Carbonyl compound, method for producing isocyanate compound, and isocyanate composition

Abstract

The present invention provides a carbonyl compound represented by general formula (I) (wherein R11 is an (n11+n12)-valent organic group, R12 is a monovalent organic group, n11 is an integer of 1-8, n12 is an integer of 0-7, and the sum of n11 and n12 is an integer of 2-8).

Description

[Technical field]

[0001] The present invention relates to a carbonyl compound, a method for producing a carbonyl compound, a method for producing an isocyanate compound, and an isocyanate composition. [Background technology]

[0002] Isocyanates are widely used as raw materials for manufacturing polyurethane foams, paints, adhesives, etc. The main industrial method for manufacturing isocyanates is the reaction of amine compounds with phosgene (phosgene process), and almost all of the world's production is by the phosgene process. However, the phosgene process has many problems.

[0003] First, a large amount of phosgene is used as a raw material. Phosgene is highly toxic, so special care must be taken in its handling to prevent exposure to workers, and special equipment is also required to remove the waste. Second, the phosgene process produces a large amount of highly corrosive hydrogen chloride as a by-product, which requires a process to remove the hydrogen chloride, and the isocyanate produced often contains hydrolyzable chlorine. Therefore, when using isocyanates produced by the phosgene process, this can have a negative effect on the weather resistance and heat resistance of polyurethane products.

[0004] In view of this background, a method for producing an isocyanate compound without using phosgene is desired. As one of the methods for producing an isocyanate compound without using phosgene, a method using thermal decomposition of a carbamate compound has been proposed. It has long been known that isocyanate and hydroxyl compounds can be obtained by thermal decomposition of a carbamate compound (for example, see Non-Patent Document 1). The basic reaction is exemplified by the following formula (A).

[0005] [ka]

[0006] (In formula (A), R is an a-valent organic group, R' is a monovalent organic group, and a is an integer of 1 or more.)

[0007] On the other hand, the thermal decomposition reaction of a carbamate compound is likely to cause various irreversible side reactions, such as undesirable thermal denaturation reactions of the carbamate compound and condensation reactions of isocyanates produced by the thermal decomposition. Examples of the side reactions include a reaction to form an isocyanurate group represented by the following formula (B), a reaction to form a carbodiimide represented by the following formula (C), a reaction to form a uretonimine group represented by the following formula (D), and a reaction to form an allophanate group represented by the following formula (E) (see, for example, Non-Patent Documents 1 to 4, etc.).

[0008] [ka]

[0009] (In formulas (B) to (E), R a ~R h are each independently a monovalent organic group.

[0010] Polyurethanes with urethane bonds are mainly produced by reacting difunctional or higher isocyanates with difunctional or higher alcohols, and are polymers with excellent tensile strength, abrasion resistance, and oil resistance, and are used in a wide range of fields, such as flexible foams, rigid foams, elastomers, adhesives, paints, binders, etc. Among them, polyurethanes made from linear or cyclic aliphatic isocyanates have excellent weather resistance and light resistance, and are used in fields where appearance quality is required, such as baking paints, automobile clear coat materials, and coil coating materials.

[0011] As the isocyanate, a diisocyanate, which is a bifunctional isocyanate, may be used, but in order to improve the physical properties of the polyurethane and to ensure the safety of workers by suppressing the vapor pressure, the diisocyanate may be polymerized to form an isocyanate polymer, for example, by the reactions represented by the following formulas (a) to (c). In the formulas, R represents a divalent organic group, and R' represents a trivalent organic group.

[0012] [ka]

[0013] The reaction represented by the above formula (a) produces an isocyanurate-type isocyanate polymer, the reaction represented by the above formula (b) produces a biuret-type isocyanate polymer, and the reaction represented by the above formula (c) produces a urethane-type isocyanate polymer. Isocyanurate-type isocyanate polymers are disclosed in Patent Documents 1 to 4. Biuret-type isocyanate polymers are disclosed in Patent Documents 5 to 10. Allophanate-type isocyanate polymers are disclosed in Patent Documents 11 and 12.

[0014] As described above, when used in fields where appearance quality is required, polyurethane is required to have little coloration. For this purpose, it is important that not only is there no coloration in the polyurethane reaction, but also that the raw material isocyanate (isocyanate with two or more functionalities) has little coloration. However, isocyanate generally tends to be easily oxidized by oxygen in the air, and to be easily altered or colored. In addition, when producing an isocyanate polymer by polymerization of diisocyanate, the isocyanate tends to be easily colored due to the catalyst or solvent used in the polymerization reaction.

[0015] As a method for suppressing the coloration of isocyanate, there is a method of producing and storing isocyanate by sealing with nitrogen gas to isolate it from air, or a method of adding ultraviolet absorbers, antioxidants, etc. and storing it. For example, Patent Document 13 discloses a method of modifying isocyanate and then treating it with peroxide to produce a polyisocyanate for a light-colored polyurethane lacquer. In addition, Patent Document 14 considers a method of producing an isocyanate with reduced coloration by contacting a colored isocyanate with an ozone-containing gas. Furthermore, Patent Document 15 also considers a method of producing an isocyanate with reduced coloration by irradiating a colored isocyanate with light of a wavelength of 200 to 600 nm. [Prior art documents] [Patent documents]

[0016] [Patent Document 1] U.S. Pat. No. 4,324,879 [Patent Document 2] U.S. Pat. No. 4,412,073 [Patent Document 3] Japanese Patent Application Publication No. 57-047319 [Patent Document 4] Japanese Patent Application Publication No. 63-057577 [Patent Document 5] U.S. Pat. No. 3,976,622 [Patent Document 6] U.S. Pat. No. 4,176,132 [Patent Document 7] U.S. Pat. No. 4,290,969 [Patent Document 8] U.S. Pat. No. 4,837,359 [Patent Document 9] U.S. Pat. No. 4,983,762 [Patent Document 10] U.S. Pat. No. 5,641,851 [Patent Document 11] British Patent No. 994890 [Patent Document 12] Japanese Patent Application Publication No. 7-304724 [Patent Document 13] Japanese Unexamined Patent Application Publication No. 2-228317 [Patent Document 14] Japanese Unexamined Patent Application Publication No. 8-291129 [Patent Document 15] Japanese Patent Application Publication for International Patent Application No. 2012-506465 [Non-Patent Document]

[0017] [Non-Patent Document 1] Third Issue, “186. A. W. Hofmann: Ueber die aromatischen Cyanate.”, Berichte der Deutschen Chemischen Gesellschaft, Vol. 3, pp. 653 - 658, 1870. [Non-Patent Document 2] Dyer E et al., “Thermal Degradation of Alkyl N-Phenylcarbamates.”, Journal of American Chemical Society, Vol. 81, pp. 2138 - 2143, 1959. [Non-Patent Document 3] Ulrich H et al., “[2+2] Cycloaddition Reactions of Unsymmetrically substituted Carbodiimides.”, Journal of Heterocyclic Chemistry, Vol. 24, pp. 1121 - 1123, 1987. [Non-Patent Document 4] Schwetlick K et al., “Kinetics and Catalysis of Consecutive Isocyanate Reactions. Formation of Carbamates, Allophanates and lsocyanurates.”, Journal of the Chemical Society, Perkin transactions II, Vol. 2, pp. 395-402, 1995. Summary of the Invention [Problem to be solved by the invention]

[0018] The above-mentioned side reactions not only lead to a decrease in the yield and selectivity of the target isocyanate compound, but also, particularly in the production of polyisocyanates, may cause precipitation of polymeric solids, clogging the reactor, etc., making long-term operation difficult. Furthermore, it is not known that compounds having a boiling point higher than that of the isocyanate compound are by-produced in addition to the compounds produced by the above-mentioned side reactions.

[0019] The present invention has been made in view of the above circumstances, and provides a novel carbonyl compound and a method for producing the same, as well as a method for producing an isocyanate compound using the carbonyl compound.

[0020] As described above, various methods have been investigated for suppressing the discoloration of isocyanates. However, in the method of adding a compound that is not necessary for the polymerization reaction to an isocyanate and storing the isocyanate, the added compound may cause discoloration during the production of polyurethane or the like.

[0021] In addition, the methods disclosed in Patent Documents 4 to 6 do not necessarily sufficiently reduce coloration, and an isocyanate with even less coloration is desired. Furthermore, distillation purification is a common method for purifying compounds, but since the isocyanate is heated during distillation purification, coloration of the isocyanate may progress or the isocyanate may be modified.

[0022] The present invention has been made in consideration of the above circumstances, and provides an isocyanate composition in which coloration is sufficiently suppressed and which has excellent storage stability. [Means for solving the problem]

[0023] That is, the present invention includes the following aspects. (1) A carbonyl compound represented by the following general formula (I):

[0024] [ka]

[0025] (In general formula (I), R 11 is an organic group with a valence of (n11+n12), and R 12 is a monovalent organic group. n11 is an integer of 1 or more and 8 or less, n12 is an integer of 0 or more and 7 or less, and the sum of n11 and n12 is an integer of 2 or more and 8 or less.

[0026] (2) The above R 11 is a divalent or tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent or trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have 1 to 4 ester groups or nitrogen atoms, and R 12 is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may contain an oxygen atom. (3) The above R 11 is a divalent or tetravalent aliphatic hydrocarbon group having 5 to 15 carbon atoms, or a divalent or trivalent aromatic hydrocarbon group having 6 to 15 carbon atoms, which may have one or more ester groups; R 12 is a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms which may contain an oxygen atom, The above n 11 is an integer between 1 and 4, The above n 12 is an integer between 0 and 3, and The above n 11 and 12 The carbonyl compound according to claim 1 or 2, wherein the sum of is an integer of 2 or more and 4 or less. (4) A method for producing the carbonyl compound according to any one of (1) to (3), comprising the steps of: one or more compounds selected from the group consisting of isocyanate compounds and carbamate compounds; one or more compounds selected from the group consisting of carbonate esters and hydroxy compounds; and heating to synthesize the carbonyl compound. (5) The method according to (4), wherein the isocyanate compound is a compound represented by the following general formula (II):

[0027] [ka]

[0028] (In general formula (II), R 21 is an organic group with a valence of n21, and has the formula: R 21 =R 11 n21 is an integer between 2 and 8, and satisfies the relation: n21 = n11 + n12.

[0029] (6) The method according to (4) or (5), wherein the carbamate compound is a compound represented by the following general formula (III):

[0030] [ka]

[0031] (In general formula (III), R 31 is an organic group with a valence of (n31+n32), and has the formula: R 31 =R 11 R 32 is a monovalent organic group, represented by the formula: R 32 =R 12n31 is an integer between 1 and 8, n32 is an integer between 0 and 7, the sum of n31 and n32 is an integer between 2 and 8, and the relation: n31+n32=n11+n12 is satisfied.

[0032] (7) The method according to any one of (4) to (6), wherein the carbonate ester is a compound represented by the following general formula (IV):

[0033] [ka]

[0034] (In general formula (IV), R 41 and R 42 are each independently a monovalent organic group represented by the formula: R 41 =R 42 =R 12 Satisfy.)

[0035] (8) The method according to any one of (4) to (7), wherein the hydroxy compound is a compound represented by the following general formula (V):

[0036] [ka]

[0037] (In general formula (V), R 51 is a monovalent organic group having the formula: R 51 =R 12 Satisfy.)

[0038] (9) A method for producing an isocyanate compound, comprising purifying a reaction liquid containing an isocyanate compound represented by the following general formula (II) by distillation in the presence of the carbonyl compound according to any one of (1) to (3), and continuously recovering the isocyanate compound as a gas phase component:

[0039] [ka]

[0040] (In general formula (II), R 21 is an organic group with a valence of n21, and has the formula: R 21 =R 11 n21 is an integer between 2 and 8, and satisfies the relation: n21 = n11 + n12. (1) based on the total mass of the isocyanate composition, 97% by mass or more of an isocyanate compound; 2.0 mass ppm or more 1.0×10 4 A carbonyl compound represented by the following general formula (I) in an amount of not more than ppm by mass; Contains The isocyanate composition, wherein the isocyanate compound and the carbonyl compound are different compounds.

[0041] [ka]

[0042] (In general formula (I), R 11 is an organic group with a valence of (n11+n12), and R 12 is a monovalent organic group. n11 is an integer of 1 or more and 8 or less, n12 is an integer of 0 or more and 7 or less, and the sum of n11 and n12 is an integer of 2 or more and 8 or less.

[0043] (2) The above R 11 is a divalent or tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a divalent or trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have 1 to 4 ester groups or nitrogen atoms, and R 12 is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may contain an oxygen atom. (3) The isocyanate composition according to (1) or (2), wherein the isocyanate compound is a compound represented by the following general formula (II):

[0044] [ka]

[0045] (In general formula (II), R 21 is an organic group with a valence of n21, and has the formula: R 21 =R 11 n21 is an integer between 2 and 8, and satisfies the relation: n21 = n11 + n12.

[0046] (4) 2.0 ppm by mass or more, based on the total mass of the isocyanate composition, 4 The isocyanate composition according to any one of (1) to (3), further comprising one or more compounds selected from the group consisting of carbamate compounds and carbonate esters in an amount of not more than ppm by mass. (5) The isocyanate composition according to (4), wherein the carbamate compound is a compound represented by the following general formula (III):

[0047] [ka]

[0048] (In general formula (III), R 31 is an organic group with a valence of (n31+n32), and has the formula: R 31 =R 11 R 32 is a monovalent organic group, represented by the formula: R 32 =R 12 n31 is an integer between 1 and 8, n32 is an integer between 0 and 7, the sum of n31 and n32 is an integer between 2 and 8, and the relation: n31+n32=n11+n12 is satisfied.

[0049] (6) The isocyanate composition according to (4) or (5), wherein the carbonate ester is a compound represented by the following general formula (IV):

[0050] [ka]

[0051] (In general formula (IV), R 41 and R 42 are each independently a monovalent organic group represented by the formula: R 41 =R 42 =R 12 Satisfy.) Effect of the Invention

[0052] According to the carbonyl compound and the production method thereof of the above-mentioned embodiment, a novel carbonyl compound can be provided. The method for producing an isocyanate compound according to the above embodiment is a method using the carbonyl compound, which can prevent by-products from adhering to an apparatus during the production of an isocyanate compound and can improve the yield of the isocyanate compound. Moreover, according to the isocyanate composition of the above embodiment, it is possible to provide an isocyanate composition in which coloration is sufficiently suppressed and which has excellent storage stability. [Brief description of the drawings]

[0053] [Figure 1] FIG. 1 is a schematic diagram showing a production apparatus for a carbamate compound used in the examples. [Diagram 2] FIG. 1 is a schematic diagram showing a pyrolysis reaction apparatus used in the examples. [Diagram 3] FIG. 2 is a schematic diagram showing a low boiling point separation device used in the examples. [Figure 4] FIG. 2 is a schematic diagram showing a high bp separation device used in the examples. [Diagram 5] 1 is a graph showing NMR spectra of the carbamate compounds (I-1a) to (I-1c) produced in Example 1-1. [Figure 6A] 1 is a graph showing NMR spectra of carbamate compounds (I-3a) to (I-3c) prepared in Examples 1-7. [Figure 6B] 1 is a graph showing the results of gas chromatography-mass spectrometry of the carbamate compounds (I-3a) to (I-3c) prepared in Examples 1-7. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0054] The present invention will be described below in detail with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and can be modified in various ways within the scope of the present invention.

[0055] In this specification, when referring to the IUPAC rules and the IUPAC Nomenclature rules (except when specifically citing IUPAC recommendations from other years) as described below, it means a reference to "Organic Chemistry and Biochemistry Nomenclature" (revised second edition published by Nankodo Publishing Co., Ltd. in 1992) which is based on the version that includes all the rules of organic chemistry and biochemistry and the rules of transliteration into Japanese, which was published as a supplement to "Chemical Domain" in 1980 based on the Recommendations 1979, and which includes all subsequent revisions and recommendations. "Organic" refers to a general group of compounds that are the subject of the nomenclature disclosed in the nomenclature. The subject may be the subject described in the Recommendation issued in 1993. However, the "organic" compounds that are the subject of the nomenclature also include organometallic compounds and metal complexes. In this embodiment, unless otherwise specified, the terms "organic group" and "substituent" mean a group composed of atoms that do not contain metal atoms and / or metalloids. Furthermore, in this embodiment, preferably, an "organic compound", an "organic group" or a "substituent" composed of atoms selected from H (hydrogen atom), C (carbon atom), N (nitrogen atom), O (oxygen atom), S (sulfur atom), Cl (chlorine atom), Br (bromine atom) and I (iodine atom) is used.

[0056] In the following description, the terms "aliphatic" and "aromatic" are used frequently. According to the above-mentioned IUPAC rules, organic compounds are classified into aliphatic compounds and aromatic compounds. An aliphatic compound is a definition of a group that follows the aliphatic compounds based on the 1995 IUPAC recommendation. In the recommendation, an aliphatic compound is defined as "acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds". In addition, the "aliphatic compound" used in the description of this embodiment refers to an "organic compound", "organic group", or "substituent" that includes both saturated and unsaturated, chain and cyclic compounds, and is composed of atoms selected from the group consisting of the above-mentioned H (hydrogen atom); C (carbon atom); N (nitrogen atom); O (oxygen atom); S (sulfur atom); Si (silicon atom); Cl (chlorine atom), Br (bromine atom), or I (iodine atom).

[0057] When an aromatic group such as an aralkyl group is bonded to an aliphatic group, it may be written as "an aliphatic group substituted with an aromatic group" or "a group consisting of an aliphatic group bonded to an aromatic group". This is based on the reactivity in this embodiment, because the properties related to the reaction of a group such as an aralkyl group are very similar to the reactivity of aliphatic groups, not aromaticity. In addition, non-aromatic reactive groups including aralkyl groups, alkyl groups, etc. may be written as "aliphatic groups which may be substituted with aromatic groups", "aliphatic groups which may be bonded to aromatic groups", etc.

[0058] In addition, when explaining the general formula of the compound used in this specification, the definition according to the nomenclature rule defined by IUPAC is used, but for the names of specific groups and the names of exemplified compounds, trivial names may be used. In addition, when the number of atoms, the number of substituents, and the number are described in this specification, they all represent integers.

[0059] In this specification, "active hydrogen" refers to a hydrogen atom (excluding aromatic hydroxyl groups) bonded to an oxygen atom, sulfur atom, nitrogen atom, silicon atom, etc., and a hydrogen atom of a terminal methine group. "Active hydrogen" refers to hydrogen contained in an atomic group such as, for example, an -OH group, a -C(=O)OH group, a -C(=O)H group, a -SH group, a -SOH group, a -SOH group, a -NH group, a -NH- group, a -SiH group, or a -C≡CH group.

[0060] Examples of compounds having a hydroxy group (-OH group) include alcohols and aromatic hydroxy compounds.

[0061] In this specification, the term "alcohol" refers to "compounds in which a hydroxy group, -OH, is attached to a saturated carbon atom: R3COH" as defined by the IUPAC definition (Rule C-201), and does not include aromatic hydroxy compounds in which a hydroxy group is attached to an aromatic ring.

[0062] In this specification, the term "aromatic hydroxy compound" refers to phenols as defined by the IUPAC definition (Rule C-202): "Compounds having one or more hydroxy groups attached to a benzene or other arene ring."

[0063] Carbonyl compounds The carbonyl compound of the present embodiment is a compound represented by the following general formula (I) (hereinafter, may be referred to as "carbonyl compound (I)").

[0064] [ka]

[0065] (In general formula (I), R 11 is an organic group with a valence of (n11+n12), and R 12 is a monovalent organic group. n11 is an integer of 1 or more and 8 or less, n12 is an integer of 0 or more and 7 or less, and the sum of n11 and n12 is an integer of 2 or more and 8 or less.

[0066] The inventors have found that the carbonyl compound (I) is generated in the production of an isocyanate compound by thermal decomposition of a carbamate compound. They have also found that, when producing an isocyanate compound by thermal decomposition from a carbamate compound, the carbonyl compound (I) is allowed to coexist, preventing adhesion of a by-product having a boiling point higher than that of the isocyanate compound (hereinafter, sometimes referred to as a "high-boiling by-product") to the equipment in the thermal decomposition step or purification step, and that the isocyanate compound can be efficiently recovered, thereby improving the yield of the isocyanate compound, and have completed the present invention.

[0067] [R 11 ] R 11 is an organic group having a valence of (n11+n12), that is, an organic group having a valence of 2 to 8. 11 is preferably an aliphatic hydrocarbon group having from 1 to 20 carbon atoms, which may have one to four ester groups or a nitrogen atom, and a divalent to tetravalent aromatic hydrocarbon group having from 6 to 20 carbon atoms, or a divalent to trivalent aromatic hydrocarbon group having from 6 to 20 carbon atoms.

[0068] R 11The aliphatic hydrocarbon group in is preferably an alkylene group or an alkanetriyl group, a cycloalkyl group, a cycloalkylene group or a cycloalkanetriyl group, or a group composed of the alkyl group, the alkylene group or the alkanetriyl group and the cycloalkyl group, the cycloalkylene group or the cycloalkanetriyl group, and more preferably a linear or branched alkylene group or alkanetriyl group, a cycloalkylene group or a cycloalkanetriyl group, or a group composed of the alkylene group or the alkanetriyl group and the cycloalkyl group, the cycloalkylene group or the cycloalkanetriyl group.

[0069] Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group, a trimethylene group, a pentylene group, an n-hexylene group, and a decamethylene group. Examples of the cycloalkylene group include a cyclobutylene group and a cyclohexylene group.

[0070] Examples of the linear or branched alkanetriyl group include a hexanetriyl group, a nonanetriyl group, and a decanetriyl group. Examples of the cycloalkanetriyl group include a cyclopropanetriyl group, a cyclobutanetriyl group, a cyclopentanetriyl group, and a cyclohexanetriyl group.

[0071] R 11 The aromatic hydrocarbon group in is preferably a substituted or unsubstituted group having an aromatic ring with 6 to 13 carbon atoms. Examples of the substituent include an alkyl group, an aryl group, and an aralkyl group. The aromatic ring may be an aromatic hydrocarbon ring or a heteroaromatic ring, and specific examples include a benzene ring, a naphthalene ring, and a pyridine ring.

[0072] R 11 When the aliphatic hydrocarbon group or aromatic group in has 1 to 4 ester groups, R 11The aryl group is preferably a group obtained by removing the terminal primary amino group of an amine compound having an ester group obtained by reacting a carboxy group of an amino acid with a hydroxy compound.

[0073] Specific examples of the amine compound having an ester group herein include 2-aminoethyl acrylate, 2-methyl-2-aminoethyl acrylate, 2-aminopropyl acrylate, 2-methyl-2-aminopropyl acrylate, 3-aminopropyl acrylate, 3-aminopropyl acrylate, 4-aminobutyl acrylate, 4-aminobutyl acrylate, 5-aminopentyl acrylate, 5-aminopentyl acrylate, 6-aminohexyl acrylate, 6-aminohexyl acrylate, 8-aminooctyl acrylate, 2-methyl-acrylic acid, and 2-methyl-acrylic acid. Acid-8-aminoctyl ester, acrylic acid-10-aminodecyl ester, 2-methyl-acrylic acid-10-aminodecyl ester, acrylic acid-11-aminodecyl ester, 2-methyl-acrylic acid-11-aminodecyl ester, acrylic acid-12-aminododecyl ester, 2-methyl-acrylic acid-12-aminododecyl ester, lysine methyl ester diamine, lysine ethyl ester diamine, 2-aminoethyl-2,5-diaminopentanoate, 2-aminoethyl-2,6-diaminohexanoate, bis(2-aminoethyl)-2-aminobutanedioate, bis(2-aminoethyl)-2-aminopentanedioate, tris(2-aminoethyl)hexane-1,3,6-tricarboxylate, and the like.

[0074] Examples of amino acids used in the production of amine compounds having an ester group include lysine, alanine, arginine, asparagine, glutamine, glycine, aspartic acid, glutamic acid, ornithine, histidine, isoleucine, leucine, methionine, phenylalanine, tryptophan, and valine. Among these, the amino acid is preferably lysine, arginine, glycine, aspartic acid, glutamic acid, or ornithine, and more preferably lysine, arginine, glycine, aspartic acid, or glutamic acid.

[0075] Examples of the hydroxy compound used in the production of the amine compound having an ester group include alcohols and aromatic hydroxy compounds. Examples of alcohols include methyl alcohol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, ethanolamine, propanolamine (1-amino-2-propanol), dimethanolamine, diethanolamine, dipropanolamine, and 1-amino-2-butanol. Examples of aromatic hydroxy compounds include monophenols such as phenol (carbolic acid), 2-methoxyphenol, cresol, xylenol, carvacrol, motil, and naphthol, and polyphenols such as catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, pyrogallol, and phloroglucinol.

[0076] R 11 When the aliphatic hydrocarbon group or aromatic group in has 1 to 4 nitrogen atoms, R 11 The amine compound having 1 to 4 secondary or tertiary amines other than the terminal of the aliphatic hydrocarbon group or aromatic group is preferably an organic group obtained by removing the terminal amino group from the amine compound having 1 to 4 secondary or tertiary amines other than the terminal of the aliphatic hydrocarbon group or aromatic group. Specific examples of the amine compound having 1 to 4 secondary or tertiary amines other than the terminal of the aliphatic hydrocarbon group or aromatic group referred to here include 2-(dimethylamino)ethyleneamine, 2-(diethylamino)ethyleneamine, 2-(diisopropylamino)ethyleneamine, 2-(cyclohexylamino)ethyleneamine, 3-(cyclohexylamino)propylamine, 3-(diethylamino)propylamine, 3-(dimethylamino)propylamine, diethylenetriamine, diisopropyltriamine, bis-(3-aminopropyl)methyleneamine, 3-(2-aminoethylamino)propylamine, N,N'-bis(3-aminopropyl)ethylenediamine, 1-(3-aminopropyl)imidazole, trisaminoethylamine, trisaminopropylamine, etc. Among these, the amine compound is preferably an amine compound having one or more and not more than two tertiary amines at other than the terminals and having an aliphatic hydrocarbon group or an aromatic group, and more preferably an amine compound having one tertiary amine at other than the terminal and having an aliphatic hydrocarbon group or an aromatic group.

[0077] Among them, R 11 is preferably a group represented by any one of the following formulae (Ia-1) to (Ia-24), and more preferably a group represented by formula (Ia-1), (Ia-2), (Ia-3), (Ia-14), (Ia-18), or (Ia-19). In each formula, the wavy line represents a bond.

[0078] [ka]

[0079] [ka]

[0080] [R 12 ] R 12 is a monovalent organic group, which may contain an oxygen atom, and is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0081] R 12 Examples of the aliphatic hydrocarbon group in the formula (I) include a methyl group, an ethyl group, a propyl group (each isomer), a butyl group (each isomer), a pentyl group (each isomer), a hexyl group (each isomer), a heptyl group (each isomer), an octyl group (each isomer), a nonyl group (each isomer), a decyl group (each isomer), an undecyl group (each isomer), a dodecyl group (each isomer), a tridecyl group (each isomer), a tetra ... Examples of alkyl groups include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group; and alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group.

[0082] R 12Examples of the aliphatic hydrocarbon group which may contain an oxygen atom in the above formula include a methoxymethyl group, a methoxyethyl group (each isomer), a methoxypropyl group (each isomer), a methoxybutyl group (each isomer), a methoxypentyl group (each isomer), a methoxyhexyl group (each isomer), a methoxyheptyl group (each isomer), a methoxyoctyl group (each isomer), a methoxynonyl group (each isomer), a methoxydecyl group (each isomer), a methoxyundecyl group (each isomer), a methoxydodecyl group (each isomer), a methoxytridecyl group (each isomer), a methoxytetradecyl group (each isomer), ), methoxypentadecyl group (each isomer), methoxyhexadecyl group (each isomer), methoxyheptadecyl group (each isomer), methoxyoctadecyl group (each isomer), methoxynonadecyl (each isomer), ethoxymethyl group, ethoxyethyl group (each isomer), ethoxypropyl group (each isomer), ethoxybutyl group (each isomer), ethoxypentyl group (each isomer), ethoxyhexyl group (each isomer), ethoxyheptyl group (each isomer), ethoxyoctyl group (each isomer), ethoxynonyl group (each isomer), ethoxydecyl group (each isomer), ethoxyundecyl group (each isomer), propyloxymethyl group (each isomer), propyloxyethyl group (each isomer), propyloxypropyl group (each isomer), propyloxybutyl group (each isomer), propyloxypentyl group (each isomer), propyloxyhexyl group (each isomer), propyloxytetradecyl group (each isomer), ethoxypentadecyl group (each isomer), ethoxyhexadecyl group (each isomer), ethoxyheptadecyl group (each isomer), ethoxyoctadecyl group (each isomer), propyloxymethyl group (each isomer), propyloxyethyl group (each isomer), propyloxypropyl group (each isomer), propyloxybutyl group (each isomer), propyloxypentyl group (each isomer), propyloxyhexyl group (each isomer), propyl Oxyheptyl group (each isomer), propyloxyoctyl group (each isomer), propyloxynonyl group (each isomer), propyloxydecyl group (each isomer), propyloxyundecyl group (each isomer), propyloxydodecyl group (each isomer), propyloxytridecyl group (each isomer), propyloxytetradecyl group (each isomer), propyloxypentadecyl group (each isomer), propyloxyhexadecyl group (each isomer), propyloxyheptadecyl group (each isomer), butyloxymethyl group (each isomer), butyloxyethyl group (each isomer),Butyloxypropyl group (each isomer), butyloxybutyl group (each isomer), butyloxypentyl group (each isomer), butyloxyhexyl group (each isomer), butyloxyheptyl group (each isomer), butyloxyoctyl group (each isomer), butyloxynonyl group (each isomer), butyloxydecyl group (each isomer), butyloxyundecyl group (each isomer), butyloxydodecyl group (each isomer), butyloxytridecyl group (each isomer), butyloxytetradecyl group (each isomer), butyloxypentadecyl group (each isomer), butyloxyhexadecyl group (each isomer), phenyl group (each isomer), pentyloxymethyl group (each isomer), pentyloxyethyl group (each isomer), pentyloxypropyl group (each isomer), pentyloxybutyl group (each isomer), pentyloxypentyl group (each isomer), pentyloxyhexyl group (each isomer), pentyloxyheptyl group (each isomer), pentyloxyoctyl group (each isomer), pentyloxynonyl group (each isomer), pentyloxydecyl group (each isomer), pentyloxyundecyl group (each isomer), pentyloxydodecyl group (each isomer), pentyloxytridecyl group (each isomer), isomer), pentyloxytetradecyl group (each isomer), pentyloxypentadecyl group (each isomer), hexyloxymethyl group (each isomer), hexyloxyethyl group (each isomer), hexyloxypropyl group (each isomer), hexyloxybutyl group (each isomer), hexyloxypentyl group (each isomer), hexyloxyhexyl group (each isomer), hexyloxyheptyl group (each isomer), hexyloxyoctyl group (each isomer), hexyloxynonyl group (each isomer), hexyloxydecyl group (each isomer), hexyloxyundecyl group (each isomer) methyloxyethyl group (each isomer), methyloxyethyl group (each isomer), methyloxypropyl group (each isomer), methyloxybutyl group (each isomer), methyloxypentyl group (each isomer), methyloxyhexyl group (each isomer), methyloxyheptyl group (each isomer), methyloxyoctyl group (each isomer), methyloxynonyl group (each isomer), methyloxydecyl group (each isomer),Heptyloxyundecyl group (each isomer), heptyloxydodecyl group (each isomer), heptyloxytridecyl group (each isomer), octyloxymethyl group (each isomer), octyloxyethyl group (each isomer), octyloxypropyl group (each isomer), octyloxybutyl group (each isomer), octyloxypentyl group (each isomer), octyloxyhexyl group (each isomer), octyloxyheptyl group (each isomer), octyloxyoctyl group (each isomer), octyloxynonyl group (each isomer), octyloxydecyl group (each isomer), octyloxy 1,2-diphenyloxydodecyl group (each isomer), octyloxydodecyl group (each isomer), nonyloxymethyl group (each isomer), nonyloxyethyl group (each isomer), nonyloxypropyl group (each isomer), nonyloxybutyl group (each isomer), nonyloxypentyl group (each isomer), nonyloxyhexyl group (each isomer), nonyloxyheptyl group (each isomer), nonyloxyoctyl group (each isomer), nonyloxynonyl group (each isomer), nonyloxydecyl group (each isomer), nonyloxyundecyl group (each isomer), decyloxymethyl group (each isomer), decyloxy Ethyl group (each isomer), decyloxypropyl group (each isomer), decyloxybutyl group (each isomer), decyloxypentyl group (each isomer), decyloxyhexyl group (each isomer), decyloxyheptyl group (each isomer), decyloxyoctyl group (each isomer), decyloxynonyl group (each isomer), decyloxydecyl group (each isomer), undecyloxymethyl group (each isomer), undecyloxyethyl group (each isomer), undecyloxypropyl group (each isomer), undecyloxybutyl group (each isomer), undecyloxypentyl group (each isomer), Undecyloxyhexyl group (each isomer), undecyloxyheptyl group (each isomer), undecyloxyoctyl group (each isomer), undecyloxynonyl group (each isomer), dodecyloxymethyl group (each isomer), dodecyloxyethyl group (each isomer), dodecyloxypropyl group (each isomer), dodecyloxybutyl group (each isomer), dodecyloxypentyl group (each isomer), dodecyloxyhexyl group (each isomer), dodecyloxyheptyl group (each isomer), dodecyldecyloxyoctyl group (each isomer), tridecyloxymethyl group (each isomer),Tridecyloxyethyl group (each isomer), tridecyloxypropyl group (each isomer), tridecyloxybutyl group (each isomer), tridecyloxypentyl group (each isomer), tridecyloxyhexyl group (each isomer), tridecyloxyheptyl group (each isomer), tetradecyloxymethyl group (each isomer), tetradecyloxyethyl group (each isomer), tetradecyloxypropyl group (each isomer), tetradecyloxybutyl group (each isomer), tetradecyloxypentyl group (each isomer), tetradecyloxyhexyl group (each isomer), pentadecyloxymethyl group, pentadecyloxyethyl group (each isomer), Examples of alkoxyalkyl groups include alkoxyalkyl groups such as alkoxyalkyl groups (each isomer), pentadecyloxypropyl group (each isomer), pentadecyloxybutyl group (each isomer), pentadecyloxypentyl group (each isomer), hexadecyloxymethyl group (each isomer), hexadecyloxyethyl group (each isomer), hexadecyloxypropyl group (each isomer), hexadecyloxybutyl group (each isomer), heptadecyloxymethyl group (each isomer), heptadecyloxyethyl group (each isomer), heptadecyloxypropyl group (each isomer), octadecyloxymethyl group (each isomer), and octadecyloxyethyl group (each isomer).

[0083] R 12Examples of the aromatic hydrocarbon group in the above formula (1) include aryl groups such as phenyl, naphthyl, anthryl, pyrenyl, and phenanthryl; methylphenyl (each isomer), ethylphenyl (each isomer), propylphenyl (each isomer), butylphenyl (each isomer), pentylphenyl (each isomer), hexylphenyl (each isomer), heptylphenyl (each isomer), octylphenyl (each isomer), nonylphenyl (each isomer), decylphenyl (each isomer), undecylphenyl (each isomer), and dodecylphenyl (each isomer). , tridecylphenyl group (each isomer), tetradecylphenyl group (each isomer), dimethylphenyl group (each isomer), methylethylphenyl group (each isomer), methylpropylphenyl group (each isomer), methylbutylphenyl group (each isomer), methylpentylphenyl group (each isomer), methylhexylphenyl group (each isomer), methylheptylphenyl group (each isomer), methyloctylphenyl group (each isomer), methylnonylphenyl group (each isomer), methyldecylphenyl group (each isomer), methylundecylphenyl group (each isomer), methyldodecylphenyl group group (each isomer), methyltridecylphenyl group (each isomer), diethylphenyl group (each isomer), ethylpropylphenyl group (each isomer), ethylbutylphenyl group (each isomer), ethylpentylphenyl group (each isomer), ethylhexylphenyl group (each isomer), ethylheptylphenyl group (each isomer), ethyloctylphenyl group (each isomer), ethylnonylphenyl group (each isomer), ethyldecylphenyl group (each isomer), ethylundecylphenyl group (each isomer), ethyldodecylphenyl group (each isomer), dipropylphenyl group (each isomer), Propylbutylphenyl group (each isomer), propylpentylphenyl group (each isomer), propylhexylphenyl group (each isomer), propylheptylphenyl group (each isomer), propyloctylphenyl group (each isomer), propylnonylphenyl group (each isomer), propyldecylphenyl group (each isomer), propylundecylphenyl group (each isomer), dibutylphenyl group (each isomer), butylpentylphenyl group (each isomer), butylhexylphenyl group (each isomer), butylheptylphenyl group (each isomer), butyloctylphenyl group (each isomer),Butylnonylphenyl group (each isomer), butyldecylphenyl group (each isomer), dipentylphenyl group (each isomer), pentylhexylphenyl group (each isomer), pentylheptylphenyl group (each isomer), pentyloctylphenyl group (each isomer), pentylnonylphenyl group (each isomer), dihexylphenyl group (each isomer), hexylheptylphenyl group (each isomer), hexyloctylphenyl group (each isomer), diheptylphenyl group (each isomer), trimethylphenyl group (each isomer), dimethylethylphenyl phenyl group (each isomer), dimethylpropylphenyl group (each isomer), dimethylbutylphenyl group (each isomer), dimethylpentylphenyl group (each isomer), dimethylhexylphenyl group (each isomer), dimethylheptylphenyl group (each isomer), dimethyloctylphenyl group (each isomer), dimethylnonylphenyl group (each isomer), dimethyldecylphenyl group (each isomer), dimethylundecylphenyl group (each isomer), dimethyldodecylphenyl group (each isomer), triethylphenyl group (each isomer), diethylmethylphenyl group nyl group (each isomer), diethylpropylphenyl group (each isomer), diethylbutylphenyl group (each isomer), diethylpentylphenyl group (each isomer), diethylhexylphenyl group (each isomer), diethylheptylphenyl group (each isomer), diethyloctylphenyl group (each isomer), diethylnonylphenyl group (each isomer), diethyldecylphenyl group (each isomer), tripropylphenyl group (each isomer), dipropylmethylphenyl group (each isomer), dipropylethylphenyl group (each isomer), dipropylbutyl Examples of the isomers include phenyl group (each isomer), dipropylpentylphenyl group (each isomer), dipropylhexylphenyl group (each isomer), dipropylheptylphenyl group (each isomer), dipropyloctylphenyl group (each isomer), tributylphenyl group (each isomer), dibutylmethylphenyl group (each isomer), dibutylethylphenyl group (each isomer), dibutylpropylphenyl group (each isomer), dibutylpentylphenyl group (each isomer), dibutylhexylphenyl group (each isomer), and cumylphenyl group (each isomer).

[0084] R 12Examples of the aromatic hydrocarbon group which may contain an oxygen atom in the formula (I) include alkoxyaryl groups such as a methoxyphenyl group (each isomer), an ethoxyphenyl group (each isomer), and the like.

[0085] Among them, R 12Examples of the isomers include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, a methylphenyl group (each isomer), an ethylphenyl group (each isomer), a propylphenyl group (each isomer), a butylphenyl group (each isomer), a pentylphenyl group (each isomer), a hexylphenyl group (each isomer), a heptylphenyl group (each isomer), an octylphenyl group (each isomer), a nonylphenyl group (each isomer), a decylphenyl group (each isomer), an undecylphenyl group (each isomer), a dodecylphenyl group (each isomer), a tridecylphenyl group (each isomer), a tetra ... Cylphenyl group (each isomer), dimethylphenyl group (each isomer), methylethylphenyl group (each isomer), methylpropylphenyl group (each isomer), methylbutylphenyl group (each isomer), methylpentylphenyl group (each isomer), methylhexylphenyl group (each isomer), methylheptylphenyl group (each isomer), methyloctylphenyl group (each isomer), methylnonylphenyl group (each isomer), methyldecylphenyl group (each isomer), methylundecylphenyl group (each isomer), methyldodecylphenyl group (each isomer), methyltridecylphenyl group (each isomer), diethylphenyl group (each isomer), ethylpropylphenyl group (each isomer), ethylbutylphenyl group (each isomer), ethylpentylphenyl group (each isomer), ethylhexylphenyl group (each isomer), ethylheptylphenyl group (each isomer), ethyloctylphenyl group (each isomer), ethylnonylphenyl group (each isomer), ethyldecylphenyl group (each isomer), ethylundecylphenyl group (each isomer), ethyldodecylphenyl group (each isomer), dipropylphenyl group (each isomer), propylbutylphenyl group (each isomer), Propylpentylphenyl group (each isomer), propylhexylphenyl group (each isomer), propylheptylphenyl group (each isomer), propyloctylphenyl group (each isomer), propylnonylphenyl group (each isomer), propyldecylphenyl group (each isomer), propylundecylphenyl group (each isomer), dibutylphenyl group (each isomer), butylpentylphenyl group (each isomer), butylhexylphenyl group (each isomer), butylheptylphenyl group (each isomer), butyloctylphenyl group (each isomer), butylnonylphenyl group (each isomer),Butyldecylphenyl group (each isomer), dipentylphenyl group (each isomer), pentylhexylphenyl group (each isomer), pentylheptylphenyl group (each isomer), pentyloctylphenyl group (each isomer), pentylnonylphenyl group (each isomer), dihexylphenyl group (each isomer), hexylheptylphenyl group (each isomer), hexyloctylphenyl group (each isomer), diheptylphenyl group (each isomer), trimethylphenyl group (each isomer), dimethylethylphenyl group (each isomer), dimethylpropylphenyl group (each isomer), dimethylbutylphenyl group (each isomer), dimethylpentylphenyl group (each isomer), dimethylhexylphenyl group (each isomer), dimethylheptylphenyl group (each isomer), dimethyloctylphenyl group (each isomer), dimethylnonylphenyl group (each isomer), dimethyldecylphenyl group (each isomer), dimethylundecylphenyl group (each isomer), dimethyldodecylphenyl group (each isomer), triethylphenyl group (each isomer), diethylmethylphenyl group (each isomer), diethylpropylphenyl group (each isomer) isomer), diethylbutylphenyl group (each isomer), diethylpentylphenyl group (each isomer), diethylhexylphenyl group (each isomer), diethylheptylphenyl group (each isomer), diethyloctylphenyl group (each isomer), diethylnonylphenyl group (each isomer), diethyldecylphenyl group (each isomer), tripropylphenyl group (each isomer), dipropylmethylphenyl group (each isomer), dipropylethylphenyl group (each isomer), dipropylbutylphenyl group (each isomer), dipropylpentylphenyl group (each isomer) isomer), dipropylhexylphenyl group (each isomer), dipropylheptylphenyl group (each isomer), dipropyloctylphenyl group (each isomer), tributylphenyl group (each isomer), dibutylmethylphenyl group (each isomer), dibutylethylphenyl group (each isomer), dibutylpropylphenyl group (each isomer), dibutylpentylphenyl group (each isomer), dibutylhexylphenyl group (each isomer), cumylphenyl group (each isomer), methoxyphenyl group (each isomer), or ethoxyphenyl group (each isomer) are preferred. Also preferred are phenyl group, cumylphenyl group (each isomer), methoxyphenyl group (each isomer),Or ethoxyphenyl group (each isomer) is more preferred.

[0086] [n11 and n12] n11 is an integer between 1 and 8 inclusive. n12 represents the number of isocyanate groups and is an integer of 0 to 7. The sum of n11 and n12 (n11+n12) is an integer of 2 to 8, preferably an integer of 2 to 6, more preferably an integer of 2 to 5, and even more preferably an integer of 3 to 4. In general, the larger the value of (n11+n12), the higher the molecular weight of the carbonyl compound (I) and the higher the boiling point, making it easier to separate from the isocyanate. On the other hand, in the production of the carbonyl compound (I), heating a highly reactive isocyanate group can cause a modification reaction, which can cause adhesion to the device or clogging. Therefore, from the viewpoint of the production efficiency of the carbonyl compound (I), it is preferable that (n11+n12) is 6 or less, more preferably that (n11+n12) is 5 or less, and even more preferably that (n11+n12) is 4 or less.

[0087] Preferred examples of the carbonyl compound (I) include compounds represented by the following formulae (I-1a) to (I-24) (hereinafter, sometimes referred to as "carbonyl compound (I-1a)"). In addition, the carbonyl compounds (I-1a) to (I-1c), carbonyl compounds (I-2a) to (I-2c), carbonyl compounds (I-3a) to (I-3c), carbonyl compounds (I-4a) to (I-4c), carbonyl compounds (I-5a) to (I-5c), carbonyl compounds (I-6a) to (I-6c), carbonyl compounds (I-7a) to (I-7b), carbonyl compounds (I-8a) to (I-8b), The carbonyl compounds (I-9a) to (I-9b), the carbonyl compounds (I-10a) to (I-10b), the carbonyl compounds (I-11a) to (I-11b), the carbonyl compounds (I-12a) to (I-12b), the carbonyl compounds (I-22a) to (I-22b), and the carbonyl compounds (I-24a) to (I-24b) may each be a mixture or each compound may be a single compound.

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] <Method for producing carbonyl compound> The method for producing a carbonyl compound according to the present embodiment includes a method for producing a carbonyl compound comprising the steps of: one or more compounds selected from the group consisting of carbonate esters and hydroxy compounds; and heating to synthesize the carbonyl compound.

[0097] The present inventors have found that the above carbonyl compound (I) is produced in the production of an isocyanate compound by the thermal decomposition reaction of a carbamate compound. Thus, examples of the method for producing the carbonyl compound of this embodiment include: 1) a production method by a thermal decomposition reaction of a carbamate compound; and 2) a method of mixing and heating one or more compounds selected from the group consisting of isocyanate compounds and carbamate compounds with one or more compounds selected from the group consisting of carbonate esters and hydroxy compounds.

[0098] <Production method by pyrolysis reaction> When a carbonyl compound is produced by a thermal decomposition reaction, a reaction to form an isocyanurate group represented by the above formula (B), a reaction to form a carbodiimide represented by the above formula (C), a reaction to form a uretonimine group represented by the above formula (D), and a reaction to form an allophanate group represented by the above formula (E) occur as side reactions. These side reactions occur by the reaction between isocyanates, between carbamate compounds, or between an isocyanate compound and a carbamate compound. In contrast, the reaction to form a carbonyl compound (I) is produced by the reaction of one or more compounds selected from the group consisting of an isocyanate compound and a carbamate compound with one or more compounds selected from the group consisting of a carbonate ester and a hydroxy compound. Therefore, in the thermal decomposition reaction of a carbamate compound, the amount of the carbonate ester used can be increased, or the thermal decomposition reaction can be carried out under reflux conditions to prevent the evaporation of excess carbonate ester, thereby relatively increasing the production ratio of the carbonyl compound (I).

[0099] The carbonyl compound (I) is presumed to be produced by a reaction mechanism represented by the following formula (F), (G) or (H).

[0100] [ka]

[0101] (In formulas (F) to (H), R j R is a divalent or higher organic group. k is a monovalent organic group.

[0102] In the thermal decomposition reaction, the amount (molar amount) of the carbonate ester used as a solvent is preferably large in terms of suppressing side reactions, but considering the size of the reactor, the amount is preferably 0.001 to 100 times, more preferably 0.01 to 80 times, and even more preferably 0.1 to 50 times, in terms of the stoichiometric ratio to the carbamate compound.

[0103] When a carbamate compound is produced by the method described below, if the carbamate compound contains a carbonate ester, the carbonate ester may be used as is, or a new carbonate ester may be added to the carbamate compound. The carbonate ester may be supplied to the reactor before the start of the reaction, during the reaction, or both. Among these, it is preferable to supply the carbonate ester to the reactor before the reaction.

[0104] The reaction temperature is usually from 100° C. to 400° C., and a high temperature is preferable to increase the reaction rate, but on the other hand, at a high temperature, the above-mentioned side reactions may be caused by one or more compounds selected from the group consisting of carbamate compounds and the product isocyanate compounds, so the reaction temperature is preferably from 130° C. to 300° C., more preferably from 150° C. to 280° C. In order to keep the reaction temperature constant, a known cooling device or heating device may be installed in the reactor.

[0105] The reaction pressure varies depending on the type of compound used and the reaction temperature, but may be reduced pressure, normal pressure, or increased pressure. It is usually 20 Pa or more and 1×10 6 The temperature is set in the range of Pa or less.

[0106] The reaction time (residence time in the case of a continuous method) is not particularly limited and is usually from 0.001 to 100 hours, preferably from 0.01 to 50 hours, and more preferably from 0.1 to 10 hours.

[0107] A catalyst can be used, and the amount of the catalyst used is preferably from 0.01% by mass to 30% by mass, more preferably from 0.5% by mass to 20% by mass, based on the mass of the carbamate compound. Examples of the catalyst include organometallic catalysts such as dibutyltin dilaurate, lead octoate, and stannous octoate; and amines such as 1,4-diazabicyclo[2,2,2]octane, triethylenediamine, and triethylamine. Among these, organometallic catalysts such as dibutyltin dilaurate, lead octoate, and stannous octoate are preferred. These compounds may be used alone or in combination of two or more.

[0108] As described above, the thermal decomposition reaction is a reaction that produces the corresponding isocyanate compound, hydroxyl compound, and carbonyl compound from a carbamate compound. In order to efficiently obtain the carbonyl compound, it is necessary to heat the isocyanate compound, carbonate ester, and carbamate compound in a state where they coexist in the thermal decomposition reaction. Therefore, in order to efficiently obtain the carbonyl compound in the thermal decomposition reaction, it is preferable to take out the hydroxyl compound, which is the product of the thermal decomposition reaction, as a gas phase component from the thermal decomposition reaction system by a method such as distillation, separate the hydroxyl compound from the carbonate ester and the isocyanate compound under conditions such as reflux, and make the carbonate ester and the isocyanate exist as liquid phase components.

[0109] After the thermal decomposition reaction, the low boiling components may be distilled off, and the distillation method is not particularly limited as long as the low boiling components can be separated as gas phase components. The "light boiling components (light boiling point components)" referred to here refer to components having a boiling point lower than that of the carbonyl compound, and are mainly one or more compounds selected from the group consisting of carbonate esters used in the thermal decomposition step, isocyanate compounds generated by the thermal decomposition reaction, and hydroxy compounds, although they vary depending on the type of compound used as a raw material for the production of the carbonyl compound.

[0110] The pressure at which the low-boiling components are distilled off varies depending on the type of compound and the reaction temperature. As long as the carbonyl compound and the low-boiling components can be separated, the pressure may be reduced, normal, or increased. The pressure should be between 20 Pa and 1×10 6 Pa or less is preferable, and 20 Pa or more is 1×10 4 Pa or less is more preferable, and 20 Pa or more is 1×10 3 Pa or less is more preferable, and 20 Pa or more to 1×10 2 Pa or less is particularly preferred.

[0111] The operation time (residence time in the case of a continuous method) when distilling off the low-boiling components is not particularly limited as long as the carbonyl compound and the low-boiling components can be separated. From the viewpoint of suppressing side reactions with the carbonyl compound, the operation time is preferably from 5 seconds to 100 hours, more preferably from 10 seconds to 50 hours, and even more preferably from 20 seconds to 10 hours.

[0112] The temperature at which the low-boiling components are distilled off is not particularly limited as long as the carbonyl compound is stable and the carbonyl compound and the low-boiling components can be separated. From the viewpoint of suppressing denaturation of the carbonyl compound, the temperature is preferably 20° C. or higher and 300° C. or lower, more preferably 30° C. or higher and 280° C. or lower, and even more preferably 40° C. or higher and 250° C. or lower.

[0113] <Production method by heating the mixture> As can be seen from the fact that the reaction mechanism of the carbonyl compound is represented by the above formula (F), (G) or (H), the carbonyl compound (I) can also be obtained by heating a mixture of an isocyanate compound (II) and a carbonate ester (IV), a mixture of a carbamate compound (III) or a carbamate compound (VI) and a carbonate ester (IV), a mixture of an isocyanate compound (II), a hydroxy compound (V) and a carbonate ester (IV), a mixture of an isocyanate compound (II), a carbamate compound (III) or a carbamate compound (VI) and a carbonate ester (IV), or a mixture of an isocyanate compound (II), a carbamate compound (III) or a carbamate compound (VI), a carbonate ester (IV) and a hydroxy compound (V) (hereinafter, these mixtures may be collectively referred to simply as the "raw material mixture").

[0114] In the raw material mixture, the amount (molar amount) of the carbonate ester is preferably large in terms of suppressing side reactions, but taking into consideration the size of the reactor, the amount is preferably 0.001 to 100 times, more preferably 0.01 to 80 times, and even more preferably 0.1 to 50 times, in terms of the stoichiometric ratio to the carbamate compound.

[0115] The heating temperature is usually from 100° C. to 400° C., and a high temperature is preferable to increase the reaction rate, but on the other hand, at a high temperature, the above-mentioned side reaction may be caused by one or more compounds selected from the group consisting of carbamate compounds and the product isocyanate compounds, so the heating temperature is preferably from 130° C. to 300° C., and more preferably from 150° C. to 280° C. In order to keep the reaction temperature constant, a known cooling device or heating device may be installed in the reactor.

[0116] The pressure during heating varies depending on the type of compound used and the reaction temperature, but may be reduced pressure, normal pressure, or increased pressure. It is usually 20 Pa or more and 1×10 6 The temperature is set in the range of Pa or less.

[0117] The heating time (residence time in the case of a continuous method) is not particularly limited and is usually from 0.001 to 100 hours, preferably from 0.01 to 50 hours, and more preferably from 0.1 to 10 hours.

[0118] In the production of carbonyl compounds by mixing and heating, the rate and amount of carbonyl compounds produced can be increased by heating the raw material mixture in contact with stainless steel. As the stainless steel, any shape can be used as long as it is made of SUS316 or SUS304, and for example, packings and metal pieces are preferably used. As the packing, there is no particular limitation, but DIXON Packing, Mc MAHON Packing, Coil PACK, MESH RING, CANNON Packing, HELI PACK, RASCHIG RING, PRICKLE RING, etc. can be used.

[0119] When the volume of the raw material solution of carbonyl compounds is V and the surface area of ​​the stainless steel is A, the larger the contact area of ​​the raw material solution with the stainless steel per unit volume, the faster the rate of carbonyl compound formation. The value of A / V is 0.001 m 2 / m 3 More than 100000m 2 / m 3 Less than 0.01m is preferable. 2 / m 3 More than 50000m 2 / m 3 Less than 0.1m is preferable. 2 / m 3 More than 10000m 2 / m 3 The following is even more preferred:

[0120] The reaction format is not particularly limited, but a reactor capable of efficiently mixing and heating the raw material mixture or the mixture and stainless steel is preferred. For example, a method in which the raw material mixture is heated in a stainless steel stirring tank or distillation column is preferred.

[0121] After heating the raw material mixture, the low boiling components may be distilled off, and the distillation method is not particularly limited as long as the low boiling components can be separated as gas phase components. The "light boiling components (light boiling point components)" referred to here refer to components having a boiling point lower than that of the carbonyl compound, and vary depending on the type of compound used as a raw material for producing the carbonyl compound, but are mainly one or more compounds selected from the group consisting of carbonate esters contained in the raw material mixture, isocyanate compounds generated by thermal decomposition reaction, and hydroxy compounds.

[0122] The pressure at which the low-boiling components are distilled off varies depending on the type of compound and the reaction temperature. As long as the carbonyl compound and the low-boiling components can be separated, the pressure may be reduced, normal, or increased. The pressure should be between 20 Pa and 1×10 6 Pa or less is preferable, and 20 Pa or more is 1×10 4 Pa or less is more preferable, and 20 Pa or more is 1×10 3 Pa or less is more preferable, and 20 Pa or more to 1×10 2 Pa or less is particularly preferred.

[0123] The operation time (residence time in the case of a continuous method) when distilling off the low-boiling components is not particularly limited as long as the carbonyl compound and the low-boiling components can be separated. From the viewpoint of suppressing side reactions with the carbonyl compound, the operation time is preferably from 5 seconds to 100 hours, more preferably from 10 seconds to 50 hours, and even more preferably from 20 seconds to 10 hours.

[0124] The temperature at which the low-boiling components are distilled off is not particularly limited as long as the carbonyl compound is stable and the carbonyl compound and the low-boiling components can be separated. From the viewpoint of suppressing denaturation of the carbonyl compound, the temperature is preferably 20° C. or higher and 300° C. or lower, more preferably 30° C. or higher and 280° C. or lower, and even more preferably 40° C. or higher and 250° C. or lower.

[0125] Next, various raw materials used in the method for producing a carbonyl compound of this embodiment will be described in detail below.

[0126] <Isocyanate compounds> As the isocyanate compound, a compound represented by the following general formula (II) (hereinafter, sometimes referred to as "isocyanate compound (II)") is preferably used.

[0127] [ka]

[0128] (In general formula (II), R 21 is an organic group with a valence of n21, and has the formula: R 21 =R 11 n21 is an integer between 2 and 8, and satisfies the relation: n21 = n11 + n12.

[0129] [R 21 ] R 21 is an organic group having a valence of n21, and has the formula: R 21 =R 11 That is, R 21 is the above R 11 is the same as:

[0130] R 21 When is an aliphatic hydrocarbon group, specific examples of the isocyanate compound (II) include aliphatic diisocyanates, aliphatic triisocyanates, and substituted cyclic aliphatic polyisocyanates.

[0131] Examples of aliphatic diisocyanates include diisocyanatoethane, diisocyanatopropane (each isomer), diisocyanatobutane (each isomer), diisocyanatopentane (each isomer), diisocyanatohexane (each isomer), and diisocyanatodecane (each isomer).

[0132] Examples of the aliphatic triisocyanates include triisocyanatohexane (each isomer), 4-isocyanatomethyl-1,8-octamethylene diisocyanate, triisocyanatononane (each isomer), and triisocyanatodecane (each isomer).

[0133] Examples of substituted cyclic aliphatic polyisocyanates include diisocyanatocyclobutane (each isomer), diisocyanatocyclohexane (each isomer), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate) (each isomer), 1,3-bis(isocyanatomethyl)cyclohexane (at least one of the cis- and trans-isomers), methylenebis(cyclohexyl isocyanate) (also known as dicyclohexylmethane diisocyanate) (each isomer), and the like.

[0134] R 21 When is an aromatic group, specific examples of the isocyanate compound (II) include aromatic diisocyanates and aromatic triisocyanates.

[0135] Examples of aromatic diisocyanates include diisocyanatobenzene (each isomer), diisocyanatotoluene (each isomer), bis(isocyanatophenyl)methane (each isomer), diisocyanatomesitylene (each isomer), diisocyanatobiphenyl (each isomer), diisocyanatodibenzyl (each isomer), bis(isocyanatophenyl)propane (each isomer), bis(isocyanatophenyl)ether (each isomer), bis(isocyanatophenoxyethane), diisocyanatomethylbenzene (each isomer), diisocyanatomethylpyridine (each isomer), diisocyanatomethylnaphthalene (each isomer), diisocyanatodiphenylmethane (each isomer), tetramethylxylylene diisocyanate (each isomer), and the like.

[0136] Examples of aromatic triisocyanates include triisocyanatobenzene (each isomer), triisocyanato-methylbenzene (each isomer), tris(isocyanatopropan-yl)benzene (each isomer), tris(isocyanatopropan-yl)-methylbenzene (each isomer), tris(isocyanatomethyl)-methylbenzene (each isomer), ((isocyanato-phenylene)bis(methylene))bis(isocyanatobenzene) (each isomer), and the like.

[0137] R 21 When R is aromatic, the electron-withdrawing effect of the aromatic group increases the reactivity of the directly bonded isocyanate group. Furthermore, the more isocyanate groups that are directly bonded to the same aromatic compound, the higher the reactivity becomes due to the mutual electron-withdrawing effect. From the viewpoint of reactivity, R 21 Preferably, the number of isocyanate groups is 2 or more, and more preferably 3 or more. On the other hand, when the reactivity of the isocyanate becomes high, reactions with moisture, with other isocyanates, and with other impurities occur, and the stability of the compound at room temperature and when heated decreases. From the viewpoint of the stability of the isocyanate compound, 21 The number of isocyanate groups directly bonded to is preferably 4 or less, and more preferably 3 or less.

[0138] R 21In the case where the aliphatic hydrocarbon group or aromatic group in the formula (I) has 1 to 4 ester groups or nitrogen atoms, specific examples of the isocyanate compound (II) include acrylic acid-2-isocyanato-ethyl ester, 2-methyl-acrylic acid-2-isocyanato-ethyl ester, acrylic acid-2-isocyanato-propyl ester, 2-methyl-acrylic acid-2-isocyanato-propyl ester, acrylic acid-3-isocyanato-propyl ester, 2-methyl-acrylic acid-3-isocyanato-propyl ester, cyanato-propyl ester, acrylic acid-4-isocyanato-butyl ester, 2-methyl-acrylic acid-4-isocyanato-butyl ester, acrylic acid-5-isocyanato-pentyl ester, 2-methyl-acrylic acid-5-isocyanato-pentyl ester, acrylic acid-6-isocyanato-hexyl ester, 2-methyl-acrylic acid-6-isocyanato-hexyl ester, acrylic acid-8-isocyanato-octyl ester, 2-methyl-acrylic acid-8-isocyanato -octyl ester, acrylic acid-10-isocyanato-decyl ester, 2-methyl-acrylic acid-10-isocyanato-decyl ester, acrylic acid-11-isocyanato-undecyl ester, 2-methyl-acrylic acid-11-isocyanato-undecyl ester, acrylic acid-12-isocyanato-dodecyl ester, 2-methyl-acrylic acid-12-isocyanato-dodecyl ester, lysine methyl ester diisocyanate, lysine ethyl ester diisocyanate, 2- Examples of such compounds include isocyanatoethyl-2,5-diisocyanatopentanoate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate (lysine triisocyanate), bis(2-isocyanatoethyl)-2-isocyanatobutanedioate, bis(2-isocyanatoethyl)-2-isocyanatopentanedioate, tris(2-isocyanatoethyl)hexane-1,3,6-tricarboxylate, trisisocyanatoethylamine, and trisisocyanatopropylamine.

[0139] The reactivity of the isocyanate group is improved by having an electron-withdrawing group such as an ester group or an N atom in the isocyanate compound. The smaller the number of carbon atoms between the isocyanate group and the ester group or nitrogen atom, the more the reactivity of the isocyanate group is improved, so the number of carbon atoms is preferably 1 to 20, more preferably 1 to 8, and even more preferably 1 to 3. On the other hand, the carbon-carbon or carbon-nitrogen bond between the isocyanate group, which is an electron-withdrawing group, and the ester group or nitrogen atom is easily dissociated, which may impair the thermal stability of the compound. Therefore, from the viewpoint of the stability of a compound in which an isocyanate group and an ester group or a nitrogen atom coexist, the more the number of carbon atoms between the isocyanate group and the ester group or nitrogen atom, the more the stability of the compound is improved, so the number of carbon atoms is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.

[0140] Isocyanate compounds (II) are often used as raw materials for paints, and are required to have the property of not discoloring when exposed to sunlight or other light (weather resistance). 21 If the resin has an aromatic group, it may absorb light energy when exposed to sunlight and become discolored. For this reason, from the viewpoint of weather resistance, R 21 It is preferable that the alkyl group does not have an aromatic group, and is more preferable that the alkyl group is a divalent or tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have 1 to 4 ester groups or a nitrogen atom.

[0141] Also, R 21 Specifically, is preferably a group represented by any one of the above formulas (Ia-1) to (Ia-24), and more preferably a group represented by formula (Ia-1), (Ia-2), (Ia-3), (Ia-14), (Ia-18), or (Ia-19).

[0142] (n21) n21 represents the number of isocyanate groups and satisfies the relational formula: n21=n11+n12. n21 is an integer of 2 or more and 8 or less, preferably an integer of 2 or more and 6 or less, more preferably an integer of 2 or more and 5 or less, and even more preferably an integer of 3 or more and 4 or less. In general, a polymer can be obtained by reacting an isocyanate having a valence of n21 or more with a dihydroxy compound or a diamine compound having an active hydrogen group. The larger the value of n21, the more crosslinking points (isocyanate groups) there are per isocyanate molecule, so the crosslinking density at the time of polymerization increases, and the curing time can be shortened and the hardness of the polymer can be improved. Note that "higher crosslinking density" here means that the average molecular chain length between crosslinking points becomes smaller. When the isocyanate molecule has 3 or more isocyanate groups (n21 is 3 or more), linear polymers can be further bonded to each other, and the molecular weight of the polymer tends to increase, so that a significant shortening of the curing time and a dramatic improvement in the physical properties of the polymer, such as hardness, can be expected. On the other hand, in isocyanate production, heating a highly reactive isocyanate compound can induce a modification reaction, which can cause adhesion to or clogging of the equipment. Therefore, the valence n21 of the isocyanate group in the isocyanate compound is preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less.

[0143] Preferred examples of the isocyanate compound (II) include 4-isocyanatomethyl-1,8-octamethylene diisocyanate (TTI), 2-isocyanatoethyl-2,6-diisocyanatohexanoate (LTI), lysine methyl ester diisocyanate (LDI), methylene bis(cyclohexyl isocyanate) (HMDI), 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), diisocyanatodiphenylmethane (MDI), and the like.

[0144] <Carbamate compounds> As the carbamate compound, a compound represented by the following general formula (III) (hereinafter, sometimes referred to as "carbamate compound (III)") or a compound represented by the following general formula (VI) (hereinafter, sometimes referred to as "carbamate compound (VI)") is preferably used.

[0145] [ka]

[0146] (In general formula (III), R 31 is an organic group with a valence of (n31+n32), and has the formula: R 31 =R 11 R 32 is a monovalent organic group, represented by the formula: R 32 =R 12 n31 is an integer between 1 and 8, n32 is an integer between 0 and 7, the sum of n31 and n32 is an integer between 2 and 8, and the relation: n31+n32=n11+n12 is satisfied.

[0147] [ka]

[0148] (In general formula (VI), R 61 is an organic group having a valence of n61, and has the formula: R 61 =R 21 R 62 is a monovalent organic group, represented by the formula: R 62 =R 12 n61 is an integer between 2 and 8, and satisfies the relation: n61 = n21.

[0149] [Carbamate compounds (III)] (R 31 ) R 31 is an organic group with a valence of (n31+n32), and has the formula: R 31 =R 11 That is, R 31 is the above R 11 is the same as:

[0150] Among them, R 31 is preferably an aliphatic hydrocarbon group having from 1 to 20 carbon atoms, which may have one to four ester groups or a nitrogen atom, and a divalent to tetravalent aromatic hydrocarbon group having from 6 to 20 carbon atoms, or a divalent to trivalent aromatic hydrocarbon group having from 6 to 20 carbon atoms.

[0151] Also, R 31 Specifically, is preferably a group represented by any one of the above formulas (Ia-1) to (Ia-24), and more preferably a group represented by formula (Ia-1), (Ia-2), (Ia-3), (Ia-14), (Ia-18), or (Ia-19).

[0152] (R 32 ) R 32 is a monovalent organic group, represented by the formula: R 32 =R 12 That is, R 32 is the above R 12 is the same as:

[0153] Among them, R 32 As the alkyl group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may contain an oxygen atom, is preferable.

[0154] Also, R 32Specific examples of the alkyl group include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, a methylphenyl group (each isomer), an ethylphenyl group (each isomer), a propylphenyl group (each isomer), a butylphenyl group (each isomer), a pentylphenyl group (each isomer), a hexylphenyl group (each isomer), a heptylphenyl group (each isomer), an octylphenyl group (each isomer), a nonylphenyl group (each isomer), a decylphenyl group (each isomer), an undecylphenyl group (each isomer), a dodecylphenyl group (each isomer), a tridecylphenyl group (each isomer), a tetra ... tridecylphenyl group (each isomer), dimethylphenyl group (each isomer), methylethylphenyl group (each isomer), methylpropylphenyl group (each isomer), methylbutylphenyl group (each isomer), methylpentylphenyl group (each isomer), methylhexylphenyl group (each isomer), methylheptylphenyl group (each isomer), methyloctylphenyl group (each isomer), methylnonylphenyl group (each isomer), methyldecylphenyl group (each isomer), methylundecylphenyl group (each isomer), methyldodecylphenyl group (each isomer), methyltridecylphenyl group nyl group (each isomer), diethylphenyl group (each isomer), ethylpropylphenyl group (each isomer), ethylbutylphenyl group (each isomer), ethylpentylphenyl group (each isomer), ethylhexylphenyl group (each isomer), ethylheptylphenyl group (each isomer), ethyloctylphenyl group (each isomer), ethylnonylphenyl group (each isomer), ethyldecylphenyl group (each isomer), ethylundecylphenyl group (each isomer), ethyldodecylphenyl group (each isomer), dipropylphenyl group (each isomer), propylbutylphenyl group (each isomer) , propylpentylphenyl group (each isomer), propylhexylphenyl group (each isomer), propylheptylphenyl group (each isomer), propyloctylphenyl group (each isomer), propylnonylphenyl group (each isomer), propyldecylphenyl group (each isomer), propylundecylphenyl group (each isomer), dibutylphenyl group (each isomer), butylpentylphenyl group (each isomer), butylhexylphenyl group (each isomer), butylheptylphenyl group (each isomer), butyloctylphenyl group (each isomer), butylnonylphenyl group (each isomer),Butyldecylphenyl group (each isomer), dipentylphenyl group (each isomer), pentylhexylphenyl group (each isomer), pentylheptylphenyl group (each isomer), pentyloctylphenyl group (each isomer), pentylnonylphenyl group (each isomer), dihexylphenyl group (each isomer), hexylheptylphenyl group (each isomer), hexyloctylphenyl group (each isomer), diheptylphenyl group (each isomer), trimethylphenyl group (each isomer), dimethylethylphenyl group (each isomer), dimethylpropylphenyl group (each isomer), dimethylbutylphenyl group (each isomer), dimethylpentylphenyl group (each isomer), dimethylhexylphenyl group (each isomer), dimethylheptylphenyl group (each isomer), dimethyloctylphenyl group (each isomer), dimethylnonylphenyl group (each isomer), dimethyldecylphenyl group (each isomer), dimethylundecylphenyl group (each isomer), dimethyldodecylphenyl group (each isomer), triethylphenyl group (each isomer), diethylmethylphenyl group (each isomer), diethylpropylphenyl group (each isomer) isomer), diethylbutylphenyl group (each isomer), diethylpentylphenyl group (each isomer), diethylhexylphenyl group (each isomer), diethylheptylphenyl group (each isomer), diethyloctylphenyl group (each isomer), diethylnonylphenyl group (each isomer), diethyldecylphenyl group (each isomer), tripropylphenyl group (each isomer), dipropylmethylphenyl group (each isomer), dipropylethylphenyl group (each isomer), dipropylbutylphenyl group (each isomer), dipropylpentylphenyl group (each isomer) isomer), dipropylhexylphenyl group (each isomer), dipropylheptylphenyl group (each isomer), dipropyloctylphenyl group (each isomer), tributylphenyl group (each isomer), dibutylmethylphenyl group (each isomer), dibutylethylphenyl group (each isomer), dibutylpropylphenyl group (each isomer), dibutylpentylphenyl group (each isomer), dibutylhexylphenyl group (each isomer), cumylphenyl group (each isomer), methoxyphenyl group (each isomer), or ethoxyphenyl group (each isomer) are preferred. Also preferred are phenyl group, cumylphenyl group (each isomer), methoxyphenyl group (each isomer),Or ethoxyphenyl group (each isomer) is more preferred.

[0155] (n31 and n32) n31 is an integer between 1 and 8 inclusive. n32 is an integer between 0 and 7. The sum of n31 and n32 is an integer between 2 and 8 inclusive, and satisfies the relation: n31+n32=n11+n12.

[0156] Preferred examples of the carbamate compound (III) include compounds represented by the following formulae (III-1a) to (III-24b). In addition, carbamate compounds (III-1a) to (III-1c), carbamate compounds (III-2a) to (III-2c), carbamate compounds (III-3a) to (III-3c), carbamate compounds (III-4a) to (III-4c), carbamate compounds (III-5a) to (III-5c), carbamate compounds (III-6a) to (III-6c), carbamate compounds (III-7a) to (III-7b), carbamate compounds (III-8a) to (III Each of the carbamate compounds (III-8b), the carbamate compounds (III-9a) to (III-9b), the carbamate compounds (III-10a) to (III-10b), the carbamate compounds (III-11a) to (III-11b), the carbamate compounds (III-12a) to (III-12b), the carbamate compounds (III-22a) to (III-22b), and the carbamate compounds (III-24a) to (III-24b) may be a mixture or each of the compounds may be a single compound.

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] [ka]

[0161] [ka]

[0162] [ka]

[0163] [ka]

[0164] [ka]

[0165] [Carbamate compounds (VI)] (R 61 ) R 61 is an organic group having a valence of n61, and has the formula: R 61 =R 21 That is, R 61 is the above R 21 is the same as:

[0166] Among them, R 61 is preferably an aliphatic hydrocarbon group having from 1 to 20 carbon atoms, which may have one to four ester groups or a nitrogen atom, and a divalent to tetravalent aromatic hydrocarbon group having from 6 to 20 carbon atoms, or a divalent to trivalent aromatic hydrocarbon group having from 6 to 20 carbon atoms.

[0167] Also, R 61Specifically, is preferably a group represented by any one of the above formulas (Ia-1) to (Ia-24), and more preferably a group represented by formula (Ia-1), (Ia-2), (Ia-3), (Ia-14), (Ia-18), or (Ia-19).

[0168] (R 62 ) R 62 is a monovalent organic group, represented by the formula: R 62 =R 12 That is, R 62 is the above R 12 is the same as:

[0169] Among them, R 62 As the alkyl group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may contain an oxygen atom, is preferable.

[0170] Also, R 62Specific examples of the alkyl group include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, a methylphenyl group (each isomer), an ethylphenyl group (each isomer), a propylphenyl group (each isomer), a butylphenyl group (each isomer), a pentylphenyl group (each isomer), a hexylphenyl group (each isomer), a heptylphenyl group (each isomer), an octylphenyl group (each isomer), a nonylphenyl group (each isomer), a decylphenyl group (each isomer), an undecylphenyl group (each isomer), a dodecylphenyl group (each isomer), a tridecylphenyl group (each isomer), a tetra ... tridecylphenyl group (each isomer), dimethylphenyl group (each isomer), methylethylphenyl group (each isomer), methylpropylphenyl group (each isomer), methylbutylphenyl group (each isomer), methylpentylphenyl group (each isomer), methylhexylphenyl group (each isomer), methylheptylphenyl group (each isomer), methyloctylphenyl group (each isomer), methylnonylphenyl group (each isomer), methyldecylphenyl group (each isomer), methylundecylphenyl group (each isomer), methyldodecylphenyl group (each isomer), methyltridecylphenyl group nyl group (each isomer), diethylphenyl group (each isomer), ethylpropylphenyl group (each isomer), ethylbutylphenyl group (each isomer), ethylpentylphenyl group (each isomer), ethylhexylphenyl group (each isomer), ethylheptylphenyl group (each isomer), ethyloctylphenyl group (each isomer), ethylnonylphenyl group (each isomer), ethyldecylphenyl group (each isomer), ethylundecylphenyl group (each isomer), ethyldodecylphenyl group (each isomer), dipropylphenyl group (each isomer), propylbutylphenyl group (each isomer) , propylpentylphenyl group (each isomer), propylhexylphenyl group (each isomer), propylheptylphenyl group (each isomer), propyloctylphenyl group (each isomer), propylnonylphenyl group (each isomer), propyldecylphenyl group (each isomer), propylundecylphenyl group (each isomer), dibutylphenyl group (each isomer), butylpentylphenyl group (each isomer), butylhexylphenyl group (each isomer), butylheptylphenyl group (each isomer), butyloctylphenyl group (each isomer), butylnonylphenyl group (each isomer),Butyldecylphenyl group (each isomer), dipentylphenyl group (each isomer), pentylhexylphenyl group (each isomer), pentylheptylphenyl group (each isomer), pentyloctylphenyl group (each isomer), pentylnonylphenyl group (each isomer), dihexylphenyl group (each isomer), hexylheptylphenyl group (each isomer), hexyloctylphenyl group (each isomer), diheptylphenyl group (each isomer), trimethylphenyl group (each isomer), dimethylethylphenyl group (each isomer), dimethylpropylphenyl group (each isomer), dimethylbutylphenyl group (each isomer), dimethylpentylphenyl group (each isomer), dimethylhexylphenyl group (each isomer), dimethylheptylphenyl group (each isomer), dimethyloctylphenyl group (each isomer), dimethylnonylphenyl group (each isomer), dimethyldecylphenyl group (each isomer), dimethylundecylphenyl group (each isomer), dimethyldodecylphenyl group (each isomer), triethylphenyl group (each isomer), diethylmethylphenyl group (each isomer), diethylpropylphenyl group (each isomer) isomer), diethylbutylphenyl group (each isomer), diethylpentylphenyl group (each isomer), diethylhexylphenyl group (each isomer), diethylheptylphenyl group (each isomer), diethyloctylphenyl group (each isomer), diethylnonylphenyl group (each isomer), diethyldecylphenyl group (each isomer), tripropylphenyl group (each isomer), dipropylmethylphenyl group (each isomer), dipropylethylphenyl group (each isomer), dipropylbutylphenyl group (each isomer), dipropylpentylphenyl group (each isomer) isomer), dipropylhexylphenyl group (each isomer), dipropylheptylphenyl group (each isomer), dipropyloctylphenyl group (each isomer), tributylphenyl group (each isomer), dibutylmethylphenyl group (each isomer), dibutylethylphenyl group (each isomer), dibutylpropylphenyl group (each isomer), dibutylpentylphenyl group (each isomer), dibutylhexylphenyl group (each isomer), cumylphenyl group (each isomer), methoxyphenyl group (each isomer), or ethoxyphenyl group (each isomer) are preferred. Also preferred are phenyl group, cumylphenyl group (each isomer), methoxyphenyl group (each isomer),Or ethoxyphenyl group (each isomer) is more preferred.

[0171] (n61) n61 represents the number of carbamate groups and satisfies the relation: n61 = n21. n61 is an integer of 2 or more and 8 or less, preferably an integer of 2 or more and 6 or less, more preferably an integer of 2 or more and 5 or less, and further preferably an integer of 3 or more and 4 or less.

[0172] Preferred examples of the carbamate compound (VI) include compounds represented by the following formulas (VI-1) to (VI-24).

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] <Carbonate ester> As the carbonate ester, a compound represented by the following general formula (IV) (hereinafter, sometimes referred to as "carbonate ester (IV)") is preferably used.

[0177] [ka]

[0178] (In general formula (IV), R 41 and R 42 are each independently a monovalent organic group represented by the formula: R 41 =R 42 =R 12 Satisfy.)

[0179] [R 41 and R 42 ] R 41 and R 42 are identical to each other, and the relation: R 41 =R 42 =R 12 That is, R 41 and R 42 As for R 12 Examples of the above-mentioned examples are the same as those exemplified in the above.

[0180] Among them, R 41 and R 42 As the group, a substituted or unsubstituted aryl group is preferable. In addition, a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, a methylphenyl group (each isomer), an ethylphenyl group (each isomer), a propylphenyl group (each isomer), a butylphenyl group (each isomer), a pentylphenyl group (each isomer), a hexylphenyl group (each isomer), a heptylphenyl group (each isomer), an octylphenyl group (each isomer), a nonylphenyl group (each isomer), a decylphenyl group (each isomer), an undecylphenyl group (each isomer), a dodecylphenyl group (each isomer), a tridecylphenyl group (each isomer), a tetradecylphenyl group (each isomer), a phenyl group (each isomer), a naphthyl group (each isomer), a phenyl ... phenyl group (each isomer), dimethylphenyl group (each isomer), methylethylphenyl group (each isomer), methylpropylphenyl group (each isomer), methylbutylphenyl group (each isomer), methylpentylphenyl group (each isomer), methylhexylphenyl group (each isomer), methylheptylphenyl group (each isomer), methyloctylphenyl group (each isomer), methylnonylphenyl group (each isomer), methyldecylphenyl group (each isomer), methylundecylphenyl group (each isomer), methyldodecylphenyl group (each isomer), methyltridecylphenyl group (each isomer), diethylphenyl group (each isomer), ethylpropylphenyl group (each isomer), ethylbutylphenyl group (each isomer), ethylpentylphenyl group (each isomer), ethylhexylphenyl group (each isomer), ethylheptylphenyl group (each isomer), ethyloctylphenyl group (each isomer), ethylnonylphenyl group (each isomer), ethyldecylphenyl group (each isomer), ethylundecylphenyl group (each isomer), ethyldodecylphenyl group (each isomer), dipropylphenyl group (each isomer), propylbutylphenyl group (each isomer), pro propylpentylphenyl group (each isomer), propylhexylphenyl group (each isomer), propylheptylphenyl group (each isomer), propyloctylphenyl group (each isomer), propylnonylphenyl group (each isomer), propyldecylphenyl group (each isomer), propylundecylphenyl group (each isomer), dibutylphenyl group (each isomer), butylpentylphenyl group (each isomer), butylhexylphenyl group (each isomer), butylheptylphenyl group (each isomer), butyloctylphenyl group (each isomer), butylnonylphenyl group (each isomer),Butyldecylphenyl group (each isomer), dipentylphenyl group (each isomer), pentylhexylphenyl group (each isomer), pentylheptylphenyl group (each isomer), pentyloctylphenyl group (each isomer), pentylnonylphenyl group (each isomer), dihexylphenyl group (each isomer), hexylheptylphenyl group (each isomer), hexyloctylphenyl group (each isomer), diheptylphenyl group (each isomer), trimethylphenyl group (each isomer), dimethylethylphenyl group (each isomer), dimethylpropylphenyl group (each isomer), dimethylbutylphenyl group (each isomer), dimethylpentylphenyl group (each isomer), dimethylhexylphenyl group (each isomer), dimethylheptylphenyl group (each isomer), dimethyloctylphenyl group (each isomer), dimethylnonylphenyl group (each isomer), dimethyldecylphenyl group (each isomer), dimethylundecylphenyl group (each isomer), dimethyldodecylphenyl group (each isomer), triethylphenyl group (each isomer), diethylmethylphenyl group (each isomer), diethylpropylphenyl group (each isomer) diethylbutylphenyl group (each isomer), diethylpentylphenyl group (each isomer), diethylhexylphenyl group (each isomer), diethylheptylphenyl group (each isomer), diethyloctylphenyl group (each isomer), diethylnonylphenyl group (each isomer), diethyldecylphenyl group (each isomer), tripropylphenyl group (each isomer), dipropylmethylphenyl group (each isomer), dipropylethylphenyl group (each isomer), dipropylbutylphenyl group (each isomer), dipropylpentylphenyl group (each isomer) More preferred are dipropylhexylphenyl group (each isomer), dipropylheptylphenyl group (each isomer), dipropyloctylphenyl group (each isomer), tributylphenyl group (each isomer), dibutylmethylphenyl group (each isomer), dibutylethylphenyl group (each isomer), dibutylpropylphenyl group (each isomer), dibutylpentylphenyl group (each isomer), dibutylhexylphenyl group (each isomer), cumylphenyl group (each isomer), methoxyphenyl group (each isomer), and ethoxyphenyl group (each isomer). Further, a phenyl group, a methoxyphenyl group (each isomer), or an ethoxyphenyl group (each isomer) is more preferred.

[0181] Preferred examples of the carbonate ester (IV) include diphenyl carbonate, bis(4-cumylphenyl) carbonate, bis(2-methoxyphenyl) carbonate, and bis(2-ethoxyphenyl) carbonate.

[0182] <Hydroxy compounds> As the hydroxy compound, a compound represented by the following general formula (V) (hereinafter, sometimes referred to as "hydroxy compound (V)") is preferably used.

[0183] [ka]

[0184] (In general formula (V), R 51 is a monovalent organic group having the formula: R 51 =R 12 Satisfy.)

[0185] [R 51 ] R 51 is a monovalent organic group having the formula: R 51 =R 12 That is, R 51 is the above R 12 is the same as:

[0186] Among them, R 51 As the alkyl group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may contain an oxygen atom, is preferable.

[0187] Also, R 51Specific examples of the alkyl group include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, a methylphenyl group (each isomer), an ethylphenyl group (each isomer), a propylphenyl group (each isomer), a butylphenyl group (each isomer), a pentylphenyl group (each isomer), a hexylphenyl group (each isomer), a heptylphenyl group (each isomer), an octylphenyl group (each isomer), a nonylphenyl group (each isomer), a decylphenyl group (each isomer), an undecylphenyl group (each isomer), a dodecylphenyl group (each isomer), a tridecylphenyl group (each isomer), a tetra ... tridecylphenyl group (each isomer), dimethylphenyl group (each isomer), methylethylphenyl group (each isomer), methylpropylphenyl group (each isomer), methylbutylphenyl group (each isomer), methylpentylphenyl group (each isomer), methylhexylphenyl group (each isomer), methylheptylphenyl group (each isomer), methyloctylphenyl group (each isomer), methylnonylphenyl group (each isomer), methyldecylphenyl group (each isomer), methylundecylphenyl group (each isomer), methyldodecylphenyl group (each isomer), methyltridecylphenyl group nyl group (each isomer), diethylphenyl group (each isomer), ethylpropylphenyl group (each isomer), ethylbutylphenyl group (each isomer), ethylpentylphenyl group (each isomer), ethylhexylphenyl group (each isomer), ethylheptylphenyl group (each isomer), ethyloctylphenyl group (each isomer), ethylnonylphenyl group (each isomer), ethyldecylphenyl group (each isomer), ethylundecylphenyl group (each isomer), ethyldodecylphenyl group (each isomer), dipropylphenyl group (each isomer), propylbutylphenyl group (each isomer) , propylpentylphenyl group (each isomer), propylhexylphenyl group (each isomer), propylheptylphenyl group (each isomer), propyloctylphenyl group (each isomer), propylnonylphenyl group (each isomer), propyldecylphenyl group (each isomer), propylundecylphenyl group (each isomer), dibutylphenyl group (each isomer), butylpentylphenyl group (each isomer), butylhexylphenyl group (each isomer), butylheptylphenyl group (each isomer), butyloctylphenyl group (each isomer), butylnonylphenyl group (each isomer),Butyldecylphenyl group (each isomer), dipentylphenyl group (each isomer), pentylhexylphenyl group (each isomer), pentylheptylphenyl group (each isomer), pentyloctylphenyl group (each isomer), pentylnonylphenyl group (each isomer), dihexylphenyl group (each isomer), hexylheptylphenyl group (each isomer), hexyloctylphenyl group (each isomer), diheptylphenyl group (each isomer), trimethylphenyl group (each isomer), dimethylethylphenyl group (each isomer), dimethylpropylphenyl group (each isomer), dimethylbutylphenyl group (each isomer), dimethylpentylphenyl group (each isomer), dimethylhexylphenyl group (each isomer), dimethylheptylphenyl group (each isomer), dimethyloctylphenyl group (each isomer), dimethylnonylphenyl group (each isomer), dimethyldecylphenyl group (each isomer), dimethylundecylphenyl group (each isomer), dimethyldodecylphenyl group (each isomer), triethylphenyl group (each isomer), diethylmethylphenyl group (each isomer), diethylpropylphenyl group (each isomer) isomer), diethylbutylphenyl group (each isomer), diethylpentylphenyl group (each isomer), diethylhexylphenyl group (each isomer), diethylheptylphenyl group (each isomer), diethyloctylphenyl group (each isomer), diethylnonylphenyl group (each isomer), diethyldecylphenyl group (each isomer), tripropylphenyl group (each isomer), dipropylmethylphenyl group (each isomer), dipropylethylphenyl group (each isomer), dipropylbutylphenyl group (each isomer), dipropylpentylphenyl group (each isomer) isomer), dipropylhexylphenyl group (each isomer), dipropylheptylphenyl group (each isomer), dipropyloctylphenyl group (each isomer), tributylphenyl group (each isomer), dibutylmethylphenyl group (each isomer), dibutylethylphenyl group (each isomer), dibutylpropylphenyl group (each isomer), dibutylpentylphenyl group (each isomer), dibutylhexylphenyl group (each isomer), cumylphenyl group (each isomer), methoxyphenyl group (each isomer), or ethoxyphenyl group (each isomer) are preferred. Also preferred are phenyl group, cumylphenyl group (each isomer), methoxyphenyl group (each isomer),Or ethoxyphenyl group (each isomer) is more preferred.

[0188] A preferred example of the hydroxy compound (V) is an aromatic hydroxy compound represented by the following general formula (V-1) (hereinafter, sometimes referred to as "aromatic hydroxy compound (V-1)").

[0189] [ka]

[0190] (In general formula (V-1), ring A 511 R is an aromatic hydrocarbon ring having 6 to 20 carbon atoms. 511 R is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or a hydroxy group. 511 is ring A 511 may be bonded to form a ring structure. n511 is an integer of 1 or more and 10 or less.

[0191] [R 511 ] R 511 Examples of the alkyl group having 1 to 20 carbon atoms in the formula (I) include a methyl group, an ethyl group, a propyl group (each isomer), a butyl group (each isomer), a pentyl group (each isomer), a hexyl group (each isomer), a heptyl group (each isomer), an octyl group (each isomer), a nonyl group (each isomer), a decyl group (each isomer), a dodecyl group (each isomer), and an octadecyl group (each isomer).

[0192] R 511Examples of the alkoxy group having 1 to 20 carbon atoms in the formula (I) include a methoxy group, an ethoxy group, a propoxy group (each isomer), a butyloxy group (each isomer), a pentyloxy group (each isomer), a hexyloxy group (each isomer), a heptyloxy group (each isomer), an octyloxy group (each isomer), a nonyloxy group (each isomer), a decyloxy group (each isomer), a dodecyloxy group (each isomer), and an octadecyloxy group (each isomer).

[0193] R 511 Examples of the aryl group having 6 to 20 carbon atoms in the formula (I) include a phenyl group and a naphthyl group.

[0194] R 511 Examples of the aryl group having an alkyl group as a substituent in the above formula (I) include a methylphenyl group (each isomer), an ethylphenyl group (each isomer), a propylphenyl group (each isomer), a butylphenyl group (each isomer), a pentylphenyl group (each isomer), a hexylphenyl group (each isomer), a heptylphenyl group (each isomer), an octylphenyl group (each isomer), a nonylphenyl group (each isomer), a decylphenyl group (each isomer), a biphenyl group (each isomer), a diphenyl group (each isomer), a dimethyl ... Examples of the isomers include ethylphenyl groups (each isomer), diethylphenyl groups (each isomer), dipropylphenyl groups (each isomer), dibutylphenyl groups (each isomer), dipentylphenyl groups (each isomer), dihexylphenyl groups (each isomer), diheptylphenyl groups (each isomer), terphenyl groups (each isomer), trimethylphenyl groups (each isomer), triethylphenyl groups (each isomer), tripropylphenyl groups (each isomer), and tributylphenyl groups (each isomer).

[0195] R 511Examples of the aryloxy group having 6 to 20 carbon atoms in the above formula (1) include a phenoxy group, a methylphenoxy group (each isomer), an ethylphenoxy group (each isomer), a propylphenoxy group (each isomer), a butylphenoxy group (each isomer), a pentylphenoxy group (each isomer), a hexylphenoxy group (each isomer), a heptylphenoxy group (each isomer), an octylphenoxy group (each isomer), a nonylphenoxy group (each isomer), a decylphenoxy group (each isomer), a phenylphenoxy group (each isomer), Examples of such groups include dimethylphenoxy groups (each isomer), diethylphenoxy groups (each isomer), dipropylphenoxy groups (each isomer), dibutylphenoxy groups (each isomer), dipentylphenoxy groups (each isomer), dihexylphenoxy groups (each isomer), diheptylphenoxy groups (each isomer), diphenylphenoxy groups (each isomer), trimethylphenoxy groups (each isomer), triethylphenoxy groups (each isomer), tripropylphenoxy groups (each isomer), and tributylphenoxy groups (each isomer).

[0196] R 511 Examples of the aralkyl group having 7 to 20 carbon atoms in the formula (I) include a phenylmethyl group, a phenylethyl group (each isomer), a phenylpropyl group (each isomer), a phenylbutyl group (each isomer), a phenylpentyl group (each isomer), a phenylhexyl group (each isomer), a phenylheptyl group (each isomer), a phenyloctyl group (each isomer), and a phenylnonyl group (each isomer).

[0197] R 511 Examples of the aralkyloxy group having 7 to 20 carbon atoms in the formula (I) include a phenylmethoxy group, a phenylethoxy group (each isomer), a phenylpropyloxy group (each isomer), a phenylbutyloxy group (each isomer), a phenylpentyloxy group (each isomer), a phenylhexyloxy group (each isomer), a phenylheptyloxy group (each isomer), a phenyloctyloxy group (each isomer), and a phenylnonyloxy group (each isomer).

[0198] [A 511 ] Ring A 511is an aromatic hydrocarbon ring having 6 to 20 carbon atoms. 511 may be a monocyclic ring, a polycyclic ring, or a condensed ring. Ring A 511 Specific examples of the ring A include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a naphthacene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a pentalene ring, an azulene ring, a heptalene ring, an indacene ring, a biphenylene ring, an acenaphthylene ring, an aceanthrylene ring, and an acephenanthrylene ring. 511 As the ring, a benzene ring, a naphthalene ring, or an anthracene ring is preferable, and a benzene ring is more preferable. In addition, these rings may be the same as those described above in R 511 R may have a substituent other than the above. 511 The substituents other than R 511 The same examples are listed in R 511 and R 511 The substituents other than the above are different functional groups.

[0199] [n511] n511 is a substituent R 511 It indicates the number of, and is an integer between 1 and 10.

[0200] In the general formula (V-1), ring A 511 Examples of the compound in which is a benzene ring include a compound represented by the following general formula (V-1-1) (hereinafter, sometimes referred to as "hydroxy compound (V-1-1)").

[0201] [ka]

[0202] (In general formula (V-1-1), R 512 ~R 516 are each independently the above R 511 is the same as

[0203] Among them, R 512 ~R 516It is preferable that at least one of R is a hydrogen atom. 512 ~R 516 It is more preferable that all of are hydrogen atoms.

[0204] Preferred hydroxy compounds (V-1-1) include, for example, phenol, 2-ethylphenol, 2-propylphenol (each isomer), 2-butylphenol (each isomer), 2-pentylphenol (each isomer), 2-hexylphenol (each isomer), 2-heptylphenol (each isomer), 2-phenylphenol, 2,6-dimethylphenol, 2,4-diethylphenol, 2,6-diethylphenol, 2,4-dipropylphenol (each isomer), 2,6-dipropylphenol (each isomer), 2,4-dibutylphenol (each isomer), 2,4-Dipentylphenol (each isomer), 2,4-Dihexylphenol (each isomer), 2,4-Diheptylphenol (each isomer), 2-Methyl-6-ethylphenol, 2-Methyl-6-propylphenol (each isomer), 2-Methyl-6-butylphenol (each isomer), 2-Methyl-6-pentylphenol (each isomer), 2-Ethyl-6-propylphenol (each isomer), 2-Ethyl-6-butylphenol (each isomer), 2-Ethyl-6-pentylphenol (each isomer), 2-Propyl-6-butylphenol (each isomer), 2-Ethyl 2-ethyl-4-methylphenol (each isomer), 2-ethyl-4-propylphenol (each isomer), 2-ethyl-4-butylphenol (each isomer), 2-ethyl-4-pentylphenol (each isomer), 2-ethyl-4-hexylphenol (each isomer), 2-ethyl-4-heptylphenol (each isomer), 2-ethyl-4-octylphenol (each isomer), 2-ethyl-4-phenylphenol (each isomer), 2-ethyl-4-cumylphenol (each isomer), 2-propyl-4-methylphenol (each isomer), 2-propyl-4-ethylphenol (each isomer), 2-propyl-4-butylphenol (each isomer), 2-propyl-4-pentylphenol (each isomer), 2-propyl-4-hexylphenol (each isomer), 2-propyl-4-heptylphenol (each isomer), 2-propyl-4-octylphenol (each isomer), 2-propyl-4-phenylphenol (each isomer), 2-propyl-4-cumylphenol (each isomer), 2-butyl-4-methylphenol (each isomer), 2-butyl-4-ethylphenol (each isomer), 2-butyl-4-propylphenol (each isomer),2-Butyl-4-pentylphenol (each isomer), 2-Butyl-4-hexylphenol (each isomer), 2-Butyl-4-heptylphenol (each isomer), 2-Butyl-4-octylphenol (each isomer), 2-Butyl-4-phenylphenol (each isomer), 2-Butyl-4-cumylphenol (each isomer), 2-pentyl-4-methylphenol (each isomer), 2-pentyl-4-ethylphenol (each isomer), 2-pentyl-4-propylphenol (each isomer), 2-pentyl-4-butylphenol (each isomer), 2-pentyl- 4-Hexylphenol (each isomer), 2-pentyl-4-heptylphenol (each isomer), 2-pentyl-4-octylphenol (each isomer), 2-pentyl-4-phenylphenol (each isomer), 2-pentyl-4-cumylphenol (each isomer), 2-hexyl-4-methylphenol (each isomer), 2-hexyl-4-ethylphenol (each isomer), 2-hexyl-4-propylphenol (each isomer), 2-hexyl-4-butylphenol (each isomer), 2-hexyl-4-pentylphenol (each isomer), 2-hexyl-4- Heptylphenol (each isomer), 2-hexyl-4-octylphenol (each isomer), 2-hexyl-4-phenylphenol (each isomer), 2-hexyl-4-cumylphenol (each isomer), 2-heptyl-4-methylphenol (each isomer), 2-heptyl-4-ethylphenol (each isomer), 2-heptyl-4-propylphenol (each isomer), 2-heptyl-4-butylphenol (each isomer), 2-heptyl-4-pentylphenol (each isomer), 2-heptyl-4-hexylphenol (each isomer), 2-heptyl-4-octylphenol 2,6-dimethyl-4-ethylphenol (each isomer), 2-heptyl-4-phenylphenol (each isomer), 2-heptyl-4-cumylphenol (each isomer), 2,4,6-trimethylphenol, 2,6-dimethyl-4-ethylphenol, 2,6-dimethyl-4-propylphenol (each isomer), 2,6-dimethyl-4-butylphenol (each isomer), 2,6-dimethyl-4-pentylphenol (each isomer), 2,6-dimethyl-4-hexylphenol (each isomer), 2,6-dimethyl-4-phenylphenol, 2,6-dimethyl-4-cumylphenol,2,4,6-triethylphenol, 2,6-diethyl-4-methylphenol, 2,6-diethyl-4-propylphenol (each isomer), 2,6-diethyl-4-butylphenol (each isomer), 2,6-diethyl-4-pentylphenol (each isomer), 2,6-diethyl-4-hexylphenol (each isomer), 2,6-diethyl-4-phenylphenol, 2,6-diethyl-4-cumylphenol, 2,4,6-tripropylphenol (each isomer), 2,6-dipropyl-4-ethylphenol (each isomer), 2,6-dipropyl- 4-Methylphenol (each isomer), 2,6-dipropyl-4-butylphenol (each isomer), 2,6-dipropyl-4-pentylphenol (each isomer), 2,6-dipropyl-4-hexylphenol (each isomer), 2,6-dipropyl-4-phenylphenol (each isomer), 2,6-dipropyl-4-cumylphenol (each isomer), 2,4-dimethyl-6-ethylphenol, 2-methyl-4,6-diethylphenol, 2-methyl-4-propyl-6-ethylphenol (each isomer), 2-methyl-4-butyl-6-ethylphenol (each isomer), 2-methyl-4-pentyl-6-ethylphenol (each isomer), 2-methyl-4-hexyl-6-ethylphenol (each isomer), 2-methyl-4-phenyl-6-ethylphenol (each isomer), 2-methyl-4-cumyl-6-ethylphenol (each isomer), 2,4-dimethyl-6-propylphenol (each isomer), 2-methyl-4,6-dipropylphenol (each isomer), 2-methyl-4-ethyl-6-propylphenol (each isomer), 2-methyl-4-butyl-6-propylphenol (each isomer), 2-methyl -4-pentyl-6-propylphenol (each isomer), 2-methyl-4-hexyl-6-propylphenol (each isomer), 2-methyl-4-phenyl-6-propylphenol (each isomer), 2-methyl-4-cumyl-6-propylphenol (each isomer), 2,4-dimethyl-6-butylphenol, 2-methyl-4,6-dibutylphenol, 2-methyl-4-propyl-6-butylphenol (each isomer), 2-methyl-4-ethyl-6-butylphenol (each isomer), 2-methyl-4-pentyl-6-butylphenol (each isomer),2-Methyl-4-hexyl-6-butylphenol (each isomer), 2-methyl-4-phenyl-6-butylphenol (each isomer), 2-methyl-4-cumyl-6-butylphenol (each isomer), 2,4-dimethyl-6-pentylphenol, 2-methyl-4,6-dipentylphenol, 2-methyl-4-propyl-6-pentylphenol (each isomer), 2-methyl-4-butyl-6-pentylphenol (each isomer), 2-methyl-4-ethyl-6-pentylphenol (each isomer), 2-methyl-4-hexyl-6-pentylphenol (each isomer), 2-methyl-4-phenyl-6-pentylphenol (each isomer), 2-methyl-4-cumyl-6-pentylphenol (each isomer), 2,4-dimethyl-6-hexylphenol, 2-methyl-4,6-dihexylphenol, 2-methyl-4-propyl-6-hexylphenol (each isomer), 2-methyl-4-butyl-6-hexylphenol (each isomer), 2-methyl-4-pentyl-6-hexylphenol (each isomer), 2-methyl-4-ethyl-6-hexylphenol (each isomer), 2-methyl-4-phenyl 2-ethyl-4-pentyl-6-propylphenol (each isomer), 2-ethyl-4-hexyl-6-propylphenol (each isomer), 2-methyl-4-cumyl-6-hexylphenol (each isomer), 2-ethyl-4-methyl-6-propylphenol (each isomer), 2,4-diethyl-6-propylphenol (each isomer), 2-ethyl-4,6-propylphenol (each isomer), 2-ethyl-4-butyl-6-propylphenol (each isomer), 2-ethyl-4-pentyl-6-propylphenol (each isomer), 2-ethyl-4-hexyl-6-propylphenol (each isomer), 2-ethyl-4-heptyl-6-propylphenol (each isomer), 2-ethyl-4-octyl-6-propylphenol (each isomer), 2-ethyl-4-phenyl-6-propylphenol (each isomer), 2-ethyl-4-cumyl-6-propylphenol (each isomer), 2-ethyl-4-methyl-6-butylphenol (each isomer), 2,4-diethyl-6-butylphenol (each isomer), 2-ethyl-4,6-butylphenol (each isomer), 2-ethyl-4-propyl-6-butylphenol (each isomer), 2-ethyl-4-pentyl-6-butylphenol (each isomer),2-Ethyl-4-hexyl-6-butylphenol (each isomer), 2-ethyl-4-heptyl-6-butylphenol (each isomer), 2-ethyl-4-octyl-6-butylphenol (each isomer), 2-ethyl-4-phenyl-6-butylphenol (each isomer), 2-ethyl-4-cumyl-6-butylphenol (each isomer), 2-ethyl-4-methyl-6-pentylphenol (each isomer), 2,4-diethyl-6-pentylphenol (each isomer), 2-ethyl-4,6-pentylphenol (each isomer), 2-ethyl-4-butyl-6 -pentylphenol (each isomer), 2-ethyl-4-propyl-6-pentylphenol (each isomer), 2-ethyl-4-hexyl-6-pentylphenol (each isomer), 2-ethyl-4-heptyl-6-pentylphenol (each isomer), 2-ethyl-4-octyl-6-pentylphenol (each isomer), 2-ethyl-4-phenyl-6-pentylphenol (each isomer), 2-ethyl-4-cumyl-6-pentylphenol (each isomer), 2-ethyl-4-methyl-6-hexylphenol (each isomer), 2,4-diethyl-6-hexyl 2-ethyl-4,6-hexylphenol (each isomer), 2-ethyl-4-propyl-6-hexylphenol (each isomer), 2-ethyl-4-pentyl-6-hexylphenol (each isomer), 2-ethyl-4-butyl-6-hexylphenol (each isomer), 2-ethyl-4-heptyl-6-hexylphenol (each isomer), 2-ethyl-4-octyl-6-hexylphenol (each isomer), 2-ethyl-4-phenyl-6-hexylphenol (each isomer), 2-ethyl-4-cumyl-6-hexylphenol (each isomer), 2-propyl-4-methyl-6-butylphenol (each isomer), 2,4-dipropyl-6-butylphenol (each isomer), 2-propyl-4,6-butylphenol (each isomer), 2-propyl-4-ethyl-6-butylphenol (each isomer), 2-propyl-4-pentyl-6-butylphenol (each isomer), 2-propyl-4-hexyl-6-butylphenol (each isomer), 2-propyl-4-heptyl-6-butylphenol (each isomer), 2-propyl-4-octyl-6-butylphenol (each isomer),Examples of the isomers include 2-propyl-4-phenyl-6-butylphenol (each isomer), cumylphenol (each isomer), 2-propyl-4-cumyl-6-butylphenol (each isomer), 2,4-dicumylphenol, methoxyphenol (each isomer), and ethoxyphenol (each isomer). Among these, phenol, cumylphenol (each isomer), methoxyphenol (each isomer), or ethoxyphenol, (Each isomer) is preferred.

[0205] <Method for producing isocyanate compound> The method for producing an isocyanate compound of the present embodiment includes purifying a reaction liquid containing the isocyanate compound (II) by distillation in the presence of the carbonyl compound (I) described above, and continuously recovering the isocyanate compound (II) as a gas phase component.

[0206] The method for producing an isocyanate compound according to the present embodiment uses the carbonyl compound (I) described above, thereby making it possible to prevent by-products from adhering to an apparatus during the production of the isocyanate compound (II) and to improve the yield of the isocyanate compound (II).

[0207] The method for producing the isocyanate compound of the present embodiment will be described in detail below.

[0208] The isocyanate compound (II) can be obtained by carrying out a thermal decomposition reaction of the carbamate compound (VI) in the presence of the carbonate ester (IV).

[0209] [Pyrolysis process] In the thermal decomposition step, the carbamate compound (VI) is thermally decomposed in the presence of a carbonate ester (IV) as a solvent to obtain an isocyanate (II). In the thermal decomposition reaction, side reactions represented by the above formulas (B) to (E) occur, and the resulting isocyanurate groups, carbodiimide groups, and allophanate groups act as crosslinking points to generate high molecular weight components, which may lead to the purification of solids and an increase in liquid viscosity. The presence of the carbonyl compound (I) in the thermal decomposition reaction system allows the carbonyl compound (I) to act as a good solvent for the high molecular weight components described above, and also acts as an end-capping agent to suppress the increase in molecular weight of by-products, thereby suppressing the generation of solids and the increase in liquid viscosity in the thermal decomposition reaction.

[0210] The carbonate ester (IV) may be fed to the reactor before the start of the reaction, during the reaction, or both, and is preferably fed to the reactor before the reaction.

[0211] In the thermal decomposition step, the amount (molar amount) of the carbonate ester (IV) used as a solvent is preferably large in terms of suppressing side reactions, but in consideration of the size of the reactor, the amount is preferably 0.001 to 100 times, more preferably 0.01 to 80 times, and even more preferably 0.1 to 50 times, in terms of the stoichiometric ratio to the carbamate compound.

[0212] When a carbamate compound is produced by the method described below and contains a carbonate ester (IV), the carbonate ester (IV) may be used as it is, or new carbonate ester (IV) may be added to the carbamate compound (VI).

[0213] The reaction temperature is usually from 100° C. to 400° C., and a high temperature is preferable to increase the reaction rate, but on the other hand, at a high temperature, the above-mentioned side reactions may be caused by one or more compounds selected from the group consisting of carbamate compounds and the product isocyanate compounds, so the reaction temperature is preferably from 130° C. to 300° C., more preferably from 150° C. to 280° C. In order to keep the reaction temperature constant, a known cooling device or heating device may be installed in the reactor.

[0214] The reaction pressure varies depending on the type of compound used and the reaction temperature, but may be reduced pressure, normal pressure, or increased pressure. It is usually 20 Pa or more and 1×10 6 The temperature is set in the range of Pa or less.

[0215] The reaction time (residence time in the case of a continuous method) is not particularly limited and is usually from 0.001 to 100 hours, preferably from 0.01 to 50 hours, and more preferably from 0.1 to 10 hours.

[0216] A catalyst can be used, and the amount of the catalyst used is preferably from 0.01% by mass to 30% by mass, more preferably from 0.5% by mass to 20% by mass, based on the mass of the carbamate compound. Examples of the catalyst include organometallic catalysts such as dibutyltin dilaurate, lead octoate, and stannous octoate; and amines such as 1,4-diazabicyclo[2,2,2]octane, triethylenediamine, and triethylamine. In particular, organometallic catalysts such as dibutyltin dilaurate, lead octoate, and stannous octoate are preferred. These compounds may be used alone or in a mixture of two or more.

[0217] As described above, the thermal decomposition reaction is a reaction that produces the corresponding isocyanate compound (II) and a hydroxy compound from the carbamate compound (VI), but the thermal decomposition reaction is an equilibrium reaction. Therefore, in order to efficiently obtain the isocyanate compound (II) in the thermal decomposition reaction, it is preferable to extract the hydroxy compound, which is the product of the thermal decomposition reaction, as a gas phase component from the thermal decomposition reaction system by a method such as distillation.

[0218] [Isocyanate composition preparation process] Since the reaction liquid obtained in the above thermal decomposition step contains the carbonyl compound (I), the reaction liquid may be used in the purification step described below as a reaction liquid (isocyanate composition) containing the isocyanate compound (II) and the carbonyl compound (I). Alternatively, the carbonyl compound (I) obtained in the "method for producing a carbonyl compound" may be mixed with a reaction liquid containing an isocyanate compound (isocyanate composition) to prepare an isocyanate composition, which may be used in the purification step described below.

[0219] As for the composition of the isocyanate composition, from the viewpoint of ensuring good distillation operability in the purification step described below, the value of {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of uretonimine groups) + 2 × (molar amount of allophanate groups)} ÷ (molar amount of carbonyl compounds) is preferably 0.00001 or more and 80.0 or less, more preferably 0.0001 or more and 40.0 or less, and even more preferably 0.001 or more and 8.0 or less.

[0220] [Refining process] In the purification step, an isocyanate compound is purified from the above-mentioned isocyanate composition. Specifically, in the purification step, first, a component (light boiling component) having a boiling point lower than that of the isocyanate compound contained in the isocyanate composition is distilled off (hereinafter referred to as "light boiling separation"), and then the isocyanate compound is recovered as a gas phase component and separated from a component (high boiling component) having a boiling point higher than that of the isocyanate compound (hereinafter referred to as "high boiling separation"), thereby purifying the isocyanate compound from the isocyanate composition.

[0221] (Light boiling separation process) The distillation method is not particularly limited as long as the low-boiling components can be separated as gas phase components. The "low-boiling components (light-boiling point components)" referred to here refer to components having a boiling point lower than that of the carbonyl compounds, and are mainly one or more compounds selected from the group consisting of carbonate esters used in the thermal decomposition step and hydroxy compounds produced as by-products in the thermal decomposition reaction, although they vary depending on the type of compound used as a raw material for the production of the isocyanate compound.

[0222] The pressure at which the low-boiling components are distilled off varies depending on the type of compound and the reaction temperature. As long as the isocyanate compound and the low-boiling components can be separated, the pressure may be reduced, normal, or increased. The pressure should be between 20 Pa and 1×10 6 Pa or less is preferable, and 20 Pa or more is 1×10 4 Pa or less is more preferable, and 20 Pa or more is 1×10 3 Pa or less is more preferable, and 20 Pa or more to 1×10 2 Pa or less is particularly preferred.

[0223] The operation time (residence time in the case of a continuous method) when distilling off the low-boiling components is not particularly limited as long as the isocyanate compound and the low-boiling components can be separated. From the viewpoint of suppressing side reactions with the isocyanate compound, the operation time is preferably from 5 seconds to 100 hours, more preferably from 10 seconds to 50 hours, and even more preferably from 20 seconds to 10 hours.

[0224] The temperature at which the low-boiling components are distilled off is not particularly limited as long as the isocyanate compound is stable and the isocyanate compound and the low-boiling components can be separated. From the viewpoint of suppressing denaturation of the isocyanate compound, the temperature is preferably 20° C. or higher and 300° C. or lower, more preferably 30° C. or higher and 280° C. or lower, and even more preferably 40° C. or higher and 250° C. or lower.

[0225] (High boiling separation process) As long as the isocyanate can be separated as a gas phase component, the distillation method is not particularly limited. The term "high boiling component (high boiling point component)" as used herein refers to a component with a boiling point higher than that of isocyanate, and varies depending on the type of compound used as a raw material for the production of isocyanate compounds, but mainly includes carbonyl compounds generated in the thermal decomposition process, carbamate compounds (III) (carbamate group-containing isocyanates) and carbamate compounds (VI) (carbamate compounds used as raw materials for the thermal decomposition process), and compounds in which some of the isocyanate groups of isocyanate compounds are converted to at least one functional group selected from the group consisting of isocyanurate groups, carbodiimide groups, uretonimine groups, and allophanate groups (hereinafter referred to as "isocyanate polymers").

[0226] In the high boiling separation step, a reaction occurs in which uretonimine groups produced as a by-product in the thermal decomposition step or the light boiling separation step are regenerated into isocyanate groups and carbodiimide groups as shown in the following formula (J), so the recovery rate of the isocyanate compounds recovered in the gas phase may exceed 100 mass%.

[0227] [ka]

[0228] (In formula (J), R m and R n are each independently a divalent or higher organic group.

[0229] On the other hand, in the high boiling point separation step, the isocyanate compound is distilled off, and the high boiling point components are concentrated and solidified, which may make it difficult to continue operation, and it becomes difficult to recover the isocyanate compound in a high yield. This is because the isocyanate (isocyanate polymer) in which a part of the isocyanate group is converted to at least one functional group selected from the group consisting of an isocyanurate group, a carbodiimide group, a uretonimine group, and an allophanate group has a high molecular weight, and the carbodiimide group generated by the formula (J) and the isocyanate group of the isocyanate polymer are bonded to each other during the high boiling point separation to form a uretonimine group (the reverse reaction of the formula (J)), and the isocyanate polymers are bonded to each other to increase the molecular weight.

[0230] The carbonyl compound (I) has a higher boiling point than the isocyanate compound and has fewer crosslinking points than the isocyanate polymer, so it acts as a solvent in the high boiling point separation step. Alternatively, it bonds to a carbodiimide group and prevents the isocyanate polymer from bonding with itself to form a high molecular weight. These actions improve the operability in the high boiling point separation step and enable the isocyanate compound to be recovered in a high yield.

[0231] The pressure for separating the high boiling components varies depending on the type of compound and the reaction temperature. However, as long as the isocyanate compound and the low boiling components can be separated, the pressure may be reduced, normal, or increased. The pressure should be between 0.1 Pa and 1×10 6 Pa or less is preferable, and 1 Pa or more to 1×10 4 Pa or less is more preferable, and 5 Pa or more to 1×10 3 Pa or less is more preferable.

[0232] The operation time (residence time in the case of a continuous method) when separating the high boiling components is not particularly limited as long as the isocyanate compound and the low boiling components can be separated. From the viewpoint of suppressing side reactions with the isocyanate compound, the operation time is preferably from 5 seconds to 100 hours, more preferably from 10 seconds to 50 hours, even more preferably from 15 seconds to 10 hours, particularly preferably from 20 seconds to 1 hour, and most preferably from 25 seconds to 10 minutes.

[0233] The temperature at which the high boiling components are separated is not particularly limited as long as the isocyanate compound is stable and the isocyanate compound and the low boiling components can be separated from each other. From the viewpoint of suppressing denaturation of the isocyanate compound, the temperature is preferably 20°C or higher and 250°C or lower, more preferably 30°C or higher and 230°C or lower, and even more preferably 40°C or higher and 200°C or lower.

[0234] [Equipment and materials] The materials of the reactor and lines in which the thermal decomposition process and the purification process are carried out may be any known materials as long as they do not adversely affect the carbamate compound, the products (hydroxy compound and isocyanate compound), and the solvent (carbonate ester). However, SUS304, SUS316, SUS316L, etc. are inexpensive and can be preferably used.

[0235] The type of reactor is not particularly limited, and known tank-type or tower-type reactors can be used. In the thermal decomposition reaction and the subsequent distillation of low-boiling components, a reactor equipped with a line for extracting the low-boiling mixture containing the generated hydroxy compound as a gas component from the reactor and extracting a part or all of the mixed liquid containing the unreacted carbamate compound and the compound not extracted as a gas component from the reactor in liquid form is preferably used. As such a reactor, various known methods can be used, such as a method using a reactor containing any of a stirring tank, a multi-stage stirring tank, a distillation column, a multi-stage distillation column, a multi-tubular reactor, a continuous multi-stage distillation column, a packed column, a thin film evaporator, a reactor equipped with a support inside, a forced circulation reactor, a falling film evaporator, a falling drop evaporator, a trickle phase reactor, and a bubble column, and a method combining these.

[0236] From the viewpoint of separating the produced hydroxy compounds and isocyanate compounds, a method using a stirring tank equipped with a distillation column or a multi-stage stirring tank is preferred, and a structure with a large gas-liquid contact area that can rapidly transfer the produced low boiling point components to the gas phase is preferred.

[0237] Among the purification steps of the isocyanate composition, in the low boiling separation step, a reactor equipped with a line for extracting the low boiling components as gas components from the reactor and extracting a part or all of the mixed liquid containing the compounds not extracted from the reactor in liquid form is preferably used.As such a reactor, for example, a method using a reactor including any of a stirring tank, a multi-stage stirring tank, a distillation column, a multi-stage distillation column, a multi-tubular reactor, a continuous multi-stage distillation column, a packed column, a thin film evaporator, a reactor equipped with a support inside, a forced circulation reactor, a falling film evaporator, a falling drop evaporator, a trickle phase reactor, and a bubble column, and a method combining these, and various other known methods are used.

[0238] In addition, in the high boiling point separation step of the purification step of the isocyanate composition, a reactor equipped with a line for extracting the isocyanate compound as a gas component from the reactor and extracting a part or all of the mixture containing the compound not extracted from the reactor in liquid form is preferably used. As such a reactor, various known methods are used, such as a method using a reactor including any of a stirring tank, a multi-stage stirring tank, a distillation column, a multi-stage distillation column, a multi-tubular reactor, a continuous multi-stage distillation column, a packed column, a thin film evaporator, a reactor equipped with a support inside, a forced circulation reactor, a falling film evaporator, a falling drop evaporator, a trickle phase reactor, and a bubble column, and a method combining these.

[0239] Next, various raw materials used in the method for producing an isocyanate compound of the present embodiment will be described in detail below.

[0240] <Method for producing carbamate compound (VI)> The carbamate compound (VI) is as exemplified in the above "Method for producing carbonyl compound". The carbamate compound (VI) is preferably produced, for example, from a carbonic acid derivative and an amine compound, or from a carbonic acid derivative, a hydroxy compound and an amine compound. The hydroxy compound used as the raw material for producing the carbamate compound (VI) is preferably the same as the hydroxy compound (V).

[0241] [Carbonic acid derivatives] Examples of carbonic acid derivatives include urea and carbonic acid esters. As the carbonate ester used as the raw material for producing the carbamate compound (VI), the same as the carbonate ester (IV) is preferably used. Among them, as the carbonic acid derivative, urea, diphenyl carbonate, or dibutyl carbonate is preferred, and urea or diphenyl carbonate is more preferred.

[0242] [Amine compounds] As the amine compound, for example, a compound represented by the following general formula (VII) (hereinafter, sometimes referred to as "amine compound (VII)") is preferably used.

[0243] [ka]

[0244] (In general formula (VII), R 71 is an organic group having a valence of n71, and has the formula: R 71 =R 61 n71 is an integer between 2 and 8, and satisfies the relation: n71 = n61.

[0245] (R 71 ) R 71 is an organic group having a valence of n71, and has the formula: R 71 =R 61 That is, R 71 is the above R 61 is the same as: Among them, R 71 is preferably an aliphatic hydrocarbon group having from 1 to 20 carbon atoms, which may have one to four ester groups or a nitrogen atom, and a divalent to tetravalent aromatic hydrocarbon group having from 6 to 20 carbon atoms, or a divalent to trivalent aromatic hydrocarbon group having from 6 to 20 carbon atoms.

[0246] Also, R 71Specifically, is preferably a group represented by any one of the above formulas (Ia-1) to (Ia-24), and more preferably a group represented by formula (Ia-1), (Ia-2), (Ia-3), (Ia-14), (Ia-18), or (Ia-19).

[0247] (n71) n71 represents the number of amino groups and satisfies the relation: n71 = n61. n71 is an integer of 2 or more and 8 or less, preferably an integer of 2 or more and 6 or less, more preferably an integer of 2 or more and 5 or less, and further preferably an integer of 3 or more and 4 or less.

[0248] Preferred examples of the amine compound (VII) include 4-aminomethyl-1,8-octanediamine, 4,4'-diaminodiphenylmethane, lysine β-aminoethyl ester, lysine methyl ester, 4,4'-methylenebis(cyclohexylamine), 1,3-di(aminomethyl)cyclohexane, and the like.

[0249] Isocyanate composition The isocyanate composition of the present embodiment contains, relative to the total mass of the isocyanate composition, 97% by mass or more of an isocyanate compound; 2.0 mass ppm or more 1.0×10 4 A carbonyl compound represented by the following general formula (I) (hereinafter, sometimes referred to as "carbonyl compound (I)") in an amount of not more than ppm by mass. Contains: The isocyanate compound and the carbonyl compound are different compounds.

[0250] [ka]

[0251] (In general formula (I), R 11 is an organic group with a valence of (n11+n12), and R 12is a monovalent organic group. n11 is an integer of 1 or more and 8 or less, n12 is an integer of 0 or more and 7 or less, and the sum of n11 and n12 is an integer of 2 or more and 8 or less.

[0252] In general, compounds containing unsaturated bonds tend to have unsaturated bonds that are easily oxidized, and unsaturated bond compounds as contaminants tend to cause coloration. However, the carbonyl compound (I) acts effectively during storage of the isocyanate composition, and has the effect of improving the stability of the isocyanate compound without coloring the isocyanate composition. It is presumed that this effect is achieved by the carbonyl group of the carbonyl compound (I) being reactive with water and oxygen and suppressing the modification reaction of the isocyanate compound caused by water and oxygen. In addition, the carbonyl compound (I) has many unsaturated bonds between carbon and oxygen, and therefore tends to have the above effect more.

[0253] In order to suppress the modification reaction of the isocyanate compound, it is preferable to increase the content of the carbonyl compound (I), but if it is too much, coloring due to the unsaturated bond as described above may occur, which may impair the appearance during use. Therefore, the lower limit of the content of the carbonyl compound (I) is 2.0 mass ppm, preferably 3.0 mass ppm, more preferably 5.0 mass ppm, and even more preferably 10 mass ppm, relative to the total mass of the isocyanate composition. On the other hand, the upper limit of the content of the carbonyl compound (I) is 1.0 x 10 4 ppm by mass, 3.0 x 10 3 It is preferably in ppm by mass, and 1.0×10 3 It is more preferably ppm by weight. That is, the content of the carbonyl compound (I) is 2.0 ppm by mass or more and 1.0 × 10 4 Mass ppm or less, 3.0 mass ppm or more 3.0 x 10 3 It is preferably 5.0 ppm by mass or less, and 1.0×10 3 It is more preferable that the concentration is 10 ppm by mass or less, and 1.0×103 It is more preferably less than ppm by mass. When the content of the carbonyl compound (I) is equal to or more than the above lower limit, the modification reaction of the isocyanate compound can be suppressed, whereas when the content is equal to or less than the above upper limit, coloration caused by unsaturated bonds can be suppressed and the appearance can be maintained good.

[0254] The content of the isocyanate compound is 97% by mass or more, preferably 98% by mass or more, and more preferably 99% by mass or more, based on the total mass of the isocyanate composition. When the content of the isocyanate compound is equal to or more than the lower limit, a composition containing a sufficient amount of the isocyanate compound, which is the target substance, can be obtained. On the other hand, the upper limit is not particularly limited, but can be less than 100% by mass.

[0255] Hereinafter, each of the components of the isocyanate composition of the present embodiment will be described in detail.

[0256] <Carbonyl compounds (I)> The carbonyl compound (I) is a compound represented by the following general formula (I).

[0257] [ka]

[0258] (In general formula (I), R 11 is an organic group with a valence of (n11+n12), and R 12 is a monovalent organic group. n11 is an integer of 1 or more and 8 or less, n12 is an integer of 0 or more and 7 or less, and the sum of n11 and n12 is an integer of 2 or more and 8 or less.

[0259] [R 11 , R 12 ] R 11 and R 12 is as described above in "Carbonyl Compounds".

[0260] [n11 and n12] n11 is an integer between 1 and 8 inclusive. n12 represents the number of isocyanate groups and is an integer of 0 to 7. The sum of n11 and n12 (n11+n12) is an integer of 2 to 8, preferably an integer of 2 to 6, more preferably an integer of 2 to 5, and even more preferably an integer of 3 to 4. In general, the larger the value of (n11+n12), the more crosslinking points (isocyanate groups) per carbonyl compound molecule, and the more structures that contribute to preventing coloring and isocyanate denaturation, so that the crosslinking density at the time of polymerization is higher, the curing time can be shortened, the hardness of the polymer can be improved, and coloring and isocyanate denaturation can be suppressed. In addition, "higher crosslinking density" means that the average molecular chain length between crosslinking points is smaller. On the other hand, in the production of carbonyl compounds, heating a highly reactive isocyanate group can induce a modification reaction, which can cause adhesion to or clogging of the equipment. Therefore, from the viewpoint of carbonyl compound synthesis, it is preferable that (n11+n12) is 6 or less, more preferably that (n11+n12) is 5 or less, and even more preferably that (n11+n12) is 4 or less.

[0261] Preferred examples of the carbonyl compound (I) include compounds represented by the following formulae (I-1a) to (I-24b) (hereinafter, sometimes referred to as "carbonyl compound (I-1a)"). In addition, the carbonyl compounds (I-1a) to (I-1c), carbonyl compounds (I-2a) to (I-2c), carbonyl compounds (I-3a) to (I-3c), carbonyl compounds (I-4a) to (I-4c), carbonyl compounds (I-5a) to (I-5c), carbonyl compounds (I-6a) to (I-6c), carbonyl compounds (I-7a) to (I-7b), carbonyl compounds (I-8a) to (I-8b), The carbonyl compounds (I-9a) to (I-9b), the carbonyl compounds (I-10a) to (I-10b), the carbonyl compounds (I-11a) to (I-11b), the carbonyl compounds (I-12a) to (I-12b), the carbonyl compounds (I-22a) to (I-22b), and the carbonyl compounds (I-24a) to (I-24b) may each be a mixture or each compound may be a single compound.

[0262] The carbonyl compound (I) may be used alone or in combination of two or more. When two or more types of carbonyl compounds (I) are used in combination, the effects of improving the stability of the isocyanate compound by each carbonyl compound (I) are the same, so that they can be mixed in any ratio.

[0263] [ka]

[0264] [ka]

[0265] [ka]

[0266] [ka]

[0267] [ka]

[0268] [ka]

[0269] [ka]

[0270] [ka]

[0271] <Isocyanate compounds> As the isocyanate compound, a compound represented by the following general formula (II) (hereinafter, sometimes referred to as "isocyanate compound (II)") is preferably used.

[0272] [ka]

[0273] (In general formula (II), R 21 is an organic group with a valence of n21, and has the formula: R 21 =R 11 n21 is an integer between 2 and 8, and satisfies the relation: n21 = n11 + n12.

[0274] [R 21 , n21" R 21 , n21 is as described in <Isocyanate compound> in <<Method for producing carbonyl compound>> above.

[0275] Preferred examples of the isocyanate compound (II) include 4-isocyanatomethyl-1,8-octamethylene diisocyanate (TTI), 2-isocyanatoethyl-2,6-diisocyanatohexanoate (LTI), lysine methyl ester diisocyanate (LDI), diisocyanatopentane (PDI), diisocyanatohexane (HDI), methylenebis(cyclohexyl isocyanate) (HMDI), 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), diisocyanatoxylene (XDI), diisocyanatodiphenylmethane (MDI), and diisocyanatotoluene (TDI).

[0276] The isocyanate composition of the present embodiment has a molecular weight of 2.0 ppm by mass or more and 1.0 × 10 4 It is preferred that the composition further contains one or more compounds selected from the group consisting of carbamate compounds and carbonate esters in an amount of not more than ppm by mass.

[0277] The carbamate compound and the carbonate ester also have the same effect as the carbonyl compound (I) described above. In order to suppress the modification reaction of the isocyanate compound, it is preferable to increase the content of these compounds in the isocyanate composition, but it is preferable that the content is not too high in consideration of the suppression of coloration and the appearance during use. For this reason, the lower limit of each of the carbamate compound and the carbonate ester is preferably 2.0 ppm by mass, more preferably 3.0 ppm by mass, even more preferably 5.0 ppm by mass, and particularly preferably 10 ppm by mass, relative to the total mass of the isocyanate composition. On the other hand, the upper limit of each of the carbamate compound and the carbonate ester is preferably 1.0×10 4 It is preferably 3.0×10 ppm by mass. 3 More preferably, it is ppm by mass, and 1.0×10 3 It is more preferably expressed as ppm by weight. That is, the content of each of the carbamate compound and the carbonate ester is 2.0 ppm by mass or more and 1.0 × 10 4 It is preferably 3.0 ppm by mass or less, and 3.0×10 3 It is more preferable that the concentration is 5.0 ppm by mass or less, and more preferably 5.0 ppm by mass or more and 1.0×10 3 It is more preferable that the concentration is 10 ppm by mass or less, and more preferably 1.0×10 3 It is particularly preferably less than ppm by mass. When the contents of the carbamate compound and the carbonate ester are equal to or more than the above-mentioned lower limits, the modification reaction of the isocyanate compound can be suppressed, whereas when the contents are equal to or less than the above-mentioned upper limits, coloration caused by unsaturated bonds can be suppressed and good appearance can be maintained.

[0278] When the isocyanate composition of the present embodiment contains all of the carbonyl compound (I), the carbamate compound, and the carbonate ester, the lower limit of the total content of these compounds is preferably 2.0 ppm by mass, more preferably 3.0 ppm by mass, further preferably 5.0 ppm by mass, and particularly preferably 10 ppm by mass, relative to the total mass of the isocyanate composition. On the other hand, the upper limit of the total content of these compounds is preferably 1.0×10 5 It is preferably in ppm by mass, and 1.0×10 4 More preferably, it is ppm by mass, and 3.0×10 3 More preferably, it is ppm by mass, and more preferably 1.0×10 3 Parts per million by weight is particularly preferred. That is, the total content of the carbonyl compound (I), the carbamate compound, and the carbonate ester is 2.0 ppm by mass or more and 1.0 × 10 5 It is preferably 3.0 ppm by mass or less, and 1.0×10 4 It is more preferable that the concentration is 5.0 ppm by mass or less, and 3.0×10 3It is more preferable that the concentration is 10 ppm by mass or less, and more preferably 1.0×10 3 It is particularly preferably less than ppm by mass. When the total content of these compounds is equal to or more than the above lower limit, the modification reaction of the isocyanate compound can be further suppressed, whereas when the total content is equal to or less than the above upper limit, coloration caused by unsaturated bonds can be further suppressed and the appearance can be maintained in a good condition.

[0279] <Carbamate compounds> As the carbamate compound, a compound represented by the following general formula (III) (hereinafter, sometimes referred to as "carbamate compound (III)") is preferably used.

[0280] [ka]

[0281] (In general formula (III), R 31 is an organic group with a valence of (n31+n32), and has the formula: R 31 =R 11 R 32 is a monovalent organic group, represented by the formula: R 32 =R 12 n31 is an integer between 1 and 8, n32 is an integer between 0 and 7, the sum of n31 and n32 is an integer between 2 and 8, and the relation: n31+n32=n11+n12 is satisfied.

[0282] [R 31 , R 31 , n31, n32] R 31 , R 31 , n31, and n32 are as described in [Carbamate compound (III)] in the above <<Production method of carbonyl compound>>.

[0283] Preferred examples of the carbamate compound (III) include compounds represented by the following formulae (III-1a) to (III-24b). In addition, carbamate compounds (III-1a) to (III-1c), carbamate compounds (III-2a) to (III-2c), carbamate compounds (III-3a) to (III-3c), carbamate compounds (III-4a) to (III-4c), carbamate compounds (III-5a) to (III-5c), carbamate compounds (III-6a) to (III-6c), carbamate compounds (III-7a) to (III-7b), carbamate compounds (III-8a) to (III Each of the carbamate compounds (III-8b), the carbamate compounds (III-9a) to (III-9b), the carbamate compounds (III-10a) to (III-10b), the carbamate compounds (III-11a) to (III-11b), the carbamate compounds (III-12a) to (III-12b), the carbamate compounds (III-22a) to (III-22b), and the carbamate compounds (III-24a) to (III-24b) may be a mixture or each of the compounds may be a single compound.

[0284] [ka]

[0285] [ka]

[0286] [ka]

[0287] [ka]

[0288] [ka]

[0289] [ka]

[0290] [ka]

[0291] [ka]

[0292] The carbamate compound (III) may be used alone or in combination of two or more. When two or more carbamate compounds (III) are used in combination, the carbamate compounds (III) can be mixed in any ratio since the effect of improving the stability of the isocyanate compound by each carbamate compound (III) is the same.

[0293] <Carbonate ester> As the carbonate ester, a compound represented by the following general formula (IV) (hereinafter, sometimes referred to as "carbonate ester (IV)") is preferably used.

[0294] [ka]

[0295] (In general formula (IV), R 41 and R 42 are each independently a monovalent organic group represented by the formula: R 41 =R 42 =R 12 Satisfy.)

[0296] (R 41 and R 42 ) R 41 and R 42is as described above in <<Method for producing carbonyl compound>> <<Carbonate ester>>.

[0297] Preferred examples of the carbonate ester (IV) include diphenyl carbonate, bis(2-methoxyphenyl) carbonate, and bis(2-ethoxyphenyl) carbonate.

[0298] <Method for producing isocyanate composition> The isocyanate composition of the present embodiment can be produced by mixing an isocyanate compound, a carbonyl compound (I), and, as necessary, one or more compounds selected from the group consisting of carbamate compounds and carbonate esters in the above-mentioned contents.

[0299] Alternatively, a carbamate compound represented by the following general formula (VI) (hereinafter, sometimes referred to as "carbamate compound (VI)") may be thermally decomposed to obtain a composition containing an isocyanate compound (II), which can be used as the isocyanate composition of this embodiment.

[0300] [ka]

[0301] In general formula (VI), R 61 is an organic group having a valence of n61 (2 to 8 valences), and has the formula: R 61 =R 21 That is, R 61 is the above R 21 is the same as: In general formula (VI), R 62 is a monovalent organic group, represented by the formula: R 62 =R 12 That is, R 62 is the above R 12 is the same as: n61 represents the number of carbamate groups, is an integer of 2 or more and 8 or less, and satisfies the relation: n61=n21. That is, n61 is the same as n21 above.

[0302] Specifically, the carbamate compound (VI) is thermally decomposed in the presence of the carbonate ester (IV) as a solvent to obtain a composition containing the isocyanate compound (II). At this time, since a hydroxy compound is produced as a by-product, it is preferable to proceed with the thermal decomposition reaction while extracting and separating the hydroxy compound. The thermal decomposition reaction is preferably carried out by a continuous method, which is a method in which a reaction liquid containing the carbamate compound (VI) is continuously supplied to a reactor, the thermal decomposition reaction of the carbamate compound (VI) is carried out, and the by-product hydroxy compound is continuously withdrawn from the reactor.

[0303] The thermal decomposition temperature varies depending on the type of carbamate compound (VI) used, but can be, for example, 140° C. or higher and 380° C. or lower. The reaction pressure may be reduced pressure, normal pressure, or increased pressure, depending on the type of compound used and the reaction temperature. The pressure may be a pressure that corresponds to the saturated vapor pressure of the aprotic solvent used, and is preferably 20 Pa or more and 10×10 6 It is preferable to carry out the process at a pressure of 0.1 Pa or less. The reaction time (residence time in the case of a continuous method) is not particularly limited, and can be from 0.001 hours to 100 hours.

[0304] The carbonyl compound (I) is presumed to be a reaction product between the isocyanate compound (II) and the carbonate ester (IV) and is considered to be produced under thermal decomposition conditions. Therefore, the isocyanate composition obtained in the thermal decomposition reaction of the carbamate compound (VI) contains a specific amount of the carbonyl compound (I).

[0305] In the thermal decomposition reaction, the carbamate compound (III) can be said to be a reaction intermediate generated from the carbamate compound (VI) before becoming the final product, the isocyanate compound (II). When the content of the isocyanate compound (II) reaches a specific amount or more, the reaction is stopped, thereby obtaining an isocyanate composition containing the carbamate compound (III), which is the reaction intermediate.

[0306] The isocyanate composition obtained in the thermal decomposition reaction of the carbamate compound (VI) contains the carbonate ester (IV) as a solvent. When the amount of the carbonate ester (IV) is large, the carbonate ester (IV) can be separated from the isocyanate composition by a known separation method such as distillation separation so that the content of the carbonate ester (IV) in the isocyanate composition falls within a specific range.

[0307] In addition, when the isocyanate composition of the present embodiment is produced by mixing an isocyanate compound, a carbonyl compound (I), and, if necessary, one or more compounds selected from the group consisting of carbamate compounds and carbonate esters in the above-mentioned amounts, the carbonyl compound, the carbamate compound, and the carbonate ester can be produced by the methods shown below. As for the isocyanate compound, the one obtained by thermally decomposing the carbamate compound (VI) can be used after purification if necessary.

[0308] [Method for producing carbonyl compound (I)] The carbonyl compound (I) can be obtained by heating a mixture of an isocyanate compound (II) and a carbonate ester (IV), or a mixture of a carbamate compound (III) or a carbamate compound (VI) and a carbonate ester (IV), or a mixture of an isocyanate compound (II), a carbamate compound (III) or a carbamate compound (VI), a carbonate ester (IV), and a hydroxy compound (hereinafter, these mixtures may be referred to as a "raw material mixture of carbonyl compound (I)"). The hydroxy compound referred to here includes the same hydroxy compound as the by-product in the thermal decomposition reaction of the carbamate compound (VI), as described in detail below.

[0309] Regarding the amount (molar amount) of the carbonate ester (IV) used, the larger the amount of the carbonate ester solvent used, the more preferable from the viewpoint of suppressing side reactions. However, taking into consideration the size of the reactor, the amount of the carbonate ester solvent used is preferably 0.001 to 100 times, more preferably 0.01 to 80 times, and even more preferably 0.1 to 50 times, in terms of the stoichiometric ratio, relative to the total molar amount of the carbamate compound (III), the carbamate compound (VI) and the isocyanate compound (II).

[0310] The reaction temperature is usually from 100° C. to 400° C., and a high temperature is preferable to increase the reaction rate, but since a side reaction may be caused by at least one of the carbamate compound and the isocyanate compound at a high temperature, the reaction temperature is preferably from 130° C. to 300° C., and more preferably from 150° C. to 280° C. In order to keep the reaction temperature constant, a known cooling device or heating device may be installed in the reactor. The reaction pressure varies depending on the type of compound used and the reaction temperature, but may be reduced pressure, normal pressure, or increased pressure. It is usually 20 Pa or more and 1×10 6 The temperature is set in the range of Pa or less. The reaction time (residence time in the case of a continuous method) is not particularly limited and is usually from 0.001 to 100 hours, preferably from 0.01 to 50 hours, and more preferably from 0.1 to 10 hours.

[0311] In the production of carbonyl compounds by mixing and heating, the rate and amount of carbonyl compounds produced can be increased by heating the raw material liquid in contact with stainless steel. As the stainless steel, any shape can be used as long as it is made of SUS316 or SUS304, and for example, packings and metal pieces are preferably used. As the packing, there is no particular limitation, but DIXON Packing, Mc MAHON Packing, Coil PACK, MESH RING, CANNON Packing, HELI PACK, RASCHIG RING, PRICKLE RING, etc. can be used.

[0312] When the volume of the raw material solution of carbonyl compounds is V and the surface area of ​​the stainless steel is A, the larger the contact area with the stainless steel per unit volume of the raw material solution, the greater the value of the carbonyl compound formation rate A / V, which is 0.001 m. 2 / m 3 More than 100000m 2 / m 3 Less than 0.01m is preferable. 2 / m 3 More than 50000m 2 / m 3 Less than 0.1m is preferable. 2 / m 3 More than 10000m 2 / m 3 The following is even more preferred:

[0313] The reaction format is not particularly limited, but a reactor capable of efficiently mixing and heating the raw material mixture of carbonyl compound (I), or the raw material mixture of carbonyl compound (I) and stainless steel, is preferred. For example, a method of heating the raw material liquid in a stainless steel stirring tank or distillation column is preferred.

[0314] The low boiling point component of the liquid obtained by heating the raw material mixture of the carbonyl compound (I) may be distilled off, and the distillation method is not particularly limited as long as the low boiling point component can be separated as a gas phase component. The low boiling point component (light boiling component) refers to a component having a boiling point lower than that of the carbonyl compound (I), and although it varies depending on the substance used, it is mainly one or more compounds selected from the group consisting of carbonate ester (IV), isocyanate compound (II), and hydroxy compound.

[0315] [Method for producing carbamate compound (III)] The carbamate compound (III) can be obtained by mixing the isocyanate compound (II) and the hydroxy compound represented by the formula (V) (hereinafter, sometimes referred to as "hydroxy compound (V)") and heating the mixture, or by thermally decomposing the carbamate compound represented by the formula (VI).

[0316] [ka]

[0317] In general formula (V), R 51 is a monovalent organic group having the formula: R 51 =R 12 That is, R 51 is the above R 12 is the same as:

[0318] When producing the resin by mixing and heating the isocyanate compound (II) and the hydroxyl compound (V), it is preferable to mix and heat the resin so that the ratio NCO:OH of the isocyanate group of the isocyanate compound (II) to the hydroxyl group of the hydroxyl compound (V) is (n31+n32):n31.

[0319] The reaction temperature is usually 40° C. or higher and 400° C. or lower, and a high temperature is preferable to increase the reaction rate, but on the other hand, since a side reaction may be caused by at least one of the carbamate compound and the isocyanate compound at a high temperature, the reaction temperature is preferably 80° C. or higher and 300° C. or lower, and more preferably 100° C. or higher and 250° C. or lower. In order to keep the reaction temperature constant, a known cooling device or heating device may be installed in the reactor. The reaction pressure varies depending on the type of compound used and the reaction temperature, but may be reduced pressure, normal pressure, or increased pressure. It is usually 20 Pa or more and 1×10 6 The temperature is set in the range of Pa or less. The reaction time (residence time in the case of a continuous method) is not particularly limited and is usually from 0.001 to 100 hours, preferably from 0.01 to 50 hours, and more preferably from 0.1 to 10 hours.

[0320] When the compound is produced by a thermal decomposition reaction, the method is the same as that described in the above-mentioned method for producing the isocyanate compound (II).

[0321] [Method for producing carbonate ester (IV)] Carbonate (IV) can be synthesized, for example, by using the method described in Japanese Patent No. 3071008 (Reference 1) and Japanese Patent No. 4137941 (Reference 2). Specifically, carbonate (IV) can be produced by a method comprising: reacting an aromatic monohydroxy compound with phosgene or a chlorocarbonate of an aromatic monohydroxy compound in the presence of activated carbon while releasing hydrogen chloride; or reacting an organometallic compound with carbon dioxide to obtain a reaction mixture containing a dialkyl carbonate formed in the reaction (1); separating the dialkyl carbonate from the reaction mixture to obtain a residual liquid (2); reacting the residual liquid with an alcohol to form at least one organometallic compound and water, and removing the water from the organometallic compound (3); and reacting the dialkyl carbonate separated in step (2) with an aromatic hydroxy compound to obtain an aromatic carbonate (4). Note that the above steps (3) and (4) can be carried out in the same order or in the reverse order, or partially or entirely simultaneously.

[0322] <Application> Since the isocyanate composition of the present embodiment is sufficiently suppressed in coloration and has excellent storage stability, it is suitably used as a curing agent raw material in fields where appearance quality is required, such as baking paints, automobile clear coat materials, and coil coating materials. EXAMPLES

[0323] The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to these examples. In the following, "%" means "% by mass" and "ppm" means "ppm by mass". In the following, Examples 1-11, 1-12, 47 to 54, 56, and 60 are referred to as reference examples.

[0324] <Analysis method> (1) 1 H-NMR analysis method The equipment used was a JNM-A400 FT-NMR system manufactured by JEOL Ltd. 1 H-NMR analysis was carried out.

[0325] (1-1) 1Preparation of samples for H-NMR analysis 0.3 g of the sample solution was weighed out, and 0.7 g of deuterated chloroform and 0.05 g of dimethyldiphenylsilane as an internal standard substance were added thereto and mixed uniformly to prepare a solution for NMR analysis.

[0326] (1-2) Quantitative analysis method Analysis was performed for each standard substance, and quantitative analysis of the analytical sample solution was performed based on the created calibration curve.

[0327] (2) Gas Chromatography Analysis Method The analysis was carried out under the following conditions:

[0328] (Measurement conditions) Equipment: Shimadzu Corporation, GC-2010 Column: DB-1 Diameter 0.25mm, length 30m, film thickness 1.0μm Column temperature: 60℃~300℃ Inlet temperature: 300℃ Carrier gas: Helium Carrier gas flow rate: 40mL / min Detector: FID (Flame Ionization Detector)

[0329] (2-1) Preparation of gas chromatography analysis sample 1.0 g of the sample solution was weighed out, and 10 g of acetonitrile and 0.1 g of anisole as an internal standard substance were added thereto to homogeneously mix the solution, which was used as a gas chromatography analysis sample.

[0330] (3) Liquid Chromatography Analysis Method The analysis was carried out under the following conditions:

[0331] (Measurement conditions) Equipment: Shimadzu Corporation, LC-10AT Column: Inertsil ODS Particle diameter 5μm, inner diameter 2.1mm, length 250mm Column temperature: 40℃ Developing solvent: water / acetonitrile = 90 / 10 Flow rate of developing solvent: 1mL / min Detector: Photodiode array detector

[0332] (3-1) Preparation of liquid chromatography analysis sample 1.0 g of the sample solution was weighed out, and 10 g of acetic acid was added and mixed uniformly to prepare a liquid chromatography analysis sample.

[0333] (3-2) Quantitative analysis method Analysis was performed for each standard substance, and quantitative analysis of the analytical sample solution was performed based on the created calibration curve.

[0334] (4) Purification method using a column fractionator The produced carbonyl compound was isolated under the following conditions.

[0335] (conditions) Equipment: Yamazen Corporation, EPCLC-AI-580S Elution position control purification chromatograph Inject column: M or L Main column: High-Flash S, M, or L Developing solvent: ethyl acetate / hexane Developing solvent flow rate: 0mL / min to 80mL / min Detector: UV detector

[0336] In addition, 1 From the measurements of H-NMR, GC and LC, the yield of the generated isocyanate compound and the value of {3×(molar amount of isocyanurate group)+2×(molar amount of carbodiimide group)+3×(molar amount of uretonimine group)+2×(molar amount of allophanate group)}÷(molar amount of carbonyl compound) were calculated. In addition, the amount of carbonyl compound was quantified from the measurement of LC.

[0337] <Evaluation method> [Preservation test] 100 g of each isocyanate composition was placed in a 200 mL screw-cap bottle and stored at 25° C. for 300 days in a nitrogen atmosphere.

[0338] [Rating 1] (Hazen color number) The Hazen color number before and after storage was measured using a Hazen meter.

[0339] [Rating 2] After storage, 100 g of each isocyanate composition was pressure filtered using a membrane filter with a pore size of 1 μm, and the filtered residue mass was determined from the filter mass before and after filtration, and the modification amount was calculated according to the formula shown below.

[0340] (Amount of modification (mass%)) = {(filter mass after filtration) - (filter mass before filtration)} x 100 / 100g

[0341] [Example 1-1] Step (1-1): Production process of carbamate compound The reaction was carried out using the apparatus shown in Figure 1. The apparatus shown in Figure 1 was also used in the production of carbamate compounds in Examples 1-1 and onward. With line 14 closed, 3.33 kg (19.2 mol) of 4-aminomethyl-1,8-octanediamine was supplied from storage tank 101 through line 11 to baffled SUS reactor 104, and 5.50 kg (58.5 mol) of phenol was supplied from storage tank 102 through line 12 to the reactor 104, and the mixture was homogenized by stirring. Next, with line 16 closed, 5.50 kg (58.5 mol) of phenol was supplied from storage tank 102 through line 15 to baffled SUS reactor 105, and 20.52 kg (95.9 mol) of diphenyl carbonate was supplied from storage tank 103 through line 13 to the reactor 105. The liquid temperature in the reaction vessel 105 was adjusted to 65° C., and the liquid was homogenized by stirring, and then a mixed liquid of 4-aminomethyl-1,8-octanediamine and phenol was supplied from the reaction vessel 104 through the line 14 so that the internal temperature did not exceed 70° C. After continuing stirring for 2 hours, the reaction liquid was heated to 120° C., and the internal pressure was set to about 1 kPa, whereby 15.53 kg of phenol in the liquid was extracted into the storage tank 107 through the line 17 and the condenser A11.

[0342] The solution after the reaction (hereinafter referred to as "reaction liquid (1-1)") was analyzed by liquid chromatography, and as a result, a carbamate compound corresponding to 4-aminomethyl-1,8-octanediamine was produced in a yield of 99 mass%. Line 16 was opened, and the reaction liquid (1-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (1-1) was 19.40 kg.

[0343] Step (1-2): Pyrolysis step of carbamate compound The reaction was carried out using the apparatus shown in Figure 2. The apparatus shown in Figure 2 was also used in the thermal decomposition of the carbamate compounds in Examples 1-1 and onward. With line 24 closed, 19.40 kg of diphenyl carbonate was supplied from storage tank 202 to baffled SUS reaction vessel 201 via line 22. The temperature of multi-stage distillation column 203 was raised to 170°C, the jacket temperature of reaction vessel 201 was heated to 228°C, and the pressure was reduced to 14 kPa. 19.40 kg of reaction liquid (1-1) recovered in storage tank 106 in step (1-1) was heated to 120°C and supplied to reaction vessel 201 via line 21 in about 15 minutes to perform thermal decomposition of carbamate compound. The pressure was adjusted to a range of 8 to 14 kPa, and phenol produced by thermal decomposition was separated from diphenyl carbonate and the product 1,8-diisocyanato-4-isocyanatomethyloctane (TTI) in distillation column 203, and recovered in storage tank 204 via line 25, condenser A21, and line 27. The reflux ratio at this time was 1.2. After the entire reaction liquid (1-1) had been transferred, extraction of phenol was continued at an internal temperature of 220° C. The reaction was terminated 4 hours after the entire reaction liquid (1-1) had been transferred, and the reaction liquid was extracted from line 28 and transferred to storage tank 205. The mass of the reaction liquid transferred to storage tank 205 was 18.63 kg. A portion of this reaction liquid (hereinafter referred to as "reaction liquid (1-2)") was purified using a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a mixture of compounds represented by the following formulae (I-1a) to (I-1c). In addition, the carbonyl compound 1 The H-NMR spectrum is shown in Figure 5.

[0344] [ka]

[0345] A calibration curve for LC was prepared from the obtained carbonyl compounds, and the carbonyl compounds were quantified by the absolute calibration curve method. In the following examples, the carbonyl compounds were not isolated, and the carbonyl compounds were quantified from the calibration curve.

[0346] Also, 1H-NMR and gas chromatography analyses showed that TTI was produced in a yield of 70 mass%, and the value of {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of uretonimine groups) + 2 × (molar amount of allophanate groups)} ÷ (molar amount of carbonyl compound) of the reaction solution at this time was 3.7.

[0347] Step (1-3): Light boiling separation step The reaction was carried out using the apparatus shown in Figure 3. The apparatus shown in Figure 3 was also used in the light boiling separation in Examples 1-1 and onwards. The reaction liquid (1-2) was continuously fed from the storage tank 205 through the line 31 to the middle stage of the continuous multi-stage distillation column 301 at 3.73 kg / hour, and the liquid phase components were separated by distillation. The heat required for the distillation separation was supplied by circulating the liquid at the bottom of the column through the reboiler A32 and the line 33. The liquid temperature at the bottom of the continuous multi-stage distillation column was 220°C, and the pressure at the top of the column was 1.5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 301 was condensed in the condenser A31 through the line 32, and continuously extracted to the storage tank 302 through the line 36. The extraction rate in the steady state of the line 34 was 1.49 kg / hour, and the gas was continuously extracted to the storage tank 303. The amount of the liquid recovered in the storage tank 303 (hereinafter referred to as "reaction liquid (1-3)") was 7.45 kg. As a result of analysis by NMR, LC, and gas chromatography, it was found that TTI was recovered in a yield of 82 mass% based on the reaction liquid (1-2) supplied, and the value of {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of uretonimine groups) + 2 × (molar amount of allophanate groups)} ÷ (molar amount of carbonyl compounds) of the reaction liquid at this time was 4.6.

[0348] Step (1-4): High boiling separation step The reaction was carried out using the apparatus shown in Figure 4. The apparatus shown in Figure 4 was also used in the high boiling point separation in Examples 1-1 and onwards. A thin-film distillation apparatus 401 (manufactured by Kobelco Eco-Solutions Co., Ltd., Japan) was heated to 190°C, and the internal pressure was set to 0.3 kPa. The reaction liquid (1-3) recovered in the storage tank 303 in the step (1-3) was supplied to the upper part of the thin-film distillation apparatus 401 at about 1.0 kg / hour via line 41, and the isocyanate and high boiling components were separated. The generated gas phase components were transferred to the storage tank 402 via line 42 and condenser A41. The liquid recovered from the storage tank 402 was 3.35 kg, and the TTI recovery rate was 121% by mass. The TTI recovery rate exceeded 100% by mass because a part of the isocyanate-modified products generated in the thermal decomposition step or the low boiling separation step was regenerated into TTI.

[0349] [Example 1-2] Step (2-2): Pyrolysis step of carbamate compound The pyrolysis reaction was carried out in the same manner as in Example 1-1, except that 19.4 kg of the reaction liquid (1-1) and 19.4 kg of diphenyl carbonate were used, the reaction liquid (1-1) was supplied to the reactor over about 13 minutes to start the reaction, the jacket temperature was 248°C, the internal temperature was 240°C, the reflux ratio was 0.4, and the pressure was in the range of 14 to 26 kPa, and the extraction of phenol was continued for 3 hours after all of the reaction liquid (1-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 20.96 kg. This reaction liquid (hereinafter referred to as "reaction liquid (2-2)") was analyzed by NMR, LC, and gas chromatography, and as a result, TTI was produced in a yield of 78 mass%. The value of {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of uretonimine groups) + 2 × (molar amount of allophanate groups)} ÷ (molar amount of carbonyl compound) of the reaction solution at this time was 4.3.

[0350] Step (2-3): Light boiling separation step The reaction liquid (2-2) was continuously fed at 4.19 kg / hour, and low boiling point separation was carried out in the same manner as in Example 1-1, except that the withdrawal rate in a steady state from line 34 was 1.26 kg / hour. The amount of liquid recovered in storage tank 303 was 6.29 kg, and analysis by NMR, LC, and gas chromatography showed that TTI was recovered in a yield of 77 mass% based on the reaction liquid (2-2) fed, and the value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction liquid at this time was 6.3.

[0351] Step (2-4): High boiling separation step High boiling point separation was carried out in the same manner as in Example 1-1, except that the liquid recovered in storage tank 303 in step (2-3) was used. The amount of liquid recovered in storage tank 402 was 3.36 kg, and the recovery rate of TTI was 116 mass%.

[0352] [Examples 1-3] Step (3-2): Pyrolysis step of carbamate compound The reaction liquid (1-1) of Example 1-1 was used in an amount of 19.4 kg, and diphenyl carbonate was used in an amount of 19.4 kg. The reaction liquid (1-1) was supplied to the reactor over about 9 minutes to start the reaction. The reaction was carried out at a jacket temperature of 258°C, an internal temperature of 250°C, a reflux ratio of 2.0, and a pressure in the range of 21 to 32 kPa. The pyrolysis reaction was carried out in the same manner as in Example 1-1, except that the extraction of phenol was continued for 2.5 hours after all of the reaction liquid (1-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 22.12 kg. This reaction liquid (hereinafter referred to as "reaction liquid (3-2)") was analyzed by NMR, LC, and gas chromatography, and as a result, TTI was produced in a yield of 73% by mass. The value of {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of uretonimine groups) + 2 × (molar amount of allophanate groups)} ÷ (molar amount of carbonyl compound) of the reaction solution at this time was 3.9.

[0353] Step (3-3): Light boiling separation step The reaction liquid (3-2) was continuously fed at 4.42 kg / hour, and low boiling point separation was carried out in the same manner as in Example 1-1, except that the withdrawal rate in a steady state from line 34 was 1.42 kg / hour. The amount of the liquid recovered in storage tank 303 was 7.08 kg, and analysis by NMR, LC, and gas chromatography showed that TTI was recovered in a yield of 80 mass% based on the reaction liquid (3-2) fed, and the value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction liquid at this time was 5.5.

[0354] Step (3-4): High boiling separation step High boiling point separation was carried out in the same manner as in Example 1-1, except that the liquid recovered in storage tank 303 in step (3-3) was used. The amount of liquid recovered in storage tank 402 was 3.35 kg, and the recovery rate of TTI was 119 mass%.

[0355] [Examples 1-4] Step (4-2): Pyrolysis step of carbamate compound The reaction liquid (1-1) of Example 1-1 was used in an amount of 19.4 kg, and diphenyl carbonate was used in an amount of 19.4 kg. The reaction liquid (1-1) was supplied to the reactor over a period of about 14 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 1.5, and a pressure in the range of 8 to 14 kPa. The pyrolysis reaction was carried out in the same manner as in Example 1-1, except that the extraction of phenol was continued for 3 hours after all of the reaction liquid (1-1) was transferred. The weight of the reaction liquid transferred to the storage tank 205 was 22.12 kg. This reaction liquid (hereinafter referred to as "reaction liquid (4-2)") was analyzed by NMR, LC, and gas chromatography, and as a result, TTI was produced in a yield of 79% by mass. The value of {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of uretonimine groups) + 2 × (molar amount of allophanate groups)} ÷ (molar amount of carbonyl compound) of the reaction solution at this time was 1.6.

[0356] Step (4-3): Light boiling separation step The reaction liquid (4-2) was continuously fed at 4.42 kg / hour, and low boiling point separation was carried out in the same manner as in Example 1-1, except that the withdrawal rate in a steady state from line 34 was 1.68 kg / hour. The amount of the liquid recovered in storage tank 303 was 8.41 kg, and analysis by NMR, LC, and gas chromatography showed that TTI was recovered in a yield of 85 mass% based on the reaction liquid (4-2) fed, and the value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction liquid at this time was 2.6.

[0357] Step (4-4): High boiling separation step High boiling point separation was carried out in the same manner as in Example 1-1, except that the liquid recovered in storage tank 303 in step (4-3) was used. The amount of liquid recovered in storage tank 402 was 4.05 kg, and the recovery rate of TTI was 125 mass%.

[0358] [Examples 1-5] Step (5-1): Production process of carbamate compound Carbamate synthesis was carried out in the same manner as in Example 1-1, except that 0.23 kg (69.2 mol) of urea was used instead of diphenyl carbonate, 25.87 kg (275.2 mol) of phenol was supplied to the storage tank 102, the reaction temperature in the reactor 104 was set to 240° C., and stirring was performed for 30 minutes. The amounts of phenol and ammonia extracted into the storage tank 107 were 24.14 kg.

[0359] The solution after the reaction (hereinafter referred to as "reaction liquid (5-1)") was analyzed by liquid chromatography, and it was found that the corresponding carbamate compound was produced in a yield of 99% by mass. Line 16 was opened, and the reaction liquid (5-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (5-1) was 10.79 kg.

[0360] Step (5-2): Pyrolysis step of carbamate compound The pyrolysis reaction was carried out in the same manner as in Example 1-1, except that 10.8 kg of the reaction liquid (5-1) and 28.0 kg of diphenyl carbonate were used, the reaction liquid (5-1) was supplied to the reactor over about 13 minutes to start the reaction, the jacket temperature was 238°C, the internal temperature was 230°C, the reflux ratio was 1.7, and the pressure was in the range of 8 to 14 kPa, and the extraction of phenol was continued for 3 hours after all of the reaction liquid (5-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 21.34 kg. This reaction liquid (hereinafter referred to as "reaction liquid (5-2)") was analyzed by NMR, LC, and gas chromatography, and as a result, TTI was produced in a yield of 78 mass%. The value of {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of uretonimine groups) + 2 × (molar amount of allophanate groups)} ÷ (molar amount of carbonyl compound) of the reaction solution at this time was 1.5.

[0361] Step (5-3): Light boiling separation step The reaction liquid (5-2) was continuously fed at 4.27 kg / hour, and low boiling point separation was carried out in the same manner as in Example 1-1, except that the withdrawal rate in a steady state from line 34 was 1.75 kg / hour. The amount of the liquid recovered in storage tank 303 was 8.75 kg, and analysis by NMR, LC, and gas chromatography showed that TTI was recovered in a yield of 84 mass% based on the reaction liquid (5-2) fed, and the value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction liquid at this time was 2.5.

[0362] Step (5-4): High boiling separation step High boiling point separation was carried out in the same manner as in Example 1-1, except that the liquid recovered in storage tank 303 in step (5-3) was used. The amount of liquid recovered in storage tank 402 was 4.05 kg, and the recovery rate of TTI was 128 mass%.

[0363] [Examples 1-6] Step (6-1): Production process of carbamate compound Carbamate synthesis was carried out in the same manner as in Example 1-5, except that 12.40 kg (58.5 mol) of 4-cumylphenol was supplied to the baffled SUS reactor 104 instead of phenol, and 18.97 kg (89.47 mol) of 4-cumylphenol was supplied to the baffled SUS reactor 105 instead of phenol. The amount of 4-cumylphenol and ammonia extracted into the storage tank 107 was 16.97 kg.

[0364] The solution after the reaction (hereinafter referred to as "reaction liquid (6-1)") was analyzed by liquid chromatography, and it was found that the corresponding carbamate compound was produced in a yield of 99% by mass. Line 16 was opened, and the reaction liquid (6-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (6-1) was 17.96 kg.

[0365] Step (6-2): Pyrolysis step of carbamate compound The pyrolysis reaction was carried out in the same manner as in Example 1-5, except that 18.0 kg of the reaction liquid (6-1) and 28.0 kg of bis(4-cumylphenyl) carbonate were used, the reaction liquid (6-1) was supplied to the reactor over about 12 minutes to start the reaction, the jacket temperature was 238°C, the internal temperature was 230°C, the reflux ratio was 1.5, and the pressure was in the range of 3 to 5 kPa, and the extraction of 4-cumylphenol was continued for 3 hours after all of the reaction liquid (6-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 32.19 kg. This reaction liquid (hereinafter referred to as "reaction liquid (6-2)") was analyzed by NMR, LC, and gas chromatography, and as a result, TTI was produced in a yield of 75% by mass. The value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction solution at this time was 1.4. A part of the reaction solution (6-2) was purified using a column fractionation apparatus to isolate the carbonyl compounds. The isolated carbonyl compounds were a mixture of compounds represented by the following formulae (I-3a) to (I-3c).

[0366] [ka]

[0367] Process (6-3): Light boiling separation process Light boiling separation was carried out in the same manner as in Example 1-1, except that the reaction liquid (6-2) was continuously fed at 16.10 kg / hour, and the withdrawal rate in a steady state from line 34 was 15.77 kg / hour. The amount of the liquid recovered in storage tank 303 was 31.55 kg, and analysis by NMR, LC, and gas chromatography showed that TTI was recovered in a yield of 95 mass% based on the reaction liquid (6-2) fed, and the value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction liquid at this time was 1.6.

[0368] Step (6-4): High boiling separation step High boiling point separation was carried out in the same manner as in Example 1-1, except that the liquid recovered in storage tank 303 in step (6-3) was used. The amount of liquid recovered in storage tank 402 was 4.19 kg, and the recovery rate of TTI was 122 mass%.

[0369] [Comparative Example 1-1] Step (1'-2): Pyrolysis step of carbamate compound The reaction liquid (1-1) of Example 1-1 was used in an amount of 19.4 kg, and barrel process oil B-03 (benzyltoluene, Matsumura Oil Co., Ltd.) in an amount of 5.45 kg. The reaction liquid (1-1) was supplied to the reactor over a period of about 14 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 1.5, and a pressure in the range of 25 to 35 kPa. The pyrolysis reaction was carried out in the same manner as in Example 1-1, except that the extraction of phenol was continued for 1.5 hours after all of the reaction liquid (1-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 5.71 kg. This reaction liquid (hereinafter referred to as "reaction liquid (1'-2)") was analyzed by NMR, LC, and gas chromatography, and as a result, TTI was produced in a yield of 69% by mass. In this reaction mixture, no carbonyl compounds were observed, but by-products having isocyanurate groups, carbodiimide groups, uretonimine groups, and allophanate groups were observed.

[0370] Process (1'-3): Light boiling separation process The reaction liquid (1'-2) was continuously fed at 4.35 kg / hour, and light boiling separation was carried out in the same manner as in Example 1-1, except that the withdrawal rate in the steady state of line 34 was 1.74 kg / hour. However, the liquid became highly viscous during the operation, making it difficult to continue the operation.

[0371] [Examples 1-7] Step (7-1): Production process of carbamate compound The reaction was carried out using the apparatus shown in FIG. With line 14 closed, 3.33 kg (16.8 mol) of 4,4'-diaminodiphenylmethane was supplied from storage tank 101 through line 11 to baffled SUS reaction vessel 104, and 2.53 kg (27.0 mol) of phenol was supplied from storage tank 102 through line 12 to the reaction vessel 104, and homogenized by stirring. Next, with line 16 closed, 2.53 kg (27.0 mol) of phenol was supplied from storage tank 102 through line 15 to baffled SUS reaction vessel 105, and 11.96 kg (55.6 mol) of diphenyl carbonate was supplied from storage tank 103 through line 13 to the reaction vessel 105. The liquid temperature in the reaction vessel 105 was adjusted to 65° C. and homogenized by stirring, and then a mixed liquid of 4,4'-diaminodiphenylmethane and phenol was supplied from the reaction vessel 104 through the line 14 so that the internal temperature did not exceed 70° C. After continuing stirring for 2 hours, the reaction liquid was heated to 120° C. and the internal pressure was set to about 1 kPa, whereby 7.58 kg of phenol in the liquid was extracted into the storage tank 107 through the line 17 and the condenser A11.

[0372] The solution after the reaction (hereinafter referred to as "reaction liquid (7-1)") was analyzed by liquid chromatography, and as a result, a carbamate compound corresponding to 4,4'-diaminodiphenylmethane was produced in a yield of 95 mass%. Line 16 was opened, and the reaction liquid (7-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (7-1) was 12.77 kg.

[0373] Step (7-2): Pyrolysis step of carbamate compound The reaction liquid (7-1) was used in an amount of 12.77 kg, and diphenyl carbonate was used in an amount of 12.77 kg. The reaction liquid (7-1) was supplied to the reactor over about 10 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 0.8, and a pressure in the range of 11 to 16 kPa. The pyrolysis reaction was carried out in the same manner as in Example 1-1, except that the extraction of phenol was continued for 3 hours after all of the reaction liquid (7-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 11.75 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (7-2)") was purified using a column fractionation device to isolate a carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-2).

[0374] [ka]

[0375] A calibration curve for LC was created from the carbonyl compounds obtained, and the carbonyl compounds were quantified by the absolute calibration curve method. In addition, analysis by NMR and gas chromatography showed that diphenylmethane diisocyanate (MDI) was produced in a yield of 70% by mass. The value of {3 x (molar amount of isocyanurate groups) + 2 x (molar amount of carbodiimide groups) + 3 x (molar amount of uretonimine groups) + 2 x (molar amount of allophanate groups)} ÷ (molar amount of carbonyl compounds) of the reaction solution at this time was 1.3.

[0376] Step (7-3): Light boiling separation step Light boiling separation was carried out in the same manner as in Example 1-1, except that the reaction liquid (7-2) was continuously fed at 2.35 kg / hour, and the withdrawal rate in a steady state from line 34 was 1.97 kg / hour. The amount of the liquid recovered in storage tank 303 was 9.87 kg, and analysis by NMR, LC, and gas chromatography showed that MDI was recovered in a yield of 79 mass% based on the reaction liquid (7-2) fed, and the value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction liquid at this time was 2.3.

[0377] Step (7-4): High boiling separation step The liquid recovered in the storage tank 303 in the step (7-3) was used to carry out high boiling separation in the same manner as in Example 1-1, except that the operating temperature was 170° C. and the internal pressure was 0.3 kPa. The amount of the liquid recovered in the storage tank 402 was 4.54 kg, and the recovery rate of MDI was 130% by mass.

[0378] [Examples 1-8] Step (8-1): Production process of carbamate compound With the line 14 closed, 3.33 kg (16.8 mol) of lysine β-aminoethyl ester trihydrochloride was supplied from the storage tank 101 through the line 11 to the baffled SUS reaction vessel 104, and 2.52 kg (26.7 mol) of phenol was supplied from the storage tank 102 through the line 12 to the reaction vessel 104, and homogenized by stirring. Next, with the line 16 closed, 2.52 kg (26.7 mol) of phenol was supplied from the storage tank 102 through the line 15 to the baffled SUS reaction vessel 105, and 11.91 kg (55.6 mol) of diphenyl carbonate was supplied from the storage tank 103 through the line 13 to the reaction vessel 105. The liquid temperature in the reaction vessel 105 was adjusted to 65°C, and homogenized by stirring, and then a mixed liquid of lysine β-aminoethyl ester trihydrochloride and phenol was supplied from the reaction vessel 104 through the line 14 so that the internal temperature did not exceed 70°C. After continuing stirring for 2 hours, the reaction liquid was heated to 120° C. and the internal pressure was adjusted to about 1 kPa, whereby 8.22 kg of phenol in the liquid was extracted into storage tank 107 via line 17 and condenser A11.

[0379] The solution after the reaction (hereinafter referred to as "reaction liquid (8-1)") was analyzed by liquid chromatography, and as a result, a carbamate compound corresponding to lysine β-aminoethyl ester was produced in a yield of 96% by mass. Line 16 was opened, and the reaction liquid (8-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (8-1) was 11.45 kg.

[0380] Step (8-2): Pyrolysis of carbamate compound The pyrolysis reaction was carried out in the same manner as in Example 1-1, except that 11.45 kg of reaction liquid (8-1) and 10.00 kg of diphenyl carbonate were used, the reaction liquid (8-1) was supplied to the reactor over about 15 minutes to start the reaction, the jacket temperature was 238°C, the internal temperature was 230°C, the reflux ratio was 3.2, and the pressure was in the range of 11 to 16 kPa, and extraction of phenol was continued for 3 hours after all of the reaction liquid (8-1) had been transferred. The mass of the reaction liquid (hereinafter referred to as "reaction liquid (8-2)") transferred to the storage tank 205 was 9.01 kg. The mass of the reaction liquid (8-2) 1 The results of H-NMR and gas chromatography mass spectrometry are shown in Figures 6A and 6B, respectively. A part of the reaction solution (8-2) was purified using a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a mixture of compounds represented by the following formulae (I-4a) to (I-4c).

[0381] [ka]

[0382] A calibration curve for LC was created from the carbonyl compound obtained, and the carbonyl compound was quantified by the absolute calibration curve method. In addition, analysis by NMR and gas chromatography showed that lysine triisocyanate (LTI) was produced in a yield of 77% by mass. The value of {3 x (molar amount of isocyanurate group) + 2 x (molar amount of carbodiimide group) + 3 x (molar amount of uretonimine group) + 2 x (molar amount of allophanate group)} ÷ (molar amount of carbonyl compound) of the reaction solution at this time was 1.4.

[0383] Step (8-3): Light boiling separation step The reaction liquid (8-2) was continuously fed at 1.80 kg / hour, and low boiling point separation was carried out in the same manner as in Example 1-1, except that the withdrawal rate in a steady state of the line 34 was 1.10 kg / hour. The amount of the liquid recovered in the storage tank 303 was 5.50 kg, and as a result of analysis by NMR, LC, and gas chromatography, it was found that LTI was recovered in a yield of 83 mass% based on the reaction liquid (8-2) fed, and the value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction liquid at this time was 2.4.

[0384] Step (8-4): High boiling separation step The liquid recovered in the storage tank 303 in the step (8-3) was used, and high boiling point separation was carried out in the same manner as in Example 1-1, except that the operating temperature was 190° C. and the internal pressure was 0.1 kPa. The amount of the liquid recovered in the storage tank 402 was 2.38 kg, and the recovery rate of LTI was 125% by mass.

[0385] [Examples 1-9] Step (9-1): Production process of carbamate compound Carbamate synthesis was carried out in the same manner as in Example 1-8, except that 0.84 kg (6.75 mol) of 2-methoxyphenol was supplied to the baffled SUS reactor 104 instead of phenol, 0.84 kg (6.75 mol) of 2-methoxyphenol was supplied to the baffled SUS reactor 105 instead of phenol, and 15.26 kg (55.6 mol) of bis(2-methoxyphenyl) carbonate was supplied to the baffled SUS reactor 105 instead of diphenyl carbonate. The amount of 2-methoxyphenol extracted into the storage tank 107 was 6.35 kg.

[0386] The solution after the reaction (hereinafter referred to as "reaction liquid (9-1)") was analyzed by liquid chromatography, and the corresponding carbamate compound was found to have been produced in a yield of 98% by mass. Line 16 was opened, and the reaction liquid (9-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (9-1) was 13.95 kg.

[0387] Step (9-2): Pyrolysis step of carbamate compound The reaction liquid (9-1) was 14.0 kg, and bis(2-methoxyphenyl) carbonate was 8.0 kg. The reaction liquid (9-1) was fed to the reactor over about 14 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 3.0, and a pressure in the range of 8 to 13 kPa. The pyrolysis reaction was carried out in the same manner as in Example 1-8, except that the extraction of 2-methoxyphenol was continued for 3 hours after all of the reaction liquid (9-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 12.05 kg. This reaction liquid (hereinafter referred to as "reaction liquid (9-2)") was analyzed by NMR, LC, and gas chromatography, and as a result, LTI was produced in a yield of 78% by mass. The value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction solution at this time was 1.5. A part of the reaction solution (9-2) was purified using a column fractionation apparatus to isolate the carbonyl compounds. The isolated carbonyl compounds were a mixture of compounds represented by the following formulae (I-5a) to (I-5c).

[0388] [ka]

[0389] Step (9-3): Light boiling separation step The reaction liquid (9-2) was continuously fed at 2.41 kg / hour under a pressure of 1.0 kPa, and low boiling point separation was carried out in the same manner as in Example 1-1, except that the withdrawal rate in a steady state of the line 34 was 1.16 kg / hour. The amount of the liquid recovered in the storage tank 303 was 5.79 kg, and analysis by NMR, LC, and gas chromatography showed that LTI was recovered in a yield of 85 mass% based on the reaction liquid (9-2) fed, and the value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction liquid at this time was 2.2.

[0390] Step (9-4): High boiling separation step High boiling point separation was carried out in the same manner as in Example 1-1, except that the liquid recovered in storage tank 303 in step (9-3) was used. The amount of liquid recovered in storage tank 402 was 2.43 kg, and the recovery rate of LTI was 123 mass%.

[0391] [Examples 1-10] Step (10-1): Production process of carbamate compound With line 14 closed, 3.33 kg (14.3 mol) of lysine methyl ester dihydrochloride was supplied from storage tank 101 through line 11 to baffled SUS reaction vessel 104, and 1.91 kg (20.3 mol) of phenol was supplied from storage tank 102 through line 12 to the reaction vessel 104, and homogenized by stirring. Next, with line 16 closed, 1.91 kg (20.3 mol) of phenol was supplied from storage tank 102 through line 15 to baffled SUS reaction vessel 105, and 10.17 kg (47.5 mol) of diphenyl carbonate was supplied from storage tank 103 through line 13 to the reaction vessel 105. The liquid temperature in the reaction vessel 105 was adjusted to 65°C, and homogenized by stirring, and then a mixed liquid of lysine methyl ester dihydrochloride and phenol was supplied from reaction vessel 104 through line 14 so that the internal temperature did not exceed 70°C. After continuing stirring for 2 hours, the reaction liquid was heated to 120° C. and the internal pressure was adjusted to about 1 kPa, whereby 5.93 kg of phenol in the liquid was extracted into storage tank 107 via line 17 and condenser A11.

[0392] The solution after the reaction (hereinafter referred to as "reaction liquid (10-1)") was analyzed by liquid chromatography, and it was found that a carbamate compound corresponding to lysine methyl ester was produced in a yield of 97% by mass. Line 16 was opened, and the reaction liquid (10-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (10-1) was 11.38 kg.

[0393] Step (10-2): Pyrolysis step of carbamate compound The reaction liquid (10-1) was used in an amount of 11.38 kg, and diphenyl carbonate was used in an amount of 11.38 kg. The reaction liquid (10-1) was supplied to the reactor over a period of about 12 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 0.9, and a pressure in the range of 20 to 29 kPa. The pyrolysis reaction was carried out in the same manner as in Example 1-1, except that the extraction of phenol was continued for 3 hours after the entire reaction liquid (10-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 19.35 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (10-2)") was purified using a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-7a) to (I-7b).

[0394] [ka]

[0395] A calibration curve for LC was created from the carbonyl compounds obtained, and the carbonyl compounds were quantified by the absolute calibration curve method. In addition, analysis by NMR and gas chromatography showed that lysine diisocyanate (LDI) was produced in a yield of 81% by mass. The value of {3 x (molar amount of isocyanurate groups) + 2 x (molar amount of carbodiimide groups) + 3 x (molar amount of uretonimine groups) + 2 x (molar amount of allophanate groups)} ÷ (molar amount of carbonyl compounds) of the reaction solution at this time was 1.4.

[0396] Step (10-3): Light boiling separation step The reaction liquid (10-2) was continuously fed at 3.87 kg / hour, and low boiling point separation was performed in the same manner as in Example 1-1, except that the withdrawal rate in a steady state from line 34 was 1.47 kg / hour. The amount of the liquid recovered in storage tank 303 was 7.35 kg, and analysis by NMR, LC, and gas chromatography showed that LDI was recovered in a yield of 86 mass% based on the reaction liquid (10-2) fed, and the value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction liquid at this time was 2.5.

[0397] Step (10-4): High boiling separation step The liquid recovered in storage tank 303 in step (10-3) was used to carry out high boiling separation in the same manner as in Example 1-1, except that the operating temperature was 180° C. and the internal pressure was 0.1 kPa. The amount of liquid recovered in storage tank 402 was 4.57 kg, and the recovery rate of LDI was 122 mass%.

[0398] [Examples 1-11] Step (11-1): Production process of carbamate compound Carbamate synthesis was carried out in the same manner as in Example 1-10, except that 3.33 kg (13.5 mol) of lysine ethyl ester dihydrochloride instead of lysine methyl ester dihydrochloride and 1.70 kg (18.04 mol) of phenol were supplied to the baffled SUS reactor 104, and 1.70 kg (18.04 mol) of phenol and 9.59 kg (44.81 mol) of diphenyl carbonate were supplied to the baffled SUS reactor 105. The amount of phenol extracted into the storage tank 107 was 5.59 kg.

[0399] The solution after the reaction (hereinafter referred to as "reaction liquid (11-1)") was analyzed by liquid chromatography, and it was found that the corresponding carbamate compound was produced in a yield of 97% by mass. Line 16 was opened, and the reaction liquid (11-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (11-1) was 10.74 kg.

[0400] Step (11-2): Pyrolysis step of carbamate compound The pyrolysis reaction was carried out in the same manner as in Example 1-10, except that 10.7 kg of the reaction liquid (11-1) and 10.74 kg of diphenyl carbonate were used, the reaction liquid (11-1) was supplied to the reactor over about 12 minutes to start the reaction, the jacket temperature was 238°C, the internal temperature was 230°C, the reflux ratio was 0.9, and the pressure was in the range of 20 to 29 kPa, and the extraction of phenol was continued for 3 hours after all of the reaction liquid (11-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 18.25 kg. This reaction liquid (hereinafter referred to as "reaction liquid (11-2)") was analyzed by NMR, LC, and gas chromatography, and as a result, LDI-Et was produced in a yield of 82 mass%. The value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction solution at this time was 1.3. A part of the reaction solution (11-2) was purified using a column fractionation apparatus to isolate the carbonyl compounds. The isolated carbonyl compounds were a mixture of compounds represented by the following formulae (I-10a) to (I-10b).

[0401] [ka]

[0402] Step (11-3): Light boiling separation step Light boiling separation was carried out in the same manner as in Example 1-1, except that the reaction liquid (11-2) was continuously fed at 3.65 kg / hour, and the withdrawal rate in a steady state from the line 34 was 1.31 kg / hour. The amount of the liquid recovered in the storage tank 303 was 6.57 kg, and as a result of analysis by NMR, LC, and gas chromatography, it was found that LDI-Et was recovered in a yield of 85 mass% based on the reaction liquid (11-2) fed, and the value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction liquid at this time was 2.2.

[0403] Step (11-4): High boiling separation step High boiling point separation was carried out in the same manner as in Example 1-1, except that the liquid recovered in the storage tank 303 in the step (11-3) was used. The amount of the liquid recovered in the storage tank 402 was 4.10 kg, and the recovery rate of LDI-Et was 120 mass%.

[0404] [Examples 1-12] Step (12-1): Production process of carbamate compound With line 14 closed, 3.33 kg (15.8 mol) of 4,4'-methylenebis(cyclohexylamine) was supplied from storage tank 101 through line 11 to baffled SUS reaction vessel 104, and 2.29 kg (24.4 mol) of phenol was supplied from storage tank 102 through line 12 to the reaction vessel 104, and the mixture was homogenized by stirring. Next, with line 16 closed, 2.29 kg (24.4 mol) of phenol was supplied from storage tank 102 through line 15 to baffled SUS reaction vessel 105, and 11.27 kg (52.7 mol) of diphenyl carbonate was supplied from storage tank 103 through line 13 to the reaction vessel 105. The liquid temperature in the reaction vessel 105 was adjusted to 65° C. and homogenized by stirring, and then a mixed liquid of 4,4'-methylenebis(cyclohexylamine) and phenol was supplied from the reaction vessel 104 through the line 14 so that the internal temperature did not exceed 70° C. After continuing stirring for 2 hours, the reaction liquid was heated to 120° C. and the internal pressure was set to about 1 kPa, whereby 6.94 kg of phenol in the liquid was extracted into the storage tank 107 through the line 17 and the condenser A11.

[0405] The solution after the reaction (hereinafter referred to as "reaction liquid (12-1)") was analyzed by liquid chromatography, and as a result, a carbamate compound corresponding to 4,4'-methylenebis(cyclohexylamine) was produced in a yield of 99 mass%. Line 16 was opened, and the reaction liquid (12-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (12-1) was 12.24 kg.

[0406] Step (12-2): Pyrolysis of carbamate compound The pyrolysis reaction was carried out in the same manner as in Example 1-1, except that 12.24 kg of reaction liquid (12-1) and 12.24 kg of diphenyl carbonate were used, the reaction liquid (12-1) was supplied to the reactor over about 10 minutes to start the reaction, the jacket temperature was 238°C, the internal temperature was 230°C, the reflux ratio was 4.5, and the pressure was in the range of 11 to 16 kPa, and the extraction of phenol was continued for 3 hours after all of the reaction liquid (12-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 9.79 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (12-2)") was purified using a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-16).

[0407] [ka]

[0408] A calibration curve for LC was created from the obtained carbonyl compound, and the carbonyl compound was quantified by the absolute calibration curve method. In addition, as a result of analysis by NMR, LC, and gas chromatography, methylene bis (cyclohexyl isocyanate) (HMDI) was produced in a yield of 76 mass%. The value of {3 x (molar amount of isocyanurate group) + 2 x (molar amount of carbodiimide group) + 3 x (molar amount of uretonimine group) + 2 x (molar amount of allophanate group)} ÷ (molar amount of carbonyl compound) of the reaction solution at this time was 2.0.

[0409] Step (12-3): Light boiling separation step Light boiling separation was carried out in the same manner as in Example 1-1, except that the reaction liquid (12-2) was continuously fed at 1.96 kg / hour, and the withdrawal rate in a steady state from line 34 was 1.65 kg / hour. The amount of the liquid recovered in storage tank 303 was 8.22 kg, and analysis by NMR, LC, and gas chromatography showed that HMDI was recovered in a yield of 82 mass% based on the reaction liquid (12-2) fed, and the value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction liquid at this time was 3.4.

[0410] Step (12-4): High boiling separation step The liquid recovered in storage tank 303 in step (12-3) was used to carry out high boiling separation in the same manner as in Example 1-1, except that the operating temperature was 190° C. and the internal pressure was 0.3 kPa. The amount of liquid recovered in storage tank 402 was 4.85 kg, and the recovery rate of HMDI was 125% by mass.

[0411] [Examples 1-13] Step (13-1): Production process of carbamate compound With line 14 closed, 3.33 kg (23.1 mol) of 1,3-di(aminomethyl)cyclohexane was supplied from storage tank 101 through line 11 to baffled SUS reaction vessel 104, and 4.11 kg (43.7 mol) of phenol was supplied from storage tank 102 through line 12 to the reaction vessel 104, and homogenized by stirring. Next, with line 16 closed, 4.11 kg (43.7 mol) of phenol was supplied from storage tank 102 through line 15 to baffled SUS reaction vessel 105, and 16.44 kg (76.8 mol) of diphenyl carbonate was supplied from storage tank 103 through line 13 to the reaction vessel 105. The liquid temperature in the reaction vessel 105 was adjusted to 65° C. and homogenized by stirring, and then a mixed liquid of 1,3-di(aminomethyl)cyclohexane and phenol was supplied from the reaction vessel 104 through the line 14 so that the internal temperature did not exceed 70° C. After continuing stirring for 2 hours, the reaction liquid was heated to 120° C. and the internal pressure was set to about 1 kPa, whereby 11.74 kg of phenol in the liquid was extracted into the storage tank 107 through the line 17 and the condenser A11.

[0412] The solution after the reaction (hereinafter also referred to as "reaction liquid (13-1)") was analyzed by liquid chromatography, and as a result, a carbamate compound corresponding to 1,3-di(aminomethyl)cyclohexane was produced in a yield of 99 mass%. Line 16 was opened, and the reaction liquid (13-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (13-1) was 16.24 kg.

[0413] Step (13-2): Pyrolysis step of carbamate compound The reaction liquid (13-1) was 16.24 kg, and diphenyl carbonate was 16.24 kg. The reaction liquid (13-1) was fed to the reactor over about 15 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 4.0, and a pressure in the range of 11 to 16 kPa. The pyrolysis reaction was carried out in the same manner as in Example 1-1, except that the extraction of phenol was continued for 3 hours after all of the reaction liquid (13-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 13.97 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (13-2)") was purified using a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-19).

[0414] [ka]

[0415] A calibration curve for LC was created from the obtained carbonyl compound, and the amount of carbonyl compound was quantified by the absolute calibration curve method. In addition, as a result of analysis by NMR, LC, and gas chromatography, 1,3-bis(isocyanatomethyl)cyclohexane (HXDI) was produced in a yield of 78% by mass. The value of {3×(molar amount of isocyanurate group)+2×(molar amount of carbodiimide group)+3×(molar amount of uretonimine group)+2×(molar amount of allophanate group)}÷(molar amount of carbonyl compound) of the reaction solution at this time was 1.7.

[0416] Step (13-3): Light boiling separation step The reaction liquid (13-2) was continuously fed at 2.79 kg / hour, and low boiling separation was performed in the same manner as in Example 1-1, except that the withdrawal rate in a steady state of the line 34 was 1.90 kg / hour. The amount of the liquid recovered in the storage tank 303 was 9.50 kg, and as a result of analysis by NMR, LC, and gas chromatography, it was found that HXDI was recovered in a yield of 77 mass% based on the reaction liquid (13-2) supplied, and the value of {3×(molar amount of isocyanurate groups)+2×(molar amount of carbodiimide groups)+3×(molar amount of uretonimine groups)+2×(molar amount of allophanate groups)}÷(molar amount of carbonyl compounds) of the reaction liquid at this time was 3.6.

[0417] Step (13-4): High boiling separation step In step (13-3), the liquid recovered in storage tank 303 was used, and high boiling point separation was carried out in the same manner as in Example 1-1, except that the operating temperature was 190° C. and the internal pressure was 0.3 kPa. The amount of liquid recovered in storage tank 402 was 4.93 kg, and the recovery rate of HXDI was 122 mass%.

[0418] <Production of an isocyanate compound and a carbonyl compound (I) corresponding to the isocyanate compound> [Synthesis Example 1-1] (Production of TTI and carbonyl compounds (I-1a) to (I-1c) corresponding to TTI) 1. Step (1-1): Production process of carbamate compound The reaction was carried out using the apparatus shown in Figure 1. The apparatus shown in Figure 1 was also used in the production of carbamate compounds in Synthesis Example 1-1 and subsequent examples. With line 14 closed, 3.33 kg (19.2 mol) of 4-aminomethyl-1,8-octanediamine was supplied from storage tank 101 through line 11 to baffled SUS reactor 104, and 5.50 kg (58.5 mol) of phenol was supplied from storage tank 102 through line 12 to the reactor 104, and the mixture was homogenized by stirring. Next, with line 16 closed, 5.50 kg (58.5 mol) of phenol was supplied from storage tank 102 through line 15 to baffled SUS reactor 105, and 20.52 kg (95.9 mol) of diphenyl carbonate was supplied from storage tank 103 through line 13 to the reactor 105. The liquid temperature in the reaction vessel 105 was adjusted to 65° C., and the liquid was homogenized by stirring, and then a mixed liquid of 4-aminomethyl-1,8-octanediamine and phenol was supplied from the reaction vessel 104 through the line 14 so that the internal temperature did not exceed 70° C. After continuing stirring for 2 hours, the reaction liquid was heated to 120° C., and the internal pressure was set to about 1 kPa, whereby 15.53 kg of phenol in the liquid was extracted into the storage tank 107 through the line 17 and the condenser A11.

[0419] The solution after the reaction (hereinafter referred to as "reaction liquid (1-1)") was analyzed by liquid chromatography, and as a result, a carbamate compound corresponding to 4-aminomethyl-1,8-octanediamine was produced in a yield of 99 mass%. Line 16 was opened, and the reaction liquid (1-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (1-1) was 19.40 kg.

[0420] 2. Step (1-2): Thermal decomposition step of carbamate compound The reaction was carried out using the apparatus shown in Figure 2. The apparatus shown in Figure 2 was also used in the thermal decomposition of the carbamate compounds in Synthesis Example 1-1 and subsequent examples. With line 24 closed, 19.40 kg of diphenyl carbonate was supplied from storage tank 202 to baffled SUS reaction vessel 201 via line 22. The temperature of multi-stage distillation column 203 was raised to 170°C, the jacket temperature of reaction vessel 201 was heated to 228°C, and the pressure was reduced to 14 kPa. 19.40 kg of reaction liquid (1-1) recovered in storage tank 106 in step (1-1) was heated to 120°C and supplied to reaction vessel 201 via line 21 in about 15 minutes to perform thermal decomposition of carbamate compound. The pressure was adjusted to a range of 8 to 14 kPa, and phenol produced by thermal decomposition was separated from diphenyl carbonate and the product 1,8-diisocyanato-4-isocyanatomethyloctane (TTI) in distillation column 203, and recovered in storage tank 204 via line 25, condenser A21, and line 27. The reflux ratio at this time was 1.2. After all of the reaction liquid (1-1) had been transferred, extraction of phenol continued at an internal temperature of 220°C. The reaction was terminated 4 hours after all of the reaction liquid (1-1) had been transferred, and the reaction liquid was extracted from line 28 and transferred to storage tank 205. The mass of the reaction liquid transferred to storage tank 205 was 18.63 kg. A portion of this reaction liquid (hereinafter referred to as "reaction liquid (1-2)") was purified using a column fractionation device to isolate the carbonyl compound. The isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-1a) to (I-1c) (hereinafter, this mixture may be referred to as "mixture (I-1)"). In addition, 1 H-NMR and gas chromatography analyses revealed that TTI was produced in a yield of 70 mass%.

[0421] [ka]

[0422] 3. Process (1-3): Light boiling separation process The reaction was carried out using the apparatus shown in Figure 3. The apparatus shown in Figure 3 was also used in the light boiling separation in Synthesis Example 1-1 and subsequent steps. The reaction liquid (1-2) was continuously fed from the storage tank 205 through the line 31 to the middle stage of the continuous multi-stage distillation column 301 at 3.73 kg / hour, and the liquid phase components were separated by distillation. The heat required for the distillation separation was supplied by circulating the liquid at the bottom of the column through the reboiler A32 and the line 33. The liquid temperature at the bottom of the continuous multi-stage distillation column was 220°C, and the pressure at the top of the column was 1.5 kPa. The gas distilled from the top of the continuous multi-stage distillation column 301 was condensed in the condenser A31 through the line 32, and continuously extracted to the storage tank 302 through the line 36. The extraction rate in the steady state of the line 34 was 1.49 kg / hour, and the gas was continuously extracted to the storage tank 303. The amount of the liquid recovered in the storage tank 303 (hereinafter referred to as "reaction liquid (1-3)") was 7.45 kg. As a result of analysis by NMR, LC, and gas chromatography, it was found that TTI was recovered in a yield of 82 mass% based on the reaction liquid (1-2) supplied.

[0423] 4. Process (1-4): High boiling separation process The reaction was carried out using the apparatus shown in Figure 4. The apparatus shown in Figure 4 was also used in the high boiling point separation in Synthesis Example 1-1 and subsequent steps. A thin-film distillation apparatus 401 (manufactured by Kobelco Eco-Solutions Co., Ltd., Japan) was heated to 190°C, and the internal pressure was set to 0.3 kPa. The reaction liquid (1-3) recovered in the storage tank 303 in the step (1-3) was supplied to the upper part of the thin-film distillation apparatus 401 at about 1.0 kg / hour via line 41, and the isocyanate and high boiling components were separated. The generated gas phase components were transferred to the storage tank 402 via line 42 and condenser A41. The liquid recovered from the storage tank 402 was 3.35 kg, and the TTI recovery rate was 121% by mass. The TTI recovery rate exceeded 100% by mass because a part of the isocyanate-modified products generated in the thermal decomposition step or the low boiling separation step was regenerated into TTI.

[0424] [Synthesis Example 1-2] (Production of TTI and carbonyl compounds (I-2a) to (I-2c) corresponding to TTI) TTI was produced in the same manner as in Synthesis Example 1-1, except that 2-methoxyphenol was used instead of phenol and bis(2-methoxyphenyl)carbonate was used instead of diphenyl carbonate. The isolated carbonyl compound was a mixture of compounds represented by the following formulae (I-2a) to (I-2c) (hereinafter, this mixture may be referred to as "mixture (I-2)").

[0425] [ka]

[0426] [Synthesis Example 1-3] (Production of TTI and carbonyl compounds (I-3a) to (I-3c) corresponding to TTI) TTI was produced in the same manner as in Synthesis Example 1-1, except that 4-cumylphenol was used instead of phenol and bis(4-cumylphenol) carbonate was used instead of diphenyl carbonate. The isolated carbonyl compounds were a mixture of compounds represented by the following formulae (I-3a) to (I-3c) (hereinafter, this mixture may be referred to as "mixture (I-3)").

[0427] [ka]

[0428] [Synthesis Example 1-4] (Production of LTI and carbonyl compounds (I-4a) to (I-4b) corresponding to LTI) 1. Step (4-1): Production process of carbamate compound With the line 14 closed, 3.33 kg (16.8 mol) of lysine β-aminoethyl ester trihydrochloride was supplied from the storage tank 101 through the line 11 to the baffled SUS reaction vessel 104, and 2.52 kg (26.7 mol) of phenol was supplied from the storage tank 102 through the line 12 to the reaction vessel 104, and homogenized by stirring. Next, with the line 16 closed, 2.52 kg (26.7 mol) of phenol was supplied from the storage tank 102 through the line 15 to the baffled SUS reaction vessel 105, and 11.91 kg (55.6 mol) of diphenyl carbonate was supplied from the storage tank 103 through the line 13 to the reaction vessel 105. The liquid temperature in the reaction vessel 105 was adjusted to 65°C, and homogenized by stirring, and then a mixed liquid of lysine β-aminoethyl ester trihydrochloride and phenol was supplied from the reaction vessel 104 through the line 14 so that the internal temperature did not exceed 70°C. After continuing stirring for 2 hours, the reaction liquid was heated to 120° C. and the internal pressure was adjusted to about 1 kPa, whereby 8.22 kg of phenol in the liquid was extracted into storage tank 107 via line 17 and condenser A11.

[0429] The solution after the reaction (hereinafter referred to as "reaction liquid (4-1)") was analyzed by liquid chromatography, and as a result, a carbamate compound corresponding to lysine β-aminoethyl ester was produced in a yield of 96 mass%. Line 16 was opened, and the reaction liquid (4-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (4-1) was 11.45 kg.

[0430] 2. Step (4-2): Thermal decomposition step of carbamate compound The reaction liquid (4-1) was used in an amount of 11.45 kg and diphenyl carbonate in an amount of 10.00 kg. The reaction liquid (4-1) was supplied to the reactor over a period of about 15 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 3.2, and a pressure in the range of 11 to 16 kPa. The pyrolysis reaction was carried out in the same manner as in Synthesis Example 1-1, except that the extraction of phenol was continued for 3 hours after the entire reaction liquid (4-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 9.01 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (4-2)") was purified using a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a mixture of compounds represented by the following formulae (I-4a) to (I-4c). (Hereinafter, this mixture may be referred to as "mixture (I-4).") Furthermore, analysis by NMR and gas chromatography revealed that lysine triisocyanate (LTI) was produced in a yield of 77 mass%.

[0431] [ka]

[0432] 3. Process (4-3): Light boiling separation process The reaction liquid (4-2) was continuously fed at 1.80 kg / hour, and low boiling point separation was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal rate in a steady state through line 34 was 1.10 kg / hour. The amount of the liquid recovered in storage tank 303 was 5.50 kg, and analysis by NMR, LC, and gas chromatography showed that LTI was recovered in a yield of 83 mass% based on the reaction liquid (4-2) fed.

[0433] 4. Process (4-4): High boiling separation process The liquid recovered in the storage tank 303 in the step (4-3) was used to carry out high boiling point separation in the same manner as in Synthesis Example 1-1, except that the operating temperature was 190° C. and the internal pressure was 0.1 kPa. The amount of the liquid recovered in the storage tank 402 was 2.38 kg, and the recovery rate of LTI was 125% by mass.

[0434] [Synthesis Example 1-5] (Production of LTI and carbonyl compounds (I-5a) to (I-5b) corresponding to LTI) LTI was produced in the same manner as in Synthesis Example 1-4, except that 2-methoxyphenol was used instead of phenol and bis(2-methoxyphenyl) carbonate was used instead of diphenyl carbonate. The isolated carbonyl compound was a mixture of compounds represented by the following formulae (I-5a) to (I-5c) (hereinafter, this mixture may be referred to as "mixture (I-5)").

[0435] [ka]

[0436] [Synthesis Example 1-6] (Production of LDI and carbonyl compounds (I-7a) to (I-7b) corresponding to LDI) 1. Step (6-1): Production process of carbamate compound With line 14 closed, 3.33 kg (14.3 mol) of lysine methyl ester dihydrochloride was supplied from storage tank 101 through line 11 to baffled SUS reaction vessel 104, and 1.91 kg (20.3 mol) of phenol was supplied from storage tank 102 through line 12 to the reaction vessel 104, and homogenized by stirring. Next, with line 16 closed, 1.91 kg (20.3 mol) of phenol was supplied from storage tank 102 through line 15 to baffled SUS reaction vessel 105, and 10.17 kg (47.5 mol) of diphenyl carbonate was supplied from storage tank 103 through line 13 to the reaction vessel 105. The liquid temperature in the reaction vessel 105 was adjusted to 65°C, and homogenized by stirring, and then a mixed liquid of lysine methyl ester dihydrochloride and phenol was supplied from reaction vessel 104 through line 14 so that the internal temperature did not exceed 70°C. After continuing stirring for 2 hours, the reaction liquid was heated to 120° C. and the internal pressure was adjusted to about 1 kPa, whereby 5.93 kg of phenol in the liquid was extracted into storage tank 107 via line 17 and condenser A11.

[0437] The solution after the reaction (hereinafter referred to as "reaction liquid (6-1)") was analyzed by liquid chromatography, and it was found that a carbamate compound corresponding to lysine methyl ester was produced in a yield of 97% by mass. Line 16 was opened, and the reaction liquid (6-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (6-1) was 11.38 kg.

[0438] 2. Step (6-2): Thermal decomposition step of carbamate compound The reaction liquid (6-1) was used in an amount of 11.38 kg, and diphenyl carbonate was used in an amount of 11.38 kg. The reaction liquid (6-1) was supplied to the reactor over a period of about 12 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 0.9, and a pressure in the range of 20 to 29 kPa. The pyrolysis reaction was carried out in the same manner as in Synthesis Example 1-1, except that the extraction of phenol was continued for 3 hours after the entire reaction liquid (6-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 19.35 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (6-2)") was purified using a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-7a) to (I-7b) (hereinafter, this mixture may be referred to as "mixture (I-7)"). Furthermore, analysis by NMR and gas chromatography revealed that lysine diisocyanate (LDI) was produced in a yield of 81% by mass.

[0439] [ka]

[0440] 3. Process (6-3): Light boiling separation process The reaction liquid (6-2) was continuously fed at 3.87 kg / hour, and low boiling point separation was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal rate in a steady state through line 34 was 1.47 kg / hour. The amount of the liquid recovered in storage tank 303 was 7.35 kg, and analysis by NMR, LC, and gas chromatography showed that LDI was recovered in a yield of 86 mass% based on the reaction liquid (6-2) fed.

[0441] 4. Process (6-4): High boiling separation process The liquid recovered in the storage tank 303 in the step (6-3) was used to carry out high boiling separation in the same manner as in Synthesis Example 1-1, except that the operating temperature was 180° C. and the internal pressure was 0.1 kPa. The amount of the liquid recovered in the storage tank 402 was 4.57 kg, and the recovery rate of LDI was 122 mass%.

[0442] [Synthesis Example 1-7] (Production of LDI and carbonyl compounds (I-8a) to (I-8b) corresponding to LDI) LDI was produced in the same manner as in Synthesis Example 1-6, except that 2-methoxyphenol was used instead of phenol and bis(2-methoxyphenyl) carbonate was used instead of diphenyl carbonate. The isolated carbonyl compound was a mixture of compounds represented by the following formulae (I-8a) to (I-8b) (hereinafter, this mixture may be referred to as "mixture (I-8)").

[0443] [ka]

[0444] [Synthesis Example 1-8] (Production of LDI-Et and carbonyl compounds (I-10a) to (I-10b) corresponding to LDI-Et) LDI-Et was produced in the same manner as in Synthesis Example 1-6, except that lysine ethyl ester dihydrochloride was used instead of lysine methyl ester dihydrochloride in Synthesis Example 1-6. The isolated carbonyl compound was a mixture of compounds represented by the following formulae (I-10a) to (I-10b) (hereinafter, this mixture may be referred to as "mixture (I-10)").

[0445] [ka]

[0446] [Synthesis Example 1-9] (Production of HDI and carbonyl compound corresponding to HDI (I-20)) 1. Step (9-1): Production process of carbamate compound The corresponding carbamate was synthesized from hexamethylenediamine in the same manner as in step (1-1), except that 3.33 kg of hexamethylenediamine and 20.40 kg of diphenyl carbonate were used instead of 4-aminomethyl-1,8-octanediamine, 5.50 kg of phenol was mixed with hexamethylenediamine, and 5.50 kg of phenol was supplied to the reactor. The reaction liquid was heated to 120°C, and the internal pressure was set to 1.0 kPa, thereby extracting 15.42 kg of phenol from the liquid.

[0447] The solution after the reaction (hereinafter referred to as "reaction liquid (9-1)") was analyzed by liquid chromatography, and it was found that a carbamate compound corresponding to hexamethylenediamine was produced in a yield of 99% by mass. The mass of the reaction liquid (9-1) was 19.31 kg.

[0448] 2. Step (9-2): Thermal decomposition step of carbamate compound The pyrolysis reaction was carried out in the same manner as in Synthesis Example 1-1, except that 19.31 kg of reaction liquid (9-1) and 19.31 kg of diphenyl carbonate were used, the reaction liquid (9-1) was fed to the reactor over about 15 minutes to start the reaction, the jacket temperature was 238°C, the internal temperature was 230°C, the reflux ratio was 2.2, and the pressure was in the range of 20 to 29 kPa, and the extraction of phenol was continued for 3 hours after all of the reaction liquid (9-1) was transferred. The mass of the reaction liquid after the reaction (hereinafter referred to as "reaction liquid (9-2)") was 33.22 kg. The carbonyl compound of the reaction liquid (9-2) was isolated. The isolated carbonyl compound was a compound represented by the following formula (I-20).

[0449] [ka]

[0450] Furthermore, analysis by NMR and gas chromatography revealed that hexamethylene diisocyanate (HDI) was produced in a yield of 78 mass %.

[0451] 3. Process (9-3): Light boiling separation process The reaction liquid (9-2) was continuously fed at 6.64 kg / hour, and low boiling point separation was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal rate in a steady state through line 34 was 0.930 kg / hour. The amount of the liquid recovered in storage tank 303 was 4.65 kg, and analysis by NMR, LC, and gas chromatography showed that HDI was recovered in a yield of 83 mass% based on the reaction liquid (9-2) fed.

[0452] 4. Process (9-4): High boiling separation process The liquid recovered in the storage tank 303 in the step (9-3) was used to carry out high boiling point separation in the same manner as in Synthesis Example 1-1, except that the operating temperature was 170° C. and the internal pressure was 0.1 kPa. The amount of the liquid recovered in the storage tank 402 was 3.55 kg, and the recovery rate of HDI was 122 mass%.

[0453] [Synthesis Example 1-10] (Production of HMDI and carbonyl compounds corresponding to HMDI (I-8)) 1. Step (10-1): Production process of carbamate compound With line 14 closed, 3.33 kg (15.8 mol) of 4,4'-methylenebis(cyclohexylamine) was supplied from storage tank 101 through line 11 to baffled SUS reaction vessel 104, and 2.29 kg (24.4 mol) of phenol was supplied from storage tank 102 through line 12 to the reaction vessel 104, and the mixture was homogenized by stirring. Next, with line 16 closed, 2.29 kg (24.4 mol) of phenol was supplied from storage tank 102 through line 15 to baffled SUS reaction vessel 105, and 11.27 kg (52.7 mol) of diphenyl carbonate was supplied from storage tank 103 through line 13 to the reaction vessel 105. The liquid temperature in the reaction vessel 105 was adjusted to 65° C. and homogenized by stirring, and then a mixed liquid of 4,4'-methylenebis(cyclohexylamine) and phenol was supplied from the reaction vessel 104 through the line 14 so that the internal temperature did not exceed 70° C. After continuing stirring for 2 hours, the reaction liquid was heated to 120° C. and the internal pressure was set to about 1 kPa, whereby 6.94 kg of phenol in the liquid was extracted into the storage tank 107 through the line 17 and the condenser A11.

[0454] The solution after the reaction (hereinafter referred to as "reaction liquid (10-1)") was analyzed by liquid chromatography, and it was found that a carbamate compound corresponding to 4,4'-methylenebis(cyclohexylamine) was produced in a yield of 99% by mass. Line 16 was opened, and the reaction liquid (10-1) was transferred to storage tank 106 via line 16. The mass of reaction liquid (8-1) was 12.24 kg.

[0455] 2. Step (10-2): Thermal decomposition step of carbamate compound The reaction liquid (10-1) was used in an amount of 12.24 kg, and diphenyl carbonate was used in an amount of 12.24 kg. The reaction liquid (10-1) was supplied to the reactor over a period of about 10 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 4.5, and a pressure in the range of 11 to 16 kPa. The pyrolysis reaction was carried out in the same manner as in Synthesis Example 1-1, except that the extraction of phenol was continued for 3 hours after the entire reaction liquid (10-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 9.79 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (10-2)") was purified using a column fractionation device to isolate a carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-16).

[0456] [ka]

[0457] Furthermore, analysis by NMR, LC, and gas chromatography revealed that methylenebis(cyclohexylisocyanate) (HMDI) was produced in a yield of 76 mass%.

[0458] 3. Process (10-3): Light boiling separation process The reaction liquid (10-2) was continuously fed at 1.96 kg / hour, and low boiling point separation was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal rate in a steady state through line 34 was 1.65 kg / hour. The amount of the liquid recovered in storage tank 303 was 8.22 kg, and analysis by NMR, LC, and gas chromatography showed that HMDI was recovered in a yield of 82 mass% based on the reaction liquid (10-2) fed.

[0459] 4. Process (10-4): High boiling separation process The liquid recovered in the storage tank 303 in the step (10-3) was used to carry out high boiling separation in the same manner as in Synthesis Example 1-1, except that the operating temperature was 190° C. and the internal pressure was 0.3 kPa. The amount of the liquid recovered in the storage tank 402 was 4.85 kg, and the recovery rate of HMDI was 125% by mass.

[0460] [Synthesis Example 1-11] (Production of HXDI and carbonyl compound (I-19) corresponding to HXDI) 1. Step (11-1): Production process of carbamate compound With line 14 closed, 3.33 kg (23.1 mol) of 1,3-di(aminomethyl)cyclohexane was supplied from storage tank 101 through line 11 to baffled SUS reaction vessel 104, and 4.11 kg (43.7 mol) of phenol was supplied from storage tank 102 through line 12 to the reaction vessel 104, and homogenized by stirring. Next, with line 16 closed, 4.11 kg (43.7 mol) of phenol was supplied from storage tank 102 through line 15 to baffled SUS reaction vessel 105, and 16.44 kg (76.8 mol) of diphenyl carbonate was supplied from storage tank 103 through line 13 to the reaction vessel 105. The liquid temperature in the reaction vessel 105 was adjusted to 65° C. and homogenized by stirring, and then a mixed liquid of 1,3-di(aminomethyl)cyclohexane and phenol was supplied from the reaction vessel 104 through the line 14 so that the internal temperature did not exceed 70° C. After continuing stirring for 2 hours, the reaction liquid was heated to 120° C. and the internal pressure was set to about 1 kPa, whereby 11.74 kg of phenol in the liquid was extracted into the storage tank 107 through the line 17 and the condenser A11.

[0461] The solution after the reaction (hereinafter also referred to as "reaction liquid (11-1)") was analyzed by liquid chromatography, and as a result, a carbamate compound corresponding to 1,3-di(aminomethyl)cyclohexane was produced in a yield of 99 mass%. Line 16 was opened, and the reaction liquid (11-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (11-1) was 16.24 kg.

[0462] 2. Step (11-2): Thermal decomposition step of carbamate compound The reaction liquid (11-1) was 16.24 kg, and diphenyl carbonate was 16.24 kg. The reaction liquid (11-1) was fed to the reactor over about 15 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 4.0, and a pressure in the range of 11 to 16 kPa. The pyrolysis reaction was carried out in the same manner as in Synthesis Example 1-1, except that the extraction of phenol was continued for 3 hours after all of the reaction liquid (11-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 13.97 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (11-2)") was purified using a column fractionator to isolate a carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-19).

[0463] [ka]

[0464] Furthermore, analysis by NMR, LC, and gas chromatography revealed that 1,3-bis(isocyanatomethyl)cyclohexane (HXDI) was produced in a yield of 78 mass%.

[0465] 3. Process (11-3): Light boiling separation process The reaction liquid (11-2) was continuously fed at 2.79 kg / hour, and low boiling point separation was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal rate in a steady state through line 34 was 1.90 kg / hour. The amount of the liquid recovered in storage tank 303 was 9.50 kg, and analysis by NMR, LC, and gas chromatography showed that HXDI was recovered in a yield of 77 mass% based on the reaction liquid (11-2) fed.

[0466] 4. Process (11-4): High boiling separation process The liquid recovered in the storage tank 303 in the step (11-3) was used to carry out high boiling separation in the same manner as in Synthesis Example 1-1, except that the operating temperature was 190° C. and the internal pressure was 0.3 kPa. The amount of the liquid recovered in the storage tank 402 was 4.93 kg, and the recovery rate of HMDI was 122 mass%.

[0467] [Synthesis Example 1-12] (Production of PDI and carbonyl compound (I-21) corresponding to PDI) 1. Step (12-1): Production process of carbamate compound The same method as in step (1-1) of Synthesis Example 1-1 was used to synthesize the corresponding carbamate from 1,5-diaminopentane, except that 3.33 kg of 1,5-diaminopentane and 23.20 kg of diphenyl carbonate were used instead of 4-aminomethyl-1,8-octanediamine, 6.48 kg of phenol was mixed with 1,5-diaminopentane, and 6.48 kg of phenol was supplied to the reactor. The reaction liquid was heated to 120°C, and the internal pressure was set to 1.0 kPa, whereby 18.01 kg of phenol in the liquid was extracted.

[0468] The solution after the reaction (hereinafter referred to as "reaction liquid (12-1)") was analyzed by liquid chromatography, and it was found that a carbamate compound corresponding to 1,5-diaminopentane was produced in a yield of 99% by mass. The amount of 1,5-diaminopentane in the reaction liquid (12-1) was 21.48 kg.

[0469] 2. Step (12-2): Thermal decomposition step of carbamate compound The reaction liquid (12-1) was 21.48 kg, and diphenyl carbonate was 21.48 kg. The reaction liquid (12-1) was fed to the reactor over about 11 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 4.5, and a pressure in the range of 20 to 29 kPa. The pyrolysis reaction was carried out in the same manner as in Synthesis Example 1-1, except that phenol extraction was continued for 3 hours after all of the reaction liquid (12-1) was transferred. The mass of the reaction liquid after the reaction was 37.38 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (12-2)") was purified using a column fractionator to isolate a carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-21).

[0470] [ka]

[0471] Furthermore, analysis by NMR and gas chromatography revealed that pentamethylene diisocyanate (PDI) was produced in a yield of 71 mass%.

[0472] 3. Process (12-3): Light boiling separation process The reaction liquid (12-2) was continuously fed at 7.48 kg / hour, and low boiling point separation was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal rate in a steady state from line 34 was 1.20 kg / hour. The amount of the liquid recovered in storage tank 303 was 5.98 kg, and analysis by NMR, LC, and gas chromatography showed that PDI was recovered in a yield of 87 mass% based on the reaction liquid (12-2) fed.

[0473] 4. Process (12-4): High boiling separation process The liquid recovered in the storage tank 303 in the step (12-3) was used to carry out high boiling point separation in the same manner as in Synthesis Example 1-1, except that the operating temperature was 160° C. and the internal pressure was 0.3 kPa. The amount of the liquid recovered in the storage tank 402 was 3.53 kg, and the recovery rate of PDI was 115%.

[0474] [Synthesis Example 1-13] (Production of IPDI and carbonyl compounds (I-22a) to (I-22b) corresponding to IPDI) 1. Step (13-1): Production process of carbamate compound The same method as in step (1-1) of Synthesis Example 1-1 was used to synthesize a corresponding carbamate from isophoronediamine, except that 3.33 kg of isophoronediamine and 13.92 kg of diphenyl carbonate were used instead of 4-aminomethyl-1,8-octanediamine, 3.22 kg of phenol was mixed with isophoronediamine, and 3.22 kg of phenol was supplied to a reactor. The reaction liquid was heated to 120°C, and the internal pressure was set to 1.0 kPa, thereby extracting 9.4 kg of phenol from the liquid.

[0475] The solution after the reaction (hereinafter referred to as "reaction liquid (13-1)") was analyzed by liquid chromatography, and it was found that a carbamate compound corresponding to isophoronediamine was produced in a yield of 99% by mass. The mass of the reaction liquid (13-1) was 14.29 kg.

[0476] 2. Step (13-2): Thermal decomposition step of carbamate compound The reaction liquid (13-2) was 14.29 kg, and diphenyl carbonate was 14.29 kg. The reaction liquid (13-2) was fed to the reactor over about 11 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 4.9, and a pressure in the range of 20 to 29 kPa. The pyrolysis reaction was carried out in the same manner as in Synthesis Example 1-1, except that phenol extraction was continued for 3 hours after all of the reaction liquid (13-2) was transferred. The mass of the reaction liquid after the reaction was 23.44 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (13-2)") was purified using a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-22a) to (I-22b) (hereinafter, this mixture may be referred to as "mixture (I-22)").

[0477] [ka]

[0478] Furthermore, analysis by NMR and gas chromatography revealed that isophorone diisocyanate (IPDI) was produced in a yield of 75 mass %.

[0479] 3. Process (13-3): Light boiling separation process The reaction liquid (13-2) was continuously fed at 4.69 kg / hour, and low boiling point separation was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal rate in a steady state from line 34 was 0.80 kg / hour. The amount of the liquid recovered in storage tank 303 was 3.98 kg, and analysis by NMR, LC, and gas chromatography showed that IPDI was recovered in a yield of 82 mass% based on the reaction liquid (13-2) fed.

[0480] 4. Process (13-4): High boiling separation process The liquid recovered in the storage tank 303 in the step (13-3) was used to carry out high boiling point separation in the same manner as in Synthesis Example 1-1, except that the operating temperature was 190° C. and the internal pressure was 0.3 kPa. The amount of the liquid recovered in the storage tank 402 was 3.18 kg, and the recovery rate of IPDI was 120 mass%.

[0481] [Synthesis Example 1-14] (Production of XDI and carbonyl compound (I-23) corresponding to XDI) 1. Step (14-1): Production process of carbamate compound The same method as in step (1-1) of Synthesis Example 1-1 was used except that 3.33 kg of xylylenediamine and 17.42 kg of diphenyl carbonate were used instead of 4-aminomethyl-1,8-octanediamine, 4.45 kg of phenol was mixed with xylylenediamine, and 4.45 kg of phenol was supplied to the reactor. The corresponding carbamate was synthesized from xylylenediamine, and the reaction liquid was heated to 120°C and the internal pressure was set to 1.0 kPa, thereby extracting 12.64 kg of phenol from the liquid.

[0482] The solution after the reaction (hereinafter referred to as "reaction liquid (14-1)") was analyzed by liquid chromatography, and it was found that a carbamate compound corresponding to xylylenediamine was produced in a yield of 98% by mass. The mass of the reaction liquid (14-1) was 16.99 kg.

[0483] 2. Step (14-2): Thermal decomposition step of carbamate compound The reaction liquid (14-1) was used in an amount of 16.99 kg, and diphenyl carbonate was used in an amount of 16.99 kg. The reaction liquid (14-1) was fed to the reactor over about 11 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 4.5, and a pressure in the range of 20 to 29 kPa. The pyrolysis reaction was carried out in the same manner as in Synthesis Example 1-1, except that the extraction of phenol was continued for 3 hours after all of the reaction liquid (14-2) was transferred. The mass of the reaction liquid after the reaction was 28.89 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (14-2)") was purified using a column fractionator to isolate a carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-23).

[0484] [ka]

[0485] Furthermore, analysis by NMR and gas chromatography revealed that xylylene diisocyanate (XDI) was produced in a yield of 78 mass%.

[0486] 3. Process (14-3): Light boiling separation process The reaction liquid (14-2) was continuously fed at 5.78 kg / hour, and low boiling point separation was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal rate in a steady state from line 34 was 0.87 kg / hour. The amount of the liquid recovered in storage tank 303 was 3.98 kg, and analysis by NMR, LC, and gas chromatography showed that XDI was recovered in a yield of 88 mass% based on the reaction liquid (14-2) fed.

[0487] 4. Process (14-4): High boiling separation process The liquid recovered in storage tank 303 in step (14-3) was used to carry out high boiling point separation in the same manner as in Synthesis Example 1-1, except that the operating temperature was 170° C. and the internal pressure was 0.3 kPa. The amount of the liquid recovered in storage tank 402 was 3.87 kg, and the recovery rate of XDI was 125 mass%.

[0488] [Synthesis Example 1-15] (Production of MDI and carbonyl compound (I-13) corresponding to MDI) 1. Step (15-1): Production process of carbamate compound With line 14 closed, 3.33 kg (16.8 mol) of 4,4'-diaminodiphenylmethane was supplied from storage tank 101 through line 11 to baffled SUS reaction vessel 104, and 2.53 kg (27.0 mol) of phenol was supplied from storage tank 102 through line 12 to the reaction vessel 104, and homogenized by stirring. Next, with line 16 closed, 2.53 kg (27.0 mol) of phenol was supplied from storage tank 102 through line 15 to baffled SUS reaction vessel 105, and 11.96 kg (55.6 mol) of diphenyl carbonate was supplied from storage tank 103 through line 13 to the reaction vessel 105. The liquid temperature in the reaction vessel 105 was adjusted to 65° C. and homogenized by stirring, and then a mixed liquid of 4,4'-diaminodiphenylmethane and phenol was supplied from the reaction vessel 104 through the line 14 so that the internal temperature did not exceed 70° C. After continuing stirring for 2 hours, the reaction liquid was heated to 120° C. and the internal pressure was set to about 1 kPa, whereby 7.58 kg of phenol in the liquid was extracted into the storage tank 107 through the line 17 and the condenser A11.

[0489] The solution after the reaction (hereinafter referred to as "reaction liquid (15-1)") was analyzed by liquid chromatography, and as a result, a carbamate compound corresponding to 4,4'-diaminodiphenylmethane was produced in a yield of 95% by mass. Line 16 was opened, and the reaction liquid (15-1) was transferred to storage tank 106 via line 16. The mass of the reaction liquid (15-1) was 12.77 kg.

[0490] 2. Step (15-2): Pyrolysis step of carbamate compound The reaction liquid (15-1) was used in an amount of 12.77 kg, and diphenyl carbonate was used in an amount of 12.77 kg. The reaction liquid (15-1) was supplied to the reactor over about 10 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 0.8, and a pressure in the range of 11 to 16 kPa. The pyrolysis reaction was carried out in the same manner as in Synthesis Example 1-1, except that the extraction of phenol was continued for 3 hours after all of the reaction liquid (15-1) was transferred. The mass of the reaction liquid transferred to the storage tank 205 was 11.75 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (15-2)") was purified using a column fractionation device to isolate a carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-13).

[0491] [ka]

[0492] Furthermore, analysis by NMR and gas chromatography revealed that MDI was produced in a yield of 70 mass%.

[0493] 3. Process (15-3): Light boiling separation process The reaction liquid (15-2) was continuously fed at 2.35 kg / hour, and low boiling point separation was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal rate in a steady state through line 34 was 1.97 kg / hour. The amount of the liquid recovered in storage tank 303 was 9.87 kg, and analysis by NMR, LC, and gas chromatography showed that MDI was recovered in a yield of 79 mass% based on the reaction liquid (15-2) fed.

[0494] 4. Process (15-4): High boiling separation process The liquid recovered in the storage tank 303 in the step (15-3) was used to carry out high boiling separation in the same manner as in Synthesis Example 1-1, except that the operating temperature was 170° C. and the internal pressure was 0.3 kPa. The amount of the liquid recovered in the storage tank 402 was 4.54 kg, and the recovery rate of MDI was 130% by mass.

[0495] [Synthesis Example 1-16] (Production of TDI and carbonyl compounds (I-24a) to (I-24b) corresponding to TDI) 1. Step (16-1): Production process of carbamate compound The same method as in step (1-1) of Synthesis Example 1-1 was used to synthesize the corresponding carbamate from tolylene-2,4-diamine, except that 3.33 kg of tolylene-2,4-diamine and 19.41 kg of diphenyl carbonate were used instead of 4-aminomethyl-1,8-octanediamine, 5.15 kg of phenol was mixed with xylylenediamine, and 5.15 kg of phenol was supplied to the reactor. The reaction liquid was heated to 120°C, and the internal pressure was set to 1.0 kPa, whereby 14.49 kg of phenol in the liquid was extracted.

[0496] The solution after the reaction (hereinafter referred to as "reaction liquid (16-1)") was analyzed by liquid chromatography, and the corresponding carbamate compound was produced in a yield of 96% by mass. The mass of the reaction liquid (16-1) was 18.54 kg.

[0497] 2. Step (16-2): Thermal decomposition step of carbamate compound The reaction liquid (16-1) was used in an amount of 18.54 kg, and diphenyl carbonate was used in an amount of 18.54 kg. The reaction liquid (16-1) was fed to the reactor over a period of about 11 minutes to start the reaction. The reaction was carried out at a jacket temperature of 238°C, an internal temperature of 230°C, a reflux ratio of 4.7, and a pressure in the range of 20 to 29 kPa. The pyrolysis reaction was carried out in the same manner as in Synthesis Example 1-1, except that phenol extraction was continued for 3 hours after all of the reaction liquid (16-1) had been transferred. The mass of the reaction liquid after the reaction was 11.75 kg. A part of this reaction liquid (hereinafter referred to as "reaction liquid (16-2)") was purified using a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-24a) to (I-24b) (hereinafter, this mixture may be referred to as "mixture (I-24)").

[0498] [ka]

[0499] Furthermore, analysis by NMR and gas chromatography revealed that toluylene diisocyanate (TDI) was produced in a yield of 71 mass%.

[0500] 3. Process (16-3): Light boiling separation process The reaction liquid (16-2) was continuously fed at 2.35 kg / hour, and low boiling point separation was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal rate in a steady state through line 34 was 0.94 kg / hour. The amount of the liquid recovered in storage tank 303 was 4.70 kg, and analysis by NMR, LC, and gas chromatography showed that TDI was recovered in a yield of 85 mass% based on the reaction liquid (16-2) fed.

[0501] 4. Process (16-4): High boiling separation process The liquid recovered in the storage tank 303 in the step (16-3) was used to carry out high boiling point separation in the same manner as in Synthesis Example 1-1, except that the operating temperature was 160° C. and the internal pressure was 0.3 kPa. The amount of the liquid recovered in the storage tank 402 was 3.27 kg, and the recovery rate of TDI was 119 mass%.

[0502] <Production of Carvert Compound (III)> [Synthesis Example 2-1] (Production of Carbamate Compounds (III-1a) to (III-24b)) To 100.0 g of each isocyanate compound, a hydroxy compound (V) of the type and amount shown in the table below was added, and the mixture was allowed to react at 120°C for 3 hours to synthesize a carbamate compound (III) corresponding to each isocyanate compound. The carbamate compounds (III-1a) to (III-1c) are referred to as the mixture (III-1), the carbamate compounds (III-2a) to (III-2c) are referred to as the mixture (III-2), the carbamate compounds (III-3a) to (III-3c) are referred to as the mixture (III-3), the carbamate compounds (III-4a) to (III-4c) are referred to as the mixture (III-4), the carbamate compounds (III-5a) to (III-5b) are referred to as the mixture (III-5), the carbamate Compounds (III-7a) to (III-7b) were obtained as a mixture (III-7), carbamate compounds (III-8a) to (III-8b) were obtained as a mixture (III-8), carbamate compounds (III-10a) to (III-10b) were obtained as a mixture (III-10), carbamate compounds (III-22a) to (III-22b) were obtained as a mixture (III-11), and carbamate compounds (III-24a) to (III-24b) were obtained as a mixture (III-24). The structures of these carbamate compounds are described below.

[0503] [Table 1]

[0504] [Examples 1 to 62 and Comparative Examples 1 to 6] (Production of Isocyanate Compositions A-a1 to A-a46 and A-b1 to A-b6) The isocyanate compound (II), the carbonyl compound (I), the carbamate compound (III), and the carbonate ester (IV) were mixed so that the types and contents thereof were as shown in each of the tables below, to obtain each isocyanate composition. The details of the types of the isocyanate compound (II), carbonyl compound (I), carbamate compound (III), and carbonate ester (IV) used are as follows:

[0505] (Isocyanate compound (II)) As the isocyanate compound (II), the compound shown below obtained by the above synthesis method was used. TTI: 4-isocyanatomethyl-1,8-octamethylene diisocyanate LTI: 2-isocyanatoethyl-2,6-diisocyanatohexanoate (lysine triisocyanate) LDI: Lysine methyl ester diisocyanate LDI-Et: Lysine ethyl ester diisocyanate HDI: Diisocyanatohexane HMDI: Methylene bis(cyclohexyl isocyanate) HXDI: 1,3-bis(isocyanatomethyl)cyclohexane PDI: Diisocyanatopentane IPDI: 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate XDI: Diisocyanatoxylene MDI: Diisocyanatodiphenylmethane TDI: Diisocyanatotoluene

[0506] (Carbonyl compounds (I)) The carbonyl compounds (I) used were the compounds represented by the following formulae (I-1a) to (I-24b) obtained by the above synthesis method. Carbonyl compounds (I-1a) to (I-1c) are the mixture (I-1), carbonyl compounds (I-2a) to (I-2c) are the mixture (I-2), carbonyl compounds (I-3a) to (I-3c) are the mixture (I-3), carbonyl compounds (I-4a) to (I-4c) are the mixture (I-4), carbonyl compounds (I-5a) to (I-5b) are the mixture (I-5), and carbonyl Compounds (I-7a) to (I-7b) were used as the mixture (I-7), carbonyl compounds (I-8a) to (I-8b) as the mixture (I-8), carbonyl compounds (I-10a) to (I-10b) as the mixture (I-10), carbonyl compounds (I-22a) to (I-22b) as the mixture (I-11), and carbonyl compounds (I-24a) to (I-24b) as the mixture (I-24).

[0507] [ka]

[0508] [ka]

[0509] [ka]

[0510] [ka]

[0511] [ka]

[0512] [ka]

[0513] (Carbamate compound (III)) The carbamate compounds (III) used were the compounds represented by the following formulae (III-1a) to (III-24b) obtained by the above synthesis method. The carbamate compounds (III-1a) to (III-1c) were the mixture (III-1), the carbamate compounds (III-2a) to (III-2c) were the mixture (III-2), the carbamate compounds (III-3a) to (III-3c) were the mixture (III-3), the carbamate compounds (III-4a) to (III-4c) were the mixture (III-4), the carbamate compounds (III-5a) to (III-5b) were the mixture (III-5), and the ... and the carbamate compounds (III-1b) were the mixture (III-1). The carbamate compounds (III-7a) to (III-7b) were used as the mixture (III-7), the carbamate compounds (III-8a) to (III-8b) were used as the mixture (III-8), the carbamate compounds (III-10a) to (III-10b) were used as the mixture (III-10), the carbamate compounds (III-22a) to (III-22b) were used as the mixture (III-11), and the carbamate compounds (III-24a) to (III-24b) were used as the mixture (III-24).

[0514] [ka]

[0515] [ka]

[0516] [ka]

[0517] [ka]

[0518] [ka]

[0519] [ka]

[0520] (Carbonate (IV)) As the carbonate ester (IV), the compound shown below was used. DPC: Diphenyl carbonate GAC: bis(2-methoxyphenyl) carbonate DPCP: Bis(4-cumylphenyl) carbonate

[0521] The obtained isocyanate compositions were subjected to the above-mentioned storage test and evaluated. The results are shown in the following tables.

[0522] [Table 2]

[0523] [Table 3]

[0524] [Table 4]

[0525] [Table 5]

[0526] [Table 6]

[0527] As can be seen from each of the above tables, in the isocyanate compositions A-a1 to A-a62 (Examples 1 to 62) containing specific amounts of the isocyanate compound (II) and the carbonyl compound (I), coloring was sufficiently suppressed and storage stability was excellent. Furthermore, in the isocyanate compositions A-a1 to A-a8, A-a11 to A-a18, and A-a21 to A-a62 (Examples 1 to 8, 11 to 18, and 21 to 62), which further contain a carbamate compound (III) and a carbonate ester (IV) in addition to the isocyanate compound (II) and the carbonyl compound (I), the change in color difference before and after storage was smaller, the amount of modification was also smaller, and the storage stability was particularly excellent. On the other hand, in the isocyanate compositions A-b1 and A-b4 (Comparative Examples 1 and 4) in which the content of the isocyanate compound (II) was less than 97 mass% relative to the total mass of the isocyanate composition, the change in color difference before and after storage was large, the amount of modification was also large, and the storage stability was poor. In addition, the carbonyl compound (I) is not contained, or the content of the carbonyl compound (I) is 1.0 × 10 4 In the isocyanate compositions A-b2, A-b3, A-b5, and A-b6 (Comparative Examples 2, 3, 5, and 6) having a content exceeding ppm by mass, the change in color difference before and after storage was large, the amount of modification was also large, and the storage stability was poor. [Industrial Applicability]

[0528] According to the carbonyl compound and the method for producing the same of the present embodiment, a novel carbonyl compound can be provided. The method for producing an isocyanate compound of the present embodiment is a method using the carbonyl compound, and can prevent by-products from adhering to an apparatus during the production of the isocyanate compound, thereby improving the yield of the isocyanate compound.

[0529] Moreover, according to the isocyanate composition of the present embodiment, it is possible to provide an isocyanate composition in which coloration is sufficiently suppressed and which has excellent storage stability. [Explanation of symbols]

[0530] 11,12,13,14,15,16,17,21,22,23,24,25,26,27,28,31,32,33,34,35,36,41,42,43: Line A11, A21, A31, A41: Capacitor A32: Reboiler 101,102,103,106,107,202,204,205,302,303,402,403:Storage tank 104, 105, 201: Stainless steel reaction vessel with baffles 203,301: Multi-stage distillation column 401: Thin film distillation apparatus

Claims

1. A carbonyl compound represented by the following general formula (I): 【Chemistry 1】 (In general formula (I), R １１ is a group represented by the following formula (Ia-1), (Ia-2), (Ia-3), (Ia-5), (Ia-6), (Ia-12), (Ia-14), (Ia-18), or (Ia-19), and R １２ is a phenyl group, a methoxyphenyl group, or a cumylphenyl group. n11 is 1, n12 is 1 or 2, and the sum of n11 and n12 is 2 or 3. 【Chemistry 2】 (In each formula, the dashed lines represent bonds.)

2. A method for producing an isocyanate compound, comprising: purifying a reaction liquid containing an isocyanate compound represented by the following general formula (II) by distillation in the presence of the carbonyl compound according to claim 1; and continuously recovering the isocyanate compound as a gas phase component. 【Chemistry 3】 (In general formula (II), R ２１ is the above R １１ n21 is 2 or 3, and satisfies the relation: n21 = n11 + n12.

3. Relative to the total mass of the isocyanate composition, 97% by mass or more of an isocyanate compound; 2.0 mass ppm or more 1.0×10 ４ A carbonyl compound represented by the following general formula (I) in an amount of not more than ppm by mass, one or more compounds selected from the group consisting of carbamate compounds and carbonate esters, each of which is 2.0 ppm by mass or more and 1.0 × 10 4 ppm by mass or less, relative to the total mass of the isocyanate composition; Contains The isocyanate composition, wherein the isocyanate compound and the carbonyl compound are different compounds. 【Chemistry 4】 (In general formula (I), R １１ is a group represented by the following formula (Ia-1), (Ia-2), (Ia-3), (Ia-5), (Ia-6), (Ia-12), (Ia-14), (Ia-18), or (Ia-19), and R １２ is a phenyl group, a methoxyphenyl group, or a cumylphenyl group. n11 is 1, n12 is 1 or 2, and the sum of n11 and n12 is 2 or 3. 【Chemistry 5】 (In each formula, the dashed lines represent bonds.)

4. The isocyanate composition according to claim 3 , wherein the isocyanate compound is a compound represented by the following general formula (II): 【Chemistry 6】 (In general formula (II), R ２１ is R １１ n21 is 2 or 3, and satisfies the relation: n21 = n11 + n12.

5. The isocyanate composition according to claim 3 or 4, wherein the carbamate compound is a compound represented by the following general formula (III): 【Chemistry 7】 (In general formula (III), R ３１ is an organic group having a valence of (n31+n32), and has the formula: R ３１ = R １１ Satisfy. R ３２ is a monovalent organic group, and has the formula: R ３２ = R １２ n31 is an integer between 1 and 8, n32 is an integer between 0 and 7, the sum of n31 and n32 is an integer between 2 and 8, and the relation: n31 + n32 = n11 + n12 is satisfied.

6. The isocyanate composition according to claim 3 or 4, wherein the carbonate ester is a compound represented by the following general formula (IV): 【Chemistry 8】 (In general formula (IV), R ４１ and R ４２ are each independently a monovalent organic group, and are represented by the formula: R ４１ = R ４２ = R １２ Satisfy.)

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