Method for producing solid material for filler and polyurethane resin

Abstract

To effectively utilize an amine compound contained in a decomposition product of a polyurethane resin.SOLUTION: The method for producing a solid material for a filler comprises reacting a polyurethane resin with a decomposing agent to form a decomposition product, adding an organic carboxylic acid-based compound to the decomposition product, and separating a solid material which is a reaction product of an amine compound derived from the decomposition product and the organic carboxylic acid-based compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing a filler solid and a polyurethane resin. [Background technology]

[0002] There is a need for technology to chemically decompose polyurethane resin and recycle it as a raw material for recycled polyurethane resin.

[0003] Patent Document 1 describes a method for producing a resin composition, which is characterized by decomposing a urethane resin with a decomposing agent having an unsaturated carbon bond. It also describes that the obtained resin composition can be used as a molding material by blending various additives as needed.

[0004] Patent Document 2 describes a method for purifying a polyol, in which at least one organic dicarboxylic acid or anhydride thereof selected from the group consisting of oxalic acid, succinic acid, maleic acid, and maleic anhydride is added to a polyol containing a polyamine, and then the precipitate is removed. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-8784 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-247917 Summary of the Invention [Problem to be solved by the invention]

[0006] Conventionally, the amine compounds contained in the decomposition products of polyurethane resins have not been effectively utilized as raw materials for recycled polyurethane resins.

[0007] The present disclosure has been made in view of the above circumstances, and aims to effectively utilize an amine compound contained in a decomposition product of a polyurethane resin. The present disclosure can be realized in the following aspects. [Means for solving the problem]

[0008] reacting a polyurethane resin with a decomposing agent to form a decomposed product; adding an organic carboxylic acid compound to the decomposition product; The method for producing a solid material for a filler includes separating a solid material that is a reaction product between the amine compound derived from the decomposition product and the organic carboxylic acid compound, thereby obtaining the solid material for a filler. [Effects of the Invention]

[0009] According to the present disclosure, a technique can be provided for effectively utilizing amine compounds contained in decomposition products of polyurethane resins. DETAILED DESCRIPTION OF THE INVENTION

[0010] Here, a preferred example of the present disclosure will be described. [1] reacting a polyurethane resin with a decomposing agent to form a decomposed product; adding an organic carboxylic acid compound to the decomposition product; The method for producing a solid material for a filler includes separating a solid material that is a reaction product between the amine compound derived from the decomposition product and the organic carboxylic acid compound, thereby obtaining the solid material for a filler. [2] The method for producing a solid material for a filler according to [1], wherein the decomposing agent is an amine compound. [3] The method for producing a solid material for a filler according to [1] or [2], wherein the organic carboxylic acid compound is a polybasic acid and / or an anhydride thereof. [4] A polyurethane resin containing a filler solid obtained by the manufacturing method according to any one of [1] to [3].

[0011] 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.

[0012] 1. Manufacturing method of filler solids The method for producing the solid material for fillers involves reacting a polyurethane resin with a decomposing agent to form a decomposition product (hereinafter also referred to as the first step), adding an organic carboxylic acid compound to the decomposition product (hereinafter also referred to as the second step), and separating the solid material that is the reaction product of the amine compound derived from the decomposition product and the organic carboxylic acid compound, thereby obtaining the solid material for fillers (hereinafter also referred to as the third step).

[0013] (1) Polyurethane resin The polyurethane resin used in the method for producing a filler solid material 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 into pieces cut to a predetermined size. The polyurethane foam may be, for example, scraps discarded during the polyurethane foam production process or used polyurethane foam to be discarded.

[0014] (2) Decomposition agent The decomposing agent is not particularly limited. From the viewpoints of reactivity and cost, the decomposing agent is preferably one or more selected from the group consisting of compounds having a hydroxyl group and amine compounds. From the viewpoint of suitably precipitating the reaction product of the amine compound derived from the decomposition product and the organic carboxylic acid compound as a solid, the decomposing agent is more preferably an amine compound. The decomposing agent can be used alone or in combination of two or more.

[0015] The amine compound used as the decomposing agent is preferably an amine compound A having a primary amino group and further having a secondary amino group and / or a tertiary amino group. The amine compound A is, for example, one or more selected from the group consisting of 3,3'-diamino-N-methyldipropylamine, 3,3'-diaminodipropylamine, diethylenetriamine, pentaethylenehexamine, tris(3-aminopropyl)amine, triethylenetetramine, N,N-bis(3-aminopropyl)butylamine, 2-(aminomethyl)piperidine, tetraethylenepentamine, N-ethylethylenediamine, 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.

[0016] The amine compound used as the decomposing agent is preferably an amine compound B having a primary hydroxyl group and further having a secondary amino group and / or a tertiary amino group. Examples of the amine compound B include one or more selected from the group consisting of diethanolamine, 2-(2-aminoethylamino)ethanol, N-methyldiethanolamine, 4-(2-hydroxyethyl)morpholine, N-ethyldiethanolamine, diisopropanolamine, triethanolamine, N-butyldiethanolamine, N-tert-butyldiethanolamine, N-(3-aminopropyl)diethanolamine, 1-[bis(2-hydroxyethyl)amino]-2-propanol, N-phenyldiethanolamine, N-benzyldiethanolamine, and p-tolyldiethanolamine.

[0017] The amount of decomposing agent added is not particularly limited. From the viewpoint of sufficiently decomposing the polyurethane resin, the amount of decomposing agent added is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more, relative to 100 parts by mass of polyurethane resin. In consideration of the effect on reactivity and physical properties when polyurethane resin decomposition products are reused as polyurethane resin raw materials, etc., the amount of decomposing agent added is preferably 75 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less. From these viewpoints, the amount of decomposing agent added is preferably 3 parts by mass or more and 75 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, and even more preferably 7 parts by mass or more and 30 parts by mass or less.

[0018] (3) Cracking catalyst The decomposing agent may be used in combination with a decomposition catalyst. The decomposition catalyst is not particularly limited. The decomposition catalyst is preferably one that is used when producing a polyurethane resin. The decomposition catalyst may be used alone or in combination of two or more.

[0019] The decomposition catalyst is more preferably a tertiary amine containing no hydroxyl group. Examples of the decomposition catalyst include one or more selected from the group consisting of diazabicycloundecene, triethylamine, tripropylamine, tributylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, diethyltriamine, 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] A metal catalyst may be used as the decomposition catalyst. The metal catalyst may be used in combination with the above-mentioned tertiary amine not containing a hydroxyl group. The metal catalyst is, for example, one or more 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] The amount of decomposition catalyst added is not particularly limited. From the viewpoint of sufficiently decomposing the polyurethane resin, the amount of decomposition catalyst added is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, relative to 100 parts by mass of polyurethane resin. In consideration of the influence on reactivity and physical properties when a polyurethane resin decomposition product is reused as a polyurethane resin raw material, the amount of the decomposition catalyst added is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less. From these viewpoints, the amount of the decomposition catalyst added is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.3 parts by mass or more and 4 parts by mass or less, and even more preferably 0.5 parts by mass or more and 3 parts by mass or less.

[0022] (4) Decomposition product The decomposition product is obtained by reacting a polyurethane resin with a decomposing agent. The decomposition product may also be obtained by treating a polyurethane resin with a decomposing agent and a decomposition catalyst. The decomposition treatment method for a polyurethane resin will be described later.

[0023] The decomposition products include, for example, polyols derived from raw polyols of polyurethane resins and amine compounds derived from raw isocyanates. In addition, the decomposition products may also include amine compounds added as decomposing agents. Furthermore, the decomposition products may also include flame retardants, decomposition catalysts, and other additives contained in the polyurethane resin.

[0024] The state of the decomposition product is not particularly limited. The decomposition product is preferably in a state where it is separated into two phases: a phase containing polyol (hereinafter also referred to as polyol phase) and a phase containing an amine compound (hereinafter also referred to as amine phase). When the decomposition agent contains an amine compound, the decomposition product can be suitably obtained in a state where it is separated into two phases: a polyol phase and an amine phase. The decomposition product is preferably obtained as a two-phase liquid. Note that the decomposition product being "obtained as a two-phase liquid" means that it is in a state where a liquid phase containing polyol derived from the raw material polyol and a liquid phase containing an amine compound derived from the raw material isocyanate are separated. The two-phase liquid may contain solid content (solid matter) that was contained in the polyurethane resin.

[0025] When the decomposition product is separated into two phases, the polyol phase has a higher purity than a decomposition product in a single phase where the polyol phase and the amine phase are not separated. However, some amine compounds produced as by-products during decomposition are dissolved in the polyol phase. According to the technology disclosed herein, the amine compounds dissolved in the polyol phase before the acid addition treatment described below can be reacted with acid and removed as precipitates such as amide compounds. As a result, the amount of amine compounds dissolved in the polyol phase can be reduced, resulting in a recycled polyol of even higher purity.

[0026] (5) Organic carboxylic acid compounds An organic carboxylic acid is an organic compound having a carboxyl group in the molecule. In the present disclosure, the organic carboxylic acid compound may be an organic carboxylic acid itself or an anhydride of an organic carboxylic acid, as long as it is a compound that reacts with an amine compound to give a structure derived from an organic carboxylic acid. The organic carboxylic acid compound may be used alone or in combination of two or more kinds.

[0027] The organic carboxylic acid of the organic carboxylic acid compound may be either an aromatic carboxylic acid or an aliphatic carboxylic acid. The number of carbon atoms in the organic carboxylic acid compound is preferably from 2 to 20, more preferably from 2 to 12, and even more preferably from 3 to 10. The number of carbon atoms here includes the number of carbon atoms contained in the carboxyl group. The boiling point or decomposition temperature of the organic carboxylic acid compound under atmospheric pressure is preferably 135° C. or higher, more preferably 140° C. or higher, and even more preferably 150° C. or higher. The upper limit of the boiling point or decomposition temperature is not particularly limited, and is usually 500° C. or lower. The melting point of the organic carboxylic acid in the organic carboxylic acid compound is preferably 300° C. or lower, more preferably 250° C. or lower, and even more preferably 220° C. or lower. The lower limit of the melting point is not particularly limited and is usually 20° C. or higher, and may be 50° C. or higher, 80° C. or higher, or 95° C. or higher.

[0028] The organic carboxylic acid compound is preferably a polybasic acid and / or its anhydride. When a polybasic acid and / or its anhydride is used, a reaction product having a larger molecular weight can be preferably obtained compared to when a monocarboxylic acid is used. Therefore, the reaction product can be preferably obtained as a solid.

[0029] The number of carboxyl groups in the polybasic acid and / or anhydride thereof is preferably 2 or more and 4 or less, and more preferably 2 or 3. The polybasic acid is, for example, one or more selected from the group consisting of oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, dipropylmalonic acid, maleic acid, trans-3-hexanoic acid, itaconic acid, phthalic acid, trimellitic acid, malic acid, L-tartaric acid, citric acid, trans-aconitic acid, and 2,3-pyridinecarboxylic acid. The acid anhydride is, for example, one or more selected from the group consisting of succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, and trimellitic anhydride.

[0030] The amount of the organic carboxylic acid compound added is not particularly limited. From the viewpoint of suppressing reactivity when reused as a polyurethane resin raw material, the amount of the organic carboxylic acid compound added is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more, relative to 100 parts by mass of polyurethane resin. In consideration of the influence on reactivity and physical properties when a polyurethane resin decomposition product is reused as a polyurethane resin raw material, the amount of the organic carboxylic acid compound added is preferably 75 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less. From these viewpoints, the amount of the decomposition catalyst added is preferably 3 parts by mass or more and 75 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, and even more preferably 7 parts by mass or more and 30 parts by mass or less.

[0031] (6) First step The first step is a step of reacting a polyurethane resin with a decomposing agent to form a decomposition product. In the first step, the polyurethane resin is preferably heated together with the decomposing agent in order to increase the reaction rate between the polyurethane resin and the decomposing agent. At this time, a decomposition catalyst may be added together with the decomposing agent, if necessary. When heating the polyurethane resin together with the decomposing agent, the mixture of the polyurethane resin and the decomposing agent is preferably stirred.

[0032] The decomposition treatment 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, in order to improve the decomposition rate while suppressing the decomposition of the polyol in 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, or 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 decomposing a polyurethane resin at a temperature between room temperature (e.g., 25°C) and below 80°C, the decomposition treatment time may be set to be longer than 24 hours.

[0033] (7)Second process The second step is adding an organic carboxylic acid compound to the decomposition product. The decomposition product may contain at least one amine compound, such as an amine compound derived from the raw isocyanate, an amine compound derived from the decomposing agent, or an amine compound produced by the reaction of these amine compounds with other components. When the amine compound derived from the decomposition product reacts with an organic carboxylic acid compound, for example, an amide bond is formed through dehydration condensation between an amino group and a carboxyl group, producing an amide compound (including an imide compound). In addition, for example, the amine compound derived from the decomposition product may react with an organic carboxylic acid compound to produce a carboxylic acid salt. It is presumed that the technology of the present disclosure can be used as a filler by reacting an amine compound with an organic carboxylic acid compound to produce a reaction product that is less likely to undergo side reactions. Note that the technology of the present disclosure is not limited by the above-presumed reaction mechanism.

[0034] In the second step, from the viewpoint of promoting the reaction between the amine compound derived from the decomposition product and the organic carboxylic acid compound, it is preferable to add the organic carboxylic acid compound to the decomposition product and heat the mixture. When adding the organic carboxylic acid compound to the decomposition product and heating the mixture, it is preferable to stir the mixture of the decomposition product and the organic carboxylic acid compound.

[0035] The temperature at which the amine compound derived from the decomposition product and the organic carboxylic acid compound are reacted is preferably 150°C or higher, and may be 160°C or higher, 170°C or higher, or 180°C or higher, from the viewpoint of suitably obtaining a solid reaction product. The upper limit of the temperature at which the amine compound derived from the decomposition product and the organic carboxylic acid compound are reacted is not particularly limited. The upper limit of the temperature is, for example, 280°C or lower, and may be 260°C or lower, 240°C or lower, or 220°C or lower, from the viewpoint of suppressing vaporization or decomposition of the organic carboxylic acid compound.

[0036] The heating may be carried out by utilizing the residual heat from the decomposition of the polyurethane resin. For example, before the temperature of the heated decomposition product is cooled to room temperature, an organic carboxylic acid compound is added and the heating is carried out. This can shorten the heating and cooling time and reduce energy consumption, such as electricity, when producing recycled polyol.

[0037] When an organic carboxylic acid compound is added and heated, dehydration condensation occurs, so in the method for producing a filler solid material, dry gas may be supplied during the heating. For example, the decomposition product and the organic carboxylic acid compound may be placed in a container and heated, and dry gas may be supplied into the container from an external gas supply source. Dry nitrogen, for example, is suitable as the dry gas.

[0038] The time for reacting the amine compound derived from the decomposition product with the organic carboxylic acid compound is, for example, from 10 minutes to 24 hours, and may be from 30 minutes to 10 hours. The end point of the reaction time may be appropriately set while confirming that the total amine value of the reaction product has been sufficiently reduced.

[0039] Hereinafter, the treated product obtained in the second step will also be referred to as an acid-added product. The state of the acid-added product is not particularly limited. The acid-added product is preferably separated into two phases: a liquid phase containing recycled polyol and a solid phase containing solids that are the reaction product of an amine compound derived from the decomposition product and an organic carboxylic acid compound. By adding an organic carboxylic acid compound to the decomposition product, an acid-added product separated into two phases, i.e., a liquid phase and a solid phase, can be preferably obtained. Note that the acid-added product being "separated into two phases, i.e., a liquid phase and a solid phase," when observed visually, means, for example, that the liquid phase exists as a single phase and a solid phase distinct from the liquid phase exists. The solid phase can be visually recognized, for example, as a precipitate in the liquid phase. In this way, when the liquid phase exists as a single phase, the effect of improving the recovery rate of recycled polyol can be expected compared to when the liquid phase exists as multiple phases.

[0040] (8) Third step The third step is a step of obtaining a solid material for filler by separating a solid material that is a reaction product between the amine compound derived from the decomposition product and the organic carboxylic acid compound.

[0041] The method for separating the solid matter, which is the reaction product of the amine compound derived from the decomposition product and the organic carboxylic acid compound, is not particularly limited. The acid-treated product obtained in the second step contains, for example, a liquid phase containing recycled polyol and a solid phase. By filtering such an acid-treated product, the solid matter, which is the reaction product, can be separated as a filtrate (filtration residue). That is, the solid matter for filler can be suitably obtained as a filtrate (filtration residue) obtained by filtering with a filter of a predetermined mesh. The filter that can be used, for example, a 20-200 mesh filter, can be used depending on the properties of the acid-treated product. The solid matter separated in this way can be used as a solid matter for filler as it is. The liquid phase obtained as a filtrate can be recycled separately as recycled polyol.

[0042] When filtering the acid-treated product, it is advisable to filter at a temperature higher than room temperature (e.g., 25°C) from the viewpoint of reducing the viscosity of the liquid phase and sufficiently separating the solid matter. The temperature during filtration is preferably 40°C or higher and 100°C or lower, more preferably 50°C or higher and 90°C or lower, and even more preferably 60°C or higher and 80°C or lower.

[0043] Furthermore, by leaving the acid-treated product to stand, it can be separated into a liquid phase and a solid phase due to the difference in specific gravity. If the specific gravity of the solid phase is greater than that of the liquid phase, the solid reaction product will precipitate. Then, only the liquid phase containing the recycled polyol may be removed from the container in which the solid reaction product has precipitated, and the solid may be separated. The solid separated in this way can be used as a solid for filler as is. The liquid phase obtained as a filtrate can be recycled separately as recycled polyol.

[0044] The filler solid may contain solids other than the solids that are reaction products of the decomposition products of the amine compound and the organic carboxylic acid compound (hereinafter also referred to as "other solids"). Examples of other solids include fillers contained in the decomposed polyurethane resin, flame retardants such as phosphorus-based flame retardants and halogen-based flame retardants, etc. According to the technology of the present disclosure, the solids contained in the polyurethane resin can also be effectively used as filler solids.

[0045] The filler solid is preferred as a filler for polyurethane resins because side reactions are suppressed, and is particularly preferred as a filler for polyurethane foams because it is less likely to adversely affect foamability. The filler solid may also be used as a filler for resins other than polyurethane resins. Examples of resins other than polyurethane resins include polyolefin resins, polystyrene resins, polycarbonate resins, polyvinyl chloride resins, polyacetal resins, polyurea resins, polyamide resins, polybutylene terephthalate resins, silicone resins, and polyethylene terephthalate resins.

[0046] 2. Polyurethane resin containing filler solids The polyurethane resin contains the above-mentioned filler solid. In the description of the polyurethane resin, the description in the above section "1. Production method of filler solid" applies as is to the filler solid.

[0047] The polyurethane resin is obtained from a polyurethane resin composition containing, for example, a polyol, an isocyanate, and a filler solid. 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.

[0048] In the polyurethane resin, the content of the filler solid is not particularly limited. From the viewpoint of improving the recycle rate, the content of the filler solid is preferably more than 0 parts by mass, more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more, based on 100 parts by mass of the polyol in the polyurethane resin composition. From the viewpoint of ensuring various physical properties, the content of the filler solid is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less. From these viewpoints, the content of the filler solid is preferably more than 0 parts by mass and 40 parts by mass or less, more preferably 2 parts by mass or more and 30 parts by mass or less, and even more preferably 5 parts by mass or more and 25 parts by mass or less. [Example]

[0049] 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 a polyurethane foam was produced as the decomposable polyurethane resin by slab foaming. The density of the resulting polyurethane foam was measured in accordance with JIS K7222:2005. The measured density is also shown in Table 1.

[0050] 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%

[0051] [Table 1]

[0052] 2. Decomposition of polyurethane resin (first step) In a 1 L separable flask, 100 g of the polyurethane resin to be decomposed was added with the decomposition agent and decomposition catalyst in the blending ratios shown in Table 2, and the mixture was heated at 200°C for 3 hours with stirring to obtain the decomposition products of Production Examples 1 to 5. Details of the decomposition agent and decomposition catalyst are as follows: Decomposer 1: Amine compounds, diethanolamine Decomposition agent 2: Amine compound, 3,3'-diamino-N-methyldipropylamine Decomposition catalyst: diazabicycloundecene (DBU)

[0053] 3. Acid treatment of the decomposition product (step 2) In a 1 L separable flask, succinic anhydride as an organic carboxylic acid compound was added to the decomposition product in the blending ratio shown in Table 2, and the mixture was heated at 200°C for 3 hours with stirring to obtain the acid-added products of Production Examples 1 to 5.

[0054] The phase states of the acid-treated products of Production Examples 1 to 5 were evaluated according to the following criteria. The results are shown in Table 2. (Evaluation of phase state, evaluation of separation state after the second step) "A": Separated into two phases: solid and liquid. "B": Separation into three phases: solid phase, liquid phase and liquid phase "C": No separation into solid and liquid phases

[0055] 4. Separation of solids for filler (third step) The acid-treated products of Production Examples 1 to 5 obtained in the second step above were filtered through a 40-mesh stainless steel mesh at 70°C to separate the filtrate containing the recycled polyol from a solid (filtrate). The solid was a reaction product of an amine compound derived from the decomposition product and an organic carboxylic acid compound, and corresponds to a solid for filler.

[0056] The filterability of the filler solid materials of Production Examples 1 to 5 was evaluated according to the following criteria. The results are shown in Table 2. (Evaluation of filterability, evaluation of filtration state in the third step) "A": Solids remain on the mesh and do not pass through the mesh "B": Some of the solids pass through the mesh "C": All solids pass through the mesh

[0057] [Table 2]

[0058] 4. Production of polyurethane resin containing filler solids The raw materials were blended according to the compositions shown in Table 3, and polyurethane foams were produced by slab foaming using polyurethane resins containing the filler solids of Examples 1 to 5 and Comparative Example 1. As a reference example, a polyurethane foam was produced in the same manner as the polyurethane resins containing the filler solids of Examples 1 to 5 and Comparative Example 1, except that no filler solids were added. In Table 3, the raw materials except for the filler solids were the same as the raw materials for the polyurethane resin to be decomposed. In calculating the isocyanate index, the amount of active hydrogen in the solid material containing the amine compound is not taken into consideration.

[0059] 5. Evaluation Method The foaming properties of the polyurethane foams of Reference Example, Examples 1 to 5, and Comparative Example 1 were evaluated according to the following criteria. The results are shown in Table 3. (Health Bubble) "Good": No defects due to gas leakage from the foam surface, and good appearance "Poor": Defects due to gas leakage 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

[0060] The cream time and rise time of the polyurethane foams of Reference Example, Examples 1 to 5, and Comparative Example 1 were measured by the following methods. Cream time: The time (seconds) required for the mixture of the above ingredients to become cloudy and creamy and for the foam to start rising was measured. Rise time: In the mixed liquid of the above raw materials, the time until the rise of the foam caused by foaming stopped was measured as the rise time (seconds). In the above measurement, the time when the composition (liquid A) and the isocyanate (liquid B) started to be mixed was set as zero seconds.

[0061] (Evaluation of foaming properties) "A": Both "Health Bubble" and "Foam State" are rated "Good" "B": At least one of the "Health Bubble" and "Foam State" ratings is "Poor"

[0062] The physical properties of the polyurethane foams of Reference Example, Examples 1 to 5, and Comparative Example 1 were measured by the following methods. The results are shown in Table 3. Apparent density: Compliant with JIS K7222:2005 25% ILD hardness: JIS K6400-2:2012 6.7 Compliant with ISO D method Rebound resilience: Compliant with JIS K6400-3:2011 Tensile strength, elongation: Compliant with JIS K6400-5:2012 No. 5.2 total, No. 2 type Tear strength: Complies with JIS K6400-5:2012 6.B method Airflow rate: Complies with JIS K6400-7:2004 3.A method Compression set: Complies with JIS K6400-4 4.5.2 A method

[0063] (Evaluation of physical properties) "A": Physical properties equivalent to the reference example (blank) "B": The physical properties are significantly different from those of the reference example (blank) or cannot be evaluated.

[0064] [Table 3]

[0065] 6.Results Examples 1 to 5 satisfy the following requirements (a) to (c): Comparative Example 1 does not satisfy the following requirement (b). Requirement (a): The polyurethane resin and the decomposing agent are reacted to produce a decomposed product. Requirement (b): Add an organic carboxylic acid compound to the decomposition product. Requirement (c): A solid material for filler is obtained by separating a solid material that is a reaction product between an amine compound derived from the decomposition product and an organic carboxylic acid compound.

[0066] Examples 1 to 5 were given an overall rating of "A" for foaming properties. Examples 1 to 5 were given an overall rating of "A" for physical properties. On the other hand, Comparative Example 1 was given an overall rating of "B" for foaming properties. Comparative Example 1 was given an overall rating of "B" for physical properties. It was found that Examples 1 to 5, which satisfy requirements (a) to (c), can be used as a filler for polyurethane resin by being made into a solid product that is a reaction product of an amine compound derived from the decomposition product and an organic carboxylic acid compound.

[0067] 7. Effects of the Example According to this example, the amine compound contained in the decomposition product of the polyurethane resin could be effectively utilized.

[0068] 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. reacting a polyurethane resin with a decomposing agent to form a decomposed product; adding an organic carboxylic acid compound to the decomposition product; The method for producing a solid material for a filler includes separating a solid material that is a reaction product between the amine compound derived from the decomposition product and the organic carboxylic acid compound, thereby obtaining the solid material for a filler.

2. The method for producing a solid material for a filler according to claim 1 , wherein the decomposing agent is an amine compound.

3. 3. The method for producing a solid material for a filler according to claim 1, wherein the organic carboxylic acid compound is a polybasic acid and / or an anhydride thereof.

4. A polyurethane resin containing a filler solid obtained by the process of claim 1 or 2.

Images