JP2024058841A - Polyol composition, polyurethane composition, and polyurethane foam - Google Patents

Abstract

[Problem] To provide a polyol composition for aerosols which contains a secondary amine catalyst and has a certain or higher curing speed when applied to polyurethane foam even after long-term storage. [Solution] A polyol composition for aerosols which contains a polyol compound and a catalyst, 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. [Selected Figure] None

Description

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

Conventionally, polyurethane foams have been used as heat insulating materials in vehicles such as automobiles, railway cars, and ships, buildings, etc. For polyurethane foams, two-component polyurethanes in which a polyol composition and a polyisocyanate composition filled in separate containers are mixed to form a foam are widely used.
Two-component polyurethanes are sometimes used in aerosol containers that allow each liquid to be discharged from a container and mixed with a relatively simple configuration, as disclosed in, for example, Patent Documents 1 to 5. When two-component polyurethanes are used in aerosol containers, one container is filled with a polyol compound and a low-boiling point compound, and the other container is filled with a polyisocyanate compound and a low-boiling point compound. A polyol liquid agent and a polyisocyanate liquid agent are discharged from each container by the vapor pressure of the low-boiling point compound, and a polyurethane foam is formed by mixing them.
The polyol composition used in such an aerosol container is often preferably used to fill in the missing parts that occur when applying the polyurethane foam. Moreover, the polyol composition for aerosol often contains an amine catalyst, particularly a secondary amine catalyst such as an imidazole catalyst, from the viewpoint of improving the reactivity with the polyisocyanate and obtaining a certain or higher curing speed.

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

However, when conventional aerosol polyol compositions are stored for a long period of time, the amine catalyst reacts with a low boiling point compound in the composition over time, causing the amine catalyst to become inactivated, and the curing speed decreases when the polyurethane foam is applied, resulting in dripping. In addition, when the curing speed decreases in this way, it is often difficult to impart good non-flammability to the polyurethane foam.
Therefore, an object of the present invention is to provide a polyol composition for aerosols which has a curing speed at least equal to a certain level when applied to a polyurethane foam, not only initially but also after long-term storage.

As a result of intensive research, the present inventors have found that the above-mentioned 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, comprising a polyol compound and a catalyst, the content of the catalyst being 15 parts by mass or more relative to 100 parts by mass of the polyol compound, the catalyst including a secondary amine catalyst, and the content of the secondary amine catalyst being 0.03 to 5 parts by mass relative to 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 mass% or less based on the total amount of the catalyst.
[3] The polyol composition for aerosols according to [1] or [2], further comprising a phosphoric acid ester.
[4] The polyol composition for aerosols according to [1] or [2], further comprising a solid flame retardant.
[5] The polyol composition for aerosols according to [4], wherein the solid flame retardant contains a red phosphorus-based flame retardant.
[6] An aerosol container containing the polyol composition for aerosols according to [1] or [2].
[7] A polyurethane composition comprising the aerosol polyol composition according to [1] or [2] and a polyisocyanate composition containing a polyisocyanate compound.
[8] A polyurethane foam formed from the polyurethane composition according to [7].
[9] A mixing system comprising a first container in which the aerosol polyol composition according to [1] or [2] is sealed, and a second container in which the polyisocyanate composition is sealed.

According to the present invention, it is possible to provide a polyol composition for aerosols that has a certain or higher curing speed when applying polyurethane foam, not only initially but also after long-term storage.

FIG. 1 is a schematic diagram illustrating one embodiment of a mixing system. FIG. 2 is a schematic diagram illustrating another embodiment of a mixing system.

[Polyol composition]
The polyol composition of the present invention is a polyol composition for aerosols, and contains a polyol compound and a catalyst. As described below, the polyol composition of the present invention is mixed with a polyisocyanate composition containing a polyisocyanate compound to produce a polyurethane foam. The polyol composition of the present invention will be described in more detail below.

<Catalyst>
The polyol composition of the present invention contains a catalyst. The catalyst contains at least a secondary amine catalyst.

(Secondary amine catalyst)
The polyol composition of the present invention contains a secondary amine catalyst. The secondary amine catalyst is usually used as a resinification catalyst. By containing the secondary amine catalyst, the reactivity between the polyol compound and the polyisocyanate compound becomes good, and the initial curing speed can be made to be at least a certain level. Therefore, a good quality polyurethane foam can be formed.
Here, the secondary amine 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 catalyst is preferably an imidazole catalyst.
The imidazole catalyst is preferably an imidazole substituted at the 1- and 2-positions with an alkyl group having 8 or less carbon atoms, and the alkyl group preferably has 6 or less carbon atoms, more preferably has 4 or less carbon atoms. A specific example of a suitable imidazole catalyst is represented by the following general formula (1).

(In general formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.)

In the general formula (1), ^R1 and ^R2 each independently represent 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 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.
When the carbon numbers of the alkyl or alkenyl groups of ^R1 and ^R2 are equal to or greater than the lower limit, steric hindrance becomes large, and when the content of the imidazole catalyst in the polyol composition is equal to or less than a certain level, the polyol composition is less susceptible to the influence of low-boiling point compounds such as hydrofluoroolefins. On the other hand, when the carbon numbers of the alkyl groups of ^R1 and ^R2 are equal to or less than the upper limit, steric hindrance does not become extremely large, so that the reaction between the polyol compound and the polyisocyanate compound can proceed quickly, and a high-quality polyurethane foam can be easily formed.
From these viewpoints, R ¹ and R ² are each independently preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group.

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 the activity of the catalyst in the presence of hydrofluoroolefins (HFOs) such as HFO-1234ze and from the viewpoint of rapidly progressing the reaction. Furthermore, 1,2-dimethylimidazole is more preferred from the viewpoint of further increasing stability.

The content of the secondary amine catalyst in the polyol composition of the present invention is 0.03 to 5 parts by mass relative to 100 parts by mass of the polyol compound. If the content of the secondary amine catalyst is less than 0.03 parts by mass, the total amount of the catalyst described below may be reduced, which may cause the polyol compound and the polyisocyanate compound to not react sufficiently, causing problems such as dripping during application, making it difficult to form a good quality polyurethane foam. In addition, if the content of the secondary amine catalyst exceeds 5 parts by mass, low boiling point compounds such as HFO, particularly HFO-1234ze, react with the secondary amine catalyst to generate a large amount of by-products, making it impossible to maintain a constant curing speed or higher when applying the polyurethane foam after long-term storage, making it difficult to impart good non-flammability to the polyurethane foam. In view of the above, the content of the secondary amine catalyst is preferably 0.05 to 4 parts by mass, more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polyol compound.

(Resinification catalyst other than secondary amine catalyst)
The polyol composition of the present invention may contain a metal catalyst (resinified metal catalyst) as a resinification catalyst. Examples of the resinified metal catalyst include metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc., and preferably organic acid metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel, etc., and among these, bismuth catalysts are preferred. Specific examples of the metal catalyst include dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatate, bismuth trioctate, bismuth tris(2-ethylhexanoate), tin dioctylate, lead dioctylate, and the like, and among these, bismuth trioctate is preferred.

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 equal to or greater than these lower limits, urethane bonds are more easily formed and the reaction proceeds quickly. On the other hand, if the content of the resinified metal catalyst is equal to or less than these upper limits, the reaction rate is easier to control.

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 equal to or greater than these lower limits, urethane bonds are more easily formed and the reaction proceeds quickly. On the other hand, if the content is equal to or less than these upper limits, the reaction rate is easier to control.

(Trimerization Catalyst)
The polyol composition of the present invention may contain a trimerization catalyst. By containing a trimerization catalyst, when the polyol composition is mixed with the polyisocyanate composition, the isocyanate group contained in the polyisocyanate compound reacts and trimers, and the production of an isocyanurate ring is promoted, so that excellent non-flammability can be imparted to the polyurethane foam. As the trimerization catalyst, nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate, and potassium octylate, tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt, and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium, tetraphenylammonium salt, and triethylmonomethylammonium salt can be used. As the ammonium salt, ammonium salts of carboxylic acids such as 2,2-dimethylpropanoic acid can be mentioned, and more specifically, quaternary ammonium salts of carboxylic acids can be mentioned.
These may be used alone or in combination of two or more.
Among these, one or more selected from alkali metal carboxylates and quaternary ammonium carboxylates are preferred, and among these, quaternary ammonium carboxylates are more preferred.

The content of the trimerization catalyst 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 content of the trimerization catalyst is equal to or greater than these lower limits, trimerization of the polyisocyanate compound is more likely to occur, and the nonflammability of the resulting polyurethane foam is improved. On the other hand, if the content of the trimerization catalyst is equal to or less than the upper limit, the reaction is easier to control.

The content of the catalyst in the polyol composition of the present invention is 15 parts by mass or more based on 100 parts by mass of the polyol compound. The content of the catalyst here refers to the total amount of the catalyst contained in the polyol composition.
If the catalyst content is less than 15 parts by mass, the catalyst content is insufficient, and the curing reaction between the polyol compound and the polyisocyanate compound cannot be sufficiently advanced, making it difficult to maintain a certain initial curing speed or higher. In particular, the curing speed is likely to decrease when applying a polyurethane foam after storing the polyol composition for a long period of time. In view of this, the catalyst content is preferably 18 parts by mass or more, more preferably 20 parts by mass or more, relative to 100 parts by mass of the polyol compound.
Furthermore, from the viewpoint of suppressing the amount of a 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 content of the catalyst 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, relative to 100 parts by mass of the polyol compound.

When a trimerization catalyst and a resinification catalyst are used in combination as catalysts, the amount of the resinification catalyst relative to the trimerization catalyst (amount of resinification catalyst/amount of trimerization 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. When the amount of the resinification catalyst is equal to or greater than the lower limit, the reactivity between the polyol compound and the polyisocyanate compound is easily improved. On the other hand, when the amount of the resinification catalyst is equal to or less than the upper limit, the proportion of the trimerization catalyst in the catalyst is equal to or greater than a certain level, making it easier to impart excellent non-flammability to the polyurethane foam.

In the polyol composition of the present invention, the content of the secondary amine catalyst based on 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. When the content of the secondary amine catalyst is equal to or less than the above upper limit, the ratio of the secondary amine catalyst to the total catalyst is equal to or less than a certain amount, and even if the polyol composition is stored for a long period of time, the curing speed when applying the polyurethane foam can be maintained at a certain level or higher. In addition, 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, from the viewpoint of obtaining a good quality polyurethane foam by improving the reactivity between the polyol compound and the polyisocyanate compound.

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

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

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.
Aliphatic polyols include, for example, alkanediols such as ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

Examples of polyester polyols include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, and condensates of hydroxycarboxylic acids and the above-mentioned 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, etc. 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, etc.
Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

Examples of polymer polyols include polymers obtained by graft-polymerizing ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate with aromatic polyols, alicyclic polyols, aliphatic polyols, and polyester polyols, polybutadiene polyols, and modified polyols of polyhydric alcohols or hydrogenated products thereof.

Examples of modified polyols of polyhydric alcohols include those obtained by reacting a raw material polyhydric alcohol with an alkylene oxide to modify it.
Examples of polyhydric alcohols include trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, and dipentaerythritol; sucrose, glucose, mannose, fructose, methyl glucoside, and derivatives thereof; 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; polyfunctional polyols (e.g., having 2 to 100 functional groups) such as castor oil polyol, (co)polymers of hydroxyalkyl (meth)acrylate, and polyvinyl alcohol; and condensates of phenol and formaldehyde (novolaks).

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

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

Preferred polyol compounds for use in the present invention are polyester polyols and polyether polyols. Among them, aromatic polyester polyols obtained by dehydration condensation of polybasic acids having aromatic rings, such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), with dihydric alcohols, such as bisphenol A, ethylene glycol, and 1,2-propylene glycol, are more preferable. Also, polyols having two hydroxyl groups are preferable.

The hydroxyl value of the polyol compound is preferably 20 to 300 mgKOH/g, more preferably 30 to 250 mgKOH/g, and even more preferably 50 to 220 mgKOH/g. When the hydroxyl value of the polyol compound is equal to or less than the upper limit, the viscosity of the polyol composition is likely to decrease, which is preferable from the viewpoint of handleability, etc. On the other hand, when the hydroxyl value of the polyol compound is equal to or more than the lower limit, the crosslink density of the polyurethane foam increases, thereby increasing the strength.
The hydroxyl value of the polyol compound can be measured in accordance with JIS K 1557-1:2007.

The content of the polyol compound 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. If the content of the polyol compound is equal to or greater than the lower limit, it is preferable because it makes it easier for the polyol and the polyisocyanate to react with each other. On the other hand, if the content of the polyol compound is equal to or less than the upper limit, it is preferable from the viewpoint of handleability because the viscosity of the polyol composition does not become too high.

<Phosphate ester>
The polyol composition in the present invention preferably contains a phosphoric acid ester.
Phosphate ester functions as a flame retardant, and the inclusion of phosphate ester makes it easier to improve the non-flammability of polyurethane foam without substantially decreasing the discharge flow rate, mixability, etc. Phosphate ester is generally a liquid flame retardant. Note that a liquid flame retardant is a flame retardant that is liquid at room temperature (23° C.) and normal pressure (1 atm).

As the phosphate ester, monophosphate ester, condensed phosphate ester, etc. can be used. A monophosphate ester is a phosphate ester having one phosphorus atom in the molecule. Examples of the monophosphate ester include, but are not limited to, 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, cresyl diphenyl phosphate, and diphenyl(2-ethylhexyl)phosphate, and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

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

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

When the polyol composition contains a phosphate ester, the content of the phosphate ester 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 even more preferably 35 to 65 parts by mass, per 100 parts by mass of the polyol compound. By making the content of the phosphate ester equal to or greater than these lower limits, the effect of including the phosphate ester is easily exerted. Furthermore, by making the content equal to or less than the upper limits, the foaming of the polyurethane foam is not inhibited by the phosphate ester.

<Filler>
The polyol composition of the present invention preferably contains a filler. By containing the filler, various performances such as flame retardancy of the polyurethane foam can be easily improved. 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. The 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.

The red phosphorus-based flame retardant may consist of red phosphorus alone, may be red phosphorus coated with a resin, metal hydroxide, metal oxide, or the like, or may be a mixture of red phosphorus and a resin, metal hydroxide, metal oxide, or the like. The resin with which red phosphorus is coated or mixed with red phosphorus is not particularly limited, but examples include thermosetting resins such as phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. From the viewpoint of flame retardancy, metal hydroxides are preferred as the compound to be coated or mixed. The metal hydroxide to be used may be appropriately selected from those described below.

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

Specific examples of phosphate-containing flame retardants include monophosphates such as aluminum phosphite and aluminum triphosphate, pyrophosphates, polyphosphates, etc. Here, the polyphosphates are not particularly limited, but include, for example, ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, etc.
The phosphate-containing flame retardant may be one or more of the above-mentioned compounds. In the present invention, aluminum tertiary phosphate is preferred.

The bromine-containing flame retardant is not particularly limited as long as it contains bromine in its molecular structure and is a solid at room temperature and pressure. Examples of the bromine-containing flame retardant include brominated aromatic ring-containing aromatic compounds.
Examples of the brominated aromatic ring-containing aromatic compound include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene bis(pentabromophenyl), ethylene bis(tetrabromophthalimide), and tetrabromobisphenol A.

The brominated aromatic ring-containing aromatic compound may be a bromine compound polymer.Specific examples of the brominated aromatic ring-containing aromatic compound include brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A as a raw material, copolymers of the polycarbonate oligomers and bisphenol A, and diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin.Further examples include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin, poly(brominated benzyl acrylate), brominated phenol condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly(-methylstyrene), and the like.
In addition, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may be used.
These bromine-containing flame retardants may be used alone or in combination of two or more. Among the above, brominated aromatic ring-containing aromatic compounds are preferred, and among them, monomeric organic bromine compounds such as hexabromobenzene are preferred.

The boron-containing flame retardant used in the present invention includes borax, boron oxide, boric acid, borate, etc. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.
Examples of borates include borates of alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the periodic table, and ammonium. Specific 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.
The boron-containing flame retardants may be used alone or in combination of two or more kinds.
The boron-containing flame retardant used in the present invention is preferably a borate, more preferably zinc borate.

Examples of antimony-containing flame retardants include antimony oxide, antimony salts, pyroantimony salts, etc. Examples of antimony oxide include antimony trioxide and antimony pentoxide, etc. Examples of antimony salts include sodium antimonate and potassium antimonate, etc. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate, etc.
The antimony-containing flame retardants may be used alone or in combination of two or more. The preferred antimony-containing flame retardant for use in the present invention is antimony trioxide.

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. The metal hydroxides may be used alone or in combination of two or more. The preferred metal hydroxide used in the present invention is aluminum hydroxide.

Examples of needle-like 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, and stainless steel fibers.
These needle-like fillers may be used alone or in combination of two or more kinds.

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. The aspect ratio can be determined by observing the needle-shaped filler with a scanning electron microscope and measuring its length and width.

The solid flame retardants used in the present invention may be used alone or in combination of two or more. When using two or more in combination, for example, two or more solid flame retardants of the same category may be used, such as a needle-like filler containing potassium titanate whiskers and aluminum borate whiskers, or one or more solid flame retardants of different categories may be used, such as a red phosphorus-based flame retardant and a needle-like filler.
When a solid flame retardant is contained, the content 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, relative to 100 parts by mass of the polyol compound. By setting the content of the solid flame retardant within the above range, it is possible to prevent the precipitation of the solid flame retardant and improve its dispersibility without increasing the solid content more than necessary.

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 contained 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 even more preferably 25 to 35 parts by mass, per 100 parts by mass of the polyol compound. When the content of the red phosphorus-based flame retardant is equal to or greater than the above lower limit, it is possible to impart good non-flammability to the polyurethane foam. In addition, by making the content equal to or less than the above upper limit, the handling properties when discharging the polyol composition are improved.

The solid flame retardant used in the present invention preferably contains a solid flame retardant other than the red phosphorus-based flame retardant in addition to the red phosphorus-based flame retardant, from the viewpoint of easily imparting superior flame retardancy to the polyurethane foam. The solid flame retardant other than the red phosphorus-based flame retardant may be appropriately selected from those described above, but it is preferable to contain at least one selected from the bromine-containing flame retardant and the boron-containing flame retardant, and it is more preferable to contain both the bromine-containing flame retardant and the boron-containing flame retardant.

The polyol composition may also contain an anti-settling agent as a filler. The use of an anti-settling agent can prevent the precipitation of solid flame retardants and the like dispersed in the polyol composition, making it easier for the solid flame retardants and the like to be discharged, and facilitating the formation of a polyurethane foam with high flame resistance. The use of an anti-settling agent also makes it easier to uniformly disperse fillers such as red phosphorus-based flame retardants.

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

The content of the anti-settling agent 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, relative to 100 parts by mass of the polyol compound. When the content of the anti-settling agent is equal to or greater than the above lower limit, the filler such as the red phosphorus-based flame retardant is prevented from precipitating in the polyol composition, and the dischargeability of the polyol composition is improved. When the content of the anti-settling agent is equal to or less than the above upper limit, the viscosity of the polyol composition does not become excessively high, making it easier to improve the dischargeability.

As the filler, inorganic fillers other than the above solid flame retardants 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 fiber, and zirconia fiber. These inorganic fillers may be used alone or in combination of two or more.

When the polyol composition of the present invention contains a filler, the content 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 even more preferably 65 to 90 parts by mass, per 100 parts by mass of the polyol compound. When the filler content is equal to or greater than the lower limit, it becomes easier to improve various properties such as flame retardancy of the polyurethane foam formed from the polyol composition. Furthermore, when the filler content is equal to or less than the upper limit, the viscosity of the polyol composition can be suppressed to a certain level or less, improving handleability.

<Low boiling point compounds>
The polyol composition of the present invention preferably contains a low-boiling compound. The low-boiling compound expels the polyol composition from the aerosol container by its vapor pressure, and vaporizes when the polyol composition is expelled, thereby foaming the polyol composition and the polyurethane composition described below. From the viewpoint of increasing the amount of the polyol composition expelled, the low-boiling compound preferably has a boiling point at 1 atmospheric pressure (hereinafter, also simply referred to as "boiling point") of 10°C or less. If the boiling point of the low-boiling compound is 10°C or less, when the polyol composition is filled, for example, in an aerosol container, the vapor pressure in the container is sufficiently increased, and the composition can be sufficiently expelled. From the viewpoint of such expellability, the low-boiling 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 compound means the boiling point of the low-boiling compound alone, and does not mean, for example, the boiling point of the azeotropic low-boiling compound with another compound.

The type of low-boiling point compound is not particularly limited as long as the polyol composition can be discharged by its vapor pressure, and hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), hydrofluoroolefins (HFOs), hydrocarbons, ether compounds, inorganic gases, etc. can be used. Among these, from the viewpoint of reducing the environmental load and improving dischargeability and mixability, hydrofluoroolefins (HFOs), hydrocarbons, ether compounds, inorganic gases, etc. can be preferably used, and among these, it is preferable to include hydrofluoroolefins (HFOs) as low-boiling point compounds. HFOs may be used alone as low-boiling point compounds, or may be used in combination with low-boiling point compounds other than HFOs, such as inorganic gases. In the polyol composition, the content of HFOs among the low-boiling point compounds is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass.

As described above, the low-boiling point HFO preferably has a boiling point of 0° C. or lower, more preferably −10° C. or lower, and even more preferably −15° C. or lower. In addition, the boiling point of the HFO is not particularly limited, but from the viewpoints of handleability, storage property, etc., it is preferably −50° C. or higher, more preferably −35° C. or higher, and even more preferably −25° C. or higher.
Examples of HFOs that are low boiling point 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), 2,3,3,3-tetrafluoropropene (HFO-1234yf), etc. HFOs may be compounds consisting of hydrogen, fluorine, and carbon, but may also be hydrochlorofluoroolefins that further contain chlorine.
Among the above HFOs, 1,3,3,3-tetrafluoropropene (HFO-1234ze) is preferred from the viewpoint of improving dischargeability, etc. Generally, HFOs, for example HFO-1234ze, tend to react with a secondary amine catalyst contained as a resinification catalyst and may deactivate the secondary amine catalyst, but in the present invention, as described above, when the content of the secondary amine catalyst is set to a certain level or less, the reaction with the secondary amine catalyst is limited, and deactivation of the secondary amine catalyst can be suppressed.

Examples of the hydrocarbon include hydrocarbons having 1 to 4 carbon atoms, such as ethane, propane, isobutane, normal butane, and various butanes. In addition, examples of the hydrocarbons having 1 to 4 carbon atoms include LPG (liquefied petroleum gas) containing propane and butanes as main components.
An example of the ether compound is dimethyl ether.
Examples of inorganic gases include nitrogen, carbon dioxide, and argon gas, and among these, nitrogen is preferred.

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

The content of HFO 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 content of HFO in the polyol composition is equal to or greater than the lower limit, the vapor pressure in the aerosol container is at a certain level or higher, and the ejection properties of the polyol composition can be improved. When the content of HFO in the polyol composition is equal to or less than the upper limit, the vapor pressure in the aerosol container is appropriate, and handling and storage properties are improved.

<Foam stabilizer>
The polyol composition of the present invention may contain a foam stabilizer. The foam stabilizer improves the foamability of the polyurethane composition obtained from the polyol composition and the polyisocyanate composition.
Examples of the foam stabilizer include surfactants such as polyoxyalkylene-based foam stabilizers such as polyoxyalkylene alkyl ethers, silicone-based foam stabilizers such as organopolysiloxanes, etc. These foam stabilizers may be used alone or in combination of two or more.
The content of the foam stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 5 parts by mass, based on 100 parts by mass of the polyol compound. When the content of the foam stabilizer is equal to or greater than these lower limits, the polyurethane composition is easily foamed, and a homogeneous polyurethane foam is easily obtained. When the content of the foam stabilizer is equal to or less than these upper limits, a good balance between the production cost and the obtained effect is obtained.

<Other ingredients>
The polyol composition may contain additives, such as phenol-based, amine-based, sulfur-based and other antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, and tackifiers such as polybutene and petroleum resins, as necessary, within the scope of the present invention.

[container]
The container of the present invention is a container in which the above-mentioned polyol composition is enclosed. The container is an aerosol container capable of discharging the polyol composition by the vapor pressure of a low-boiling point compound. The aerosol container, for example, comprises a container body filled with the polyol composition and a cap part sealing the upper part of the container body, and when a button or the like provided on the cap part is pressed, a valve or the like is opened to release the internal pressure, and the polyol composition is discharged from a discharge port provided on the cap part by the vapor pressure of the low-boiling point compound.
The method of sealing the polyol composition in the container is not particularly limited, but the components other than the low-boiling compound are mixed as necessary using a disperser or the like, then filled into the container, the container is sealed, and then the low-boiling compound is filled in. The filling of the low-boiling compound can be performed, for example, by opening a valve provided in the cap of the container and injecting the low-boiling compound into the container.

When the polyol composition is discharged from the container, each component constituting the polyol composition is discharged in a state in which it is uniformly mixed. In order to uniformly mix each component constituting the polyol composition, it is recommended to shake the container thoroughly before discharging. The container can be shaken, for example, by holding the container by hand and shaking it up and down. The method of uniformly mixing the polyol composition is not limited to the above-mentioned method. In addition, the temperature of the container when discharging is preferably, for example, 10°C or higher and 40°C or lower. If it is 10°C or higher, the liquid temperature is high to a certain extent, so discharging is good, and if it is 40°C or lower, the container is prevented from bursting.

[Polyurethane composition]
The polyurethane composition of the present invention comprises a polyol composition and a polyisocyanate composition containing a polyisocyanate compound. That is, the above-mentioned polyol composition of the present invention is used as a polyol composition for two-component polyurethane, and is mixed with a polyisocyanate composition containing a polyisocyanate compound to be used as a polyurethane composition. 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 below.
The polyurethane composition obtained by mixing the polyol composition and the polyisocyanate composition reacts with each other and foams due to the low-boiling point compound contained in the polyol composition described above or the low-boiling point compound contained in the polyisocyanate composition described below, thereby becoming a polyurethane foam.

<Polyisocyanate Composition>
As the polyisocyanate compound contained in the polyisocyanate composition of the present invention, various polyisocyanate compounds having two or more isocyanate groups, such as aromatic, alicyclic, and aliphatic polyisocyanate compounds, can be used. It is preferable to use liquid diphenylmethane diisocyanate (MDI) because of 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 examples of commercially available liquid MDI include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.) and "Millionate MR-200" (Nippon Polyurethane Industry Co., Ltd.). In addition, uretonimine-containing MDI (for example, commercially available product "Millionate MTL": manufactured by Nippon Polyurethane Industry Co., Ltd.) may also be used. Also, a polyisocyanate compound may be used in which a part of the isocyanate active groups in the polyisocyanate compound has been reacted with a hydroxyl group-containing compound to enhance the affinity with the polyol in advance. In addition to liquid MDI, other polyisocyanate compounds may be used in combination, and the polyisocyanate compounds to be used in combination may be any polyisocyanate compounds known in the technical field of polyurethanes, without any limitations.

The isocyanate index of the polyurethane composition of the present invention is preferably equal to or greater than 100, more preferably equal to or greater than 150, and even more preferably equal to or greater than 2000. If the isocyanate index is equal to or greater than these lower limits, the amount of the polyisocyanate compound relative to the polyol compound becomes excessive, which makes it easier for isocyanurate bonds to be formed by trimerization of the polyisocyanate, and as a result, the nonflammability of the polyurethane foam is improved.
The isocyanate index of the polyurethane composition is preferably not more than 600, more preferably not more than 550, and even more preferably not more than 500. When the isocyanate index is not more than these upper limit values, the resulting polyurethane foam has a good balance between nonflammability and production costs.
The isocyanate index (INDEX) is calculated by the following method.

INDEX = number of equivalents of polyisocyanate compound ÷ (number of equivalents of polyol compound + number of equivalents of water) × 100
here,
Equivalent number of polyisocyanate compound=number of parts of polyisocyanate compound used×NCO content (%)×100/NCO molecular weight Equivalent number of polyol compound=OHV×number of parts of polyol compound used÷molecular weight of KOH, OHV is the hydroxyl value of polyol (mgKOH/g),
Equivalent number of water = parts of water used x number of OH groups of water / molecular weight of water. In the above formula, the unit 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 convenience of unit conversion in the above formula, the molecular weight of KOH is 56100, the molecular weight of water is 18, and the number of OH groups of water is 2.

In addition to the polyisocyanate compound described above, the polyisocyanate composition preferably contains a low-boiling compound. By containing a low-boiling compound, the polyisocyanate composition can easily eject the polyisocyanate compound from an aerosol container. As the low-boiling compound contained in the polyisocyanate composition, the low-boiling compounds described above as the low-boiling compounds contained in the polyol composition can be used without any particular restrictions. 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. As the low-boiling compound contained in the polyisocyanate composition, HFO, hydrocarbons having 1 to 4 carbon atoms, ether compounds, inorganic gases, etc. can be suitably used, and among them, it is preferable to contain hydrofluoroolefin (HFO) as the low-boiling compound. HFO may be used in combination with a low-boiling compound other than HFO, such as an inorganic gas.

Although HFO may be used alone as a low boiling point compound, it is more preferable to use HFO and inorganic gas in combination, and it is even more preferable to use HFO and nitrogen in combination. By including inorganic gas together with HFO, the discharge amount of polyisocyanate compound can be increased, and thus polyurethane foam having better non-flammability can be formed.
In the polyisocyanate composition, when HFO and inorganic gas are used in combination, the content 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 content ratio of inorganic gas to HFO is equal to or higher than the lower limit, the vapor pressure in the container filled with the polyisocyanate composition increases, so that the discharge amount of the polyisocyanate compound becomes equal to or higher than a certain level, and it becomes easier to form a polyurethane foam having excellent non-flammability. When the content ratio of inorganic gas to HFO is equal to or lower than the upper limit, the discharge amount of the polyisocyanate compound is appropriately controlled, and a good quality polyurethane foam can be formed.

The content of the low-boiling point compound in the polyisocyanate composition is preferably 0.5 to 10 parts by 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 point compound is equal to or greater than the above lower limit, the vapor pressure in the container filled with the polyisocyanate composition increases, so that the discharge amount of the polyisocyanate compound becomes equal to or greater than a certain amount, making it easier to form a polyurethane foam with excellent non-flammability. If the content of the low-boiling point compound is equal to or less than the above upper limit, the discharge amount of the polyisocyanate compound is appropriately controlled, making it possible to form a good quality polyurethane foam.

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

[Mixed System]
The present invention also provides a mixing system for mixing a polyol composition and a polyisocyanate composition. As shown in Fig. 1, the mixing system 10 includes a first container 11 in which the polyol composition is sealed, and a second container 12 in which the polyisocyanate composition is sealed. 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 point 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 point compound contained in the polyisocyanate composition. In the first container 11, the low boiling point compound is partially vaporized to form a gas phase. The same is true in the second container 12.
The polyol composition and the polyisocyanate composition discharged from the first and second containers 11, 12 are foamed by a low-boiling point compound while being mixed, and the polyisocyanate compound reacts with the polyol compound to form a polyurethane foam.

The mixing system 10 may include a mixer 13. The outlets 11A and 12A of the first and second containers 11 and 12 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 applied using a sprayer or the like.

The mixer 13 is preferably a static mixer, so-called a static mixer. A static mixer is a mixer without a driving section, and the fluids are mixed by passing through the inside of the tube. An example of a static mixer is one in which a mixer element 13B is arranged inside a tube 13A as shown in FIG. 1. The mixer element 13B may be one formed in a spiral shape or one formed with a plurality of baffles.
The static mixer may also function as an injector, in which case the mixture of the polyol composition and the polyisocyanate composition mixed inside the pipe 13A may be sprayed from the tip 13C of the pipe as shown in Fig. 1. Note that Fig. 1 shows an embodiment in which the polyol composition and the polyisocyanate composition discharged from the first and second containers 11 and 12 are introduced into the mixer, but the mixing system 10 may be provided with a discharge gun or a jig at a position prior to the introduction into the mixer.

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

In the present invention, the polyurethane foam formed from the polyurethane composition can be used for various purposes, but is preferably used as a thermal insulation material. The polyurethane foam has a large number of cells, which provides a thermal insulation effect.
The polyurethane foam is particularly preferably used as a thermal insulation material for vehicles or buildings, such as railroad cars, automobiles, ships, and aircraft.
In addition, in the present invention, a polyurethane foam can be formed with a simple structure using an aerosol container. In addition, since the foam can be formed using a container, it is particularly suitable for cases where the surface to be worked on is relatively small, such as when replenishing a portion where the polyurethane foam is missing. Therefore, it is preferable to use it for repair purposes, for example, by spraying it onto a portion of an existing heat-resistant material that has deteriorated or been damaged. Of course, it is not limited to such uses, and it may also be used to form a new heat-resistant material.

In the polyurethane composition of the present invention, when the polyol composition and the polyisocyanate composition are allowed to stand at 30°C for 2 weeks and then mixed to produce a polyurethane foam, the produced polyurethane foam preferably has a total calorific value of 8 MJ or less when heated for 10 minutes at a radiant heat intensity of 50 kW/ ^m2 in accordance with the ISO-5660 test method. The total calorific value is more preferably 7 MJ or less, and even more preferably 6.5 MJ or less. When the total calorific value of the polyurethane foam is equal to or less than the upper limit, the polyurethane foam has excellent non-flammability even after long-term storage of the polyol composition.
The total calorific value of the polyurethane foam of the present invention can be measured by a cone calorimeter test, specifically, by the method described in the examples.

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

[Evaluation method]
In the examples and comparative examples, the curing speed of the polyol composition and the non-flammability of the polyurethane foam were evaluated by the following evaluation methods.

<Initial curing speed>
The polyol composition was discharged from the first aerosol container obtained in each Example and Comparative Example, mixed with the polyisocyanate composition discharged from the second aerosol container in a static mixer, and then sprayed onto a gypsum board under the following spraying conditions so that the polyurethane foam had a thickness of 30 mm or less. The surface curing time (tack-free time) after spraying was measured, and the measured value was taken as the initial curing speed.
(Spraying conditions)
Heating temperature of the first and second aerosol containers: 30° C. That is, the above spraying was carried out in a state where the first and second aerosol containers were maintained at 30° C.
- Base material: gypsum board (thickness 12.5 mm)
Substrate temperature: 5°C ± 1°C
Ambient temperature: 5°C ± 1°C

The initial curing speed was evaluated according to the following criteria.
(Evaluation criteria)
◎: Less than 30 seconds 〇: 30 seconds or more but less than 60 seconds ×: 60 seconds or more

<Initial non-flammability>
The polyol composition was discharged from the first aerosol container obtained in each Example and Comparative Example, mixed with the polyisocyanate composition discharged from the second aerosol container in a static mixer, and then sprayed onto a gypsum board to obtain a polyurethane foam. The spraying conditions were the same as those in the test for evaluating the initial curing rate.
From the foam obtained by the above method, a sample for a cone calorimeter test was cut out to have a size of 10 cm x 10 cm x 5 cm, and the total calorific value was measured when heated for 10 minutes at a radiant heat intensity of 50 kW/ ^m2 in accordance with ISO-5660. Based on the measured value, the initial non-flammability was evaluated according to the following evaluation criteria.
(Evaluation criteria)
⊚: 6.5 MJ or less 10 minutes after the start of heating.
◯: More than 6.5 MJ and 8 MJ or less 10 minutes after the start of heating.
×: More than 8 MJ 10 minutes after the start of heating.

<Curing speed after aging>
The first aerosol container obtained in each Example and Comparative Example was left for 2 weeks at 30° C. After leaving it, the polyol composition was discharged from the first aerosol container and mixed with the polyisocyanate composition discharged from the second aerosol container using a static mixer, and then sprayed onto a gypsum board so that the thickness of the polyurethane foam became 30 mm or less. The spraying conditions were the same as those in the test for evaluating the initial curing speed.
The time it took for the surface to harden (tack-free time) after spraying was measured, and this measured value was taken as the hardening speed after aging.

The curing speed after aging was evaluated according to the following criteria.
(Evaluation criteria)
◎: Less than 30 seconds 〇: 30 seconds or more but less than 60 seconds ×: 60 seconds or more

<Non-flammable after aging>
The first and second aerosol containers obtained in each Example and Comparative Example were left for 2 weeks at 30° C. After leaving the container, the polyol composition was discharged from the first aerosol container, mixed with the polyisocyanate composition discharged from the second aerosol container in a static mixer, and then sprayed onto a gypsum board to obtain a polyurethane foam. The spraying conditions were the same as those in the test for evaluating the initial curing rate.
From the foam obtained by the above method, a sample for a cone calorimeter test was cut out to have a size of 10 cm x 10 cm x 5 cm, and the total calorific value was measured when heated for 10 minutes at a radiant heat intensity of 50 kW/ ^m2 in accordance with ISO-5660. Based on the measured value, the non-flammability after aging was evaluated according to the following evaluation criteria.
(Evaluation criteria)
⊚: 6.5 MJ or less 10 minutes after the start of heating.
◯: More than 6.5 MJ and 8 MJ or less 10 minutes after the start of heating.
×: More than 8 MJ 10 minutes after the start of heating.

[Materials used]
In each of the examples and comparative examples, the following materials were used.

<Polyol Compound>
Phthalic acid polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH/g)
<Catalyst>
Trimerization catalyst: quaternary ammonium carboxylate (active ingredient amount 45% by mass, diluted with ethylene glycol) (manufactured by Evonik Japan, product name: DABCO TMR-7)
Resinification catalyst 1: bismuth trioctate (active ingredient amount 85% by mass, manufactured by Shepherd Chemical Company, product name: Bicat 8210)
Resinification 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 Rinkagaku Kogyo Co., Ltd., product name: Nova Excel 140)
・Zinc borate (manufactured by Hayakawa Shoji Co., Ltd., product name: Firebreak ZB)
Bromine-containing flame retardant, ethylene bis(pentabromophenyl) (manufactured by Albemarle Corporation, 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 (Honeywell, product name: Soltis GBA) Boiling point: -19°C
Nitrogen boiling point -195.8℃
<Polyisocyanate Compound>
・MDI (manufactured by Sumika Covestro Urethane Co., Ltd., product name: 44V-20)

[Example 1]
According to the formulation in Table 1, the components other than the low-boiling point compound were weighed out into a 1000 ml polypropylene beaker and mixed using a disper at 1500 rpm for 5 minutes. The components were then transferred to an aerosol container and sealed using a vacuum crimper, after which the low-boiling point compound was further added to obtain a first aerosol container with the polyol composition sealed inside.
Similarly, a low-boiling compound was filled into another aerosol container together with the polyisocyanate compound according to the formulation in Table 1 to obtain a second aerosol container containing a polyisocyanate composition. Each evaluation test was carried out using the obtained first and second aerosol containers.

[Example 2]
A first aerosol container and a second aerosol container were produced and polyurethane foams were obtained in the same manner as in Example 1, except that the composition of the polyol composition was changed as shown in Table 1 and the evaluation of the initial and aged nonflammability was not performed. The evaluation results are shown in Table 1.

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

*The content of each catalyst in Table 1 is the mass part of the product. The total amount of catalyst is the sum of the net content of each catalyst (the mass part of the product minus the solvent).

As is clear from the above examples, the aerosol polyol composition satisfying the requirements of the present invention was able to maintain a constant or higher curing rate when applying polyurethane foam not only in the initial stage but also after long-term storage. In addition, as shown in Examples 1, 3, and 4, by blending a solid flame retardant into the polyol composition, a polyurethane foam with excellent non-flammability could be formed.
In contrast, the polyol compositions for aerosols prepared in the comparative examples had a total catalyst content less than the specified amount or a secondary amine catalyst content greater than the specified amount, so that the curing speed at the time of applying the polyurethane foam after long-term storage was significantly reduced. Furthermore, in each of the comparative examples, even when the solid flame retardant was blended in the same manner as in Examples 1, 3, and 4, it was not possible to form a polyurethane foam with excellent non-flammability.

REFERENCE SIGNS LIST 10 Mixing system 11 First container 12 Second container 11A, 12A Discharge port 11B, 12B Supply line 13 Mixer 13A Tube 13B Mixer element 13C Tip 14 Discharge gun 14A Lever 20 Mixing system

Claims (9)

A polyol composition for aerosols, comprising a polyol compound and a catalyst,
The content of the catalyst is 15 parts by mass or more relative to 100 parts by mass of the polyol compound,
the catalyst comprises a secondary amine catalyst;
The content of the secondary amine catalyst is 0.03 to 5 parts by mass based on 100 parts by mass of the polyol compound. The polyol composition for aerosols according to claim 1, wherein the content of the secondary amine catalyst is 25 mass% or less based on the total amount of catalyst. The aerosol polyol composition according to claim 1 or 2, further comprising a phosphoric acid ester. The aerosol polyol composition according to claim 1 or 2, further comprising a solid flame retardant. The aerosol polyol composition according to claim 4, wherein the solid flame retardant comprises a red phosphorus-based flame retardant. An aerosol container containing the aerosol polyol composition according to claim 1 or 2. A polyurethane composition comprising the aerosol polyol composition according to claim 1 or 2 and a polyisocyanate composition containing a polyisocyanate compound. A polyurethane foam formed from the polyurethane composition according to claim 7. A mixing system comprising a first container in which the aerosol polyol composition according to claim 1 or 2 is sealed, and a second container in which the polyisocyanate composition is sealed.