Polyol-containing composition, foamed polyurethane composition, and polyurethane foam

Abstract

The present invention provides a polyol-containing composition, a foamable polyurethane composition, and a polyurethane foam that achieve both stability and foamability. [Solution] A polyol-containing composition for obtaining polyurethane foam by reacting with polyisocyanate, comprising a polyol compound, a blowing agent, and a catalyst, wherein the catalyst comprises a potassium carboxylate salt, an ammonium carboxylate salt, a heterocyclic compound having a nitrogen atom, and a transition metal salt.

Description

[Technical Field]

[0001] The present invention relates to a polyol-containing composition, a foamed polyurethane composition, and a polyurethane foam. [Background technology]

[0002] Due to its excellent thermal insulation and adhesive properties, polyurethane foam is used as insulation material in buildings such as apartment buildings, detached houses, various school facilities, and commercial buildings. Polyurethane foam is obtained at the construction site of a building by mixing a polyol-containing composition with polyisocyanate, foaming it, and then spraying it onto objects such as ceilings, walls, and roofs using a spray device.

[0003] The polyol-containing composition contains resinification catalysts and trimerization catalysts as catalysts. Resinification catalysts are catalysts that promote the reaction between polyols and isocyanates, while trimerization catalysts are catalysts that promote the formation of isocyanurates by the reaction of isocyanates with each other, thereby increasing the proportion of isocyanurates. Polyol-containing compositions incorporating catalysts may experience a decrease in catalyst performance and effervescence during storage due to reactions between the catalyst and the blowing agent. While hydrofluorocarbons (HFCs) were previously widely used as blowing agents, there is a growing shift towards hydrofluoroolefins (HFOs), which have a lower global warming potential. Hydrofluoroolefins, in particular, tend to react more readily with catalysts than other blowing agents, making them even more susceptible to a decrease in catalyst performance and effervescence. To solve these problems, methods have been proposed for determining the proportions of trimerization catalyst and resinification catalyst (see, for example, Patent Document 1), and for using a trimerization catalyst having a predetermined structure (see, for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2018-30975 [Patent Document 2] International Publication No. 2018 / 105730 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, in conventional polyol-containing compositions, the foaming agent, such as HFO, reacts with the catalyst, causing the catalyst to become inactive and reducing the stability of the polyol-containing composition. This makes it difficult to achieve both stability and improved foaming properties.

[0006] Therefore, the object of the present invention is 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 foaming properties. [Means for solving the problem]

[0007] As a result of diligent research, the inventors have found that the above problems can be solved by including potassium carboxylate salts, ammonium carboxylate salts, heterocyclic compounds having nitrogen atoms, and transition metal salts as catalysts in the 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 obtaining polyurethane foam by reaction with polyisocyanate, 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 carboxylic acid salt 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 carboxylic acid salt has 5 or more carbon atoms. [4] The carboxylic acid in the ammonium carboxylate salt is at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid, and the polyol-containing composition according to any one of [1] to [3]. [5] The carboxylic acid in the ammonium carboxylate salt has 5 or more carbon atoms, and the polyol-containing composition according to any one of [1] to [4]. [6] The ammonium ion in the ammonium carboxylate salt is a quaternary ammonium ion, and the polyol-containing composition according to any one of [1] to [5]. [7] The ammonium ion in the ammonium carboxylate salt is at least one selected from the group consisting of triethylmethylammonium ion, tetramethylammonium ion, hydroxybutyltrimethylammonium ion, and hydroxypropyltrimethylammonium ion, and the polyol-containing composition according to any one of [1] to [6]. [8] The ammonium carboxylate salt is tetramethylammonium 2,2-dimethylpropanoate, and the polyol-containing composition according to any one of [1] to [7]. [9] The transition metal in the transition metal salt is at least one selected from the group consisting of bismuth and tin, and the polyol-containing composition according to any one of [1] to [8].

[10] The transition metal salt is a metal salt of a carboxylic acid having 5 or more carbon atoms, and the polyol-containing composition according to any one of [1] to [9].

[11] The transition metal in the transition metal salt is bismuth, and the polyol-containing composition according to any one of [1] to

[10] .

[12] The transition metal salt is a metal salt of 2-ethylhexanoic acid, and the polyol-containing composition according to any one of [1] to

[11] .

[13] The heterocyclic compound is an imidazole derivative, and the polyol-containing composition according to any one of [1] to

[12] .

[14] The polyol-containing composition according to any one of [1] to

[13] , wherein the imidazole derivative is an imidazole substituted at the 1-position and 2-position independently 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 foaming agent contains hydrofluoroolefin.

[18] A foaming polyurethane composition comprising the polyol-containing composition according to any one of [1] to

[17] and a polyisocyanate.

[19] The foaming polyurethane composition according to

[18] , wherein the isocyanate index is 250 or more.

[20] A polyurethane foam obtained by reacting and foaming the foaming polyurethane composition according to

[18] or

[19] .

Advantages of the Invention

[0008] According to the present invention, it is possible to provide a polyol-containing composition, a foaming polyurethane composition, and a polyurethane foam that achieve both excellent stability and good foaming properties.

Modes for Carrying Out the Invention

[0009] Hereinafter, the present invention will be described in detail. [Polyol-Containing Composition] The polyol-containing composition of the present invention is a polyol-containing composition for obtaining polyurethane foam by reacting with polyisocyanate, and contains a polyol, a blowing agent, and a catalyst, wherein the catalyst contains potassium carboxylate salts, ammonium carboxylate salts, heterocyclic compounds having nitrogen atoms, and transition metal salts. The polyol-containing composition of the present invention can achieve both excellent stability and good foaming properties by containing potassium carboxylate salts, ammonium carboxylate salts, heterocyclic compounds having nitrogen atoms, and transition metal salts as catalysts. The components of the polyol-containing composition of the present invention will be described in detail below.

[0010] <Polyol> The polyol-containing composition of the present invention contains a polyol as a raw material for polyurethane foam. Examples of polyols used in the present invention include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

[0011] Examples of polylactone polyols include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of polycarbonate polyols include polyols obtained by the de-alcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, etc.

[0012] Examples of aromatic polyols include bisphenol A, bisphenol F, phenol novolac, and cresol novolac. Examples of alicyclic polyols include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol. Examples of aliphatic polyols include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

[0013] Examples of polyester polyols include polymers obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, and condensates of hydroxycarboxylic acids and the aforementioned polyhydric alcohols. Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), and succinic acid. Examples of polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

[0014] Examples of polymer polyols include polymers obtained by graft polymerization of ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate onto aromatic polyols, alicyclic polyols, aliphatic polyols, and polyester polyols, as well as polybutadiene polyols, modified polyols of polyhydric alcohols, or hydrogenated versions thereof.

[0015] Examples of modified polyols of polyhydric alcohols include those obtained by reacting a polyhydric alcohol with alkylene oxide. Examples of polyhydric alcohols include trihydric alcohols such as glycerin and trimethylolpropane, tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl glucoside and its derivatives, polyols such as phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene, castor oil polyols, (co)polymers of hydroxyalkyl (meth)acrylates, and polyfunctional polyols (e.g., 2 to 100 functional groups) such as polyvinyl alcohol, and condensates of phenol and formaldehyde (novolacs).

[0016] The method for modifying polyhydric alcohols is not particularly limited, but a method involving the addition of alkylene oxides (hereinafter also referred to as "AO") is preferably used. Examples of AOs include AOs having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter also referred to as "EO"), 1,2-propylene oxide (hereinafter also referred to as "PO"), 1,3-propyloxide, 1,2-butylene oxide, and 1,4-butylene oxide. Among these, PO, EO, and 1,2-butylene oxide are preferred from the viewpoint of properties and reactivity, with PO and EO being more preferred. When two or more AOs are used (for example, PO and EO), the addition method may be block addition, random addition, or a combination of these.

[0017] Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, or tetrahydrofuran in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogen atoms. Examples of low molecular weight active hydrogen compounds having two or more active hydrogen atoms include bisphenol A, ethylene glycol, propylene glycol, butylene glycol, diols such as 1,6-hexanediol, triols such as glycerin and trimethylolpropane, ethylenediamine, and amines such as butylenediamine.

[0018] Polyols used in the present invention include polyester polyols and polyether polyols. Polyols having two hydroxyl groups are also preferred. Among these, aromatic polyester polyols, which are polyester polyols having aromatic rings, are preferred from the viewpoint of enhancing flame retardancy. As aromatic polyester polyols, those obtained by dehydration condensation of a polybasic acid having an aromatic ring, such as isophthalic acid (m-phthalic acid) or terephthalic acid (p-phthalic acid), with a dihydric alcohol, such as bisphenol A, ethylene glycol, or 1,2-propylene glycol are more preferred.

[0019] The hydroxyl value of the polyol is preferably 20 to 300 mg KOH / g, more preferably 30 to 250 mg KOH / g, and even more preferably 50 to 220 mg KOH / g. When the hydroxyl value of the polyol is below the upper limit, the viscosity of the polyol-containing composition tends to decrease, which is preferable from the viewpoint of handling and other factors. On the other hand, when the hydroxyl value of the polyol is above the lower limit, the crosslinking density of the polyurethane foam increases, resulting in higher strength. The hydroxyl value of polyols can be measured according to JIS K 1557-1:2007.

[0020] <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 types of catalysts, the polyol-containing composition of the present invention can suppress the decomposition of the foaming agent by the catalyst and enhance the activity of the catalyst to improve foaming properties.

[0021] Potassium carboxylate salts The polyol-containing composition of the present invention contains a potassium carboxylate salt. The potassium carboxylate salt acts as a trimerization catalyst, facilitating the formation of isocyanurate bonds by the trimerized polyisocyanate. In the present invention, the carboxylic acid in the potassium carboxylic acid salt may have 1 or more carbon atoms, but preferably 5 or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, and more preferably a saturated aliphatic carboxylic acid. The number of carbon atoms in the carboxylic acid is, for example, 20 or less, but preferably 12 or less, and more preferably 8 or less. The carboxylic acid may be linear or have a branched structure, but it is preferable to have a branched structure. Having a branched structure tends to reduce reactivity with blowing agents such as hydrofluoroolefins due to steric hindrance, thereby improving the stability of the polyol-containing composition.

[0022] Potassium carboxylate salts are preferably those represented by the following general formula (1). Potassium carboxylate salts represented by the following general formula (1) have appropriate steric hindrance, which can suppress the reaction that decomposes the foaming agent and also prevent a decrease in catalytic activity.

[0023] [ka] (In general formula (1), R 1 and R 2 Each of these independently represents an alkyl group, and R 3 represents a hydrogen atom or an alkyl group. Also, K + (This represents potassium ions.)

[0024] R in General Formula (1) 1 and R 2 each independently represents an alkyl group, 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 have a branched structure. Also, R 3 represents a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 6 carbon atoms. Further, R 3 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. R 1 , R 2 and R 3 When the number of carbon atoms of R 1 , R 2 and R 3 is equal to or greater than the lower limit value, the steric hindrance becomes large, so that the reaction for decomposing the hydrofluoroolefin can be suppressed. On the other hand, when the number of carbon atoms of R

[0025] In the present invention, the potassium carboxylate salt may be used alone or in combination of two or more.

[0026] ​The amount of potassium carboxylate salt 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 salt is above 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 salt is below the upper limit, the reaction becomes easier to control.

[0027] Ammonium carboxylate salts The polyol-containing composition of the present invention contains an ammonium carboxylate salt. The ammonium carboxylate salt acts as a trimerization catalyst, facilitating the formation of isocyanurate bonds by the trimerized polyisocyanate. In the present invention, the carboxylic acid in the ammonium carboxylic acid salt may have 1 or more carbon atoms, but it is preferable that it has 5 or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, and more preferably a saturated aliphatic carboxylic acid. The number of carbon atoms in the carboxylic acid is, for example, 20 or less, but is preferably 12 or less, and more preferably 8 or less. The carboxylic acid may be linear or have a branched structure, but it is preferable that it has a branched structure. Having a branched structure tends to reduce reactivity with blowing agents such as hydrofluoroolefins due to steric hindrance, thereby improving the stability of the polyol-containing composition.

[0028] Among the ammonium carboxylate salts, the ammonium carboxylate salt represented by the following general formula (2) is preferred. The ammonium carboxylate salt represented by the following general formula (2) has appropriate steric hindrance, which can suppress the reaction that decomposes the foaming agent and also prevent a decrease in catalytic activity.

[0029] [ka] (In general formula (2), R 4 and R 5 Each of these independently represents an alkyl group, and R6 represents a hydrogen atom or an alkyl group. Also, M + (This represents the ammonium ion.)

[0030] R in general formula (2) 4 and R 5 Each of these independently represents an alkyl group, specifically, alkyl groups having 1 to 6 carbon atoms are preferred, alkyl groups having 1 to 4 carbon atoms are more preferred, and alkyl groups having 1 to 2 carbon atoms are even more preferred. The alkyl group may be linear or have a branched structure. Also, R 6 R represents a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 6 carbon atoms. 6 Alkyl alkyl groups are preferred, C1-C4 alkyl groups are more preferred, and C1-C2 alkyl groups are even more preferred. R 4 , R 5 and R 6 If the number of carbon atoms is greater than or equal to the lower limit, steric hindrance increases, which can suppress the reaction that decomposes hydrofluoroolefins. On the other hand, R 4 , R 5 and R 6 If the number of carbon atoms is below the aforementioned upper limit, steric hindrance does not become too large, thus preventing the reaction from becoming slow. M + This represents the ammonium ion, and details about the ammonium ion will be explained later.

[0031] A suitable specific example of the carboxylic acid in the ammonium carboxylate salt is at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. Carboxylic acids as shown in general formula (2) are also preferred, with 2-ethylhexanoic acid and 2,2-dimethylpropanoic acid being more preferred, and 2,2-dimethylpropanoic acid being even more preferred. In this invention, the ammonium carboxylate salt may be used alone or in combination of two or more types.

[0032] In ammonium carboxylate salts, the ammonium ion is preferably a quaternary ammonium ion, more preferably a tetraalkylammonium ion or a hydroxyalkyltrialkylammonium ion, and even more preferably a tetraalkylammonium ion.

[0033] Each alkyl group in the tetraalkylammonium ion is, for example, an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms, and more preferably a methyl group. Specific examples of tetraalkylammonium ions include tetramethylammonium ions and triethylmethylammonium ions.

[0034] Each alkyl group in the hydroxyalkyltrialkylammonium ion is, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, an ethyl group, or a butyl group. A hydroxyalkyl group is a group in which one of the hydrogen atoms in the alkyl group is substituted with a hydroxyl group, for example, having 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms, and more preferably 3 or 4 carbon atoms. Examples of hydroxyalkyl groups include hydroxyethyl group, hydroxypropyl group, and hydroxybutyl group. Specific examples of hydroxyalkyltrialkylammonium ions include, for example, hydroxybutyltrimethylammonium ions, hydroxypropyltrimethylammonium ions, and hydroxyethyltrimethylammonium ions.

[0035] 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, and even more preferably tetramethylammonium ion.

[0036] Furthermore, suitable specific examples of ammonium carboxylate salts include tetramethylammonium 2,2-dimethylpropanoate, triethylmethylammonium 2-ethylhexanoate, and hydroxybutyltrimethylammonium 2-ethylhexanoate. Among these, tetramethylammonium 2,2-dimethylpropanoate is preferred from the viewpoint of facilitating the formation of isocyanurate bonds by the trimer of the polyisocyanate. In this invention, the ammonium carboxylate salt may be used alone or in combination of two or more types.

[0037] 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. If the amount of ammonium carboxylate salt is above 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 salt is below the upper limit, the reaction becomes easier to control.

[0038] Transition metal salts The polyol-containing composition of the present invention contains a transition metal salt as a resinification catalyst. When a polyol-containing composition contains a transition metal salt as a resinification catalyst, it suppresses decomposition by the blowing agent, enhances stability, and facilitates the reaction between the polyol and the polyisocyanate.

[0039] Examples of transition metal salts used in the present invention include metal salts made of bismuth, tin, zinc, copper, iron, and lead, among which metal salts made of bismuth or tin are preferred, and metal salts made of bismuth are more preferred.

[0040] The transition metal salt is preferably an organic acid metal salt, and more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. Having 5 or more carbon atoms in the carboxylic acid provides good stability of the polyol-containing composition with respect to blowing agents, particularly hydrofluoroolefins. Furthermore, from the viewpoint of catalytic activity, the number of carbon atoms in the carboxylic acid is preferably 18 or less, and more preferably 12 or less. The carboxylic acid is preferably an aliphatic carboxylic acid, and more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or have a branched structure, but it is preferable to have a branched structure. Specific examples of carboxylic acids include octyl acid (2-ethylhexanoic acid), lauric acid, versatic acid, pentanoic acid, and acetic acid, with octyl acid being preferred among these. In other words, the transition metal salt is preferably a metal salt of 2-ethylhexanoic acid. Preferred metal salts of carboxylic acids include bismuth salts and tin salts of carboxylic acids, with bismuth salts of octic acid being particularly preferred. The metal salt of the carboxylic acid may also be an alkyl metal carboxylate. For example, the tin salt of the carboxylic acid may be a dialkyltin carboxylate, and preferably a dioctyltin carboxylate. Specific examples of metal salts of carboxylic acids include bismastrioctate, dioctyl tin versatate, dibutyl tin dilaurate, dioctyl tin dilaurate, tin dioctylate, and lead dioctylate, with bismastrioctate and dioctyl tin versatate being preferred, and bismastrioctate being more preferred.

[0041] 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 still more preferably 5 to 12 parts by mass, per 100 parts by mass of polyol. If the amount of transition metal salt is above the lower limit, the curing reaction speed of the foamed polyurethane composition can be improved. On the other hand, if the amount of transition metal salt is below the upper limit, the reaction becomes easier to control.

[0042] Heterocyclic compounds containing a nitrogen atom The polyol-containing composition of the present invention contains a heterocyclic compound having a nitrogen atom as a resinification catalyst. When a polyol-containing composition contains a heterocyclic compound having a nitrogen atom as a resinification catalyst, it becomes less susceptible to the influence of hydrofluoroolefins, increasing stability and facilitating the reaction between the polyol and polyisocyanate.

[0043] There are no particular restrictions on the heterocyclic compounds containing nitrogen atoms used in the present invention, but compounds containing nitrogen atoms in the heterocycle are preferred. For example, heterocyclic compounds with 4 to 8 membered rings containing nitrogen atoms are more preferred, and more specifically, examples include imidazole derivatives, pyridine derivatives, piperazine derivatives, etc. Among these, imidazole derivatives are preferred. The imidazole derivative is an imidazole in which the 1st and 2nd positions are independently substituted with alkyl groups having 8 or fewer carbon atoms, where the alkyl groups preferably have 6 or fewer carbon atoms, more preferably 4 or fewer carbon atoms. Furthermore, the alkyl groups may have 1 or more carbon atoms. A suitable specific example of an imidazole derivative is represented by the following general formula (3).

[0044] [ka] (In general formula (3), R 7 and R 8 Each of these independently represents an alkyl group having 1 to 8 carbon atoms.

[0045] In the above general formula (3), R 7 and R8 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, with alkyl groups having 1 to 6 carbon atoms being preferred, and alkyl groups having 1 to 4 carbon atoms being more preferred. 7 and R 8 If the number of carbon atoms in the alkyl group is greater than or equal to the lower limit, the steric hindrance increases, making it less susceptible to the effects of blowing agents such as hydrofluoroolefins, which is preferable. On the other hand, R 4 and R 5 If the number of carbon atoms in the alkyl group is below the aforementioned upper limit, the steric hindrance does not become excessively large, allowing the reaction between the polyol and the polyisocyanate to proceed rapidly. The alkyl groups may be linear or branched. Examples of imidazole derivatives 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 viewpoint of improving the catalytic activity in the presence of hydrofluoroolefins and promoting rapid reaction. Furthermore, 1,2-dimethylimidazole is more preferred from the viewpoint of further enhancing stability.

[0046] 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 above the lower limit, urethane bond formation is more likely to occur, and the reaction proceeds rapidly. On the other hand, if the amount of the heterocyclic compound having a nitrogen atom is below the upper limit, the reaction rate is easier to control, which is preferable.

[0047] <Foaming agent> The polyol-containing composition of the present invention contains a blowing agent. Preferably, the blowing agent contains a hydrofluoroolefin. In the present invention, even when a hydrofluoroolefin is used as the blowing agent, the stability of the blowing agent is high and the catalytic activity does not easily decrease. Examples of hydrofluoroolefins include fluoroalkenes having approximately 3 to 6 carbon atoms. The hydrofluoroolefin may also be a hydrochlorofluoroolefin having a chlorine atom, and therefore, it may also be a chlorofluoroalkene having approximately 3 to 6 carbon atoms. More specifically, examples include trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorotrifluoropropene such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetrafluoropropene. More specifically, 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-hexafluorobuto-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-hexafluorobuto-2-ene. Among these, HFO-1233zd is preferred. These hydrofluoroolefins may be used individually or in combination of two or more types.

[0048] The amount of hydrofluoroolefin added 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 added 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 hydrofluoroolefin added is below the upper limit, excessive foaming can be suppressed.

[0049] The polyol-containing composition of the present invention may contain blowing agents other than hydrofluoroolefins. Examples of blowing agents other than hydrofluoroolefins include water, low-boiling hydrocarbons such as 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 ease of handling, and water is preferred from the viewpoint of adjusting the isocyanate index and ease of handling.

[0050] The amount of foaming 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 foaming 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 foaming agent is below the upper limit, excessive foaming can be suppressed.

[0051] <Filler> The polyol-containing composition of the present invention preferably contains a filler. The filler is a solid component in the polyol-containing composition and is generally present in granular or powdery form. The filler can be any component that is solid at room temperature (23°C) and atmospheric pressure (1 atm) and does not dissolve in the polyol-containing composition. As a filler, it is preferable to use a solid flame retardant. Preferred solid flame retardants include red phosphorus-based flame retardants, boron-containing flame retardants, bromine-containing flame retardants, phosphate-containing flame retardants, chlorine-containing flame retardants, antimony-containing flame retardants, metal hydroxides, and needle-shaped fillers.

[0052] <Red phosphorus-based flame retardant> Red phosphorus-based flame retardants may consist of pure red phosphorus, but they may also be red phosphorus coated with a resin, metal hydroxide, metal oxide, etc., or red phosphorus mixed with a resin, metal hydroxide, metal oxide, etc. The resin used to coat or mix with red phosphorus is not particularly limited, but examples include thermosetting resins such as phenolic resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. From the viewpoint of flame retardancy, metal hydroxides are preferred as the compound used for coating or mixing. The metal hydroxides described later may be appropriately selected and used.

[0053] <Boron-containing flame retardant> Examples of boron-containing flame retardants used in the present invention include borax, boron oxide, boric acid, and borates. Examples of boron oxides include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide. Examples of borates include alkali metals, alkaline earth metals, elements from groups 4, 12, and 13 of the periodic table, and ammonium borates. Specifically, examples include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate; alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate; zirconium borate, zinc borate, aluminum borate, and ammonium borate. Boron-containing flame retardants may be used alone or in combination of two or more types. The boron-containing flame retardant used in the present invention is preferably a borate, and more preferably zinc borate.

[0054] <Bromine-containing flame retardant> Bromine-containing flame retardants are not particularly limited as long as they contain bromine in their molecular structure and are solid at room temperature and pressure, but examples include aromatic compounds containing brominated aromatic rings. Examples of brominated aromatic ring-containing aromatic compounds include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0055] Furthermore, the brominated aromatic ring-containing aromatic compound may also be a brominated polymer. Specifically, examples include polycarbonate oligomers produced using brominated bisphenol A as a raw material, brominated polycarbonates such as copolymers of this polycarbonate oligomer and bisphenol A, and diexo compounds produced by the reaction of brominated bisphenol A and epichlorohydrin. In addition, examples include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A and cyanuryl chloride condensates, brominated polystyrene such as brominated (polystyrene), poly(brominated styrene), and crosslinked brominated polystyrene, and crosslinked or non-crosslinked brominated poly(methylstyrene). Furthermore, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may also be used. These bromine-containing flame retardants may be used individually or in combination of two or more. Among the above, brominated aromatic ring-containing aromatic compounds are preferred, and among these, monomer-based organic bromine compounds such as ethylenebis(pentabromophenyl) are preferred.

[0056] <Phosphate-containing flame retardant> Examples of phosphate-containing flame retardants include phosphates comprising salts of various phosphoric acids with at least one metal or compound selected from metals of groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Phosphates are not particularly limited, but examples include monophosphates, pyrophosphates, and polyphosphates. Examples of metals in groups IA through IVB of the periodic table include lithium, sodium, calcium, barium, iron(II), iron(III), and aluminum. Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and piperazine. Examples of aromatic amines include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, and 3-(trifluoromethyl)aniline. Examples of heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, and melamine.

[0057] Specific examples of phosphate-containing flame retardants include monophosphates such as trialuminum phosphate, pyrophosphates, and polyphosphates. Here, the polyphosphate is not particularly limited, but examples include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, and aluminum polyphosphate. One or more of the above-mentioned phosphate-containing flame retardants may be used.

[0058] <Chlorine-containing flame retardant> Examples of 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 "Dechloran Plus."

[0059] <Antimony-containing flame retardant> Examples of antimony-containing flame retardants include antimony oxide, antimonate salts, and pyroantimonate salts. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonate salts include sodium antimonate and potassium antimonate. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate. Antimony-containing flame retardants may be used alone or in combination of two or more types. The preferred antimony-containing flame retardant used in this invention is antimony trioxide.

[0060] <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, and tin hydroxide. A single metal hydroxide may be used, or two or more may be used in combination.

[0061] <Needle-shaped filler> Examples of needle-shaped fillers 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-shaped fillers can be used individually or in combination of two or more types.

[0062] The aspect ratio (length / diameter) of the needle-shaped filler used in the present invention is preferably in the range of 5 to 50, and more preferably in the range of 10 to 40. This aspect ratio can be determined by observing 50 needle-shaped fillers with a scanning electron microscope and measuring their length and width.

[0063] Furthermore, other inorganic fillers besides the flame retardants mentioned above may be used as fillers. Suitable inorganic fillers 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, fly ash, etc. Inorganic fillers may be used individually or in combination of two or more types.

[0064] 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. A filler content of 20 parts by mass or more makes it easier to improve the mechanical strength and flame retardancy of the resulting polyurethane foam. Furthermore, a filler content of 120 parts by mass or less makes it less likely for foaming to be inhibited by the filler.

[0065] (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 becomes liquid at room temperature (23°C) and normal pressure (1 atm). A specific example of a liquid flame retardant is a phosphate ester. 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 prone to precipitation during storage, and the flame retardancy of the polyurethane composition of the present invention can be further 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.

[0066] As the phosphate ester, it is preferable to use monophosphate esters, condensed phosphate esters, etc. 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; trialkoxy phosphates such as tributoxyethyl phosphate; aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, cresyldiphenyl phosphate, and diphenyl(2-ethylhexyl) phosphate; and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

[0067] Examples of condensed phosphate esters include aromatic condensed phosphate esters such as trialkyl polyphosphates, resorcinol polyphenyl phosphates, bisphenol A polycresyl phosphates, and bisphenol A polyphenyl phosphates. Examples of commercially available condensed phosphate esters include "CR-733S," "CR-741," and "CR747" from Daihachi Chemical Industry Co., Ltd., and "ADEKA Stab PFR" and "FP-600" from ADEKA Corporation.

[0068] The liquid flame retardant may be used alone from among those listed above, or two or more may be used in combination. 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.

[0069] 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. An amount of 20 parts by mass or more makes it easier to improve the flame retardancy of the resulting polyurethane foam. Furthermore, an amount of 60 parts by mass or less makes it less likely for foaming to be inhibited by the phosphate ester.

[0070] <Foam stabilizer> The polyol-containing composition of the present invention may optionally contain a foam stabilizer for the purpose of facilitating foaming of a mixture of the polyol-containing composition and isocyanate. Examples of foam stabilizers include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and surfactants such as silicone foam stabilizers such as octamethylcyclotetrasiloxane and organopolysiloxane. These foam stabilizers may be used individually or in combination of two or more.

[0071] The foam stabilizer content 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 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 below the upper limit, the balance between manufacturing cost and the obtained effect is optimized.

[0072] <Other ingredients> The polyol-containing composition may, as necessary and without impairing the objectives of the present invention, contain one or more additives selected from antioxidants such as phenolic, amine, and sulfur-based agents, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, and pigments.

[0073] <Method for producing polyol-containing compositions> There are no particular limitations on the method for producing the polyol-containing composition of the present invention. For example, it can be produced by stirring each component at approximately 20 to 40°C using a homodisper or the like for approximately 30 seconds to 20 minutes.

[0074] [Foamed polyurethane composition and polyurethane foam] The foamable polyurethane composition of the present invention comprises 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 foamed polyurethane composition used in the present invention is generally a two-component type. The polyol-containing composition of the present invention and a polyisocyanate, stored separately, are mixed and reacted and foamed to obtain a polyurethane foam. The polyisocyanate may also contain other components, such as the additives mentioned above, as needed.

[0075] <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.

[0076] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0077] Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0078] Among these, aromatic polyisocyanates are preferred from the viewpoint of ease of use and availability, and diphenylmethane diisocyanate is more preferred. Polyisocyanates may be used individually or in mixtures of two or more types. Furthermore, before mixing the polyisocyanate with the polyol-containing composition, known additives that are incorporated into polyisocyanates may be added as appropriate.

[0079] Furthermore, it is preferable that the volume of the polyol-containing composition and the polyisocyanate mixed with the polyol-containing composition are substantially the same. 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.

[0080] <Isocyanate Index> There are no particular limitations on the isocyanate index in the foamed polyurethane composition of the present invention, but a value of 250 or higher is preferred. When the isocyanate index is above the lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, making it easier to form isocyanurate bonds by the trimer of polyisocyanate, resulting in improved flame retardancy of the polyurethane foam. It also becomes possible to impart non-flammability. Furthermore, when the index is above the lower limit, combined with the use of at least the four catalysts described above, it becomes easier to produce a polyurethane foam with sufficient isocyanurate bonds, that is, a polyurethane foam that combines flame retardancy and heat insulation at a high level. From these viewpoints, an isocyanate index of 270 or higher is more preferred, and 300 or higher is even more preferred. Furthermore, the isocyanate index is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less. When the isocyanate index is below the above upper limit, a good balance is achieved between the flame retardancy of the resulting polyurethane foam and the manufacturing cost.

[0081] The isocyanate index can be calculated using 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 weight of polyisocyanate = Amount of polyisocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (moles) × 100 • Equivalent weight of polyol = OHV × Amount of polyol used (g) ÷ Molecular weight of KOH (millimoles) OHV is the hydroxyl value (mgKOH / g) of a polyol. • Equivalent amount of water = Amount of water used (g) / Molecular weight of water (moles) × Number of OH groups in water In the above formulas, the molecular weight of NCO is 42 moles, the molecular weight of KOH is 56100 millimoles, the molecular weight of water is 18 moles, and the number of OH groups in water is 2.

[0082] <Method for manufacturing polyurethane foam> There are no particular restrictions on the method for manufacturing polyurethane foam, but it is preferable to foam and cure a foamable polyurethane composition obtained by mixing polyisocyanate and a polyol-containing composition. Specifically, it is preferable to crush-mix the polyisocyanate and the polyol-containing composition and apply it by spraying using a spray gun or the like. In the present invention, polyurethane foam may be obtained by mixing a polyisocyanate and a polyol-containing composition, then injecting the mixture into a container such as a mold or frame material, and allowing it to foam and harden.

[0083] <Applications of polyurethane foam> The polyurethane foam of the present invention has no particular limitations on its applications, but because it has excellent flame retardancy and heat insulation properties, it can be suitably used in buildings such as walls, ceilings, roofs, and floors. It can also be suitably used as a filling material for any openings in a building, including joints and holes between structural materials. [Examples]

[0084] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to these examples.

[0085] (1) Polyol-containing composition [Polyol] • p-phthalate polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g)

[0086] 〔catalyst〕 • Trimerization catalyst, tetramethylammonium 2,2-dimethylpropanoate (Air Products, product name: DABCO TMR7), concentration approximately 45% by mass Trimerization catalyst, triethylmethylammonium 2-ethylhexanoate (manufactured by Sunapro Co., Ltd., product name: U-CAT 18X), concentration approximately 100% by mass. Trimerization catalyst, hydroxybutyltrimethylammonium 2-ethylhexanoate (manufactured by Kao Corporation, product name: Kaolizer No. 420), concentration approximately 100% by mass. • Resinized amine catalyst: 1,2-dimethylimidazole (manufactured by Kao Corporation, product name: Kaolizer No. 390), concentration 65-75% by mass • Resinized amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT(registered trademark)-DM70), concentration 65-75% by mass • Resin-based amine catalyst, 1-isobutyl-2-methylimidazole (Air Products, product name: DABCO NC-IM), concentration approximately 100% by mass • Resin-based metal catalyst, bismuth 2-ethylhexanoate (manufactured by Nitto Chemical Co., Ltd., product name: Bi28), concentration 81-90% by mass • Resin-based metal catalyst, dioctyl (2-ethylhexyl) suzubatesate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-830), concentration approximately 99% by mass Trimerized metal catalyst, potassium 2-ethylhexanoate (Air Products, product name: DABCO K-15), concentration 70-80% by mass • Trimerized amine catalyst, tetramethylammonium acetate (manufactured by Tosoh Corporation, product name: TOYOCAT(registered trademark)-TRX), concentration 60-70% 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

[0087] [Foaming agent] • Hydrofluoroolefin (manufactured by Honeywell Japan Co., Ltd., product name: Soltis LBA, trans-1-chloro-3,3,3-trifluoropropene) ·water

[0088] [Liquid flame retardant] • Tris(β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)

[0089] [Filler] • Wollastonite (SiO2·CaO) (manufactured by Kinsei Matec Co., Ltd., product name: SH-1250)

[0090] (2) Polyisocyanates • 4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Chemical Japan Co., Ltd., product name: PM200)

[0091] <Examples 1-12, Comparative Examples 1-6> A polyol-containing composition was prepared according to the formulation shown in Table 1.

[0092] [Evaluation of foaming properties] The polyol-containing composition prepared by the above method and polyisocyanate were mixed according to the formulations shown in Table 1. Under the following conditions, the mixture was sprayed onto gypsum board using a sprayer so that the urethane foam thickness was 1 mm or less, and the surface hardening time (tack-free time) after spraying was measured. The surface hardening time was defined as t1, and a value of less than 27 seconds was marked "◎", a value of 27 seconds or more and 30 seconds or less was marked "〇", and a value of more than 30 seconds was marked "×". The results are shown in Table 1. <Condition> • Spraying machine: Graco H-25 spraying device • Settings (heater and pressure settings) Isocyanate heater: 38℃ Premix heater: 38℃ Hose heater: 38℃ Pressure: Adjust as needed to ensure the mist forms a wide, circular area. • Base material: Gypsum board (12.5mm thick) ·Substrate temperature: 0℃±1℃ ·Environmental temperature: 0℃±1℃

[0093] [Evaluation of Stability] The polyol-containing composition described above was placed in a pressure-resistant container and stored in a constant-temperature bath at 45°C for two days. Afterward, spraying was performed in the same manner as described above, and the surface hardening time after spraying was measured. The surface hardening time was defined as t2, and the difference between t2 and t1 was marked as "◎" if it was less than 4 seconds, "〇" if it was between 4 seconds and 6 seconds, and "×" if it exceeded 6 seconds. The results are shown in Table 1.

[0094] [Table 1] The numbers in parentheses in the polyols represent the hydroxyl value (mgKOH / g). The mass parts of each catalyst represent the mass parts of the product.

[0095] As is clear from the results of the above examples, by using potassium carboxylate salts, ammonium carboxylate salts, heterocyclic compounds containing nitrogen atoms, and transition metal salts in combination, the reaction between the blowing agent and the catalyst that causes catalyst deactivation is suppressed, the stability of the polyol-containing composition is enhanced, and both excellent stability and good foaming properties can be achieved. In contrast, polyol-containing compositions that did not contain even one of the four catalysts mentioned above showed impairment in at least one of the following: foaming properties or stability.

Claims

1. A polyol-containing composition for obtaining polyurethane foam by reacting with polyisocyanate, 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 claim 1, wherein the carboxylic acid in the potassium carboxylic acid salt 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 claim 1 or 2, wherein the carboxylic acid in the potassium carboxylic acid salt has 5 or more carbon atoms.

4. The polyol-containing composition according to any one of claims 1 to 3, wherein the carboxylic acid in the ammonium carboxylate salt 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 claims 1 to 4, wherein the carboxylic acid in the ammonium carboxylate salt has 5 or more carbon atoms.

6. The polyol-containing composition according to any one of claims 1 to 5, wherein the ammonium ion in the ammonium carboxylate salt is a quaternary ammonium ion.

7. The polyol-containing composition according to any one of claims 1 to 6, wherein the ammonium ion in the ammonium carboxylate salt 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 claims 1 to 7, wherein the ammonium carboxylate salt is tetramethylammonium 2,2-dimethylpropanoate.

9. The polyol-containing composition according to any one of claims 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 claims 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 claims 1 to 10, wherein the transition metal in the transition metal salt is bismuth.

12. The polyol-containing composition according to any one of claims 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 claims 1 to 12, wherein the heterocyclic compound is an imidazole derivative.

14. The polyol-containing composition according to any one of claims 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 fewer carbon atoms.

15. The polyol-containing composition according to any one of claims 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 claims 1 to 15, wherein the imidazole derivative is 1,2-dimethylimidazole.

17. The polyol-containing composition according to any one of claims 1 to 16, wherein the foaming agent contains a hydrofluoroolefin.

18. A foamed polyurethane composition comprising a polyol-containing composition according to any one of claims 1 to 17 and a polyisocyanate.

19. The foamable polyurethane composition according to claim 18, wherein the isocyanate index is 250 or higher.

20. A polyurethane foam obtained by reacting and foaming the foamable polyurethane composition according to claim 18 or 19.

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