Polyol-based compounding liquid composition for the manufacture of hydrochlorofluoroolefin foamed polyurethane foam, and its applications

Abstract

To provide a polyol-based mixed liquid composition that, in the production of a hydrochlorofluoroolefin polyurethane foam using an amine catalyst, causes the foaming reaction of mixed liquid to rapidly start and suppresses dripping in a spraying process, and a method for producing a polyurethane foam.SOLUTION: A polyol-based mixed liquid composition is for producing a polyurethane foam and includes (i) a carbonate (A) of an amine compound having an amino group of a specific structure at each end of a linear hydrocarbon group or an amine compound having an amino group of a specific structure at each end of a diethyl ether structure, (ii) a foamer comprising a hydrochlorofluoroolefin (B), and (iii) a polyol (C).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyol-based compounding liquid used in the production of hydrofluorochloroolefin foamed polyurethane foam. More specifically, it relates to a polyol-based compounding liquid composition containing a polyol, hydrofluorochloroolefins, and a specific amine carbonate, which has excellent initial foaming properties and storage stability, and a method for producing a polyurethane foam using the polyol-based compounding liquid composition and an organic polyisocyanate.

Background Art

[0002] Polyurethane foam can be produced by the reaction of a polyol and an isocyanate. Typically, a production method can be cited in which a polyol-based compounding liquid containing a tertiary amine catalyst, a foaming agent, a surfactant, etc. is reacted with an organic polyisocyanate. In this production method of the polyurethane foam, it is important to mix and contact the polyol-based compounding liquid 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 liquid spray-coated on the wall surface or the like.

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

[0004] Hydrochlorofluorocarbons are known to decompose over time under the action of the above-mentioned tertiary amine catalysts, and due to the influence of acids such as hydrofluoric acid and hydrochloric acid generated during the decomposition, the reaction between the polyol-based composition and the organic polyisocyanate is known to slow down. For this reason, long-term storage of polyol-based formulations containing hydrochlorofluorocarbons has been difficult, and there has been a problem that industrial use is difficult.

[0005] As methods for solving the above problems, an example of using an organic acid-containing amine catalyst (Patent Document 1) and an example of using a sterically hindered amine catalyst (Patent Document 2) have been proposed.

[0006] Also, although unrelated to the above problems, a method of using carbonates of primary and secondary amines is known as a technique for refining the cells of polyurethane foam (see Patent Document 3). [[ID=io]]

[0007] Also, although unrelated to the above problems, a composite blowing agent containing a mixture of hexafluorobutene and an alkanolamine salt has been proposed (Patent Document 4).

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0009] In examples using the organic acid-containing amine catalyst described in Patent Document 1 and the sterically hindered amine catalyst described in Patent Document 2, there is a problem in that the mixed solution does not start the foaming reaction quickly, which leads to the problem of dripping in spray application methods. [Means for solving the problem]

[0010] As a result of diligent research to solve the above-mentioned problems, the present inventors found that incorporating a specific amine compound carbonate into a polyol-based compounding solution for the production of hydrochlorofluoroolefin foamed polyurethane foam is effective in solving the problems, and thus completed the present invention.

[0011] In other words, the present invention relates to a polyol-based compounding liquid composition for the production of hydrochlorofluoroolefin foamed polyurethane foam as described below, or to a method for producing polyurethane foam using the polyol-based compounding liquid composition.

[0012] [1] A polyol-based compounding liquid composition for manufacturing polyurethane foam, (i) A carbonate (A) of an amine compound represented by the following general formula (1), (2), or (4), (ii) A foaming agent containing hydrochlorofluoroolefin (B), (iii) Polyol (C) A composition containing the following:

[0013] [ka]

[0014] (In the above formula, R 1 and R 2 Each of these independently represents an alkyl group having 2 to 6 carbon atoms, which may have a hydroxyl group. R 1 and R 2 These may be bonded to each other to form a morpholine ring. m represents an integer between 0 and 4.

[0015] [Chemical formula]

[0016] (In the above formula, R 3 and R 4 each independently represent an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group. R 3 and R 4 may be bonded to each other to form a morpholine ring. m represents an integer from 0 to 4. R 5 is an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group, or the following general formula (3)

[0017] [Chemical formula]

[0018] (In the above formula, * represents the linking site in formula (2). R 6 and R 7 each independently represent an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group. R 6 and R 7 may be bonded to each other to form a morpholine ring. m represents an integer from 0 to 4.) represents a group represented by.)

[0019] [Chemical formula]

[0020] (In the formula, R 8 and R 9 each independently represent an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group. R 8 and R 9 may be bonded to each other to form a morpholine ring. R10 This represents an alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or a hydroxyl group. R 11 This is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group, or the following general formula (5)

[0021] [ka]

[0022] (In the formula, * represents the connection point in general formula (4). R 12 represents a hydrogen atom or a methyl group. n represents an integer between 0 and 2. (Represents the base represented by .) [2] In the above general formula (1), -NR 1 R 2 The composition according to [1] above, characterized in that the group represented by is a diethylamino group, an ethyl(n-propyl)amino group, a di(n-propyl)amino group, or a morpholino group.

[0023] [3] In the general formulas (2) and (3) above, -NR 3 R 4 , and -NR 6 R 7 The composition according to [1], characterized in that at least one of the groups represented by is a dimethylamino group, a diethylamino group, an ethyl(n-propyl)amino group, a di(n-propyl)amino group, or a morpholino group.

[0024] [4] In the general formula (4) above, -NR 8 R 9 The composition according to [1] above, characterized in that the group represented by is a dimethylamino group, a diethylamino group, an ethyl(n-propyl)amino group, a di(n-propyl)amino group, or a morpholino group.

[0025] [5] The carbonate (A) of the amine compound represented by the above general formula (1), (2), or (4) is N,N-diethyl-1,2-ethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-diisopropyl-1,2-ethylenediamine, N,N-isopropyl-1,3-diaminopropane, 4-(2-aminoethyl)morpholine, N-(3-aminopropyl)morpholine, N-(2-aminopropyl)morpholine, N,N-diethyl-N'-methyl-1,2-ethylenediamine, N,N,N'-triethyl-1,2-ethylenediamine, N,N-diethyl-N'-methyl-1,3-propanediamine, N,N,N'-triethyl-1,3-propanediamine, N,N-diethyl-N'-methyl-1,4-butanediamine, N,N,N'-triethyl-1,4-butanediamine, 4-(2-aminoethyl)morpholine, N-(3-aminopropyl)morpholine, N-(2-aminopropyl)morpholine, 3,3'-iminobis(N,N-dimethylpropylamine), 3,3'-iminobis(N,N-diethylpropylamine), 2,2'-iminobis(N,N-diethylethylamine), N-(3-aminopropyl)-N,N',N'-trimethyl-[2,2'-oxybis(ethylamine)], N-(3-aminopropyl)-N,N',N'-triethyl-[2,2'-oxybis(ethylamine)], and [2-[2-(diethylamino)ethoxy]ethyl](ethyl)amine The composition according to [1] above, wherein (A) is a carbonate of one or more amine compounds selected from the group consisting of the following.

[0026] [6] The carbonate (A) of the amine compound represented by the above general formula (1), (2), or (4) is N,N-diethyl-1,2-ethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-diisopropyl-1,2-ethylenediamine, 3,3'-Iminobis(N,N-dimethylpropylamine), 3,3'-Iminobis(N,N-diethylpropylamine), 2,2'-Iminobis(N,N-diethylethylamine), N-(3-aminopropyl)-N,N',N'-trimethyl-[2,2'-oxybis(ethylamine)], N-(3-aminopropyl)-N,N',N'-triethyl-[2,2'-oxybis(ethylamine)], and [2-[2-(diethylamino)ethoxy]ethyl](ethyl)amine The composition according to [1] above, wherein (A) is a carbonate of one or more amine compounds selected from the group consisting of the following.

[0027] [7] The aforementioned hydrochlorofluoroolefin (B) 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-trifluoropropene The composition according to [1] above, characterized by being one or more selected from the group consisting of ruolopropene, 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.

[0028] [8] The composition according to [1], wherein the hydrochlorofluoroolefin (B) is trans-1-chloro-3,3,3-trifluoropropene or 1-chloro-2,3,3,3-tetrafluoropropene.

[0029] [9] The composition according to [1], characterized in that the carbonate (A) of the amine compound represented by the general formula (1), (2), or (4) is in the range of 2 to 30 parts by weight per 100 parts by weight of the amine compound represented by the general formula (1), (2), or (4).

[0030]

[10] The composition according to [1], wherein the weight ratio of component (A) to (C) is 2 to 6 parts by weight of component (A) per 100 parts by weight of component (C).

[0031]

[11] The composition according to [1], wherein the weight ratio of component (B) to (C) is 10 to 30 parts by weight of component (B) per 100 parts by weight of component (C).

[0032]

[12] A method for producing polyurethane foam, characterized by reacting a composition described in any of the above [1] to

[11] with a polyisocyanate compound. [Effects of the Invention]

[0033] Compared to conventional polyol-based formulations using organic acid-containing amine catalysts and sterically hindered amine catalysts, the polyol-based formulation of the present invention can initiate a rapid foaming reaction and suppress dripping during spray application.

[0034] Furthermore, compared to conventional polyol-based formulations using a composite foaming agent containing primary and secondary amine carbonates and alkanolamine salts, the polyol-based formulation of the present invention can suppress the degradation of hydrochlorofluoroolefins over time, enabling longer-term storage.

[0035] For the reasons stated above, the polyol-based compound liquid of the present invention offers the exceptional advantage of enabling a rapid foaming reaction without dripping, even in cold seasons, particularly in spray application methods, and maintaining quality for extended periods even in hot seasons. This allows for the stable production of high-quality hydrochlorofluoroolefin foamed polyurethane foam without being affected by changes in ambient temperature. [Modes for carrying out the invention]

[0036] Next, the present invention will be described in detail.

[0037] One aspect of the present invention relates to a polyol-based compounding liquid composition for manufacturing polyurethane foam.

[0038] The polyol-based compounding liquid composition for the manufacture of polyurethane foam of the present invention is characterized by comprising (i) a carbonate (A) of an amine compound represented by the following general formula (1), (2), or (4), (ii) a blowing agent containing a hydrochlorofluoroolefin (B), and (iii) a polyol (C).

[0039] The amine compounds represented by the general formula (1) above are as follows:

[0040] [ka]

[0041] (In the above formula, R 1 and R 2 Each of these independently represents an alkyl group having 2 to 6 carbon atoms, which may have a hydroxyl group. R 1 and R 2 These may be bonded to each other to form a morpholine ring. m represents an integer between 0 and 4. The amine compounds represented by the general formula (2) above are as follows:

[0042] [ka]

[0043] (In the above formula, R 3 and R 4 Each of these independently represents an alkyl group having 1 to 6 carbon atoms, which may have a hydroxyl group. R 3 and R 4 These may be bonded to each other to form a morpholine ring. m represents an integer between 0 and 4. R 5 This is an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group, or the following general formula (3)

[0044] [ka]

[0045] (In the above formula, * represents the connecting part in formula (2). R 6 and R 7 Each of these independently represents an alkyl group having 1 to 6 carbon atoms, which may have a hydroxyl group. R 6 and R 7 These may be bonded to each other to form a morpholine ring. m represents an integer between 0 and 4. (Represents the base represented by .) The amine compounds represented by the general formula (4) above are as follows:

[0046] [ka]

[0047] (In the formula, R 8 and R 9 Each of these independently represents an alkyl group having 1 to 6 carbon atoms, which may have a hydroxyl group. R 8 and R 9 These may be bonded to each other to form a morpholine ring. R 10This represents an alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or a hydroxyl group. R 11 This is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group, or the following general formula (5)

[0048] [ka]

[0049] (In the formula, * represents the connection point in general formula (4). R 12 represents a hydrogen atom or a methyl group. n represents an integer between 0 and 2. (Represents the base represented by .) The definitions in the above general formulas (1), (2), (3), (4), and (5) will now be explained.

[0050] In general formula (1), R 1 and R 2 Each of these independently represents an alkyl group having 2 to 6 carbon atoms, which may have a hydroxyl group.

[0051] The C2-C6 alkyl group which may have a hydroxyl group can be rephrased as an ethyl group which may have a hydroxyl group, or a linear, branched, or cyclic alkyl group which may have a hydroxyl group and has C3-C6, and is not particularly limited, but examples include ethyl group, 2-hydroxyethyl group, n-propyl group, i-propyl group, cyclopropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, cyclobutyl group, 2-hydroxybutyl group, pentyl group, 2-hydroxypentyl group, hexyl group, cyclohexyl group, or 2-hydroxyhexyl group.

[0052] Furthermore, as stated above, in general formula (1), R 1 and R 2 These may be bonded to each other to form a morpholine ring.

[0053] In general formula (1), m represents an integer between 0 and 4.

[0054] In general formula (1), m independently represents an integer from 0 to 4, but from the viewpoint of improving the storage stability of polyol-based compounding liquids for the manufacture of polyurethane foam containing hydrochlorofluoroolefin, it is preferable that each independent value be an integer from 0 to 2, more preferably 0, 1, or 2, and even more preferably 0 or 1.

[0055] Regarding the amine compound represented by the above general formula (1), from the viewpoint of improving the storage stability of polyol-based compounding solutions for the manufacture of polyurethane foam containing hydrochlorofluoroolefins, the general formula (1) is defined as -NR 1 R 2 The group represented is preferably a diethylamino group, an ethyl(n-propyl)amino group, a di(n-propyl)amino group, or a morpholino group.

[0056] With respect to the carbonate of the amine compound represented by the general formula (1) above, from the viewpoint of improving the storage stability of polyol-based compounding solutions for the production of polyurethane foam containing hydrochlorofluoroolefins, it is preferable that the carbonate is one or more amine compounds selected from the group consisting of N,N-diethyl-1,2-ethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-diisopropyl-1,2-ethylenediamine, N,N-isopropyl-1,3-diaminopropane, 4-(2-aminoethyl)morpholine, N-(3-aminopropyl)morpholine, and N-(2-aminopropyl)morpholine, and more preferably that it is a carbonate of N,N-diethyl-1,2-ethylenediamine, a carbonate of N,N-diethyl-1,3-diaminopropane, or a carbonate of N,N-diisopropyl-1,2-ethylenediamine.

[0057] In general formulas (2) and (3), R 3 , R 4 , R 5 , R 6, and R 7 The C1-C6 alkyl group which may have a hydroxyl group can be rephrased as a C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 ethyl group which may have a hydroxyl group, or a linear, branched, or cyclic alkyl group which may have a hydroxyl group, and is not particularly limited, but examples include a C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 alkyl group which may have a hydroxyl group, and is not particularly limited, but examples include a C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 alkyl group which may have a hydroxyl group, and a C1-C6 alkyl group which may have a hydroxyl group.

[0058] Furthermore, as stated above, in general formulas (2) and (3), R 3 and R 4 , and R 6 and R 7 These may be bonded to each other to form a morpholine ring.

[0059] In general formulas (2) and (3), m independently represents an integer from 0 to 4. However, from the viewpoint of improving the storage stability of polyol-based compounding liquids for the manufacture of polyurethane foam containing hydrochlorofluoroolefins, it is preferable that each m independently be an integer from 0 to 2, more preferably 0, 1, or 2, and even more preferably 0 or 1.

[0060] Regarding the amine compounds represented by the above general formula (2), from the viewpoint of improving the storage stability of polyol-based compounding solutions for the manufacture of polyurethane foam containing hydrochlorofluoroolefins, in general formulas (2) and (3), -NR 3 R 4 , and -NR 6 R 7 Preferably, at least one of the groups represented is a dimethylamino group, a diethylamino group, an ethyl(n-propyl)amino group, a di(n-propyl)amino group, or a morpholino group.

[0061] Regarding the carbonates of the amine compounds represented by the above general formula (2), from the viewpoint of improving the storage stability of polyol-based formulations for the manufacture of polyurethane foam containing hydrochlorofluoroolefins, N,N-diethyl-N'-methyl-1,2-ethylenediamine, N,N-diethyl-N'-methyl-1,2-ethylenediamine, N,N-diethyl-N'-methyl-1,3-propanediamine, N,N,N'-triethyl-1,3-propanediamine, N,N-diethyl-N'-methyl-1,4-butanediamine, N,N,N'-triethyl-1,4-butanediamine, 4-(2-aminoethyl)morpholine, N- It is preferable that the carbonate is one or more amine compounds selected from the group consisting of (3-aminopropyl)morpholine, N-(2-aminopropyl)morpholine, 3,3'-iminobis(N,N-dimethylpropylamine), 3,3'-iminobis(N,N-diethylpropylamine), and 2,2'-iminobis(N,N-diethylethylamine), and more preferably a carbonate of 3,3'-iminobis(N,N-dimethylpropylamine), a carbonate of 3,3'-iminobis(N,N-diethylpropylamine), or a carbonate of 2,2'-iminobis(N,N-diethylethylamine).

[0062] In general formula (4), R 8 , R 9 , R 10 , and R 11 The C1-C6 alkyl group which may have a hydroxyl group can be rephrased as a C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 ethyl group which may have a hydroxyl group, or a linear, branched, or cyclic alkyl group which may have a hydroxyl group, and is not particularly limited, but examples include a C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 alkyl group which may have a hydroxyl group, and is not particularly limited, but examples include a C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 alkyl group which may have a hydroxyl group, an C1-C6 alkyl group which may have a hydroxyl group, and a C1-C6 alkyl group which may have a hydroxyl group.

[0063] Furthermore, as stated above, in general formula (4), R 8 and R 9 These may be bonded to each other to form a morpholine ring.

[0064] In general formula (5), n represents an integer from 0 to 2, but from the viewpoint of improving the storage stability of polyol-based compounding liquids for the manufacture of polyurethane foam containing hydrochlorofluoroolefin, it is more preferably 1 or 2, and more preferably 2.

[0065] Regarding the amine compound represented by the above general formula (4), from the viewpoint of improving the storage stability of polyol-based compounding solutions for the manufacture of polyurethane foam containing hydrochlorofluoroolefins, the general formula (4) is represented as -NR 8 R 9 The group represented is preferably a dimethylamino group, a diethylamino group, an ethyl(n-propyl)amino group, a di(n-propyl)amino group, an imidazole group, or a morpholino group.

[0066] With respect to the carbonate of the amine compound represented by the general formula (4) above, it is more preferable that it be a carbonate (A) of one or more amine compounds selected from the group consisting of N-(3-aminopropyl)-N,N',N'-trimethyl-[2,2'-oxybis(ethylamine)], N-(3-aminopropyl)-N,N',N'-triethyl-[2,2'-oxybis(ethylamine)], and [2-[2-(diethylamino)ethoxy]ethyl](ethyl)amine.

[0067] As stated above, with respect to the carbonate (A) of the amine compound represented by the general formula (1), (2), or (4) above, from the viewpoint of initial foaming properties during the manufacture of polyurethane foam, N,N-diethyl-1,2-ethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-diisopropyl-1,2-ethylenediamine, N,N-isopropyl-1,3-diaminopropane, N,N-diethyl-N'-methyl-1,2-ethylenediamine, N,N,N'-triethyl-1,2-ethylenediamine, N,N-diethyl-N'-methyl-1,3-propanediamine, N,N,N'-triethyl-1,3-propanediamine, N,N-diethyl-N'-methyl-1,4-butanediamine, N,N,N'-triethyl-1,4-butanediamine, 4-(2-aminoethyl)morpholine, N-(3-aminopropyl)morpholine, N-(2-aminopropyl)morpholine, 3,3'-Iminobis(N,N-dimethylpropylamine), 3,3'-Iminobis(N,N-diethylpropylamine), 2,2'-Iminobis(N,N-diethylethylamine), N-(3-aminopropyl)-N,N',N'-trimethyl-2,2'-oxybis(ethylamine), N-(3-aminopropyl)-N,N',N'-triethyl-2,2'-oxybis(ethylamine), and [2-[2-(diethylamino)ethoxy]ethyl](ethyl)amine It is preferably a carbonate (A) of one or more amine compounds selected from the group consisting of the following: N,N-diethyl-1,2-ethylenediamine, N,N-diisopropyl-1,2-ethylenediamine, N,N-diethyl-1,3-diaminopropane, 3,3'-Iminobis(N,N-dimethylpropylamine), 3,3'-Iminobis(N,N-diethylpropylamine), 2,2'-Iminobis(N,N-diethylethylamine), N-(3-aminopropyl)-N,N',N'-trimethyl-2,2'-oxybis(ethylamine), N-(3-aminopropyl)-N,N',N'-triethyl-2,2'-oxybis(ethylamine), and [2-[2-(diethylamino)ethoxy]ethyl](ethyl)amine It is more preferable that it is a carbonate (A) of one or more amine compounds selected from the group consisting of the following: Particularly preferred are carbonates of N,N-diethylethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-diisopropyl-1,2-ethylenediamine, 3,3'-iminobis(N,N-dimethylpropylamine), or N-(3-aminopropyl)-N,N',N'-trimethyl-[2,2'-oxybis(ethylamine)].

[0068] The carbonate (A) of the amine compound mentioned above refers to a mixture of the amine compound and carbon dioxide. In the carbonate (A) of the amine compound, the mixing ratio of the amine compound and carbon dioxide is not particularly limited, but for example, in terms of excellent foaming properties of polyurethane foam, it is preferable that the amount of carbon dioxide is 0.1 to 1.0 moles per amino group of the amine compound, and more preferably 0.2 to 0.5 moles per amino group of the amine compound. For example, in the case of an amine compound having two amino groups, it is preferable that the amount of carbon dioxide mixed is 0.2 to 2 moles per mole of the amine compound, and more preferably 0.4 to 1.0 moles. In the case of an amine compound having three amino groups, it is preferable that the amount of carbon dioxide mixed is 0.3 to 3 moles per mole of the amine compound, and more preferably 0.6 to 1.5 moles.

[0069] Furthermore, in the carbonate (A) of the amine compound, the carbon dioxide content, which is a component of the carbonate, is not particularly limited, but for example, in terms of excellent foaming properties of polyurethane foam, it is preferably in the range of 1 to 50 parts by weight, more preferably 1 to 40 parts by weight, more preferably 2 to 30 parts by weight, and more preferably 3 to 20 parts by weight per 100 parts by weight of the amine compound.

[0070] As described above, the polyol-based compounding liquid composition for the manufacture of polyurethane foam of the present invention is characterized by comprising (i) a carbonate (A) of an amine compound represented by the general formula (1), (2), or (4) above, (ii) a blowing agent containing a hydrochlorofluoroolefin (B), and (iii) a polyol (C). The carbonate (A) of the amine compound represented by the general formula (1), (2), or (4) above may be used without a solvent or dissolved in a solvent (containing a solvent).

[0071] If the carbonate (A) of the amine compound represented by the general formula (1), (2), or (4) is a solid at room temperature, it is preferable to use it dissolved in a solvent for ease of handling. The solvent is not particularly limited and examples include water, ethylene glycol, diethylene glycol, dipropylene glycol, or butanediol. In this case, if the carbonate (A) of the amine compound represented by the general formula (1), (2), or (4) contains these solvents, the polyol-based compound liquid composition for the manufacture of polyurethane foam of the present invention will further contain these solvents in addition to (i), (ii), and (iii) above. The solvent component may be used as part of the polyol, blowing agent, or crosslinking agent described later.

[0072] When using a carbonate (A) of the amine compound represented by the general formula (1), (2), or (4) above that contains a solvent, the amount of the solvent is not particularly limited, but in order to minimize the effect on the foam properties, it is preferably 50% by weight or less, more preferably 20% by weight or less, and even more preferably 10% by weight or less, relative to the total weight of the carbonate (A) of the amine compound and the solvent.

[0073] The polyol-based liquid composition of the present invention is characterized by containing polyol (C).

[0074] The polyol (C) in the polyol-based liquid composition of the present invention 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.

[0075] 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.). Specific examples of such polyester polyols are not limited to those mentioned above, but include, for example, 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.

[0076] 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.

[0077] 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.

[0078] Of these polyols, polyethers or polyester polyols are preferred because they are suitable for the production of rigid polyurethane foam. Furthermore, for suitability in 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.

[0079] In the polyol-based liquid composition of the present invention, the content of the carbonate (A) of the amine compound represented by the general formula (1), (2), or (4) is not particularly limited, but is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, more preferably 0.1 to 10 parts by weight, more preferably 2 to 6 parts by weight, and more preferably 3 to 5 parts by weight, when the polyol (C) is 100 parts by weight.

[0080] The polyol-based liquid composition of the present invention is characterized by containing a foaming agent comprising hydrochlorofluoroolefin (B).

[0081] The hydrochlorofluoroolefin (B) mentioned above is not particularly limited, but for example, it is preferable that its global warming potential (GWP) is 150 or less, more preferably 100 or less, and even more preferably 75 or less.

[0082] The hydrochlorofluoroolefin (B) mentioned above 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.

[0083] The aforementioned hydrochlorofluoroolefin (B) 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). The hydrochlorofluoroolefins exemplified above encompass all structural isomers, geometric isomers, and stereoisomers. Hydrochlorofluoroolefin (B) can be used individually or as a mixture of two or more of the examples given above.

[0084] Of these hydrochlorofluoroolefins (B), trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) or 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) are preferred due to their excellent thermal insulation performance in polyurethane foam. Note that the hydrochlorofluoroolefins (B) exemplified above can be used individually or as a mixture of two or more.

[0085] The blowing agent containing the aforementioned hydrochlorofluoroolefin (B) may consist solely of hydrochlorofluoroolefin (B), or it may consist of hydrochlorofluoroolefin (B) and other blowing agents.

[0086] Other blowing agents mentioned above are not limited to, but include, for example, 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. These other blowing agents can be used individually or in combination.

[0087] As stated above, the entire amount of the blowing agent may be the hydrochlorofluoroolefin (B) described above, or it may be a mixture of the hydrochlorofluoroolefin (B) and other blowing agents. When a mixture of hydrochlorofluoroolefin (B) and other blowing agents is used, the content of hydrochlorofluoroolefin (B) in the blowing agent is preferably 5 to 90% by weight, more preferably 7 to 80% by weight, and more preferably 10 to 70% by weight, of the total weight of the blowing agent. Conversely, the content of the other blowing agents is preferably 10 to 95% by weight, more preferably 20 to 93% by weight, and more preferably 30 to 90% by weight, of the total weight of the blowing agent.

[0088] In the polyol-based liquid composition of the present invention, the content of the blowing agent containing hydrochlorofluoroolefin (B) is not particularly limited, but can be 0.1 to 100 parts by weight when polyol (C) is 100 parts by weight. However, from the viewpoint of the thermal insulation performance of the polyurethane foam, it is preferably 1 to 50 parts by weight, more preferably 10 to 30 parts by weight, and more preferably 15 to 25 parts by weight.

[0089] The polyol-based liquid composition of the present invention may contain components other than those listed above ((i), (ii), (iii), solvent, and other foaming agents), and is not particularly limited, but examples include quaternary ammonium salt compounds, organometallic catalyst compounds, foam stabilizers, crosslinking agents, chain extenders, solvents, colorants, flame retardants, antioxidants, and other known additives.

[0090] 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, tetraalkylammonium organic acid salts such as tetramethylammonium acetate and tetramethylammonium 2-ethylhexanoate, and hydroxyalkylammonium organic acid salts such as 2-hydroxypropyltrimethylammonium formate and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

[0091] The content of the quaternary ammonium salt compound in the polyol-based liquid composition of the present invention is not particularly limited, but it can be 0.1 to 100 parts by weight when the polyol (C) is 100 parts by weight.

[0092] 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, and cobalt naphthenate.

[0093] The content of the organometallic catalyst compound in the polyol-based liquid composition of the present invention is not particularly limited, but it can be 0.01 to 10 parts by weight when the polyol (C) is 100 parts by weight.

[0094] 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.

[0095] 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, and glycerin; low molecular weight amine polyols such as diethanolamine and triethanolamine; and polyamines such as ethylenediamine, xylylenediamine, and methylenebisorthochloroaniline.

[0096] Regarding the types of additives described above (quaternary ammonium salt compounds, organometallic catalyst compounds, foam stabilizers, crosslinking agents, chain extenders, solvents, colorants, flame retardants, and antioxidants), and their content in polyol-based liquid compositions, it is preferable to use commonly used types within commonly used content ranges.

[0097] The content of the crosslinking agent or chain extender is not particularly limited, but it is preferably 70 parts by weight or less when the polyol (C) is 100 parts by weight.

[0098] The polyol-based compounding composition of the present invention can be used to produce a polyurethane resin by mixing and stirring it 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.

[0099] Examples of the above-mentioned polyisocyanates include known polyisocyanates, and more specifically, aromatic polyisocyanates such as toluene diisocyanate (TDI), TDI derivatives, diphenylmethane diisocyanate (MDI), MDI derivatives, naphthylene diisocyanate, or 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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).

[0104] 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]

[0105] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0106] Synthesis Example 1: Synthesis of N-(3-aminopropyl)-N,N',N'-trimethyl-[2,2'-oxybis(ethaneamine)] 499 g of dimethylaminoethoxyethanol (3.8 mol) and 38 g of copper / zinc oxide / alumina catalyst were charged into a 2-liter stainless steel autoclave (hereinafter referred to as "reaction vessel 1"). After purging reaction vessel 1 with nitrogen and hydrogen, the catalyst was reduced in system for 9 hours under conditions of a hydrogen pressure of 5.6 MPa and a temperature of 195°C. Next, reaction vessel 1 was cooled to 25°C and depressurized to atmospheric pressure, after which 177 g of monomethylamine (5.7 mol) was injected into reaction vessel 1 under pressure using a nitrogen pressure of 0.7 MPa. Reaction vessel 1 was again pressurized with hydrogen to 1.5 MPa and heated to 195°C, and the temperature and pressure were maintained for 24 hours. 326 g of distillate was obtained from the resulting reaction solution by distillation. The main components of the distillate were N,N,N'-trimethylbis(aminoethyl) ether and dimethylaminoethoxyethanol.

[0107] Next, 326 g of the distillation product was placed in a three-necked flask equipped with a reflux valve, and the temperature was raised to 55°C. 71 g of acrylonitrile (1.3 mol) was then poured into the distillation product over 2 hours. Temperature control and stirring were continued for a further 5 hours. As a result, reaction product A was obtained in which N,N,N'-trimethylbis(aminoethyl) ether (the starting component) was present in a concentration of 1% or less.

[0108] Next, 20 g of chromium-added nickel sponge catalyst and 150 g of 28 wt% aqueous solution of ammonium hydroxide were charged into a 1-liter stainless steel autoclave (hereinafter referred to as reaction vessel 2). After purging reaction vessel 2 with nitrogen and hydrogen, the temperature was raised to 90°C and pressurized to 8.2 MPa with hydrogen. The entire amount of reaction product A obtained from the above reaction was supplied to reaction vessel 2 by pump over 3.5 hours, and then temperature control and stirring were continued for another hour. The pressure in reaction vessel 2 was released, and the reaction solution inside vessel 2 was removed. The catalyst was removed from the reaction solution by filtration, and then 140 g of N-(3-aminopropyl)-N,N',N'-trimethyl-[2,2'-oxybis(ethaneamine)] was obtained by vacuum distillation (top temperature: 124~133°C, vacuum: 13 hPa).

[0109] Manufacturing example 1. 26.0 g (0.20 mol) of N,N-diethyl-1,3-diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.6 g (0.20 mol) of pure water were placed in a 190 cc pressure vessel, and the pressure vessel was sealed. The liquid was stirred with a magnetic stirrer, and carbon dioxide was blown into the gas phase over 15 hours while maintaining the vessel temperature at 25°C. 35.8 g of reaction solution (aqueous solution of N,N-diethyl-1,3-diaminopropane carbonate) was obtained.

[0110] The composition of the reaction solution, calculated from the weight of absorbed carbon dioxide, was as follows: • N,N-diethyl-1,3-diaminopropane: 74.6% by weight ·Pure water: 8.3% by weight • Carbon dioxide: 17.1% by weight This composition shall be referred to as (A-1).

[0111] Manufacturing example 2. In the above-mentioned Production Example 1, the procedure was carried out in the same manner as in Production Example 1, except that 37.5 g (0.20 mol) of 3,3'-iminobis(N,N-dimethylpropylamine) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 26.0 g (0.20 mol) of N,N-diethyl-1,3-diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 45.8 g of the reaction solution (aqueous solution of 3,3'-iminobis(N,N-dimethylpropylamine carbonate)) was obtained.

[0112] Based on the weight of absorbed carbon dioxide, the composition of the reaction solution was estimated to be as follows: • 3,3'-Iminobis(N,N-dimethylpropylamine): 81.9% by weight ·Pure water: 7.9% by weight • Carbon dioxide: 10.3% by weight This composition shall be referred to as (A-2).

[0113] Manufacturing example 3. In the above-mentioned Production Example 1, the procedure was carried out in the same manner as in Production Example 1, except that 40.7 g (0.20 mol) of N-(3-aminopropyl)-N,N',N'-trimethyl-[2,2'-oxybis(ethaneamine)] (synthesized product shown in Preparation Example 1 above) was used instead of 26.0 g (0.20 mol) of N,N-diethyl-1,3-diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 49.1 g of the reaction solution (aqueous solution of N-(3-aminopropyl)-N,N',N'-trimethyl-[2,2'-oxybis(ethaneamine)] carbonate) was obtained.

[0114] Based on the weight of absorbed carbon dioxide, the composition of the reaction solution was estimated to be as follows: N-(3-aminopropyl)-N,N',N'-trimethyl-[2,2'-oxybis(ethaneamine)]: 82.9% by weight ·Pure water: 7.3% by weight • Carbon dioxide: 9.8% by weight This composition shall be referred to as (A-3).

[0115] The following describes examples of polyurethane foam manufacturing and evaluation results. The following raw materials, other than the compounds mentioned above, were used in relation to the present invention.

[0116] Polyol A: Maximol RDK-133 (aromatic polyester polyol, OH value = 319 mg KOH / g, manufactured by Kawasaki Chemical Industries, Ltd.) Polyol B: DK Polyol 3776 (Mannich-type polyether polyol, OH value = 349 mg KOH / g, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 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 Polyisocyanate solution: Polymeric MDI (manufactured by Tosoh Corporation, Millionate® MR200, NCO content = 31.0%) Example 1. Rigid polyurethane foam was produced using the catalyst for polyurethane foam production of the present invention.

[0117] 70 parts by weight of polyol A, 30 parts by weight of polyol B, 20 parts by weight of flame retardant, and 2.0 parts by weight of foam stabilizer A were weighed out and thoroughly stirred and mixed to obtain a mixture. Next, 36.6 g of the mixture was placed in a 300 ml polyethylene cup, and 1.21 g of composition (A-1) was added (4.02 parts by weight per 100 parts by weight of polyol (A+B), resulting in 3 parts by weight of amine added to composition (A-1) and 3.69 parts by weight of amine carbonate added to composition (A-1)). 0.50 g of blowing agent B (water) was added (the total amount of water in composition (A-1) and blowing agent B (water) being 2 parts by weight per 100 parts by weight of the aforementioned polyol (A+B)). 4.5 g of blowing agent A (equivalent to 15.0 parts by weight per 100 parts by weight of polyol (A+B)) was added to produce a polyol-based liquid composition. The resulting polyol-based liquid composition was then heated to 20°C.

[0118] The composition of the obtained polyol-based liquid composition is as follows.

[0119] [Table 1]

[0120] 42.8 g of the polyol-based composite composition obtained above, which was temperature-controlled to 20°C, was placed in a 300 ml polyethylene cup. Then, 37.3 g of polyisocyanate solution (Millionate MR200), also temperature-controlled to 20°C (corresponding to an amount that results in an isocyanate index [[isocyanate group] / [OH group] (molar ratio) × 100)] of 110 was added. The mixture was then quickly stirred at 7000 rpm for 2 seconds using a stirrer. The stirred mixture was then transferred to a 1 L polyethylene cup temperature-controlled to 23°C to carry out the foaming reaction, and the reactivity during foaming was measured using the method described below. In addition, the core density of the obtained rigid polyurethane foam was recorded by cutting out the center.

[0121] [Measurement of reactivity] • Cream Time: Visually measure the time when the mixed and stirred mixture turns white and the foam begins to rise. [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 weight.

[0122] Next, the polyol-based composition prepared by the above method was placed in a sealed container and stored in a constant temperature room at 40°C for 7 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. The results are shown in Table 4.

[0123] Example 2. In Example 1, composition (A-2) was used instead of composition (A-1), and the amount added was adjusted. The same procedure as in Example 1 was followed to produce a polyol-based compound liquid composition with the following composition.

[0124] [Table 2]

[0125] The polyol-based liquid composition prepared here was used to carry out a foaming reaction under the same conditions as in Example 1, and evaluated using the method described in Example 1. The results are shown in Table 5.

[0126] Example 3. In Example 1, composition (A-3) was used instead of composition (A-1), and the amount added was adjusted. The same procedure as in Example 1 was followed to produce a polyol-based compound liquid composition with the following composition.

[0127] [Table 3]

[0128] The polyol-based liquid composition prepared here was used to carry out a foaming reaction under the same conditions as in Example 1, and evaluated using the method described in Example 1. The results are shown in Table 6.

[0129] Comparative Example 1. In Example 1, the experimental procedure was carried out in the same manner as in Example 1, except that 3.00 parts by weight of N,N-diethyl-1,3-diaminopropane was used instead of 4.02 parts by weight of composition (A-1), and evaluation data was obtained. The results are shown in Table 4.

[0130] Comparative Example 2. In Example 1, the same experimental procedure as in Example 2 was performed, except that 3,3'-iminobis(N,N-dimethylpropylamine) 3.00 parts by weight was used instead of 3.66 parts by weight of composition (A-2), and evaluation data was obtained. The results are shown in Table 4.

[0131] Comparative Example 3. In Example 1, the experimental procedure was carried out in the same manner as in Example 3, except that 3.00 parts by weight of N-(3-aminopropyl)-N,N',N'-trimethyl-[2,2'-oxybis(ethaneamine)] obtained in Preparation Example 1 was used instead of 3.62 parts by weight of composition (A-3), and evaluation data was obtained. The results are shown in Table 4.

[0132] [Table 4]

[0133] [Table 5]

[0134] [Table 6]

[0135] Manufacturing example 4. In the above-mentioned Production Example 1, the procedure was carried out in the same manner as in Production Example 1, except that 17.4 g (0.15 mol) of N,N-diethyl-1,2-diaminoethane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.7 g (0.15 mol) of pure water were used instead of 26.0 g (0.20 mol) of N,N-diethyl-1,3-diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.6 g (0.20 mol) of pure water. A reaction solution (aqueous solution of N,N-diethyl-1,2-diaminoethane carbonate) was obtained.

[0136] Based on the weight of absorbed carbon dioxide, the composition of the reaction solution was estimated to be as follows: • N,N-diethyl-1,2-diaminoethane: 70.5% by weight ·Pure water: 10.9% by weight • Carbon dioxide: 18.5% by weight This composition shall be referred to as (A-4).

[0137] Manufacturing example 5. In the above-mentioned Production Example 1, the procedure was carried out in the same manner as in Production Example 1, except that 14.4 g (0.10 mol) of N,N-diisopropyl-1,2-diaminoethane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.8 g (0.10 mol) of pure water were used instead of 26.0 g (0.20 mol) of N,N-diethyl-1,3-diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.6 g (0.20 mol) of pure water. A reaction solution (aqueous solution of N,N-diisopropyl-1,2-diaminoethane carbonate) was obtained.

[0138] Based on the weight of absorbed carbon dioxide, the composition of the reaction solution was estimated to be as follows: • N,N-diisopropyl-1,2-diaminoethane: 74.0% by weight ·Pure water: 9.2% by weight • Carbon dioxide: 16.7% by weight This composition shall be referred to as (A-5).

[0139] Manufacturing example 6. In the above-mentioned Production Example 1, the procedure was carried out in the same manner as in Production Example 1, except that 9.4 g (0.20 mol) of 2-aminoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 26.0 g (0.20 mol) of N,N-diethyl-1,3-diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 17.2 g of reaction solution (aqueous solution of 2-aminoethanol carbonate) was obtained.

[0140] Based on the weight of absorbed carbon dioxide, the composition of the reaction solution was estimated to be as follows: • 2-Aminoethanol: 61.6% by weight ·Pure water: 18.2% by weight • Carbon dioxide: 20.2% by weight This composition shall be referred to as (A-6).

[0141] Manufacturing example 7. In the above-mentioned Production Example 1, the procedure was carried out in the same manner as in Production Example 1, except that 12.2 g (0.20 mol) of 2-(methylamino)ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 26.0 g (0.20 mol) of N,N-diethyl-1,3-diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 19.9 g of reaction solution (aqueous solution of 2-(methylamino)ethanol carbonate) was obtained.

[0142] Based on the weight of absorbed carbon dioxide, the composition of the reaction solution was estimated to be as follows: 2-(methylamino)ethanol: 64.2% by weight ·Pure water: 15.4% by weight • Carbon dioxide: 20.4% by weight This composition shall be referred to as (A-7).

[0143] Manufacturing example 8. The procedure was carried out in the same manner as in Production Example 1, except that 17.8 g (0.20 mol) of 2-(dimethylamino)ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 26.0 g (0.20 mol) of N,N-diethyl-1,3-diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.), to obtain 23.5 g of reaction solution (aqueous solution of 2-(dimethylamino)ethanol carbonate).

[0144] Based on the weight of absorbed carbon dioxide, the composition of the reaction solution was estimated to be as follows: 2-(dimethylamino)ethanol: 75.8% by weight ·Pure water: 15.3% by weight • Carbon dioxide: 8.9% by weight This composition shall be referred to as (A-8).

[0145] Manufacturing example 9. The procedure was carried out in the same manner as in Production Example 1, except that 20.4 g (0.20 mol) of N,N-dimethyl-1,3-diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 26.0 g (0.20 mol) of N,N-diethyl-1,3-diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.), to obtain 31.4 g of reaction solution (aqueous solution of N,N-dimethyl-1,3-diaminopropane carbonate).

[0146] Based on the weight of absorbed carbon dioxide, the composition of the reaction solution was estimated to be as follows: • N,N-dimethyl-1,3-diaminopropane: 65.1% by weight ·Pure water: 23.4% by weight • Carbon dioxide: 11.5% by weight This composition shall be referred to as (A-9).

[0147] Manufacturing example 10. In the above-mentioned Production Example 1, the procedure was carried out in the same manner as in Production Example 1, except that 13.2 g (0.15 mol) of N,N-dimethyl-1,2-diaminoethane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.7 g (0.15 mol) of pure water were used instead of 26.0 g (0.20 mol) of N,N-diethyl-1,3-diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.6 g (0.20 mol) of pure water. A reaction solution (aqueous solution of N,N-dimethyl-1,2-diaminoethane carbonate) was obtained.

[0148] Based on the weight of absorbed carbon dioxide, the composition of the reaction solution was estimated to be as follows: • N,N-dimethyl-1,2-diaminoethane: 62.0% by weight ·Pure water: 25.3% by weight • Carbon dioxide: 12.7% by weight This composition shall be referred to as (A-10).

[0149] Example 4. In Example 1, composition (A-4) was used instead of composition (A-1), and the amount added was adjusted. The same procedure as in Example 1 was followed to produce a polyol-based liquid composition with the following composition.

[0150] [Table 7]

[0151] The polyol-based liquid composition prepared here was used to carry out a foaming reaction under the same conditions as in Example 1, and evaluated using the method described in Example 1. The results are shown in the table.

[0152] [Table 8]

[0153] Example 5. In Example 1, composition (A-5) was used instead of composition (A-1), and the amount added was adjusted. The same procedure as in Example 1 was followed to produce a polyol-based compound liquid composition with the following composition.

[0154] [Table 9]

[0155] The polyol-based liquid composition prepared here was used to carry out a foaming reaction under the same conditions as in Example 1, and evaluated using the method described in Example 1. The results are shown in the table.

[0156] [Table 10]

[0157] Comparative Example 4. In Example 1, composition (A-6) was used instead of composition (A-1), and the amount added was adjusted. The same procedure as in Example 1 was followed to produce a polyol-based compound liquid composition with the following composition.

[0158] [Table 11]

[0159] The polyol-based liquid composition prepared here was used to carry out a foaming reaction under the same conditions as in Example 1, and evaluated using the method described in Example 1. The results are shown in the table.

[0160] [Table 12]

[0161] Comparative Example 5. In Example 1, composition (A-7) was used instead of composition (A-1), and the amount added was adjusted. The same procedure as in Example 1 was followed to produce a polyol-based compound liquid composition with the following composition.

[0162] [Table 13]

[0163] The polyol-based liquid composition prepared here was used to carry out a foaming reaction under the same conditions as in Example 1, and evaluated using the method described in Example 1. The results are shown in the table.

[0164] [Table 14]

[0165] Comparative Example 6. In Example 1, composition (A-8) was used instead of composition (A-1), and the amount added was adjusted. The same procedure as in Example 1 was followed to produce a polyol-based compound liquid composition with the following composition.

[0166] [Table 15]

[0167] The polyol-based liquid composition prepared here was used to carry out a foaming reaction under the same conditions as in Example 1, and evaluated using the method described in Example 1. The results are shown in the table.

[0168] [Table 16]

[0169] Comparative Example 7. In Example 1, composition (A-9) was used instead of composition (A-1), and the amount added was adjusted. The same procedure as in Example 1 was followed to produce a polyol-based compound liquid composition with the following composition.

[0170] [Table 17]

[0171] The polyol-based liquid composition prepared here was used to carry out a foaming reaction under the same conditions as in Example 1, and evaluated using the method described in Example 1. The results are shown in the table.

[0172]

Table 18

[0173] Comparative Example 8. In Example 1, the same operations as in Example 1 were carried out except that Composition (A-10) was used instead of Composition (A-1) and the addition amount was adjusted, and a polyol-based blended liquid composition having the following composition was produced.

[0174]

Table 19

[0175] Using the polyol-based blended liquid composition produced here, a foaming reaction was carried out under the same conditions as in Example 1 and evaluated by the method described in Example 1. The results are shown in the table.

[0176]

Table 20

[0177] Summarizing the above results, they are as shown in Table 21.

[0178]

Table 21

[0179] As is clear from Table 21, in Examples 1 to 5 using the polyol-based blended liquid composition for producing a polyurethane foam containing the amine carbonate of the present invention, the cream time before storage is 5 seconds or less and the initial foaming property is fast. Also, the cream time after storage is 6 seconds or less, showing the feature that the reaction delay after storage is small.

[0180] On the other hand, in Comparative Examples 1 to 5, the cream time before storage is 6 seconds or more and the initial foaming property is slow, and the cream time after storage is 9 seconds or more, significantly delaying the initial foaming property.

[0181] In Comparative Example 6, the cream time before storage was 3 seconds, indicating rapid initial foaming, but the cream time after storage was 7 seconds, showing a significant reaction delay.

[0182] In Comparative Example 7, the cream time before storage was 4 seconds, indicating rapid initial foaming, but the cream time after storage was 7 seconds, showing a significant reaction delay.

[0183] In Comparative Example 8, the cream time before storage was quite rapid, less than 2 seconds, but it was not possible to produce a foam with properties suitable for physical property evaluation. Furthermore, the cream time after storage was 5 seconds, indicating a significant reaction delay. The large change in reactivity makes it difficult to use in industrial applications where stability and reliability are required.

[0184] Furthermore, while Examples 1-5 had the advantage of small changes in foam density before and after storage, Comparative Examples 4-7 showed large changes in foam density before and after storage, posing challenges for industrial use.

[0185] In other words, the composition of the present invention has high storage stability and can be used with confidence in industrial applications where high reliability is required.

Claims

1. A polyol-based compounding liquid composition for manufacturing polyurethane foam, (i) A carbonate (A) of an amine compound represented by the following general formula (1), (2), or (4), (ii) A foaming agent containing hydrochlorofluoroolefin (B), (iii) Polyol (C) A composition containing the following: 【Chemistry 1】 (In the above formula, R １ and R ２ Each of these independently represents an alkyl group having 2 to 6 carbon atoms, which may have a hydroxyl group. R １ and R ２ These may be bonded to each other to form a morpholine ring. m represents an integer between 0 and 4. 【Chemistry 2】 (In the above formula, R ３ and R ４ Each of these independently represents an alkyl group having 1 to 6 carbon atoms, which may have a hydroxyl group. R ３ and R ４ These may be bonded to each other to form a morpholine ring. m represents an integer between 0 and 4. R ５ is an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group, or the following general formula (3) 【Transformation 3】 (In the above formula, * represents the connection point in formula (2). R ６ and R ７ Each of these independently represents an alkyl group having 1 to 6 carbon atoms, which may have a hydroxyl group. R ６ and R ７ These may be bonded to each other to form a morpholine ring. m represents an integer between 0 and 4. (This represents the base represented by [this symbol].) 【Chemistry 4】 (In the formula, R ８ and R ９ Each of these independently represents an alkyl group having 1 to 6 carbon atoms, which may have a hydroxyl group. R ８ and R ９ These may be bonded to each other to form a morpholine ring. R １０ This represents an alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or a hydroxyl group. R １１ This is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group, or the following general formula (5) 【Transformation 5】 (In the formula, * represents the connection point in general formula (4). R １２ represents a hydrogen atom or a methyl group. n represents an integer between 0 and 2. (This represents the base represented by [this symbol].)

2. In the above general formula (1), -NR １ R ２ The composition according to claim 1, characterized in that the group represented is a diethylamino group, an ethyl(n-propyl)amino group, a di(n-propyl)amino group, or a morpholino group.

3. In the above general formulas (2) and (3), -NR ３ R ４ , and -NR ６ R ７ The composition according to claim 1, characterized in that at least one of the groups represented is a dimethylamino group, a diethylamino group, an ethyl(n-propyl)amino group, a di(n-propyl)amino group, or a morpholino group.

4. In the above general formula (4), -NR ８ R ９ The composition according to claim 1, characterized in that the group represented is a dimethylamino group, a diethylamino group, an ethyl(n-propyl)amino group, a di(n-propyl)amino group, or a morpholino group.

5. The carbonate (A) of the amine compound represented by the above general formula (1), (2), or (4) is N,N-diethyl-1,2-ethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-diisopropyl-1,2-ethylenediamine, N,N-isopropyl-1,3-diaminopropane, 4-(2-aminoethyl)morpholine, N-(3-aminopropyl)morpholine, N-(2-aminopropyl)morpholine, N,N-diethyl-N'-methyl-1,2-ethylenediamine, N,N,N'-triethyl-1,2-ethylenediamine, N,N-diethyl-N'-methyl-1,3-propanediamine, N,N,N'-triethyl-1,3-propanediamine, N,N-diethyl-N'-methyl-1,4-butanediamine, N,N,N'-triethyl-1,4-butanediamine, 4-(2-aminoethyl)morpholine, N-(3-aminopropyl)morpholine, N-(2-aminopropyl)morpholine, 3,3'-iminobis(N,N-dimethylpropylamine), 3,3'-iminobis(N,N-diethylpropylamine), 2,2'-iminobis(N,N-diethylethylamine), N-(3-aminopropyl)-N,N',N'-trimethyl-[2,2'-oxybis(ethylamine)], N-(3-aminopropyl)-N,N',N'-triethyl-[2,2'-oxybis(ethylamine)], and [2-[2-(diethylamino)ethoxy]ethyl](ethyl)amine The composition according to claim 1, wherein (A) is a carbonate of one or more amine compounds selected from the group consisting of the following.

6. The carbonate (A) of the amine compound represented by the above general formula (1), (2), or (4) is N,N-diethyl-1,2-ethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-diisopropyl-1,2-ethylenediamine, 3,3'-Iminobis(N,N-dimethylpropylamine), 3,3'-Iminobis(N,N-diethylpropylamine), 2,2'-Iminobis(N,N-diethylethylamine), N-(3-aminopropyl)-N,N',N'-trimethyl-[2,2'-oxybis(ethylamine)], N-(3-aminopropyl)-N,N',N'-triethyl-[2,2'-oxybis(ethylamine)], and [2-[2-(diethylamino)ethoxy]ethyl](ethyl)amine The composition according to claim 1, wherein (A) is a carbonate of one or more amine compounds selected from the group consisting of the following.

7. The aforementioned hydrochlorofluoroolefin (B) 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-trifluoropropene The composition according to claim 1, characterized in that it is one or more selected from the group consisting of ruolopropene, 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.

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

9. The composition according to claim 1, characterized in that the carbonate (A) of the amine compound represented by the general formula (1), (2), or (4) is in the range of 2 to 30 parts by weight per 100 parts by weight of the amine compound represented by the general formula (1), (2), or (4).

10. The composition according to claim 1, wherein the weight ratio of component (A) to (C) is 2 to 6 parts by weight of component (A) per 100 parts by weight of component (C).

11. The composition according to claim 1, wherein the weight ratio of component (B) to (C) is 10 to 30 parts by weight of component (B) per 100 parts by weight of component (C).

12. A method for producing polyurethane foam, characterized by reacting a composition according to any one of claims 1 to 11 with a polyisocyanate compound.

Images