Polyol composition, polyurethane composition, and polyurethane foam

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

Technical Field

[0001] 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.

Background Art

[0002] Conventionally, polyurethane foams have been used as heat insulating materials in vehicles such as automobiles, railway vehicles, and ships, and buildings. Two-component polyurethanes in which a polyol composition and a polyisocyanate composition filled in separate containers are mixed to form a foam are widely used. Two-component polyurethanes may be used, for example, in aerosol containers in which each liquid can be discharged from the container and mixed with a relatively simple configuration as disclosed in Patent Documents 1 to 5. When a two-component polyurethane is used in an aerosol container, one container is filled with a polyol compound and a low-boiling compound, and the other container is filled with a polyisocyanate compound and a low-boiling compound. From each container, a polyol liquid agent and a polyisocyanate liquid agent are discharged by the vapor pressure of the low-boiling compound, and they are mixed to form a polyurethane foam. The polyol composition used in such an aerosol container is often suitably used as an aerosol polyol composition to replenish defective portions generated when applying a polyurethane foam.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0004] However, while conventional aerosol polyol compositions offer excellent dispensing properties, the polyurethane foam formed from these compositions lacks sufficient flammability and is easily combustible. Therefore, aerosol polyol compositions are required to possess properties that improve the flammability of the polyurethane foam. Therefore, the object of the present invention is to provide a polyol composition for aerosols that can form a polyurethane foam with excellent non-flammability. [Means for solving the problem]

[0005] As a result of diligent research, the inventors of the present invention have found that the above problems 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 aerosols comprising a polyol compound, a red phosphorus-based flame retardant, and a low-boiling-point compound with a boiling point of 10°C or less. [2] The aerosol polyol composition according to [1], comprising HFO as the low boiling point compound. [3] The aerosol polyol composition according to [1] or [2], further comprising a catalyst having a morpholine skeleton. [4] A polyol composition for aerosols according to any one of [1] to [3], further comprising a phosphate ester. [5] A polyol composition for aerosols according to any one of [1] to [4], further comprising a red phosphorus-based flame retardant and a flame retardant other than a phosphate ester. An aerosol container containing the polyol composition for aerosols described in any of [6][1] to [5]. A polyurethane composition comprising a polyol composition for aerosols described in any of [7][1] to [5] and a polyisocyanate composition containing a polyisocyanate compound. A polyurethane foam formed from the polyurethane composition described in [8] and [7]. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide a polyol composition for aerosols that can form a polyurethane foam with excellent non-flammability. [Brief explanation of the drawing]

[0007] [Figure 1] This is a schematic diagram showing one embodiment of the mixing system. [Figure 2] This is a schematic diagram showing another embodiment of the mixing system. [Modes for carrying out the invention]

[0008] [Polyol composition] The polyol composition of the present invention is an aerosol polyol composition and comprises a polyol compound, a red phosphorus-based flame retardant, and a low-boiling-point compound with a boiling point of 10°C or lower. The polyol composition of the present invention is used to produce polyurethane foam by mixing it with a polyisocyanate composition containing a polyisonate compound, as described later. The following provides a more detailed explanation.

[0009] <Red phosphorus-based flame retardant> The polyol composition of the present invention contains a red phosphorus-based flame retardant. The red phosphorus-based flame retardant is included as a filler in the polyol composition. The filler is included as a solid flame retardant in the polyol composition and is generally a component that exists in granular or powder form in the polyol composition. In the present invention, by including a red phosphorus-based flame retardant as a filler, the non-flammability of polyurethane foam formed by spraying from a container such as an aerosol container can be improved.

[0010] The red phosphorus-based flame retardant may consist of elemental red phosphorus, or may be red phosphorus coated with a resin, metal hydroxide, metal oxide, etc., or may be a mixture of red phosphorus with a resin, metal hydroxide, metal oxide, etc. The resin for coating or mixing with red phosphorus is not particularly limited, but examples thereof include thermosetting resins such as phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. From the viewpoint of nonflammability, metal hydroxides are preferable as the compound to be coated or mixed. The metal hydroxides described later may be appropriately selected and used.

[0011] The content of the red phosphorus-based flame retardant in the polyol composition is preferably 1 to 70 parts by mass, more preferably 5 to 50 parts by mass, still more preferably 10 to 40 parts by mass, and even more preferably 15 to 35 parts by mass with respect to 100 parts by mass of the polyol compound. When the content of the red phosphorus-based flame retardant is at least the above lower limit value, it becomes possible to impart good nonflammability to the polyurethane foam. Also, by setting it to be not more than the above upper limit value, the handleability when discharging the polyol composition and the like become good.

[0012] <Phosphoric acid ester> The polyol composition in the present invention preferably contains a phosphoric acid ester. The phosphoric acid ester functions as a flame retardant. By using it in combination with the red phosphorus-based flame retardant, it becomes easy to improve the nonflammability of the polyurethane foam without substantially reducing the discharge flow rate, miscibility, etc. The phosphoric acid ester is generally a liquid flame retardant. Note that a liquid flame retardant is a flame retardant that is liquid at normal temperature (23°C) and normal pressure (1 atm).

[0013] As the phosphate ester, monophosphate ester, condensed phosphate ester, etc. can be used. A monophosphate ester is a phosphate ester having one phosphorus atom in the molecule. The monophosphate ester is not particularly limited, and examples thereof include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, halogen-containing phosphate esters such as tris(β-chloropropyl) phosphate, trialkoxy phosphates such as tributoxyethyl phosphate, aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, cresyldiphenyl phosphate, diphenyl(2-ethylhexyl) phosphate, acidic phosphate esters such as monoisodecyl phosphate, diisodecyl phosphate, and the like.

[0014] Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, bisphenol A polyphenyl phosphate. Examples of commercially available products of the condensed phosphate ester include "CR-733S", "CR-741", "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., "ADEKA STAB PFR", "FP-600" manufactured by ADEKA Corporation, and the like.

[0015] The phosphate ester may be used alone or in combination of two or more thereof. Among these, from the viewpoint of easily adjusting the viscosity of the polyol compound and improving the nonflammability of the polyurethane foam, monophosphate ester is preferred, and halogen-containing phosphate esters such as tris(β-chloropropyl) phosphate are more preferred.

[0016] When the polyol composition contains a phosphate ester, the phosphate ester content is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, even more preferably 20 to 70 parts by mass, and still more preferably 35 to 65 parts by mass, per 100 parts by mass of the polyol compound. By setting the phosphate ester content above these lower limits, the effect of including the phosphate ester becomes easier to achieve. Furthermore, by setting it below the upper limit, the foaming of the polyurethane foam is not inhibited by the phosphate ester.

[0017] <Other flame retardants> The present invention may also contain flame retardants other than red phosphorus-based flame retardants and phosphate 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, needle-shaped fillers, and the like. These solid flame retardants may be used individually or in combination of two or more. Note that solid flame retardants are flame retardants that become solid at room temperature (23°C) and normal pressure (1 atm), and are included as fillers, similar to red phosphorus-based flame retardants.

[0018] (Phosphate-containing flame retardant) Examples of phosphate-containing flame retardants include phosphates composed of salts of various phosphoric acids with at least one metal or compound selected from metals of groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. The term "various phosphoric acids" is a concept that includes not only phosphoric acid but also phosphorous acid, hypophosphorous acid, etc. Examples of metals in groups IA through IVB of the periodic table include lithium, sodium, calcium, barium, iron(II), iron(III), and aluminum. Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and piperazine. Examples of aromatic amines include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, and 3-(trifluoromethyl)aniline. Examples of heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, and melamine.

[0019] Specific examples of phosphate-containing flame retardants include monophosphates and polyphosphates. Monophosphates are not particularly limited, but examples include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; and zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite. Here, the polyphosphate is not particularly limited, but examples include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, and aluminum polyphosphate. The phosphate-containing flame retardants may be used individually from the above-mentioned types, or two or more types may be used in combination.

[0020] (Bromine-containing flame retardant) Bromine-containing flame retardants are not particularly limited as long as they contain bromine in their molecular structure and are solid at room temperature (23°C) and normal pressure (1 atm), but examples include aromatic compounds containing brominated aromatic rings. Examples of brominated aromatic ring-containing aromatic compounds include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0021] Furthermore, the brominated aromatic ring-containing aromatic compound may also be a brominated polymer. Specifically, examples include polycarbonate oligomers produced using brominated bisphenol A as a raw material, brominated polycarbonates such as copolymers of this polycarbonate oligomer and bisphenol A, and diexo compounds produced by the reaction of brominated bisphenol A and epichlorohydrin. In addition, examples include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuryl chloride, and uncrosslinked or crosslinked brominated polystyrene. Furthermore, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may also be used. These bromine-containing flame retardants may be used individually or in combination of two or more types.

[0022] (Boron-containing flame retardant) Examples of boron-containing flame retardants used in the present invention include borax, boron oxide, boric acid, and borates. Examples of boron oxides include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide. Examples of borates include alkali metals, alkaline earth metals, elements from groups 4, 12, and 13 of the periodic table, and ammonium borates. Specifically, examples include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate; alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate; zirconium borate, zinc borate, aluminum borate, and ammonium borate. Boron-containing flame retardants may be used alone or in combination of two or more types. The boron-containing flame retardant used in the present invention is preferably a borate, and more preferably zinc borate.

[0023] (Antimony-containing flame retardant) Examples of antimony-containing flame retardants include antimony oxide, antimonate salts, and pyroantimonate salts. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonate salts include sodium antimonate and potassium antimonate. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate. Antimony-containing flame retardants may be used alone or in combination of two or more types. The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

[0024] (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, which is sold under the trade name "Dechloran Plus."

[0025] (metal hydroxide) Examples of metal hydroxides used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, and tin hydroxide. A single metal hydroxide may be used, or two or more may be used in combination. Aluminum hydroxide is preferred as the metal hydroxide.

[0026] (Needle-shaped filler) Examples of needle-shaped 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, graphite fibers, metal fibers, slag fibers, gypsum fibers, silica fibers, alumina fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, and stainless steel fibers. The use of needle-shaped fillers can effectively improve the mechanical properties of polyurethane foams. These needle-shaped fillers can be used individually or in combination of two or more types. The aspect ratio (length / diameter) of the needle-shaped filler used in the present invention is preferably in the range of 5 to 50, and more preferably in the range of 10 to 40. This aspect ratio can be determined by observing the needle-shaped filler with a scanning electron microscope and measuring its length and width.

[0027] 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, more preferably 10 to 70 parts by mass, even more preferably 15 to 60 parts by mass, and still more preferably 35 to 50 parts by mass, per 100 parts by mass of the polyol compound. If the total content of the other flame retardants is above the lower limit, it becomes easier to impart good non-flammability to the polyurethane foam. Furthermore, if it is below the upper limit, the handling properties when extruding the polyol composition become better.

[0028] Furthermore, the polyol composition may contain fillers other than the solid flame retardant described above, and such fillers include anti-settlement agents. By using a settling inhibitor, the settling of solid flame retardants and other materials dispersed in the polyol composition can be prevented, making it easier to discharge the solid flame retardants and other materials, thus facilitating the formation of highly flame-retardant polyurethane foam. Furthermore, the use of a settling inhibitor makes it easier to uniformly disperse fillers such as red phosphorus-based flame retardants.

[0029] There are no particular limitations on the settling inhibitor, but it is preferable to use one or more selected from, for example, carbon black, powdered silica, organic clay, etc., with powdered silica being more preferable among these. Carbon black used as a settling inhibitor can be manufactured using methods such as the furnace process, channel process, or thermal process. Commercially available carbon black can be selected and used as appropriate. Furthermore, fumed silica, colloidal silica, and silica gel can be used as powdered silica. Among these, fumed silica is preferred. As fumed silica, Aerosil (registered trademark) from Nippon Aerosil Co., Ltd. can be used.

[0030] The content of the settling inhibitor in the polyol composition is preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass, even more preferably 10 to 40 parts by mass, and still more preferably 15 to 35 parts by mass, per 100 parts by mass of the polyol compound. If the content of the settling inhibitor is above the lower limit, fillers such as red phosphorus-based flame retardants are prevented from settling in the polyol composition, resulting in good discharge properties for the polyol composition. If the content of the settling inhibitor is below the upper limit, the viscosity of the polyol composition does not become excessively high, making it easier to achieve good discharge properties.

[0031] The polyol composition may contain fillers other than solid flame retardants and settling inhibitors as fillers, for example, other inorganic fillers. Suitable 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, calcium sulfate, 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. These inorganic fillers may be used individually or in combination of two or more.

[0032] The total filler content in the polyol composition is preferably 20 to 150 parts by mass, more preferably 25 to 130 parts by mass, and even more preferably 30 to 120 parts by mass, per 100 parts by mass of the polyol compound. If the filler content is above the lower limit, it is possible to impart good non-flammability and good mechanical properties to the polyurethane foam. On the other hand, if the filler content is below the upper limit, the handling properties when extruding the polyol composition will be improved.

[0033] <Low boiling point compounds> The polyol composition of the present invention contains a low-boiling-point compound. The low-boiling-point compound, through its vapor pressure, causes the polyol composition to be discharged from an aerosol container, and also causes foaming of the polyol composition and the polyurethane composition described later by vaporizing during the discharge. From the viewpoint of increasing the discharge amount of the polyol composition, the low-boiling-point compound has a boiling point at 1 atmosphere (hereinafter also simply referred to as "boiling point") of 10°C or lower. If the boiling point of the low-boiling-point compound exceeds 10°C, when the polyol composition is filled, for example, into an aerosol container, the vapor pressure inside the container cannot be sufficiently increased, making it difficult to discharge the composition sufficiently. From the viewpoint of discharge performance, the low-boiling-point compound is preferably one with a boiling point of 0°C or lower, more preferably one with a boiling point of -10°C or lower, and even more preferably one with a boiling point of -15°C or lower. Here, the boiling point of the low-boiling-point compound refers to the boiling point of the low-boiling-point compound alone, and does not refer to the azeotropic boiling point when, for example, the low-boiling-point compound azeotropes with other compounds.

[0034] The type of low-boiling compound is not particularly limited as long as it is possible to discharge the polyol composition by its vapor pressure, and hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), hydrofluoroolefins (HFOs), hydrocarbons, ether compounds, inorganic gases, etc., can be used. Among these, hydrofluoroolefins (HFOs), hydrocarbons, ether compounds, and inorganic gases can be suitably used from the viewpoint of reducing environmental impact and improving dischargeability and mixability, and among these, it is preferable to include hydrofluoroolefins (HFOs) as the low-boiling compound. HFOs may be used alone as a low-boiling compound, or they may be used in combination with other low-boiling compounds such as inorganic gases. In the polyol composition, the content of HFOs 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.

[0035] As mentioned above, low-boiling point compounds (HFOs) are preferably those with a boiling point of 0°C or lower, more preferably those with a boiling point of -10°C or lower, and even more preferably those with a boiling point of -15°C or lower. Furthermore, while the boiling point of HFOs is not particularly limited, from the viewpoint of handling and storage, it is preferably -50°C or higher, more preferably -35°C or higher, and even more preferably -25°C or higher. Examples of low-boiling point HFO compounds include 1,1,3,3-tetrafluoropropene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,1,3,3-pentafluoropropene (HFO-1225zc), and 2,3,3,3-tetrafluoropropene (HFO-1234yf). HFO may be a compound consisting of hydrogen, fluorine, and carbon, but it may also be a hydrochlorofluoroolefin further containing chlorine. Among the above, 1,3,3,3-tetrafluoropropene (HFO-1234ze) is preferred from the viewpoint of improving discharge performance. Generally, HFO, such as HFO-1234ze, readily reacts with catalysts such as resin catalysts and may deactivate them. However, in the present invention, as described later, using a catalyst having a morpholine skeleton as the resin catalyst can prevent the deactivation of the resin catalyst.

[0036] Examples of hydrocarbons include hydrocarbons with 1 to 4 carbon atoms, such as ethane, propane, isobutane, and various types of butanes like n-butane. Furthermore, suitable specific examples of hydrocarbons with 1 to 4 carbon atoms include LPG (liquefied petroleum gas), which is mainly composed of propane and butanes. Examples of ether compounds include dimethyl ether. Examples of inorganic gases include nitrogen, carbon dioxide, and argon gas, with nitrogen being preferred among these.

[0037] The content of the low-boiling 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, per 100 parts by mass of the polyol compound. When the content of the low-boiling compound in the polyol composition is above the lower limit, the vapor pressure inside the aerosol container will be kept above a certain level, and the discharge performance of the polyol composition can be improved. Furthermore, when the content of the low-boiling compound in the polyol composition is below the upper limit, the vapor pressure inside the aerosol container will be appropriate, improving handling and storage properties.

[0038] <Polyol compounds> The polyol composition of the present invention contains a polyol compound that serves as a raw material for polyurethane foam. Examples of polyol compounds include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols. Polyol compounds are usually liquid at room temperature (23°C) and atmospheric pressure (1 atm).

[0039] Examples of polylactone polyols include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of polycarbonate polyols include polyols obtained by the de-alcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, etc.

[0040] Examples of aromatic polyols include bisphenol A, bisphenol F, phenol novolac, and cresol novolac. Examples of alicyclic polyols include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol. Examples of aliphatic polyols include ethylene glycol, propylene glycol, butanediol, pentanediol, and alkanediols such as hexanediol.

[0041] Examples of polyester polyols include polymers obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, and condensates of hydroxycarboxylic 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. Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

[0042] Examples of polymer polyols include polymers obtained by graft polymerization of ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate onto aromatic polyols, alicyclic polyols, aliphatic polyols, and polyester polyols, as well as polybutadiene polyols, modified polyols of polyhydric alcohols, or hydrogenated versions thereof.

[0043] Examples of modified polyols of polyhydric alcohols include those obtained by reacting a polyhydric alcohol with alkylene oxide. Examples of polyhydric alcohols include trihydric alcohols such as glycerin and trimethylolpropane, tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl glucoside and its derivatives, polyols such as phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene, castor oil polyols, (co)polymers of hydroxyalkyl (meth)acrylates, and polyfunctional polyols (e.g., 2 to 100 functional groups) such as polyvinyl alcohol, and condensates of phenol and formaldehyde (novolacs).

[0044] The method for modifying polyhydric alcohols is not particularly limited, but a method involving the addition of alkylene oxides (hereinafter also referred to as "AO") is preferably used. Examples of AOs include AOs having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter also referred to as "EO"), 1,2-propylene oxide (hereinafter also referred to as "PO"), 1,3-propyloxide, 1,2-butylene oxide, and 1,4-butylene oxide. Among these, PO, EO, and 1,2-butylene oxide are preferred from the viewpoint of properties and reactivity, with PO and EO being more preferred. When two or more AOs are used (for example, PO and EO), the addition method may be block addition, random addition, or a combination of these.

[0045] Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, or tetrahydrofuran in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogen atoms. Examples of low molecular weight active hydrogen compounds having two or more active hydrogen atoms include bisphenol A, ethylene glycol, propylene glycol, butylene glycol, diols such as 1,6-hexanediol, triols such as glycerin and trimethylolpropane, ethylenediamine, and amines such as butylenediamine.

[0046] Polyol compounds used in the present invention include polyester polyols and polyether polyols. Among these, aromatic polyester polyols obtained by dehydration condensation of a polybasic acid having an aromatic ring, such as isophthalic acid (m-phthalic acid) or terephthalic acid (p-phthalic acid), with a dihydric alcohol, such as bisphenol A, ethylene glycol, or 1,2-propylene glycol, are more preferred. Polyols having two hydroxyl groups are also preferred.

[0047] The hydroxyl value of the polyol compound is preferably 20 to 300 mg KOH / g, more preferably 30 to 250 mg KOH / g, and even more preferably 50 to 220 mg KOH / 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 handling and other factors. On the other hand, when the hydroxyl value of the polyol compound is above the lower limit, the crosslinking density of the polyurethane foam increases, resulting in higher strength. The hydroxyl value of polyol compounds can be measured according to JIS K 1557-1:2007.

[0048] The polyol compound content in the polyol composition of the present invention is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, and even more preferably 20 to 50% by mass. A polyol compound content above the lower limit is preferable because it facilitates the reaction between the polyol compound and the polyisocyanate compound. On the other hand, a polyol compound content below the upper limit is preferable from the viewpoint of handling ease because it prevents the viscosity of the polyol composition from becoming too high.

[0049] <Catalyst> The polyol composition in the present invention preferably contains a catalyst. The catalyst preferably contains at least one of a trimerizing catalyst and a resinification catalyst, and more preferably contains both a trimerizing catalyst and a resinification catalyst.

[0050] Trimerization catalysts are catalysts that react with polyisocyanate compounds to trimerize the isocyanate groups contained in them, thereby promoting the formation of isocyanurate rings. Suitable 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 salts of carboxylic acids such as potassium acetate, potassium 2-ethylhexanoate, and potassium octoate; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt; and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, and triethylmonomethylammonium salt. Examples of ammonium salts include ammonium salts of carboxylic acids such as 2,2-dimethylpropanoic acid, and more specifically, quaternary ammonium salts of carboxylic acids. These can be used individually or in combination of two or more types. Among these, one or more selected from alkali metal carboxylates and quaternary ammonium carboxylates are preferred, with quaternary ammonium carboxylates being more preferred.

[0051] The trimerization catalyst content is preferably 1 to 25 parts by mass, more preferably 3 to 18 parts by mass, and even more preferably 5 to 15 parts by mass, per 100 parts by mass of the polyol compound. If the trimerization catalyst content is above these lower limits, trimerization of the polyisocyanate compound is more likely to occur, improving the non-flammability of the resulting polyurethane foam. On the other hand, if the trimerization catalyst content is below the upper limit, the reaction becomes easier to control.

[0052] Resin-based catalysts are catalysts that promote the reaction between polyol compounds and polyisocyanate compounds. Examples of resin-based catalysts include imidazole compounds, catalysts having a morpholine skeleton, and metal-based catalysts. Among these, catalysts having a morpholine skeleton are preferred.

[0053] Catalysts having a morpholine skeleton have low reactivity with low-boiling point compounds such as HFOs, thus preventing deactivation through reaction with low-boiling point compounds. Therefore, by including a catalyst having a morpholine skeleton in the polyol composition, a polyurethane foam with excellent non-flammability can be formed even after long-term storage. 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 containing one morpholine skeleton include N-ethylmorpholine. Examples of catalysts having two morpholine skeletons include 2,2'-dimorpholinodiethyl ether and 1,3-dimorpholino-2-methyl-1,3-butadiene. Among catalysts having a morpholine skeleton, using a catalyst with two morpholine skeletons as a resinification catalyst makes it easier to prevent catalyst deactivation. Furthermore, the reaction between the polyol compound and the polyisocyanate compound becomes easier to control, enabling the formation of a higher quality polyurethane foam with superior non-flammability. Therefore, among catalysts having a morpholine skeleton, catalysts having two morpholine skeletons are more preferable, and among these, 2,2'-dimorpholinodiethyl ether is even more preferable.

[0054] The content of the catalyst having a morpholine skeleton in the polyol composition is preferably 3 to 20 parts by mass, more preferably 5 to 15 parts by mass, and even more preferably 8 to 12 parts by mass, per 100 parts by mass of the polyol compound. If the content of the catalyst having a morpholine skeleton is above these lower limits, urethane bonds are more easily formed, and the reaction proceeds rapidly. On the other hand, if it is below these upper limits, the reaction rate becomes easier to control.

[0055] Examples of imidazole compounds include tertiary amines obtained by substituting the secondary amine at position 1 of the imidazole ring with an alkyl group, alkenyl group, etc. Specifically, these include N-methylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Imidazole compounds in which the secondary amine in the imidazole ring is substituted with a cyanoethyl group are also acceptable.

[0056] Examples of metal catalysts include metal salts composed of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. Preferably, they are organic acid metal salts composed of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc., with bismuth-based catalysts being preferred. Specifically, examples of metal catalysts include dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatate, bismastrioctate, bismastrith(2-ethylhexanoate), tin dioctate, lead dioctate, etc., with bismastrioctate being preferred.

[0057] The resinification catalyst may be used alone or in combination of two or more types. The polyol composition of the present invention preferably contains a catalyst having a morpholine skeleton and a metal-based catalyst, more preferably a catalyst having a morpholine skeleton and a bismuth-based catalyst, and even more preferably a catalyst having two morpholine skeletons and a bismuth-based catalyst. By using such a combination of resinification catalysts in the polyol composition, it becomes easier to improve the non-flammability of polyurethane while appropriately controlling the reaction between the polyol compound and the polyisocyanate compound.

[0058] The content of the metal catalyst in the polyol composition is preferably 0.3 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1.5 to 5 parts by mass, per 100 parts by mass of the polyol compound. If the content of the metal catalyst is above these lower limits, urethane bonds are more easily formed, and the reaction proceeds rapidly. On the other hand, if the content of the metal catalyst is below these upper limits, the reaction rate becomes easier to control.

[0059] The content of the resinification catalyst is preferably 1 to 25 parts by mass, more preferably 5 to 20 parts by mass, and even more preferably 8 to 15 parts by mass, per 100 parts by mass of the polyol compound. If the content of the resinification catalyst is above these lower limits, urethane bonds are more easily formed, and the reaction proceeds rapidly. On the other hand, if it is below these upper limits, the reaction rate becomes easier to control.

[0060] When a trimerizing catalyst and a resinifying catalyst are used in combination as catalysts, the amount of resinifying catalyst relative to the trimerizing catalyst (amount of resinifying catalyst / amount of trimerizing catalyst) is preferably 0.8 to 3, and more preferably 1 to 2.5, from the viewpoint of reducing the shrinkage rate of the resulting polyurethane foam.

[0061] Furthermore, the total amount of catalyst in the polyol composition is not particularly limited, but is preferably 2 to 50 parts by mass, more preferably 8 to 35 parts by mass, even more preferably 10 to 40 parts by mass, and even more preferably 12 to 25 parts by mass. If the amount is above these lower limits, the formation of urethane bonds and trimerization proceed appropriately, and good non-flammability is likely to be achieved. If the amount is below these upper limits, the urethane formation and trimerization reactions can be easily controlled.

[0062] <Foam stabilizer> The polyol composition of the present invention may contain a foam stabilizer. The foam stabilizer improves the foaming properties of the polyurethane composition obtained from the polyol composition and the polyisocyanate composition. Examples of foam stabilizers include polyoxyalkylene-based foam stabilizers such as polyoxyalkylene alkyl ethers, and surfactants such as silicone-based foam stabilizers such as organopolysiloxanes. These foam stabilizers may be used individually or in combination of two or more types. The foam stabilizer content is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the polyol compound. If the foam stabilizer content is above these lower limits, the polyurethane composition becomes easier to foam, and a homogeneous polyurethane foam is easier to obtain. On the other hand, if the foam stabilizer content is below these upper limits, a good balance is achieved between manufacturing costs and the obtained effects.

[0063] <Other ingredients> The polyol composition may optionally contain additives such as antioxidants (phenol-based, amine-based, sulfur-based, etc.), heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, polybutenes, petroleum resins, etc., to the extent that it does not impair the objectives of the present invention.

[0064] [container] The container of the present invention is a container that encloses the polyol composition described above. The container is an aerosol container capable of discharging the polyol composition by the vapor pressure of a low-boiling compound. The aerosol container comprises, for example, a container body filled with the polyol composition and a cap that seals the top of the container body. When a button or the like provided on the cap is pressed, a valve or the like opens and the internal pressure is released, and the polyol composition is discharged from a discharge port provided on the cap by the vapor pressure of the low-boiling compound. The method for sealing the polyol composition in the container is not particularly limited, but each component other than the low-boiling compound is mixed as needed using a disperser or the like, then filled into the container and sealed, and then the low-boiling compound is filled in. The low-boiling compound can be filled in, for example, by opening a valve provided in the cap of the container and injecting the low-boiling compound into the container.

[0065] When dispensing a polyol composition from a container, it should be dispensed in a state where each component constituting the polyol composition is uniformly mixed. To ensure uniform mixing of each component constituting the polyol composition, it is advisable to shake the container thoroughly before dispensing. Shaking the container can be done, for example, by holding the container by hand and shaking it up and down. The method for uniformly mixing the polyol composition is not limited to the method described above. Furthermore, the temperature of the container during dispensing is preferably, for example, between 10°C and 40°C. A temperature of 10°C or higher ensures good dispensing because the liquid temperature is sufficiently high, while a temperature of 40°C or lower prevents the container from bursting.

[0066] [Polyurethane composition] The polyurethane composition of the present invention comprises 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 in a mass ratio such that the isocyanate index falls within a predetermined range, as described later. The polyurethane composition obtained by mixing the polyol composition and the polyisocyanate composition reacts and foams up with the low-boiling compound contained in the polyol composition or the low-boiling compound contained in the polyisocyanate composition described later, thereby becoming a polyurethane foam.

[0067] <Polyisocyanate composition> As the polyisocyanate compound included in the polyurethane composition of the present invention, various polyisocyanate compounds such as aromatic, alicyclic, and aliphatic compounds having two or more isocyanate groups can be used. Preferably, liquid diphenylmethane diisocyanate (MDI) is used due to its ease of handling, rapid reaction, excellent physical properties of the resulting polyurethane foam, and low cost. Examples of liquid MDI include crude MDI (also called polymeric MDI). Specific commercially available liquid MDIs include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.) and "Millionate MR-200" (Nippon Polyurethane Industry Co., Ltd.). Alternatively, uretonimine-containing MDI (for example, "Millionate MTL": manufactured by Nippon Polyurethane Industry Co., Ltd. as a commercially available product) may also be used. Furthermore, a polyisopolycyanate compound may be used that has been treated in advance to increase its affinity with polyols by reacting some of the isocyanate active groups in the polyisopolycyanate compound with a hydroxyl group-containing compound. In addition to liquid MDI, other polyisocyanate compounds may be used in combination, and any polyisocyanate compound known in the field of polyurethanes can be used without limitation.

[0068] The isocyanate index of the polyurethane composition of the present invention is preferably 100 or higher, more preferably 150 or higher, and even more preferably 2000 or higher. When the isocyanate index is above these lower limits, the amount of polyisocyanate compound relative to the polyol compound becomes excessive, making it easier for isocyanurate bonds to be formed by the trimer of polyisocyanate, resulting in improved non-flammability of the polyurethane foam. Furthermore, the isocyanate index of the polyurethane composition is preferably 600 or less, more preferably 550 or less, and even more preferably 500 or less. When the isocyanate index is below these upper limits, a good balance is achieved between the non-flammability of the resulting polyurethane foam and the manufacturing cost. The isocyanate index (INDEX) is calculated using the following method.

[0069] INDEX = Equivalent weight of polyisocyanate compound ÷ (Equivalent weight of polyol compound + Equivalent weight of water) × 100 Here, Equivalent weight of polyisocyanate compound = Number of parts of polyisocyanate compound used × NCO content (%) × 100 / NCO molecular weight The equivalent weight of the polyol compound = OHV × the amount of polyol compound used ÷ the molecular weight of KOH, where OHV is the hydroxyl value of the polyol (mgKOH / g). Equivalent amount 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, the NCO content is the proportion of NCO groups in the polyisocyanate compound expressed as mass%, and for the sake of unit conversion in the above formula, the molecular weight of KOH is assumed to be 56100, the molecular weight of water is assumed to be 18, and the number of OH groups in water is assumed to be 2.

[0070] The low-boiling point compounds included in the polyisocyanate composition can be any of the low-boiling point compounds included in the polyol composition as described above, without any particular limitations. The low-boiling point compounds used in the polyisocyanate composition may be the same as or different from the low-boiling point compounds used in the polyol composition. Suitable low-boiling point compounds to be included in the polyisocyanate composition include HFO, hydrocarbons having 1 to 4 carbon atoms, ether compounds, and inorganic gases, and among these, it is preferable to include hydrofluoroolefin (HFO) as the low-boiling point compound. HFO may be used in combination with other low-boiling point compounds such as inorganic gases.

[0071] HFO may be used alone as a low-boiling point compound, but it is more preferable to use HFO in combination with an inorganic gas, and even more preferable to use HFO in combination with nitrogen. By including an inorganic gas together with HFO, the discharge rate of the polyisocyanate compound can be increased, thereby forming a polyurethane foam with superior fire resistance. In polyisocyanate compositions, when HFO is used in combination with an inorganic gas, the ratio of inorganic gas to HFO is preferably 0.5 / 10 to 10 / 10, more preferably 0.7 / 10 to 5 / 10, and even more preferably 1 / 10 to 3 / 10. When the ratio of inorganic gas to HFO is above the lower limit, the vapor pressure inside the container filled with the polyisocyanate composition increases, so that the discharge rate of the polyisocyanate compound remains above a certain level, making it easier to form a polyurethane foam with excellent non-flammability. Furthermore, when the ratio of inorganic gas to HFO is below the upper limit, the discharge rate of the polyisocyanate compound is appropriately controlled, and a high-quality polyurethane foam can be formed.

[0072] The content of the low-boiling compound in the polyisocyanate composition is preferably 0.5 to 10 parts by mass, more preferably 1 to 7 parts by mass, and even more preferably 3 to 5 parts by mass, per 100 parts by mass of the polyisocyanate compound. If the content of the low-boiling compound is above the lower limit, the vapor pressure in the container filled with the polyisocyanate composition increases, so that the discharge rate of the polyisocyanate compound is kept above a certain level, making it easier to form a polyurethane foam with excellent non-flammability. On the other hand, if the content of the low-boiling compound is below the upper limit, the discharge rate of the polyisocyanate compound is appropriately controlled, and a high-quality polyurethane foam can be formed.

[0073] Furthermore, 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.

[0074] [Mixed System] The present invention also provides a mixing system for mixing a polyol composition and a polyisocyanate composition. As shown in Figure 1, the mixing system 10 comprises a first container 11 containing the polyol composition and a second container 12 containing the 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 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 compound contained in the polyisocyanate composition. Inside the first container 11, some of the low-boiling compound vaporizes to form a gas phase. The same occurs inside 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 compound, and the polyisocyanate compound and polyol compound react to form a polyurethane foam.

[0075] The mixing system 10 may include a mixer 13. The discharge ports 11A and 12A of the first and second containers 11 and 12, respectively, are connected to the 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 may be sprayed onto the surface to be treated using a sprayer or the like.

[0076] The mixer 13 is preferably a static mixer, also known as a static mixer. A static mixer is a mixer without a drive unit, in which the fluid is mixed as it passes through the inside of a pipe. An example of a static mixer is one in which a mixer element 13B is arranged inside a pipe 13A, as shown in Figure 1. Mixer elements 13B can be spirally shaped or have multiple baffles formed on them. The stationary mixer may also function as an injector. In this case, as shown in Figure 1, the mixture of the polyol composition and the polyisocyanate composition mixed inside the tube 13A is injected from the tip 13C of the tube. Although Figure 1 shows how the polyol composition and polyisocyanate composition discharged from the first and second containers 11 and 12 are introduced into the mixer, a discharge gun or jig may be provided before the mixture is introduced into the mixer.

[0077] Figure 2 shows a mixing system 20 as an example of a configuration equipped with a dispensing gun before being introduced into the mixer. The mixing system 20 comprises a first container 11, a second container 12, supply lines 11B and 12B, a dispensing 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. The polyol composition and the polyisocyanate composition are supplied from the first and second containers to the dispensing gun 14 via supply lines 11B and 12B, respectively. The dispensing gun 14 is equipped with a lever 14A and has an ON-OFF mechanism for liquid supply. Specifically, when the lever 14A is pulled, the polyol composition and the polyisocyanate composition are supplied to the mixer 13, and when the lever 14A is released, the supply to the mixer 13 is stopped. By using a mixing system 20 equipped with a discharge gun 14, liquid can be supplied as needed, thereby improving work efficiency when forming polyurethane foam.

[0078] In this invention, the polyurethane foam formed from the polyurethane composition can be used for various applications, but it is preferably used as an insulating material. The polyurethane foam has a large number of air bubbles, and therefore has an insulating effect. Polyurethane foam is particularly preferable for use as insulation in vehicles or buildings. Examples of vehicles include railway cars, automobiles, ships, and aircraft. Furthermore, the present invention allows for the formation of polyurethane foam using an aerosol container with a simple configuration. Because the foam can be formed using a container, it is particularly suitable for applications where the surface to be treated is relatively small, such as replenishing areas where polyurethane foam is missing. Therefore, it is preferable to use it for repair purposes, such as spraying it onto deteriorated or damaged areas of existing heat-resistant materials. Of course, it is not limited to such applications and may also be used to form new heat-resistant materials. [Examples]

[0079] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0080] [Evaluation Method] In the examples and comparative examples, the discharge properties of the polyol composition and the polyisocyanate composition, as well as the non-flammability of the polyurethane foam, were evaluated using the following evaluation methods.

[0081] <Dischargeability> The dispensing of the polyol composition from the first aerosol container and the polyisocyanate composition from the second aerosol container at 25°C was visually confirmed, and the dispensing performance was evaluated according to the following evaluation criteria. ○: Both polyol compositions and polyisocyanate compositions can be dispensed. ×: At least one of the polyol composition or polyisocyanate composition cannot be dispensed.

[0082] <Nonflammable> From the polyurethane foam obtained in each example and comparative example, a sample for cone calorimeter testing was cut to 10cm x 10cm x 5cm, and the radiant thermal intensity was measured in accordance with ISO-5660 at 50kW / m². 2 The total heat output was measured when heated for 10 minutes. Based on these measurements, the non-flammability was evaluated according to the following criteria. ◎◎: 5MJ or less ◎: More than 5MJ but less than 6.5MJ ○: More than 6.5MJ but less than 8MJ ×: More than 8MJ

[0083] <Non-flammable over 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 dispensed from the first aerosol container and mixed with the polyisocyanate composition dispensed from the second aerosol container to obtain a polyurethane foam. A sample for cone calorimeter testing was cut from the foam to a size of 10 cm × 10 cm × 5 cm, and the radiant heat intensity was measured to 50 kW / m² in accordance with ISO-5660. 2 The total heat output was measured when heated for 10 minutes. Based on these measurements, the non-flammability was evaluated according to the following criteria. ◎◎: 5MJ or less ◎: More than 5MJ but less than 6.5MJ ○: More than 6.5MJ but less than 8MJ ×: More than 8MJ

[0084] [Materials used] The following materials were used in each example and comparative example.

[0085] <Polyol compounds> • Phthalate polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g) <Catalyst> • Trimerization catalyst: Quaternary ammonium carboxylic acid salt (active ingredient content 45-55% by mass, diluted with ethylene glycol) (manufactured by Evonik Japan, product name: DABCO TMR-7) • Resinization catalyst 1: Bismastrioctate (active ingredient content 28% by mass, manufactured by Shepherd Chemical, product name: Bicat 8210) • Resinization catalyst 2: 2,2'-dimorpholinodiethyl 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 Chemical Industry Co., Ltd., product name: TMCPP) <Filler> • Red phosphorus (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140) • Zinc borate (manufactured by Hayakawa Trading 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 compounds> • HFO-1234ze (manufactured by Honeywell, product name: Solstice GBA) Boiling point -19℃ Nitrogen boiling point -195.8℃ <Polyisocyanate compounds> • MDI (manufactured by Sumika Covestro Urethane Co., Ltd., product name: 44V-20)

[0086] [Example 1] According to the formulation in Table 1, components other than the low-boiling compound were measured into a 1000 ml polypropylene beaker, mixed at 1500 rpm for 5 minutes using a disperser, then transferred to an aerosol container, sealed using a vacuum crimper, and then filled with the low-boiling compound to obtain a first aerosol container with the polyol composition sealed inside. Similarly, following the formulations in Table 1, a low-boiling point compound was added to another aerosol container along with the polyisocyanate compound to obtain a second aerosol container containing the polyisocyanate composition. Polyol composition and polyisocyanate composition were dispensed from the first and second aerosol containers described above, respectively. These were mixed in a static mixer to obtain a polyurethane composition, which was then sprayed onto a gypsum board from the nozzle to obtain a polyurethane foam. The evaluation results are shown in Table 1.

[0087] [Examples 2-9, Comparative Examples 1-3] A polyurethane foam was obtained by preparing a first aerosol container and a second aerosol container in the same manner as in Example 1, except that the composition of the polyol composition was changed as shown in Table 1. The evaluation results for each are shown in Table 1.

[0088] [Table 1] *The values ​​in the columns for polyol composition and polyisocyanate composition are in parts by mass.

[0089] As is clear from the above examples, the polyol composition satisfying the requirements of the present invention exhibits excellent discharge properties, and the polyurethane foam formed from the composition exhibits excellent non-flammability, even after time has passed. In contrast, the polyol composition prepared in Comparative Example 1, while exhibiting excellent discharge properties similar to the examples, did not contain red phosphorus. Therefore, the polyurethane foam formed from this composition could not exhibit excellent non-flammability. Furthermore, the polyol compositions prepared in Comparative Examples 2 and 3 did not contain low-boiling point compounds and thus could not exhibit excellent discharge properties. Consequently, it was not possible to produce polyurethane foam, and even evaluating non-flammability was impossible. [Explanation of Symbols]

[0090] 10 Mixing System 11 The first container 12 Second container 11A, 12A outlet 11B, 12B supply lines 13 Mixer 13A Body 13B Mixer Element 13C tip 14 Discharge gun 14A Lever 20 Mixing System

Claims

1. It contains a polyol compound, a red phosphorus-based flame retardant, and a low-boiling-point compound with a boiling point of 10°C or lower. The low-boiling point compound includes HFO-1234ze, The catalyst further comprises a catalyst having a morpholine skeleton and an organic acid metal salt made of bismuth. The content of the catalyst having the morpholine skeleton is 3 to 20 parts by mass per 100 parts by mass of the polyol compound. A polyol composition for aerosols, wherein the content of the organic acid metal salt is 0.3 to 10 parts by mass per 100 parts by mass of the polyol compound.

2. The polyol composition for aerosols according to claim 1, further comprising a phosphate ester.

3. The aerosol polyol composition according to claim 1 or 2, further comprising a red phosphorus-based flame retardant and a flame retardant other than a phosphate ester.

4. An aerosol container containing the polyol composition for aerosols described in claim 1 or 2.

5. A polyurethane composition comprising the aerosol polyol composition according to claim 1 or 2 and a polyisocyanate composition containing a polyisocyanate compound.

6. A polyurethane foam formed from the polyurethane composition described in claim 5.

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