Polyol composition, polyurethane composition, and polyurethane foam

Abstract

To provide a polyol composition for aerosol that comprises a secondary amine catalyst and ensures a minimum specified curing rate for polyurethane foam applications, even after extended storage.SOLUTION: A polyol composition for aerosol comprises a polyol compound and a catalyst. The content of the catalyst is 15 pts.mass or more relative to 100 pts.mass of the polyol compound. The catalyst comprises a secondary amine catalyst. The content of the secondary amine catalyst is 0.03-5 pts.mass relative to 100 pts.mass of the polyol compound.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 technology]

[0002] Conventionally, polyurethane foam has been used as an insulating material in vehicles such as automobiles, railway cars, and ships, as well as in buildings. Two-component polyurethanes, which form a foam by mixing a polyol composition and a polyisocyanate composition filled in separate containers, are widely used as polyurethane foams. Two-component polyurethanes are sometimes used in aerosol containers, such as those disclosed in Patent Documents 1 to 5, which allow each liquid to be dispensed and mixed from the container in a relatively simple configuration. When 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. The vapor pressure of the low-boiling compound causes the polyol liquid and the polyisocyanate liquid to be dispensed from each container, and by mixing them, a polyurethane foam is formed. Polyol compositions used in such aerosol containers are often suitably used to fill in defects that occur during the construction of polyurethane foam. Furthermore, aerosol polyol compositions often contain amine-based catalysts, particularly secondary amine catalysts such as imidazole-based catalysts, in order to ensure good reactivity with polyisocyanates and to obtain a curing rate above a certain level. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2020 / 067139 [Patent Document 2] Japanese Patent Publication No. 2021-155506 [Patent Document 3] International Publication No. 2021 / 193871 [Patent Document 4] International Publication No. 2021 / 193872 [Patent Document 5] International Publication No. 2012 / 034492 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, conventional aerosol polyol compositions, when stored for extended periods, suffer from a problem where the amine catalyst reacts with the low-boiling compound in the composition over time, deactivating the amine catalyst and reducing the curing speed when applying polyurethane foam, leading to dripping. Furthermore, when the curing speed is reduced in this way, it often becomes difficult to impart good non-flammability to the polyurethane foam. Therefore, the object of the present invention is to provide a polyol composition for aerosols in which the curing speed when applying polyurethane foam is above a certain level, not only initially but also after long-term storage. [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 [9]. [1] A polyol composition for aerosols containing a polyol compound and a catalyst, wherein the content of the catalyst is 15 parts by mass or more per 100 parts by mass of the polyol compound, the catalyst includes a secondary amine catalyst, and the content of the secondary amine catalyst is 0.03 to 5 parts by mass per 100 parts by mass of the polyol compound. [2] The polyol composition for aerosols according to [1], wherein the content of the secondary amine catalyst is 25% by mass or less based on the total amount of catalyst. [3] The aerosol polyol composition according to [1] or [2], further comprising a phosphate ester. [4] The aerosol polyol composition according to [1] or [2], further containing a solid flame retardant. [5] The aerosol polyol composition according to [4], comprising a red phosphorus-based flame retardant. An aerosol container containing the aerosol polyol composition described in [6][1] or [2]. A polyurethane composition comprising the aerosol polyol composition described in [7][1] or [2] and a polyisocyanate composition containing a polyisocyanate compound. A polyurethane foam formed from the polyurethane composition described in [8] and [7]. A mixing system comprising a first container containing the aerosol polyol composition described in [9][1] or [2], and a second container containing the polyisocyanate composition. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide a polyol composition for aerosols in which the curing speed when applying polyurethane foam is above a certain level, not only initially but also after long-term storage. [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 a polyol composition for aerosols, which contains a polyol compound and a catalyst. As described below, the polyol composition of the present invention is used for producing a polyurethane foam by mixing with a polyisocyanate composition containing a polyisocyanate compound. A more detailed description is given below.

[0009] <Catalyst> The polyol composition of the present invention contains a catalyst. As the catalyst, at least a secondary amine-based catalyst is contained.

[0010] (Secondary Amine-based Catalyst) The polyol composition of the present invention contains a secondary amine-based catalyst. The secondary amine-based catalyst is generally used as a resinification catalyst. By containing the secondary amine-based catalyst, the reactivity between the polyol compound and the polyisocyanate compound is improved, and the initial curing rate can be maintained at or above a certain level. Therefore, a high-quality polyurethane foam can be formed. Here, the secondary amine-based catalyst refers to a catalyst containing one or more secondary amines. A secondary amine is an amine in which one hydrogen atom is bonded to a nitrogen atom. The secondary amine-based catalyst is preferably an imidazole-based catalyst. The imidazole-based catalyst is preferably an imidazole in which the 1-position and 2-position are each independently substituted with an alkyl group having 8 or fewer carbon atoms; the alkyl group preferably has 6 or fewer carbon atoms, more preferably 4 or fewer carbon atoms. Preferred specific examples of the imidazole-based catalyst are represented by the following general formula (1).

[0011]

Chemical Formula

[0012] In general formula (1), R 1 and R2 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. The alkyl group and the alkenyl group may each be linear or may have a branched structure. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a hexyl group, a heptyl group, and an octyl group. Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. R 1 and R 2 When the number of carbon atoms in the alkyl group or alkenyl group of is not less than the above lower limit, steric hindrance increases, and when the content of the imidazole-based catalyst in the polyol composition is not more than a certain value, the composition is less susceptible to the influence of low-boiling-point compounds such as hydrofluoroolefins. On the other hand, R 1 and R 2 When the number of carbon atoms in the alkyl group of is not more than the above upper limit, steric hindrance does not become excessively large, so that the reaction between the polyol compound and the polyisocyanate compound can proceed rapidly, and a high-quality polyurethane foam is easily formed. From these viewpoints, R 1 and R 2 each independently is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.

[0013] Examples of imidazole catalysts represented by general formula (1) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Among these, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferred from the viewpoint of improving catalyst activity in the presence of hydrofluoroolefins (HFOs) such as HFO-1234ze and from the viewpoint of rapidly advancing the reaction. Furthermore, 1,2-dimethylimidazole is more preferred from the viewpoint of further enhancing stability.

[0014] The content of the secondary amine catalyst in the polyol composition of the present invention is 0.03 to 5 parts by mass per 100 parts by mass of the polyol compound. If the content of the secondary amine catalyst is less than 0.03 parts by mass, it may result in a decrease in the total amount of catalyst, as described later, which can prevent sufficient reaction between the polyol compound and the polyisocyanate compound, leading to problems such as dripping during application and making it difficult to form a high-quality polyurethane foam. Furthermore, if the content of the secondary amine catalyst exceeds 5 parts by mass, the secondary amine catalyst reacts with low-boiling-point compounds such as HFO, particularly HFO-1234ze, generating many by-products. This makes it difficult to maintain a certain curing rate when applying the polyurethane foam after long-term storage, and makes it difficult to impart good non-flammability to the polyurethane foam. Considering the above, the content of the secondary amine catalyst is preferably 0.05 to 4 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the polyol compound.

[0015] (Resin-based catalysts other than secondary amine catalysts) The polyol composition of the present invention may contain a metal catalyst (metal-based resin catalyst) as a resin catalyst. Examples of metal-based resin catalysts include metal salts consisting of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. Preferably, they are organic acid metal salts consisting of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc., and among these, bismuth catalysts are preferred. Specific examples of metal catalysts include dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatate, bismastrioctate, bismastrith(2-ethylhexanoate), tin dioctylate, lead dioctylate, etc., and among these, bismastrioctate is preferred.

[0016] The content of the resinified metal catalyst in the polyol composition is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and even more preferably 5 to 12 parts by mass, per 100 parts by mass of the polyol compound. If the content of the resinified 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 resinified metal catalyst is below these upper limits, the reaction rate becomes easier to control.

[0017] The content of the resinification catalyst is preferably 1 to 25 parts by mass, more preferably 3 to 20 parts by mass, and even more preferably 6 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.

[0018] (trimerization catalyst) The polyol composition of the present invention may contain a trimerizing catalyst. By including a trimerizing catalyst, when the polyol composition is mixed with a polyisocyanate composition, the isocyanate groups in the polyisocyanate compound react and trimerize, promoting the formation of isocyanurate rings, thereby imparting excellent non-flammability to the polyurethane foam. Suitable trimerizing 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 may 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.

[0019] The trimerization catalyst content is preferably 2 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 trimerization catalyst content is above these lower limits, trimerization of the polyisocyanate compound becomes easier, and the non-flammability of the resulting polyurethane foam is improved. On the other hand, if the trimerization catalyst content is below the upper limit, the reaction becomes easier to control.

[0020] The catalyst content in the polyol composition of the present invention is 15 parts by mass or more per 100 parts by mass of the polyol compound. The catalyst content referred to herein is the total amount of catalyst contained in the polyol composition. If the catalyst content is less than 15 parts by mass, the catalyst content will be insufficient, and the curing reaction between the polyol compound and the polyisocyanate compound will not proceed sufficiently, making it difficult to maintain a certain initial curing rate. In particular, the curing rate tends to decrease when applying polyurethane foam after the polyol composition has been stored for a long period of time. From this perspective, the catalyst content is preferably 18 parts by mass or more, and more preferably 20 parts by mass or more, per 100 parts by mass of the polyol compound. Furthermore, from the viewpoint of suppressing the amount of catalyst that reacts with low-boiling-point compounds, particularly HFOs such as HFO-1234ze, and maintaining the curing rate even after long-term storage of the polyol composition, the catalyst content is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less, per 100 parts by mass of the polyol compound.

[0021] 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 not particularly limited, but is preferably 0.1 to 2.2, more preferably 0.3 to 2, and even more preferably 0.35 to 1.5. If the amount of resinifying catalyst is above the lower limit, it becomes easier to improve the reactivity between the polyol compound and the polyisocyanate compound. On the other hand, if the amount of resinifying catalyst is below the upper limit, the proportion of the trimerizing catalyst in the catalyst becomes above a certain level, making it easier to impart excellent non-flammability to the polyurethane foam.

[0022] In the polyol composition of the present invention, the content of the secondary amine catalyst on a basis of the total amount of catalyst (hereinafter also referred to as the "content of the secondary amine catalyst") is preferably 25% by mass or less, more preferably 18% by mass or less, and even more preferably 15% by mass or less. By keeping the content of the secondary amine catalyst below the above upper limit, the proportion of the secondary amine catalyst in the total catalyst remains below a certain level, and even when the polyol composition is stored for a long period of time, the curing speed when applying the polyurethane foam can be maintained at or above a certain level. Furthermore, from the viewpoint of obtaining a high-quality polyurethane foam by ensuring good reactivity between the polyol compound and the polyisocyanate compound, the lower limit of the content of the secondary amine catalyst is preferably 0.05% by mass or more, more preferably 0.2% by mass or more, and even more preferably 2% by mass or more.

[0023] <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).

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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).

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] The polyol compound content in the polyol composition of the present invention is preferably 15 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 25 to 55% by mass. A polyol compound content above the lower limit is preferable because it facilitates the reaction between the polyol and the polyisocyanate. 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.

[0034] <Phosphate esters> The polyol composition in the present invention preferably contains a phosphate ester. Phosphate esters function as flame retardants, and their inclusion makes it easier to improve the non-flammability of polyurethane foams without significantly reducing discharge flow rate or mixability. Phosphate esters are generally liquid flame retardants. A liquid flame retardant is a flame retardant that becomes liquid at room temperature (23°C) and normal pressure (1 atm).

[0035] As phosphate esters, monophosphate esters, condensed phosphate esters, etc., can be used. A monophosphate ester is a phosphate ester that has one phosphorus atom in its molecule. Monophosphate esters are not particularly limited, but examples include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl) phosphate; halogen-containing phosphate esters such as tris(β-chloropropyl) phosphate; trialkoxy phosphates such as tributoxyethyl phosphate; aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, cresyldiphenyl phosphate, and diphenyl(2-ethylhexyl) phosphate; and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

[0036] Examples of condensed phosphate esters include aromatic condensed phosphate esters such as trialkyl polyphosphates, resorcinol polyphenyl phosphates, bisphenol A polycresyl phosphates, and bisphenol A polyphenyl phosphates. Examples of commercially available condensed phosphate esters include "CR-733S," "CR-741," and "CR747" from Daihachi Chemical Industry Co., Ltd., and "ADEKA Stab PFR" and "FP-600" from ADEKA Corporation.

[0037] The phosphate esters may be used individually from the above-mentioned types, or two or more may be used in combination. Among these, monophosphate esters are preferred from the viewpoint of making it easier to adjust the viscosity of the polyol compound and improving the non-flammability of the polyurethane foam, and halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate are more preferred.

[0038] 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.

[0039] <Filler> The polyol composition of the present invention preferably contains a filler. Including a filler makes it easier to improve various properties of the polyurethane foam, such as flame retardancy. The filler preferably contains a solid flame retardant. By using a solid flame retardant as a filler, high flame retardancy can be imparted to the polyurethane foam. A solid flame retardant is a flame retardant that becomes solid at room temperature (23°C) and normal pressure (1 atm). Examples of solid flame retardants include red phosphorus-based flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, metal hydroxides, and needle-shaped fillers.

[0040] Red phosphorus-based flame retardants may consist of pure red phosphorus, but they may also be red phosphorus coated with a resin, metal hydroxide, metal oxide, etc., or a mixture of red phosphorus and a resin, metal hydroxide, metal oxide, etc. The resin used to coat or mix with red phosphorus is not particularly limited, but examples include thermosetting resins such as phenolic resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. From the viewpoint of flame retardancy, metal hydroxides are preferred as the compound used for coating or mixing. The metal hydroxides described later may be appropriately selected and used.

[0041] Examples of phosphate-containing flame retardants include phosphates comprising 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 phosphates are not particularly limited, but may be monophosphates such as phosphoric acid, phosphorous acid, and hypophosphorous acid, or pyrophosphate, polyphosphate, 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.

[0042] Specific examples of phosphate-containing flame retardants include monophosphates such as aluminum phosphite and trialuminum phosphate, pyrophosphates, and polyphosphates. Here, the polyphosphates are not particularly limited, but examples include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, and aluminum polyphosphate. One or more of the above-mentioned phosphate-containing flame retardants can be used. In the present invention, trialuminum phosphate is preferred.

[0043] Bromine-containing flame retardants are not particularly limited as long as they contain bromine in their molecular structure and are solid at room temperature and pressure, 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.

[0044] 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, poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A and cyanuryl chloride condensates, brominated polystyrene such as brominated (polystyrene), poly(brominated styrene), and crosslinked brominated polystyrene, and crosslinked or non-crosslinked brominated poly(methylstyrene). 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. Among the above, brominated aromatic ring-containing aromatic compounds are preferred, and among these, monomer-based organic bromine compounds such as hexabromobenzene are preferred.

[0045] 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.

[0046] 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 preferred antimony-containing flame retardant used in this invention is antimony trioxide.

[0047] 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. A preferred metal hydroxide used in the present invention is aluminum hydroxide.

[0048] Examples of needle-shaped fillers include potassium titanate whiskers, aluminum borate whiskers, magnesium-containing whiskers, silicon-containing whiskers, silicon-based fillers, 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, stainless steel fibers, and the like. These needle-shaped fillers may be used individually or in combination of two or more types.

[0049] 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.

[0050] The solid flame retardants used in the present invention may be used individually or in combination of two or more types. When using two or more types in combination, for example, two or more solid flame retardants of the same classification may be used, such as containing potassium titanate whiskers and aluminum borate whiskers as needle-shaped fillers, or one or more solid flame retardants of different classifications may be used, such as containing a red phosphorus-based flame retardant and needle-shaped fillers. When a solid flame retardant is included, the amount of the solid flame retardant is not particularly limited, but is, for example, 30 to 120 parts by mass, preferably 40 to 100 parts by mass, more preferably 50 to 90 parts by mass, and even more preferably 60 to 85 parts by mass, per 100 parts by mass of the polyol compound. By keeping the amount of the solid flame retardant within the above range, the settling of the solid flame retardant can be prevented without unnecessarily increasing the solid content, and its dispersibility can be improved.

[0051] The solid flame retardant used in the present invention preferably contains a red phosphorus-based flame retardant. When a red phosphorus-based flame retardant is included as the solid flame retardant, the content of the red phosphorus-based flame retardant is not particularly limited, but is preferably 10 to 60 parts by mass, more preferably 15 to 50 parts by mass, even more preferably 20 to 40 parts by mass, and still more preferably 25 to 35 parts by mass per 100 parts by mass of the polyol compound. If the content of the red phosphorus-based flame retardant is above the lower limit, it becomes possible 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.

[0052] In the present invention, the solid flame retardant used is preferably a solid flame retardant other than a red phosphorus-based flame retardant, in addition to a red phosphorus-based flame retardant, from the viewpoint of easily imparting excellent non-flammability to the polyurethane foam. The solid flame retardant other than the red phosphorus-based flame retardant may be appropriately selected from the above, but it is preferable to include at least one selected from bromine-containing flame retardants and boron-containing flame retardants, and it is more preferable to include both a bromine-containing flame retardant and a boron-containing flame retardant.

[0053] Furthermore, the polyol composition may contain a settling inhibitor as a filler. By using a settling inhibitor, the settling of solid flame retardants and the like dispersed in the polyol composition can be prevented, making it easier to discharge the solid flame retardants and the like, and thus easier to form a highly non-flammable polyurethane foam. In addition, the use of a settling inhibitor makes it easier to uniformly disperse fillers such as red phosphorus-based flame retardants.

[0054] 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.

[0055] The content of the settling inhibitor in the polyol composition is preferably 1 to 6 parts by mass, more preferably 1.5 to 5.5 parts by mass, even more preferably 2 to 5 parts by mass, and even more preferably 2.5 to 4.5 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.

[0056] As fillers, inorganic fillers other than the solid flame retardants mentioned above may be used. Examples of inorganic fillers other than solid flame retardants include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass beads, silica balloons, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon balloons, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash, silica alumina fibers, and zirconia fibers. These inorganic fillers may be used individually or in combination of two or more types.

[0057] When the polyol composition of the present invention contains a filler, the amount is not particularly limited, but is preferably 30 to 130 parts by mass, more preferably 40 to 110 parts by mass, even more preferably 55 to 95 parts by mass, and still more preferably 65 to 90 parts by mass per 100 parts by mass of the polyol compound. A filler content above the lower limit makes it easier to improve various properties, such as flame retardancy, of the polyurethane foam formed from the polyol composition. Furthermore, a filler content below the upper limit allows the viscosity of the polyol composition to be kept below a certain level, resulting in good handling.

[0058] <Low boiling point compounds> The polyol composition of the present invention preferably contains a low-boiling-point compound. The low-boiling-point compound causes the polyol composition to be discharged from the aerosol container by its vapor pressure, and also causes the polyol composition and the polyurethane composition described later to foam by vaporizing when the polyol composition is discharged. From the viewpoint of increasing the discharge amount of the polyol composition, the low-boiling-point compound preferably has a boiling point at 1 atmosphere (hereinafter also simply referred to as "boiling point") of 10°C or less. If the boiling point of the low-boiling-point compound is 10°C or less, when the polyol composition is filled, for example, into an aerosol container, the vapor pressure inside the container can be sufficiently increased, and the composition can be discharged sufficiently. From the viewpoint of such discharge performance, the low-boiling-point compound preferably has a boiling point of 0°C or less, more preferably -10°C or less, and even more preferably -15°C or less. 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 boiling point of the azeotrope when the low-boiling-point compound azeotropes with other compounds, for example.

[0059] 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.

[0060] 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 properties. Generally, HFO, such as HFO-1234ze, readily reacts with secondary amine catalysts contained as resinification catalysts, and may deactivate the secondary amine catalysts. However, in the present invention, as described above, by keeping the content of the secondary amine catalyst below a certain level, the reaction with the secondary amine catalyst is limited, and the deactivation of the secondary amine catalyst can be suppressed.

[0061] 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.

[0062] 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.

[0063] The HFO content in the polyol composition is preferably 10 to 110 parts by mass, more preferably 20 to 90 parts by mass, and even more preferably 30 to 65 parts by mass, per 100 parts by mass of the polyol compound. When the HFO content in the polyol composition is above the lower limit, the vapor pressure inside the aerosol container is kept above a certain level, resulting in good dispensing of the polyol composition. When the HFO content in the polyol composition is below the upper limit, the vapor pressure inside the aerosol container becomes appropriate, improving handling and storage properties.

[0064] <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.

[0065] <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.

[0066] [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.

[0067] 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.

[0068] [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.

[0069] <Polyisocyanate composition> As the polyisocyanate compound included in the polyisocyanate 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.

[0070] 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.

[0071] 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 water units 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 in 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.

[0072] The polyisocyanate composition preferably contains a low-boiling compound in addition to the polyisocyanate compound described above. The inclusion of a low-boiling compound in the polyisocyanate composition allows for easy dispensing of the polyisocyanate compound from an aerosol container. The low-boiling compound included in the polyisocyanate composition can be any of the low-boiling compounds described above that are included in the polyol composition, without any particular limitations. The low-boiling compound used in the polyisocyanate composition may be the same as or different from the low-boiling compound used in the polyol composition. Suitable low-boiling compounds to be included in the polyisocyanate composition include HFO, hydrocarbons having 1 to 4 carbon atoms, ether compounds, and inorganic gases. Among these, it is preferable to include hydrofluoroolefin (HFO) as the low-boiling compound. HFO may be used in combination with other low-boiling compounds, such as inorganic gases.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] [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 may be discharged by the vapor pressure of the low-boiling compound contained in the polyol composition. The polyisocyanate composition sealed in the second container 12 may be discharged by the vapor pressure of the low-boiling compound contained in the polyisocyanate composition. In 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 foamed by low-boiling point compounds while being mixed, and the polyisocyanate compound and polyol compound react to form a polyurethane foam.

[0077] 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.

[0078] 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, the mixing system 10 may be equipped with a discharge gun or jig at a position prior to the introduction into the mixer.

[0079] Figure 2 shows a mixing system 20 as an example of a configuration in which a discharge gun is located before the mixture is introduced into the mixer. The mixing system 20 comprises 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. The polyol composition and the polyisocyanate composition are supplied 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 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.

[0080] 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.

[0081] The polyurethane composition of the present invention, when a polyurethane foam is produced by mixing a polyol composition and a polyisocyanate composition after leaving them at 30°C for two weeks, exhibits a radiant thermal intensity of 50 kW / m² in accordance with the ISO-5660 test method. 2 It is preferable that the total heat generated when heated for 10 minutes is 8 MJ or less. More preferably, the total heat generated is 7 MJ or less, and even more preferably 6.5 MJ or less. If the total heat generated by the polyurethane foam is below the above upper limit, the non-flammability of the polyurethane foam will be excellent even after long-term storage of the polyol composition. The total calorific value of the polyurethane foam of the present invention was measured by a cone calorimeter test, and in detail, it can be measured by the method described in the examples. [Examples]

[0082] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0083] [Evaluation Method] In the examples and comparative examples, the curing rate of the polyol composition and the non-flammability of the polyurethane foam were evaluated using the following evaluation methods.

[0084] <Initial curing speed> In each example and comparative example, the polyol composition was dispensed from the first aerosol container and mixed with the polyisocyanate composition dispensed from the second aerosol container using a static mixer. The mixture was then sprayed onto gypsum board under the following spraying conditions to a thickness of 30 mm or less of polyurethane foam. The surface hardening time (tack-free time) after spraying was measured, and this measured value was defined as the initial hardening rate. (Spraying conditions) • Heating temperature of the first and second aerosol containers: 30°C. That is, the spraying was performed while the first and second aerosol containers were maintained at 30°C. • Base material: Gypsum board (12.5mm thick) ·Substrate temperature: 5℃±1℃ ·Environmental temperature: 5℃±1℃

[0085] Furthermore, the initial curing speed was evaluated according to the following criteria. (Evaluation Criteria) ◎: Less than 30 seconds 〇: 30 seconds or more, less than 60 seconds ×: More than 60 seconds

[0086] <Initial nonflammability> Polyol compositions were dispensed from the first aerosol container obtained in each example and comparative example, and mixed with the polyisocyanate composition dispensed from the second aerosol container using a static mixer. The mixture was then sprayed onto gypsum board to obtain polyurethane foam. The spraying conditions were the same as those used in the test to evaluate the initial curing rate. From the foam obtained by the above method, 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 initial non-flammability was evaluated according to the following criteria. (Evaluation Criteria) ◎: At 10 minutes from the start of heating, the reading was 6.5 MJ or less. ○: At 10 minutes from the start of heating, the reading was between 6.5 MJ and 8 MJ. ×: At 10 minutes from the start of heating, the reading was over 8 MJ.

[0087] <Curing speed 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 using a static mixer. The mixture was then sprayed onto gypsum board so that the thickness of the polyurethane foam was 30 mm or less. The spraying conditions were the same as those used in the test to evaluate the initial curing rate. The surface hardening time (tack-free time) after spraying was measured, and this measured value was defined as the hardening rate over time.

[0088] Furthermore, the curing rate over time was evaluated according to the following criteria. (Evaluation Criteria) ◎: Less than 30 seconds 〇: 30 seconds or more, less than 60 seconds ×: More than 60 seconds

[0089] <Non-flammable over time> The first and second 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 using a static mixer. The mixture was then sprayed onto gypsum board to obtain polyurethane foam. The spraying conditions were the same as those used in the test to evaluate the initial curing rate. From the foam obtained by the above method, 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 over time was evaluated according to the following evaluation criteria. (Evaluation Criteria) ◎: At 10 minutes from the start of heating, the reading was 6.5 MJ or less. ○: At 10 minutes from the start of heating, the reading was between 6.5 MJ and 8 MJ. ×: At 10 minutes from the start of heating, the reading was over 8 MJ.

[0090] [Materials used] The following materials were used in each example and comparative example.

[0091] <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% by mass, diluted with ethylene glycol) (manufactured by Evonik Japan, product name: DABCO TMR-7) • Resinization catalyst 1: Bismastrioctate (active ingredient content 85% by mass, manufactured by Shepherd Chemical, product name: Bicat 8210) • Resinization catalyst 2: 1,2-dimethylimidazole (active ingredient amount 70% 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, ethylenebis(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)

[0092] [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. Evaluation tests were conducted using the obtained first and second aerosol containers.

[0093] [Example 2] The first and second aerosol containers were prepared in the same manner as in Example 1, except that the composition of the polyol composition was changed as shown in Table 1, and no evaluation of nonflammability was performed initially or over time. Polyurethane foam was obtained by this method. The evaluation results are shown in Table 1.

[0094] [Examples 3-4, Comparative Examples 1-5] The procedure was carried out in the same manner as in Example 1, except that the composition of the polyol composition was changed as shown in Table 1. The results of each evaluation are shown in Table 1.

[0095] [Table 1] *The content of each catalyst in Table 1 is in parts by mass of the product. The total amount of catalyst is the sum of the net content of each catalyst (parts by mass of the product minus the solvent content).

[0096] As is clear from the above examples, the aerosol polyol composition satisfying the requirements of the present invention was able to maintain a curing rate above a certain level when applying polyurethane foam, not only initially but also after long-term storage. Furthermore, as shown in Examples 1, 3, and 4, by incorporating a solid flame retardant into the polyol composition, it was possible to form a polyurethane foam with excellent non-flammability. In contrast, the polyol compositions for aerosols prepared in the comparative examples had a total catalyst content below a predetermined amount, or a secondary amine catalyst content exceeding a predetermined amount, resulting in a significant decrease in the curing speed when applying polyurethane foam after long-term storage. Furthermore, in each comparative example, even when solid flame retardants were blended in the same manner as in Examples 1, 3, and 4, it was not possible to form polyurethane foam with excellent flame retardancy. [Explanation of Symbols]

[0097] 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. An aerosol container in which a polyol composition for aerosols is sealed inside, The aerosol polyol composition contains a polyol compound, a catalyst, and a low-boiling point compound. The content of the catalyst is 15 parts by mass or more per 100 parts by mass of the polyol compound. The catalyst includes an imidazole-based catalyst, The content of the imidazole-based catalyst is 0.03 to 5 parts by mass per 100 parts by mass of the polyol compound, and the content of the imidazole-based catalyst is 25% by mass or less based on the total amount of catalyst. An aerosol container having a boiling point of 10°C or less at 1 atmosphere for the low-boiling compound.

2. The aerosol container according to claim 1, wherein the aerosol polyol composition further contains a phosphate ester.

3. The aerosol container according to claim 1 or 2, further comprising a solid flame retardant in the aerosol polyol composition.

4. The aerosol container according to claim 3, wherein the solid flame retardant comprises a red phosphorus-based flame retardant.

5. The aerosol container according to claim 1 or 2, wherein the polyol composition for aerosols contains a resin-based metal catalyst and / or a trimerizing catalyst.

6. The aerosol container comprises the aerosol container according to claim 1 or 2, and an aerosol container in which a polyisocyanate composition containing a polyisocyanate compound and a low boiling point compound is sealed inside, A mixing system wherein the boiling point of the low-boiling compound at 1 atmosphere is 10°C or less.

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