preferably -15°C or lower. Further, the boiling point of HFO is not particularly limited, but from the viewpoint of handling, storage, etc., it is preferably -50°C or higher, more preferably -35°C or higher, and even more preferably -25°C or higher.
Examples of the low boiling point compound HFO include 1,1,3,3-tetrafluoropropene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), and 1,3,3,3-tetrafluoropropene. Fluoropropene (HFO-1234ze), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 2,3, Examples include 3,3-tetrafluoropropene (HFO-1234yf). HFO may be a compound consisting of hydrogen, fluorine, and carbon, but may also be a hydrochlorofluoroolefin further containing chlorine.
Among the above-mentioned HFOs, 1,3,3,3-tetrafluoropropene (HFO-1234ze) is preferable from the viewpoint of improving ejection properties. Generally, HFO, such as HFO-1234ze, tends to react with a catalyst such as a resinization catalyst and may deactivate the resinization catalyst, but in the present invention, as described later, morpholine is used as a resinization catalyst. When a catalyst having a skeleton is used, deactivation of the resinization catalyst can be prevented.

Examples of hydrocarbons include hydrocarbons having 1 to 4 carbon atoms, such as various butanes such as ethane, propane, isobutane, and normal butane. Further, as the hydrocarbon having 1 to 4 carbon atoms, for example, LPG (liquefied petroleum gas) whose main components are propane and butanes can be cited as a preferable example.
Examples of the ether compound include dimethyl ether.
Examples of the inorganic gas include nitrogen, carbon dioxide, and argon gas, and among these, nitrogen is preferred.

The content of the low boiling point compound in the polyol composition is preferably 10 to 120 parts by mass, more preferably 20 to 100 parts by mass, and even more preferably 30 to 70 parts by mass, based on 100 parts by mass of the polyol compound. It is. When the content of the low-boiling compound in the polyol composition is equal to or higher than the above lower limit, the vapor pressure in the aerosol container becomes equal to or higher than a certain level, and the dischargeability of the polyol composition can be improved. Moreover, when the content of the low boiling point compound in the polyol composition is below the above upper limit, the vapor pressure in the aerosol container becomes appropriate, and handling properties, storage properties, etc. are improved.

<Polyol compound>
The polyol composition of the present invention contains a polyol compound that is a raw material for polyurethane foam. Examples of the polyol compound include polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polymer polyol, and polyether polyol. A polyol compound usually becomes a liquid at normal temperature (23° C.) and normal pressure (1 atmosphere).

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 aromatic polyols include bisphenol A, bisphenol F, phenol novolak, and cresol novolak.
Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.
Examples of aliphatic polyols include alkanediols such as ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

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.

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 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 derivatives thereof. Tetra- to octahydric alcohols such as phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8 - Polyols such as tetrahydroxyanthracene, castor oil polyols, (co)polymers of hydroxyalkyl (meth)acrylates, polyfunctional (e.g. functional groups 2 to 100) polyols such as polyvinyl alcohol, condensates of phenol and formaldehyde (novolak) can be mentioned.

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.

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

As the polyol compound used in the present invention, polyester polyols and polyether polyols are preferred. Among them, polybasic acids having an aromatic ring such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), and dihydric alcohols such as bisphenol A, ethylene glycol, and 1,2-propylene glycol. More preferred is an aromatic polyester polyol obtained by dehydration condensation. Moreover, a polyol having two hydroxyl groups is preferable.

The hydroxyl value of the polyol compound is preferably 20 to 300 mgKOH/g, more preferably 30 to 250 mgKOH/g, even more preferably 50 to 220 mgKOH/g. When the hydroxyl value of the polyol compound is below the upper limit, the viscosity of the polyol composition tends to decrease, which is preferable from the viewpoint of ease of handling. On the other hand, when the hydroxyl value of the polyol compound is equal to or higher than the lower limit, the crosslinking density of the polyurethane foam increases, thereby increasing the strength.
Note that the hydroxyl value of the polyol compound can be measured according to JIS K 1557-1:2007.

The content of the polyol compound in the polyol composition of the present invention is preferably 10 to 70% by weight, more preferably 15 to 60% by weight, and still more preferably 20 to 50% by weight. It is preferable that the content of the polyol compound is equal to or higher than the lower limit because it becomes easier to react the polyol compound and the polyisocyanate compound. On the other hand, when the content of the polyol compound 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.

<Catalyst>
The polyol composition in the present invention preferably contains a catalyst. The catalyst preferably contains at least one of a trimerization catalyst and a resinization catalyst, and more preferably both a trimerization catalyst and a resinization catalyst.

The trimerization catalyst is a catalyst that causes the isocyanate groups contained in the polyisocyanate compound 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 carboxylic acids are preferred, with quaternary ammonium carboxylic acids being more preferred.

The content of the trimerization catalyst is preferably 1 to 25 parts by weight, more preferably 3 to 18 parts by weight, and even more preferably 5 to 15 parts by weight, based on 100 parts by weight of the polyol compound. When the content of the trimerization catalyst is at least these lower limits, trimerization of the polyisocyanate compound will easily occur, and the nonflammability of the resulting polyurethane foam will improve. On the other hand, when the content of the trimerization catalyst is below the upper limit, the reaction can be easily controlled.

The resinization catalyst is a catalyst that promotes the reaction between a polyol compound and a polyisocyanate compound. Examples of the resinization catalyst include imidazole compounds, catalysts having a morpholine skeleton, and metal catalysts. Among these, it is preferable to use a catalyst having a morpholine skeleton.

Since a catalyst having a morpholine skeleton has low reactivity with a low-boiling compound such as HFO, it can be prevented from being deactivated due to reaction with a low-boiling compound. Therefore, by containing a catalyst having a morpholine skeleton, the polyol composition can form a polyurethane foam with excellent nonflammability even when stored for a long period of time. The catalyst having a morpholine skeleton may be a catalyst having one morpholine skeleton, or a catalyst having two or more morpholine skeletons.
Examples of catalysts having one morpholine skeleton include N-ethylmorpholine and the like.
Examples of the catalyst having two morpholine skeletons include 2,2'-dimorpholino diethyl ether and 1,3-dimorpholino-2-methyl-1,3-butadiene.
Among catalysts having a morpholine skeleton, when a catalyst having two morpholine skeletons is used as a resinization catalyst, deactivation of the catalyst can be more easily prevented. In addition, the reaction between the polyol compound and the polyisocyanate compound can be easily controlled, making it possible to form a polyurethane foam of higher quality and excellent nonflammability. Therefore, the catalyst having a morpholine skeleton is more preferably a catalyst having two morpholine skeletons, and among them, 2,2'-dimorpholino diethyl ether is even more preferable.

The content of the catalyst having a morpholine skeleton in the polyol composition is preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight, and even more preferably 8 to 12 parts by weight, based on 100 parts by weight of the polyol compound. When the content of the catalyst having a morpholine skeleton is equal to or higher than these lower limits, urethane bonds are easily formed and the reaction proceeds rapidly. On the other hand, when it is below these upper limits, the reaction rate becomes easier to control.

Examples of imidazole compounds 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 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. Of these, bismuth-based catalysts are preferred. Specific examples of the metal catalyst include dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatate, bismuth trioctate, bismuth tris (2-ethylhexanoate), tin dioctylate, lead dioctylate, and the like. Among them, bismuth trioctate is preferred.

The resin-forming catalyst may be used alone or in combination of two or more. The polyol composition of the present invention preferably contains a catalyst having a morpholine skeleton and a metal catalyst, more preferably a catalyst having a morpholine skeleton and a bismuth catalyst, and a catalyst having two morpholine skeletons. and a bismuth-based catalyst. By using such a combination of resin-forming catalysts in the polyol composition, it becomes easier to improve the nonflammability of polyurethane while appropriately controlling the reaction between the polyol compound and the polyisocyanate compound.

The content of the metal catalyst in the polyol composition is preferably 0.3 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, and 1.5 to 5 parts by weight based on 100 parts by weight of the polyol compound. is even more preferable. When the content of the metal 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 the content of the metal catalyst is below these upper limits, the reaction rate becomes easier to control.

The content of the resinization catalyst is preferably 1 to 25 parts by weight, more preferably 5 to 20 parts by weight, and even more preferably 8 to 15 parts by weight, based on 100 parts by weight of the polyol compound. When the content of the resin-forming catalyst is equal to or higher than these lower limits, urethane bonds are likely to be formed, and the reaction proceeds rapidly. On the other hand, when it is below these upper limits, the reaction rate becomes easier to control.

When a trimerization catalyst and a resinization catalyst are used together as catalysts, the amount of the resinization catalyst relative to the trimerization catalyst (amount of resinization catalyst/amount of trimerization catalyst) will affect the shrinkage rate of the resulting polyurethane foam. From the viewpoint of making it smaller, it is preferably 0.8 to 3, more preferably 1 to 2.5.

Further, the total amount of catalyst in the polyol composition is not particularly limited, but is preferably 2 to 50 parts by weight, more preferably 8 to 35 parts by weight, even more preferably 10 to 40 parts by weight, even more preferably 12 parts by weight. ~25 parts by mass. When the content is above these lower limits, formation of urethane bonds and trimerization proceed appropriately, and nonflammability 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 polyurethane composition obtained from a polyol composition and a polyisocyanate composition.
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 content 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 content 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 content 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 phenol-based, amine-based, sulfur-based antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, etc., as necessary, within a range that does not impair the purpose of the present invention. Additives such as crosslinking agents, lubricants, softeners, pigments, polybutenes, tackifiers such as petroleum resins, etc. can be included.

[container]
The container of the present invention is a container in which the above-described polyol composition is sealed. The container is an aerosol container capable of discharging the polyol composition using the vapor pressure of the low-boiling compound. An aerosol container, for example, includes a container body filled with a polyol composition and a cap part that seals the top of the container body, and when a button or the like provided on the cap part is pressed, a valve or the like opens and the internal pressure is released. The polyol composition is discharged from the discharge port provided in the cap part due to the vapor pressure of the low boiling point compound.
The method of enclosing the polyol composition in the container is not particularly limited, but after mixing each component other than the low boiling point compound as necessary using a disper or the like, filling the inside of the container and sealing the container, and then Fill with low-boiling compounds. The low-boiling compound can be filled, for example, by opening a valve provided in the cap of the container and injecting the low-boiling compound into the container.

When discharging the polyol composition from the container, the components constituting the polyol composition are discharged in a uniformly mixed state. In order to uniformly mix the components constituting the polyol composition, the container may be sufficiently shaken before discharging. The container can be shaken, for example, by holding the container in your hand and shaking it up and down. The method for uniformly mixing the polyol composition is not limited to the method described above. Further, the temperature of the container at the time of discharging is preferably, for example, 10° C. or more and 40° C. or less. When the temperature is 10° C. or higher, the liquid temperature is high to a certain extent, so discharging is good, and when the temperature is 40° C. or lower, rupture of the container is prevented.

[Polyurethane composition]
The polyurethane composition of the present invention includes a polyol composition and a polyisocyanate composition containing a polyisocyanate compound. That is, the polyol composition of the present invention described above is used as a polyol composition for a two-component polyurethane, and is used as a polyurethane composition by mixing it with a polyisocyanate composition containing a polyisocyanate compound. The polyol composition and the polyisocyanate composition are preferably mixed at a mass ratio such that the isocyanate index falls within a predetermined range, as described below.
The polyurethane composition obtained by mixing the polyol composition and the polyisocyanate composition reacts and contains the low boiling point compound contained in the polyol composition described above or the low boiling point compound contained in the polyisocyanate composition described below. It becomes a polyurethane foam by foaming with a boiling point compound.

<Polyisocyanate composition>
As the polyisocyanate compound contained in the polyurethane composition of the present invention, various polyisocyanate compounds having two or more isocyanate groups, such as aromatic, alicyclic, and aliphatic, can be used. Preferably, liquid diphenylmethane diisocyanate (MDI) is used because of its ease of handling, speed of reaction, excellent physical properties of the resulting polyurethane foam, and low cost. Examples of liquid MDI include crude MDI (also referred to as polymeric MDI). Specific commercial products of liquid MDI include "44V-10", "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.), and "Millionate MR-200" (Japan Polyurethane Industries). Alternatively, MDI containing uretonimine (for example, "Millionate MTL" as a commercially available product, manufactured by Nippon Polyurethane Industries) may be used. Alternatively, a polyisopolycyanate compound which has been treated in advance to increase its affinity with a polyol by reacting a part of the isocyanate active groups with a hydroxyl group-containing compound may be used. In addition to liquid MDI, other polyisocyanate compounds may be used in combination, and any polyisocyanate compound known in the technical field of polyurethane can be used without limitation.

The isocyanate index of the polyurethane composition of the present invention is preferably 100 or more, more preferably 150 or more, and even more preferably 2000 or more. When the isocyanate index is equal to or higher than these lower limits, the amount of the polyisocyanate compound relative to the polyol compound becomes excessive, and isocyanurate bonds due to trimerization of polyisocyanate are likely to be formed, thereby improving the nonflammability of the polyurethane foam.
Further, the isocyanate index of the polyurethane composition is preferably 600 or less, more preferably 550 or less, and still more preferably 500 or less. When the isocyanate index is below these upper limits, the resulting polyurethane foam has a good balance between nonflammability and manufacturing cost.
Isocyanate index (INDEX) is calculated by the following method.

INDEX = number of equivalents of polyisocyanate compound ÷ (number of equivalents of polyol compound + number of equivalents of water) x 100
here,
Number of equivalents of polyisocyanate compound = Number of parts of polyisocyanate compound used x NCO content (%) x 100/NCO molecular weight Number of equivalents of polyol compound = OHV x Number of parts of polyol compound used ÷ Molecular weight of KOH, OHV is the hydroxyl value of the polyol ( mgKOH/g),
Number of equivalents of water=number of parts of water used×number of OH groups in water/molecular weight of water. In the above formula, the unit of the number of parts used is weight (g), the molecular weight of the NCO group is 42, and the NCO content is the proportion of NCO groups in the polyisocyanate compound expressed in mass%. For convenience of unit conversion, the molecular weight of KOH is 56,100, the molecular weight of water is 18, and the number of OH groups in water is 2.

As the low-boiling compound contained in the polyisocyanate composition, those mentioned above as the low-boiling compound contained in the polyol composition can be used without particular limitation. Note that the low boiling point compound used in the polyisocyanate composition may be the same as or different from the low boiling point compound used in the polyol composition. As the low boiling point compound contained in the polyisocyanate composition, HFO, hydrocarbons having 1 to 4 carbon atoms, ether compounds, inorganic gases, etc. can be preferably used. Preferably, it contains fluoroolefins (HFO). HFO may be used in combination with a low boiling point compound other than HFO, such as an inorganic gas.

Although HFO may be used alone as a low boiling point compound, it is more preferable to use HFO and an inorganic gas in combination, and even more preferably to use HFO and nitrogen in combination. By including an inorganic gas together with HFO, the discharge amount of the polyisocyanate compound can be increased, so that a polyurethane foam with better nonflammability can be formed.
In the polyisocyanate composition, when HFO and inorganic gas are used together, the content ratio of inorganic gas to HFO is preferably 0.5/10 to 10/10, and preferably 0.7/10 to 5/10. It is more preferably 10, and even more preferably 1/10 to 3/10. When the content ratio of the inorganic gas to HFO is equal to or higher than the above lower limit, the vapor pressure in the container filled with the polyisocyanate composition increases, and the amount of the polyisocyanate compound discharged exceeds a certain level, resulting in excellent nonflammability. It becomes easier to form polyurethane foam. Moreover, when the content ratio of the inorganic gas to HFO is below the above-mentioned upper limit, the discharge amount of the polyisocyanate compound can be appropriately controlled, and a high-quality polyurethane foam can be formed.

The content of the low boiling point compound in the polyisocyanate composition is preferably 0.5 to 10 parts by weight, more preferably 1 to 7 parts by weight, and even more preferably 3 to 5 parts by weight, based on 100 parts by weight of the polyisocyanate compound. When the content of the low boiling point compound is equal to or higher than the above lower limit, the vapor pressure inside the container filled with the polyisocyanate composition increases, and the discharge amount of the polyisocyanate compound exceeds a certain level, resulting in a polyurethane foam with excellent nonflammability. becomes easier to form. Moreover, when the content of the low boiling point compound is below the above upper limit value, the discharge amount of the polyisocyanate compound can be appropriately controlled, and a high-quality polyurethane foam can be formed.

The polyisocyanate composition may appropriately contain additives such as flame retardants, antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, and pigments. .

[Mixing system]
The present invention also provides a mixing system for mixing polyol compositions and polyisocyanate compositions. As shown in FIG. 1, the mixing system 10 includes a first container 11 containing a polyol composition and a second container 12 containing a polyisocyanate composition. Both the first container 11 and the second container 12 are aerosol containers (spray cans).
The polyol composition sealed in the first container 11 is discharged by the vapor pressure of the low boiling point compound contained in the polyol composition. The polyisocyanate composition sealed in the second container 12 is discharged by the vapor pressure of the low boiling point compound contained in the polyisocyanate composition. Note that inside the first container 11, a part of the low boiling point compound is vaporized to form a gas phase. The same applies to the inside of the second container 12.
The polyol composition and polyisocyanate composition discharged from the first and second containers 11 and 12 are mixed while being foamed with a low-boiling point compound, and the polyisocyanate compound and the polyol compound react to form polyurethane. Form a foam.

Mixing system 10 may include a mixer 13 . Discharge ports 11A and 12A of the first and second containers 11 and 12 are connected to a mixer 13 via supply lines 11B and 12B. The polyol composition and polyisocyanate composition discharged from the first and second containers 11 and 12 are supplied to the mixer 13 via supply lines 11B and 12B, respectively, and are mixed in the mixer 13. . The polyol composition and polyisocyanate composition mixed in the mixer 13 are preferably sprayed onto the construction target surface using a sprayer or the like.

The mixer 13 is preferably a static mixer called a static mixer. A static mixer is a mixer without a driving part, and the fluids are mixed by passing through the inside of the tube. An example of a static mixer is one in which a mixer element 13B is arranged inside a tube body 13A, as shown in FIG. 1. Examples of the mixer element 13B include one formed in a spiral shape and one formed with a plurality of baffle plates.
The static mixer may also have the function of an injector, and in that case, as shown in FIG. It is best to spray from Note that although FIG. 1 shows a mode in which the polyol composition and polyisocyanate composition discharged from the first and second containers 11 and 12 are introduced into the mixer, before being introduced into the mixer , a discharge gun, a jig, etc. may be provided.

A mixing system 20 is shown in FIG. 2 as an example embodiment with a dispensing gun before being introduced into a mixer. The mixing system 20 includes a first container 11, a second container 12, supply lines 11B and 12B, a discharge gun 14, and a mixer 13. The first container 11 and the second container 12 are as described above, and contain a polyol composition and a polyisocyanate composition, respectively. A polyol composition and a polyisocyanate composition are fed from the first and second containers to the discharge gun 14 via supply lines 11B and 12B, respectively. The discharge gun 14 is equipped with a lever 14A, and has a liquid feeding ON/OFF mechanism. Specifically, when the lever 14A is pulled, the polyol composition and the polyisocyanate composition are fed to the mixer 13, and when the lever 14A is released, the liquid feeding to the mixer 13 is stopped. By using the mixing system 20 equipped with the discharge gun 14, liquid can be fed as needed, improving workability when forming a polyurethane foam.

In the present invention, the polyurethane foam formed from the polyurethane composition can be used in a variety of applications, but is preferably used as a heat insulating material. Polyurethane foam has a large number of cells and therefore has a heat insulating effect.
Polyurethane foams are particularly preferably used as insulation materials for vehicles or buildings. Examples of vehicles include railway vehicles, automobiles, ships, and aircraft.
Moreover, in the present invention, a polyurethane foam can be formed with a simple structure using an aerosol container. Furthermore, since the foam can be formed using a container, it is particularly suitable when the surface to be constructed is relatively small, for example, when replenishing a place where the polyurethane foam is missing. Therefore, it is preferable to use it, for example, for repair purposes in which existing heat-resistant materials are sprayed to repair locations where they have deteriorated or been damaged. Of course, the present invention is not limited to such a use, and may be used to form a newly installed heat-resistant material.

Hereinafter, the present invention will be explained in more detail using Examples, but the present invention is not limited to these Examples.

[Evaluation method]
In Examples and Comparative Examples, the discharge properties of the polyol composition and the polyisocyanate composition, and the nonflammability of the polyurethane foam were evaluated by the following evaluation methods.

<Dischargeability>
Whether or not the polyol composition from the first aerosol container and the polyisocyanate composition from the second aerosol container could be discharged at 25° C. was visually confirmed, and the dischargeability was evaluated according to the following evaluation criteria.
○: Both the polyol composition and the polyisocyanate composition can be discharged. ×: At least one of the polyol composition or the polyisocyanate composition cannot be discharged.

<Nonflammability>
A cone calorimeter test sample was cut out from the polyurethane foam obtained in each example and comparative example to a size of 10 cm x 10 cm x 5 cm, and was heated for 10 minutes at a radiant heat intensity of 50 kW/m ² in accordance with ISO-5660. The total calorific value during heating was measured. Based on the measured values, nonflammability was evaluated using the following evaluation criteria.
◎◎: 5MJ or less ◎: More than 5MJ and less than 6.5MJ ○: More than 6.5MJ and less than 8MJ ×: More than 8MJ

<Nonflammability after time>
The first aerosol containers obtained in each Example and Comparative Example were left at 30° C. for two weeks. After standing, the polyol composition was discharged from the first aerosol container and mixed with the polyisocyanate composition discharged from the second aerosol container to obtain a polyurethane foam. A cone calorimeter test sample was cut out from the foam to a size of 10 cm x 10 cm x 5 cm, and the total calorific value was measured when heated for 10 minutes at a radiant heat intensity of 50 kW/m ² in accordance with ISO-5660. did. Based on the measured values, nonflammability was evaluated using the following evaluation criteria.
◎◎: 5MJ or less ◎: More than 5MJ and less than 6.5MJ ○: More than 6.5MJ and less than 8MJ ×: More than 8MJ

[Materials used]
In each Example and Comparative Example, the following materials were used.

<Polyol compound>
・Phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RLK-087, hydroxyl value = 200mgKOH/g)
<Catalyst>
・Trimerization catalyst: carboxylic acid quaternary ammonium salt (active ingredient amount 45-55% by mass, diluted with ethylene glycol) (manufactured by Evonik Japan, product name: DABCO TMR-7)
・Resinization catalyst 1: Bismuth trioctate (active ingredient amount 28% by mass, manufactured by Shepherd Chemical Company, product name: Bicat 8210)
・Resinization catalyst 2: 2,2'-dimorpholino diethyl ether (active ingredient amount 100% by mass, manufactured by Mitsui Chemicals Fine Co., Ltd., product name: DMDEE)
・Resinization catalyst 3: N-ethylmorpholine (active ingredient amount 98% by mass, manufactured by Momentive Performance Materials Japan LLC, product name: DMDEE)
・Resinization catalyst 4: Imidazole compound (active ingredient amount 65-75% by mass, manufactured by Kao Corporation, product name: Kaolizer No. 390)
<Liquid flame retardant>
・Phosphate ester: Tris (β-chloropropyl) phosphate (manufactured by Daihachi Kagaku Kogyo Co., Ltd., product name: TMCPP)
<Filler>
・Red phosphorus (manufactured by Rin Kagaku Kogyo Co., Ltd., product name: Nova Excel 140)
・Zinc borate (manufactured by Hayakawa Shoji Co., Ltd., product name: Firebreak ZB)
- Bromine-containing flame retardant: Ethylene bis (pentabromophenyl) (manufactured by Albemarle, product name: SAYTEX 8010)
・Anti-settling agent: Fumed silica (manufactured by Nippon Aerosil Co., Ltd., product name: Aerosil R967S)
<Low boiling point compound>
・HFO-1234ze (manufactured by Honeywell, product name: Soltis GBA) Boiling point -19°C
・Nitrogen boiling point -195.8℃
<Polyisocyanate compound>
・MDI (manufactured by Sumika Covestro Urethane Co., Ltd., product name: 44V-20)

[Example 1]
According to the formulation in Table 1, components other than low boiling point compounds were measured into a 1000 ml polypropylene beaker, mixed for 5 minutes at 1500 rpm using a disper, transferred to an aerosol container, sealed using a vacuum crimper, and further lowered. A first aerosol container filled with a boiling point compound and having a polyol composition sealed therein was obtained.
Similarly, according to the formulation in Table 1, a low boiling point compound was further filled in another aerosol container together with the polyisocyanate compound to obtain a second aerosol container containing the polyisocyanate composition.
A polyol composition and a polyisocyanate composition are discharged from the first aerosol container and the second aerosol container, respectively, and mixed with a static mixer to obtain a polyurethane composition, which is injected from the tip. A polyurethane foam was obtained by spraying it onto a plasterboard. The results of each evaluation are shown in Table 1.

[Examples 2 to 9, Comparative Examples 1 to 3]
A first aerosol container and a second aerosol container were produced in the same manner as in Example 1, except that the composition of the polyol composition was changed as shown in Table 1, and a polyurethane foam was obtained. The results of each evaluation are shown in Table 1.

*Each value in the polyol composition and polyisocyanate composition columns is parts by mass.

As is clear from the above examples, the polyol composition that meets the requirements of the present invention has excellent discharge properties, and the polyurethane foam formed from the composition has excellent nonflammability even after aging. was.
On the other hand, although the polyol composition produced in Comparative Example 1 had excellent discharge properties as in Examples, it did not contain red phosphorus, so the polyurethane foam formed from the composition It was not possible to exhibit excellent nonflammability. Further, the polyol compositions prepared in Comparative Examples 2 and 3 did not contain a low boiling point compound, and therefore could not exhibit excellent discharge properties. Therefore, it was not possible to produce a polyurethane foam, and it was not even possible to evaluate its nonflammability.

10 Mixing System 11 First Container 12 Second Container 11A, 12A Discharge Port 11B, 12B Supply Line 13 Mixer 13A Tube 13B Mixer Element 13C Tip 14 Discharge Gun 14A Lever 20 Mixing System

Claims (8)

A polyol composition for aerosol, comprising a polyol compound, a red phosphorus flame retardant, and a low boiling point compound having a boiling point of 10°C or less. The polyol composition for aerosol according to claim 1, comprising HFO as the low boiling point compound. The polyol composition for aerosol according to claim 1 or 2, further comprising a catalyst having a morpholine skeleton. The polyol composition for aerosol according to claim 1 or 2, further comprising a phosphoric acid ester. The polyol composition for aerosol according to claim 1 or 2, further comprising a flame retardant other than a red phosphorus flame retardant and a phosphoric acid ester. An aerosol container containing the aerosol polyol composition according to claim 1 or 2. A polyurethane composition comprising the aerosol polyol composition according to claim 1 or 2 and a polyisocyanate composition containing a polyisocyanate compound. A polyurethane foam formed from the polyurethane composition of claim 7.