Polyol-based compounding solution for the manufacture of hydrochlorofluoroolefin foamed polyurethane foam.

Abstract

In spray-applied polyurethane foam insulation, there is a need to reduce the density of the polyurethane foam to minimize environmental impact. Generally, this requires increasing the amount of blowing agent used, but increasing the amount of hydrochlorofluoroolefins further reduces the storage stability of the polyol-based compound. Therefore, there is a need for a technology that can reduce density without increasing the amount of hydrochlorofluoroolefins. [Solution] A polyol-based compounding liquid composition for manufacturing polyurethane foam is used, characterized by comprising the following (i), (ii), (iii), and (iv). (i) Tertiary amine (A) (ii) Secondary amines having 2 to 12 carbon atoms (B) (iii) Hydrochlorofluoroolefin (C) (iv) Polyol (D)

Description

Technical Field

[0001] The present invention relates to a polyol-based formulation used in the production of hydrochlorofluorolefin foamed polyurethane foam.

Background Art

[0002] Polyurethane foam can be produced by the reaction of a polyol and an isocyanate. Typically, examples of production methods include reacting a polyol-based formulation containing a tertiary amine catalyst, a foaming agent, a surfactant, etc. with an organic polyisocyanate. In the production method of the polyurethane foam, it is important to mix and contact the polyol-based formulation and the organic polyisocyanate to cause a rapid foaming reaction. For example, in the spraying method of polyurethane foam for heat insulation, a good foamed resin heat insulation layer can be obtained by the rapid initiation of the foaming reaction of the mixed solution spray-coated on the wall surface or the like.

[0003] In recent years, regarding the above-mentioned foaming agents, hydrochlorofluorolefins (HCFOs) with a low global warming potential have begun to be used. Specific examples of hydrochlorofluorolefins include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), and the like.

[0004] Hydrochlorofluorolefins are known to decompose over time under the action of the above-mentioned tertiary amine catalyst. It is known that the reaction between the polyol-based formulation and the organic polyisocyanate is slowed down by the influence of acids such as hydrofluoric acid and hydrochloric acid generated during the decomposition. Therefore, there has been a problem that long-term storage of the polyol-based formulation containing hydrochlorofluorolefins is difficult and industrial use is difficult.

[0005] As a method to solve the above problems, examples using organic acid-containing amine catalysts (Patent Document 1) and examples using sterically hindered amine catalysts (Patent Document 2) have been proposed.

[0006] Furthermore, although unrelated to the above issues, a method using primary and secondary amine carbonates is known as a technique for miniaturizing the cells of polyurethane foam (see Patent Document 3). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Special Publication No. 2011-500893 [Patent Document 2] International Publication No. 2009 / 048807 Pamphlet [Patent Document 3] Japanese Patent Publication No. 2000-239339 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] In spray-applied polyurethane foam insulation, there is a need to reduce the density of the polyurethane foam in order to reduce the amount of raw materials used, and thus reduce the environmental impact. One way to reduce density is to increase the amount of blowing agent used, but increasing the amount of hydrochlorofluoroolefins further reduces the storage stability of the polyol-based compound. Therefore, there is a need for a technology that can reduce density without increasing the amount of hydrochlorofluoroolefins. [Means for solving the problem]

[0009] As a result of diligent research to solve the above-mentioned problems, the present inventors have discovered a polyol-based compounding solution for the production of hydrochlorofluoroolefin foamed polyurethane foam, and have completed the present invention.

[0010] In other words, the present invention relates to a polyol-based compounding liquid composition for producing the polyurethane foam described below, and a method for producing the polyurethane foam using the said composition.

[0011] [1] A polyol-based compounding liquid composition for manufacturing polyurethane foam, characterized by comprising the following (i), (ii), (iii), and (iv). (i) Tertiary amine (A) (ii) Secondary amines having 2 to 12 carbon atoms (B) (iii) Hydrochlorofluoroolefin (C) (iv) Polyol (D) [2] The aforementioned hydrochlorofluoroolefin (C) is 1-chloro-2,3,3,3-tetrafluoropropene, 2-chloro-1,3,3,3-tetrafluoropropene, 1-chloro-1,3,3,3-tetrafluoropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-2,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3-trifluoropropene, 2-chloro-1,3,3-trifluoropropene, 2-chloro-1,1,3-trifluoropropene, 3-chloro-1,2,3- The composition according to [1] above, which is one or more selected from the group consisting of trifluoropropene, 3-chloro-1,1,2-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, 2,3-dichloro-3,3-difluoropropene, 1,2,3-trichloro-3,3-difluoropropene, 2,3-dichloro-1,1-difluoropropene, 2,3,3-trichloro-3-fluoropropene, 1,3-dichloro-2,3,3-trifluoropropene, and 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene.

[0012] [3] The composition according to [1] above, wherein the hydrofluorochloroolefin (C) is trans-1-chloro-3,3,3-trifluoropropene or 1-chloro-2,3,3,3-tetrafluoropropene.

[0013] [4] The composition according to any one of [1] to [3] above, wherein the secondary amine (B) having 2 to 12 carbon atoms is a secondary amine having 2 to 6 carbon atoms.

[0014] [5] The composition according to [1] above, wherein the tertiary amine (A) is a tertiary amine represented by the following formula (1).

[0015] [Chemical formula]

[0016] [In the above formula (1), R1 and R2 each independently represent an alkyl group or a hydroxyalkyl group having 2 to 8 carbon atoms. Z represents

[0017] [Chemical formula]

[0018] represents, and R3 and R4 above each independently represent an alkyl group or a hydroxyalkyl group having 2 to 8 carbon atoms. X represents

[0019] [Chemical formula]

[0020] represents, and R5 represents an alkyl group or a hydroxyalkyl group having 2 to 8 carbon atoms. However, R1 or R2 and R5 may combine to form an alkylene group having 2 to 8 carbon atoms. m and n each independently represent an integer of 2 to 6, and a represents an integer of 0 to 5.] [6] A method for producing polyurethane foam, characterized by reacting a composition described in any of [1] to [5] above with a polyisocyanate compound. [Effects of the Invention]

[0021] The composition of the present invention has the effect of reducing the density of urethane foam without increasing the amount of hydrochlorofluoroolefins used. [Modes for carrying out the invention]

[0022] The following describes in detail one aspect of this disclosure. In this disclosure, "~" includes the numbers at both ends and therefore means the following numerical range.

[0023] A polyol-based compounding liquid composition for producing polyurethane foam according to one aspect of this disclosure (hereinafter referred to as "the Composition") has the remarkable effect of reducing the density of urethane foam in the production of hydrochlorofluoroolefin foam without increasing the amount of hydrochlorofluoroolefins used.

[0024] This remarkable effect is presumed to be due to the low-density foaming action produced by combining a tertiary amine (A) with a secondary amine (B) having 2 to 12 carbon atoms.

[0025] Furthermore, the composition according to one aspect of this disclosure provides the effect of excellent storage stability, which is a challenge for hydrochlorofluoroolefin foams.

[0026] Furthermore, the composition according to one aspect of this disclosure exhibits the remarkable effect of a short rise time, that is, a rapid progression of the polyurethane foam's effect.

[0027] Thus, the composition according to one aspect of this disclosure has the exceptional effect of reducing foam density without increasing the amount of foaming agent used, accelerating the curing of the foam, having excellent long-term storage stability, and enabling the stable production of high-quality hydrochlorofluoroolefin foamed polyurethane foam without being affected by changes in ambient temperature.

[0028] One aspect of the present disclosure relates to a polyol-based compounding liquid composition for manufacturing polyurethane foam, characterized by comprising the following (i), (ii), (iii), and (iv). (i) Tertiary amine (A) (ii) Secondary amines having 2 to 12 carbon atoms (B) (iii) Hydrochlorofluoroolefin (C) (iv) Polyol (D) Regarding the aforementioned tertiary amine (A), there are no particular limitations on the number of carbon atoms or amino groups, but it is preferable that it be a tertiary amine represented by the following formula (1) in terms of excellent storage stability of the polyol-based liquid composition.

[0029] [ka]

[0030] [In the above formula (1), R1 and R2 each independently represent an alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms. Z is,

[0031] [ka]

[0032] This represents R3 and R4, respectively, independently representing an alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms. X is

[0033] [ka]

[0034] R5 represents an alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms. However, R1 or R2 and R5 may be bonded together to form an alkylene group having 2 to 8 carbon atoms. m and n each independently represent an integer from 2 to 6, and a represents an integer from 0 to 5. In the above general formula (1), R1, R2, R3, R4, and R5 each independently represent an alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms.

[0035] The alkyl groups having 2 to 8 carbon atoms are not particularly limited, but examples include ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, cyclopentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, cyclohexyl group, n-heptyl group, 1-methylhexyl group, cycloheptyl group, n-octyl group, t-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, or cyclooctyl group.

[0036] Examples of the hydroxyalkyl groups having 2 to 8 carbon atoms include hydroxyalkyl groups in which at least one hydrogen atom in the above-mentioned hydroxyalkyl group having 2 to 8 carbon atoms is substituted with a hydroxyl group.

[0037] In the above general formula (1), the alkylene group having 2 to 8 carbon atoms formed by the bonding of R1 or R2 and R5 is not particularly limited, but examples include a 1,2-ethanediyl group, a 1,2-propanediyl group, a 1,3-propanediyl group, a 1,2-butanediyl group, a 1,4-butanediyl group, or a 1,6-hexanediyl group.

[0038] In the general formula (1) above, m and n each independently represent integers from 2 to 6.

[0039] Regarding m and n, in terms of excellent storage stability of the polyol-based liquid composition, they are each preferably an integer of 2 or 3, and more preferably both are 2.

[0040] In the general formula (1) above, a represents an integer from 0 to 5.

[0041] With respect to (a), it is preferably 0, 1, or 2, and more preferably 0 or 1, in terms of excellent storage stability of the polyol-based liquid composition.

[0042] The above tertiary amine (A) is not particularly limited, but from the viewpoint of storage stability of the polyol-based liquid composition, for example, 1,2-bis(diethylamino)ethane, N,N,N',N'-tetraethylpropanediamine, N,N,N',N'-tetraethylhexamethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,1,4,7,7-pentaethyldiethylenetriamine, bis[2-(diethylamino)ethyl]ether, N,N-diethylaminoethanol, 2-[2-(diethylamino)ethoxy]ethanol, 2-[2-[2-(diethylamino)ethoxy]ethoxy]ethanol Examples include tertiary amine compounds such as 6-(diethylamino)-1-hexanol, 4,4'-(oxydiethylene)dimorpholine, 2-[[2-(diethylamino)ethyl](ethyl)amino]ethanol, 1,8-bis(diethylamino)-3,6-diethyl-3,6-diazaoctane, 1-ethyl-4-[2-(diethylamino)ethyl]piperazine, 1,3,6,9-tetraethyl-3,6,9-triaza-1-decanol, 1-[bis[3-(diethylamino)propyl]amino]-2-propanol, 1,1'-[[3-(dimethylamino)propyl]imino]bis(2-propanol), or 6-(diethylamino)-1-hexanol, 4,4'-(oxydiethylene)dimorpholine, etc.

[0043] Furthermore, the tertiary amine (A) may consist of a single compound or of two or more compounds.

[0044] A polyol-based liquid composition according to one aspect of this disclosure may further contain tertiary amine compounds other than tertiary amine (A).

[0045] Examples of tertiary amine compounds other than the above-mentioned tertiary amine (A) include N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropyldiamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, N,N,N',N'',N''-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N'',N''-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylguanidine, and 1,3,5-tris(N,N-dimethylamino Examples include propyl)hexahydro-S-triazine, 1,8-diazabicyclo[5.4.0]undecene-7, triethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, or 1-dimethylaminopropylimidazole.

[0046] In a polyol-based liquid composition according to one aspect of the present disclosure, the content of tertiary amine (A) is not particularly limited, but in terms of excellent storage stability of the polyol-based liquid composition, it is usually in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass, per 100 parts by mass of polyol (D).

[0047] The secondary amine (B) having 2 to 12 carbon atoms is not particularly limited, but examples include dimethylamine, methylethylamine, diethylamine, ethylpropylamine, ethylisopropylamine, dipropylamine, diisopropylamine, dihexylamine, diethanolamine, dipropanolamine, or diisopropanolamine.

[0048] Regarding the secondary amine (B) having 2 to 12 carbon atoms, it is preferable that it is a secondary amine having 2 to 6 carbon atoms, more preferably a secondary monoamine having 2 to 6 carbon atoms, more preferably diethylamine, diisopropylamine, or diethanolamine, and most preferably diethylamine.

[0049] In a polyol-based liquid composition according to one aspect of the present disclosure, the content of the secondary amine (B) having 2 to 12 carbon atoms is not particularly limited, but in terms of excellent storage stability of the polyol-based liquid composition, it is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 1 part by mass per 100 parts by mass of polyol (D).

[0050] A polyol-based compound liquid composition according to one aspect of this disclosure is characterized by containing hydrochlorofluoroolefin (C).

[0051] In a polyol-based compound liquid composition according to one aspect of the present disclosure, the hydrochlorofluoroolefin (C) is not particularly limited, but for example, it is preferably one whose global warming potential (GWP) is 150 or less, more preferably 100 or less, and even more preferably 75 or less.

[0052] The aforementioned hydrochlorofluoroolefin (C) is not particularly limited, but for example, it is preferable that its ozone depletion potential (ODP) is 0.05 or less, more preferably 0.02 or less, and even more preferably 0.01 or less.

[0053] The aforementioned hydrochlorofluoroolefin (C) is not particularly limited, but examples include 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), 1-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224zb), and 2-chloro-3,3,3-trifluoropropene. (HCFO-1233xf), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb), 2-chloro-1,3,3-trifluoropropene (HCFO-1233xe), 2-chloro-1,1,3-trifluoropropene (HC FO-1233xc), 3-chloro-1,2,3-trifluoropropene (HCFO-1233ye), 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc), 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), 1,2,3-trichloro-3,3-difluoropropene Examples include (HCFO-1222xd), 2,3-dichloro-1,1-difluoropropene (HCFO-1232xc), 2,3,3-trichloro-3-fluoropropene (HCFO-1231xf), 1,3-dichloro-2,3,3-trifluoropropene (HCFO-1223yd), or 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc).

[0054] The aforementioned hydrochlorofluoroolefin (C) includes not only the hydrochlorofluoroolefin exemplified above, but also all structural isomers, geometric isomers, and stereoisomers of said hydrochlorofluoroolefin.

[0055] Furthermore, the hydrochlorofluoroolefin (C) mentioned above can be used individually or as a mixture of two or more types.

[0056] Of these hydrochlorofluoroolefins (C), trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) or 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) are preferred because they yield polyurethane foam with excellent thermal insulation properties.

[0057] In a polyol-based liquid composition according to one aspect of the present disclosure, the content of hydrochlorofluoroolefin (C) is not particularly limited, but can be 0.1 to 100 parts by mass per 100 parts by mass of polyol (D). However, it is preferably 0.1 to 50 parts by mass, and more preferably 0.1 to 20 parts by mass, in order to obtain a polyurethane foam with excellent heat insulation performance.

[0058] The aforementioned hydrochlorofluoroolefin (C) functions as a foaming agent.

[0059] In a polyol-based liquid composition according to one aspect of the present disclosure, the foaming agent may consist solely of hydrochlorofluoroolefin (C), or it may consist of hydrochlorofluoroolefin (C) and other foaming agents.

[0060] Other foaming agents mentioned above include, but are not limited to, water, formic acid, organic acid compounds (e.g., acetic acid, propionic acid, etc., which react with isocyanate groups to generate CO2), ethers, halogenated ethers, hydrocarbons (e.g., isobutane, n-pentane, isopentane, or cyclopentane), or hydrofluoroolefins.

[0061] The foaming agents exemplified can be used individually or in combination.

[0062] In a polyol-based liquid composition according to one aspect of the present disclosure, the content of the foaming agent is not particularly limited, but can be 0.1 to 100 parts by mass per 100 parts by mass of polyol (D). However, it is preferably 0.1 to 50 parts by mass, and more preferably 0.1 to 20 parts by mass, in order to obtain a polyurethane foam with excellent heat insulation performance.

[0063] As stated above, the entire amount of the blowing agent may be the hydrochlorofluoroolefin (C), or it may be a mixture of the hydrochlorofluoroolefin (C) and other blowing agents. When using a mixture of hydrochlorofluoroolefin (C) and other blowing agents, the content of hydrochlorofluoroolefin (C) in the blowing agent is preferably 5 to 90% by mass, more preferably 7 to 80% by mass, and more preferably 10 to 70% by mass, of the total mass of the blowing agent. Conversely, the content of the other blowing agents is preferably 10 to 95% by mass, more preferably 20 to 93% by mass, and more preferably 30 to 90% by mass, of the total weight of the blowing agent.

[0064] A polyol-based compound liquid composition according to one aspect of this disclosure is characterized by containing polyol (D).

[0065] The polyol (D) in a polyol-based liquid composition according to one aspect of this disclosure is not particularly limited, but examples include commonly known polyester polyols, polyether polyols, or polymer polyols. The polyol may be used alone or as a mixture.

[0066] Known polyester polyols typically include polymerization products of dibasic acids (e.g., adipic acid, phthalic acid, succinic acid, azelaic acid, sebacic acid, ricinoleic acid, etc.) and hydroxy compounds (e.g., glycols, etc.).

[0067] Specific examples of the polyester polyol include, but are not limited to, polyester polyols derived from by-products of DMT (dimethyl terephthalate) production or phthalic anhydride production, or polyester polyols derived from by-products of nylon production, TMP (trimethylolpropane) production, pentaerythritol production, or phthalic acid-based polyester production.

[0068] Examples of known polyether polyols include polyhydric alcohols (e.g., glycols, glycerin, pentaerythritol, trimethylolpropane, sorbitol, sucrose, etc.), aliphatic amine compounds (e.g., ammonia, ethylenediamine, ethanolamine, etc.), aromatic amine compounds (e.g., toluenediamine, diphenylmethane-4,4'-diamine, etc.), active hydrogen-containing compounds such as Mannich polyols, and those obtained by reacting these with ethylene oxide and / or propylene oxide.

[0069] Known polymer polyols include those obtained by reacting the above-mentioned polyether polyol with an ethylenically unsaturated monomer (e.g., butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst.

[0070] Of these polyols, polyether polyols or polyester polyols are preferred because they are suitable for the production of rigid polyurethane foam. Furthermore, in terms of suitability for the production of rigid polyurethane foam, the average functional value of the polyol is preferably 4 to 8, and the average hydroxyl value of the polyol is preferably 200 to 800 mg KOH / g, more preferably 300 to 700 mg KOH / g.

[0071] A polyol-based liquid composition according to one aspect of this disclosure is essential for (i) a tertiary amine (A), (ii) a secondary amine having 2 to 12 carbon atoms (B), (iii) a hydrochlorofluoroolefin (C), and (iv) a polyol (D), and may also contain other components (hereinafter referred to as "additives").

[0072] The aforementioned additives are not limited to, but examples include quaternary ammonium salt compounds, organometallic catalyst compounds, foam stabilizers, crosslinking agents, chain extenders, solvents, colorants, flame retardants, UV absorbers, or antioxidants.

[0073] The above-mentioned quaternary ammonium salt compounds are not particularly limited, but examples include tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetramethylammonium acetate, or tetraalkylammonium organic acid salts such as tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, or 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

[0074] The content of the quaternary ammonium salt compound is not particularly limited, but it can be 0.1 to 100 parts by mass when the polyol (D) is 100 parts by mass.

[0075] The aforementioned organometallic catalyst compounds are not particularly limited, but examples include stanus diacetate, stanus dioctoate, stanus dioleate, stanus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead octanoate, lead naphthenate, nickel naphthenate, or cobalt naphthenate.

[0076] The content of the organometallic catalyst compound is not particularly limited, but it can be 0.01 to 10 parts by mass when the polyol (D) is 100 parts by mass.

[0077] The foam stabilizers mentioned above are not particularly limited, but examples include known silicone foam stabilizers, and more specifically, examples include nonionic surfactants such as organosiloxane-polyoxyalkylene copolymers or silicone-grease copolymers. These silicone foam stabilizers can be used individually or as a mixture.

[0078] The above-mentioned crosslinking agents or chain extenders are not particularly limited, but examples include low molecular weight polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol, or glycerin; low molecular weight amine polyols such as diethanolamine or triethanolamine; or polyamines such as ethylenediamine, xylylenediamine, or methylenebisorthochloroaniline.

[0079] The content of the crosslinking agent or chain extender is not particularly limited, but it is preferably 70 parts by mass or less when the polyol (D) is 100 parts by mass.

[0080] The aforementioned solvent is not particularly limited, but examples include dipropylene glycol, ethylene glycol, or 1,4-butanediol.

[0081] The solvent is preferably used as a mismixture when mixing the aforementioned tertiary amine (A) with other tertiary amine compounds, quaternary ammonium salt compounds, and / or organometallic catalyst compounds.

[0082] The amount of the solvent is not particularly limited, but it is preferably 70% by mass or less, based on the total amount of the catalyst (representing the sum of tertiary amine (A), other tertiary amine compounds, quaternary ammonium salt compounds, and organometallic catalyst compounds) and the solvent being 100% by mass.

[0083] The catalyst prepared in this manner may be added to polyol (D) and used, or each catalyst component may be added to polyol (D) separately and used; there are no particular limitations.

[0084] Regarding the types of additives described above and their content in the polyol-based liquid composition, it is preferable to use commonly used types within the range of commonly used content.

[0085] A polyurethane resin can be produced by mixing and stirring a polyol-based liquid composition according to one aspect of this disclosure with a polyisocyanate and reacting the mixture. The polyurethane resin is not particularly limited, but examples include rigid polyurethane foam or isocyanurate-modified rigid polyurethane foam.

[0086] Examples of the above-mentioned polyisocyanates include known polyisocyanates, and more specifically, examples include aromatic polyisocyanates such as toluene diisocyanate (TDI), TDI derivatives, diphenylmethane diisocyanate (MDI), MDI derivatives, naphthylene diisocyanate, and xylylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, free isocyanate-containing prepolymers obtained by the reaction of the above-mentioned polyisocyanates with polyols, modified polyisocyanates such as carbodiimide-modified polyisocyanates, or mixed polyisocyanates thereof.

[0087] Examples of toluene diisocyanate (TDI) include 2,4-toluene diisocyanate or 2,6-toluene diisocyanate, which may be used alone or in mixtures. Examples of TDI derivatives include TDI prepolymers having terminal isocyanate groups, which are reaction products of TDI and polyols.

[0088] Examples of diphenylmethane diisocyanate (MDI) include 4,4'-diphenylmethane diisocyanate or 4,2'-diphenylmethane diisocyanate, which may be used alone or in mixtures. Examples of MDI derivatives include polyphenylpolymethylene diisocyanate, which is a polymer of MDI, or MDI prepolymers having terminal isocyanate groups, which are reaction products of MDI and polyols.

[0089] Of these, MDI or MDI derivatives are preferred because they are suitable for the manufacture of rigid polyurethane foam, and they may be used in mixtures.

[0090] Rigid polyurethane foam typically has a highly cross-linked, closed-cell structure and is a non-reversibly deformable foam, possessing properties entirely different from those of flexible and semi-rigid polyurethane foam. While the physical properties of rigid polyurethane foam are not particularly limited, they generally have a density of 20-100 kg / m³. 3 Preferably, the compressive strength is within the range of 0.5 to 10 kgf / cm². 2 It is preferable that the pressure be in the range of (50 to 1000 kPa).

[0091] Polyurethane resins produced using the polyol-based liquid composition of the present invention can be used for a variety of applications. For example, they can be used as thermal insulation building materials, insulation materials for freezers, and insulation materials for refrigerators. [Examples]

[0092] Examples are shown below, but the present invention is not limited to these examples. The analytical instruments and measurement methods used in these examples are listed below. Unless otherwise specified, the percentages "%" indicating the content in the following examples and comparative examples are based on mass.

[0093] (Evaluation methods for polyurethane foam) The following materials, other than the above-mentioned compounds, were used as raw materials related to the present invention.

[0094] Polyol A: STEPANPOL PS-3152 (Aromatic polyester polyol, OH value = 315 mg KOH / g, manufactured by Stepan) Polyol B: Puranol RF3776 (Mannich-type polyether polyol, OH value = 330 mg KOH / g, Jiahua Chemicals) Polyol C: YD-401P (Polyether polyol, OH value = 400 mg KOH / g, Yadong Chemical Group) Flame retardant: TMCPP (containing halogenated phosphate ester, manufactured by Daihachi Chemical Industry Co., Ltd.) Foam stabilizer: NIAX® SILICONE L-5420 (Silicone foam stabilizer, manufactured by Momentive Performance Materials Japan LLC) Foaming agent A: Solstice® LBA (1-chloro-3,3,3-trifluoropropene, manufactured by Honeywell Japan Ltd.) Foaming agent B: Water Tertiary amine (A): N,N,N',N'-tetraethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) Secondary amines with 2 to 12 carbon atoms (B): Diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) Polyisocyanate solution: Polymeric MDI (manufactured by Tosoh Corporation, Millionate® MR200, NCO content = 31.0%) Example 1. 35 parts by mass of polyol A as polyol (D), 15 parts by mass of polyol B, 50 parts by mass of polyol C, 25 parts by mass of flame retardant, 2.0 parts by mass of foam stabilizer, 1.0 part by mass of foaming agent B (water), 3.9 parts by mass of N,N,N',N'-tetraethylethylenediamine as tertiary amine (A), and 0.2 parts by mass of diethylamine as secondary amine (B) having 2 to 12 carbon atoms were weighed and thoroughly stirred to obtain a mixture. Next, 15 parts by mass of foaming agent A as hydrochlorofluoroolefin (C) was weighed and mixed with the mixture, and quickly stirred to produce the polyol-based liquid composition of the present invention.

[0095] 40.0 g of the aforementioned polyol-based liquid composition, which had been heated to 20°C, was placed in a 300 ml polyethylene cup. Then, 40.0 g of polyisocyanate solution (Millionate MR200), also heated to 20°C (corresponding to an amount that results in an isocyanate index [[isocyanate group] / [OH group] (molar ratio) × 100)] of 144 was added, and the mixture was quickly stirred at 6000 rpm for 2 seconds. Immediately afterward, the stirred mixture was transferred to a 1 L polyethylene cup heated to 23°C to carry out the foaming reaction, and the reactivity during foaming was measured using the method shown below. Furthermore, the core density of the rigid polyurethane foam obtained after the reaction had progressed sufficiently (more than 20 hours had passed since the start of the reaction) was measured using the method shown below. [Measurement of reactivity] • Cream Time: The time from the start of stirring of the polyol-based liquid composition and polyisocyanate liquid to the point when the mixed liquid turns white and the foam begins to expand is measured visually. [Core density of polyurethane foam] • Core density: The core density was determined by cutting out a 10 x 6 x 6 cm section from the center of the hardened foam in a 1L polyethylene cup and measuring its mass.

[0096] Next, the polyol-based liquid composition prepared by the above method was placed in a sealed container and stored in a constant temperature room at 50°C for 7, 14, and 28 days. After that, the foaming reaction was carried out under the same conditions as above, and the [reactivity measurement] and [core density of polyurethane foam] were evaluated.

[0097] Example 2. 35 parts by mass of polyol A as polyol (D), 15 parts by mass of polyol B, 50 parts by mass of polyol C, 25 parts by mass of flame retardant, 2.0 parts by mass of foam stabilizer, 1.0 part by mass of foaming agent B (water), 3.7 parts by mass of N,N,N',N'-tetraethylethylenediamine as tertiary amine (A), and 0.4 parts by mass of diethylamine as secondary amine (B) having 2 to 12 carbon atoms were weighed and thoroughly stirred to obtain a mixture. Next, 15 parts by mass of foaming agent A as hydrochlorofluoroolefin (C) was weighed and mixed with the mixture, and quickly stirred to produce the polyol-based liquid composition of the present invention.

[0098] 40.0 g of the aforementioned polyol-based liquid composition, which had been heated to 20°C, was placed in a 300 ml polyethylene cup. Then, 40.0 g of polyisocyanate liquid (Millionate MR200), also heated to 20°C (corresponding to an amount that results in an isocyanate index [[isocyanate group] / [OH group] (molar ratio) × 100)] of 144 was added, and the mixture was quickly stirred at 6000 rpm for 2 seconds. Immediately afterward, the stirred mixture was transferred to a 1 L polyethylene cup heated to 23°C to carry out the foaming reaction, and the reactivity during foaming was measured using the method shown in Example 1 above. Furthermore, the core density of the rigid polyurethane foam obtained after the reaction had progressed sufficiently (more than 20 hours had elapsed since the start of the reaction) was measured using the method shown in Example 1 above.

[0099] Next, the polyol-based liquid composition prepared by the above method was placed in a sealed container and stored in a constant temperature room at 50°C for 7, 14, and 28 days. After that, the foaming reaction was carried out under the same conditions as above, and the [reactivity measurement] and [core density of polyurethane foam] were evaluated.

[0100] Comparative Example 1. 35 parts by mass of polyol A, 15 parts by mass of polyol B, 50 parts by mass of polyol C, 25 parts by mass of flame retardant, 2.0 parts by mass of foam stabilizer, 1.0 part by mass of blowing agent B (water), and 4.1 parts by mass of N,N,N',N'-tetraethylethylenediamine as tertiary amine (A) were weighed and thoroughly stirred to obtain a mixture. Next, 15 parts by mass of blowing agent A as hydrochlorofluoroolefin (C) was weighed and mixed with the mixture, and quickly stirred to produce a polyol-based liquid composition. This polyol-based liquid composition does not contain a secondary amine (B) having 2 to 12 carbon atoms.

[0101] 40.0 g of the aforementioned polyol-based liquid composition, which had been heated to 20°C, was placed in a 300 ml polyethylene cup. Then, 40.0 g of polyisocyanate liquid (Millionate MR200), also heated to 20°C (corresponding to an amount that results in an isocyanate index [[isocyanate group] / [OH group] (molar ratio) × 100)] of 144 was added, and the mixture was quickly stirred at 6000 rpm for 2 seconds. Immediately afterward, the stirred mixture was transferred to a 1 L polyethylene cup heated to 23°C to carry out the foaming reaction, and the reactivity during foaming was measured using the method shown in Example 1 above. Furthermore, the core density of the rigid polyurethane foam obtained after the reaction had progressed sufficiently (more than 20 hours had elapsed since the start of the reaction) was measured using the method shown in Example 1 above.

[0102] Next, the polyol-based liquid composition prepared by the above method was placed in a sealed container and stored in a constant temperature room at 50°C for 7, 14, and 28 days. After that, the foaming reaction was carried out under the same conditions as above, and the [reactivity measurement] and [core density of polyurethane foam] were evaluated.

[0103] The results for Examples 1 and 2 and Comparative Example 1 are shown in Table 1.

[0104] [Table 1]

[0105] As is clear from Table 1, Examples 1 and 2, which used polyol-based liquid compositions corresponding to the present invention, showed a lower foam core density than Comparative Example 1, which does not correspond to the present invention. Furthermore, Examples 1 and 2 were found to maintain good initial foaming properties even after storage, and also exhibited good curing properties.

[0106] Based on the above, the polyol-based liquid composition of the present invention can reduce foam density without increasing the amount of hydrochlorofluoroolefin blowing agent. Furthermore, the polyol-based liquid composition of the present invention has excellent long-term storage stability and can be used industrially.

Claims

1. A polyol-based compounding liquid composition for manufacturing polyurethane foam, characterized by comprising the following (i), (ii), (iii), and (iv). (i) Tertiary amine (A) (ii) Secondary amines with 2 to 12 carbon atoms (B) (iii) Hydrochlorofluoroolefin (C) (iv) Polyol (D)

2. The aforementioned hydrochlorofluoroolefin (C) is 1-chloro-2,3,3,3-tetrafluoropropene, 2-chloro-1,3,3,3-tetrafluoropropene, 1-chloro-1,3,3,3-tetrafluoropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-2,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene, 1-chloro-1,3,3-trifluoropropene, 2-chloro-1,3,3-trifluoropropene, 2-chloro-1,1,3-trifluoropropene, 3-chloro-1,2,3- The composition according to claim 1, wherein one or more are selected from the group consisting of trifluoropropene, 3-chloro-1,1,2-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, 2,3-dichloro-3,3-difluoropropene, 1,2,3-trichloro-3,3-difluoropropene, 2,3-dichloro-1,1-difluoropropene, 2,3,3-trichloro-3-fluoropropene, 1,3-dichloro-2,3,3-trifluoropropene, and 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene.

3. The composition according to claim 1, wherein the hydrochlorofluoroolefin (C) is trans-1-chloro-3,3,3-trifluoropropene or 1-chloro-2,3,3,3-tetrafluoropropene.

4. The composition according to claim 1, wherein the secondary amine (B) having 2 to 12 carbon atoms is a secondary amine having 2 to 6 carbon atoms.

5. The composition according to claim 1, wherein the tertiary amine (A) is a tertiary amine represented by the following formula (1). 【Chemistry 1】 [In the above formula (1), R １ , R ２ Each of these independently represents an alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms. Z is 【Chemistry 2】 Represents the above R ３ , R ４ Each of these independently represents an alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms. X is 【Transformation 3】 Represents R ５ R represents an alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms. １ or R ２ and R ５ These may combine to form an alkylene group having 2 to 8 carbon atoms. m and n each independently represent an integer from 2 to 6, and a represents an integer from 0 to 5.

6. A method for producing polyurethane foam, characterized by reacting a composition according to any one of claims 1 to 5 with a polyisocyanate compound.

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