Method for producing solids, method for producing filler solids, polyurethane resin, filler solids, polyol composition, and method for producing polyurethane foam

Abstract

This invention provides technology for utilizing by-product amine compounds resulting from the decomposition of polyurethane resins. [Solution] The method for producing the solid involves reacting a polyurethane resin with a decomposition agent to produce a decomposition product, adding an acidic compound to the decomposition product, and reacting an isocyanate compound with a composition containing the reaction product of the amine compound derived from the decomposition product and the acidic compound to obtain the solid.

Description

[Technical Field]

[0001] This disclosure relates to a method for producing solids, a method for producing filler solids, polyurethane resins, filler solids, polyol compositions, and a method for producing polyurethane foam. [Background technology]

[0002] Patent Document 1 describes a method for treating decomposed and recovered polyols containing amines, obtained by decomposing polyurethane resin, by adding an isocyanate compound. It states that the isocyanate group of the isocyanate compound selectively reacts with the amino group of the amines to produce polyurea, thereby inactivating the amines. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2001-081234 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Patent Document 1 describes the inactivation of amines in recovered polyols with isocyanate compounds, but it does not consider the use of by-product amine compounds.

[0005] This disclosure is made in view of the above circumstances and aims to provide technology for the utilization of by-product amine compounds associated with the decomposition of polyurethane resins. This disclosure can be implemented in the following forms. [Means for solving the problem]

[0006] A decomposition agent is reacted with polyurethane resin to produce decomposition products. An acidic compound is added to the aforementioned decomposition product. A method for producing a solid, comprising reacting an isocyanate compound with a composition containing a reaction product of an amine compound derived from the decomposition product and an acidic compound to obtain a solid. [Effects of the Invention]

[0007] This disclosure provides a technology for utilizing by-product amine compounds associated with the decomposition of polyurethane resins. [Brief explanation of the drawing]

[0008] [Figure 1] This figure shows the melting point, boiling point, and structural formula of polycarboxylic acids or acid anhydrides. [Figure 2] This figure shows an example of a flow chart for the manufacturing method of polyurethane foam. [Figure 3] This is a microscopic image of a solid material used as a filler. [Figure 4] This graph shows the cumulative distribution of the number of solid filler particles. [Modes for carrying out the invention]

[0009] Herein lies a preferred example of this disclosure. [1] A decomposition agent is reacted with polyurethane resin to produce decomposition products. An acidic compound is added to the aforementioned decomposition product. A method for producing a solid, comprising reacting an isocyanate compound with a composition containing a reaction product of an amine compound derived from the decomposition product and an acidic compound to obtain a solid. [2] The method for producing a solid according to [1], wherein the acidic compound is a carboxylic acid having two or more carboxyl groups and / or an anhydride thereof. [3] The method for producing a solid according to [1], wherein the composition is semi-solid. [4] A method for producing a filler solid, comprising crushing a solid obtained by any one of the manufacturing methods described in [1] to [3]. A polyurethane resin containing a filler solid obtained by the manufacturing method described in [5] [4]. [6] A solid filler obtained by pulverizing a solid obtained by the production method according to any one of [1] to [3], wherein in the microscopic image of the solid filler, when measuring the maximum diameter of 100 randomly selected particles, at least 70 of the particles have a maximum diameter of 200 μm or less. [7] A polyol composition in which the solid filler according to [6] is dispersed in a polyol. [8] A method for producing a polyurethane foam, using the solid filler according to [6] as a raw material. [9] A method for producing a polyurethane foam, using the solid filler according to [6] and recycled polyol as raw materials.

[0010] Hereinafter, the present disclosure will be described in detail. In this specification, for a description using "~" for a numerical range, unless otherwise specified, it includes the lower limit value and the upper limit value. For example, in the description of "10~20", both the lower limit value "10" and the upper limit value "20" are included. That is, "10~20" has the same meaning as "10 or more and 20 or less". Also, in this specification, the upper limit value and the lower limit value of each numerical range can be arbitrarily combined.

[0011] 1. Method for producing a solid X The method for producing a solid is to react a polyurethane resin with a decomposing agent to obtain a decomposed product (hereinafter also referred to as the first step), add an acid-based compound to the decomposed product (hereinafter also referred to as the second step), and react an isocyanate compound with the reaction product of the amine compound derived from the decomposed product and the acid-based compound to obtain a solid (hereinafter also referred to as the third step).

[0012] 1-1 The first step The first step involves reacting a decomposition agent with the polyurethane resin to produce decomposition products. The decomposition method for reacting the polyurethane resin with the decomposition agent to produce decomposition products is not particularly limited. Preferred decomposition methods include amine decomposition, glycol decomposition, and hydrolysis. It is desirable that the decomposition method for reacting the polyurethane resin with the decomposition agent to produce decomposition products yields the decomposition products in a phase-separated state. The decomposition agent should, for example, chemically decompose the urethane bonds and liquefy them.

[0013] (1) Polyurethane resin The polyurethane resin is not particularly limited. For example, the polyurethane resin is polyurethane foam. The polyurethane foam may be flexible polyurethane foam, semi-rigid polyurethane foam, or rigid polyurethane foam. The polyurethane foam may be open-cell polyurethane foam or closed-cell polyurethane foam. The polyurethane foam may be crushed to a predetermined size. Alternatively, the polyurethane foam may be cut pieces to a predetermined size. The polyurethane foam may be, for example, scraps discharged during the manufacturing process of polyurethane foam, or used polyurethane foam that is scheduled to be discarded.

[0014] (2) Decomposing agent From the standpoint of reactivity and cost, it is preferable that the decomposition agent be one or more selected from the group consisting of amine compounds and compounds having a hydroxyl group. The amine compound is preferably one or more selected from the group consisting of, for example, diethanolamine, diglycolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, propanediamine, 2-ethylhexylamine, isopropanolamine, 2-(2-aminoethylamino)ethanol, 2-amino-2-hydroxymethyl-1,3-propanediol, ethylaminoethanol, aminobutanol, n-propylamine, di-n-propylamine, n-amylamine, isobutylamine, methyldiethylamine, monoethanolamine, triethanolamine, cyclohexylamine, piperazine, piperidine, aniline, toluidine, benzylamine, phenylenediamine, xylylenediamine, chloroaniline, pyridine, picoline, N-methylmorpholine, ethylmorpholine, and pyrazole. These amine compounds can be used individually or in combination of two or more. The compound having a hydroxyl group is preferably one or more selected from the group consisting of, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentadiol, 1,6-hexanediol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, and polyethylene glycol. These compounds having a hydroxyl group can be used individually or in combination of two or more.

[0015] The decomposition agent preferably contains an amine compound. That is, the decomposition product is preferably obtained by amine decomposition. When the decomposition agent contains an amine compound, the amine compound used as the decomposition agent can also be removed as a solid by adding an acidic compound. As a result, a high-purity polyurethane resin-derived polyol (also called a recycled polyol) can be obtained.

[0016] The amount of decomposition agent added is not particularly limited. From the viewpoint of sufficiently decomposing the polyurethane resin, the amount of decomposition agent added is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 8 parts by mass or more, per 100 parts by mass of polyurethane resin. The amount of decomposition agent added is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less, taking into consideration the effect on the reactivity and physical properties when the decomposed polyurethane resin is reused as a polyurethane resin raw material, etc. From these viewpoints, the amount of decomposition agent added is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, and even more preferably 8 parts by mass or more and 40 parts by mass or less.

[0017] (3) Decomposition catalyst The decomposition agent may be used in combination with a decomposition catalyst. The decomposition catalyst is not particularly limited. Preferably, the decomposition catalyst is one used in the production of polyurethane resin. Examples of decomposition catalysts include diazabicycloundecene, triethylamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropane-1,3-diamine, N,N,N',N'-tetramethylhexane-1,6-diamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyldipropylenetriamine, tetramethylguanidine, triethylenediamine, N,N'-dimethylpiperazine, N,-methyl,N'-(2-dimethylamino)ethylpiperazine, N-methylmorpholine, N-(N',N'-dimethylaminoethyl)-morpholine, 1,2-dimethylimidazole, hexamethylenete It is preferable that the catalyst is one or more selected from the group consisting of lamin, dimethylaminoethanol, dimethylaminoethoxyethanol, N,N,N'-trimethylaminoethylethanolamine, N-methyl-N'-(2-hydroxyethyl)-piperazine, N-(2-hydroxyethyl)morpholine, bis(2-dimethylaminoethyl) ether, ethylene glycol bis(3-dimethyl)-aminopropyl ether, stanus octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutylindimaleate, dioctyltin mercaptide, dioctyltin thiocarboxylate, lead octenoate, potassium acetate, and potassium octoate. These decomposition catalysts can be used individually or in combination of two or more.

[0018] 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 0.5 parts by mass or more, and may be 1 part by mass or more, per 100 parts by mass of polyurethane resin. The amount of decomposition catalyst added is preferably 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less, taking into consideration the effect on the reactivity and physical properties when the decomposed polyurethane resin is reused as a polyurethane resin raw material, etc. From these viewpoints, the amount of decomposition catalyst added is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 0.5 parts by mass or more and 30 parts by mass or less.

[0019] (4) Decomposition conditions for polyurethane resin The conditions for decomposing polyurethane resin are not particularly limited. From the viewpoint of improving the decomposition rate, it is preferable to decompose the polyurethane resin by heating it together with a decomposing agent. When heating the polyurethane resin together with a decomposing agent, it is preferable to stir the mixture of polyurethane resin and decomposing agent.

[0020] The decomposition treatment temperature is preferably 80°C to 300°C, more preferably 100°C to 270°C, and even more preferably 150°C to 250°C, in order to improve the decomposition rate while suppressing the decomposition of polyols as polyurethane decomposition products, i.e., polyols derived from the raw material polyol. The decomposition treatment time may be, for example, 10 minutes to 24 hours, or 30 minutes to 10 hours. The end point of the decomposition treatment time may be set appropriately while checking the progress of the decomposition of the polyurethane resin, depending on the size of the polyurethane resin, whether or not it is stirred, etc. Also, for example, when decomposing the polyurethane resin at room temperature (e.g., 25°C) or below 80°C, the decomposition treatment time may be set to be longer than 24 hours.

[0021] Decomposition products include, for example, polyols derived from the raw material polyol of the polyurethane resin, and amine compounds derived from the raw material isocyanate. In addition, decomposition products may include amine compounds added as decomposition agents, flame retardants, decomposition catalysts, and other additives that were contained in the polyurethane resin.

[0022] The state of the decomposition product is not particularly limited. Preferably, the decomposition product is separated into two phases: a phase containing a polyol (hereinafter also referred to as the polyol phase) and a phase containing an amine compound (hereinafter also referred to as the amine phase). When the decomposition agent contains an amine compound, the decomposition product can be suitably obtained in a state separated into two phases: the polyol phase and the amine phase. Preferably, the decomposition product is obtained as a two-phase liquid. Note that "obtained as a two-phase liquid" means that the liquid phase containing the polyol derived from the raw material polyol and the liquid phase containing the amine compound derived from the raw material isocyanate are separated. The two-phase liquid may also contain solid components that were contained in the polyurethane resin. Examples of solid components that were contained in the polyurethane resin include fillers, polymer-derived components of polymer polyols containing polymers such as styrene and acrylonitrile, and flame retardants such as phosphorus-based flame retardants and halogen-based flame retardants.

[0023] When the decomposition product separates into two phases, the polyol phase is of higher purity compared to the decomposition product in a single phase where the polyol phase and amine phase are not separated. Nevertheless, some amine compounds produced as by-products during decomposition remain dissolved in the polyol phase. According to the technology of this disclosure, in the second step described later, the amine compounds dissolved in the polyol phase can be removed as precipitates such as amide compounds by reacting them with an acid. As a result, the amount of amine compounds dissolved in the polyol phase can be reduced, and an even higher purity polyol can be obtained from the polyol phase.

[0024] 1-2 2nd process The second step involves adding an acidic compound to the decomposition product. (1) Acid compounds The acidic compounds of this disclosure are compounds that react with amine compounds to produce reaction products. The acidic compounds can be used alone or in combination of two or more. Organic carboxylic acid compounds are preferred as the acidic compounds. It is also preferred that the acidic compounds are carboxylic acids having two or more carboxyl groups and / or their anhydrides. Hereinafter, carboxylic acids having two or more carboxyl groups and / or their anhydrides will also be simply referred to as polycarboxylic acids and / or their anhydrides. The number of carboxyl groups in polycarboxylic acids and / or their anhydrides is preferably 2 or more and 4 or less, and more preferably 2 or 3. In this disclosure, "number of carboxyl groups in polycarboxylic acids and / or their anhydrides" refers to the number of carboxyl groups before dehydration condensation in the case of acid anhydrides in which carboxyl groups have undergone dehydration condensation. In the following description, the structure of the portion in which carboxyl groups have undergone dehydration condensation is also referred to as the acid anhydride group. Polycarboxylic acids and / or their anhydrides may be aromatic carboxylic acids or aliphatic carboxylic acids. The number of carbon atoms in polycarboxylic acids and / or their anhydrides is preferably 2 to 20, more preferably 2 to 12, and even more preferably 3 to 10. The number of carbon atoms as used herein includes the number of carbon atoms in the carboxyl group. The boiling point or decomposition temperature of polycarboxylic acids and / or their anhydrides at 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 above boiling point or decomposition temperature is not particularly limited, and is usually 500°C or lower. The melting point of polycarboxylic acids and / or their anhydrides at atmospheric pressure 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 above melting point is not particularly limited, and is usually 20°C or higher, but may be 50°C or higher, 80°C or higher, or 95°C or higher.

[0025] The polycarboxylic acid and / or its anhydride is preferably one or more selected from the group consisting of, for example, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanediic acid, dipropylmalonic acid, maleic acid, trans-3-hexenodioic acid, itaconic acid, phthalic acid, malic acid, L(+)-tartaric acid, citric acid, trans-aconitic acid, 2,3-pyridinedicarboxylic acid, succinic anhydride, maleic anhydride, phthalic anhydride, and trimellitic anhydride. The melting point, boiling point, and structural formula of the above compounds are shown in Figure 1. For compounds where the boiling point column is blank or "-", the boiling point or decomposition temperature is 150°C or higher.

[0026] The amount of acidic compound added is not particularly limited. When the acidic compound is a polycarboxylic acid and / or its anhydride, the amount of acidic compound added should be as follows: In other words, the method for producing the solid is to add a polycarboxylic acid and / or its anhydride to a decomposition product obtained by treating a polyurethane resin with a decomposition agent, such that the ratio of the molar amount of carboxyl groups and carboxyl groups derived from the acid anhydride group of the anhydride to the molar amount of amino groups in the decomposition product is 0.5 or more and 1.2 or less. The ratio of the molar amount of carboxyl groups to the molar amount of amino groups in the decomposition product is more preferably 0.6 or more and 1.1 or less, and even more preferably 0.65 or more and 1.0 or less. If the above molar ratio is greater than or equal to the above lower limit, the amine compounds in the decomposition products can be suitably precipitated as precipitates. Furthermore, if the above molar ratio is less than or equal to the above upper limit, the amount of acidic compounds mixed into the polyol phase when the polyol phase is recovered can be suitably reduced.

[0027] The molar amount of amino groups in the decomposition product can be calculated by measuring the total amine value in accordance with JIS K 1557-7. If the decomposition product is separated into a polyol phase and an amine phase, the molar amount of amino groups in the decomposition product can be calculated by measuring the total amine value of each phase in accordance with JIS K 1557-7 and using a weighted average from the mass ratio of the polyol phase and the amine phase.

[0028] The total amine value of the polyol phase is not particularly limited. For example, the total amine value of the polyol phase may be between 30 mg KOH / g and 300 mg KOH / g, between 40 mg KOH / g and 200 mg KOH / g, or between 60 mg KOH / g and 180 mg KOH / g. The total amine value of the amine phase is not particularly limited. For example, the total amine value of the amine phase may be between 80 mg KOH / g and 500 mg KOH / g, between 100 mg KOH / g and 400 mg KOH / g, or between 150 mg KOH / g and 350 mg KOH / g. The mass ratio of the polyol phase to the amine phase (polyol phase:amine phase) is not particularly limited. For example, the polyol phase:amine phase ratio may be 10:90 to 90:10, 25:75 to 80:20, or 40:60 to 75:25.

[0029] The molar amount of carboxyl groups can be calculated as the sum of the value obtained by multiplying the molar amount of the added polycarboxylic acid by the number of carboxyl groups, and the value obtained by multiplying the molar amount of the added acid anhydride by twice the number of acid anhydride groups.

[0030] (2) Conditions for adding acidic compounds In the second step, it is preferable to add an acidic compound to the decomposition product and heat it. The heating temperature is not particularly limited. From the viewpoint of precipitate formation, the heating temperature should be 150°C or higher, but may be 160°C or higher, 170°C or higher, or 180°C or higher. The upper limit of the heating temperature is not particularly limited. From the viewpoint of suppressing vaporization and decomposition of the acidic compound, the upper limit of the heating temperature should be, for example, 280°C or lower, but may be 260°C or lower, 240°C or lower, or 220°C or lower.

[0031] The above heating may be carried out using the residual heat generated during the decomposition process of the polyurethane resin. For example, by adding an acidic compound before the heated decomposition product cools to room temperature and then performing the above heating, the heating and cooling time during the addition of the acidic compound can be shortened, and energy such as electricity can be reduced.

[0032] The heating time may be, for example, 10 minutes to 24 hours, or 30 minutes to 10 hours. The end point of the heating time may be set as appropriate, while confirming that the total amine value and / or hydroxyl value of the decomposition product have been sufficiently reduced.

[0033] In the second step, the mixture of the decomposition product and the polycarboxylic acid and / or its anhydride may be stirred during the heating process described above. When polycarboxylic acids and / or their anhydrides are added and heated, dehydration condensation occurs. Therefore, in the method for producing the solid, a dry gas may be supplied during the heating process. For example, the decomposition product and the polycarboxylic acid and / or its anhydride may be placed in a container and heated, and a dry gas may be supplied into the container from an external gas source. Dry nitrogen is a suitable dry gas, for example. Furthermore, the removal of moisture may be accelerated by reducing the pressure. There are no particular restrictions on the degree of vacuum during this reduction, but for example, 10 4 Pa or less is preferable, 10 3 Pa or less is more preferable, 10 2 Pa or lower is even more preferable.

[0034] (3) Composition containing reaction products When an acidic compound is added to the decomposition product, a composition is obtained that contains a reaction product between the amine compound derived from the decomposition product and the acidic compound. The reaction product is not particularly limited. The type of reaction product can be appropriately controlled depending on the type of amine compound and acidic compound, the heating temperature, etc. It is presumed that the reaction product is one or more selected from the group consisting of, for example, salts of the amine compound and the acidic compound, and amide compounds (including imide compounds) having a structure derived from the amine compound and / or the acidic compound. The composition contains at least a reaction product between the amine compound derived from the decomposition product and the acidic compound, and may also contain one or more selected from the group consisting of an amine compound that has not reacted with the acidic compound, a polyol, a decomposition agent, an acidic compound, and their reaction products.

[0035] The composition is preferably in a semi-solid state. In this specification, "semi-solid state" means "a state in which the viscosity at 25°C is 10,000 mPa·s or more and which can be easily deformed by the application of force." The method for measuring viscosity will be described later. For example, a product obtained by adding an acidic compound to a decomposition product (hereinafter also referred to as an acid-added product) may be obtained in a state separated into two phases: a polyol phase and a semi-solid phase. In this case, the composition containing the reaction product can be suitably recovered as a semi-solid phase while being separated from the polyol phase. Furthermore, if the composition is in a semi-solid phase, it is easily mixed with the isocyanate compound in the third step described later. In this disclosure, the semi-solid phase may exist separately from the polyol phase, for example, as a phase containing a large amount of precipitate. Furthermore, the composition is not limited to the form obtained as a semi-solid phase, and may be obtained as a liquid phase with higher viscosity than the polyol phase, or as a phase containing some or all of the polyol component.

[0036] If the composition is in a semi-solid phase, the semi-solid phase may be recovered from the acid-treated material and used as part of the composition in the third step. The method for recovering the semi-solid phase from the acid-treated material is not particularly limited. For example, the semi-solid phase can be recovered by filtering the acid-treated material. Alternatively, the semi-solid phase can be recovered by removing only the polyol phase from the container holding the acid-treated material. The polyol phase separated after recovering the semi-solid phase can be used directly as a raw material for recycled polyols.

[0037] The total amine value of the semi-solid phase is not particularly limited. Preferably, the total amine value of the semi-solid phase is 130 mgKOH / g or less, more preferably 120 mgKOH / g or less, and even more preferably 110 mgKOH / g or less. The lower limit of the total amine value of the semi-solid phase is not particularly limited. For example, the total amine value of the semi-solid phase is 50 mgKOH / g or more. The total amine value of the semi-solid phase can be measured in accordance with JIS K 1557-7.

[0038] The hydroxyl value of the semi-solid phase is not particularly limited. For example, the hydroxyl value of the semi-solid phase may be 100 mg KOH / g or more and 500 mg KOH / g or less, 150 mg KOH / g or more and 400 mg KOH / g or less, or 200 mg KOH / g or more and 350 mg KOH / g or less. The hydroxyl value of the semi-solid phase can be measured in accordance with JIS K 1557-1. The hydroxyl groups in the semi-solid phase may include, for example, hydroxyl groups derived from the decomposition agent, as well as hydroxyl groups derived from the polyurethane resin.

[0039] By performing the second step described above, the number of amino groups contained in the decomposition product can be reduced, making it easier to adjust the reactivity of the composition subjected to the third step. For example, if an isocyanate compound is reacted with the decomposition product itself, the reaction may be too fast if the decomposition product contains a large number of amino groups. On the other hand, if an isocyanate compound is reacted with a composition that has gone through the second step, the reaction rate with the isocyanate compound can be kept at an appropriate level. Furthermore, when polyurethane resins derived from aromatic isocyanates are decomposed, harmful aromatic amine compounds may be contained in the decomposition product. By using the decomposition product as a composition that has gone through the second step in the third step, the various operations described later can be performed with a reduced amount of aromatic amine compounds, thereby improving safety during the work.

[0040] 1-3 3rd process The third step involves reacting an isocyanate compound with a composition containing a reaction product between an amine compound derived from a decomposition product and an acidic compound to obtain a solid. (1) Isocyanate compounds The isocyanate compound is not particularly limited. At least one selected from the group consisting of aromatic isocyanates, alicyclic isocyanates, and aliphatic isocyanates is preferably used. One or more aliphatic isocyanates and one or more aromatic isocyanates may be used in combination. Furthermore, from the viewpoint of preferably obtaining a solid product, the isocyanate compound is preferably a polyisocyanate. The polyisocyanate may be a bifunctional polyisocyanate having two isocyanate groups in one molecule, or a trifunctional or more polyisocyanate having three or more isocyanate groups in one molecule, and may be used alone or in combination of several.

[0041] For example, difunctional polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, and 3,3'-dimethoxy-4,4'-biphenylenediisocyanate. Examples include aromatic isocyanates such as phenylenediisocyanate, alicyclic isocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and methylcyclohexane diisocyanate, and aliphatic isocyanates such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylenediisocyanate, methylene diisocyanate, and lysine isocyanate. Furthermore, examples of polyisocyanates with three or more functions include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, biphenyl-2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, triphenylmethane-4,4',4"-triisocyanate, polymeric MDI, etc. In addition, urethane prepolymers, carbodiimide-modified isocyanates, isocyanurate-modified isocyanates, and burette-modified isocyanates can also be used.

[0042] The amount of isocyanate compound is not particularly limited. The isocyanate index is preferably 70 to 120, and more preferably 80 to 110. The isocyanate index (NCO-index) is the value obtained by multiplying the ratio of the number of moles of isocyanate groups of the isocyanate compound to the total number of moles of hydroxyl groups and amino groups contained in the polyurethane resin composition by 100, and is calculated as [(equivalent amount of isocyanate groups of the isocyanate compound / (total equivalent amount of hydroxyl groups and amino groups in the composition) × 100].

[0043] (2) Conditions for adding isocyanate compounds The third step involves mixing the composition with the isocyanate compound in order to allow the isocyanate compound to react sufficiently with the composition. The mixing method can be appropriately determined by stirring, kneading, etc., depending on the properties of the composition. The kneading method is not particularly limited and can be carried out using various devices. The devices used for kneading can be appropriately selected from, for example, a stirring mixer, a disper mixer, a single-screw or twin-screw extruder, a Banbury mixer, a kneader, a mixing roll, and a planetary mixer.

[0044] In the third step, it is preferable to heat the mixture when reacting the above composition with an isocyanate compound. The heating temperature is not particularly limited. From the viewpoint of solid formation, the heating temperature is 50°C or higher, and may be 60°C or higher, or 70°C or higher. The upper limit of the heating temperature is not particularly limited. For example, the upper limit of the heating temperature may be 150°C or lower, and may be 120°C or lower, or 100°C or lower.

[0045] The heating time may be, for example, 10 minutes to 8 hours, or 30 minutes to 5 hours. The end point of the heating time may be set as appropriate while confirming that solid matter has been formed.

[0046] (3) Solids The solid is obtained by reacting an isocyanate compound with a composition containing a reaction product between an amine compound derived from decomposition products and an acidic compound. The mechanism by which the solid is obtained is not clear, but it is presumed to be as follows. This disclosure is not to be interpreted as being limited to this presumed mechanism. If the composition contains an amine compound, it is thought that the amino group reacts with the isocyanate group of the isocyanate compound to form a urea bond. If the composition contains a compound having a hydroxyl group, it is thought that the hydroxyl group reacts with the isocyanate group of the isocyanate compound to form a urethane bond. In addition, if the above reaction product has an amide group, it is possible that the amide group reacts with the isocyanate group of the isocyanate compound to form an acylurea bond. In the third step, it is presumed that resinification proceeds through one or more of these reactions to produce a solid. That is, the solid may contain a compound that includes one or more of the urea bond, urethane bond, and acylurea bond.

[0047] The resulting solid is, for example, in the form of a lump. When an isocyanate compound is reacted with a semi-solid phase, the resulting solid is, for example, in the form of a lump where the precipitates in the semi-solid phase are integrated. The use of the resulting solid is not particularly limited. The solid may be used as filler solid A or filler solid B as described later, may be used for other purposes, or may be discarded as is.

[0048] 2. Method for producing filler solid A The method for producing filler solid A involves crushing the above-mentioned solid to obtain filler solid A. In the method for producing filler solid A, the description of the solid is the same as the description in "1. Method for producing solid".

[0049] The method for crushing solid materials is not particularly limited and can be carried out using various devices. The devices used for crushing can be appropriately selected from, for example, crushers, grinders, and mills. Specific examples of devices used for crushing include joke crushers, gyroscopes, corn crushers, impact crushers, roll crushers, stamp mills, stone mill type grinders, pulverizers, ring mills, roll mills, cutter mills, hammer mills, turbo mills, jet mills, pin mills, chopper mills, pulverizers, Rotoplex, and Ultrarotors.

[0050] The particle size of filler solid A is not particularly limited. Preferably, the particle size of filler solid A is 1 mm or less, more preferably 0.5 mm or less, and even more preferably 0.2 mm or less. The lower limit of the particle size of filler solid A is not particularly limited. Normally, when pulverization is performed, fine powdery particles are included, so the lower limit of the particle size of filler solid A is sufficient as long as it is greater than 0 mm. The lower limit of the particle size of filler solid A may be set to a size suitable for filler (for example, 0.001 mm or more) after appropriate classification to remove fine particles.

[0051] The filler solid A of this embodiment is less likely to affect the formation of the resin used as a filler and is easy to use as a filler. For example, if the composition containing the above reaction product is used as a filler in the production of resin, it may inhibit the resin formation reaction and prevent the acquisition of resin. The reason for this is not clear, but it is possible that various reactive groups in the composition containing the reaction product affect the resin formation reaction. On the other hand, in the filler solid A of this embodiment, the various reactive groups in the composition are reduced by the reaction with the isocyanate group of the isocyanate compound, so it is less likely to affect the resin formation reaction. In other words, the filler solid A of this embodiment can suppress reaction inhibition when reused. Furthermore, since the filler solid A in this embodiment is reused after polymerizing the components in the composition, bleeding and elution can be suppressed when used as a filler for polyurethane resin (polyurethane foam).

[0052] 3. Polyurethane resin containing filler solid A This polyurethane resin contains the above-mentioned filler solid A. In this polyurethane resin, the description of filler solid A is the same as described in "2. Method for producing filler solid A".

[0053] This polyurethane resin can be obtained, for example, from a polyurethane resin composition containing a polyol, an isocyanate, and a filler solid A. Polyurethane resin can be manufactured by known methods. When obtaining polyurethane foam, foaming methods include slab foaming and mold foaming, and either method may be used. Slab foaming involves extruding a mixed recycled polyurethane resin composition onto a belt conveyor and foaming it under atmospheric pressure at room temperature. On the other hand, mold foaming involves filling a mold with a mixed recycled polyurethane resin composition and foaming it within the mold.

[0054] In polyurethane resin, the content of filler solid A is not particularly limited. From the viewpoint of improving the utilization rate of recycled materials in polyurethane foam, the content of filler solid A is preferably more than 0 parts by mass, more preferably 2 parts by mass or more, even more preferably 5 parts by mass or more, and particularly preferably 8 parts by mass or more, when the polyol in the polyurethane resin composition is 100 parts by mass. From the viewpoint of ensuring various physical properties, the content of filler solid A is preferably 45 parts by mass or less, more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 25 parts by mass or less. From these viewpoints, the content of filler solid A is preferably more than 0 parts by mass and 45 parts by mass or less, more preferably 2 parts by mass or more and 35 parts by mass or less, even more preferably 5 parts by mass or more and 30 parts by mass or less, and particularly preferably 8 parts by mass or more and 25 parts by mass or less.

[0055] 4. Filler solid B Filler solid B is a filler solid obtained by crushing the above-mentioned solid. When the maximum diameter of 100 randomly selected particles was measured in a microscopic image of filler solid B, at least 70 particles had a maximum diameter of 200 μm or less. Based on this observation, it is estimated that D70 in the number-based cumulative frequency distribution of filler solid B is 200 μm or less. In the following explanation, the maximum diameter of at least 70 particles when the maximum diameter of 100 randomly selected particles is measured will also be simply referred to as the number-based D70 of filler solid B. The explanation of the solid will be the same as the explanation in "1. Method for manufacturing the solid".

[0056] The number criterion D70 for filler solid B is 200 μm or less, preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. The lower limit of the number criterion D70 for filler solid B is not particularly limited. The number criterion D70 for filler solid B is usually 1 μm or more, but may be 5 μm or more, or 8 μm or more. The number criterion D70 for filler solid B can be adjusted as appropriate, for example, depending on the method for crushing the solid, as described later. In order to adjust the number criterion D70, the crushed material obtained by crushing the solid may be appropriately classified to obtain filler solid B.

[0057] The method for grinding solid material is not particularly limited, as long as the number criterion D70 of the filler solid material B is 200 μm or less. The grinding of solid material may include, for example, a primary grinding step in which the solid material is ground so that the number criterion D70 is greater than 200 μm, and a secondary grinding step in which the material obtained from the primary grinding is ground so that the number criterion D70 is 200 μm or less. The equipment used for grinding can be appropriately selected from, for example, crushers, grinders, and mills. Specific examples of equipment used for grinding include joke crushers, gyroscopes, corn crushers, impact crushers, roll crushers, stamp mills, millstone grinders, pulverizers, ring mills, roll mills, cutter mills, hammer mills, turbo mills, jet mills, pin mills, chopper mills, pulverizers, Rotoplex, Ultrarotors, etc. For the primary grinding step, for example, a crushing method is preferred. For the secondary grinding step, for example, a milling method is preferred. To adjust the number standard D70, a tertiary grinding step may be performed in which the pulverized material obtained by secondary grinding is further ground.

[0058] The filler solid B of this embodiment, like the filler solid A described above, has little effect on the formation of the resin used as a filler and is easy to use as a filler. Regarding the point that it has little effect on the formation of the resin used as a filler, the explanation for filler solid A is applied directly to filler solid B, and a detailed explanation is omitted.

[0059] Furthermore, since the filler solid B of this embodiment has a particle size D70 of 200 μm or less, it is easy to uniformly disperse it in the resin raw material when used as a filler. Also, when the filler solid B of this embodiment is used as a filler in polyurethane foam, a uniform foam structure is easily obtained. The reason for this is not clear, but it is possible that (1) the particle size of the filler solid B of this embodiment is finer, resulting in a lighter weight, and the shear force between the dispersion solvent and the filler solid B exceeds the weight of the filler solid B, preventing precipitation, or (2) the weight of the filler solid B is light enough to be affected by Brownian motion in the dispersion solvent, preventing precipitation, thus suppressing the adverse effect on the foaming properties of the polyurethane foam. In addition, since the filler solid B of this embodiment has a particle size D70 of 200 μm or less, it is possible to suppress the non-uniformity of the resin strength caused by the presence of solid parts with larger particle sizes in the resin. Thus, the filler solid B of this embodiment is useful for producing recycled resin products (e.g., recycled polyurethane foam) of stable quality.

[0060] 5. Method for producing polyol compositions and polyurethane foams (Part 1) The polyol composition is obtained by dispersing the above-mentioned filler solid B in a polyol. The method for producing polyurethane foam (part 1) uses filler solid B as a raw material to produce polyurethane foam. An example of the flow of the method for producing polyurethane foam (part 1) is shown in Figure 2.

[0061] The inventors of this application have diligently studied a method for manufacturing polyurethane foam using the above-mentioned filler solid B as a raw material. The above-mentioned filler solid B sometimes forms clumps (like lumps) in the polyurethane foam raw material, indicating room for improvement in terms of dispersibility. The inventors of this application have newly discovered that the dispersibility of filler solid B can be improved by pre-dispersing filler solid B in a polyol composition, and have developed the polyol composition and method for manufacturing polyurethane foam of this disclosure. This disclosure is not limited by the above-mentioned development history. For example, the polyol composition of this disclosure may be used for purposes other than the manufacture of polyurethane foam. Furthermore, the method for manufacturing polyurethane foam of this disclosure may be used by directly adding filler solid B to the polyurethane foam raw material without going through the polyol composition.

[0062] (1) Preferred polyol composition The polyol used in the polyol composition is not particularly limited. From the viewpoint of ensuring the dispersibility of the filler solid B mentioned above, the polyol used in the polyol composition is preferably a polyol with a number average molecular weight of 3000 or more. The number average molecular weight of the polyol is more preferably 4000 or more, and even more preferably 5000 or more. The upper limit of the number average molecular weight of the polyol is not particularly limited, and is usually 12000 or less, but may also be 10000 or less, or 8000 or less. The number average molecular weight is measured, for example, by gel permeation column chromatography (GPC).

[0063] From the viewpoint of improving the utilization rate of recycled materials in polyurethane foam, the polyol used in the polyol composition is preferably a recycled polyol contained in the decomposition product obtained by reacting polyurethane resin with a decomposition agent. For example, the recycled polyol can be a recycled polyol derived from the polyol phase, as described in the section "1. Method for producing solids" and "(3) Composition containing reaction products" above. In addition, various recycled polyols obtained by chemical recycling can be used as appropriate.

[0064] The amount of filler solid B in the polyol composition is not particularly limited. From the viewpoint of improving the utilization rate of recycled raw materials in polyurethane foam, the amount of filler solid B is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, when the entire polyol composition is considered to be 100% by mass. From the viewpoint of obtaining the polyol composition as a liquid, the amount of filler solid B is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. From these viewpoints, the amount of filler solid B is preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 50% by mass or less, and even more preferably 30% by mass or more and 40% by mass or less.

[0065] The filler solid B can be dispersed in a polyol using, for example, a dispersion apparatus. Specific examples of dispersion apparatuses include bead mills, ball mills, sand mills, and roll mills. Glass beads can be used as the dispersion medium. Such a dispersion process can also produce effects such as further refinement of the filler solid B and spheroidization (rounding of corners) of each particle of the filler solid B. Furthermore, if heat is generated during the dispersion process due to collisions of the dispersion medium, it can also have the effect of inactivating the NCO groups of the filler solid B.

[0066] According to the polyol composition of this embodiment, for example, compared to the case where the filler solid B is directly added to the polyurethane foam raw material without going through the polyol composition, the dispersibility of the filler solid B can be ensured even more favorably.

[0067] (2) Preferred method for producing polyurethane foam (Part 1) Method 1 for producing polyurethane foam involves, for example, using the above-mentioned polyol composition and an isocyanate compound as raw materials to produce polyurethane foam. Method 1 for producing polyurethane foam may further involve using at least one of the following as raw materials: polyol (excluding the above-mentioned polyol composition), blowing agent, catalyst, foam stabilizer, crosslinking agent, and foam defoamer.

[0068] Polyurethane foam can be produced by known foaming methods, which involve stirring and mixing a polyurethane resin composition to react a polyol with an isocyanate. Foaming methods include slab foaming and mold foaming, and either method may be used. Slab foaming involves extruding the mixed polyurethane resin composition onto a belt conveyor and foaming it at atmospheric pressure and room temperature. Mold foaming, on the other hand, involves filling a mold with the mixed polyurethane resin composition and foaming it within the mold. The first method for producing polyurethane foam is suitable for producing molded polyurethane foam.

[0069] (3) Use rate of recycled materials in polyurethane foam The percentage of recycled materials used in polyurethane foam is not particularly limited. If only filler solid B is used as the recycled material in polyurethane foam, the percentage of recycled materials used can be calculated as the amount of filler solid B added. From the viewpoint of improving the utilization rate of recycled materials in polyurethane foam, the utilization rate of recycled materials is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, when the total polyurethane foam is considered to be 100% by mass. From the viewpoint of ensuring the various physical properties of polyurethane foam, the utilization rate of recycled materials is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 12% by mass or less. From these viewpoints, the utilization rate of recycled materials is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and even more preferably 5% by mass or more and 12% by mass or less.

[0070] (4) Physical properties of polyurethane foam The physical properties of the polyurethane foam obtained by the method for manufacturing polyurethane foam (Part 1) can be appropriately set according to the application, etc. The polyurethane foam is preferably a flexible polyurethane foam. The polyurethane foam preferably possesses the following physical properties.

[0071] The 25% hardness (JIS K6400-2:2012 Method D) is preferably between 10N and 600N, and more preferably between 100N and 400N. A hardness of 600N or less is highly flexible and is preferable for polyurethane foam.

[0072] The hysteresis loss rate (JIS K6400-2:2012 Method B) is preferably 30% or less, and more preferably 25% or less. The lower limit of the hysteresis loss rate is not particularly limited, but is usually 5.0% or more.

[0073] The stress relaxation rate is preferably 20% or less. The lower limit of the stress relaxation rate is not particularly limited, but is usually 1.0% or higher. The stress relaxation rate (%) can be measured as follows. A circular pressure plate with a diameter of 200 mm was used to compress the polyurethane foam at a speed of 50 mm / min over a distance equivalent to 75% of its initial thickness. The load was then removed and the foam was left to stand for 1 minute. The load was then reapplied at the same speed, and the pressure plate was stopped when the load reached 196 N (20 kgf). The load was then read after a 5-minute rest. The stress relaxation rate was then calculated using the following formula. Stress relaxation rate (%) = 100 × [Load at the time the pressure plate stops (196N) - Load after 5 minutes of standing] / Load at the time the pressure plate stops (196N)

[0074] The apparent core density (JIS K7222:2005) is 10 kg / m³. 3 More than 150kg / m 3 The following is preferable: 30 kg / m 3 Less than 80kg / m 3 The following are preferable.

[0075] The rebound elasticity (JIS K6400-3:2011) is preferably 5% to 80%, more preferably 20% to 70%, and even more preferably 30% to 65%.

[0076] The tensile strength (JIS K6400-5:2012, No.2 type) is preferably 45 kPa or higher, more preferably 70 kPa or higher, and even more preferably 95 kPa or higher. The upper limit of the tensile strength is not particularly limited, for example, 220 kPa or less. The elongation (JIS K6400-5:2012, No.2 type) is preferably 50%-500%, more preferably 60%-300%, and preferably 70%-150%. If the elongation is 50% or more, it is highly flexible and is preferable as a polyurethane foam. The tear strength (JIS K6400-5:2012 Method B) is preferably 2.0 N / cm or higher, more preferably 3.5 N / cm or higher, and even more preferably 5.0 N / cm or higher. The upper limit of the tear strength is not particularly limited, for example, 10 N / cm or less.

[0077] The compression residual strain (JIS K6400-4:2004 4.5 Method A, 50% compression, dry heat distortion) is preferably 20% or less, and may be 15% or less, 10% or less, or 5% or less. The wet heat compression residual strain (JIS K6400-4:2004) is preferably 25% or less, more preferably 20% or less, and may be 15% or less. The repeated compression residual strain (JIS K6400-4:2004 6.1 Method A) is preferably 20% or less, and may be 15% or less, 10% or less, 5% or less, or 3% or less. The change rate of 25% hardness under repeated compression is preferably 10% or less. The change rate of 25% hardness under repeated compression can be calculated by the following formula by performing a repeated compression residual strain test in accordance with JIS K6400-4:2004 6.1 Method A and measuring the above-mentioned 25% hardness. Change rate of 25% hardness under repeated compression = ((H1 - H2) / H1) × 100 H1: Initial 25% hardness (N) H2: 25% hardness after the test (N)

[0078] The air permeability (JIS K6400-7:2012 Method B) is preferably 10 cm 3 / cm 2 / s or more, and more preferably 30 cm 3 / cm 2 / s or more. The upper limit value of the air permeability is not particularly limited. For example, it is 100 cm 3 / cm 2 / s or less. The air permeability (ASTM D3574) is preferably 30 L / min or more, and more preferably 50 L / min or more. The upper limit value of the air permeability is not particularly limited. For example, it is​​​​​​

[0080] 6. Method for manufacturing polyurethane foam (Part 2) The second method for manufacturing polyurethane foam uses filler solid B and recycled polyol as raw materials to produce polyurethane foam. The explanation for filler solid B is the same as the explanation in "4. Filler Solid B". The second method for manufacturing polyurethane foam differs from the first method for manufacturing polyurethane foam described above, in that it uses recycled polyol as a raw material, while the use of recycled polyol is optional. The explanation for recycled polyol is the same as the explanation in "5. Polyol Composition, Method for Manufacturing Polyurethane Foam (Part 1)" and "(1) Preferred Polyol Composition".

[0081] The second method for producing polyurethane foam involves using, for example, the above-mentioned polyol composition using recycled polyol and an isocyanate compound as raw materials to produce polyurethane foam. The second method for producing polyurethane foam may further use at least one of the following as raw materials: virgin polyol, blowing agent, catalyst, foam stabilizer, crosslinking agent, and defoaming agent.

[0082] The foaming method in the method for manufacturing polyurethane foam (part 2) is as described in the section "5. Polyol composition, method for manufacturing polyurethane foam (part 1)" and "(2) Preferred method for manufacturing polyurethane foam (part 1)".

[0083] The percentage of recycled materials used in polyurethane foam is not particularly limited. If only filler solid B and recycled polyol are used as recycled materials in polyurethane foam, the percentage of recycled materials used can be calculated as the total amount of filler solid B and recycled polyol blended together. From the viewpoint of improving the utilization rate of recycled materials in polyurethane foam, the utilization rate of recycled materials is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, when the total polyurethane foam is considered to be 100% by mass. From the viewpoint of ensuring the various physical properties of polyurethane foam, the utilization rate of recycled materials is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. From these viewpoints, the utilization rate of recycled materials is preferably 10% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and even more preferably 20% by mass or more and 35% by mass or less.

[0084] According to the polyurethane foam manufacturing method (part 2) of this embodiment, a polyurethane foam using filler solid B and recycled polyol can be suitably manufactured. According to the polyurethane foam manufacturing method (part 2) of this embodiment, the utilization rate of recycled raw materials in the polyurethane foam can be suitably improved compared to the case in which recycled polyol is not used. [Examples]

[0085] <Experiment 1> 1. Manufacturing of biodegradable polyurethane resin Polyurethane foam compositions (liquid A and liquid B) were prepared in the proportions shown in Table 1, and polyurethane foam was produced as a decomposable polyurethane resin by slab foaming. The density of the obtained polyurethane foam was measured in accordance with JIS K7222:2005. The measured densities are also shown in Table 1.

[0086] Details of each ingredient are as follows: • Polyol: Polyether polyol, number average molecular weight 3000, number of functional groups 3, hydroxyl value 56.1 mgKOH / 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 octylate, Product name: MRH-110, Manufactured by Johoku Chemical Industry Co., Ltd. • Foaming agent: Water • Isocyanate: Tolylene diisocyanate, product name Cosmonate T-80, manufactured by Mitsui Chemicals, NCO%: 48.2%

[0087] [Table 1]

[0088] 2. Decomposition treatment of polyurethane resin (first step) In a 1 L separable flask, 100 g of the polyurethane resin to be decomposed was mixed with 15 g of decomposition agent [1] and 0.5 g of decomposition catalyst. The mixture was heated at 200 °C for 6 hours with stirring to obtain decomposition product [1]. Decomposition product [2] was obtained in the same manner, except that 15 g of decomposition agent [2] was used instead of 15 g of decomposition agent [1]. Details of decomposition agent [1], decomposition agent [2], and decomposition catalyst are as follows. The decomposition product was separated into two phases: a polyol phase (upper phase) and an amine phase (lower phase). • Decomposing agents [1]: Amine compounds, diglycolamine • Decomposing agents [2]: Amine compounds, diethanolamine • Decomposition catalyst: Diazabicycloundecene (DBU)

[0089] The total amine value and hydroxyl value of the polyol phase and amine phase of the obtained decomposition product [1] were measured in accordance with JIS K 1557-7 and JIS K 1557-1. The mass percentage (mass%) of the polyol phase and the amine phase were also calculated, assuming the entire decomposition product [1] was 100% by mass. The total amine value and hydroxyl value of the entire decomposition product [1] were calculated based on the following equations 1 and 2. Similarly, for the decomposition product [2], the total amine value and hydroxyl value of the polyol phase and amine phase were measured, and the mass percentage (mass%) of the polyol phase and amine phase, as well as the total amine value and hydroxyl value of the entire decomposition product [2], were calculated. These results are shown in Table 2. Total amine value of decomposition products = Total amine value of the polyol phase × Mass ratio of the polyol phase + Total amine value of the amine phase × Mass ratio of the amine phase ... (Equation 1) Hydroxyl value of decomposition products = Hydroxyl value of the polyol phase × Mass ratio of the polyol phase + Hydroxyl value of the amine phase × Mass ratio of the amine phase ... (Equation 2)

[0090] [Table 2]

[0091] 3. Addition of acidic compounds (second step) The obtained decomposition product [1] was combined with the acidic compounds listed in Table 2 to obtain samples of compositions [1] to [5]. The obtained decomposition product [2] was combined with the acidic compounds listed in Table 2 to obtain a sample of composition [6]. First, polycarboxylic acids listed in Table 2 were added to the decomposition product [1] or decomposition product [2] in a 1 L separable flask. The amount of polycarboxylic acid added was adjusted so that the ratio of the molar amount of carboxyl groups to the molar amount of amino groups in the decomposition product matched the value in the "mol ratio" column of Table 2. The ratio of the molar amount of carboxyl groups to the molar amount of amino groups in the decomposition product. = Molar amount of carboxyl groups in acidic compounds / Molar amount of amino groups in decomposition products

[0092] The molar amount of amino groups in the decomposition product was calculated from the total amine value of the above decomposition product [1] or decomposition product [2]. The molar amount of carboxyl groups was calculated by multiplying the molar amount of the added acidic compound by the number of carboxyl groups, or by multiplying the molar amount of the added acid anhydride by twice the number of acid anhydride groups. For example, the molar amount of carboxyl groups in 1 mole of adipic acid was assumed to be 2 moles.

[0093] The above acidic compounds were added to the decomposition product [1] or decomposition product [2] and heated at a reaction temperature of 150°C or higher and below the boiling point of the acidic compound (or the decomposition temperature if the acidic compound does not have a boiling point). The heating time was 3 hours. After the addition of the acidic compound, dehydration condensation occurred, so the reaction was carried out while flowing dry nitrogen. After the reaction, each sample separated into two phases: a liquid phase and a semi-solid phase.

[0094] Each reaction sample was filtered through a 300-mesh stainless steel mesh to separate and recover each phase, and the semi-solid phase was recovered as compositions [1] to [6]. The viscosity of the recovered compositions [1] and others was measured using E-type viscosity. E-type viscosity was measured at a measurement temperature of 25°C using a "TV25 type viscometer Type H" (maximum measurement limit: 500,000 mPa·s) manufactured by Toki Sangyo Co., Ltd. For each of compositions [1] to [6], the total amine value and hydroxyl value were measured in accordance with JIS K 1557-7. The results are shown in Table 3.

[0095] [Table 3]

[0096] 4. Addition of isocyanate compound (Step 3) Compositions [1] to [6] were reacted with isocyanate compounds to obtain solid samples [1] to [9]. First, the isocyanate compounds listed in Table 4 were added to the obtained compositions [1] to [6]. Details of the isocyanate compounds are as follows. • MDI: Tosoh Corporation's Millionate MTL (Carbodiimide-modified monomeric MDI) • TDI: Cosmonate T-80, manufactured by Mitsui Chemicals, Inc.

[0097] The amount of isocyanate compound added was adjusted to achieve the isocyanate index (NCO-index) shown in Table 4. The isocyanate index was calculated as [(equivalent amount of isocyanate group in the isocyanate compound / (total equivalent amount of hydroxyl and amino groups in the composition) × 100)]. The equivalent amounts of active hydrogen and amino groups in the composition were calculated based on the hydroxyl value and total amine value of compositions [1] to [6] described above.

[0098] Compositions [1] to [6] and an isocyanate compound were stirred and mixed, and the reaction was accelerated by heating at 80°C for 2 hours. As a result, lumpy solids [1] to solids [9] were obtained.

[0099] After heating was complete, the obtained solids [1] to solids [9] were crushed to obtain particulate (powdered) filler solids [1] to solids [9].

[0100] [Table 4]

[0101] 5. Manufacturing of polyurethane resin containing filler solids Polyurethane foams of Examples 1 to 10 were prepared using polyurethane resins containing the obtained filler solids [1] to solids [9]. First, polyurethane foam compositions (liquid A and liquid B) with the same formulation as the decomposable polyurethane resin were prepared. For every 100 parts by mass of polyol in the polyurethane foam composition, the filler solids [1] to [9] listed in Table 5 were added as fillers to produce the polyurethane foams of Examples 1 to 10. Comparative Example 1 used the amine phase of the above-mentioned decomposition product [1] (a decomposition product treated with diglycolamine) instead of the filler solids [1] to solids [9]. In other words, Comparative Example 1 used an untreated amine phase that had not undergone the addition of acidic compounds or isocyanate compounds. The polyurethane foam of Comparative Example 1 was prepared in the same manner as in Examples 1 to 10. Comparative Example 2 used the above composition [1] instead of the filler solids [1] to solids [9]. That is, Comparative Example 2 used an amine phase in which an acidic compound was added, but an isocyanate compound was not added. The polyurethane foam of Comparative Example 2 was prepared in the same manner as in Examples 1 to 10.

[0102] [Table 5]

[0103] The polyurethane foams of Examples 1 to 10, Comparative Example 1, and Comparative Example 2 were visually evaluated for their reactivity during foaming and their appearance according to the following criteria. The results are shown in Table 5. <Reactivity> Good: The foam exhibits good reactivity during foaming. Acceptable: The reaction rate during foam formation is slightly slow or fast, but still usable. A description of the reactivity is provided in Table 5. Defective: The reaction rate during foam formation is either too slow or too fast, making it unsuitable for practical use. A description of the reactivity is provided in Table 5. <Exterior> Good: The appearance is good. Defective: The product has a defective appearance. A description of the defect is provided in Table 5.

[0104] 6. Results of Experiment 1 The methods for producing solids in Examples 1 to 10 satisfy the following requirements (a) to (c). The method for producing solids in Comparative Example 1 does not satisfy the following requirements (b) and (c). The method for producing solids in Comparative Example 2 does not satisfy the following requirements (b) and (c). • Requirement (a): Decompose the polyurethane resin by reacting it with a decomposition agent to produce decomposition products. Requirement (b): Add an acidic compound to the decomposition product. Requirement (c): A solid is obtained by reacting an isocyanate compound with a composition containing a reaction product of an amine compound derived from a decomposition product and an acidic compound.

[0105] Comparative Example 1 was evaluated as "poor" in terms of reactivity. Comparative Example 1 was evaluated as "poor" in terms of appearance. It is presumed that in Comparative Example 1, the reaction rate was too fast due to the influence of the amine compound contained in the amine phase of the decomposition product [1], and therefore the foam could not be formed properly. Furthermore, Comparative Example 2 received a "poor" evaluation for reactivity. Comparative Example 2 also received a "poor" evaluation for appearance. It is presumed that Comparative Example 2 failed to form a foam properly because the reaction rate was too slow due to the influence of the carboxyl group of the acidic compound contained in composition [1].

[0106] On the other hand, the reactivity of Examples 1 to 10 was evaluated as "good" or "acceptable". The appearance of Examples 1 to 10 was evaluated as "good" or "acceptable". The solids of Examples 1 to 10 were found to be useful as filler solids. Furthermore, it was suggested that the solids of Examples 1 to 10 had reduced levels of harmful aromatic amine compounds and inactivated reactive functional groups. The solids of Examples 1 to 10 were found to have excellent handling properties and be applicable to various uses.

[0107] 7. Effects of the Example in Experiment 1 This embodiment provides a technology for utilizing by-product amine compounds resulting from the decomposition of polyurethane resins.

[0108] <Experiment 2> 1. Decomposition treatment of polyurethane resin (first step) In a 60L reaction vessel, 3,3'-diaminodipropylamine was added as a decomposition agent to 40 kg of polyether-based molded polyurethane foam and heated at 190°C for 4 hours with stirring to obtain the decomposition product [3]. The amount of 3,3'-diaminodipropylamine added was 15 parts by mass per 100 parts by mass of polyurethane foam.

[0109] 2. Addition of acidic compounds (second step) Next, succinic anhydride was added to the resulting decomposition product as an acidic compound, and the mixture was heated at 200°C for 3 hours. The amount of succinic anhydride added was 17.4 parts by mass per 100 parts by mass of polyurethane foam. The sample after the reaction separated into a liquid phase (polyol phase) and a solid phase.

[0110] Each sample after the reaction was filtered through a 40-mesh stainless steel mesh, and the solid phase was recovered as a composition [7] containing the reaction product of an amine compound derived from the decomposition product and an acidic compound.

[0111] 3. Addition of isocyanate compound (Third step) The obtained composition [7] was reacted with the following isocyanate compound A to obtain a sample of solid matter

[10] . The amount of isocyanate compound A added was 372.7 parts by mass per 1000.3 parts by mass of composition [7]. Details of isocyanate compound A are as follows. • MDI: Covestro Desmodur® 44V20

[0112] The mixture of composition [7] and isocyanate compound A was stirred and mixed, and after standing at room temperature for 1-2 days, the reaction was accelerated by heating in a drying oven at 80°C for 8 hours. As a result, a lump-like solid

[10] was obtained.

[0113] 4. Grinding of solid materials The obtained solid

[10] was subjected to hammer grinding (crushing) as a primary grinding to obtain a pulverized material. A microscopic image of the primary grinding pulverized material is shown in the "Hammer Grinding" column on the left in Figure 3. The maximum diameter of 100 randomly selected particles was measured in the microscopic image of the primary grinding pulverized material. The results are shown as white bar graphs in the cumulative distribution graph of particle counts in Figure 4. The particle count criterion D70 of the pulverized material obtained by primary grinding was greater than 200 μm.

[0114] As a preliminary experiment, we attempted to manufacture polyurethane foam using the pulverized material obtained from the primary grinding. First, the pulverized material obtained from the primary grinding was dispersed in a polyol with a number-average molecular weight of 7000 using a bead mill to obtain a polyol composition. The amount of pulverized material from the primary grinding in this polyol composition was adjusted to 25% by mass. When polyurethane foam was made using the obtained polyol composition, it was observed that the pulverized material from the primary grinding did not mix well with the other raw materials and partially precipitated in the polyurethane foam. The inventors of this application hypothesized that the precipitation of the pulverized material could be reduced by reducing the particle size of the pulverized material, and conducted the following experiment to further grind the pulverized material from the primary grinding.

[0115] The material obtained from the primary grinding was subjected to secondary grinding using a stone mill to obtain a single-pass ground material. The stone mill used was made of white granite from Okazaki, with a sanded finish (whetstone finish), measuring 30 cm in diameter and 23 cm in height, manufactured by Oshima Stone Co., Ltd. A microscopic image of the single-pass ground material is shown in the center of Figure 3, in the "Single-Pass" column. The maximum diameter of 100 randomly selected particles was measured in the microscopic image of the single-pass ground material. The results are shown as a dot pattern bar graph in the cumulative distribution graph of the particle count in Figure 4. The particle count criterion D70 of the single-pass ground material was greater than 50 μm and less than or equal to 200 μm. Hereinafter, the single-pass ground material will also be referred to as filler solid material [10-1].

[0116] The single-ground material was further ground using the aforementioned millstone to obtain a double-ground material. A microscopic image of the double-ground material is shown in the "Double-ground" column on the right in Figure 3. The maximum diameter of 100 randomly selected particles was measured in the microscopic image of the double-ground material. The results are shown as black bar graphs in the cumulative particle count distribution graph in Figure 4. The particle count criterion D70 of the double-ground material was 50 μm or less. Hereinafter, the double-ground material will also be referred to as filler solids [10-2].

[0117] 5. Production of polyol compositions The obtained filler solids [10-1] and [10-2] were dispersed in polyol A to produce polyol compositions [1] and [2]. Details of the polyols are as follows. • Polyol A: Polypropylene glycol, 3 functional groups, hydroxyl value 33 mgKOH / g, number average molecular weight 5000, No. 38, manufactured by Sanyo Chemical Industries, Ltd.

[0118] (1) Polyol composition [1] 150 g of polyol and 80 g of filler solid [10-1] were mixed together and stirred for 20 minutes at 6200 rpm using a dispersion apparatus (Homodisper 2.5 type, blade shape φ40 mm (crown type), manufactured by Primix) with 150 g of glass beads (bead particle size 3 mm). The mixture was then filtered through a 40-mesh wire mesh to remove the glass beads and obtain a polyol composition [1] in which the filler solid [10-1] was dispersed in the polyol. The amount of filler solid [10-1] in polyol composition [1] is 35% by mass.

[0119] (2) Polyol composition [2] 150 g of polyol and 80 g of filler solid [10-2] were mixed together and stirred for 20 minutes at 6200 rpm using the dispersion apparatus described above, along with 150 g of glass beads (bead particle size 1 mm). The mixture was then filtered through a 40-mesh wire mesh to remove the glass beads, and a polyol composition [2] was obtained in which filler solid [10-1] was dispersed in the polyol. The amount of filler solid [10-2] in polyol composition [2] was 35% by mass.

[0120] 6. Manufacturing of polyurethane resin containing filler solids Polyurethane foams of Examples 11 and 12 were prepared using the obtained polyol compositions [1] and [2]. The method for producing the polyurethane resin in this Experiment 2 corresponds to the method for producing polyurethane foam (part 1) described in the embodiments.

[0121] First, polyurethane foam compositions (solutions A and B) were prepared in the proportions shown in Table 6, and polyurethane foam was manufactured by mold foaming. For comparison, a polyurethane foam of Comparative Example 3 was prepared without using filler solids. The amount of solution B added was adjusted to achieve the isocyanate index shown in Table 6.

[0122] Details of each ingredient are as follows: • Polyol A: Polypropylene glycol, 3 functional groups, hydroxyl value 33 mgKOH / g, number average molecular weight 5000, No. 38, manufactured by Sanyo Chemical Industries, Ltd. • Polyol B: Polypropylene glycol, 3 functional groups, hydroxyl value 24 mgKOH / g, number average molecular weight 7000, EP902N, manufactured by Mitsui Chemicals, Inc. • Polyol composition [1]: A polyol composition in which filler solids [10-1] (50 μm < number basis D70 ≤ 200 μm) are dispersed in polyol A, with a solid content of 35% by mass. • Polyol composition [2]: A polyol composition in which filler solids [10-2] (number basis D70 ≤ 50 μm) are dispersed in polyol A, with a solid content of 35% by mass. • Polyol C: Polymer polyol, 3 functional groups, hydroxyl value 25 mg KOH / g, number average molecular weight 5000, FM5704, manufactured by Sanyo Chemical Industries, Ltd. • Crosslinking agent 1: Glycerin, manufactured by NOF Corporation • Crosslinking agent 2: DEA-80, manufactured by Mitsui Chemicals, Inc. • Foaming catalyst: BL-19, manufactured by EVONIK Corporation • Resin-based catalyst: 33LSI, manufactured by EVONIK. • Foam stabilizer 1: L3184J, manufactured by Momentive Inc. • Foam stabilizer 2: B8738LF2, manufactured by EVONIK. • Antifoaming agent: Polyether polyol, molecular weight 5000, number of functional groups 3, hydroxyl value 37 mgKOH / g, S240, manufactured by Covestro. • Foaming agent: Water • Isocyanate compound B: TM-30, mixture of TDI and MDI, NCO%: 43.7% In Examples 11 and 12, the usage rate of solid filler material, which is recycled raw material, was 7% by mass when the total polyurethane foam is considered to be 100% by mass.

[0123] [Table 6]

[0124] 7. Evaluation Method The following physical properties were evaluated for the polyurethane foams of Example 11, Example 12, and Comparative Example 3. The results are shown in Table 7.

[0125] ·hardness The 25% hardness (N / φ200) of the polyurethane foam was measured in accordance with JIS K6400-2:2012 Method D. The 50% hardness (N / φ200) of the polyurethane foam was measured in the same manner as the 25% hardness measurement described above, except that the compression ratio was set to 50%. The entire molded body having a skin layer with the mass and thickness listed in Table 7 was used for the measurements.

[0126] • Hysteresis loss rate and compressive deflection coefficient The hysteresis loss rate (%) and compression deflection coefficient of polyurethane foam were measured in accordance with JIS K6400-2:2012 Method E. • Stress relaxation rate The stress relaxation rate (%) of the polyurethane foam was measured by the method described in the embodiment. ·density Apparent core density of polyurethane foam (g / cm³) 3 The values ​​were measured in accordance with JIS K7222:2005. • Rebound elasticity The rebound elasticity (%) of polyurethane foam was measured in accordance with JIS K6400-3:2011. Test specimens for rebound elasticity measurement were taken from the core.

[0127] • Tensile strength, elongation, tear strength Tensile strength (kPa) and elongation (%) were measured using No.2 type in accordance with JIS K6400-5:2012. Tear strength was measured in accordance with JIS K6400-5:2012 Method B. In the table, if "Skin" is indicated, the measurement value is from a test specimen with a skin layer on one side. If "Core" is indicated, the measurement value is from a test specimen obtained from a core.

[0128] • Strain characteristics The compression residual strain (%) was measured at 50% compression in accordance with JIS K6400-4:2004 4.5 A method. The moist heat compression residual strain (%) was measured in accordance with JIS K6400-4:2004. The repeated compressive residual strain (repeated CLD change rate, %) was measured in accordance with JIS K6400-4:2004 6.1 Method A. The percentage change in hardness at 25% repeated compression was calculated using the method described in the embodiment. The specimens used for measuring compressive residual strain (dry heat strain), moist heat compressive residual strain, repeated compressive residual strain, and 25% hardness change rate after repeated compression were taken from the core.

[0129] • Ventilation Air permeability (cm 3 / cm 2 The values ​​( / s) were measured in accordance with JIS K6400-7:2012 Method B. The results are listed in the "JIS" column of Table 7. Air permeability (L / min) was measured in accordance with ASTM D3574. The results are listed in the "ASTM" column of Table 7. In the table, if "Skin" is indicated, the measurement value is from a test specimen with a skin layer on one side. If "Core" is indicated, the measurement value is from a test specimen obtained from a core.

[0130] [Table 7]

[0131] 8. Results of Experiment 2 The evaluation results are shown in Table 7. The methods for producing solids in Examples 11 and 12 satisfy the following requirements (a) to (c). • Requirement (a): Decompose the polyurethane resin by reacting it with a decomposition agent to produce decomposition products. Requirement (b): Add an acidic compound to the decomposition product. Requirement (c): A solid is obtained by reacting an isocyanate compound with a composition containing a reaction product of an amine compound derived from a decomposition product and an acidic compound.

[0132] Furthermore, the filler solids of Examples 11 and 12 satisfy the following requirements (d) and (e). Requirement (d): A filler solid obtained by crushing a solid obtained by a manufacturing method that satisfies requirements (a) to (c). Requirement (e): In a microscopic image of the filler solid, when the maximum diameter of 100 randomly selected particles is measured, the maximum diameter of at least 70 of the particles must be 200 μm or less.

[0133] Example 11 showed properties equivalent to or better than Comparative Example 3 (blank) in all properties except stress relaxation rate, elongation, and moist heat compression residual strain. Example 12 showed superior properties compared to Example 11, and in all properties except stress relaxation rate, it showed properties equivalent to or better than Comparative Example 3 (blank). Examples 11 and 12 were able to produce polyurethane foam that is usable as a product. The solids of Examples 11 and 12 were found to be useful as filler solids. Furthermore, it was suggested that the solids of Examples 11 and 12 had reduced levels of harmful aromatic amine compounds and inactivated reactive functional groups. The solids of Examples 11 and 12 were found to be easy to handle and applicable to various uses.

[0134] 9. Effects of the Example in Experiment 2 This embodiment provides a technology for utilizing by-product amine compounds resulting from the decomposition of polyurethane resins.

[0135] <Experiment 3> 1. Manufacturing of polyurethane resin containing filler solids Using the above-mentioned filler solid [10-2], the polyurethane foam of Example 13 was prepared. The method for producing the polyurethane resin in this Experiment 3 corresponds to the method for producing polyurethane foam (part 2) described in the embodiment.

[0136] First, polyurethane foam compositions (solutions A and B) were prepared in the proportions shown in Table 8, and polyurethane foam was manufactured by mold foaming. The amount of solution B added was adjusted so that the isocyanate index (Index) was 100.

[0137] Details of each ingredient are as follows. For ingredients identical to those in Experiment 2, the above description applies directly, and detailed explanations are omitted. • Recycled polyols: Manufactured as follows: In a 3L separable flask, 3,3'-diaminodipropylamine was added as a decomposition agent and diazabicycloundecene (DBU) as a decomposition catalyst to 1 kg of polyether-based molded polyurethane foam. The mixture was heated at 180°C for 6 hours with stirring to obtain a polyol-containing decomposition product. The amount of 3,3'-diaminodipropylamine added was 15 parts by mass per 100 parts by mass of polyurethane foam. The amount of diazabicycloundecene (DBU) added was 1 part by mass per 100 parts by mass of polyurethane foam. The polyol was separated from the decomposition product to obtain a regenerated polyol. • Filler solids [10⁻²]: Filler solids [10⁻²] obtained in Experiment 2 above (double-ground material, number of particles D70 ≤ 50 μm) • Crosslinking agent 3: Product name IR94, manufactured by Mitsui Chemicals, Inc. • Isocyanate compound C: TM-20, NCO%: 45.2% In Example 13, the total usage rate of recycled raw materials, specifically filler solids and recycled polyols, was 30% by mass, when the total polyurethane foam is considered to be 100% by mass.

[0138] [Table 8]

[0139] The polyurethane foam of Example 13 was visually evaluated for its reactivity during foaming and its appearance. The polyurethane foam of Example 13 showed good reactivity during foaming. Although the polyurethane foam of Example 13 exhibited a yellow to brown color, foam was obtained and its appearance as a foam was good.

[0140] 2. Results of Experiment 3 The method for producing the solid in Example 13 satisfies the following requirements (a) to (c). • Requirement (a): Decompose the polyurethane resin by reacting it with a decomposition agent to produce decomposition products. Requirement (b): Add an acidic compound to the decomposition product. Requirement (c): A solid is obtained by reacting an isocyanate compound with a composition containing a reaction product of an amine compound derived from a decomposition product and an acidic compound.

[0141] Furthermore, the filler solid of Example 13 satisfies the following requirements (d) and (e). Requirement (d): A filler solid obtained by crushing a solid obtained by a manufacturing method that satisfies requirements (a) to (c). Requirement (e): In a microscopic image of the filler solid, when the maximum diameter of 100 randomly selected particles is measured, the maximum diameter of at least 70 of the particles must be 200 μm or less.

[0142] Example 13 demonstrated that the use of recycled materials in polyurethane foam could be improved by using a filler solid in combination with recycled polyol. The solid in Example 13 was found to be useful as a filler solid. Furthermore, it was suggested that the solid in Example 13 had reduced levels of harmful aromatic amine compounds and inactivated reactive functional groups. The solid in Example 13 was found to have excellent handling properties and be applicable to a variety of uses.

[0143] 3. Effects of the example in Experiment 3 This embodiment provides a technology for utilizing by-product amine compounds resulting from the decomposition of polyurethane resins.

[0144] This disclosure is not limited to the embodiments detailed above, and various modifications or changes are possible within the scope of this disclosure.

Claims

1. A decomposition agent is reacted with polyurethane resin to produce decomposition products. An acidic compound is added to the aforementioned decomposition product. A method for producing a solid, comprising reacting an isocyanate compound with a composition containing a reaction product of an amine compound derived from the decomposition product and an acidic compound to obtain a solid.

2. The method for producing a solid product according to claim 1, wherein the acidic compound is a carboxylic acid having two or more carboxyl groups and / or an anhydride thereof.

3. The method for producing a solid substance according to claim 1, wherein the composition is semi-solid.

4. A method for producing a filler solid, comprising crushing a solid obtained by the manufacturing method described in any one of claims 1 to 3 to obtain a filler solid.

5. A polyurethane resin containing a filler solid obtained by the manufacturing method described in claim 4.

6. A filler solid obtained by crushing a solid obtained by the manufacturing method described in any one of claims 1 to 3, A filler solid in which, when the maximum diameter of 100 randomly selected particles is measured in a microscopic image of the filler solid, at least 70 of the particles have a maximum diameter of 200 μm or less.

7. A polyol composition comprising the filler solid described in claim 6 dispersed in a polyol.

8. A method for producing polyurethane foam, comprising using the filler solid described in claim 6 as a raw material.

9. A method for producing polyurethane foam, comprising using the filler solid described in claim 6 and recycled polyol as raw materials.

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