Polyurethane decomposition composition, method for producing recycled polyol, method for producing amine compound-containing solid, and polyurethane resin

Abstract

To provide a technique that enables easy and efficient acquisition of a recycled raw material by decomposing a polyurethane resin.SOLUTION: A polyurethane decomposition composition includes an amine compound having a primary amino group and further having a secondary amino group and / or a tertiary amino group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a composition for decomposing polyurethanes, a method for producing recycled polyols, a method for producing a solid material containing an amine compound, and a polyurethane resin. [Background technology]

[0002] Technologies have been developed for chemically decomposing polyurethane resins and recovering and reusing the polyols. Patent Document 1 discloses a polyurethane recycling method. In this method, urethane is decomposed with monoalkanolamine, the polyol is extracted with a hydrocarbon solvent, and recycled polyol is synthesized by adding alkylene oxide. Patent Document 2 discloses a method for purifying urethane resin decomposition products. In this method, urethane is decomposed with diethanolamine and the polyol is recovered by vacuum distillation. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 7-126344 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-262174 Summary of the Invention [Problem to be solved by the invention]

[0004] The technology of Patent Document 1 requires alkylene oxide addition to synthesize recycled polyol, and a simpler method is desired. The technology of Patent Document 2 requires purified recycled polyol by vacuum distillation, and a simpler method is desired. In addition, a technology for improving the recycling efficiency of polyurethane resins is also desired.

[0005] The present disclosure has been made in view of the above circumstances, and aims to solve at least one of the above problems. The present disclosure can be realized in the following aspects. [Means for solving the problem]

[0006] A composition for decomposing polyurethanes, comprising an amine compound having a primary amino group and further having a secondary amino group and / or a tertiary amino group. [Effects of the Invention]

[0007] The present disclosure can solve at least one of the above problems. For example, it can provide a technology for decomposing polyurethane resin to obtain recycled raw materials simply and efficiently. DETAILED DESCRIPTION OF THE INVENTION

[0008] Here, a preferred example of the present disclosure will be described. [1] A composition for decomposing polyurethanes, comprising an amine compound having a primary amino group and further having a secondary amino group and / or a tertiary amino group. [2] The polyurethane decomposition composition according to [1], wherein the amine compound is at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2): [ka] (In formula (1), R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n represents an integer of 2 to 7, and m represents an integer of 2 to 7.) [ka] (In formula (2), R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n represents an integer of 2 to 7, and m represents an integer of 2 to 7.) [3] A method for producing recycled polyol, comprising decomposing a polyurethane resin using the polyurethane decomposition composition according to [1] or [2] to obtain recycled polyol. [4] The method for producing a recycled polyol according to [3], wherein the recycled polyol is obtained by separating solid matter from a decomposition product obtained by decomposing the polyurethane resin. [5] A method for producing a solid material containing an amine compound, comprising decomposing a polyurethane resin using the polyurethane decomposition composition according to [1] or [2], and separating a solid material containing an amine compound from a decomposition product obtained by decomposing the polyurethane resin. [6] A polyurethane resin comprising a solid material containing an amine compound obtained by the method according to [5].

[0009] The present disclosure will be described in detail below. In this specification, when a numerical range is indicated using "-", it is intended to include both the lower limit and the upper limit unless otherwise specified. For example, the expression "10-20" includes both the lower limit "10" and the upper limit "20". In other words, "10-20" has the same meaning as "10 or more and 20 or less". In addition, in this specification, the upper limit and lower limit of each numerical range can be combined in any way.

[0010] 1. Polyurethane decomposition composition The polyurethane decomposition composition contains an amine compound having a primary amino group and further having a secondary amino group and / or a tertiary amino group.

[0011] (1) Polyurethane resin The polyurethane decomposition composition is used for decomposing polyurethane resins. The polyurethane resin is not particularly limited. The polyurethane resin is, for example, polyurethane foam. The polyurethane foam may be any of flexible polyurethane foam, semi-rigid polyurethane foam, and rigid polyurethane foam. The polyurethane foam may be an open-cell polyurethane foam or a closed-cell polyurethane foam. The polyurethane foam may be a pulverized product pulverized to a predetermined size. The polyurethane foam may also be cut to a predetermined size. The polyurethane foam may be, for example, scraps discarded during the polyurethane foam manufacturing process, or used polyurethane foam to be discarded.

[0012] (2) Amine compounds The amine compound contained in the polyurethane decomposition composition has a primary amino group and further has a secondary amino group and / or a tertiary amino group. The amine compound may be of only one type or of two or more types. The amine compound of the present disclosure acts as a decomposing agent. The polyurethane decomposition composition may contain the above-mentioned amine compound and a decomposing agent other than the above-mentioned amine compound.

[0013] The amine compound of the present disclosure is not particularly limited as long as it has a primary amino group and further has a secondary amino group and / or a tertiary amino group. The amine compound may be, for example, an aliphatic amine compound, an alicyclic amine compound, a heterocyclic amine compound, or an aromatic amine compound. The number of carbon atoms in the aliphatic amine compound is, for example, 4 to 18. The number of carbon atoms in the alicyclic amine compound is, for example, 4 to 15. The number of carbon atoms in the heterocyclic amine compound is, for example, 4 to 15. The number of carbon atoms in the aromatic amine compound is, for example, 6 to 20. The number of primary amino groups in the amine compound is not particularly limited as long as it is at least one per molecule, and the number of primary amino groups in the amine compound is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. The total number of secondary amino groups and tertiary amino groups in the amine compound is not particularly limited as long as it is at least 1. The total number of secondary amino groups and tertiary amino groups in the amine compound is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, even more preferably 1 or more and 2 or less, and particularly preferably 1. The molecular weight of the amine compound is not particularly limited. The molecular weight of the amine compound is preferably 600 or less, more preferably 450 or less, and even more preferably 300 or less. The lower limit of the molecular weight of the amine compound is not particularly limited, and is, for example, 70 or more.

[0014] The amine compound of the present disclosure is preferably one or more selected from the group consisting of bis(3-aminopropyl)amine, 3,3′-diamino-N-methyldipropylamine, 2-(2-aminoethylamino)ethanol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-ethylethylenediamine, N,N-dimethylethylenediamine, N-(3-aminopropyl)cyclohexylamine, N-methyl-1,3-diaminopropane, N-(2-hydroxypropyl)ethylenediamine, N-(2-aminoethyl)morpholine, N-(3-aminoethyl)morpholine, N-(2-aminoethyl)piperazine, 1,4-bis(3-aminopropyl)piperazine, 2-picolylamine, 4-picolylamine, and N,N-dimethyl-1,4-phenylenediamine. Among these, bis(3-aminopropyl)amine, 3,3'-diamino-N-methyldipropylamine, or 2-(2-aminoethylamino)ethanol is more preferred.

[0015] Moreover, the polyurethane decomposition composition preferably contains, as the amine compound, one or more compounds selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2): [ka] (In formula (1), R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n represents an integer of 2 to 7, and m represents an integer of 2 to 7.) [ka] (In formula (2), R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n represents an integer of 2 to 7, and m represents an integer of 2 to 7.)

[0016] The amine compound of the present disclosure does not necessarily have any functional groups other than amino groups, and may have any functional groups other than amino groups as long as the effects of the present invention are not impaired. When the amine compound of the present disclosure has a hydroxyl group, the number of hydroxyl groups is preferably not more than 1. It is also preferable that the amine compound of the present disclosure does not have an ether bond.

[0017] The amount of the amine compound added is not particularly limited. From the viewpoint of sufficiently decomposing the polyurethane resin, the amount of the amine compound added is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of the polyurethane resin. In consideration of the effect on reactivity and physical properties when the decomposition product is reused as a recycled raw material, the amount of the amine compound added is preferably 50 parts by mass or less, more preferably 35 parts by mass or less, and even more preferably 20 parts by mass or less. From these viewpoints, the amount of the amine compound added is preferably 3 parts by mass or more and 50 parts by mass or less, more preferably 4 parts by mass or more and 20 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less.

[0018] (3) Catalyst (optional component) The polyurethane decomposition composition may contain a catalyst. The catalyst is preferably, for example, a tertiary amine compound that does not have a primary amino group. Only one type of catalyst may be used, or two or more types may be used in combination.

[0019] The tertiary amine compound having no primary amino group is preferably at least one selected from the group consisting of diazabicycloundecene, triethylamine, tripropylamine, tributylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, N,N,N',N'-tetramethylhexanediamine, N,N,N',N'-tetramethylpropanediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, N,N',N'-trimethylaminoethylpiperazine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethylethylenediamine, and 1,4-diazabicyclo[2.2.2]octane.

[0020] The catalyst may be a combination of the above-mentioned tertiary amine compound having no primary amino group and another catalyst. The other catalyst may be, for example, a metal catalyst. The metal catalyst is preferably at least one selected from the group consisting of stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin mercaptide, dioctyltin thiocarboxylate, lead octoate, potassium acetate, and potassium octoate.

[0021] (4) Decomposition products The decomposition product is obtained by decomposing a polyurethane resin with the polyurethane decomposition composition.

[0022] The conditions for decomposing the polyurethane resin are not particularly limited. From the viewpoint of improving the decomposition rate, the method for decomposing the polyurethane resin preferably involves heating the polyurethane resin together with the polyurethane decomposition composition. When heating the polyurethane resin together with the polyurethane decomposition composition, it is preferable to stir the mixture of the polyurethane resin and the polyurethane decomposition composition.

[0023] The heating temperature is preferably 80°C or higher and 300°C or lower, more preferably 100°C or higher and 270°C or lower, and even more preferably 150°C or higher and 250°C or lower, from the viewpoint of improving the decomposition rate while suppressing decomposition of the polyol as the decomposition product, i.e., the polyol derived from the raw material polyol. The decomposition treatment time is, for example, from 10 minutes to 24 hours, and may be from 30 minutes to 10 hours. The end point of the decomposition treatment time may be appropriately set while checking the progress of decomposition of the polyurethane resin depending on the size of the polyurethane resin, whether stirring is performed, etc. Furthermore, when the polyurethane resin is decomposed at a temperature of from room temperature (e.g., 25°C) to less than 80°C, the decomposition treatment time may be set to be longer than 24 hours.

[0024] The decomposition product includes, for example, polyol derived from the raw material polyol of the polyurethane resin and amine components derived from the raw material isocyanate, as well as flame retardants, catalysts, and other additives contained in the polyurethane resin.

[0025] The decomposition product is preferably in a state where it is separated into two phases: a liquid phase containing polyol (hereinafter also referred to as a polyol phase) and a solid phase. In the present disclosure, the decomposition product being "separated into two phases: a polyol phase and a solid phase" means that only one liquid phase is visually observed, and when the decomposition product is filtered at 70°C through a 40-mesh stainless steel filter, a solid can be separated as a filtration residue. When the decomposition agent contains the amine compound of the present disclosure, the decomposition product can be suitably obtained in a state where it is separated into two phases: a polyol phase and a solid phase.

[0026] The polyurethane decomposition composition containing the amine compound of the present disclosure can suitably separate the decomposition product into two phases: a liquid phase (polyol phase) and a solid phase. The reason for this is unclear, but is presumed to be as follows. However, the present disclosure is not limited to this presumed reason. Unlike the amine compounds of the present disclosure, when a polyurethane decomposition composition containing diethanolamine was used, the decomposition product separated into three phases: a polyol phase, a liquid phase (hereinafter also referred to as a second liquid phase) separate from the polyol phase, and a solid phase. Because diethanolamine has two hydroxyl groups, it is possible that it creates affinity between the polyol and solids, causing some of the polyol to migrate from the polyol phase to the solid phase or the second liquid phase. It is also possible that diethanolamine combined with some of the solid components of the solid phase to form a liquid compound. It is speculated that this mechanism led to the formation of the second liquid phase when a polyurethane decomposition composition containing diethanolamine was used. In contrast, when a polyurethane decomposition composition containing bis(3-aminopropyl)amine, one of the amine compounds of the present disclosure, was used, the decomposition product separated into two phases: a liquid phase (polyol phase) and a solid phase. Bis(3-aminopropyl)amine is a compound in which the two hydroxyl groups of diethanolamine are each replaced with a primary amino group. Furthermore, when a polyurethane decomposition composition containing 2-(2-aminoethylamino)ethanol, another type of amine compound of the present disclosure, was used, the decomposition product also separated into two phases: a liquid phase (polyol phase) and a solid phase. 2-(2-aminoethylamino)ethanol is a compound with a structure in which one of the two hydroxyl groups of diethanolamine is replaced with a primary amino group. In other words, it is believed that the phase separation into two phases, a liquid phase (polyol phase) and a solid phase, was achieved by replacing one or two hydroxyl groups of diethanolamine with a primary amino group. Furthermore, unlike the amine compounds disclosed herein, when a polyurethane decomposition composition containing polyetheramine was used, only a solid phase was obtained as a decomposition product. Polyetheramine is an amine compound that has two primary amino groups and no secondary or tertiary amino groups. This result suggests that the presence of a secondary or tertiary amino group in addition to a primary amino group can promote the generation of a liquid phase (polyol phase). Thus, it is presumed that an amine compound having a primary amino group and further having a secondary amino group and / or a tertiary amino group can simultaneously promote the formation of a polyol phase and inhibit the formation of a second liquid phase.

[0027] The use of the decomposition product is not particularly limited. The decomposition product can be phase-separated into two phases, a liquid phase (polyol phase) and a solid phase, and is therefore suitable as a recycled raw material. The recycled raw material may be, for example, recycled polyol or a solid material containing an amine compound. Recycled polyol is suitable as a raw material for recycled polyurethane resin. The solid material containing an amine compound can also be used as a raw material for recycled polyurethane resin, for example, as a filler. Methods for producing recycled polyol and methods for producing solid materials containing an amine compound will be described later.

[0028] (5) Effects of this embodiment When the polyurethane decomposition composition of this embodiment is used, the decomposition product can be suitably separated into two phases, a liquid phase (polyol phase) and a solid phase, and thus recycled polyol can be efficiently recovered as the liquid phase. Furthermore, when the decomposition product is separated into two phases, a liquid phase (polyol phase) and a solid phase, by-products (solids) other than the liquid phase (polyol phase) can be easily separated by filtration, and for example, the by-products can be separated from the recycled polyol simply by filtration at 70°C through a stainless steel 40 mesh. Therefore, according to this embodiment, the by-products can be easily separated and the quality of the recycled polyol can be improved. Furthermore, when the polyurethane decomposition composition of this embodiment is used, the solid matter in the decomposition product is less likely to soften. When the solid matter in the decomposition product softens, the amount of the liquid phase (polyol phase) may also decrease. In contrast, in this embodiment, the solid matter in the decomposition product is less likely to soften, so that a sufficient amount of the liquid phase (polyol phase) in the decomposition product can be ensured, and the recovery rate of the liquid phase can be improved. Furthermore, when the polyurethane decomposition composition of this embodiment is used, the obtained solid can be used as a raw material for polyurethane resin, despite containing an amine compound. Conventionally, there has been a problem that the amine compound produced by the decomposition of polyurethane resin has an adverse effect when the decomposition product is reused. This embodiment is groundbreaking in that it can provide a new solution to the problem associated with the amine compound in the decomposition product.

[0029] 2.Recycled polyol manufacturing method In the method for producing recycled polyol, a polyurethane resin is decomposed using the polyurethane decomposition composition to obtain recycled polyol. In the explanation of the method for producing recycled polyol, the description in the above section "1. Composition for polyurethane decomposition" applies as is to the composition for polyurethane decomposition.

[0030] In the method for producing recycled polyol of the present disclosure, the recycled polyol is preferably obtained by separating solids from a decomposition product obtained by decomposing a polyurethane resin. That is, the recycled polyol is preferably obtained as the liquid phase of the decomposition product that has been phase-separated into two phases, a liquid phase (polyol phase) and a solid phase. The method for separating the solids from the decomposition product is not particularly limited. For example, the decomposition product may be filtered to separate the solids as residue. Alternatively, only the liquid phase (polyol phase) may be extracted from the decomposition product that has been phase-separated into two phases, a liquid phase (polyol phase) and a solid phase, and the solids may be separated. The separated solids may be discarded or used as a raw material for the polyurethane resin described below.

[0031] The solid matter may contain at least one amine compound, for example, an amine compound derived from the raw isocyanate, an amine compound contained in the polyurethane decomposition composition, or an amine compound produced by the reaction of these amine compounds with other components. The amine compound separated as a solid matter is a component that may affect the foamability and reactivity of recycled polyol when used as a recycled raw material. According to the technology disclosed herein, the amine compound in the decomposition product can be suitably separated as a solid matter, thereby obtaining a high-quality recycled polyol.

[0032] In the method for producing recycled polyol, the recovery rate of recycled polyol is not particularly limited. The recovery rate of recycled polyol can be evaluated by the following formula as the recovery rate of the liquid phase when the decomposition product is filtered at 70°C through a 40-mesh stainless steel filter. Liquid phase recovery rate (%) = (A / B) x 100 A: Mass of the recovered liquid phase (g) B: Total mass (g) of the polyurethane resin subjected to decomposition and the decomposition agent

[0033] From the viewpoint of efficiently obtaining recycled polyol, the recovery rate of the liquid phase is preferably 30% or more, more preferably 40% or more, and even more preferably 45% or more. The upper limit of the recovery rate of the liquid phase is not particularly limited, and may be 95% or less, 80% or less, 70% or less, or 60% or less.

[0034] The method for producing recycled polyol of the present disclosure may obtain the decomposition product as recycled polyol directly without separating the solids from the decomposition product. That is, the recycled polyol may contain a liquid phase (polyol phase) and a solid phase of the decomposition product. According to the method for producing recycled polyol of the present disclosure, at least a portion of the amine compound in the decomposition product can be present as a solid. Therefore, even when the decomposition product is used as recycled polyol directly, the impact of the amine compound on foamability and reactivity can be reduced compared to when the entire amine compound is present in the liquid phase (polyol phase).

[0035] The use of the recycled polyol is not particularly limited. The recycled polyol is suitable as a raw material for recycled polyurethane resin.

[0036] 3. Method for producing solid material containing amine compound The method for producing the amine compound-containing solid material comprises decomposing a polyurethane resin with the polyurethane decomposition composition described above, and separating the amine compound-containing solid material from the decomposition product obtained by decomposing the polyurethane resin. In the explanation of the method for producing a solid material containing an amine compound, the description in the above section "1. Composition for decomposing polyurethane" applies as is to the composition for decomposing polyurethane.

[0037] The method for separating the solid matter from the decomposition product is not particularly limited. For example, the decomposition product can be filtered to separate the solid matter as a residue. The liquid phase obtained as the filtrate can be used for various purposes as a recycled polyol.

[0038] The solid matter may contain at least one amine compound, such as an amine compound derived from the raw material isocyanate, an amine compound contained in the polyurethane decomposition composition, or an amine compound produced by the reaction of these amine compounds with other components. The amine compound-containing solid matter may further contain solid components originally contained in the polyurethane resin. Examples of solid components originally contained in the polyurethane resin include components derived from polymer polyols containing polymers such as styrene and acrylonitrile, and flame retardants such as phosphorus-based flame retardants and halogen-based flame retardants. According to the technology disclosed herein, the solid components originally contained in the polyurethane resin can also be suitably separated as a solid phase.

[0039] The use of the amine compound-containing solid material is not particularly limited. The amine compound-containing solid material can be used as a raw material for polyurethane resin, for example, as a filler. Unlike the polyurethane decomposition composition described above, when a polyurethane decomposition composition containing diethanolamine is used, the solid material separated from the decomposition product deteriorates the foamability and reactivity of the polyurethane resin and is not suitable as a raw material for polyurethane resin. On the other hand, the amine compound-containing solid material of the present disclosure can be used as a raw material for polyurethane resin without deteriorating the foamability and reactivity of the polyurethane resin.

[0040] 4. Polyurethane resin The polyurethane resin contains the above-mentioned amine compound-containing solid material, which is contained as a so-called filler in the polyurethane resin. In the explanation of the polyurethane resin, the description in the above section "3. Method for producing a solid material containing an amine compound" applies as is to the solid material containing an amine compound.

[0041] The polyurethane resin is obtained from a polyurethane resin composition containing, for example, a polyol, an isocyanate, and a solid material containing an amine compound. Polyurethane resins can be produced by known methods. Foaming methods for obtaining polyurethane foam include slab foaming and mold foaming, and either molding method may be used. Slab foaming is a method in which a mixed recycled polyurethane resin composition is discharged onto a belt conveyor and foamed at atmospheric pressure and room temperature. On the other hand, mold foaming is a method in which a mixed recycled polyurethane resin composition is filled into a mold (forming die) and foamed within the mold.

[0042] In the polyurethane resin, the content of the amine compound-containing solid matter is not particularly limited, and is preferably more than 0 and 30 parts by mass or less, more preferably 2 parts by mass or more and 20 parts by mass or less, and even more preferably 5 parts by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the polyol in the polyurethane resin composition. [Example]

[0043] 1. Manufacturing of decomposable polyurethane resin A polyurethane foam composition (liquid A and liquid B) was prepared in the proportions shown in Table 1, and polyurethane foam was produced as the decomposable polyurethane resin by slab foaming. In Table 1, "Index" represents the isocyanate index. The density of the resulting polyurethane foam was measured in accordance with JIS K7222:2005. The measured densities are also shown in Table 1.

[0044] The details of each raw material are as follows: Polyol: Polyether polyol, number average molecular weight 3000, functionality 3, hydroxyl value 56.1 mg KOH / g, product name: Sannix GP-3050NS, manufactured by Sanyo Chemical Industries, Ltd. Amine catalyst: Product name: DABCO 33LSI, manufactured by EVONIK Foam stabilizer: Silicone foam stabilizer, product name: L-595, manufactured by Momentive Tin catalyst: Stannous octoate, product name: MRH-110, manufactured by Johoku Chemical Industry Co., Ltd. Foaming agent: Water Isocyanate: Tolylene diisocyanate, product name: Coronate T-80, manufactured by Tosoh Corporation, NCO%: 48.2%

[0045] [Table 1]

[0046] 2.Decomposition of polyurethane resin Compositions for decomposing polyurethanes of Examples and Comparative Examples were prepared containing the components shown in Tables 2 and 3. The polyurethane foams described above were decomposed using the compositions for decomposing polyurethanes of Examples and Comparative Examples.

[0047] The polyurethane decomposition compositions of Examples 1 to 12 contain an amine compound having a primary amino group and further having a secondary amino group and / or a tertiary amino group. Details of the amine compound are as follows: Examples 1-4: Bis(3-aminopropyl)amine Examples 5-8: 3,3'-diamino-N-methyldipropylamine Examples 9-12: 2-(2-aminoethylamino)ethanol Comparative Examples 1 and 2: Diethanolamine Comparative Example 3: Polyetheramine (average molecular weight 400)

[0048] Furthermore, the polyurethane decomposition compositions of Examples 1, 2, 5, 6, 9, and 10 and Comparative Examples 1 and 2 contain diazabicycloundecene as a catalyst.

[0049] In a 1 L separable flask, the polyurethane decomposition compositions of the Examples and Comparative Examples were added to 100 g of each polyurethane foam. The amounts of each component of the polyurethane decomposition composition added are shown in Tables 2 and 3. After adding the polyurethane decomposition composition, the mixture was heated at 210°C for 3 hours with stirring to obtain a decomposition product.

[0050] The resulting decomposition product was filtered at 70°C through a stainless steel 40 mesh filter.

[0051] [Table 2]

[0052] [Table 3]

[0053] 3. Evaluation of decomposition treatment of polyurethane resin (1) Phase state after decomposition The decomposition products obtained were visually inspected for the presence or absence of phase separation, and the "phase state after decomposition" was evaluated. The evaluation criteria were as follows: A: The substance is separated into two phases: liquid and solid. B: Phase separation occurs into three phases: liquid, liquid, and solid. C: Solid phase only.

[0054] (2) Filterability The decomposition product was filtered, and the filtrate and the filtration residue were observed to evaluate the "filterability" of the decomposition product. The evaluation criteria were as follows: A: The solid matter remains on the mesh and hardly passes through. B: Some of the solids pass through the mesh. C: All solids pass through the mesh.

[0055] (3) Liquid phase recovery rate The recovery rate of the liquid phase was calculated by the method described in the embodiment. The calculated recovery rate of the liquid phase was evaluated according to the following criteria. A: The liquid phase recovery rate is 40% or more. B: The recovery rate of the liquid phase is 30% or more but less than 40%. C: The recovery rate of the liquid phase is less than 30%.

[0056] (4) Overall Judgment The examples and comparative examples were evaluated comprehensively according to the following criteria. A: The "phase state after decomposition" was rated "A", the "filterability" was rated "A", and the "liquid phase recovery rate" was rated "A". B: The evaluation of "phase state after decomposition," "filterability," or "liquid phase recovery rate" received a "B," and none of them received a "C." C: "C" was given in the evaluation of "phase state after decomposition," "filterability," or "liquid phase recovery rate."

[0057] 4. Results regarding decomposition treatment of polyurethane resin The evaluation results are shown in Tables 2 and 3. Examples 1 to 12 satisfy the following requirement (a): Comparative Examples 1 to 3 do not satisfy the following requirement (a). Requirement (a): The composition for decomposing polyurethane contains an amine compound having a primary amino group and further having a secondary amino group and / or a tertiary amino group.

[0058] Examples 1 to 12 received an overall rating of "A." On the other hand, Comparative Examples 1 to 3 received an overall rating of "C." It was found that Examples 1 to 12, which satisfy requirement (a), were able to recover polyol more efficiently than Comparative Examples 1 to 3. Examples 1 to 12, which satisfy requirement (a), were able to easily obtain a solid material containing recycled polyol and an amine compound.

[0059] 5. Effects of Examples 1 to 12 According to Examples 1 to 12, a technique for decomposing polyurethane resin to obtain recycled raw materials simply and efficiently was provided.

[0060] 6. Production of polyurethane foam containing solids containing amine compounds The raw materials were blended according to the compositions shown in Table 4, and polyurethane foams of Reference Example, Examples 13 and 14, and Comparative Examples 4 and 5 were produced by slab foaming. Note that the amount of active hydrogen in the amine compound-containing solid matter was not taken into consideration when calculating the isocyanate index (INDEX).

[0061] Details of the amine compound-containing solids and each raw material are as follows. Each amine compound-containing solid was dispersed in polyol in advance and then mixed with the other raw materials. The reference example is an example (blank) in which no amine compound-containing solid was used. Amine compound-containing solid 1 (solid of Example 1): filtration residue obtained in Example 1 Amine compound-containing solid 2 (solid of Example 2): filtration residue obtained in Example 2 Amine compound-containing solid 3 (solid of Comparative Example 1): filtration residue obtained in Comparative Example 1 Amine compound-containing solid 4 (solid of Comparative Example 2): filtration residue obtained in Comparative Example 2 Polyol: Sannix GP-3050NS, manufactured by Sanyo Chemical Industries, Ltd. Amine catalyst: Kao Raiser No. 25, manufactured by Kao Chemical Co., Ltd. Foam stabilizer: SZ1136, manufactured by Toray Dow Corning Foaming agent: Water Tin catalyst: Stannous octoate, product name: MRH-110, manufactured by Johoku Chemical Industry Co., Ltd. Isocyanate: Tolylene diisocyanate, product name: Coronate T-80, manufactured by Tosoh Corporation

[0062] [Table 4]

[0063] 7. Evaluation of the production of polyurethane foam containing solids containing amine compounds (1) Foaming Foamability was evaluated for the Reference Example, Examples 13 and 14, and Comparative Examples 4 and 5. Foamability was evaluated by visually observing the appearance and evaluating "Health Bubble," which relates to gas escape from the foam surface, and "Foam State," which relates to cracks and shrinkage behavior inside the foam, according to the following criteria. <Foaming: Health Bubble> Good: No defects due to gas leakage from the foam surface, and the appearance is good. Poor: Defects due to gas escape from the foam surface, and poor appearance. <Foam State> Good: No cracks inside the foam or defects due to shrinkage behavior were found, and the appearance was good. Poor: Cracks inside the foam, defects due to shrinkage behavior, and poor appearance.

[0064] If both "Health Bubble" and "Foam State" are rated "Good," the polyurethane foam will be uniform in shape. If at least one of "Health Bubble" and "Foam State" is rated "Poor," the polyurethane foam will be uneven, with cracks and other defects.

[0065] (2) Reactivity For the Reference Example, Examples 13 and 14, and Comparative Examples 4 and 5, the reactivity (cream time, rise time) was measured by the following method. Cream time: The time (seconds) from when the mixed liquid of the ingredients became cloudy and creamy until the foam began to rise was measured. Rise time: The time it takes for the foam to stop rising due to foaming in the mixed liquid of raw materials was measured as the rise time (seconds). In the above measurement, the time when mixing of the mixture of raw materials other than isocyanate (liquid A) with the isocyanate (liquid B) was started was set as zero seconds. The evaluation was performed visually.

[0066] (3) Foam properties The polyurethane foams of Reference Example and Examples 13 and 14 were measured for the following various physical properties. Apparent density (density) The density was measured in accordance with JIS K7222:2005. 25% ILD hardness The 25% ILD hardness was measured in accordance with JIS K6400-2:2012 6.7 ISO D method. Rebound elasticity The impact resilience was measured in accordance with JIS K6400-3:2011. Tensile strength and elongation The tensile strength and elongation were measured in accordance with JIS K6400-5:2012 No. 5.2 meter, No. 2 type. Tear strength The tear strength was measured in accordance with JIS K6400-5:2012 6.B method. Ventilation The air permeability was measured in accordance with JIS K6400-7:2004 3.A method. ·Compression residual strain The compressive residual strain was measured in accordance with JIS K6400-4 4.5.2 Method A.

[0067] 8. Results on the production of polyurethane foam containing solids containing amine compounds The evaluation results are shown in Table 4. Examples 13 and 14 had foaming properties and reactivity substantially equivalent to those of the reference example (blank). In contrast, Comparative Examples 4 and 5 had poor foaming properties and reactivity. It was found that the amine compound-containing solids of Examples 1 and 2 used in Examples 13 and 14 are solids that can be used as recycled raw materials. The polyurethane foams of Examples 13 and 14 had good physical properties.

[0068] 9. Effects of Examples 13 and 14 According to Examples 13 and 14, a technology was provided that enables the amine components in the decomposition product, which have been difficult to use as recycled raw materials in the past, to be used as recycled raw materials.

[0069] The present disclosure is not limited to the above-described embodiments, and various modifications and variations are possible within the scope of the present disclosure.

Claims

1. A composition for decomposing polyurethanes, comprising an amine compound having a primary amino group and further having a secondary amino group and / or a tertiary amino group.

2. The composition for decomposing polyurethanes according to claim 1, wherein the amine compound is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2): 【Chemistry 1】 (In formula (1), R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n represents an integer of 2 to 7, and m represents an integer of 2 to 7.) 【Chemistry 2】 (In formula (2), R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n represents an integer of 2 to 7, and m represents an integer of 2 to 7.)

3. A method for producing a recycled polyol, comprising decomposing a polyurethane resin using the polyurethane decomposition composition according to claim 1 or 2 to obtain a recycled polyol.

4. The method for producing a recycled polyol according to claim 3, wherein the recycled polyol is obtained by separating solid matter from a decomposition product obtained by decomposing the polyurethane resin.

5. 3. A method for producing a solid material containing an amine compound, comprising decomposing a polyurethane resin with the polyurethane decomposition composition according to claim 1 or 2, and separating an amine compound-containing solid material from a decomposition product obtained by decomposing the polyurethane resin.

6. A polyurethane resin comprising a solid material containing an amine compound obtained by the method according to claim 5.

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