JP7613840B2 - 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 for buildings such as apartment complexes, detached houses, various school facilities, and commercial buildings. Polyurethane foam is obtained by mixing a polyol-containing composition and a polyisocyanate at the construction site of a building, foaming the mixture, and spraying the mixture onto objects such as ceilings, walls, and roofs using a spray device or the like.

The polyol-containing composition contains a resinification catalyst, a trimerization catalyst, etc. as catalysts. The resinification catalyst is a catalyst that promotes the reaction between a polyol, etc. and an isocyanate, and the trimerization catalyst is a catalyst that promotes the production of isocyanurate by the reaction of isocyanates with each other, thereby increasing the ratio of isocyanurate.
In the polyol-containing composition containing a catalyst, the catalyst and the blowing agent may react during storage, causing a decrease in catalytic performance and a decrease in foaming property. Hydrofluorocarbons (HFCs) have been widely used as blowing agents in the past, but the switch to hydrofluoroolefins (HFOs) with low global warming potential as blowing agents is progressing. Among blowing agents, hydrofluoroolefins tend to react particularly easily with catalysts, which makes the decrease in catalytic performance and the decrease in foaming property more likely to occur.
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.

JP 2018-30975 A International Publication No. 2018/105730

However, in conventional polyol-containing compositions, the catalyst may 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 suppresses catalyst deactivation and achieves both excellent stability and good foamability.

As a result of intensive research, the present inventors have found that the above problems can be solved by incorporating a potassium carboxylate, an ammonium carboxylate, 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 reacting with a polyisocyanate to obtain a polyurethane foam, comprising a polyol, a blowing agent, and a catalyst,
The catalyst is a polyol-containing composition that contains a potassium carboxylate, an ammonium carboxylate, 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 carboxylic acid in the ammonium carboxylate has 5 or more carbon atoms.
[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 1- and 2-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 provides a polyol-containing composition, a foamable polyurethane composition, and a polyurethane foam that have 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 obtaining 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. The polyol-containing composition of the present invention can achieve both excellent stability and good foamability by containing the potassium carboxylate salt, the ammonium carboxylate salt, the heterocyclic compound having a nitrogen atom, and the transition metal salt as the catalyst.
Each component in 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 a polyurethane foam.
Examples of the polyol 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 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.
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, 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.

Polyols used in the present invention are preferably polyester polyols and polyether polyols. Also, polyols having two hydroxyl groups are preferred. Among them, from the viewpoint of enhancing flame retardancy, aromatic polyester polyols, which are polyester polyols having aromatic rings, are preferred. More preferred aromatic polyester polyols are those 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.

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 is likely 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 the 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, an ammonium carboxylate, a heterocyclic compound having a nitrogen atom, and a transition metal salt as catalysts. By containing the above four types of 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 to improve the foaming property.

Potassium carboxylate
The polyol-containing composition of the present invention contains a potassium carboxylate. The potassium carboxylate is a trimerization catalyst and facilitates the formation of an isocyanurate bond through a trimer of a polyisocyanate.
In the present invention, the carboxylic acid in the potassium carboxylate may have 1 or more carbon atoms, but preferably has 5 or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The number of carbon atoms of the carboxylic acid is, for example, 20 or less, preferably 12 or less, more preferably 8 or less. In addition, 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, the reactivity with a blowing agent such as hydrofluoroolefin tends to be low due to steric hindrance, and the stability of the polyol-containing composition is improved.

Among them, the potassium carboxylate is preferably a potassium carboxylate represented by the following general formula (1). The potassium carboxylate represented by the following general formula (1) has a moderate steric hindrance, so that it 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 the 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.
Furthermore, ^R3 represents a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 6 carbon atoms. Furthermore, ^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, the steric hindrance becomes large, and the reaction of decomposing the hydrofluoroolefin can be suppressed. 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, the steric hindrance does not become too large, and the reactivity can be prevented 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 the above general formula (1), and among these, 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 kinds.

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. If the amount of potassium carboxylate is equal to or greater than the lower limit, trimerization of the polyisocyanate is more likely to occur, improving the flame retardancy of the resulting polyurethane foam. On the other hand, if the amount of potassium carboxylate is equal to or less than the upper limit, the reaction is easier to control.

Ammonium carboxylates
The polyol-containing composition of the present invention contains an ammonium carboxylate. The ammonium carboxylate is a trimerization catalyst and facilitates the formation of an isocyanurate bond through a trimer of a polyisocyanate.
In the present invention, the carboxylic acid in the ammonium carboxylate may have 1 or more carbon atoms, but preferably has 5 or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The number of carbon atoms of the carboxylic acid is, for example, 20 or less, preferably 12 or less, more preferably 8 or less. In addition, 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, the reactivity with a blowing agent such as hydrofluoroolefin tends to be reduced due to steric hindrance, and the stability of the polyol-containing composition is improved.

Among them, 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 steric hindrance, so that it 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 the 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, the steric hindrance becomes large, and the reaction of decomposing the hydrofluoroolefin can be suppressed. On the other hand, when the carbon numbers of R ⁴ , R ⁵ and R ⁶ are equal to or less than the upper limit, the steric hindrance does not become too large, and the reactivity can be prevented from slowing down.
M ⁺ represents an ammonium ion, and the details of the ammonium ion will be described later.

A specific example of a suitable 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 kinds.

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

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 by a trimer of polyisocyanate.
In the present invention, the ammonium carboxylates may be used alone or in combination of two or more kinds.

The amount of ammonium carboxylate 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. If the amount of ammonium carboxylate is equal to or greater than the lower limit, trimerization of the polyisocyanate is more likely to occur, improving the flame retardancy of the resulting polyurethane foam. On the other hand, if the amount of ammonium carboxylate is equal to or less than the upper limit, the reaction is easier to control.

<<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 easily reacted with the polyol and the polyisocyanate while suppressing decomposition by a blowing agent and increasing stability.

The transition metal salts used in the present invention include, for example, metal salts of bismuth, tin, zinc, copper, iron, and lead, among which 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. The carboxylic acid has 5 or more carbon atoms, so that the stability of the polyol-containing composition is good against a blowing agent, particularly against hydrofluoroolefin. In addition, the carbon number of the carboxylic acid is preferably 18 or less, more preferably 12 or less, from the viewpoint of catalytic activity. 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, and among these, 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 preferable, and among them, bismuth salt of octylic acid is preferable. In addition, the metal salt of carboxylic acid may be a carboxylate of an alkyl metal. For example, the tin salt of carboxylic acid 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, of which bismuth trioctate and dioctyltin versatate are preferred, and bismuth trioctate is 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 equal to or greater than 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 equal to or less than the upper limit, the reaction can be easily controlled.

<Heterocyclic compounds having 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 the polyisocyanate are easily reacted with each other.

The heterocyclic compound having a nitrogen atom used in the present invention is not particularly limited, but is preferably a compound containing a nitrogen atom in the heterocycle, more preferably a 4- to 8-membered heterocyclic compound containing a nitrogen atom in the heterocycle, more specifically, imidazole derivatives, pyridine derivatives, piperazine derivatives, etc. Among these, imidazole derivatives are preferred.
The imidazole derivative is an imidazole substituted at the 1-position and the 2-position 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. The alkyl group may have 1 or more carbon atoms. A specific example of a suitable imidazole derivative is represented by the following general formula (3).

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

In the general formula (3), R ⁷ and R ⁸ 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 carbon number of the alkyl group of R ⁷ and R ⁸ is equal to or greater than the lower limit, steric hindrance becomes large, and the alkyl group is less susceptible to the influence of a foaming agent such as hydrofluoroolefin, which is preferable. On the other hand, when the carbon number of the alkyl group of R ⁴ and R ⁵ is equal to or less than the upper limit, the steric hindrance does not become extremely large, and the reaction between the polyol and the polyisocyanate can be rapidly promoted. The alkyl groups may each be linear or have a branched structure.
Examples of the imidazole derivative represented by the general formula (3) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole, and 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 a hydrofluoroolefin and from the viewpoint of rapidly progressing the reaction. Furthermore, 1,2-dimethylimidazole is more preferred from the viewpoint of further increasing 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 equal to or greater than the lower limit, urethane bonds are more likely to be formed and the reaction proceeds quickly. On the other hand, if the amount of the heterocyclic compound having a nitrogen atom is equal to or less than the upper limit, the reaction rate is more easily controlled, which is preferable.

<Foaming 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 the catalytic activity is not easily reduced. Examples of the hydrofluoroolefin 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, chlorodifluoropropenes, chlorotrifluoropropenes, and chlorotetrafluoropropenes. More specifically, examples thereof 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 kinds.

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. When the amount of hydrofluoroolefin blended is equal to or greater than the lower limit, foaming is promoted and the density of the resulting polyurethane foam can be reduced. On the other hand, when the amount of hydrofluoroolefin blended is equal to or less than 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 point 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. Among these, water, oxygen gas, and carbon dioxide gas are preferred from the viewpoint of handleability, and water is preferred from the viewpoint of adjusting the isocyanate index and ease of handling.

The amount of the blowing agent other than the 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 the polyol. When the amount of the blowing agent is equal to or greater than the lower limit, foaming is promoted and the density of the resulting polyurethane foam can be reduced. On the other hand, when the amount of the blowing agent is equal to or less than the upper limit, excessive foaming can be prevented.

<Filler>
The polyol-containing composition of the present invention preferably contains a filler. The filler is a component that is contained as a solid in the polyol-containing composition and is generally present in the form of particles or powder in the polyol-containing composition.
The filler may be any component that is solid at room temperature (23° C.) and normal pressure (1 atm) 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-based flame retardants>
The red phosphorus-based flame retardant may be made of red phosphorus alone, may be red phosphorus coated with a resin, a metal hydroxide, a metal oxide, or may be red phosphorus mixed with a resin, a metal hydroxide, a metal oxide, or the like. The resin that coats the red phosphorus or mixes with the red phosphorus is not particularly limited, but examples thereof include thermosetting resins such as phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. From the viewpoint of flame retardancy, metal hydroxide is preferable as the compound to be coated or mixed. The metal hydroxide to be used may be appropriately selected from those described later.

<Boron-containing flame retardants>
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.

<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 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 ethylenebis(pentabromophenyl) are 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 the group consisting of metals in 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-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 the phosphate-containing flame retardant include monophosphates such as 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 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 naphthalenes, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene 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 include sodium pyroantimonate and potassium pyroantimonate.
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.

<Metal hydroxide>
Examples of the metal hydroxide 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 hydroxide may be used alone or in combination of two or more kinds.

<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, stainless steel fibers, and the like.
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 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 fillers with a scanning electron microscope and measuring their length and width.

In addition, inorganic fillers other than the above-mentioned flame retardants may be blended as the filler. As inorganic fillers, 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, fly ash, etc. may be appropriately used. The inorganic fillers may be used alone or in combination of two or more.

The content of the filler 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 making the content 20 parts by mass or more, it becomes easier to improve the mechanical strength, flame retardant, etc. of the obtained polyurethane foam. In addition, by making the content 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. The liquid flame retardant is a flame retardant that is liquid at room temperature (23°C) and normal pressure (1 atm). Specific examples of liquid flame retardants include phosphoric acid esters. By including a liquid flame retardant in the polyurethane composition raw material liquid, the polyurethane composition raw material liquid of the present invention is less likely to precipitate during storage, and the flame retardancy of the polyurethane composition of the present invention is more easily improved. 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.

As the phosphate ester, it is preferable to use monophosphate ester, condensed phosphate ester, etc. Examples of monophosphate ester include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl)phosphate, halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate, trialkoxy phosphates such as tributoxyethyl phosphate, aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)phosphate, 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 to facilitate 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. By making the amount 20 parts by mass or more, it becomes easier to improve the flame retardancy of the resulting polyurethane foam. Also, by making the amount 60 parts by mass or less, foaming is less likely to 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 a mixture of the polyol-containing composition and an isocyanate.
Examples of the foam stabilizer include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and surfactants such as 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 the foam stabilizer is equal to or greater than the lower limit, the mixture of the polyol-containing composition and the polyisocyanate is easily foamed, making it possible to obtain a homogeneous polyurethane foam. When the amount of the foam stabilizer is equal to or less than the upper limit, the balance between the production cost and the obtained effect is optimal.

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

<Method of producing polyol-containing composition>
There is no particular limitation on the method for producing the polyol-containing composition of the present invention. For example, the composition can be produced by stirring each component 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 it is preferable to mix the polyol-containing composition of the present invention and a polyisocyanate, which are stored separately, and react and foam them to obtain a polyurethane foam. Note that the polyisocyanate may contain components other than the polyisocyanate, such as the additives described above, as necessary.

<Polyisocyanate>
Examples of the polyisocyanate 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, the polyisocyanate may be appropriately mixed with known additives that are mixed with polyisocyanates before being mixed with the polyol-containing composition.

It is preferable that the polyol-containing composition and the polyisocyanate mixed into the polyol-containing composition have substantially the same volume. Specifically, the volume ratio of the polyisocyanate to the 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 in the foamable polyurethane composition of the present invention is not particularly limited, but is preferably 250 or more. If the isocyanate index is equal to or more than the lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, and isocyanurate bonds due to the trimer of polyisocyanate are easily formed, resulting in improved flame retardancy of the polyurethane foam. It is also possible to impart non-flammability. Furthermore, if the isocyanate index is equal to or more than the lower limit, combined with the use of at least four of the above-mentioned catalysts, it is easy to produce a polyurethane foam having sufficient isocyanurate bonds, that is, a polyurethane foam having both flame retardancy and heat insulation at a high level. From these viewpoints, the isocyanate index is more preferably 270 or more, and even more preferably 300 or more.
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 x amount of polyol used (g) ÷ molecular weight of KOH (mmol)
OHV is the hydroxyl value of the polyol (mg KOH/g).
Number of water equivalents = 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>
The method for producing the polyurethane foam is not particularly limited, but it is preferable to mix a polyisocyanate with a polyol-containing composition to obtain a foamable polyurethane composition, and then foam and cure the composition. Specifically, it is preferable to mix the polyisocyanate with the polyol-containing composition by collision and spray the mixture with 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, and then pouring the mixture into a container such as a mold or a 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 since it has excellent flame retardancy and heat insulation, it can be suitably used in buildings such as walls, ceilings, roofs, floors, etc. 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 materials of buildings.

The present invention will be explained in more detail below with reference to 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 salt (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

[Foaming 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 Industry Co., Ltd., product name: TMCPP)

[Filler]
Wollastonite ( _SiO2.CaO ) (Kinsei Matec 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 Foamability]
The polyol-containing composition prepared by the above method and the polyisocyanate were mixed according to the formulation shown in Table 1, and the mixture was sprayed on a gypsum board using a spraying machine under the following conditions so that the urethane foam thickness was 1 mm or less, and the surface curing time (tack-free time) after spraying was measured. The surface curing time was designated _t1 , and when _t1 was less than 27 seconds, it was marked as "◎", when it was 27 seconds or more but less than 30 seconds, it was marked as "◯", and when it was more than 30 seconds, it was marked as "×". The results are shown in Table 1.
<Conditions>
・Spraying machine: Graco H-25 spraying machine
・Settings (heater and pressure settings)
Isocyanate heater: 38℃
Premix heater: 38℃
Hose heater: 38℃
Pressure: Adjust so that the mist becomes a wide circular shape. Substrate: Gypsum board (thickness 12.5 mm)
・Substrate temperature: 0℃±1℃
・Environmental temperature: 0℃±1℃

[Evaluation of stability]
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 performed in the same manner as described above, and the surface curing time after spraying was measured. The surface curing time was designated _t2 , and the difference between _t2 and t1 was designated "◎" if it was less than 4 seconds, "◯" if it was 4 seconds or more and 6 seconds or less, and "×" if it was more than 6 seconds. The results are shown in Table 1.

The value in parentheses for the polyol indicates the hydroxyl value (mg KOH/g).
The parts by mass of each catalyst represent the 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 reaction between the blowing agent and the catalyst and the deactivation of the catalyst, thereby increasing the stability of the polyol-containing composition and enabling both excellent stability and good foamability to be achieved.
In contrast, a polyol-containing composition that did not contain any one of the four types of catalysts was impaired in at least one of the foaming property and stability.

Claims (12)

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 blowing agent contains a hydrofluoroolefin,
The catalyst contains a potassium carboxylate, an ammonium carboxylate, a heterocyclic compound having a nitrogen atom, and at least one metal salt selected from the group consisting of bismuth and tin,
the carboxylic acid in the potassium carboxylate has 5 or more carbon atoms;
the number of carbon atoms of the carboxylic acid in the ammonium carboxylate is 5 or more, and the ammonium ion in the ammonium carboxylate is a quaternary ammonium ion,
the metal salt is a metal salt of a carboxylic acid having 5 or more carbon atoms,
A polyol-containing composition, wherein the heterocyclic compound is an imidazole derivative, and the imidazole derivative is an imidazole in which the 1- and 2-positions are each independently substituted with an alkyl group having 4 or less carbon atoms (however, those containing a tetraalkylguanidine or a vinyl polymerizable compound are excluded). The polyol-containing composition according to claim 1, wherein the carboxylic acid in the carboxylate potassium salt is at least one selected from the group consisting of 2-ethylhexanoic acid and 2,2-dimethylpropanoic 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 and 2,2-dimethylpropanoic acid . The polyol-containing composition according to any one of claims 1 to 3, 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. The polyol-containing composition according to any one of claims 1 to 4, wherein the ammonium carboxylate is tetramethylammonium 2,2-dimethylpropanoate. The polyol-containing composition according to any one of claims 1 to 5, wherein the metal in the metal salt is bismuth. The polyol-containing composition according to any one of claims 1 to 6, wherein the metal salt is a metal salt of 2-ethylhexanoic acid. The polyol-containing composition according to any one of claims 1 to 7, wherein the imidazole derivative is at least one selected from the group consisting of 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole. The polyol-containing composition according to any one of claims 1 to 8, wherein the imidazole derivative is 1,2-dimethylimidazole. A foamable polyurethane composition comprising the polyol-containing composition according to any one of claims 1 to 9 and a polyisocyanate. The foamable polyurethane composition according to claim 10, having an isocyanate index of 250 or more. A polyurethane foam obtained by reacting and foaming the foamable polyurethane composition according to claim 10 or 11.