Polyol composition, polyurethane composition, and polyurethane foam

Abstract

To provide a polyol composition for aerosols that ensures a consistent curing rate when applying polyurethane foam, even after long-term storage, and that the resulting polyurethane foam exhibits good non-flammability. [Solution] A polyol composition for aerosols containing a polyol compound, a flame retardant, a low boiling point compound, a catalyst, and a nucleophilic inhibitor.

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] Polyurethane foam is used as insulation material in buildings such as apartment buildings, detached houses, various school facilities, and commercial buildings due to its excellent heat insulation and adhesive properties. Polyurethane foam can be obtained, for example, by mixing a polyol composition and polyisocyanate in a foaming machine, foaming the mixture, and then spraying it onto objects such as ceilings, walls, and roofs using a spray device, as described in Patent Documents 1 and 2. In addition, as a method different from the spraying method using such a foaming machine, there is also a known method for forming polyurethane foam using aerosol containers that allow each liquid to be discharged and mixed from the container in a relatively simple configuration, as disclosed in Patent Documents 3 to 6. Specifically, one container is filled with a polyol compound and a low-boiling-point compound, and the other container is filled with a polyisocyanate compound and a low-boiling-point compound. From each container, the vapor pressure of the low-boiling-point compound causes the polyol liquid and the polyisocyanate liquid to be discharged respectively, and by mixing them, a polyurethane foam is formed. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2022-159929 [Patent Document 2] International Publication No. 2022 / 215440 [Patent Document 3] Japanese Patent Publication No. 2023-81650 [Patent Document 4] Japanese Patent Publication No. 2024-23087 [Patent Document 5] Japanese Patent Publication No. 2024-58840 [Patent Document 6] Japanese Patent Publication No. 2024-58841 [Overview of the project] [Problems that the invention aims to solve]

[0004] The polyol compositions used in the aerosol containers described above are often suitably used to fill in defects that occur when polyurethane foam is applied, and therefore good non-flammability is required. However, conventional aerosol polyol compositions, when stored for extended periods, tend to exhibit problems such as a decrease in the curing speed when applying polyurethane foam, leading to dripping, and a decrease in the non-flammability of the resulting foam. In particular, when a large amount of metal-based flame retardants are used, the catalyst is more likely to become deactivated, and the aforementioned problems become more pronounced. Therefore, the object of the present invention is to provide a polyol composition for aerosols in which the curing speed when applying polyurethane foam remains above a certain level even after long-term storage, and the resulting polyurethane foam exhibits good non-flammability. [Means for solving the problem]

[0005] As a result of diligent research, the inventors have found that the above problems can be solved by an aerosol polyol composition containing a polyol compound, a flame retardant, a low boiling point compound, a catalyst, and a nucleophilic inhibitor, and have completed the present invention. That is, the present invention provides the following [1] to

[11] .

[0006] [1] A polyol composition for aerosols containing a polyol compound, a flame retardant, a low boiling point compound, a catalyst, and a nucleophilic inhibitor. [2] The aerosol polyol composition according to [1] above, wherein the flame retardant comprises a metal-based flame retardant. [3] The polyol composition for an aerosol according to the above [1] or [2], wherein the nucleophilic inhibitor is at least one selected from the group consisting of an alkali metal compound and an alkaline earth metal compound. [4] The polyol composition for an aerosol according to any one of the above [1] to [3], wherein the low-boiling compound contains a hydrofluoroolefin. [5] The polyol composition for an aerosol according to any one of the above [1] to [4], wherein the catalyst contains a catalyst having a morpholine skeleton. [6] The polyol composition for an aerosol according to any one of the above [1] to [5], wherein the catalyst contains a potassium salt. [7] The polyol composition for an aerosol according to any one of the above [1] to [6], wherein the catalyst contains a bismuth-based catalyst. [8] The polyol composition for an aerosol according to any one of the above [1] to [7], wherein the flame retardant contains a phosphorus-based flame retardant. [9] A polyurethane composition comprising the polyol composition for an aerosol according to any one of the above [1] to [8] and a polyisocyanate composition containing a polyisocyanate compound.

[10] A polyurethane foam formed from the polyurethane composition according to the above [9].

[11] A mixing system comprising a first container enclosing the polyol composition for an aerosol according to any one of the above [1] to [8] and a second container enclosing a polyisocyanate composition containing a polyisocyanate compound. [Effect of the Invention]

[0007] According to the present invention, even when stored for a long time, it is possible to provide a polyol composition for an aerosol in which the curing rate during the construction of a polyurethane foam is at a certain level or higher and the nonflammability of the formed polyurethane foam is good. [Brief Description of the Drawings]

[0008] [Figure 1] It is a schematic diagram showing one embodiment of the mixing system. [Figure 2]It is a schematic diagram showing another embodiment of the hybrid system.

Embodiments for Carrying out the Invention

[0009] The polyol composition for aerosol of the present invention contains a polyol, a flame retardant, a low-boiling compound, a catalyst, and a nucleophilic inhibitor. The polyol composition for aerosol is used after being enclosed in an aerosol container described later. Incidentally, the polyol composition for aerosol may be simply described as a polyol composition. The polyol composition of the present invention is used to produce a polyurethane foam by mixing it with a polyisocyanate composition containing a polyisocyanate compound as described later. This will be described in more detail below.

[0010] <Polyol Compound> The polyol composition in the present invention contains a polyol compound. Examples of the polyol compound include polycaprolactone polyol, polycarbonate polyol, polyester polyol, polymer polyol, and polyether polyol.

[0011] Examples of the polycaprolactone polyol include polypropionolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of the polycarbonate polyol include polyols obtained by a dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, etc.

[0012] Examples of the polyester polyol include polymers obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, and condensates of a hydroxycarboxylic acid and the polyhydric alcohol, etc. Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), o-phthalic acid (phthalic acid), naphthalenedicarboxylic 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.

[0013] 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, or hydrogenated versions thereof.

[0014] Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one C2-C6 alkylene oxide, specifically 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, such as a polyhydric alcohol. Examples of alkylene oxides include at least one of ethylene oxide and propylene oxide. 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, tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl glucoside and its derivatives, phloroglucinol, and cresol. Examples include polyols such as 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; polyfunctional polyols (e.g., 2 to 100 functional groups) such as polyvinyl alcohol; condensates of phenol and formaldehyde (novolac); amines such as ethylenediamine and butylenediamine. As the polyether polyol, a Mannich-type polyether polyol may be used. A Mannich-type polyether polyol is obtained using the Mannich reaction and is a Mannich condensate having two or more hydroxyl groups in the molecule, or a polyether polyol obtained by adding an alkylene oxide to such a Mannich condensate.

[0015] Polyol compounds used in the present invention include polyester polyols and polyether polyols. Polyols having two hydroxyl groups are also preferred. Among these, aromatic polyester polyols, which are polyester polyols having an aromatic ring, are preferred from the viewpoint of improving the flame retardancy of polyurethane foam. The aromatic polyester polyol is preferably a condensate of an aromatic dicarboxylic acid such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), or naphthalenedicarboxylic acid with a glycol. In particular, from the viewpoint of improving the flame retardancy of the polyurethane foam, especially its ability to prevent the spread of flame, the aromatic polyester polyol is more preferably a phthalic acid-based polyester polyol, which is a condensate of phthalic acid and glycol. Furthermore, it is even more preferable that the aromatic polyester polyol includes at least one selected from p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid and glycol, and o-phthalic acid-based polyester polyol, which is a condensate of o-phthalic acid and glycol.

[0016] When the polyol compound contains an aromatic polyester polyol, the amount is not particularly limited, but is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, and even more preferably 100 parts by mass, per 100 parts by mass of the polyol compound.

[0017] The weighted average hydroxyl value of the polyol compound is preferably 20 to 350 mg KOH / g, more preferably 50 to 300 mg KOH / g, and even more preferably 100 to 280 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 and better workability during spraying. The hydroxyl value of polyol compounds can be measured according to JIS K 1557-1:2007.

[0018] Here, the weighted average hydroxyl value of a polyol compound is determined by the sum of the products of the hydroxyl values ​​of the individual polyol compounds constituting the polyol compound and the weight fraction of each individual polyol compound in the polyol compound. For example, when two types of polyol compounds, (d1) and (d2), are used as the polyol compound, if the hydroxyl value of polyol compound (d1) is X1 and the amount added is m1, and the hydroxyl value of polyol compound (d2) is X2 and the amount added is m2, then the weighted average hydroxyl value is expressed by the following formula. Note that the amounts m1 and m2 are parts by mass in 100 parts by mass of the polyol compound. Weighted average hydroxyl value (mgKOH / g)=X1×(m1 / (m1+m2))+X2×(m2 / (m1+m2))

[0019] <Nucleophilic inhibitors> The polyol composition for aerosols of the present invention contains a nucleophilic inhibitor. The electrophilic nucleophilic inhibitor can suppress the deactivation of the catalyst in the polyol composition. The reason for this is unclear, but it is presumed to be as follows: Low-boiling-point compounds (e.g., hydrofluoroolefins such as HFO-1234ze, described later) and flame retardants (e.g., metal-based flame retardants, described later) contained in the polyol composition tend to act on the catalyst and deactivate it. On the other hand, nucleophilic inhibitors act on the catalyst preferentially over low-boiling-point compounds or flame retardants, and gently, to the extent that the catalyst's activity is not impaired, thereby suppressing the reaction between low-boiling-point compounds and the catalyst, or between flame retardants and the catalyst. Therefore, by including a nucleophilic inhibitor in the polyol composition, the reaction between the flame retardant and the catalyst, or between the low-boiling point compound and the catalyst, can be suppressed. This ensures that even when the polyol composition is stored for a long period, the curing rate when applying the polyurethane foam remains above a certain level, and further improves the non-flammability of the resulting polyurethane foam.

[0020] Examples of nucleophilic inhibitors used in the present invention include alkali metal compounds, alkaline earth metal compounds, and transition metal compounds. Examples of alkali metal compounds used as nucleophilic inhibitors include alkali metal hydroxides, carbonates, and carboxylates. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of alkali metal carbonates include lithium carbonate, sodium carbonate, and potassium carbonate. Examples of alkali metal carboxylates include alkali metal acetates such as lithium acetate, sodium acetate, and potassium acetate.

[0021] Examples of alkaline earth metal compounds include hydroxides, carbonates, and sulfates of alkaline earth metals. Examples of alkaline earth metal hydroxides include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. Examples of alkaline earth metal carbonates include beryllium carbonate, magnesium carbonate, strontium carbonate, and barium carbonate. Examples of alkaline earth metal sulfates include beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, and barium sulfate. Examples of transition metal compounds include transition metal hydroxides. Examples of transition metal hydroxides include manganese(II) hydroxide, iron(II) hydroxide, iron(III) hydroxide, nickel(II) hydroxide, copper(II) hydroxide, zinc hydroxide, vanadium hydroxide, and chromium(III) hydroxide.

[0022] The nucleophilic inhibitors used in the present invention may be used individually or in combination of two or more, but it is preferable to use one individual inhibitor. Furthermore, as the nucleophilic inhibitor used in the present invention, at least one selected from the group consisting of alkali metal compounds and alkaline earth metal compounds is preferred. Among the above, alkaline earth metal compounds are more preferred because they readily exhibit the effect of a nucleophilic inhibitor, and hydroxides of alkaline earth metals are even more preferred. Furthermore, magnesium hydroxide, lithium hydroxide, sodium acetate, potassium carbonate, barium sulfate, and copper(II) hydroxide are preferred as nucleophilic inhibitors, with magnesium hydroxide being particularly preferred among them.

[0023] The content of the nucleophilic inhibitor in the polyol composition of the present invention is preferably 0.2 to 80 parts by mass, more preferably 0.5 to 60 parts by mass, even more preferably 1 to 30 parts by mass, and particularly preferably 2 to 10 parts by mass, per 100 parts by mass of the polyol compound. A content of the nucleophilic inhibitor above the lower limit ensures reliable suppression of catalyst deactivation. On the other hand, a content of the nucleophilic inhibitor below the upper limit allows for appropriate maintenance of catalyst activity and also maintains a low viscosity of the polyol composition.

[0024] <Low boiling point compounds> The polyol composition of the present invention contains a low-boiling-point compound. The low-boiling-point compound, due to its vapor pressure, causes the polyol composition to be discharged from the 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, it is preferable that the boiling point of the low-boiling-point compound at 1 atmosphere (hereinafter also simply referred to as "boiling point") is 10°C or lower. When the boiling point of the low-boiling-point compound is 10°C or lower, the vapor pressure inside the container can be sufficiently increased when the polyol composition is filled, for example, into an aerosol container, and the composition can be discharged sufficiently. From the viewpoint of such discharge performance, it is preferable that the low-boiling-point compound has a boiling point of 0°C or lower, more preferably -10°C or lower, and even more preferably -15°C or lower. Here, the boiling point of the low-boiling-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.

[0025] 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.

[0026] 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 catalysts such as resin catalysts and may deactivate them. However, the polyol composition of the present invention contains the nucleophilic inhibitor described above, which can suppress the deactivation of the catalyst. Furthermore, as will be described later, using a catalyst having a morpholine skeleton in the polyol composition of the present invention more effectively suppresses catalyst deactivation by HFO.

[0027] 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 them.

[0028] 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.

[0029] 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.

[0030] <Catalyst> The polyol composition of the present invention contains a catalyst. Examples of catalysts include resinification catalysts and trimerization catalysts, and it is preferable to contain both resinification catalysts and trimerization catalysts.

[0031] (Resin-based catalyst) The polyol composition of the present invention preferably contains a catalyst having a morpholine skeleton. Catalysts having a morpholine skeleton are typically included as resinification catalysts. Because catalysts having a morpholine skeleton have low reactivity with low-boiling point compounds, particularly HFOs such as HFO-1234ze, due to steric hindrance caused by the morpholine skeleton, the inclusion of such a catalyst suppresses catalyst deactivation even when the polyol composition is stored for a long period, allowing the curing speed during polyurethane foam construction to be maintained above a certain level. 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 further suppresses catalyst deactivation due to reaction with low-boiling point compounds, making it easier to maintain a certain curing rate when applying polyurethane foam. In addition, the reaction between polyol compounds and polyisocyanate compounds becomes easier to control, enabling the formation of 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.

[0032] 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, catalyst deactivation is suppressed, making it easier to maintain a constant curing rate when applying polyurethane foam even after long-term storage of the polyol composition. On the other hand, if it is below these upper limits, the reaction rate becomes easier to control.

[0033] The polyol composition of the present invention preferably contains a metal-based 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., and preferably organic acid metal salts consisting of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc.

[0034] Examples of resin-based metal catalysts include dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatate, bismastrioctate, bismastrith (2-ethylhexanoate), tin dioctate, and lead dioctate, among which bismuth-based catalysts, bismastrioctate, are preferred. Among resin-based metal catalysts, compounds containing bismuth (bismuth-based catalysts) are preferred. Including a bismuth-based catalyst improves foaming properties and the adhesive strength of the resulting polyurethane foam.

[0035] The polyol composition of the present invention preferably contains a resinifying metal catalyst in addition to a catalyst having a morpholine skeleton as the resinifying catalyst, more preferably contains a catalyst having a morpholine skeleton and a bismuth-based catalyst, and even more preferably contains a catalyst having two morpholine skeletons and a bismuth-based catalyst. By using such a combination of resinifying catalysts in the polyol composition, it becomes easier to maintain a curing speed above a certain level when applying polyurethane foam even after long-term storage of the polyol composition, and it becomes easier to improve the non-flammability of polyurethane.

[0036] The content of the resinified metal catalyst in the polyol composition is preferably 1 to 15 parts by mass, more preferably 2 to 10 parts by mass, and even more preferably 3 to 6 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.

[0037] When a polyol composition uses both a catalyst having a morpholine skeleton and a resin-based metal catalyst, the ratio of the morpholine skeleton catalyst to the resin-based metal catalyst (hereinafter also referred to as "morpholine / metal") is not particularly limited, but is, for example, 0.1 to 10, preferably 0.5 to 8, and more preferably 1 to 4. When the morpholine / metal ratio is within the above range, catalyst deactivation is suppressed, making it easier to maintain a curing rate above a certain level when applying polyurethane foam.

[0038] The total content of the resinification catalyst is preferably 4 to 35 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 8 to 23 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.

[0039] The polyol composition of the present invention may use an imidazole compound as a resinification catalyst, but it is preferable that it is substantially free of imidazole compounds. Generally, imidazole compounds readily react with low-boiling point compounds, especially HFOs such as HFO-1234ze. Therefore, by substantially omitting the imidazole compound as a resinification catalyst, the deactivation of the resinification catalyst due to reaction with low-boiling point compounds can be suppressed. As a result, even after long-term storage of the polyol composition, the curing rate when mixed with a polyisocyanate composition can be maintained at or above a certain level. Here, "substantially free of imidazole compounds" means that, based on the total amount of catalyst in the polyol composition, the content of imidazole compounds is 0.05% by mass or less, preferably 0.01% by mass or less, and more preferably 0% by mass.

[0040] Here, an imidazole compound is a compound having an imidazole skeleton, and an example of such a compound is the one represented by the following general formula (1).

[0041] [ka] (In general formula (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.

[0042] R in general formula (1) 1 and R 2 Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. Alkyl and alkenyl groups are not limited to linear structures; they also include those with branched structures. Specific examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, isopentyl group, sec-pentyl group, hexyl group, heptyl group, octyl group, and the like. Specific examples of alkenyl groups include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, and octenyl groups. Examples of imidazole compounds 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.

[0043] (trimerization catalyst) When a polyol composition is mixed with a polyisocyanate composition, the isocyanate groups in the polyisocyanate compound react and trimerize, promoting the formation of isocyanurate rings. This trimer catalyst can impart excellent non-flammability to polyurethane foams. The trimerizing catalyst preferably contains at least one selected from amine-based catalysts, quaternary ammonium salts, and potassium salts, and more preferably contains at least a potassium salt, and more preferably contains both a quaternary ammonium salt and a potassium salt.

[0044] Quaternary ammonium salts Examples of quaternary ammonium salts include quaternary ammonium carboxylates. The carboxylic acid in the quaternary ammonium carboxylate may have one or more carbon atoms, but it is preferable that it has two or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, and more preferably a saturated aliphatic carboxylic acid. The number of carbon atoms in the carboxylic acid is, for example, 20 or less, but is preferably 12 or less, and more preferably 8 or less. The carboxylic acid may be linear or have a branched structure, but it is preferable that it has a branched structure. Having a branched structure makes it easier to reduce reactivity with low-boiling point compounds such as hydrofluoroolefins due to steric hindrance, thus improving the stability of the polyol composition.

[0045] Suitable specific examples of carboxylic acids in quaternary ammonium carboxylates include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. Among these, at least one selected from acetic acid and 2,2-dimethylpropanoic acid is preferred, and 2,2-dimethylpropanoic acid is more preferred.

[0046] In quaternary ammonium carboxylates, the quaternary ammonium ion is preferably a tetraalkylammonium ion or a hydroxyalkyltrialkylammonium ion, and more preferably a tetraalkylammonium ion.

[0047] Each alkyl group in the tetraalkylammonium ion is, for example, an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms, and more preferably a methyl group. Specific examples of tetraalkylammonium ions include tetramethylammonium ions and triethylmethylammonium ions.

[0048] Each alkyl group in the hydroxyalkyltrialkylammonium ion is, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, an ethyl group, or a butyl group. A hydroxyalkyl group is a group in which one of the hydrogen atoms in the alkyl group is substituted with a hydroxyl group, for example, having 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms, and more preferably 3 or 4 carbon atoms. Examples of hydroxyalkyl groups include hydroxyethyl group, hydroxypropyl group, and hydroxybutyl group. Specific examples of hydroxyalkyltrialkylammonium ions include, for example, hydroxybutyltrimethylammonium ions, hydroxypropyltrimethylammonium ions, and hydroxyethyltrimethylammonium ions.

[0049] The ammonium ion in the quaternary ammonium carboxylate is preferably at least one selected from the group consisting of triethylmethylammonium ion, tetramethylammonium ion, hydroxybutyltrimethylammonium ion, and hydroxypropyltrimethylammonium ion, more preferably at least one selected from the group consisting of triethylmethylammonium ion, tetramethylammonium ion, and hydroxybutyltrimethylammonium ion, and even more preferably tetramethylammonium ion.

[0050] Furthermore, suitable specific examples of quaternary ammonium carboxylates include tetramethylammonium acetate, tetramethylammonium 2,2-dimethylpropanoate, triethylmethylammonium 2-ethylhexanoate, and hydroxybutyltrimethylammonium 2-ethylhexanoate. Among these, at least one selected from tetramethylammonium acetate and tetramethylammonium 2,2-dimethylpropanoate is preferred, and tetramethylammonium 2,2-dimethylpropanoate is more preferred, from the viewpoint of facilitating the formation of isocyanurate bonds by the trimer of polyisocyanate and facilitating the imparting of excellent flame retardancy to polyurethane foam. In this invention, the quaternary ammonium carboxylate salt may be used alone or in combination of two or more types.

[0051] The content of the quaternary ammonium salt is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 7 parts by mass, per 100 parts by mass of polyol.

[0052] Potassium salts Examples of the potassium salt include potassium carboxylate salts. The carboxylic acid in the potassium carboxylate salt may have 1 or more carbon atoms, preferably 5 or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The number of carbon atoms of the carboxylic acid is, for example, 20 or less, preferably 12 or less, and more preferably 8 or less. Further, the carboxylic acid may be linear or may have a branched structure, but preferably has a branched structure. Having a branched structure tends to reduce the reactivity with hydrofluoroolefins and the like due to steric hindrance, thus improving the stability of the polyol composition.

[0053] Among the potassium carboxylate salts, the potassium carboxylate salt represented by the following general formula (2) is preferred. The potassium carboxylate salt represented by the following general formula (2) has appropriate steric hindrance, so that a decrease in catalytic activity can be prevented.

[0054] [Chemical formula] (In general formula (2), R 3 and R 4 each independently represents an alkyl group, and R 5 represents a hydrogen atom or an alkyl group. Further, K + represents a potassium ion.)

[0055] R 3 and R 4 in general formula (2) each independently represents an alkyl group. Specifically, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 4 carbon atoms is more preferred, and an alkyl group having 1 to 2 carbon atoms is even more preferred. The alkyl group may be linear or may have a branched structure. R 3 and R 4 having the number of carbon atoms equal to or more than the lower limit value results in a large steric hindrance, so that the reactivity with hydrofluoroolefins decreases, and it becomes easier to suppress the deactivation of the catalyst. On the other hand, R 3 , and R 4If the number of carbon atoms is below the aforementioned upper limit, steric hindrance does not become too large, thus preventing the reaction from becoming slow. Also, R 5 R represents a hydrogen atom or an alkyl group, with a hydrogen atom being preferred. 5 If the alkyl group is an alkyl group, it is preferably one to six carbon atoms, more preferably one to four carbon atoms, and even more preferably one to two carbon atoms.

[0056] Preferred specific examples of carboxylic acids in potassium carboxylic acid salts include at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. Furthermore, carboxylic acids as shown in the above general formula (2) are preferred, with 2,2-dimethylpropanoic acid and 2-ethylhexanoic acid being more preferred, and 2-ethylhexanoic acid being even more preferred. In this invention, the potassium carboxylate salt may be used alone or in combination of two or more types.

[0057] The potassium salt content is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 2 to 5 parts by mass, per 100 parts by mass of polyol.

[0058] The trimerization catalyst content is preferably 1 to 25 parts by mass, more preferably 2 to 18 parts by mass, and even more preferably 4 to 12 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.

[0059] 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 0.5 to 5, more preferably 1 to 4, and even more preferably 1.2 to 2.5. When the ratio (amount of resinifying catalyst / amount of trimerizing catalyst) is above the lower limit, the reactivity between the polyol compound and the polyisocyanate compound is easily improved. When the ratio (amount of resinifying catalyst / amount of trimerizing 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.

[0060] Furthermore, the total amount of catalyst in the polyol composition is not particularly limited, but is preferably 7 to 50 parts by mass, more preferably 10 to 40 parts by mass, even more preferably 15 to 35 parts by mass, and even more preferably 20 to 30 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.

[0061] <Flame retardant> The polyol composition of the present invention contains a flame retardant. The flame retardant is not particularly limited, but preferably contains a metallic flame retardant. As described above, metallic flame retardants can cause catalyst deactivation, but in the present invention, by using a nucleophilic inhibitor, it is possible to improve flame retardancy while suppressing catalyst deactivation.

[0062] Examples of metal-based flame retardants include metal borates, metal phosphates, stanates, sulfides, halides, and sulfates, with metal borates and metal phosphates being preferred among these. Note that the metal salts mentioned above, used as nucleophilic inhibitors, are not included in the definition of metal-based flame retardants. Examples of metallic borates include alkali metals, alkaline earth metals, and borates of elements from groups 4, 12, and 13 of the periodic table. 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. Among these, zinc borate is preferred. Examples of metal phosphates include 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; zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite; and aluminum salts such as monoaluminum phosphate, dialuminum phosphate, trialuminum phosphate, aluminum phosphite, and aluminum hypophosphite. Among these, aluminum salts are preferred, and aluminum phosphite is more preferred. Among the metal-based flame retardants mentioned above, zinc borate and aluminum phosphite are preferred, with zinc borate being more preferred. Metal-based flame retardants may be used individually or in combination of two or more types.

[0063] The content of the metal-based flame retardant is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, even more preferably 15 to 40 parts by mass, and still more preferably 18 to 30 parts by mass, per 100 parts by mass of the polyol compound. Generally, while a high content of metal-based flame retardants tends to improve the flame retardancy of foams, it also tends to deactivate catalysts and reduce the curing rate over time. However, because the polyol composition of the present invention contains a nucleophilic inhibitor, it can maintain a good curing rate even when the polyol composition is stored for a long period of time. In particular, by using both a nucleophilic inhibitor and a catalyst having a morpholine skeleton in the present invention, the curing rate can be maintained even more effectively after long-term storage.

[0064] The flame retardant contained in the polyol composition of the present invention may include flame retardants other than the metal-based flame retardants described above, i.e., non-metallic flame retardants. The non-metallic flame retardant is not particularly limited, but from the viewpoint of obtaining good flame retardancy, examples include phosphorus-based flame retardants such as phosphate ester flame retardants and red phosphorus flame retardants, bromine-based flame retardants, and chlorine-based flame retardants. Among these, it is preferable to contain a phosphorus-based flame retardant, and more preferable to contain a phosphate ester flame retardant. Furthermore, it is even more preferable to contain at least one of a bromine-based flame retardant and a red phosphorus-based flame retardant together with a phosphate ester flame retardant, and it is even more preferable to use at least a phosphate ester flame retardant and a red phosphorus-based flame retardant in combination. Furthermore, from the viewpoint of further improving flame retardancy, it is preferable to use non-metallic flame retardants in combination with metallic flame retardants.

[0065] Examples of phosphate ester-based flame retardants include tricresyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, and octyl diphenyl phosphate. Alternatively, halogenated phosphate ester-based flame retardants such as tri(chloroethyl) phosphate, trisdichloropropyl phosphate, and tris(β-chloropropyl) phosphate may be used. Among these, at least one selected from the group consisting of tris(β-chloropropyl) phosphate and triphenyl phosphate is preferred, with tris(β-chloropropyl) phosphate being more preferred.

[0066] Red phosphorus-based flame retardants may consist of pure red phosphorus, or they may be coated with resin, metal hydroxide, metal oxide, etc., or they may be mixed with red phosphorus and formed into a powder. When metal hydroxide is used as a coating on red phosphorus or mixed with red phosphorus to form a powder, it shall be used separately from the nucleophilic inhibitor mentioned above. For red phosphorus-based flame retardants, commercially available products such as NovaRed 120, NovaExcel 140 (both manufactured by Phosphorus Chemical Industry Co., Ltd.), and HishiGuard (manufactured by Nippon Chemical Industrial Co., Ltd.) can be used as is.

[0067] 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 aromatic compounds containing brominated aromatic rings include monomer-based 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.

[0068] 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. When the polyol composition of the present invention contains a brominated flame retardant, it is preferable that the brominated flame retardant contains ethylenebis(pentabromophenyl).

[0069] Examples of chlorine-based flame retardants include chlorinated paraffin, chlorinated polyethylene, dodecachloropentacyclooctadeca-7,15-diene (Dechloran Plus 25® (manufactured by Occidental Chemicals)), and hetic anhydride.

[0070] The flame retardant may be contained as a single agent or as a combination of two or more agents. When two or more agents are used in combination, one or more metallic flame retardants and one or more non-metallic flame retardants may be used together, two or more metallic flame retardants may be used together, or two or more non-metallic flame retardants may be used together. Therefore, the combination of flame retardants is not particularly limited, but from the viewpoint of improving the flame retardancy of polyurethane foam, the flame retardant contained in the polyol composition of the present invention preferably contains a metallic flame retardant, more preferably contains zinc borate, and even more preferably contains zinc borate in combination with one or more non-metallic flame retardants.

[0071] The content of the nonmetallic flame retardant is preferably 45 to 260 parts by mass, more preferably 80 to 200 parts by mass, and even more preferably 120 to 180 parts by mass, per 100 parts by mass of polyol.

[0072] The amount of flame retardant in the polyol composition of the present invention is preferably 50 to 360 parts by mass, more preferably 90 to 250 parts by mass, and even more preferably 140 to 210 parts by mass, per 100 parts by mass of polyol.

[0073] <Filler> The polyol composition of the present invention may contain fillers other than the flame retardant described above. Examples of such fillers include anti-settlement agents. By using a settling inhibitor, the precipitation of solid flame retardants (metallic flame retardants, red phosphorus flame retardants, etc.) dispersed in the polyol composition can be prevented, making it easier to discharge the flame retardants and thus easier to form a highly flame-retardant polyurethane foam. In addition, the use of a settling inhibitor makes it easier to uniformly disperse metallic flame retardants and red phosphorus flame retardants.

[0074] 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.

[0075] The content of the anti-settling agent in the polyol composition is preferably 1 to 8 parts by mass, more preferably 1.5 to 7 parts by mass, and even more preferably 2 to 6 parts by mass, per 100 parts by mass of the polyol compound. If the content of the anti-settling agent is above the lower limit, the metal-based flame retardant and red phosphorus-based flame retardant will not precipitate in the polyol composition, resulting in good discharge properties for the polyol composition. Furthermore, if the content of the anti-settling agent is below the upper limit, the viscosity of the polyol composition will not become excessively high, making it easier to achieve good discharge properties.

[0076] As fillers, inorganic fillers other than the above-mentioned flame retardants and settling inhibitors may be used. Examples of such inorganic fillers include diatomaceous earth, alumina, titanium oxide, iron oxide, tin oxide, antimony oxide, ferrites, zinc carbonate, dawsonite, hydrotalcite, calcium silicate, talc, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass beads, silica balloons, aluminum nitride, boron nitride, silicon nitride, graphite, carbon balloons, charcoal powder, various metal powders, potassium titanate, 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.

[0077] <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.

[0078] <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. There are no particular limitations on the method for producing the polyol composition of the present invention; for example, it can be produced by mixing each component.

[0079] [container] In the present invention, a container containing the above-described polyol composition can be provided. 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 portion that seals the top of the container body. When a button or the like provided on the cap portion 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 portion 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.

[0080] 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.

[0081] [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.

[0082] <Polyisocyanate composition> The polyisocyanate composition contains a polyisocyanate compound. As the polyisocyanate compound, known polyisocyanate compounds used for forming polyurethane foams can be used. Examples of polyisocyanate compounds include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI).

[0083] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate. Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0084] Among these, aromatic polyisocyanates are preferred from the viewpoint of ease of use and availability, and diphenylmethane diisocyanate, polymeric MDI, or mixtures thereof are more preferred. Polyisocyanates may be used individually or as a mixture of two or more.

[0085] 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 200 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.

[0086] 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 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.

[0087] 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.

[0088] 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.

[0089] The content of the low-boiling compound in the polyisocyanate composition is preferably 0.5 to 20 parts by mass, more preferably 3 to 18 parts by mass, and even more preferably 8 to 15 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.

[0090] 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.

[0091] [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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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 The total heat generated when heated for 10 minutes was 8 MJ / m². 2 The following is preferable: The total heat generation is 7 MJ / m³. 2 It is more preferable that the following conditions are met: 6.5 MJ / m 2 It is even more preferable that the following conditions are met: If the total heat generated by the polyurethane foam is less than or equal to the above upper limit, the polyurethane foam will exhibit excellent non-flammability even after long-term storage of the polyol composition. The total calorific value of the polyurethane foam of the present invention is measured by a cone calorimeter test, and in detail, it can be measured by the method described in the examples. [Examples]

[0097] The present invention will be described in more detail by reference to examples, but the present invention is not limited in any way by these examples.

[0098] [Evaluation Method] In the examples and comparative examples, the curing speed during application of the polyurethane foam and the non-flammability of the polyurethane foam were evaluated using the following evaluation methods.

[0099] <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℃

[0100] <Workability after time has passed (curing speed)> 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 a gypsum board so that the thickness of the polyurethane foam was 30 mm or less. The surface hardening time (tack-free time) after spraying was measured, and this measurement was defined as the hardening rate over time. The spraying conditions were the same as those used in the test to evaluate the initial hardening rate.

[0101] Furthermore, based on the above measurements, the curing rate over time was evaluated according to the following criteria. (Evaluation Criteria) ◎: Less than 15 seconds ○: 15 seconds or more but less than 30 seconds ×: More than 30 seconds

[0102] <Workability over time (sagging and falling during ceiling construction)> 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 under the following spraying conditions so that the polyurethane foam thickness was 30 mm or less. After spraying, it was checked whether or not the polyurethane foam fell off. (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℃ • Spraying direction: Spray perpendicular to the gypsum board, from bottom to top. (Evaluation Criteria) ○: The urethane foam hardens and does not fall. ×: The liquid falls before it hardens.

[0103] <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 was evaluated according to the following criteria. (Evaluation Criteria) ◎: 6.5 MJ / m³ at 10 minutes after the start of heating. 2 The results were as follows: ○: 6.5 MJ / m³ at 10 minutes after the start of heating. 2 Super 8MJ / m 2 The results were as follows: ×: 8 MJ / m² at 10 minutes after heating begins 2 It was incredible.

[0104] The details of each component used in each example and comparative example are as follows. <Polyol compounds> • p-phthalate polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g)

[0105] <Metal-based flame retardants> • Zinc borate (manufactured by Hayakawa Trading Co., Ltd., product name: Firebrake ZB) • Aluminum phosphite (manufactured by Taihei Chemical Industry Co., Ltd., product name: APA-100) <Non-metallic flame retardants> • Phosphate ester-based flame retardant (1) Tris(β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP) • Red phosphorus-based flame retardant (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140)

[0106] <Low boiling point compounds> • HFO-1234ze (manufactured by Honeywell, product name: Solstice GBA) Boiling point -19℃ Nitrogen boiling point -195.8℃

[0107] <Nucleophilic inhibitors> • Magnesium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: Magnesium hydroxide) • Lithium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: Lithium hydroxide) • Sodium acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: Sodium Acetate) • Potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: Potassium carbonate) • Barium sulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: Barium Sulfate) • Copper(II) hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: Copper(II) hydroxide)

[0108] <Non-nucleophilic inhibitors> • Diisopropylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: Diisopropylamine)

[0109] <Catalyst> • Trimerization catalyst: Tetramethylammonium 2,2-dimethylpropanoate, a 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) • Trimerization catalyst: Potassium 2-ethylhexanoate (active ingredient content 70-80% by mass) (manufactured by Evonik Japan, product name: K-15) • Resinization catalyst: Bismastrioctate (active ingredient content 85% by mass, manufactured by Shepherd Chemicals, product name: Bicat 8210) • Resinization catalyst: 2,2'-dimorpholinodiethyl ether (active ingredient amount 100% by mass, manufactured by Mitsui Chemicals Fine Co., Ltd., product name: DMDEE)

[0110] <Filler> • Anti-settling agent: Fumed silica (manufactured by Nippon Aerosil Co., Ltd., product name: Aerosil R967S)

[0111] <Polyisocyanate compounds> • Diphenylmethane-4,4'-diisocyanate (MDI) (manufactured by Bayer, product name "DESMODUR® 44LV20")

[0112] [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 formulation shown 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. The results of each evaluation are shown in Table 1.

[0113] [Examples 2-7, Comparative Examples 1-3] 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.

[0114] [Table 1]

[0115] Note that the mass parts of each catalyst represent the mass parts of the product.

[0116] Each example is a polyol composition for aerosols according to the present invention, containing a polyol compound, a flame retardant, a low boiling point compound, a catalyst, and a nucleophilic inhibitor. Even after long-term storage, the curing rate when applying polyurethane foam was high, and the resulting polyurethane foam exhibited good non-flammability. In contrast, the polyol compositions in each comparative example did not contain nucleophilic inhibitors, exhibited slow curing rates after long-term storage, and had inferior non-flammability. [Explanation of symbols]

[0117] 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. A polyol composition for aerosols containing a polyol compound, a flame retardant, a low boiling point compound, a catalyst, and a nucleophilic inhibitor.

2. The polyol composition for aerosols according to claim 1, wherein the flame retardant comprises a metal-based flame retardant.

3. The polyol composition for aerosols according to claim 1 or 2, wherein the nucleophilic inhibitor is at least one selected from the group consisting of alkali metal compounds and alkaline earth metal compounds.

4. The polyol composition for aerosols according to claim 1 or 2, wherein the low-boiling compound comprises a hydrofluoroolefin.

5. The polyol composition for aerosols according to claim 1 or 2, wherein the catalyst comprises a catalyst having a morpholine skeleton.

6. The aerosol polyol composition according to claim 1 or 2, wherein the catalyst comprises a potassium salt.

7. The aerosol polyol composition according to claim 1 or 2, wherein the catalyst comprises a bismuth-based catalyst.

8. The aerosol polyol composition according to claim 1 or 2, wherein the flame retardant comprises a phosphorus-based flame retardant.

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

10. A polyurethane foam formed from the polyurethane composition described in claim 9.

11. A mixing system comprising a first container containing the aerosol polyol composition described in claim 1 or 2, and a second container containing a polyisocyanate composition comprising a polyisocyanate compound.

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