Polyol-containing composition and polyurethane foam

Abstract

To provide a polyol-containing composition that can prevent deterioration of catalytic activity while improving stability even when using hydrofluoroolefin as a foaming agent and can inhibit peeling caused between an object to be sprayed and polyurethane foam even when performing spraying construction under low temperature and to provide polyurethane foam using the polyol-containing composition.SOLUTION: The polyol-containing composition is used for producing polyurethane foam by reacting with polyisocyanate and contains polyol, a carboxylic acid ammonium salt represented by the general formula (1) as given below, a heterocyclic compound having a nitrogen atom, hydrofluoroolefin and a foam stabilizer. (In the general formula (1), R1 and R2 each independently represent an alkyl group; R3 represents a hydrogen atom or an alkyl group; and M+ represents a quaternary ammonium ion.)SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Conventionally, hydrofluorocarbon (HFC) has been used as a blowing agent for foaming polyurethane. However, since hydrofluorocarbon has a high global warming potential and there are also regulatory movements, a switch to alternative materials is being considered. Examples of the alternative materials include hydrofluoroolefin (HFO). However, hydrofluoroolefin decomposes the catalyst used in the production of polyurethane foam and reduces the activity of the catalyst, so there is a problem that the reaction between polyol and polyisocyanate does not proceed sufficiently. As a method for solving such problems, Patent Document 1 discloses a polyol premix composition containing a blowing agent, a polyol, a silicone surfactant, and a specific sterically hindered amine catalyst.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] By the way, in order to enhance the flame retardancy or make the polyurethane foam non-flammable, it is necessary to increase the isocyanurate bonds by trimerization of the polyisocyanate. In addition, polyurethane foam is applied to, for example, the wall surface of a building by spraying. However, if the activity of the catalyst is not sufficiently high, the reaction between the polyol and the polyisocyanate does not proceed sufficiently, and lateral expansion occurs in the polyurethane foam. When the spraying target has a corner portion, peeling may occur between the spraying target and the foam. In particular, when spraying is carried out at a low temperature of about 0 °C, the activity of the catalyst tends to decrease, and thus the above peeling problem is likely to occur.

[0005] On the other hand, Patent Document 1 features the use of a specific catalyst, but does not mention enhancing the catalyst activity to suppress the lateral expansion of the foam in a polyurethane foam having isocyanurate bonds. Furthermore, in order to obtain a polyurethane foam having many isocyanurate bonds, it is necessary to use a trimerization catalyst and a resinification catalyst in combination. However, when a polyol-containing composition containing these is used with hydrofluoroolefin, problems such as a decrease in stability and inappropriate foaming are likely to occur.

[0006] Therefore, an object of the present invention is to provide a polyol-containing composition that can prevent a decrease in catalyst activity while improving stability even when a trimerization catalyst and a resinification catalyst are used as catalysts and a hydrofluoroolefin is used as a foaming agent, and that is less likely to cause lateral expansion due to a decrease in catalyst activity even in, for example, spraying construction at a low temperature.

Means for Solving the Problems

[0007] As a result of intensive studies by the present inventors to solve the above problems, it has been found that when a specific ammonium carboxylate salt and a heterocyclic compound having a nitrogen atom are used in combination as catalysts, even when a hydrofluoroolefin is used as a foaming agent, the activity of the catalyst does not decrease and the stability of the polyol-containing composition is increased, and the present invention has been completed.

[0008] The present invention has the following gists [1] to

[10] . [1] A polyol-containing composition for obtaining a polyurethane foam by reacting with a polyisocyanate, the polyol-containing composition containing a polyol, an ammonium carboxylate represented by the following general formula (1), a heterocyclic compound having a nitrogen atom, a hydrofluoroolefin, and a foam stabilizer. [Chemical formula] (In the general formula (1), R 1 and R 2 each independently represent an alkyl group, and R 3 represents a hydrogen atom or an alkyl group. Further, M + represents a quaternary ammonium ion.) [2] The polyol-containing composition according to [1] above, wherein the blending amount of the ammonium carboxylate is 1 to 22 parts by mass with respect to 100 parts by mass of the polyol. [3] The polyol-containing composition according to [1] or [2] above, wherein R 3 in the general formula (1) is an alkyl group. [4] The polyol-containing composition according to any one of [1] to [3] above, wherein M + in the general formula (1) is a tetramethylammonium ion. [5] The polyol-containing composition according to any one of [1] to [4] above, wherein the ammonium carboxylate represented by the general formula (1) is an ammonium 2,2-dimethylpropionate. [6] The polyol-containing composition according to any one of [1] to [5] above, wherein the blending amount of the heterocyclic compound having a nitrogen atom is 1 to 23 parts by mass with respect to 100 parts by mass of the polyol. [7] The polyol-containing composition according to any one of [1] to [6] above, wherein the heterocyclic compound having a nitrogen atom is an imidazole derivative represented by the following general formula (2). [Chemical formula] (In general formula (2), R 4 and R 5 each independently represent an alkyl group or an alkenyl group having 1 to 8 carbon atoms.) [8] The polyol-containing composition according to any one of [1] to [7] above, wherein the heterocyclic compound having a nitrogen atom is 1,2-dimethylimidazole. [9] A polyurethane foam which is a reaction product of the polyol-containing composition according to any one of [1] to [8] above and a polyisocyanate.

[10] The polyurethane foam according to [9] above, wherein the isocyanate index is 200 or more. [Advantages of the Invention]

[0009] According to the present invention, even when a trimerization catalyst and a resinification catalyst are used in combination as a catalyst and a hydrofluoroolefin is used as a blowing agent, the stability can be improved and a decrease in catalyst activity can be prevented. For example, a polyol-containing composition in which lateral expansion hardly occurs even in spray application at low temperatures can be provided. [Modes for Carrying Out the Invention]

[0010] 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 reacting with a polyisocyanate to obtain a polyurethane foam, and contains a polyol, an ammonium carboxylate represented by the following general formula (1), a heterocyclic compound having a nitrogen atom, a hydrofluoroolefin, and a foam stabilizer.

[0011] [Chemical Formula] (In general formula (1), R 1 and R 2 each independently represent an alkyl group, and R 3 represents a hydrogen atom or an alkyl group. Further, M +represents a quaternary ammonium ion.)

[0012] In the polyol-containing composition of the present invention, since a specific ammonium carboxylate and a heterocyclic compound having a nitrogen atom are used in combination as catalysts, even when a hydrofluoroolefin is used as a foaming agent, while enhancing stability, the activity of the catalyst does not decrease and the reaction between the polyol and the polyisocyanate can proceed rapidly. As a result, for example, even when spraying construction is carried out at a low temperature of about 0 °C, the horizontal elongation is suppressed and peeling is prevented. The two types of catalysts used in the present invention are likely to form an isocyanurate bond of a six-membered ring derived from a trimer of polyisocyanate by adjusting the amounts of the polyol and the polyisocyanate. And the polyurethane foam having the isocyanurate bond of this six-membered ring structure forms a carbonized layer during combustion and becomes difficult to burn, so the flame retardancy of the polyurethane foam is improved.

[0013] <Polyol> The polyol-containing composition of the present invention contains a polyol as a raw material for a polyurethane foam. Examples of the polyol used in the present invention include polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polymer polyol, and polyether polyol.

[0014] Examples of the polylactone polyol include polypropionolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of the polycarbonate polyol include polyols obtained by a dealcoholization reaction between a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol and ethylene carbonate, propylene carbonate, etc.

[0015] Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolak, and cresol novolak. Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol. Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

[0016] Examples of the polyester polyol include a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, a polymer obtained by ring-opening polymerization of a lactone such as ε-caprolactone and α-methyl-ε-caprolactone, and a condensate of a hydroxycarboxylic acid and the polyhydric alcohol or the like. Examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), and succinic acid. Examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, and neopentyl glycol. Examples of the hydroxycarboxylic acid include castor oil and a reaction product of castor oil and ethylene glycol.

[0017] Examples of the polymer polyol include a polymer obtained by graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate to an aromatic polyol, an alicyclic polyol, an aliphatic polyol, and a polyester polyol, a polybutadiene polyol, and a modified polyol of a polyhydric alcohol or a hydrogenated product thereof.

[0018] Examples of the modified polyol of the polyhydric alcohol include those obtained by modifying the starting polyhydric alcohol by reacting it with an alkylene oxide. Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., sucrose, glucose, mannose, fructose, methyl glucoside and its derivatives, etc., tetra- to octavalent alcohols, phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene, etc., polyols, castor oil polyol, polyfunctional (e.g., the number of functional groups is 2 to 100) polyols such as (co)polymers of hydroxyalkyl (meth)acrylate and polyvinyl alcohol, and condensates (novolac) of phenol and formaldehyde.

[0019] The method for modifying the polyhydric alcohol is not particularly limited, but a method of adding an alkylene oxide (hereinafter also referred to as "AO") is preferably used. Examples of AO include those having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter also referred to as "EO"), 1,2-propylene oxide (hereinafter also referred to as "PO"), 1,3-propylene oxide, 1,2-butylene oxide, and 1,4-butylene oxide. Among these, from the viewpoints of properties and reactivity, PO, EO, and 1,2-butylene oxide are preferred, and PO and EO are more preferred. When using two or more kinds of AO (for example, PO and EO), the addition method may be block addition, random addition, or a combination of these.

[0020] Examples of the polyether polyol include polymers obtained by ring-opening polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran in the presence of at least one low-molecular-weight active hydrogen compound having two or more active hydrogens. Examples of the low-molecular-weight active hydrogen compound 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.

[0021] As the polyol used in the present invention, from the viewpoint of suppressing the occurrence of lateral elongation, polyester polyol and polyether polyol are preferable. Further, a polyol having two hydroxyl groups is preferable. Among them, a polyester polyol obtained by dehydration condensation of a polybasic acid having an aromatic ring such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid) and a dihydric alcohol such as bisphenol A, ethylene glycol, and 1,2-propylene glycol is more preferable.

[0022] The hydroxyl value of the polyol is preferably 20 to 300 mgKOH / g, more preferably 30 to 250 mgKOH / g, and still more preferably 50 to 220 mgKOH / g. When the hydroxyl value of the polyol is not more than the above upper limit value, the viscosity of the polyol-containing composition is likely to decrease, which is preferable from the viewpoint of handleability and the like. On the other hand, when the hydroxyl value of the polyol is not less than the above lower limit value, the crosslink density of the polyurethane foam increases, resulting in higher strength. The hydroxyl value of the polyol can be measured according to JIS K 1557-1:2007.

[0023] The content of the polyol in the polyol-containing composition of the present invention is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 25 to 60% by mass. When the content of the polyol is at least the above lower limit value, it is preferable because it becomes easier to react the polyol with the polyisocyanate. On the other hand, when the content of the polyol is at most the above upper limit value, it is preferable from the viewpoint of handleability because the viscosity of the polyol-containing composition does not become too high.

[0024] <Ammonium carboxylate salt represented by the general formula (1) (trimerization catalyst)> The polyol-containing composition of the present invention contains an ammonium carboxylate salt represented by the following general formula (1) as a trimerization catalyst for polyisocyanate. The ammonium carboxylate salt represented by the following general formula (1) has appropriate steric hindrance, so it is hardly affected by hydrofluoroolefin and can prevent the decrease in catalytic activity. Therefore, even when using hydrofluoroolefin as a blowing agent, it is possible to suppress the problem of lateral expansion during spraying construction. Further, in the present invention, since the ammonium carboxylate salt represented by the following general formula (1) and a heterocyclic compound having a nitrogen atom described later are used in combination, it is easy to form an isocyanurate bond by a trimer of polyisocyanate, and a polyurethane foam excellent in flame retardancy can be obtained.

[0025] [Chemical formula] (In the 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. Further, M + represents a quaternary ammonium ion.)

[0026] R in the general formula (1) 1 and R 2Each independently represents an alkyl group, specifically, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 4 carbon atoms is more preferred, and an alkyl group having 1 to 2 carbon atoms is even more preferred. 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. Also, 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 carbon number of R 1 、R 2 and R 3 is equal to or greater than the lower limit value, the steric hindrance becomes large, so it becomes less susceptible to the influence of the hydrofluoroolefin. On the other hand, when the carbon number of R

[0027] M + represents a quaternary ammonium ion, and examples thereof include tetramethylammonium ion, tetraethylammonium ion, and triethylmonomethylammonium ion. Among them, tetramethylammonium ion and triethylmonomethylammonium ion are preferred, and tetramethylammonium ion is more preferred.

[0028] Specific examples of the ammonium carboxylate salt represented by the general formula (1) include 2,2-dimethylpropanoic acid tetramethylammonium salt in which R 1 、R 2 and R 3 are all methyl groups and M + is a tetramethylammonium ion, and R 1 、R 2 and R 3 are all methyl groups and M +Examples of the ammonium salt of 2,2-dimethylpropanoic acid include the triethylmethylammonium salt of 2,2-dimethylpropanoic acid, which is a triethylmethylammonium ion. Among these, the tetramethylammonium salt of 2,2-dimethylpropanoic acid is preferred. In the present invention, the ammonium carboxylate salt may be used alone or in combination of two or more.

[0029] The amount of the ammonium carboxylate salt in the polyol-containing composition is preferably 1 to 22 parts by mass, more preferably 2 to 19 parts by mass, still more preferably 4 to 17 parts by mass, even more preferably 4 to 14 parts by mass, and even more preferably 4 to 11 parts by mass, based on 100 parts by mass of the polyol. When the amount of the ammonium carboxylate salt is at least the lower limit value, the trimerization of the polyisocyanate is likely to occur, and the flame retardancy of the resulting polyurethane foam is improved. On the other hand, when the amount of the ammonium carboxylate salt is at most the upper limit value, the reaction is easier to control.

[0030] <Heterocyclic compound having a nitrogen atom (resinification catalyst)> 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, it is less susceptible to the influence of hydrofluoroolefins, enhances stability, makes it easier to react the polyol and the polyisocyanate, and makes it easier to prevent lateral expansion and the like.

[0031] The heterocyclic compound having a nitrogen atom used in the present invention is not particularly limited, but a compound containing a nitrogen atom in the heterocyclic ring is preferred. For example, a 4- to 8-membered heterocyclic compound containing a nitrogen atom in the heterocyclic ring is more preferred. More specifically, imidazole derivatives, pyridine derivatives, piperazine derivatives, and the like can be mentioned. Among these, imidazole derivatives are preferred, and imidazole derivatives represented by the following general formula (2) are more preferred.

[0032]

Chemical formula

[0033] R in the general formula (2) 4 and R 5 each independently represent an alkyl group or an alkenyl group having 1 to 8 carbon atoms, preferably an alkyl group or an alkenyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. When the number of carbon atoms of the alkyl group or alkenyl group of R 4 and R 5 is at least the lower limit value, the steric hindrance becomes large and it is less likely to be affected by the hydrofluoroolefin, which is preferable. On the other hand, when the number of carbon atoms of the alkyl group or alkenyl group of R 4 and R 5 is at most the upper limit value, the steric hindrance does not become extremely large, and thus the reaction between the polyol and the polyisocyanate can proceed rapidly. The alkyl group and the alkenyl group may each be linear or may have a branched structure.) Examples of the imidazole derivative represented by the 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, from the viewpoints of improving the activity of the catalyst in the presence of the hydrofluoroolefin and allowing the reaction to proceed rapidly, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferable. Further, from the viewpoint of further enhancing the stability, 1,2-dimethylimidazole is more preferable.)

[0034] The blending amount of the heterocyclic compound having a nitrogen atom in the polyol-containing composition is preferably 1 to 23 parts by mass, more preferably 3 to 19 parts by mass, still more preferably 5 to 15 parts by mass, and even more preferably 5 to 11 parts by mass with respect to 100 parts by mass of the polyol. When the blending amount of the heterocyclic compound having a nitrogen atom is at least the above lower limit value, the formation of urethane bonds is likely to occur and the reaction proceeds rapidly. On the other hand, when the blending amount of the heterocyclic compound having a nitrogen atom is at most the above upper limit value, it is preferable because the reaction rate is easily controlled.

[0035] <Hydrofluoroolefin (foaming agent)> The polyol-containing composition of the present invention contains a hydrofluoroolefin as a foaming agent. Examples of the hydrofluoroolefin include fluoroalkenes having about 3 to 6 carbon atoms. The hydrofluoroolefin may be a hydrochlorofluoroolefin having a chlorine atom, and thus may be a chlorofluoroalkene having about 3 to 6 carbon atoms. More specifically, trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorotrifluoropropenes such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetrafluoropropene can be mentioned. More specifically, 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 can be mentioned. Among these, HFO-1233zd is preferable. These hydrofluoroolfins may be used alone or in combination of two or more thereof.

[0036] In the present invention, the global warming potential (GWP) of the hydrofluoroolfin used is preferably 150 or less, more preferably 100 or less, and still more preferably 75 or less. The "GWP" is a value defined in "The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meteorological Association’s Global Ozone Research and Monitoring Project", and is a value measured relatively with respect to the GWP of carbon dioxide on a 100-year time scale. In addition, the ozone depletion potential (ODP) of the hydrofluoroolfin is preferably 0.05 or less, more preferably 0.02 or less, and still more preferably substantially 0. The "ODP" is a value defined in "The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association’s Global Ozone Research and Monitoring Project".

[0037] The blending amount of the hydrofluoroolefin is preferably 10 to 60 parts by mass, more preferably 20 to 55 parts by mass, still more preferably 25 to 50 parts by mass, and even more preferably 30 to 45 parts by mass with respect to 100 parts by mass of the polyol. When the blending amount of the hydrofluoroolefin is at least the lower limit value, foaming is promoted and the density of the resulting polyurethane foam can be reduced. On the other hand, when the blending amount of the hydrofluoroolefin is at most the upper limit value, excessive progress of foaming can be suppressed.

[0038] <Blowing agent other than hydrofluoroolefin> The polyol-containing composition of the present invention may contain a blowing agent other than a hydrofluoroolefin. Examples of the blowing agent other than the hydrofluoroolefin include low-boiling hydrocarbons such as water, propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane; chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride; organic physical blowing agents such as ether compounds such as diisopropyl ether; and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Among these, from the viewpoint of handleability, water, oxygen gas, and carbon dioxide gas are preferable, and water is preferable from the viewpoints of adjusting the isocyanate index and ease of handling.

[0039] The blending 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 still more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the polyol. When the blending amount of the blowing agent is at least the lower limit value, foaming is promoted and the density of the resulting polyurethane foam can be reduced. On the other hand, when the blending amount of the blowing agent is at most the upper limit value, excessive progress of foaming can be suppressed.

[0040] <Foam stabilizer> The polyol-containing composition of the present invention contains a foam stabilizer for the purpose of facilitating the foaming of a mixture of the polyol-containing composition and an isocyanate. Examples of the foam stabilizer include surfactants such as polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and silicone foam stabilizers such as organopolysiloxanes. These foam stabilizers may be used alone or in combination of two or more.

[0041] The blending amount of the foam stabilizer in the polyol-containing composition of the present invention is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and still more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyol. When the blending amount of the foam stabilizer is at least the above lower limit value, it becomes easy to foam the mixture of the polyol-containing composition and the polyisocyanate, so that a homogeneous polyurethane foam can be obtained. Further, when the blending amount of the foam stabilizer is at most the above upper limit value, the balance between the production cost and the obtained effect becomes optimal.

[0042] <Flame retardant> The polyol-containing composition of the present invention may contain a flame retardant. The polyurethane foam produced using the polyol-containing composition of the present invention contains an isocyanurate bond formed by the trimerization of the polyisocyanate, and thus has excellent flame retardancy. However, the use of a flame retardant can further improve the flame retardancy of the polyurethane foam. Preferred flame retardants for use in the present invention include red phosphorus, phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boric acid-containing flame retardants, antimony-containing flame retardants, and metal hydroxides. More preferred are red phosphorus, phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boric acid-containing flame retardants, antimony-containing flame retardants, and metal hydroxides.

[0043] As the phosphate ester, it is preferable to use a monophosphate ester, a condensed phosphate ester, etc. For example, 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, cresyldiphenyl phosphate, xylenyl diphenyl phosphate, diphenyl(2-ethylhexyl) phosphate, di(isopropylphenyl)phenyl phosphate, monoisodecyl 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 methane phosphonate, diethyl phenylphosphonate, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), phosphaphenanthrene, and tris(β-chloropropyl) phosphate, etc. may be mentioned.

[0044] Examples of the condensed phosphate ester include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly(di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name PX-200), hydroquinone poly(2,6-xylyl) phosphate, and condensed phosphate esters such as condensates thereof.

[0045] Among these, from the viewpoints of reducing the viscosity of the mixture of the polyol-containing composition and the polyisocyanate to facilitate production and improving the flame retardancy of the polyurethane foam, monophosphate ester is preferable, and tris(β-chloropropyl) phosphate is more preferable.

[0046] When the polyol-containing composition of the present invention contains a flame retardant, the blending amount is preferably 10 to 150 parts by mass, more preferably 20 to 140 parts by mass, still more preferably 30 to 130 parts by mass, and even more preferably 40 to 125 parts by mass with respect to 100 parts by mass of the polyol. When the blending amount of the flame retardant is at least the lower limit value, sufficient flame retardancy can be imparted to the polyurethane foam produced using the polyol-containing composition. On the other hand, when the blending amount of the flame retardant is at most the upper limit value, foaming during the production of the polyurethane foam is not inhibited.

[0047] <Other components> In the present invention, in addition to the ammonium carboxylate represented by the general formula (1), a trimerization catalyst may be included. Examples of such a catalyst include metal salts of the carboxylic acid represented by the general formula (1). Further, ammonium salts, metal salts, etc. of carboxylic acids having a structure other than the above general formula (1) are also included. When a metal salt is included, the ammonium carboxylate represented by the general formula (1) may be partially a metal salt of the carboxylic acid.

[0048] The polyol-containing composition of the present invention may contain components other than the polyol, the ammonium carboxylate represented by the general formula (1), the heterocyclic compound having a nitrogen atom, the hydrofluoroolefin, and the foam stabilizer. For example, it may contain an inorganic filler. Examples of the inorganic filler 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 pearl, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon pearl, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum porate, 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. The polyol-containing composition of the present invention may or may not contain an inorganic filler. When it contains an inorganic filler, the blending amount of the inorganic filler is preferably 1 to 100 parts by mass, more preferably 10 to 80 parts by mass, and still more preferably 20 to 70 parts by mass with respect to 100 parts by mass of the polyol.

[0049] In addition, the polyol-containing composition may contain one or more selected from antioxidants such as phenolic, amine-based, and sulfur-based antioxidants, heat stabilizers, metal deactivators, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, etc., as necessary within a range not impairing the object of the present invention.

[0050] [Method for producing polyol-containing composition] There is no particular limitation on the method for producing the polyol-containing composition of the present invention. For example, it can be produced by stirring each component at about 20 to 40 ° C for about 30 seconds to 20 minutes using a homodisper or the like.

[0051] [Polyurethane foam] The polyurethane foam of the present invention is a reaction product of the polyol-containing composition of the present invention and a polyisocyanate. As described above, since the polyol-containing composition of the present invention uses a specific ammonium carboxylate salt and a heterocyclic compound having a nitrogen atom as a catalyst, even when a hydrofluoroolefin is used as a foaming agent, it has high stability and is less likely to have a decrease in catalytic activity. Therefore, the polyurethane foam of the present invention can suppress the problem of lateral expansion even when spray application is performed at a low temperature.

[0052] <Polyisocyanate> Examples of the polyisocyanate include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Examples of the aromatic polyisocyanate include phenylenediisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

[0053] Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0054] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0055] Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred. The polyisocyanate may be used alone or in combination of two or more. In addition, before being mixed with the polyol-containing composition, the polyisocyanate may be appropriately blended with known additives to be blended in the polyisocyanate.

[0056] Note that the polyol-containing composition and the polyisocyanate to be mixed with the polyol-containing composition preferably 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.

[0057] <Isocyanate index> There is no particular limitation on the isocyanate index of the polyurethane foam of the present invention, but it is preferably 200 or more. When the isocyanate index is equal to or higher than the lower limit value, the amount of polyisocyanate relative to the polyol becomes excessive, and an isocyanurate bond formed by the trimer of polyisocyanate is likely to be generated. As a result, the flame retardancy of the polyurethane foam is improved. In addition, it becomes possible to impart nonflammability. Furthermore, when the value is equal to or higher than the above lower limit value, in combination with the combined use of an ammonium carboxylate salt and a heterocyclic compound having a nitrogen atom, a polyurethane foam having an isocyanurate bond, that is, a polyurethane foam having high levels of flame retardancy and heat insulation can be easily produced. From these viewpoints, the isocyanate index is more preferably 250 or more, even more preferably 300 or more, and particularly preferably 400 or more. In addition, 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 equal to or lower than the upper limit value, the balance between the flame retardancy and the production cost of the resulting polyurethane foam is improved.

[0058] Note that the isocyanate index can be calculated by the following method. Isocyanate index = Equivalent number of polyisocyanate ÷ (Equivalent number of polyol + Equivalent number of water) × 100 Here, each equivalent number can be calculated as follows. · Equivalent number of polyisocyanate = Amount of polyisocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (mol) × 100 · Equivalent number of polyol = OHV × Amount of polyol used (g) ÷ Molecular weight of KOH (mmol) OHV is the hydroxyl value (mgKOH / g) of the polyol. · Equivalent number of water = Amount of water used (g) / Molecular weight of water (mol) × Number of OH groups in water In the above formulas, the molecular weight of NCO is 42 (mol), the molecular weight of KOH is 56100 (mmol), the molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

[0059] <Method for producing polyurethane foam> The method for producing the polyurethane foam of the present invention is not particularly limited, but it is preferable to mix and foam and react a polyisocyanate and a polyol-containing composition. Specifically, it is preferable to collide and mix the polyisocyanate and the polyol-containing composition using a spray gun or the like and perform spraying construction. More specifically, the polyisocyanate and the polyol-containing composition are mixed at a liquid temperature of about 10 to 50°C using a spray gun, and sprayed onto the surface to be constructed at a discharge pressure of about 800 to 2000 psi to cause foaming, whereby it can be produced. In the present invention, since a specific ammonium carboxylate salt and a heterocyclic compound having a nitrogen atom are used in combination as a catalyst, the activity of the catalyst can be maintained even under conditions where the outside air temperature is low. Therefore, a polyurethane foam can be produced without problems even when foamed and cured at a low temperature of about 0 to 15°C of the outside air temperature. In the present invention, after mixing the polyisocyanate and the polyol-containing composition, a polyurethane foam may be obtained by injecting it into a container such as a mold or a frame material and curing it.

[0060] <Use of polyurethane foam> The use of the polyurethane foam of the present invention is not particularly limited, but since it is excellent in flame retardancy and heat insulation, it can be suitably used for buildings such as building walls, ceilings, roofs, and floors. It can also be suitably used as a member for filling any openings formed in a building, including joints and holes formed between structural members of the building.

Examples

[0061] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

[0062] <Materials used> 〔Polyisocyanate〕 4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Wanhua Chemical Japan Co., Ltd., product name: PM200) 〔Polyol〕 p-Phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g) 〔Trimerization catalyst〕 · Ammonium carboxylate Tetramethylammonium 2,2-dimethylpropionate (manufactured by Evonik Japan Co., Ltd., product name: DABCO TMR-7), mixture with ethylene glycol (tetramethylammonium 2,2-dimethylpropionate 45 to 55% by mass, ethylene glycol 45 to 55% by mass) · Comparative trimerization catalyst (1) Tetramethylammonium acetate (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-TRX) · Comparative trimerization catalyst (2) Potassium 2-ethylhexanoate (manufactured by Evonik Japan Co., Ltd., product name: DABCO K-15)

[0063] 〔Resinification catalyst〕 · Heterocyclic compound (1) 1,2-Dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-DM70, mixture with ethylene glycol (65 - 75% by mass of 1,2-dimethylimidazole and 25 - 35% by mass of ethylene glycol)) · Heterocyclic compound (2) 1-Isobutyl-2-methylimidazole (manufactured by Evonik Japan Co., Ltd., product name: NICM) · Comparative resinification catalyst (1) N,N,N’,N’’,N’’-Pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-TT)

[0064] [Blowing agent] · Hydrofluoroolefin (manufactured by Honeywell Japan Co., Ltd., product name: Solstice LBA, trans-1-chloro-3,3,3-trifluoropropene) · Water [Cell stabilizer] Silicone-based cell stabilizer (manufactured by Toray Dow Corning, product name: SH-193, octamethylcyclotetrasiloxane)

[0065] [Flame retardant] Tris(β-chloropropyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TMCPP) [Inorganic filler] Calcium silicate (manufactured by Kinsemattec Co., Ltd., product name: SH1250)

[0066] <Examples 1 - 9, Comparative Examples 1 - 3> A polyol-containing composition was prepared by stirring at a rotational speed of 3600 rpm for 10 minutes using a homodisper to make the total amount of each component 10 L according to the formulation shown in Table 1.

[0067] <Stability in the presence of hydrofluoroolefin> First, the polyol-containing composition prepared by the above method and the polyisocyanate were mixed homogeneously according to the formulation described in Table 1, and the cream time and gel time of the resulting mixture were measured as follows. Next, as a comparison, a polyol mixture separately prepared by the above method was placed in a pressure-resistant container and stored in a constant-temperature bath at 60°C for 3 days. Then, this polyol mixture and the polyisocyanate were mixed homogeneously, and the cream time and gel time of the resulting mixture were measured as follows. The measurement results when the polyol-containing composition was prepared without being stored in a constant-temperature bath for 3 days were compared with the measurement results after storage. When the difference between the two was less than 10% for both the cream time and the gel time, it was evaluated as "5"; when it was less than 20% for both, it was evaluated as "4"; when it was less than 30% for both, it was evaluated as "3"; when it was less than 40% for both, it was evaluated as "2"; and in other cases, it was evaluated as "1". The results are shown in Table 1.

[0068] 〔Cream time〕 The cream time refers to the time (seconds) from the start of stirring and mixing the polyol-containing composition and the isocyanate until the mixture becomes cloudy in a cream-like state. 〔Gel time〕 The gel time refers to the time (seconds) from the mixing of the reaction stock solution until the foam during foaming pulls a thread when a rod is stabbed into the foam.

[0069] <Horizontal elongation> The polyurethane resin composition prepared by the above method was spray-applied to an L-shaped substrate (gypsum board) at a low temperature (0°C). After 1 day had passed since the spray application, the interface between the polyurethane resin and the substrate was observed. When no peeling occurred at all, it was evaluated as "5"; when the peeled area was less than 10%, it was evaluated as "4"; when the peeled area was less than 30%, it was evaluated as "3"; when the peeled area was less than 50%, it was evaluated as "2"; and when the peeled area was 50% or more, it was evaluated as "1". The results are shown in Table 1.

[0070]

Table 1

[0071] In Table 1, the parts by mass of the ammonium carboxylate salt and the parts by mass of the heterocyclic compound (1) each indicate the blending amount of the mixture with ethylene glycol.

[0072] In all of the examples and comparative examples, the volume ratio of the polyisocyanate to the polyol-containing composition was 1.

[0073] As is clear from the results of the above examples, according to the polyol-containing composition of the present invention, when a specific ammonium carboxylate salt and a heterocyclic compound having a nitrogen atom are used in combination as a catalyst, even when a hydrofluoroolefin is used as a foaming agent, the stability is good and lateral expansion can be sufficiently prevented.

Claims

1. A polyol-containing composition for producing a polyurethane foam by reacting with a polyisocyanate, the polyol-containing composition containing a polyol, an ammonium carboxylate represented by the following general formula (1), a heterocyclic compound having a nitrogen atom, a hydrofluoroolefin, and a foam stabilizer: 【Chemistry 1】 (In general formula (1), R １ and R ２ each independently represents an alkyl group; R ３ represents a hydrogen atom or an alkyl group. ＋ represents a quaternary ammonium ion.)

2. The polyol-containing composition according to claim 1, wherein the amount of the ammonium carboxylate is 1 to 22 parts by mass per 100 parts by mass of the polyol.

3. R in the general formula (1) ３ The polyol-containing composition according to claim 1 or 2, wherein is an alkyl group.

4. M in the general formula (1) ＋ The polyol-containing composition according to any one of claims 1 to 3, wherein is a tetramethylammonium ion.

5. The polyol-containing composition according to any one of claims 1 to 4, wherein the ammonium carboxylate represented by the general formula (1) is ammonium 2,2-dimethylpropanoate.

6. The polyol-containing composition according to any one of claims 1 to 5, wherein the amount of the heterocyclic compound having a nitrogen atom is 1 to 23 parts by mass per 100 parts by mass of the polyol.

7. The polyol-containing composition according to any one of claims 1 to 6, wherein the heterocyclic compound having a nitrogen atom is an imidazole derivative represented by the following general formula (2): 【Chemistry 2】 (In general formula (2), R ４ and R ５ each independently represents an alkyl or alkenyl group having 1 to 8 carbon atoms.

8. The polyol-containing composition according to any one of claims 1 to 7, wherein the heterocyclic compound having a nitrogen atom is 1,2-dimethylimidazole.

9. A polyurethane foam which is the reaction product of the polyol-containing composition according to any one of claims 1 to 8 and a polyisocyanate.

10. 10. The polyurethane foam of claim 9 having an isocyanate index of 200 or greater.

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