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

Abstract

To provide a polyol-containing composition, a foamable polyurethane composition and a polyurethane foam, achieving both of the stability of a foaming agent to a catalyst and excellent foaming properties.SOLUTION: A polyol-containing composition for obtaining a foamable polyurethane composition by reacting with polyisocyanate, contains polyol, a foaming agent and a catalyst, the catalyst containing a carboxylic acid ammonium salt that is a quaternary ammonium salt of a carboxylic acid having 5 or more carbon atoms, a heterocyclic compound having a nitrogen atom, and a transition metal salt.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Due to its excellent heat insulating properties and adhesive properties, polyurethane foam is used as a heat insulating material for buildings such as apartment complexes, detached houses, various school facilities, commercial buildings, etc. Polyurethane foam can be obtained by mixing a polyol-containing composition and a polyisocyanate and foaming the mixture.

[0003] The polyol-containing composition contains catalysts such as a resinification catalyst and a trimerization catalyst. The resinification catalyst promotes the reaction between polyols and isocyanates, and the trimerization catalyst promotes the reaction of isocyanates with each other to produce isocyanurates, thereby increasing the proportion of isocyanurates. In polyol-containing compositions containing a catalyst, the catalyst and blowing agent may react during storage, causing a decrease in catalytic performance and a decrease in foaming ability. Hydrofluorocarbons (HFCs) have traditionally been widely used as blowing agents, but there has been a shift to hydrofluoroolefins (HFOs), which have a low global warming potential. Among blowing agents, hydrofluoroolefins tend to react particularly easily with catalysts, making them more susceptible to a decrease in catalytic performance and a decrease in foaming ability. To solve these 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. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2018-30975 A, [Patent Document 2] International Publication No. 2018 / 105730 Summary of the Invention [Problem to be solved by the invention]

[0005] However, with conventional polyol-containing compositions, it is difficult to achieve both stability against the catalyst of the blowing agent and improved foaming properties.

[0006] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a polyol-containing composition, a foamable polyurethane composition, and a polyurethane foam that have both stability to the catalyst of the blowing agent and good foamability. [Means for solving the problem]

[0007] As a result of extensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by incorporating, as a catalyst, an ammonium carboxylate salt, which is a quaternary ammonium salt of a carboxylic acid having 5 or more carbon atoms, a heterocyclic compound having a nitrogen atom, and a transition metal salt, and have thus completed the present invention.

[0008] The present invention is summarized as follows [1] to

[17] . [1] A polyol-containing composition for producing a polyurethane foam by reacting with a polyisocyanate, comprising a polyol, a blowing agent, and a catalyst; The catalyst is a polyol-containing composition containing an ammonium carboxylate, which is a quaternary ammonium salt of a carboxylic acid having 5 or more carbon atoms, 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 ammonium carboxylate is at least one selected from the group consisting of 2-ethylhexanoic acid and 2,2-dimethylpropanoic acid. [3] The polyol-containing composition according to [1] or [2], wherein the quaternary ammonium ion in the ammonium carboxylate is at least one selected from the group consisting of triethylmethylammonium ion and tetramethylammonium ion. [4] The polyol-containing composition according to any one of [1] to [3], wherein the ammonium carboxylate is 2,2-dimethylpropanoic acid tetramethylammonium salt. [5] The polyol-containing composition according to any one of [1] to [4], wherein the heterocyclic compound is an imidazole derivative. [6] The polyol-containing composition according to any one of [1] to [5], wherein the imidazole derivative is an imidazole substituted at the 1st and 2nd positions with an alkyl group having 4 or less carbon atoms. [7] The polyol-containing composition according to any one of [1] to [6], wherein the imidazole derivative is at least one selected from the group consisting of 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole. [8] The polyol-containing composition according to any one of [1] to [7], wherein the imidazole derivative is 1,2-dimethylimidazole. [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 octylic acid.

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

[12] , wherein the blowing agent is a hydrofluoroolefin.

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

[13] , which contains a foam stabilizer.

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

[14] and a polyisocyanate.

[16] The foamable polyurethane composition according to

[15] , having an isocyanate index of 250 or more.

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

[15] or

[16] . [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a polyol-containing composition, a foamable polyurethane composition, and a polyurethane foam that have both stability to the catalyst of the blowing agent and good foamability. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. [Polyol-containing composition] The polyol-containing composition of the present invention is a polyol-containing composition for producing a polyurethane foam by reacting with a polyisocyanate, and contains a polyol, a blowing agent, and a catalyst, and the catalyst contains an ammonium carboxylate salt which is a quaternary ammonium salt of a carboxylic acid having 5 or more carbon atoms, a heterocyclic compound having a nitrogen atom, and a transition metal salt. By containing an ammonium carboxylate salt which is a quaternary ammonium salt of a carboxylic acid having 5 or more carbon atoms, a heterocyclic compound having a nitrogen atom, and a transition metal salt as catalysts, the polyol-containing composition of the present invention can achieve both stability of the blowing agent against the catalyst and good foamability.

[0011] <Polyol> The polyol-containing composition of the present invention contains a polyol as a raw material for polyurethane foam. Examples of polyols that can be used in the present invention include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

[0012] Examples of polylactone polyols include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of polycarbonate polyols include polyols obtained by dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like.

[0013] 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.

[0014] Examples of polyester polyols include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, and condensates of hydroxycarboxylic acids and the above-mentioned polyhydric alcohols. Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), and succinic acid. Examples of polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

[0015] Examples of polymer polyols include polymers obtained by graft polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, or methacrylate with an aromatic polyol, an alicyclic polyol, an aliphatic polyol, or a polyester polyol; polybutadiene polyol; and modified polyols of polyhydric alcohols or hydrogenated products thereof.

[0016] 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 (novolak).

[0017] Although the method for modifying the polyhydric alcohol is not particularly limited, a method of adding alkylene oxide (hereinafter also referred to as "AO") is preferably used. Examples of 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, PO, EO, and 1,2-butylene oxide are preferred from the viewpoints of properties and reactivity, 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, random addition, or a combination of these.

[0018] Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one alkylene oxide, such as ethylene oxide, propylene oxide, or tetrahydrofuran, in the presence of at least one low-molecular-weight active hydrogen compound having two or more active hydrogens. Examples of low-molecular-weight active hydrogen compounds having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol, triols such as glycerin and trimethylolpropane, and amines such as ethylenediamine and butylenediamine.

[0019] Polyols used in the present invention are preferably polyester polyols and polyether polyols. Polyols having two hydroxyl groups are also preferred. Among these, aromatic polyester polyols, which are polyester polyols having an aromatic ring, are preferred from the viewpoint of enhancing flame retardancy. More preferred aromatic polyester polyols are those obtained by dehydration condensation of polybasic acids having an aromatic ring, such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), with dihydric alcohols, such as bisphenol A, ethylene glycol, and 1,2-propylene glycol.

[0020] The hydroxyl value of the polyol is preferably 20 to 300 mgKOH / g, more preferably 30 to 250 mgKOH / g, and even more preferably 50 to 220 mgKOH / g. When the hydroxyl value of the polyol is equal to or less than the upper limit, the viscosity of the polyol-containing composition tends to decrease, which is preferable from the viewpoint of handleability, etc. On the other hand, when the hydroxyl value of the polyol is equal to or more than the lower limit, the crosslink density of the polyurethane foam increases, thereby increasing its strength. The hydroxyl value of the polyol can be measured in accordance with JIS K 1557-1:2007.

[0021] The polyol content in the polyol-containing composition of the present invention is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 25 to 60% by mass. A polyol content of at least the lower limit is preferred because it facilitates the reaction between the polyol and the polyisocyanate. On the other hand, a polyol content of at most the upper limit is preferred from the viewpoint of ease of handling because the viscosity of the polyol-containing composition does not become too high.

[0022] <Catalyst> The polyol-containing composition of the present invention uses three catalysts in combination: an ammonium carboxylate salt, which is a quaternary ammonium salt of a carboxylic acid having 5 or more carbon atoms, a heterocyclic compound having a nitrogen atom, and a transition metal salt. By using these three catalysts in combination, the polyol-containing composition of the present invention can suppress the decomposition of the blowing agent by the catalyst and increase the activity of the catalyst, thereby improving the foaming property.

[0023] Ammonium carboxylate (trimerization catalyst) The polyol-containing composition of the present invention contains an ammonium carboxylate salt, which is a trimerization catalyst and facilitates the formation of an isocyanurate bond by a trimer of polyisocyanate. In the present invention, the ammonium carboxylate is a quaternary ammonium salt of a carboxylic acid having 5 or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The number of carbon atoms in the carboxylic acid is, for example, 20 or less, preferably 12 or less, more preferably 8 or less. The carboxylic acid may be linear or may have a branched structure, but preferably has a branched structure. If the carboxylic acid has a branched structure, steric hindrance tends to reduce the reactivity with a blowing agent such as hydrofluoroolefin.

[0024] The quaternary ammonium ion used in the ammonium carboxylate is preferably a tetraalkylammonium ion, wherein 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 suitable quaternary ammonium ions include tetramethylammonium ion, tetraethylammonium ion, and triethylmethylammonium ion, etc. Among these, trimethylethylammonium ion and tetramethylammonium ion are more preferred, and tetramethylammonium ion is even more preferred.

[0025] Among these, the ammonium carboxylate salt is preferably an ammonium carboxylate salt represented by the following general formula (1): The ammonium carboxylate salt represented by the following general formula (1) has an appropriate degree of steric hindrance, and therefore can suppress the reaction that decomposes the blowing agent and can also prevent a decrease in catalytic activity.

[0026] [ka] (In general formula (1), R 1 and R 2 each independently represents an alkyl group, and R 3 represents a hydrogen atom or an alkyl group. + represents a quaternary ammonium ion.)

[0027] R in general formula (1) 1 and R 2 are each independently 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. Also, R 3 represents a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 6 carbon atoms. 3is 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 If the number of carbon atoms in R is equal to or greater than the lower limit, the steric hindrance becomes large, and the reaction of decomposing the hydrofluoroolefin can be suppressed. 1 , R 2 and R 3 When the number of carbon atoms is equal to or less than the upper limit, the steric hindrance is not too large, and the reactivity can be prevented from slowing down. M + represents a quaternary ammonium ion, and the details of the quaternary ammonium ion are as described above.

[0028] Specific examples of the carboxylic acid in the ammonium carboxylate include R 1 , R 2 and R 3 2,2-dimethylpropanoic acid, where R 1 is an ethyl group, R 2 is a butyl group, R 3 is a hydrogen atom. Among these, 2,2-dimethylpropanoic acid is particularly preferred. Specific examples of suitable ammonium carboxylates include tetramethylammonium 2,2-dimethylpropanoate and triethylmethylammonium 2-ethylhexanoate. Tetramethylammonium 2,2-dimethylpropanoate is more preferred, as it facilitates the formation of an isocyanurate bond with a trimer of polyisocyanate. In the present invention, the ammonium carboxylate may be used alone or in combination of two or more kinds.

[0029] The amount of ammonium carboxylate salt in the polyol-containing composition is preferably 1 to 28 parts by mass, more preferably 2 to 26 parts by mass, even more preferably 3 to 24 parts by mass, even more preferably 4 to 22 parts by mass, even more preferably 5 to 20 parts by mass, and particularly preferably 6 to 15 parts by mass, per 100 parts by mass of polyol. When the amount of ammonium carboxylate salt is equal to or greater than the lower limit, trimerization of polyisocyanate is likely to occur, improving the flame retardancy of the resulting polyurethane foam. On the other hand, when the amount of ammonium carboxylate salt is equal to or less than the upper limit, the reaction can be more easily controlled.

[0030] <Heterocyclic compounds containing nitrogen atoms (resinification catalysts)> The polyol-containing composition of the present invention contains a heterocyclic compound having a nitrogen atom as a resinification catalyst. When the polyol-containing composition contains a heterocyclic compound having a nitrogen atom as a resinification catalyst, the polyol-containing composition is less susceptible to the influence of hydrofluoroolefin, and the stability is improved, and the polyol and polyisocyanate are easily reacted.

[0031] Although there is no particular limitation on the heterocyclic compound having a nitrogen atom used in the present invention, a compound containing a nitrogen atom in the heterocycle is preferred, for example, a 4- to 8-membered heterocyclic compound containing a nitrogen atom in the heterocycle is more preferred, more specifically, imidazole derivatives, pyridine derivatives, piperazine derivatives, etc. Among these, imidazole derivatives are preferred. The imidazole derivative is an imidazole substituted at the 1st and 2nd positions with an alkyl group having 8 or less carbon atoms, and the alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms. A preferred specific example of the imidazole derivative is represented by the following general formula (2).

[0032] [ka] (In general formula (2), R 4 and R 5 each independently represents an alkyl group having 1 to 8 carbon atoms.

[0033] R in the general formula (2) 4 and R 5 R each independently represents 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. 4 and R 5 If the number of carbon atoms in the alkyl group of R is equal to or greater than the lower limit, steric hindrance increases, making the copolymer less susceptible to the influence of blowing agents such as hydrofluoroolefins, which is preferable. 4 and R 5 When the number of carbon atoms in the alkyl group is equal to or less than the upper limit, the steric hindrance is not excessively large, and the reaction between the polyol and the polyisocyanate can proceed quickly. The alkyl group may be linear or may have a branched structure. Examples of the imidazole derivative represented by general formula (2) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Among them, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferred from the viewpoint of improving the activity of the catalyst in the presence of hydrofluoroolefin and promoting the reaction rapidly. Furthermore, 1,2-dimethylimidazole is even more preferred from the viewpoint of further enhancing stability.

[0034] The amount of the heterocyclic compound having a nitrogen atom in the polyol-containing composition is preferably 0.7 to 21 parts by mass, more preferably 0.8 to 19 parts by mass, even more preferably 0.9 to 17 parts by mass, and even more preferably 1.0 to 15 parts by mass, per 100 parts by mass of the polyol. When the amount of the heterocyclic compound having a nitrogen atom is equal to or greater than the lower limit, urethane bond formation occurs more easily, and the reaction proceeds rapidly. On the other hand, when the amount of the heterocyclic compound having a nitrogen atom is equal to or less than the upper limit, the reaction rate can be easily controlled, which is preferable.

[0035] <<Transition metal salts (resinification catalysts)>> The polyol-containing composition of the present invention contains a transition metal salt as a resinification catalyst. When the polyol-containing composition contains a transition metal salt as a resinification catalyst, the polyol-containing composition is more likely to react with the polyisocyanate while suppressing decomposition by a blowing agent and increasing stability.

[0036] The transition metal salt used in the present invention is not particularly limited, and examples thereof include metal salts of bismuth, tin, zinc, copper, iron, lead, etc., and among these, metal salts of bismuth or tin are preferred, and metal salts of bismuth are more preferred.

[0037] The transition metal salt is preferably an organic acid metal salt, more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. When the carboxylic acid has 5 or more carbon atoms, the stability with a blowing agent, particularly a hydrofluoroolefin, is improved. Furthermore, from the viewpoint of catalytic activity, the number of carbon atoms of the carboxylic acid is preferably 18 or less, more preferably 12 or less. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or may have a branched structure, but preferably has a branched structure. Specific examples of carboxylic acids include octylic acid, lauric acid, versatic acid, pentanoic acid, and acetic acid, among which octylic acid is preferred. That is, the transition metal salt is preferably a metal salt of octylic acid. These carboxylic acids may be linear as described above, but may also have a branched structure. An example of an octylic acid having a branched structure is 2-ethylhexanoic acid. As the metal salt of carboxylic acid, bismuth salt of carboxylic acid and tin salt of carboxylic acid are preferred, and among them, bismuth salt of octylic acid is preferred. Furthermore, the metal salt of carboxylic acid may be a carboxylate of an alkyl metal. For example, the tin carboxylate may be a dialkyltin carboxylate, and preferably a dioctyltin carboxylate. Specific examples of metal salts of carboxylic acids include bismuth trioctate, dioctyltin versatate, dibutyltin dilaurate, dioctyltin dilaurate, tin dioctylate, and lead dioctylate, with bismuth trioctate and dioctyltin versatate being preferred, and bismuth trioctate being more preferred.

[0038] The amount of transition metal salt in the polyol-containing composition is preferably 0.1 to 8 parts by mass, more preferably 0.2 to 7 parts by mass, even more preferably 0.3 to 6 parts by mass, and even more preferably 0.4 to 5 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 more easily controlled.

[0039] <Foaming agent> The polyol-containing composition of the present invention preferably contains a hydrofluoroolefin as a blowing agent. 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 is not likely to decrease. Examples of hydrofluoroolefins include fluoroalkenes having about 3 to 6 carbon atoms. The hydrofluoroolefin may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having about 3 to 6 carbon atoms. More specific examples include trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorotrifluoropropenes such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetrafluoropropene. More specific examples include 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3,3,3-hexafluorobut-2-ene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yez), 1-chloro-3,3,3-trifluoropropene (HFO-1233zd), and 1,1,1,4,4,4-hexafluorobut-2-ene. Of these, HFO-1233zd is preferred. These hydrofluoroolefins may be used alone or in combination of two or more.

[0040] The amount of hydrofluoroolefin blended is preferably 10 to 60 parts by mass, more preferably 20 to 55 parts by mass, even more preferably 25 to 50 parts by mass, and even more preferably 30 to 45 parts by mass, per 100 parts by mass of polyol. When the amount of hydrofluoroolefin blended is equal to or greater than the above 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 above upper limit, excessive foaming can be suppressed.

[0041] The polyol-containing composition of the present invention may contain a blowing agent other than hydrofluoroolefin.Examples of blowing agents other than hydrofluoroolefin include low-boiling hydrocarbons such as water, propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane, chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride, and other 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.

[0042] The amount of the blowing agent other than the hydrofluoroolefin in the polyol-containing composition is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 2 parts 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 suppressed.

[0043] <Foam stabilizer> The polyol-containing composition of the present invention may contain a foam stabilizer for the purpose of facilitating foaming of the mixture of the polyol-containing composition and the isocyanate. Examples of the foam stabilizer include surfactants such as polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and silicone foam stabilizers such as octamethylcyclotetrasiloxane and organopolysiloxanes. These foam stabilizers may be used alone or in combination of two or more.

[0044] The amount of 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 1 to 5 parts by mass, per 100 parts by mass of polyol. When the amount of foam stabilizer is equal to or greater than the above-mentioned 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 foam stabilizer is equal to or less than the above-mentioned upper limit, the balance between production costs and the obtained effects is optimal.

[0045] <Flame retardant> The polyol-containing composition of the present invention may contain a flame retardant. A polyurethane foam produced using the polyol-containing composition of the present invention has excellent flame retardancy because it contains an isocyanurate bond formed by the trimerization of polyisocyanate, and the flame retardancy of the polyurethane foam can be further improved by using a flame retardant. The flame retardant used in the present invention is preferably red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boric acid-containing flame retardant, antimony-containing flame retardant, metal hydroxide, or the like.

[0046] As the red phosphorus, commercially available red phosphorus can be used, but from the viewpoint of safety, such as moisture resistance and prevention of spontaneous combustion during kneading, red phosphorus particles whose surfaces are coated with a resin are preferably used.

[0047] As the phosphate ester, it is preferable to use monophosphate ester, condensed phosphate ester, etc., and examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)phosphate, tris(phenylphenyl)phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl(2-ethylhexyl)phosphate, di(isopropylphenyl)phenyl phosphate, monoisopropyl phosphate, Examples of suitable phosphates include silyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resylcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), phosphaphenanthrene, and tris(β-chloropropyl)phosphate.

[0048] Examples of condensed phosphate esters include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly(di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name PX-200), hydroquinone poly(2,6-xylyl) phosphate, and condensates thereof.

[0049] Examples of phosphate-containing flame retardants include phosphates consisting of salts of various phosphoric acids and at least one metal or compound selected from metals of Groups IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. 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, and piperazine. Examples of aromatic amines include pyridine, triazine, melamine, and ammonium.

[0050] Specific examples of phosphate-containing flame retardants include monophosphates and polyphosphates. The monophosphate salt is not particularly limited, and examples thereof include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; and zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite. The polyphosphate is not particularly limited, but examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate. The phosphate-containing flame retardants may be used singly or in combination.

[0051] The bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure, and examples thereof include aromatic brominated compounds. Specific examples of aromatic brominated compounds include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene-bis(tetrabromophthalimide), and tetrabromobisphenol A; brominated polycarbonate oligomers produced from brominated bisphenol A as a raw material; and copolymers of polycarbonate oligomers and bisphenol A. Examples of the brominated epoxy compounds include carbonates, diepoxy compounds produced by reacting brominated bisphenol A with epichlorohydrin, and monoepoxy compounds obtained by reacting brominated phenols with epichlorohydrin; poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, condensates of cyanuric chloride and brominated phenols; brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, and halogenated bromine compound polymers such as crosslinked or non-crosslinked brominated poly(methylstyrene). The bromine-containing flame retardants may be used singly or in combination.

[0052] The boric acid-containing flame retardant is preferably at least one selected from the group consisting of boron oxide, boric acid, and metal borate salts.

[0053] Examples of antimony-containing flame retardants include antimony oxide, antimonates, and pyroantimonates. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonates include sodium antimonate and potassium antimonate. Examples of pyroantimonate include sodium pyroantimonate and potassium pyroantimonate. The antimony-containing flame retardants may be used singly or in combination of two or more.

[0054] Examples of metal hydroxides include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, zinc hydroxide, titanium hydroxide, copper hydroxide, tin hydroxide, and vanadium hydroxide. The metal hydroxides can be used alone or in combination of two or more.

[0055] When the polyol-containing composition of the present invention contains a flame retardant, the blending amount thereof is preferably 10 to 150 parts by mass, more preferably 20 to 140 parts by mass, even more preferably 30 to 130 parts by mass, and even more preferably 40 to 125 parts by mass, per 100 parts by mass of polyol. When the blending amount of the flame retardant is equal to or greater than the above-mentioned lower limit, sufficient flame retardancy can be imparted to a polyurethane foam produced using the polyol-containing composition. On the other hand, when the blending amount of the flame retardant is equal to or less than the above-mentioned upper limit, foaming during production of the polyurethane foam is not inhibited.

[0056] Among the above-mentioned flame retardants, phosphate esters are preferred from the viewpoints of compatibility with polyols, solubility, etc. Furthermore, as the phosphate ester, monophosphate esters are preferred, and tris(β-chloropropyl)phosphate is more preferred, from the viewpoints of reducing the viscosity of a mixture of a polyol-containing composition and a polyisocyanate to facilitate production, and of improving the flame retardancy of a polyurethane foam. In the polyol-containing composition, a phosphate ester may be used alone as the flame retardant, or a phosphate ester may be used in combination with another flame retardant. The amount of the phosphate ester in the polyol-containing composition is preferably 5 to 100 parts by mass, more preferably 12 to 90 parts by mass, even more preferably 20 to 75 parts by mass, and even more preferably 32 to 65 parts by mass, per 100 parts by mass of the polyol.

[0057] <Inorganic fillers> Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, wollastonite, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica palan, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon palan, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, and zirconia fiber. These inorganic fillers may be used alone or in combination of two or more.

[0058] The polyol-containing composition of the present invention may or may not contain an inorganic filler. When the polyol-containing composition contains an inorganic filler, the amount of the inorganic filler is preferably 1 to 100 parts by mass, more preferably 10 to 80 parts by mass, and even more preferably 20 to 70 parts by mass, per 100 parts by mass of the polyol.

[0059] <Other ingredients> The polyol-containing composition may contain one or more selected from phenolic, amine, sulfur-based and other antioxidants, heat stabilizers, metal inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, etc., as needed, within the scope of the object of the present invention.

[0060] <Method of producing polyol-containing composition> There are no particular limitations on the method for producing the polyol-containing composition of the present invention, and it can be produced, for example, by stirring each component at about 20 to 40° C. for about 30 seconds to 20 minutes using a homodisper or the like.

[0061] [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, and is obtained by mixing them. The polyurethane foam of the present invention is a reaction product obtained by reacting and foaming the foamable polyurethane composition.

[0062] <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.

[0063] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0064] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0065] Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred. One type of polyisocyanate may be used alone, or two or more types may be used in combination. Furthermore, known additives that are blended into polyisocyanates may be appropriately blended into the polyisocyanate before mixing with the polyol-containing composition.

[0066] It is preferable that the polyol-containing composition and the polyisocyanate mixed therein 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.

[0067] <Isocyanate Index> The isocyanate index of the polyurethane foam of the present invention is not particularly limited, but is preferably 250 or higher. If the isocyanate index is equal to or higher than the above-mentioned lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, facilitating the formation of isocyanurate bonds due to the polyisocyanate trimer, resulting in improved flame retardancy of the polyurethane foam. It also makes it possible to impart non-flammability. Furthermore, when the isocyanate index is equal to or higher than the above-mentioned lower limit, combined with the use of the above-mentioned ammonium carboxylate salt, heterocyclic compound having a nitrogen atom, and transition metal salt, it is easy to produce a polyurethane foam having sufficient isocyanurate bonds, i.e., a polyurethane foam that combines high levels of flame retardancy and thermal insulation. From these perspectives, the isocyanate index is more preferably 300 or higher, even more preferably 350 or higher, and even more preferably 400 or higher. The isocyanate index is preferably not more than 1,000, more preferably not more than 800, and even more preferably not more than 600. When the isocyanate index is not more than the above upper limit, the resulting polyurethane foam will have a good balance between flame retardancy and production costs.

[0068] The isocyanate index can be calculated by the following method. Isocyanate Index = number of equivalents of polyisocyanate ÷ (number of equivalents of polyol + number of equivalents of water) × 100 Here, each equivalent number can be calculated as follows: Polyisocyanate equivalent number = Amount of polyisocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (mol) × 100 Equivalent weight of polyol = OHV × amount of polyol used (g) ÷ molecular weight of KOH (mmol) OHV is the hydroxyl value of the polyol (mg KOH / g). Equivalents 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 (mol), the molecular weight of KOH is 56,100 (mmol), the molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

[0069] <Method of manufacturing polyurethane foam> Although there is no particular limitation on the method for producing the polyurethane foam, it is preferable to foam and react the foamable polyurethane composition obtained by mixing the polyisocyanate and the polyol-containing composition. Specifically, it is preferable to mix the polyisocyanate and the polyol-containing composition by collision mixing using a spray gun or the like, and then spray the mixture. In the present invention, the foamable polyurethane composition may be obtained by mixing the polyisocyanate and the polyol-containing composition, pouring the mixture into a container such as a mold or frame, and curing the mixture.

[0070] <Applications of polyurethane foam> The uses of the polyurethane foam of the present invention are not particularly limited, but because of its excellent flame retardancy and heat insulation, it can be suitably used in buildings such as walls, ceilings, roofs, and floors of buildings. It can also be suitably used as a member for filling any openings that occur in buildings, including joints and holes that occur between structural members of buildings. [Example]

[0071] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0072] 1. Polyurethane foam manufacturing The polyurethane foams according to the examples and comparative examples were prepared in two parts: (1) a polyol-containing composition and (2) a polyisocyanate, according to the formulations shown in Table 1. The details of each component in the table are as follows:

[0073] (1) Polyol-containing composition [Polyol] p-Phthalic acid polyester polyol (Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g)

[0074] [Foam stabilizer] Silicone foam stabilizer (manufactured by Toray Dow Corning Co., Ltd., product name: SH-193, octamethylcyclotetrasiloxane)

[0075] 〔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 99% 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 98% by mass Resinized metal catalyst, bismuth trioctate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600) concentration 55-58% by mass Resinized metal catalyst, dioctyltin versatate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-830), concentration approximately 99% by mass Trimerization amine catalyst, tetramethylammonium acetate (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-TRX) concentration 60 to 70% by mass Trimerization metal catalyst, potassium 2-ethylhexanoate (manufactured by Air Products, product name: DABCO K-15) concentration 70-80% by mass Resinized amine catalyst, N,N,N',N'',N''-pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-TT) concentration approximately 99% by mass

[0076] [Blowing Agent] Hydrofluoroolefin (Honeywell Japan, product name: Soltis LBA, trans-1-chloro-3,3,3-trifluoropropene) ·water

[0077] [Flame retardant] Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)

[0078] [Inorganic filler] Wollastonite (SiO₂·CaO) (Kinseimatec Co., Ltd., product name: SH-1250)

[0079] (2) Polyisocyanate 4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (Manka Chemical Japan Co., Ltd., product name: PM200)

[0080] The foamable polyurethane resin composition was formed according to the following procedure. (1) 200 g of TMCPP was added to 100 g of a kneaded mixture of the components of the polyol-containing composition for dilution (3-fold dilution), and (2) polyisocyanate was added. The mixture was then stirred for 3 seconds at 8,000 rpm with a hand mixer (PRIMIX Corporation's high-speed disperser, Homodisper 2.5 type) at an ambient temperature of 20°C and a liquid temperature of 15±1°C to produce a foamable polyurethane resin composition. (At this time, 3 times the amount of polyisocyanate was also added for dilution.)

[0081] 2. Evaluation The examples and comparative examples were evaluated according to the following criteria. [Foaming] The gel time of the foamable polyurethane resin composition prepared by the above method was measured. Gel times shorter than 10 seconds indicated high reaction activity and poor foaming, while gel times longer than 16 seconds indicated low reaction activity and poor curing. Therefore, gel times of 12 to 14 seconds were rated "A," more than 14 to 16 seconds "B," and less than 10 seconds or more than 16 seconds "C." The results are shown in Table 1. The gel time refers to the time from stirring the foamable polyurethane resin composition until the resin starts to form strings around a metal rod when a metal rod is pierced into the foamable polyurethane resin composition during the reaction, or the time until a hole made by piercing a metal rod into the foamable polyurethane resin composition during the reaction is closed.

[0082] [Stability] The foamable polyurethane resin composition prepared by the above method was placed in a pressure-resistant container and stored in a thermostatic chamber at 60°C for 3 days. The gel time was then measured in the same manner, with results of 20 seconds or less being rated "A," more than 20 seconds but not exceeding 23 seconds being rated "B," and more than 23 seconds being rated "C." The results are shown in Table 1.

[0083] [Table 1]

[0084] As is clear from the results of the above examples, by using three catalysts in combination, namely, an ammonium carboxylate salt, which is a quaternary ammonium salt of a carboxylic acid having 5 or more carbon atoms, a heterocyclic compound having a nitrogen atom, and a transition metal salt, it is possible to suppress the decomposition of the blowing agent by the catalyst and obtain stability of the blowing agent against the catalyst. In other words, the polyol-containing composition of the present invention can increase the activity of the catalyst and improve the foaming property.

Claims

1. A polyol-containing composition for reacting with a polyisocyanate to obtain a polyurethane foam, the composition comprising a polyol, a blowing agent, and a catalyst; the catalyst contains a carboxylic acid ammonium salt, which is a quaternary ammonium salt of a carboxylic acid having 5 or more carbon atoms, a heterocyclic compound having a nitrogen atom, and a metal salt of a carboxylic acid having 5 or more carbon atoms; the heterocyclic compound is an imidazole derivative, and the imidazole derivative is at least one selected from the group consisting of 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole; the metal in the metal salt of a carboxylic acid having 5 or more carbon atoms is bismuth, The polyol-containing composition, wherein the blowing agent comprises a hydrofluoroolefin.

2. The polyol-containing composition according to claim 1, 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.

3. 3. The polyol-containing composition according to claim 1, wherein the quaternary ammonium ion in the ammonium carboxylate is at least one selected from the group consisting of a triethylmethylammonium ion and a tetramethylammonium ion.

4. The polyol-containing composition according to any one of claims 1 to 3, wherein the ammonium carboxylate is 2,2-dimethylpropanoic acid tetramethylammonium salt.

5. The polyol-containing composition according to any one of claims 1 to 4, further comprising a foam stabilizer.

6. A foamable polyurethane composition comprising the polyol-containing composition according to any one of claims 1 to 5 and a polyisocyanate.

7. 7. The foamable polyurethane composition of claim 6, having an isocyanate index of 250 or greater.

8. A polyurethane foam obtained by reacting and foaming the foamable polyurethane composition according to claim 6 or 7.

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