JP7828431B2 - Polyol-containing composition, foamable polyurethane composition, and polyurethane foam - Google Patents

Description

The present invention relates to a polyol-containing composition, a foamable polyurethane composition, and a polyurethane foam.

Due to its excellent insulating and adhesive properties, polyurethane foam is used as an insulating material in buildings such as apartment complexes, detached houses, various school facilities, and commercial buildings. Polyurethane foam is produced at the construction site by mixing a polyol-containing composition and a polyisocyanate, foaming the mixture, and spraying it onto ceilings, walls, roofs, and other surfaces using a spray device.

The polyol-containing composition contains catalysts such as a resinification catalyst and a trimerization catalyst. The resinification catalyst promotes the reaction between polyols and isocyanates, and the trimerization catalyst promotes the reaction of isocyanates with each other to produce isocyanurates, thereby increasing the proportion of isocyanurates.
In polyol-containing compositions containing a catalyst, the catalyst and the blowing agent may react during storage, causing a decrease in catalytic performance and a decrease in foaming ability. Hydrofluorocarbons (HFCs) have traditionally been widely used as blowing agents, but there has been a shift to hydrofluoroolefins (HFOs), which have low global warming potentials. Among blowing agents, hydrofluoroolefins tend to react particularly easily with catalysts, making them more likely to cause a decrease in catalytic performance and a decrease in foaming ability.
As methods for solving such problems, a method of specifying the blending amounts of a trimerization catalyst and a resinification catalyst (see, for example, Patent Document 1) and a method of using a trimerization catalyst having a predetermined structure (see, for example, Patent Document 2) have been proposed.

Japanese Patent Application Laid-Open No. 2018-30975 International Publication No. 2018/105730

However, in conventional polyol-containing compositions, the catalyst can react with a blowing agent such as HFO, deactivating the catalyst and reducing the stability of the polyol-containing composition, making it difficult to achieve both stability and improved foamability.

The present invention aims to provide a polyol-containing composition, a foamable polyurethane composition, and a polyurethane foam that suppress catalyst deactivation and achieve both excellent stability and good foamability.

As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by incorporating a potassium carboxylate salt, an ammonium carboxylate salt, a heterocyclic compound having a nitrogen atom, and a transition metal salt as catalysts in a polyol-containing composition, and have completed the present invention. That is, the present invention provides the following [1] to [20].
[1] A polyol-containing composition for producing a polyurethane foam by reacting with a polyisocyanate, the composition comprising a polyol, a blowing agent, and a catalyst;
The catalyst is a polyol-containing composition containing a potassium carboxylate salt, an ammonium carboxylate salt, a heterocyclic compound having a nitrogen atom, and a transition metal salt.
[2] The polyol-containing composition according to [1], wherein the carboxylic acid in the potassium carboxylate is at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid.
[3] The polyol-containing composition according to [1] or [2], wherein the carboxylic acid in the potassium carboxylate has 5 or more carbon atoms.
[4] The polyol-containing composition according to any one of [1] to [3], wherein the carboxylic acid in the ammonium carboxylate is at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid.
[5] The polyol-containing composition according to any one of [1] to [4], wherein the number of carbon atoms of the carboxylic acid in the ammonium carboxylate is 5 or more.
[6] The polyol-containing composition according to any one of [1] to [5], wherein the ammonium ion in the ammonium carboxylate is a quaternary ammonium ion.
[7] The polyol-containing composition according to any one of [1] to [6], wherein the ammonium ion in the ammonium carboxylate is at least one selected from the group consisting of triethylmethylammonium ion, tetramethylammonium ion, hydroxybutyltrimethylammonium ion, and hydroxypropyltrimethylammonium ion.
[8] The polyol-containing composition according to any one of [1] to [7], wherein the ammonium carboxylate is 2,2-dimethylpropanoic acid tetramethylammonium salt.
[9] The polyol-containing composition according to any one of [1] to [8], wherein the transition metal in the transition metal salt is at least one selected from the group consisting of bismuth and tin.
[10] The polyol-containing composition according to any one of [1] to [9], wherein the transition metal salt is a metal salt of a carboxylic acid having 5 or more carbon atoms.
[11] The polyol-containing composition according to any one of [1] to [10], wherein the transition metal in the transition metal salt is bismuth.
[12] The polyol-containing composition according to any one of [1] to [11], wherein the transition metal salt is a metal salt of 2-ethylhexanoic acid.
[13] The polyol-containing composition according to any one of [1] to [12], wherein the heterocyclic compound is an imidazole derivative.
[14] The polyol-containing composition according to any one of [1] to [13], wherein the imidazole derivative is an imidazole in which the 1st and 2nd positions are each independently substituted with an alkyl group having 4 or less carbon atoms.
[15] The polyol-containing composition according to any one of [1] to [14], wherein the imidazole derivative is at least one selected from the group consisting of 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole.
[16] The polyol-containing composition according to any one of [1] to [15], wherein the imidazole derivative is 1,2-dimethylimidazole.
[17] The polyol-containing composition according to any one of [1] to [16], wherein the blowing agent contains a hydrofluoroolefin.
[18] A foamable polyurethane composition comprising the polyol-containing composition according to any one of [1] to [17] and a polyisocyanate.
[19] The foamable polyurethane composition according to [18], having an isocyanate index of 250 or more.
[20] A polyurethane foam obtained by reacting and foaming the foamable polyurethane composition according to [18] or [19].

The present invention makes it possible to provide a polyol-containing composition, a foamable polyurethane composition, and a polyurethane foam that exhibit both excellent stability and good foamability.

The present invention will be described in detail below.
[Polyol-containing composition]
The polyol-containing composition of the present invention is a polyol-containing composition for producing a polyurethane foam by reacting with a polyisocyanate, and contains a polyol, a blowing agent, and a catalyst, and the catalyst contains a potassium carboxylate salt, an ammonium carboxylate salt, a heterocyclic compound having a nitrogen atom, and a transition metal salt. By containing the potassium carboxylate salt, the ammonium carboxylate salt, the heterocyclic compound having a nitrogen atom, and the transition metal salt as catalysts, the polyol-containing composition of the present invention can achieve both excellent stability and good foamability.
Each component of the polyol-containing composition of the present invention will be described in detail below.

<Polyol>
The polyol-containing composition of the present invention contains a polyol as a raw material for polyurethane foam.
Examples of polyols that can be used in the present invention include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

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

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

Examples of modified polyols of polyhydric alcohols include those obtained by modifying raw material polyhydric alcohols by reacting them with alkylene oxides.
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.

Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one alkylene oxide, such as ethylene oxide, propylene oxide, or tetrahydrofuran, in the presence of at least one low-molecular-weight active hydrogen compound having two or more active 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 polyols for use in the present invention are polyester polyols and polyether polyols. Furthermore, polyols having two hydroxyl groups are preferred. Among these, aromatic polyester polyols, which are polyester polyols having an aromatic ring, are preferred from the viewpoint of enhancing flame retardancy. More preferred aromatic polyester polyols are those obtained by dehydration condensation of polybasic acids having an aromatic ring, 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.

The hydroxyl value of the polyol 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 is equal to or less than the upper limit, the viscosity of the polyol-containing composition tends to decrease, which is preferable from the viewpoint of handleability, etc. On the other hand, when the hydroxyl value of the polyol is equal to or more than the lower limit, the crosslink density of the polyurethane foam increases, thereby increasing its strength.
The hydroxyl value of the polyol can be measured in accordance with JIS K 1557-1:2007.

<Catalyst>
The polyol-containing composition of the present invention contains a potassium carboxylate salt, an ammonium carboxylate salt, a heterocyclic compound having a nitrogen atom, and a transition metal salt as catalysts. By containing these four catalysts, the polyol-containing composition of the present invention can suppress the decomposition of the blowing agent by the catalyst and increase the activity of the catalyst, thereby improving the foaming property.

Potassium carboxylate
The polyol-containing composition of the present invention contains a potassium carboxylate, which is a trimerization catalyst and facilitates the formation of an isocyanurate bond by a trimer of polyisocyanate.
In the present invention, the carboxylic acid in the potassium carboxylate 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 in the carboxylic acid is, for example, 20 or less, preferably 12 or less, more preferably 8 or less. The carboxylic acid may be linear or may have a branched structure, but preferably has a branched structure. If the carboxylic acid has a branched structure, steric hindrance tends to reduce the reactivity with a blowing agent such as a hydrofluoroolefin, thereby improving the stability of the polyol-containing composition.

Among potassium carboxylates, potassium carboxylates represented by the following general formula (1) are preferred. The potassium carboxylates represented by the following general formula (1) have a moderate degree of steric hindrance, which can suppress the reaction that decomposes the blowing agent and also prevent a decrease in catalytic activity.

(In general formula (1), ^R1 and ^R2 each independently represent an alkyl group, ^R3 represents a hydrogen atom or an alkyl group, and K ⁺ represents a potassium ion.)

^R1 and ^R2 in general formula (1) each independently represent an alkyl group, and specifically, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 1 to 2 carbon atoms is even more preferable. The alkyl group may be linear or may have a branched structure.
^R3 represents a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 6 carbon atoms. ^R3 is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 2 carbon atoms.
When the carbon numbers of R ¹ , R ² and R ³ are equal to or greater than the lower limit, steric hindrance becomes large, thereby suppressing the reaction of decomposing the hydrofluoroolefin. On the other hand, when the carbon numbers of R ¹ , R ² and R ³ are equal to or less than the upper limit, steric hindrance does not become too large, thereby preventing the reactivity from slowing down.

A preferred specific example of the carboxylic acid in the potassium carboxylate is at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. Also preferred are carboxylic acids as shown in general formula (1), of which 2,2-dimethylpropanoic acid and 2-ethylhexanoic acid are more preferred, and 2-ethylhexanoic acid is even more preferred.
In the present invention, the potassium carboxylates may be used alone or in combination of two or more.

The amount of potassium carboxylate in the polyol-containing composition is preferably 1.0 to 10.0 parts by mass, more preferably 1.5 to 8.0 parts by mass, and even more preferably 1.8 to 7.0 parts by mass, per 100 parts by mass of polyol. When the amount of potassium carboxylate is at or above the lower limit, trimerization of the polyisocyanate occurs more easily, improving the flame retardancy of the resulting polyurethane foam. On the other hand, when the amount of potassium carboxylate is at or below the upper limit, the reaction is easier to control.

Ammonium carboxylate
The polyol-containing composition of the present invention contains an ammonium carboxylate salt, which is a trimerization catalyst and facilitates the formation of an isocyanurate bond by a trimer of polyisocyanate.
In the present invention, the carboxylic acid in the ammonium carboxylate 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 in the carboxylic acid is, for example, 20 or less, preferably 12 or less, more preferably 8 or less. The carboxylic acid may be linear or may have a branched structure, but preferably has a branched structure. If the carboxylic acid has a branched structure, steric hindrance tends to reduce the reactivity with a blowing agent such as a hydrofluoroolefin, thereby improving the stability of the polyol-containing composition.

Among these, the ammonium carboxylate salt is preferably an ammonium carboxylate salt represented by the following general formula (2). The ammonium carboxylate salt represented by the following general formula (2) has a moderate degree of steric hindrance, which can suppress the reaction that decomposes the blowing agent and also prevent a decrease in catalytic activity.

(In general formula (2), ^R4 and ^R5 each independently represent an alkyl group, ^R6 represents a hydrogen atom or an alkyl group, and M ⁺ represents an ammonium ion.)

^R4 and ^R5 in general formula (2) each independently represent an alkyl group, and specifically, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 1 to 2 carbon atoms is even more preferable. The alkyl group may be linear or may have a branched structure.
Furthermore, ^R6 represents a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 6 carbon atoms. Furthermore, ^R6 is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 2 carbon atoms.
When the carbon numbers of R ⁴ , R ⁵ and R ⁶ are equal to or greater than the lower limit, steric hindrance becomes large, thereby suppressing the reaction of decomposing the hydrofluoroolefin, whereas when the carbon numbers of R ⁴ , R ⁵ and R ⁶ are equal to or less than the upper limit, steric hindrance does not become too large, thereby preventing the reactivity from slowing down.
M ⁺ represents an ammonium ion, and the details of the ammonium ion will be described later.

A preferred specific example of the carboxylic acid in the ammonium carboxylate is at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. Also preferred are carboxylic acids as shown in general formula (2), with 2-ethylhexanoic acid and 2,2-dimethylpropanoic acid being more preferred, and 2,2-dimethylpropanoic acid being even more preferred.
In the present invention, the ammonium carboxylates may be used alone or in combination of two or more.

The ammonium ion in the ammonium carboxylate salt is preferably a quaternary ammonium ion, more preferably a tetraalkylammonium ion or a hydroxyalkyltrialkylammonium ion, and even more preferably a tetraalkylammonium ion.

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 the tetraalkylammonium ion include a tetramethylammonium ion and a triethylmethylammonium ion.

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. The hydroxyalkyl group is an alkyl group in which one of the hydrogen atoms has been substituted with a hydroxy group, and has, for example, 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms, and more preferably 3 or 4 carbon atoms. Examples of the hydroxyalkyl group include a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.
Specific examples of the hydroxyalkyltrialkylammonium ion include a hydroxybutyltrimethylammonium ion, a hydroxypropyltrimethylammonium ion, and a hydroxyethyltrimethylammonium ion.

The ammonium ion in the ammonium carboxylate salt 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, with tetramethylammonium ion being even more preferred.

Specific preferred examples of the ammonium carboxylate include tetramethylammonium 2,2-dimethylpropanoate, triethylmethylammonium 2-ethylhexanoate, and hydroxybutyltrimethylammonium 2-ethylhexanoate. Of these, tetramethylammonium 2,2-dimethylpropanoate is preferred from the viewpoint of facilitating the formation of an isocyanurate bond with a trimer of polyisocyanate.
In the present invention, the ammonium carboxylates may be used alone or in combination of two or more.

The amount of ammonium carboxylate salt in the polyol-containing composition is preferably 2.0 to 20 parts by mass, more preferably 2.5 to 15 parts by mass, and even more preferably 3.0 to 8.0 parts by mass, per 100 parts by mass of polyol. When the amount of ammonium carboxylate salt is at or above the lower limit, trimerization of the polyisocyanate occurs more easily, improving the flame retardancy of the resulting polyurethane foam. On the other hand, when the amount of ammonium carboxylate salt is at or below the upper limit, it becomes easier to control the reaction.

<<Transition metal salts>>
The polyol-containing composition of the present invention contains a transition metal salt as a resinification catalyst. When the polyol-containing composition contains a transition metal salt as a resinification catalyst, the polyol-containing composition is more likely to react with the polyisocyanate while suppressing decomposition by a blowing agent and increasing stability.

Transition metal salts used in the present invention include, for example, metal salts of bismuth, tin, zinc, copper, iron, and lead. Of these, metal salts of bismuth or tin are preferred, and metal salts of bismuth are more preferred.

The transition metal salt is preferably an organic acid metal salt, more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. When the carboxylic acid has 5 or more carbon atoms, the stability of the polyol-containing composition is improved with respect to a blowing agent, particularly a hydrofluoroolefin. Furthermore, from the viewpoint of catalytic activity, the number of carbon atoms of the carboxylic acid is preferably 18 or less, more preferably 12 or less. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or may have a branched structure, but preferably has a branched structure.
Specific examples of the carboxylic acid include octylic acid (2-ethylhexanoic acid), lauric acid, versatic acid, pentanoic acid, and acetic acid, among which octylic acid is preferred. That is, the transition metal salt is preferably a metal salt of 2-ethylhexanoic acid.
As the metal salt of carboxylic acid, bismuth salt of carboxylic acid and tin salt of carboxylic acid are preferred, and among them, bismuth salt of octylic acid is preferred. Furthermore, the metal salt of carboxylic acid may be a carboxylate of an alkyl metal. For example, the tin carboxylate may be a dialkyltin carboxylate, and preferably a dioctyltin carboxylate.
Specific examples of metal salts of carboxylic acids include bismuth trioctate, dioctyltin versatate, dibutyltin dilaurate, dioctyltin dilaurate, tin dioctylate, and lead dioctylate, with bismuth trioctate and dioctyltin versatate being preferred, and bismuth trioctate being more preferred.

The amount of transition metal salt in the polyol-containing composition is preferably 2 to 25 parts by mass, more preferably 3 to 20 parts by mass, even more preferably 4 to 15 parts by mass, and even more preferably 5 to 12 parts by mass, per 100 parts by mass of polyol. When the amount of transition metal salt is at or above the lower limit, the curing reaction speed of the foamable polyurethane composition can be improved. On the other hand, when the amount of transition metal salt is at or below the upper limit, the reaction can be more easily controlled.

<Heterocyclic compounds containing nitrogen atoms>
The polyol-containing composition of the present invention contains a heterocyclic compound having a nitrogen atom as a resinification catalyst. When the polyol-containing composition contains a heterocyclic compound having a nitrogen atom as a resinification catalyst, the polyol-containing composition is less susceptible to the influence of hydrofluoroolefin, and the stability is improved, and the polyol and polyisocyanate are easily reacted.

Although there is no particular limitation on the heterocyclic compound having a nitrogen atom used in the present invention, a compound containing a nitrogen atom in the heterocycle is preferred, and for example, a 4- to 8-membered heterocyclic compound containing a nitrogen atom in the heterocycle is more preferred, and more specific examples include imidazole derivatives, pyridine derivatives, piperazine derivatives, etc. Among these, imidazole derivatives are preferred.
The imidazole derivative is 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 4 or less carbon atoms. The alkyl group may also have 1 or more carbon atoms. A specific example of a suitable imidazole derivative is represented by the following general formula (3):

(In general formula (3), ^R7 and ^R8 each independently represent an alkyl group having 1 to 8 carbon atoms.)

In the general formula (3), ^R7 and ^R8 each independently represent an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. When the number of carbon atoms in the alkyl groups of ^R7 and ^R8 is equal to or greater than the lower limit, steric hindrance becomes large, making the compound less susceptible to the influence of blowing agents such as hydrofluoroolefins, which is preferable. On the other hand, when the number of carbon atoms in the alkyl groups of ^R4 and ^R5 is equal to or less than the upper limit, steric hindrance does not become extremely large, making it possible to rapidly proceed with the reaction between the polyol and the polyisocyanate. The alkyl groups may each be linear or have a branched structure.
Examples of the imidazole derivative represented by general formula (3) 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 viewpoints of improving the activity of the catalyst in the presence of a hydrofluoroolefin and of allowing the reaction to proceed rapidly. Furthermore, 1,2-dimethylimidazole is more preferred from the viewpoint of further enhancing stability.

The amount of the heterocyclic compound having a nitrogen atom in the polyol-containing composition is preferably 4.0 to 15 parts by mass, more preferably 5.0 to 13 parts by mass, and even more preferably 5.5 to 10 parts by mass, per 100 parts by mass of polyol. If the amount of the heterocyclic compound having a nitrogen atom is at or above the lower limit, urethane bond formation occurs more easily and the reaction proceeds quickly. On the other hand, if the amount of the heterocyclic compound having a nitrogen atom is at or below the upper limit, the reaction rate can be more easily controlled, which is preferable.

<Blowing Agent>
The polyol-containing composition of the present invention contains a blowing agent. The blowing agent preferably contains a hydrofluoroolefin. In the present invention, even when a hydrofluoroolefin is used as the blowing agent, the blowing agent is highly stable and its catalytic activity is unlikely to decrease. Examples of hydrofluoroolefins include fluoroalkenes having about 3 to 6 carbon atoms. The hydrofluoroolefin may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having about 3 to 6 carbon atoms.
More specific examples include trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorotrifluoropropenes such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetrafluoropropene. More specific examples include 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3,3,3-hexafluorobut-2-ene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yez), 1-chloro-3,3,3-trifluoropropene (HFO-1233zd), and 1,1,1,4,4,4-hexafluorobut-2-ene. Of these, HFO-1233zd is preferred.
These hydrofluoroolefins may be used alone or in combination of two or more.

The amount of hydrofluoroolefin blended is preferably 20 to 50 parts by mass, more preferably 22 to 45 parts by mass, and even more preferably 25 to 40 parts by mass, per 100 parts by mass of polyol. If the amount of hydrofluoroolefin blended is at or above the lower limit, foaming is promoted, and the density of the resulting polyurethane foam can be reduced. On the other hand, if the amount of hydrofluoroolefin blended is at or below the upper limit, excessive foaming can be suppressed.

The polyol-containing composition of the present invention may contain a blowing agent other than hydrofluoroolefin. Examples of blowing agents other than hydrofluoroolefin include low-boiling hydrocarbons such as water, propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane; chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride; organic physical blowing agents such as ether compounds such as diisopropyl ether; and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Of these, water, oxygen gas, and carbon dioxide gas are preferred from the standpoint of handleability, and water is preferred from the standpoint of adjusting the isocyanate index and ease of handling.

The amount of blowing agent other than hydrofluoroolefin in the polyol-containing composition is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and even more preferably 0.4 to 1 part by mass, per 100 parts by mass of polyol. If the amount of blowing agent is above the lower limit, foaming is promoted, and the density of the resulting polyurethane foam can be reduced. On the other hand, if the amount of blowing agent is below the upper limit, excessive foaming can be prevented.

<Filler>
The polyol-containing composition of the present invention preferably contains a filler. The filler is contained as a solid component in the polyol-containing composition and is generally present in the polyol-containing composition as a granular or powdery component.
The filler may be any component that is solid at room temperature (23° C.) and normal pressure (1 atmosphere) and does not dissolve in the polyol-containing composition.
As the filler, a solid flame retardant is preferably used, such as a red phosphorus-based flame retardant, a boron-containing flame retardant, a bromine-containing flame retardant, a phosphate-containing flame retardant, a chlorine-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide, and a needle-shaped filler.

<Red phosphorus flame retardants>
The red phosphorus-based flame retardant may consist of red phosphorus alone, or may be red phosphorus coated with a resin, metal hydroxide, metal oxide, or the like, or may be red phosphorus mixed with a resin, metal hydroxide, metal oxide, or the like. The resin that coats or mixes with red phosphorus is not particularly limited, but examples include thermosetting resins such as phenolic 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.

<Boron-containing flame retardants>
Examples of the boron-containing flame retardant used in the present invention include borax, boron oxide, boric acid, borate salts, etc. Examples of the 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.
The boron-containing flame retardant used in the present invention is preferably a borate, more preferably zinc borate.

<Bromine-containing flame retardants>
The bromine-containing flame retardant is not particularly limited as long as it contains bromine in its molecular structure and is a compound that is solid at room temperature and normal pressure, and examples thereof 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, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

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

<Phosphate-containing flame retardants>
Examples of the phosphate-containing flame retardant include phosphates formed from salts of various phosphoric acids and at least one metal or compound selected from metals of Groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring.
The phosphoric acid is not particularly limited, but examples thereof include monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid.
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-toliidine, 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 triphosphate, pyrophosphates, polyphosphates, etc. Here, the polyphosphates are not particularly limited, but examples include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, etc.
The phosphate-containing flame retardant may be used alone or in combination of two or more of the above-mentioned compounds.

<Chlorine-containing flame retardants>
Chlorine-containing flame retardants include those commonly used in flame-retardant resin compositions, such as polychlorinated naphthalene, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene, which is sold under the trade name "Dechlorane Plus."

<Antimony-containing flame retardants>
Examples of antimony-containing flame retardants include antimony oxide, antimony salts, and pyroantimony salts. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimony salts include sodium antimonate and potassium antimonate. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate.
The antimony-containing flame retardant 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.

<Metal hydroxide>
Examples of metal hydroxides used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, etc. The metal hydroxides may be used alone or in combination of two or more.

<Needle filler>
Examples of the needle-like filler used in the present invention include potassium titanate whiskers, aluminum borate whiskers, magnesium-containing whiskers, silicon-containing whiskers, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fibers, carbon fibers, graphite fibers, metal fibers, slag fibers, gypsum fibers, silica fibers, alumina fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, and stainless steel fibers.
These needle-like fillers can be used alone or in combination of two or more.

The aspect ratio (length/diameter) of the needle-shaped filler particles 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 50 needle-shaped filler particles with a scanning electron microscope and measuring their length and width.

In addition, inorganic fillers other than the flame retardants mentioned above may be blended as fillers. Examples of inorganic fillers that can be used include alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, imogolite, sericite, glass beads, silica balloon, aluminum nitride, boron nitride, silicon nitride, graphite, carbon balloon, charcoal powder, various metal powders, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, various magnetic powders, and fly ash. These inorganic fillers may be used alone or in combination.

The filler content in the polyol-containing composition of the present invention is preferably 20 to 120 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 45 to 90 parts by mass, per 100 parts by mass of polyol. By using an amount of 20 parts by mass or more, it becomes easier to improve the mechanical strength, flame retardant content, etc. of the resulting polyurethane foam. Furthermore, by using an amount of 120 parts by mass or less, foaming is less likely to be inhibited by the filler.

(liquid flame retardant)
The polyol-containing composition of the present invention preferably contains a liquid flame retardant. A liquid flame retardant is a flame retardant that is liquid at room temperature (23°C) and normal pressure (1 atmosphere). Specific examples of liquid flame retardants include phosphate esters. By including a liquid flame retardant in the polyurethane composition raw material liquid, the polyurethane composition raw material liquid of the present invention becomes less likely to precipitate during storage, making it easier to further improve the flame retardancy of the polyurethane composition of the present invention. From the viewpoint of improving flame retardancy, it is more preferable to use the liquid flame retardant in combination with the above-mentioned filler, particularly a solid flame retardant.

It is preferable to use monophosphate esters, condensed phosphate esters, etc. as the phosphate ester. Examples of monophosphate esters include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl)phosphate; halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate; trialkoxyphosphates 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 liquid flame retardants may be used alone or in combination of two or more of the above. Among these, monophosphate esters are preferred, and tris(β-chloropropyl)phosphate is more preferred, from the viewpoint of reducing the viscosity of the mixture of the polyol-containing composition of the present invention and isocyanate, thereby facilitating the production of polyurethane foam, and from the viewpoint of improving the flame retardancy of the polyurethane foam.

The amount of phosphate ester in the polyol-containing composition is preferably 20 to 60 parts by mass, more preferably 25 to 55 parts by mass, and even more preferably 30 to 50 parts by mass, per 100 parts by mass of polyol. Increasing the amount to 20 parts by mass or more makes it easier to improve the flame retardancy of the resulting polyurethane foam. Furthermore, keeping the amount to 60 parts by mass or less makes it less likely that foaming will be inhibited by the phosphate ester.

<Foam stabilizer>
The polyol-containing composition of the present invention may contain a foam stabilizer, if necessary, for the purpose of facilitating foaming of the mixture of the polyol-containing composition and the isocyanate.
Examples of the foam stabilizer include surfactants such as polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and silicone foam stabilizers such as octamethylcyclotetrasiloxane and organopolysiloxanes. These foam stabilizers may be used alone or in combination of two or more.

The content of the foam stabilizer in the polyol-containing composition of the present invention is preferably 0.1 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. When the amount of foam stabilizer is at or above the lower limit, the mixture of the polyol-containing composition and polyisocyanate is easily foamed, making it possible to obtain a homogeneous polyurethane foam. Furthermore, when the amount of foam stabilizer is at or below the upper limit, the balance between production costs and the obtained effects is optimal.

<Other ingredients>
The polyol-containing composition may contain one or more additives selected from phenolic, amine, sulfur-based and other antioxidants, heat stabilizers, metal inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, and the like, as needed, within the scope of the present invention.

<Method of producing polyol-containing composition>
There are no particular limitations on the method for producing the polyol-containing composition of the present invention, and it can be produced, for example, by stirring the components at about 20 to 40° C. for about 30 seconds to 20 minutes using a homodisper or the like.

[Foamable polyurethane composition and polyurethane foam]
The foamable polyurethane composition of the present invention contains the polyol-containing composition of the present invention and a polyisocyanate. The polyurethane foam of the present invention is a reaction product obtained by reacting and foaming a mixture of the polyol-containing composition and the polyisocyanate.
The foamable polyurethane composition used in the present invention is generally a two-component type, and may be prepared by mixing the polyol-containing composition of the present invention and a polyisocyanate, which have been stored separately, and reacting and foaming the mixture to obtain a polyurethane foam. Note that the polyisocyanate may contain components other than the polyisocyanate, such as the additives described above, as needed.

<Polyisocyanate>
Examples of polyisocyanates 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.

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.

Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred. The polyisocyanates may be used alone or in combination of two or more.
Furthermore, known additives that are blended into polyisocyanates may be appropriately blended into the polyisocyanate before mixing with the polyol-containing composition.

It is preferable that the polyol-containing composition and the polyisocyanate mixed with the polyol-containing composition have substantially the same volume. Specifically, the volume ratio of polyisocyanate to polyol-containing composition is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05.

<Isocyanate Index>
The isocyanate index of the foamable polyurethane composition of the present invention is not particularly limited, but is preferably 250 or higher. If the isocyanate index is equal to or higher than the lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, facilitating the formation of isocyanurate bonds by the polyisocyanate trimer, resulting in improved flame retardancy of the polyurethane foam. It also becomes possible to impart non-flammability. Furthermore, if the isocyanate index is equal to or higher than the lower limit, combined with the use of at least four of the catalysts described above, it becomes easier to produce a polyurethane foam with sufficient isocyanurate bonds, i.e., a polyurethane foam that combines high levels of flame retardancy and thermal insulation. From these perspectives, the isocyanate index is more preferably 270 or higher, and even more preferably 300 or higher.
The isocyanate index is preferably not more than 1000, more preferably not more than 800, and even more preferably not more than 600. When the isocyanate index is not more than the upper limit, the resulting polyurethane foam has a good balance between flame retardancy and production costs.

The isocyanate index can be calculated by the following method.
Isocyanate index = equivalents of polyisocyanate ÷ (equivalents of polyol + equivalents of water) × 100
Here, each equivalent number can be calculated as follows:
Equivalent number of polyisocyanate = Amount of polyisocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (mol) × 100
Equivalent number of polyol = OHV × amount of polyol used (g) ÷ molecular weight of KOH (mmol)
OHV is the hydroxyl value of the polyol (mg KOH/g).
Number of equivalents of water = amount of water used (g) / molecular weight of water (moles) × number of OH groups in water In each of the above formulas, the molecular weight of NCO is 42 (moles), the molecular weight of KOH is 56,100 (mmoles), the molecular weight of water is 18 (moles), and the number of OH groups in water is 2.

<Method of manufacturing polyurethane foam>
Although there are no particular limitations on the method for producing the polyurethane foam, it is preferable to foam and cure a foamable polyurethane composition obtained by mixing a polyisocyanate and a polyol-containing composition. Specifically, it is preferable to impinge-mix the polyisocyanate and the polyol-containing composition and spray the mixture using a spray gun or the like.
In the present invention, the polyurethane foam may be obtained by mixing the polyisocyanate and the polyol-containing composition, then pouring the mixture into a container such as a mold or frame, and allowing it to foam and harden.

<Applications of polyurethane foam>
The uses of the polyurethane foam of the present invention are not particularly limited, but because of its excellent flame retardancy and heat insulation, it can be suitably used in buildings such as walls, ceilings, roofs, and floors of buildings. It can also be suitably used as a member for filling any openings that occur in buildings, including joints and holes that occur between structural members of buildings.

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

(1) Polyol-containing composition [Polyol]
p-phthalic acid polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH/g)

〔catalyst〕
Trimerization catalyst, 2,2-dimethylpropanoic acid tetramethylammonium salt (manufactured by Air Products, product name: DABCO TMR7) concentration: approximately 45% by mass
Trimerization catalyst, 2-ethylhexanoic acid triethylmethylammonium salt (manufactured by San-Apro Co., Ltd., product name: U-CAT 18X), concentration approximately 100% by mass
Trimerization catalyst, 2-ethylhexanoic acid hydroxybutyltrimethylammonium salt (Kao Corporation, product name: Kaolizer No. 420), concentration approximately 100% by mass
Resinized amine catalyst: 1,2-dimethylimidazole (Kao Corporation, product name: Kaolizer No. 390) concentration: 65 to 75% by mass
Resinized amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-DM70) concentration 65 to 75% by mass
Resinized amine catalyst, 1-isobutyl-2-methylimidazole (manufactured by Air Products, product name: DABCO NC-IM), concentration approximately 100% by mass
Resinized metal catalyst, bismuth 2-ethylhexanoate (manufactured by Nitto Kasei Co., Ltd., product name: Bi28) concentration 81 to 90% by mass
Resinized metal catalyst, dioctyl (2-ethylhexyl) tin versatate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-830), concentration approximately 99% by mass
Trimerization metal catalyst, potassium 2-ethylhexanoate (manufactured by Air Products, product name: DABCO K-15), concentration 70 to 80% by mass
Trimeric amine catalyst, tetramethylammonium acetate (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-TRX) concentration 60 to 70% by mass
Resinized amine catalyst, N,N,N',N'',N''-pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-TT), concentration approximately 100% by mass

[Blowing Agent]
Hydrofluoroolefin (manufactured by Honeywell Japan, product name: Soltis LBA, trans-1-chloro-3,3,3-trifluoropropene)
·water

[Liquid flame retardant]
Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)

[Filler]
Wollastonite (SiO ₂ · CaO) (manufactured by Kinseimatec Co., Ltd., product name: SH-1250)

(2) Polyisocyanate 4,4'-diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Chemical Japan Co., Ltd., product name: PM200)

<Examples 1 to 12 and Comparative Examples 1 to 6>
Polyol-containing compositions were prepared according to the formulations shown in Table 1.

[Evaluation of Foaming Property]
The polyol-containing composition prepared by the above method and polyisocyanate were mixed according to the formulation shown in Table 1, and sprayed onto gypsum board using a sprayer under the following conditions, scattering the urethane foam so that the thickness was 1 mm or less. The surface curing time (tack-free time) after spraying was measured. The surface curing time was designated _t1 , _and a value of "◎" was given for a value of less than 27 seconds, "◯" for a value of 27 to 30 seconds, and "×" for a value of more than 30 seconds. The results are shown in Table 1.
<Conditions>
・Spraying machine: Graco H-25 spraying machine
・Settings (heater and pressure settings)
Isocyanate heater: 38°C
Premix heater: 38°C
Hose heater: 38°C
Pressure: Adjust appropriately so that the mist becomes a wide circle. Base material: Gypsum board (thickness 12.5 mm)
・Substrate temperature: 0℃±1℃
・Environmental temperature: 0℃±1℃

[Stability evaluation]
The polyol-containing composition was placed in a pressure-resistant container and stored in a thermostatic chamber at 45°C for 2 days. Thereafter, spraying was carried out in the same manner as described above, and the surface curing time after spraying was measured. The surface curing time was designated _t2 , and a difference between t2 and _t1 was evaluated as "◎" if it was less than 4 seconds, "◯" if it was 4 seconds or more but 6 seconds or less, and "×" if it was more than 6 seconds. The results are shown in Table 1.

The value in parentheses in the polyol indicates the hydroxyl value (mgKOH/g).
The parts by mass of each catalyst represent parts by mass of the product.

As is clear from the results of the above examples, the combined use of a potassium carboxylate, an ammonium carboxylate, a heterocyclic compound having a nitrogen atom, and a transition metal salt suppresses the deactivation of the catalyst due to the reaction between the blowing agent and the catalyst, thereby increasing the stability of the polyol-containing composition and enabling both excellent stability and good foamability to be achieved.
In contrast, polyol-containing compositions that did not contain any one of the four catalysts were impaired in at least one of foaming properties and stability.

Claims (8)

A polyol-containing composition for reacting with a polyisocyanate to obtain a polyurethane foam, the composition comprising a polyol, a blowing agent, and a catalyst;
the catalyst contains a potassium carboxylate salt, an ammonium carboxylate salt, a heterocyclic compound having a nitrogen atom, and a metal salt of bismuth;
the heterocyclic compound having a nitrogen atom is an imidazole derivative,
The blowing agent contains a hydrofluoroolefin.
A polyol-containing composition for forming insulation by spraying into a building. The polyol-containing composition according to claim 1, wherein the carboxylic acid in the potassium carboxylate is at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. The polyol-containing composition according to claim 1 or 2, wherein the carboxylic acid in the ammonium carboxylate is at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. The polyol-containing composition according to any one of claims 1 to 3, wherein the ammonium ion in the ammonium carboxylate salt is a quaternary ammonium ion. The polyol-containing composition according to any one of claims 1 to 4, wherein the metal salt is a metal salt of a carboxylic acid having 5 or more carbon atoms. The polyol-containing composition according to any one of claims 1 to 5, wherein the imidazole derivative is an imidazole in which the 1st and 2nd positions are each independently substituted with an alkyl group having 4 or less carbon atoms. A foamable polyurethane composition for forming a thermal insulation material by spraying it onto a building, comprising the polyol-containing composition according to any one of claims 1 to 6 and a polyisocyanate. The foamable polyurethane composition according to claim 7, having an isocyanate index of 250 or more.