Polyisocyanate composition and method for producing isocyanate compound

Abstract

A polyisocyanate composition containing at least one compound represented by any one of general formulae (I), (II), and (III), and a polyisocyanate compound. A method for producing an isocyanate compound, which comprises a reaction step for obtaining an isocyanate compound by decomposing a blocked isocyanate compound into a blocking agent and an isocyanate compound by heat-treating the blocked isocyanate compound in the presence of a compound having a structure represented by general formula (I) and / or general formula (II).

Description

Technical Field

[0001] This invention relates to a method for manufacturing polyisocyanate compositions and isocyanate compounds.

[0002] This application claims priority based on Japanese Patent Application Nos. 2023-094942, 2023-094699, 2023-094710, 2023-094723 and 2023-094958, filed on June 8, 2023, the contents of which are incorporated herein by reference. Background Technology

[0003] Polyisocyanate compounds are used in polyurethane synthesis, curing agents, and are widely used in flexible foams, rigid foams, elastomers, adhesives, coatings, and bonding agents.

[0004] For example, Patent Document 1 describes an isocyanate composition containing an isocyanate compound with three or more functions and a compound having at least one unsaturated bond other than the unsaturated bond constituting the aromatic ring.

[0005] Patent document 2 discloses a polyisocyanate composition comprising: a polyisocyanate; and at least one inert compound having an unsaturated bond, or selected from the group consisting of hydrocarbon compounds, ether compounds, sulfide compounds, halogenated hydrocarbon compounds, silicon-containing hydrocarbon compounds, silicon-containing ether compounds, and silicon-containing sulfide compounds.

[0006] In addition, isocyanates are widely used as raw materials in the manufacture of polyurethane foams, coatings, adhesives, etc. The main industrial manufacturing method of isocyanates is the reaction of amine compounds with phosgene (phosgene process), and almost all of the world's production is produced through the phosgene process. However, there are many problems with phosgene as a raw material and hydrogen chloride as a byproduct in the phosgene process.

[0007] Against this backdrop, there is a desire for a method to manufacture isocyanates without using phosgene. For example, Patent Document 3 describes a method for producing 1,6-hexamethylene diisocyanate by thermally decomposing 1,6-hexamethylene dicarboxylate in the presence of a specific catalyst. Furthermore, Patent Document 4 describes a method for synthesizing a carbamate compound by reacting a diamine with dimethyl carbonate in the presence of a basic catalyst, followed by thermally decomposing the carbamate compound in the presence of a catalyst to produce a diisocyanate compound.

[0008] Furthermore, isocyanates are highly reactive and readily react with compounds such as water. Therefore, to improve stability, isocyanates are sometimes converted into terminal-capped isocyanates, which are then regenerated into isocyanates by heating to dissociate the capping agent before use. Terminal-capped isocyanates exhibit low reactivity with active hydrogen compounds, can be stored stably, and are less toxic than isocyanates, making them useful as single-component coatings, adhesives, and molding compounds.

[0009] Furthermore, capped isocyanates possess the property of dissociating into isocyanates and capping agents through thermal decomposition. Therefore, capped isocyanates can be thermally decomposed into isocyanates and capping agents, and the resulting isocyanates and capping agents can be separated after or simultaneously with thermal decomposition. The separated isocyanates and capping agents can also be used as raw materials in the manufacture of isocyanates, thus proving useful.

[0010] Various methods are known for manufacturing capped isocyanates. Examples include: methods that directly react isocyanates with capping agents to produce capped isocyanates; methods that react amines with phosgene and then react the resulting carbamoyl chloride with a capping agent to produce capped isocyanates; methods that react carbamic acid with a capping agent and a condensing agent to produce capped isocyanates; methods that react amines with carbonate derivatives to produce capped isocyanates containing compounds derived from carbonate derivatives; and methods that react amines with carbonate derivatives and a capping agent to produce capped isocyanates.

[0011] In cases where amines are used as raw materials to manufacture capped isocyanates, as described in Patent Document 5, a side reaction sometimes occurs with the resulting capped isocyanate to generate ureidyl groups.

[0012] In the case of manufacturing isocyanates by thermally decomposing such a ureidyl group-capped isocyanate composition into isocyanate and capping agent, and separating the resulting isocyanate and capping agent after or simultaneously with thermal decomposition, the formation of biuret through the reaction of the generated isocyanate with the ureidyl group may be accompanied by an increase in the amount of byproducts generated.

[0013] Existing technical documents

[0014] Patent documents

[0015] Patent Document 1: International Publication No. 2018 / 070539

[0016] Patent Document 2: International Publication No. 2014 / 069605

[0017] Patent Document 3: Japanese Patent Application Publication No. 6-239826

[0018] Patent Document 4: Japanese Patent Application Publication No. 64-85956

[0019] Patent Document 5: Japanese Patent Application Publication No. 2022-180170 Summary of the Invention

[0020] The problem that the invention aims to solve

[0021] In applications where appearance quality is critical, such as in the production of polyurethane raw materials, the minimal coloring of polyisocyanates is important. However, isocyanates are prone to oxidation due to oxygen in the air, making them susceptible to deterioration or discoloration. Furthermore, when isocyanate polymers are manufactured through the polymerization of diisocyanates, the isocyanates are also prone to discoloration due to the catalysts or solvents used in the polymerization reaction.

[0022] Furthermore, in the method for manufacturing isocyanate compounds, when end-capped isocyanate compounds are thermally decomposed in the presence of a catalyst to obtain isocyanate compounds, increasing the thermal decomposition rate will be accompanied by an increase in the amount of byproducts generated.

[0023] One aspect of the present invention is made in view of the above circumstances, and its object is to provide a polyisocyanate composition with excellent storage stability and color inhibition.

[0024] One aspect of the present invention is made in view of the above circumstances, and its object is to provide a method for manufacturing isocyanate compounds that can increase the thermal decomposition rate of the end-capped isocyanate compounds without increasing the amount of by-products generated.

[0025] Methods for solving problems

[0026] That is, the present invention includes the following methods.

[0027] [1] A polyisocyanate composition comprising at least one compound represented by any one of the following general formulas (I), (II), (III), and a polyisocyanate compound.

[0028] [Chemistry 1]

[0029]

[0030] (In general formula (I), R) 1 and R 2 Each is an independent monovalent organic group. R 1 and R 2 They can independently form ring structures from carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds. R 3 (It is an aliphatic hydrocarbon group or a hydrocarbon group containing an aromatic group.)

[0031] [Chemistry 2]

[0032]

[0033] (In general formula (II), R) 210 R is a monovalent organic group. 220 R 230 R 240 and R 250 Each is independently a monovalent organic group or hydrogen. R 210 and R 220 They can bond with each other and form ring structures from carbon-carbon, carbon-oxygen-carbon, or carbon-nitrogen-carbon bonds.

[0034] [Chemistry 3]

[0035]

[0036] (In general formula (III), R) 310 For (n+m) valence organic groups, n is an integer from 0 to 12, m is an integer from 1 to 12, n+m is an integer less than 13, R 320 and R 330 Each is an independent monovalent organic group. R 320 and R 330 They can bond with each other and form ring structures from carbon-carbon, carbon-oxygen-carbon, or carbon-nitrogen-carbon bonds. R 320 and R 330 At least one of them has an aromatic group.

[0037] [2] The polyisocyanate composition as described in [1], wherein, based on the total mass of the above-mentioned polyisocyanate compounds, it contains 1.0 × 10⁻¹⁰ ppm or more by mass. 4 At least one compound represented by any one of the above general formulas (I), (II), and (III) in the mass of less than ppm.

[0038] [3] A method for manufacturing an isocyanate compound, comprising the following reaction steps: in the presence of a compound having a structure represented by any one or both of the following general formulas (I) and (II), the end-capped isocyanate compound is decomposed into a capping agent and an isocyanate compound by heat treatment to obtain the isocyanate compound.

[0039] [Chemistry 4]

[0040]

[0041] (In general formula (I), R) 1 and R 2 Each is an independent monovalent organic group. R1 and R 2 They can independently form ring structures from carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds. R 3 (It is an aliphatic hydrocarbon group or a hydrocarbon group containing an aromatic group.)

[0042] [Chemistry 5]

[0043]

[0044] (In general formula (II), R) 210 R is a monovalent organic group. 220 R 230 R 240 and R 250 Each is independently a monovalent organic group or hydrogen. R 210 and R 220 They can bond with each other and form ring structures from carbon-carbon, carbon-oxygen-carbon, or carbon-nitrogen-carbon bonds.

[0045] [4] The method for manufacturing isocyanate compounds as described in [3], wherein the capping agent comprises one or more compounds selected from the group consisting of hydroxyl compounds, amine compounds and ammonia.

[0046] [5] A method for manufacturing an isocyanate compound as described in [3] or [4], wherein the isocyanate compound is an isocyanate compound represented by the following general formula (IV).

[0047] [Chemistry 6]

[0048]

[0049] (In general formula (IV), R) 21 (This refers to an organic group with a valence of n21. n21 is an integer between 1 and 12.)

[0050] [6] A method for manufacturing an isocyanate compound as described in [3] or [4], wherein the capping agent is an aromatic hydroxy compound represented by the following general formula (V).

[0051] [Chemistry 7]

[0052]

[0053] (In general formula (V), ring A) 31 It is an aromatic hydrocarbon ring with 6 to 20 carbon atoms. 31It can be a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, an alkoxycarbonyl group with 1 to 20 carbon atoms, an alkylcarbonyloxy group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aryloxy group with 6 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, or an arylalkyloxy group with 7 to 20 carbon atoms. R 31 Can be used with ring A 31 Bonding forms a ring structure. Additionally, n31 is an integer from 1 to 10.

[0054] [7] A method for manufacturing an isocyanate compound as described in [3] or [4], wherein the capping agent is an aliphatic hydroxy compound represented by the following general formula (VI).

[0055] [Chemistry 8]

[0056]

[0057] (In general formula (VI), R) 41 (Aliphatic hydrocarbon group with 1 to 24 carbon atoms, which may be substituted or unsubstituted and may have an ether, carbonyl, or ester group.)

[0058] [8] A method for manufacturing an isocyanate compound as described in [3] or [4], wherein the capping agent is a secondary amine compound represented by the following general formula (VII).

[0059] [Chemistry 9]

[0060]

[0061] (In general formula (VII), R) 51 and R 52 Each is an independent monovalent organic group. R 51 and R 52 They can bond with each other and form ring structures from carbon-carbon, carbon-oxygen-carbon, or carbon-nitrogen-carbon bonds.

[0062] [9] A method for manufacturing an isocyanate compound as described in [3] or [4], wherein, in the above reaction step, the amount of a compound having the structure represented by any one or both of the above general formulas (I) and (II) is 1 ppm by mass or more relative to the above-described end-capped isocyanate compound.

[0063] The effects of the invention

[0064] The polyisocyanate compositions according to the above method can provide polyisocyanate compositions with excellent storage stability and color inhibition.

[0065] According to the method described above, a method for manufacturing isocyanate compounds can be provided that increases the thermal decomposition rate of end-capped isocyanate compounds without increasing the amount of by-products generated. Detailed Implementation

[0066] The following provides a detailed description of specific embodiments of the present invention (hereinafter referred to as "this embodiment"). This embodiment is merely an illustration of the present invention, and the present invention is not limited to this embodiment. The present invention can be suitably implemented with modifications within its essential scope.

[0067] It should be noted that, in this specification, "active hydrogen" refers to hydrogen atoms bonded to oxygen, sulfur, or nitrogen atoms, as well as hydrogen atoms in active methylene groups. Examples include hydrogen atoms contained in radicals such as -OH, -C(=O)OH, -SH, -NH2, -NH-, and -C(=O)-C(-H)2-C(=O)-.

[0068] <Polyisocyanate Compositions>

[0069] The polyisocyanate composition of this embodiment contains at least one compound represented by any one of general formulas (I), (II), and (III), as well as a polyisocyanate compound.

[0070] The polyisocyanate composition of this embodiment may contain optional components other than compounds (I), (II), (III) and polyisocyanate compounds, depending on the use, purpose, etc.

[0071] The polyisocyanate composition of this embodiment can be used in polyurethane synthetic materials, curing agents, etc.

[0072] The polyisocyanate composition of this embodiment can be used in a wide range of fields such as flexible foams, rigid foams, elastomers, adhesives, coatings, and binders.

[0073] The polyisocyanate composition 1 of this embodiment contains a compound represented by general formula (I) and a polyisocyanate compound. Hereinafter, "the compound represented by general formula (I)" will sometimes be referred to as "compound (I)".

[0074] The polyisocyanate composition 2 of this embodiment contains a compound represented by general formula (II) and a polyisocyanate compound. Hereinafter, "the compound represented by general formula (II)" will sometimes be referred to as "compound (II)".

[0075] The polyisocyanate composition 3 of this embodiment contains a compound represented by general formula (III) and a polyisocyanate compound. Hereinafter, "compound represented by general formula (III)" will sometimes be referred to as "compound (III)".

[0076] The polyisocyanate composition 4 of this embodiment contains two or more compounds represented by general formulas (I), (II), and (III), as well as a polyisocyanate compound.

[0077] One embodiment of the polyisocyanate composition 4 contains compounds represented by general formulas (I), (II) and (III), as well as a polyisocyanate compound.

[0078] Polyisocyanate Composition 1

[0079] The polyisocyanate composition 1 of this embodiment contains compound (I) and a polyisocyanate compound.

[0080] [Compound (I)]

[0081] Compound (I) is represented by the following general formula (I).

[0082] [Chemistry 10]

[0083]

[0084] (In general formula (I), R) 1 and R 2 Each is an independent monovalent organic group. R 1 and R 2 They can independently form ring structures from carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds. R 3 (It is an aliphatic hydrocarbon group or a hydrocarbon group containing an aromatic group.)

[0085] [R 1 and R 2 ]

[0086] In the above general formula (I), R 1 and R 2 Each is an independent monovalent organic group. R 1 and R 2 They can form ring structures independently of each other by carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds.

[0087] Where R 1 and R 2 Each is preferably a monovalent aliphatic hydrocarbon group with or without substituents and a monovalent aromatic hydrocarbon group with or without substituents and a carbon number of 6 to 70.

[0088] R 1 and R 2 When at least one of them is selected as an aliphatic hydrocarbon group, the number of carbon atoms is preferably 1 to 70 or less, more preferably 1 to 20 or less, even more preferably 1 to 12 or less, and particularly preferably 1 to 10 or less.

[0089] As R 1 and R 2 The aliphatic hydrocarbon groups in the text can be exemplified by straight-chain alkyl groups (without substitution or with substituents), branched alkyl groups, cycloalkyl groups, etc. Substituents for these aliphatic hydrocarbon groups can include, for example, hydroxyl groups, cyano groups, halogen atoms, etc. Halogen atoms can be exemplified by, for example, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0090] As R 1 and R 2 The aliphatic hydrocarbon group in the formula can specifically include isomers of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, and cyclohexyl. Preferably, the aliphatic hydrocarbon group is unsubstituted and has 1 to 12 carbon atoms, and preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl.

[0091] R 1 and R 2 When an aromatic hydrocarbon group is selected from at least one of the groups, the number of carbon atoms is preferably 6 or more and 70 or less, more preferably 6 or more and 20 or less, even more preferably 6 or more and 12 or less, and particularly preferably 6 or more and 10 or less.

[0092] As R 1 and R 2 Aromatic hydrocarbon groups in R can include unsubstituted or substituted aryl and aralkyl groups. Substituents for these aromatic hydrocarbon groups can include aliphatic hydrocarbon groups, hydroxyl groups, cyano groups, and halogen atoms. 1 and R 2 Aliphatic hydrocarbon groups selected as substituents for aromatic hydrocarbon groups can be exemplified by those in R... 1 and R 2 The same group is exemplified as an aliphatic hydrocarbon group. Examples of halogen atoms that can be substituents include fluorine, chlorine, bromine, and iodine atoms.

[0093] As R 1 and R 2 The aromatic hydrocarbon groups in it, specifically, can include phenyl, naphthyl, anthraceneyl, pyrene, phenanthryl, o-tolyl, m-tolyl, p-tolyl, benzyl, phenethyl, etc.

[0094] In R 1 and R 2 When they bond together to form a ring structure, R 1 and R 2 The bonded groups are divalent organic groups. As R... 1 and R 2 The bonded groups are preferably substituted or unsubstituted divalent aliphatic hydrocarbon groups with 1 to 70 carbon atoms or divalent aromatic hydrocarbon groups with 6 to 70 carbon atoms, and may have ether, carbonyl, ester, imino (-NH-), amide or imide groups.

[0095] [R 3 ]

[0096] In general formula (I), R 3 It is an aliphatic hydrocarbon group or a hydrocarbon group with an aromatic group.

[0097] As R 3 The aliphatic hydrocarbon group in the formula can specifically include isomers of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, and cyclohexyl. Preferably, the aliphatic hydrocarbon group is unsubstituted and has 1 to 12 carbon atoms, and preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl.

[0098] In R 3 When an aromatic hydrocarbon group is selected, the number of carbon atoms is preferably 6 or more and 70 or less, more preferably 6 or more and 20 or less, even more preferably 6 or more and 12 or less, and particularly preferably 6 or more and 10 or less.

[0099] As R 3 Aromatic hydrocarbon groups in R can include unsubstituted or substituted aryl and aralkyl groups. Substituents for these aromatic hydrocarbon groups can include aliphatic hydrocarbon groups, hydroxyl groups, cyano groups, and halogen atoms. 3 Aliphatic hydrocarbon groups selected as substituents for aromatic hydrocarbon groups can be exemplified by those in R... 3 The same group is exemplified as an aliphatic hydrocarbon group. Examples of halogen atoms that can be substituents include fluorine, chlorine, bromine, and iodine atoms.

[0100] As R 3 The aromatic hydrocarbon groups in it, specifically, can include phenyl, naphthyl, anthraceneyl, pyrene, phenanthryl, o-tolyl, m-tolyl, p-tolyl, benzyl, phenethyl, etc.

[0101] As compound (I), the compound represented by the following general formula (I-1) is preferred.

[0102] [Chemistry 11]

[0103]

[0104] In general formula (I-1), R 11 R is a monovalent aliphatic hydrocarbon group with 1 to 70 carbon atoms (substituted or unsubstituted) or a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms (substituted or unsubstituted). 12 R is a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted, or a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms, either substituted or unsubstituted. 13 It is a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted, or a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms, either substituted or unsubstituted.

[0105] [R 11 ]

[0106] In general formula (I-1), R 11 It refers to a monovalent aliphatic hydrocarbon group with 1 to 70 carbon atoms, either substituted or unsubstituted, or a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms, either substituted or unsubstituted. As R 11 Specifically, examples include isomers of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, and p-tolyl. Preferably, the isomers are unsubstituted aliphatic hydrocarbon groups with 1 to 12 carbon atoms, and preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl.

[0107] [R 12 ]

[0108] In general formula (I-1), R 12 It is a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted, or a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms, either substituted or unsubstituted. As R 12Specifically, examples include isomers of hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, etc. Preferably, the isomers are unsubstituted aliphatic hydrocarbon groups with 1 to 12 carbon atoms, and preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl.

[0109] [R 13 ]

[0110] In general formula (I-1), R 13 R is a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted, or a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms, either substituted or unsubstituted. 13 Examples of examples include monovalent aliphatic hydrocarbon groups with 1 to 12 carbon atoms, either substituted or unsubstituted, and monovalent aromatic hydrocarbon groups with 6 to 12 carbon atoms. As R 13 Specifically, examples include isomers of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, and p-tolyl. Preferably, the isomers are unsubstituted aliphatic hydrocarbon groups with 1 to 12 carbon atoms, and preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl.

[0111] In general formula (I-1), R 13 When the group is a monovalent aromatic hydrocarbon with 6 to 12 carbon atoms, it is preferably a phenyl group with or without substituents. As R 13 The phenyl group may have substituents, such as aliphatic hydrocarbon groups or aromatic hydrocarbon groups, and may include alkyl groups with 1 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, or aralkyl groups with 7 to 12 carbon atoms.

[0112] Examples of substituents on the benzene ring that are ether groups include alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 6 to 12 carbon atoms, or aralkyloxy groups with 7 to 12 carbon atoms. Examples of substituents on the benzene ring that are carbonyl groups include alkylcarbonyl groups with 1 to 12 carbon atoms, arylcarbonyl groups with 6 to 12 carbon atoms, or aralkylcarbonyl groups with 7 to 12 carbon atoms.

[0113] Examples of substituents on the benzene ring that have an ester group include alkoxycarbonyl or alkylcarbonyloxy groups with 1 to 12 carbon atoms, aryloxycarbonyl or arylcarbonyloxy groups with 6 to 12 carbon atoms, or aralkyloxycarbonyl or aralkylcarbonyloxy groups with 7 to 12 carbon atoms.

[0114] Specifically, examples of substituents for the benzene ring include various isomers of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, and cumyl. Among these, unsubstituted aliphatic hydrocarbon groups with 1 to 12 carbon atoms are preferred, with methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl being the most preferred.

[0115] As compound (I), the compound represented by the following general formula (I-2) is preferred.

[0116] [Chemistry 12]

[0117]

[0118] In general formula (I-2), R 22 R is a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted, or a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms, either substituted or unsubstituted. 23 It is a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted, or a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms, either substituted or unsubstituted.

[0119] [R 22 ]

[0120] In general formula (I-2), R 22 The specific details are the same as those for R above. The R is a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted, or a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms, either substituted or unsubstituted. 12 The explanation is the same as in the previous text.

[0121] In general formula (I-2), R 22 Preferably, it is a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or an unsubstituted phenyl group.

[0122] [R 23 ]

[0123] In general formula (I-2), R 23The specific details are the same as those for R above. The R is a monovalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted, or a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms, either substituted or unsubstituted. 13 The explanation is the same as in the previous text.

[0124] In general formula (I-2), R 23 Preferably, it is a straight-chain or branched alkyl group, substituted or unsubstituted phenyl group having 1 to 10 carbon atoms. 23 In the case of a phenyl group having a substituent, examples of substituents include straight-chain or branched alkyl groups having 1 to 10 carbon atoms.

[0125] Compound (I) functions as an ultraviolet absorber. Therefore, by using a polyisocyanate composition containing compound (I), the color modification of the polyisocyanate compound caused by ultraviolet radiation can be reduced even when stored outdoors.

[0126] Compound (I) suppresses light-induced excitation of the chromophore, thus reducing the likelihood of free radical generation upon light irradiation. Compound (I) also acts as a storage stabilizer, resulting in excellent storage stability of polyisocyanate compositions containing compound (I).

[0127] To improve the storage stability and color inhibition of the polyisocyanate composition, it is preferable to increase the content of compound (I). However, if the content of compound (I) is too high, it may affect the manufacturing cost and application of the polyisocyanate composition.

[0128] Based on the total mass of the polyisocyanate compounds, polyisocyanate composition 1 preferably contains 1.0 ppm or more of 5.0 × 10⁻⁶. 4 Compound (I) containing less than 1.0 ppm by mass, more preferably containing 1.0 × 10⁻¹⁰ ppm by mass or more. 4 Compounds (I) with a mass of less than ppm.

[0129] Compound (I) can be a commercially available product or a compound synthesized by a known manufacturing method.

[0130] Commercially available examples of compound (I) include: Angene International Limited, product number: AG00AJDF, name: N-Methylcarbanilic acid phenylester 95%, CAS number: 13599-69-4.

[0131] As a method for synthesizing compound (I), the corresponding chloroformate and the corresponding amine are stirred under reflux from room temperature in a suitable solvent in the presence of a neutralizing agent such as hydrochloric acid, which is a byproduct of triethylamine. Alternatively, the corresponding carbamoyl chloride and the corresponding alcohol are stirred under reflux from room temperature in a suitable solvent in the presence of a neutralizing agent such as hydrochloric acid, which is a byproduct of triethylamine. A catalyst such as N,N-dimethyl-4-aminopyridine (DMAP) may also be used as needed. The resulting compound (I) is purified using existing methods.

[0132] Polyisocyanate Composition 2

[0133] The polyisocyanate composition 2 of this embodiment contains compound (II) and a polyisocyanate compound.

[0134] [Compound (II)]

[0135] Compound (II) is represented by the following general formula (II). Compound (II) is sometimes referred to as "quinazolinedione compound (II)".

[0136] [Chemistry 13]

[0137]

[0138] (In general formula (II), R) 210 R is a monovalent organic group. 220 R 230 R 240 and R 250 Each is independently a monovalent organic group or hydrogen. R 210 and R 220 They can bond with each other and form ring structures from carbon-carbon, carbon-oxygen-carbon, or carbon-nitrogen-carbon bonds.

[0139] The quinazoline dione compound (II) has a quinazoline-2,4(1H,3H)-dione structure (sometimes referred to below as the "quinazoline dione structure"). The quinazoline dione structure contains an active hydrogen in the -C(=O)-NH-C(=O)- group.

[0140] The -C(=O)-NH-C(=O)- group contained in the quinazolinidone structure can exhibit tautomerism represented by -C(-OH)=NC(=O)- or -C(=O)-N=C(-OH)-.

[0141] The inventors discovered that by manufacturing end-capped isocyanates in the presence of specific amine compounds having aromatic groups, the problems of thermal modification and coloring can be solved, thus completing the present invention.

[0142] It is known in the prior art that compounds containing an amino group and in which the amino group is bonded to an aromatic carbon atom are easily oxidized, resulting in coloring. Therefore, although compounds containing an amino group and in which the amino group is bonded to an aromatic carbon atom can be used in products where coloring is not a problem, such as rubber anti-deterioration agents, they cannot be used in products where coloring is a problem.

[0143] On the other hand, according to the polyisocyanate composition 2 of this embodiment, it has now been surprisingly demonstrated for the first time that even when using a specific amine compound having an aromatic group, it exhibits not only no coloring problem, but also an effect of improving (suppressing) thermal modification and coloring.

[0144] [R 210 R 220 R 230 R 240 and R 250 ]

[0145] In the above general formula (II), R 210 R is a monovalent organic group. 220 R 230 R 240 and R 250 Each is independently a monovalent organic group or hydrogen. R 210 and R 220 They can bond with each other and form ring structures by carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds.

[0146] Among them, R 210 Preferably, it is a monovalent aliphatic hydrocarbon group with 1 to 70 carbon atoms or a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms, and may be substituted or unsubstituted and may have an ether group, carbonyl group, ester group, imino (-NH-), amide group or imide group.

[0147] Additionally, R 220 R 230 R 240 and R 250 Preferably, each group is a monovalent aliphatic hydrocarbon group with 1 to 70 carbon atoms, a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms, or hydrogen, and may be substituted or unsubstituted and may have an ether group, carbonyl group, ester group, imino (-NH-), amide group, or imide group.

[0148] In R 210 R 220 R 230 R 240 and R 250When at least one of them is selected as an aliphatic hydrocarbon group, the number of carbon atoms is preferably 1 to 70 or less, more preferably 1 to 20 or less, even more preferably 1 to 12 or less, and particularly preferably 1 to 10 or less.

[0149] As R 210 R 220 R 230 R 240 and R 250 The aliphatic hydrocarbon groups in the text can be exemplified by straight-chain alkyl groups (without or with substituents), branched alkyl groups, cycloalkyl groups, etc. Substituents for these aliphatic hydrocarbon groups can include, for example, hydroxyl groups, cyano groups, and halogen atoms. Halogen atoms that can be substituents can include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0150] As R 210 R 220 R 230 R 240 and R 250 The aliphatic hydrocarbon group in the formula can specifically include isomers of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, and cyclohexyl. Preferably, the aliphatic hydrocarbon group is unsubstituted and has 1 to 12 carbon atoms, and preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl.

[0151] In R 210 R 220 R 230 R 240 and R 250 When an aromatic hydrocarbon group is selected from at least one of the groups, the number of carbon atoms is preferably 6 or more and 70 or less, more preferably 6 or more and 20 or less, even more preferably 6 or more and 12 or less, and particularly preferably 6 or more and 10 or less.

[0152] As R 210 R 220 R 230 R 240 and R 250 Aromatic hydrocarbon groups in R can include unsubstituted or substituted aryl and aralkyl groups. Substituents for these aromatic hydrocarbon groups can include aliphatic hydrocarbon groups, hydroxyl groups, cyano groups, and halogen atoms. 210 R 220 R 230 R 240 and R 250 Aliphatic hydrocarbon groups selected as substituents for aromatic hydrocarbon groups can be exemplified by those in R... 210 R220 R 230 R 240 and R 250 The same group is exemplified as an aliphatic hydrocarbon group. Examples of halogen atoms that can be used as substituents include fluorine, chlorine, bromine, and iodine atoms.

[0153] As R 210 R 220 R 230 R 240 and R 250 The aromatic hydrocarbon groups in it, specifically, can include phenyl, naphthyl, anthraceneyl, pyrene, phenanthryl, o-tolyl, m-tolyl, p-tolyl, benzyl, phenethyl, etc.

[0154] In R 210 and R 220 When they bond together to form a ring structure, R 210 and R 220 The groups formed by mutual bonding are divalent organic groups. As R 210 and R 220 The groups formed by mutual bonding are preferably substituted or unsubstituted and may be divalent aliphatic hydrocarbon groups with 1 to 70 carbon atoms or divalent aromatic hydrocarbon groups with 6 to 70 carbon atoms, having an ether group, carbonyl group, ester group, imino (-NH-), amide group or imide group.

[0155] As R 210 and R 220 Examples of divalent aliphatic hydrocarbon groups that are bonded together include alkylene groups such as methylene, ethylene, propylene, and trimethylene.

[0156] As R 210 and R 220 Examples of divalent aromatic hydrocarbon groups formed by mutual bonding include phenylene, naphthylene, and other arylene groups.

[0157] Regarding R 210 Regardless of whether it is R 210 and R 220 In cases where mutual bonding forms a ring structure, a carbon atom is preferably present at the position where it bonds to the nitrogen atom of the quinazolinidone structure. 210 In the middle, R is located at the position where it bonds to the nitrogen atom in the quinazolinidone structure. 210 The carbon atoms are preferably primary carbon atoms, secondary carbon atoms, tertiary carbon atoms, aromatic carbon atoms, or carbonyl carbon atoms.

[0158] Preferred quinazolinone compounds (II) include (II-1), (II-2), and (II-3) described below.

[0159] Regarding (II-1), R in the above general formula (II) 210 R is a monovalent organic group. 220 R 230 R 240 and R 250 Each is an independent monovalent organic group or hydrogen.

[0160] In (II-1), as R 210 Examples include monovalent aliphatic hydrocarbon groups with 1 to 12 carbon atoms, either substituted or unsubstituted, and monovalent aromatic hydrocarbon groups with 6 to 12 carbon atoms. As R 210 Specifically, examples include isomers of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, and p-tolyl. Preferably, the isomers are unsubstituted aliphatic hydrocarbon groups with 1 to 12 carbon atoms, and preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl.

[0161] In (II-1), R 220 R 230 R 240 and R 250 The number of monovalent organic groups is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

[0162] R 220 R 230 R 240 and R 250 When any one or more of the following are monovalent organic groups, they become substituents of the benzene ring in the quinazolinidone structure (hereinafter sometimes referred to as "substituents of the benzene ring"). Examples of substituents of the benzene ring include aliphatic hydrocarbon groups with 1 to 12 carbon atoms, or aromatic hydrocarbon groups with 6 to 12 carbon atoms, whether substituted or unsubstituted. Substituents of the benzene ring can be ether groups, carbonyl groups, or ester groups.

[0163] Examples of substituents on the benzene ring that are aliphatic or aromatic hydrocarbon groups include alkyl groups with 1 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, and aralkyl groups with 7 to 12 carbon atoms.

[0164] Examples of substituents on the benzene ring that have an ether group include alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 6 to 12 carbon atoms, or aralkyloxy groups with 7 to 12 carbon atoms.

[0165] Examples of carbonyl substituents on the benzene ring include alkyl carbonyl groups with 1 to 12 carbon atoms, aryl carbonyl groups with 6 to 12 carbon atoms, and aralkyl carbonyl groups with 7 to 12 carbon atoms.

[0166] Examples of substituents on the benzene ring that have an ester group include alkoxycarbonyl or alkylcarbonyloxy groups with 1 to 12 carbon atoms, aryloxycarbonyl or arylcarbonyloxy groups with 6 to 12 carbon atoms, or aralkyloxycarbonyl or aralkylcarbonyloxy groups with 7 to 12 carbon atoms.

[0167] Specifically, examples of substituents for the benzene ring include isomers of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, and p-tolyl. Among these, unsubstituted aliphatic hydrocarbon groups with 1 to 12 carbon atoms are preferred, with methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl being the most preferred.

[0168] Regarding (II-2), R in the above general formula (II) 210 and R 220 The mutual bonding merges to form a ring structure through carbon-carbon bonds, R 230 R 240 and R 250 Each is independently a monovalent organic group or hydrogen. R 210 and R 220 The groups formed by mutual bonding are divalent aliphatic hydrocarbon groups with 1 to 12 carbon atoms, substituted or unsubstituted, or divalent aromatic hydrocarbon groups with 6 to 12 carbon atoms.

[0169] As R 210 and R 220 Groups formed by mutual bonding, specifically, can include methylene, ethylene, propylene, trimethylene, phenylene, etc.

[0170] R 230 R 240 and R 250 The number of substituents forming the benzene ring is an integer of 0 to 3, preferably 0 or 1, more preferably 0. R in (II-2) 230 R 240 and R 250 Specific examples of substituents of the benzene ring can be given as the same groups that are exemplified as substituents of the benzene ring in (II-1).

[0171] Regarding (II-3), R in the above general formula (II) 210and R 220 Mutual bonding combines to form ring structures from carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds, R 230 R 240 and R 250 Each is independently a monovalent organic group or hydrogen. R 210 and R 220 The groups formed by mutual bonding have the general formula -R 311 -Z 311 - represents a divalent organic group. For the structure of quinazolinidone, R 311 Bonded to R 210 The nitrogen atoms that are bonded together are the same, Z 311 Bonded to R 220 The bonded atoms are carbon atoms that are the same. Z 311 It can be -O-, -NH-, or -C(=O)-. R 311 It is a divalent aliphatic hydrocarbon group with 1 to 12 carbon atoms or a divalent aromatic hydrocarbon group with 6 to 12 carbon atoms, either substituted or unsubstituted.

[0172] As R 311 Specifically, examples include methylene, ethylene, propylene, trimethylene, and phenylene.

[0173] R 230 R 240 and R 250 The number of substituents forming the benzene ring is an integer of 0 to 3, more preferably 0 or 1, and even more preferably 0. R in (II-3) 230 R 240 and R 250 Specific examples of substituents on the benzene ring can be given as the same groups exemplified as substituents on the benzene ring in (II-1).

[0174] In the above general formulas (II) and (II-1), (II-2) and (II-3), from the perspective of further improving the tinting reduction effect, R 210 R 220 R 230 R 240 and R 250 and R 210 and R 220 The groups formed by mutual bonding preferably do not contain olefinic or acetylene-type unsaturated carbon-carbon bonds. 210 R 220 R 230 R 240 and R 250 and R 210 and R 220The hydrocarbon groups contained in the mutually bonded groups are preferably saturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups.

[0175] In addition, from the perspective of thermal stability, R 210 R 220 R 230 R 240 and R 250 and R 210 and R 220 The groups formed by mutual bonding are preferably Z except for (II-3). 311 Other than that, it is a structure composed only of carbon and hydrogen atoms.

[0176] In (II-1), R is preferred. 210 It is a monovalent aliphatic hydrocarbon group, R 220 R 230 R 240 and R 250 Three or more of them are hydrogen, R 220 R 230 R 240 and R 250 One of them is an aliphatic hydrocarbon group with 1 to 12 carbon atoms or an aromatic hydrocarbon group with 6 to 12 carbon atoms, which is unsubstituted.

[0177] As a more preferred option (II-1), R is preferred. 210 R is a monovalent aliphatic hydrocarbon group with 1 to 12 carbon atoms. 220 R 230 R 240 and R 250 Three or more of them are hydrogen, R 220 R 230 R 240 and R 250 One of them is methyl or ethyl.

[0178] In (II-2), R is preferred. 210 and R 220 The groups formed by mutual bonding are divalent aliphatic hydrocarbon groups, R 230 R 240 and R 250 Two or more of them are hydrogen, R 230 R 240 and R 250 One of them is an aliphatic hydrocarbon group with 1 to 12 carbon atoms or an aromatic hydrocarbon group with 6 to 12 carbon atoms, which is unsubstituted.

[0179] As a more preferred option (II-2), R is preferred. 210 and R 220The groups formed by mutual bonding are divalent aliphatic hydrocarbon groups with 1 to 12 carbon atoms, R 230 R 240 and R 250 Two or more of them are hydrogen, R 230 R 240 and R 250 One of them is methyl or ethyl.

[0180] In (II-3), R is preferred. 310 It is a divalent aliphatic hydrocarbon group, R 230 R 240 and R 250 Two or more of them are hydrogen, R 230 R 240 and R 250 One of them is an aliphatic hydrocarbon group with 1 to 12 carbon atoms or an aromatic hydrocarbon group with 6 to 12 carbon atoms, which is unsubstituted.

[0181] As a more preferred option (II-3), R is preferred. 310 R is a divalent aliphatic hydrocarbon group with 1 to 12 carbon atoms. 230 R 240 and R 250 Two or more of them are hydrogen, R 230 R 240 and R 250 One of them is methyl or ethyl.

[0182] [Method for manufacturing quinazolinidone compound (II)]

[0183] Quinazolinedione compound (II) can be synthesized by known manufacturing methods. One example of a method for synthesizing quinazolinedione compound (II) is the reaction of an aniline compound with a carbonic acid derivative. The carbonic acid derivative used in the synthesis of quinazolinedione compound (II) can be one or more types.

[0184] In the synthesis of quinazolinedion compound (II), the aniline compound used has an unsubstituted or monosubstituted nitrogen atom, and at least one of the carbon atoms in the benzene ring adjacent to the nitrogen atom is unsubstituted. A -C(=O)-NH-C(=O)- group is formed between the nitrogen atom and an adjacent carbon atom in the aniline compound, thereby yielding quinazolinedion compound (II).

[0185] Examples of the aforementioned aniline compounds include unsubstituted anilines or those having an R-reactivity with quinazolinidone compound (II). 210 R 220 R 230 R 240 and R 250A substituted aniline is a substituted aniline in which at least one of the organic groups is the same as the substituent. 210 and R 220 They can bond with each other and form ring structures by carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds.

[0186] There are no particular limitations on the aforementioned carbonate derivatives, but from the perspective of ease of acquisition, it is preferred to use compounds represented by the following general formula (A) (hereinafter sometimes referred to as "carbonate derivative (A)").

[0187] R 61 -C(=O)-R 62 (A)

[0188] In the above general formula (A), R 61 and R 62 Each of them is independently an amino group, an alkoxy group with 1 to 20 carbon atoms (substituted or unsubstituted), an aryloxy group with 6 to 20 carbon atoms, or an alkylamino group with 1 to 20 carbon atoms (substituted or unsubstituted), or an arylamino group with 6 to 20 carbon atoms (substituted or unsubstituted).

[0189] R 61 and R 62 They can be the same or different. Alkylamino can be monoalkylamino or dialkylamino. Arylamino can be monoarylamino, diarylamino, or alkyl(aryl)amino.

[0190] As R 61 and R 62 Alkoxy groups with 1 to 20 carbon atoms include, for example, isomers of methoxy, ethoxy, propoxy, butoxy, and hexoxy.

[0191] As R 61 and R 62 The aryloxy group has 6 to 20 carbon atoms, such as phenoxy and naphthyloxy.

[0192] As R 61 and R 62 Alkylamino groups with 1 to 20 carbon atoms include, for example, isomers of methylamino, ethylamino, propylamino, butylamino, and hexylamino.

[0193] As R 61 and R 62 Arylamino groups with 6 to 20 carbon atoms, such as phenylamino and naphthylamino, are examples.

[0194] Examples of substituents found in alkoxy, aryloxy, alkylamino, and arylamino groups include alkyl and alkoxy groups.

[0195] Among them, as R 61 and R 62 Preferably, each is an amino group, an aryloxy group with 6 or more carbon atoms or less that is substituted or unsubstituted, or an arylamino group with 6 or more carbon atoms or less that is substituted or unsubstituted.

[0196] Preferred carbonate derivatives (A) include, for example, urea compounds, carbamates, and carbonates.

[0197] [Urea compounds]

[0198] As a urea compound, R in the above general formula (A) can be cited as an example. 61 and R 62 Each compound is an alkylamino or arylamino group, whether substituted or unsubstituted. Among urea compounds, those represented by the following general formula (A-1) are preferred.

[0199] R 611 -(R 612 -)NC(=O)-N(-R 613 )-R 614 (A-1)

[0200] In the above general formula (A-1), R 611 R 612 R 613 and R 614 Each of the following is independently an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydrogen atom. It constitutes R. 611 and R 612 The total number of carbon atoms is an integer between 0 and 20, constituting R. 613 and R 614 The total number of carbon atoms is an integer between 0 and 20.

[0201] Examples of urea compounds include unsubstituted urea compounds, monosubstituted urea compounds, N,N-disubstituted urea compounds, N,N'-disubstituted urea compounds, trisubstituted urea compounds, and tetrasubstituted urea compounds.

[0202] [Carbamate]

[0203] As an urethane ester, R in the above general formula (A) can be cited as an example. 61 and R 62 One of them is an amino group, or a substituted or unsubstituted alkylamino or arylamino group, R 61 and R62 The other is a compound with or without substituted alkoxy or aryloxy groups. Among carbamates, compounds represented by the following general formula (A-2) are preferred.

[0204] R 622 -(R 623 -)NC(=O)-OR 621 (A-2)

[0205] In the above general formula (A-2), R 621 It is an alkyl group with 1 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms. R 622 and R 623 Each of them is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0206] Examples of carbamates include N-unsubstituted carbamates, N-monosubstituted carbamates, and N,N-disubstituted carbamates.

[0207] [carbonate]

[0208] As a carbonate, R in the above general formula (A) can be cited as an example. 61 and R 62 Compounds that are independently substituted or unsubstituted alkoxy or aryloxy groups. Among carbonates, compounds represented by the following general formula (A-3) are preferred.

[0209] R 631 -OC(=O)-OR 632 (A-3)

[0210] In the above general formula (A-3), R 631 and R 632 Each of them is independently an aralkyl group with 7 to 20 carbon atoms, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms.

[0211] Quinazolinedione compound (II) possesses active hydrogen, exhibiting excellent storage stability and color inhibition in polyisocyanate composition 2. Quinazolinedione compound (II) inhibits the formation of 1-nylon body structures, which are described later as "compounds with UV absorption in the region of isocyanate decamer or higher in GPC," thus acting as a stabilizer during storage.

[0212] Regarding the quinazolinedion compound (II), due to the presence of a benzene ring in the quinazolinedion structure, the volume surrounding the active hydrogen is large, resulting in minimal or no addition reaction with the isocyanate group. Furthermore, because the benzene ring is electron-withdrawing, the active hydrogen in the quinazolinedion structure is abstracted by a base, stabilizing the resulting anion and inhibiting the formation of the 1-nylon body structure.

[0213] To improve the storage stability and color inhibition of polyisocyanate composition 2, it is preferable to increase the content of quinazolinedione compound (II). However, if the content of quinazolinedione compound (II) is too high, it may affect the manufacturing cost and use of polyisocyanate composition 2.

[0214] In polyisocyanate composition 2, based on the total mass of the polyisocyanate compounds, it is preferable to contain 5.0 × 10⁻¹⁰ ppm or more. 4 Quinazolinedione compound (II) with a mass concentration of less than ppm, more preferably containing 1.0 × 10⁻¹ ppm or more. 4 Quinazolinedione compounds (II) with a mass of less than ppm.

[0215] The polyisocyanate composition 2 of this embodiment may contain optional components other than quinazolinidone compound (II) and polyisocyanate compound, depending on the use, purpose, etc.

[0216] The polyisocyanate composition 2 of this embodiment can be used in polyurethane synthetic materials, curing agents, etc.

[0217] The polyisocyanate composition 2 of this embodiment can be used in a wide range of fields such as flexible foam, rigid foam, elastomer, adhesive, coating, and bonding agent.

[0218] [Compounds that exhibit UV absorption in regions of isocyanate decadal or higher in GPC]

[0219] In gel permeation chromatography (hereinafter sometimes referred to as "GPC"), compounds that have UV absorption in the region of isocyanate decamer or above in GPC are preferably compounds with a 1-nylon body structure represented by the following general formula (W) as the main skeleton.

[0220] -[N(-R W )-C(=O)] W - (W)

[0221] In the above general formula (W), R W This indicates the residue remaining after removing one isocyanate group from a polyisocyanate compound, where W represents an integer greater than or equal to 1. Additionally, terminal groups are not described.

[0222] In the GPC-based measurement spectrum, the isocyanate constituting the compound having UV absorption in the region of the isocyanate decamer or more can be the same isocyanate as the isocyanate compound constituting the isocyanate composition of this embodiment, or it can be a different isocyanate.

[0223] The compound was defined by GPC determination. Specifically, in GPC with tetrahydrofuran as the developing solvent, and using polystyrene as the molecular weight standard, a UV absorption peak with a wavelength of 254 nm was observed in the region of the decameric isocyanate and above.

[0224] In GPC-based measurements, the concentration of compounds with UV absorption in the region of isocyanate decadal and above can be determined by the area (A) of the peak of isocyanate with dual or higher functionality in the UV absorption (wavelength 210 nm) of a PDA-based detector and the area (B) of the peak of compounds with UV absorption (wavelength 254 nm) in the region of isocyanate decadal and above, calculated by the value of (B) / (A).

[0225] Polyisocyanate Composition 3

[0226] The polyisocyanate composition 3 of this embodiment contains a trisubstituted urea compound (III) and a polyisocyanate compound.

[0227] [Compound (III)]

[0228] Compound (III) is represented by the following general formula (III). Hereinafter, the compound represented by the following general formula (III) will sometimes be referred to as "trisubstituted urea compound (III)".

[0229] [Chemistry 14]

[0230]

[0231] (In general formula (III), R) 310 For (n+m) valence organic groups, n is an integer from 0 to 12, m is an integer from 1 to 12, n+m is an integer less than 13, R 320 and R 330 Each is an independent monovalent organic group. R 320 and R 330 They can bond with each other and form ring structures from carbon-carbon, carbon-oxygen-carbon, or carbon-nitrogen-carbon bonds. R 320 and R 330 At least one of them has an aromatic group.

[0232] The trisubstituted urea compound (III) has (OCN) bonded to the urea molecule represented by H2N-CO-NH2. n -R 310 -base, R 320 base and R 330 The structure with the radical as a substituent (hereinafter sometimes referred to as the "trisubstituted urea structure"). The trisubstituted urea structure is -NH-C(=O)-N(-R) in the above general formula (III). 330 )-R 320 The monovalent group represented.

[0233] The trisubstituted urea structure contains an active hydrogen atom in the -NH-C(=O)-N< group. The -NH-C(=O)-N< group in the trisubstituted urea structure can exhibit tautomerism represented by -N=C(-OH)-N<.

[0234] The inventors discovered that by manufacturing end-capped isocyanates in the presence of specific amine compounds having aromatic groups, the problems of thermal modification and coloring can be solved, thus completing the present invention.

[0235] It is known in the prior art that compounds containing an amino group and in which the amino group is bonded to an aromatic carbon atom are easily oxidized, resulting in coloring. Therefore, although compounds containing an amino group and in which the amino group is bonded to an aromatic carbon atom can be used in products where coloring is not a problem, such as rubber anti-deterioration agents, they cannot be used in products where coloring is a problem.

[0236] On the other hand, the polyisocyanate composition according to this embodiment has now surprisingly demonstrated for the first time that, even when using a specific amine compound having an aromatic group, it exhibits not only no coloring problem, but also an effect of improving (suppressing) thermal modification and coloring.

[0237] [R 310 ]

[0238] In the above general formula (III), R 310 For (n+m) valence organic groups, n is an integer from 0 to 12, m is an integer from 1 to 12, and n+m is an integer from 13 to 13.

[0239] n represents the relationship with R 310 The number of bonded isocyanate groups (OCN-). m represents the number of bonds with R. 310 The number of bonded trisubstituted urea structures. Since n is an integer greater than or equal to 0 and m is an integer greater than or equal to 1, n+m is an integer greater than or equal to 1.

[0240] Trisubstituted urea compounds (III) are compounds having n isocyanate groups. Therefore, R 310 It is an organic group that does not contain an isocyanate group.

[0241] Trisubstituted urea compound (III) is a compound having m trisubstituted urea structures. Therefore, R 310 It is an organic group that does not contain a trisubstituted urea structure.

[0242] In trisubstituted urea compounds (III), except where the trisubstituted urea structure corresponds to a capped isocyanate group, it can be a compound without a capped isocyanate group. In this case, R 310 It is an organic group that does not contain a capped isocyanate group.

[0243] The capped isocyanate group is the group shown on the left side of the following reaction formula (K), which is a group that can be thermally dissociated into an isocyanate group and a capping agent represented by the general formula BL-H, as shown on the right side of the reaction formula (K).

[0244] -NH-C(=O)-BL → -N=C=O + BL-H (K)

[0245] In the above reaction formula (K), the capping agent represented by BL-H is a compound with active hydrogen. Examples of capping agents include phenolic capping agents, alcoholic capping agents, thiol capping agents, amine capping agents, ammonia capping agents, oxime capping agents, hydroxylamine capping agents, and active methylene capping agents.

[0246] Examples of phenolic end-capping agents include organic compounds having an -OH group that is bonded to an aromatic carbon atom.

[0247] As alcohol-based end-capping agents, examples include organic compounds that have a -OH group and that the -OH group is bonded to a non-aromatic carbon atom.

[0248] Examples of thiol-based end-capping agents include organic compounds with -SH groups.

[0249] As amine-based end-capping agents, examples include organic compounds having -NH2 or -NH- groups. Triazole compounds, pyrazole compounds, etc., are also included among amine-based end-capping agents having -NH- groups.

[0250] Ammonia can be cited as an example of an ammonia-based capping agent.

[0251] Examples of oxime-based end-capping agents include organic compounds having an =N-OH group bonded to a carbon atom.

[0252] Examples of hydroxylamine-based end-capping agents include organic compounds with >N-OH groups bonded to two carbon atoms.

[0253] Examples of active methylene-based end-capping agents include acetoacetate compounds, malonate diester compounds, and acetylacetone, which are organic compounds containing atomic groups such as -C(=O)-C(-H)2-C(=O)-.

[0254] Trisubstituted urea compounds (III) can be compounds that do not have units that constitute isocyanate polymers. In this case, R... 310 It does not contain organic groups that constitute the units of the isocyanate polymer.

[0255] The unit constituting the isocyanate polymer refers to the isocyanurate group, biuret group, iminooxadiazine diketone group, ureidyl group (-NH-C(=O)-NH-), ureocarbamate group, ureidyl diketone group and carbamate group in a nitrogen-containing unit from one or more isocyanate groups.

[0256] As R 310 Preferably, the aliphatic hydrocarbon group with 1 to 70 carbon atoms or an aromatic hydrocarbon group with 6 to 70 carbon atoms is substituted or unsubstituted and may have an ether group, carbonyl group, ester group, imino (-NH-), amide group or imide group.

[0257] As R 310 The monovalent aliphatic hydrocarbon group in the group can be substituted or unsubstituted alkyl groups, cycloalkyl groups, etc.

[0258] As R 310 The divalent aliphatic hydrocarbon groups in the group can include substituted or unsubstituted alkylene groups, cycloalkylene groups, etc.

[0259] As R 310 The trivalent aliphatic hydrocarbon group in the name can be exemplified by substituted or unsubstituted alkane trimethyl groups, cycloalkane trimethyl groups, etc.

[0260] As R 310 The tetravalent aliphatic hydrocarbon group in the text can be exemplified by substituted or unsubstituted alkane tetrayl groups, cycloalkane tetrayl groups, etc.

[0261] As R 310 The pentavalent aliphatic hydrocarbon group in the name can be substituted or unsubstituted alkyl pentamethyl groups, cycloalkanes pentamethyl groups, etc.

[0262] As R 310 The hexavalent aliphatic hydrocarbon group in the hexavalent hydrocarbon group can be substituted or unsubstituted alkane hexamethyl groups, cycloalkane hexamethyl groups, etc.

[0263] As R 310The heptavalent aliphatic hydrocarbon group in the heptavalent group can be substituted or unsubstituted alkane heptavalents, cycloalkane heptavalents, etc.

[0264] As R 310 The octyl aliphatic hydrocarbon group in the text can be substituted or unsubstituted alkane octyl groups, cycloalkane octyl groups, etc.

[0265] As R 310 The 9-valent aliphatic hydrocarbon group can be exemplified by substituted or unsubstituted alkane nonyl groups, cycloalkanes nonyl groups, etc.

[0266] As R 310 Examples of 10-valent aliphatic hydrocarbon groups include substituted or unsubstituted alkyl decayl groups and cycloalkanes decayl groups.

[0267] As R 310 Examples of 11-valent aliphatic hydrocarbon groups include substituted or unsubstituted alkane undecyl groups and cycloalkane undecyl groups.

[0268] As R 310 Examples of 12-valent aliphatic hydrocarbon groups include substituted or unsubstituted alkane dodecyl groups and cycloalkanes dodecyl groups.

[0269] As R 310 The 13-valent aliphatic hydrocarbon group in the name can be exemplified by substituted or unsubstituted alkane tridecyl groups, cycloalkanes tridecyl groups, etc.

[0270] In R 310 When an aliphatic hydrocarbon group is selected, the number of carbon atoms is preferably 1 to 70 or less, more preferably 1 to 20 or less, even more preferably 1 to 12 or less, and particularly preferably 1 to 10 or less.

[0271] As R 310 Substituents in the aliphatic hydrocarbon group can include, for example, hydroxyl, cyano, and halogen atoms. Halogen atoms that can be substituents can include fluorine, chlorine, bromine, and iodine atoms. The number of substituents is not particularly limited, but is preferably 0 to 10.

[0272] As R 310 The aliphatic hydrocarbon group in the formula can specifically include isomers of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, and cyclohexyl. Preferably, the aliphatic hydrocarbon group is unsubstituted and has 1 to 12 carbon atoms, and preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl.

[0273] As R 310 The monovalent aromatic hydrocarbon group in the text can be substituted or unsubstituted aryl groups, etc.

[0274] As R 310 The divalent aromatic hydrocarbon groups in the group can include substituted or unsubstituted arylene groups, etc.

[0275] As R 310 The trivalent aromatic hydrocarbon group in the text can be exemplified by substituted or unsubstituted aromatic trimethyl groups.

[0276] As R 310 The tetravalent aromatic hydrocarbon group in the text can be exemplified by substituted or unsubstituted aromatic tetramethyl groups.

[0277] As R 310 The five-valent aromatic hydrocarbon groups in the text can be substituted or unsubstituted aromatic pentamethyl groups, etc.

[0278] As R 310 Examples of hexavalent aromatic hydrocarbon groups in this context include substituted or unsubstituted hexavalent aromatic hydrocarbon groups.

[0279] As R 310 The heptavalent aromatic hydrocarbon group in the text can be exemplified by substituted or unsubstituted aromatic heptavalent groups.

[0280] As R 310 The octyl aromatic hydrocarbon group in the text can be substituted or unsubstituted aromatic octyl groups, etc.

[0281] As R 310 The 9-valent aromatic hydrocarbon group can be exemplified by substituted or unsubstituted aromatic nonyl groups.

[0282] As R 310 Examples of 10-valent aromatic hydrocarbon groups include substituted or unsubstituted aromatic decayl groups.

[0283] As R 310 Examples of 11-valent aromatic hydrocarbon groups include substituted or unsubstituted aromatic undecyl groups.

[0284] As R 310 Examples of 12-valent aromatic hydrocarbon groups include substituted or unsubstituted aromatic dodecyl groups.

[0285] As R 310 Examples of 13-valent aromatic hydrocarbon groups include substituted or unsubstituted aromatic tridecyl groups.

[0286] In R 310 When an aromatic hydrocarbon group is selected, the number of carbon atoms is preferably 6 or more and 70 or less, more preferably 6 or more and 20 or less, even more preferably 6 or more and 12 or less, and particularly preferably 6 or more and 10 or less.

[0287] As R 310Aryl groups in phenyl groups can be exemplified by phenyl, naphthyl, anthraceneyl, pyrene, and phenanthrene groups.

[0288] As R 310 Examples of arylene groups in this context include phenylene, naphthylene, anthraceneylene, pyreneylene, and phenanthrene.

[0289] As R 310 Aromatic rings contained in aromatic hydrocarbon groups with a valence of 3 or higher but less than 13 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, pyrene ring, and phenanthrene ring.

[0290] As R 310 Substituents of aromatic hydrocarbon groups in R can include, for example, aliphatic hydrocarbon groups, hydroxyl groups, cyano groups, halogen atoms, etc. 310 Aliphatic hydrocarbon groups selected as substituents for aromatic hydrocarbon groups can be exemplified by those used as R... 310 The aliphatic hydrocarbon group is the same group as the one shown. Examples of halogen atoms that can be substituents include fluorine, chlorine, bromine, and iodine atoms. The number of substituents is not particularly limited, but is preferably 0 to 10.

[0291] R 310 Preferably, a carbon atom is present at the position where it is bonded to the nitrogen atom of the isocyanate group or the trisubstituted urea structure. 310 In the context, R represents the position where the nitrogen atom of the isocyanate group or trisubstituted urea structure bonds. 310 The carbon atoms are preferably primary carbon atoms, secondary carbon atoms, tertiary carbon atoms, aromatic carbon atoms, or carbonyl carbon atoms.

[0292] Trisubstituted urea compounds (III) can be compounds represented by the following general formula (III-a).

[0293] (Z 311 -) k1 -R 410 -L 311 -R 420 -(-Z 312 ) k2 ・・・(III-a)

[0294] In the above general formula (III-a), R 410 For cyclic aliphatic or aromatic hydrocarbon groups with a valence of (k1+1), L 311 R is a single bond or a divalent acyclic aliphatic hydrocarbon group. 420 A cyclic aliphatic or aromatic hydrocarbon group with a valence of (k2+1). Z 311 and Z 312 Each is independently an isocyanate group or a trisubstituted urea structure. Z 311 and Z 312For the range where the number of isocyanate groups is n of general formula (III), Z 311 and Z 312 The number of trisubstituted urea structures is within the range of m of general formula (III), and k1+k2 is within the range of n+m, where k1 and k2 are integers greater than or equal to 1.

[0295] -R in general formula (III-a) 410 -L 311 -R 420 -The basis corresponds to R in general formula (III) 310 As R 410 R 420 and L 311 The cyclic or acyclic aliphatic or aromatic hydrocarbon groups in the formula (III) can be exemplified by those that are R in general formula (III). 310 The aliphatic or aromatic hydrocarbon groups are the same groups shown in the example.

[0296] Trisubstituted urea compounds (III) can be compounds represented by the following general formula (III-b).

[0297] (Z 313 -) k3 -R 313 -L 313 -R 314 -(-Z 314 ) k4 ・・・(III-b)

[0298] In the above general formula (III-b), R 313 For aliphatic or aromatic hydrocarbon groups with a valence of (k3+1), L 313 It can be an ether group, carbonyl group, ester group, imino group (-NH-), amide group or imide group, R 314 Aliphatic or aromatic hydrocarbon group with a valence of (k4+1). 313 and Z 314 Each is independently an isocyanate group or a trisubstituted urea structure. Z 313 and Z 314 For the range where the number of isocyanate groups is n of general formula (III), Z 313 and Z 314 The number of trisubstituted urea structures is within the range of m of general formula (III), and k3+k4 is within the range of n+m, where k3 and k4 are integers greater than or equal to 0.

[0299] -R in general formula (III-b) 313 -L 313 -R 314 -The basis corresponds to R in general formula (III) 310 As R313 and R 314 The aliphatic or aromatic hydrocarbon groups in the formula (III) can be exemplified by those that are R in general formula (III). 310 The aliphatic or aromatic hydrocarbon groups are the same groups shown in the example.

[0300] In trisubstituted urea compounds (III), R was specifically identified. 310 Examples can be given by compounds represented by the following general formulas (1) to (10).

[0301] [Chemistry 15]

[0302]

[0303] In the above general formula (1), Z 1a and Z 1b Each is independently an isocyanate group or a trisubstituted urea structure. Z 1a and Z 1b The number of isocyanate groups is 0 or 1, Z 1a and Z 1b The number of trisubstituted urea structures is 1 or 2, Z 1a and Z 1b The total number of isocyanate groups or trisubstituted urea structures is 2.

[0304] [Chemistry 16]

[0305]

[0306] In the above general formula (2), Z 2a and Z 2b Each is independently an isocyanate group or a trisubstituted urea structure. Z 2a and Z 2b The number of isocyanate groups is 0 or 1, Z 2a and Z 2b The number of trisubstituted urea structures is 1 or 2, Z 2a and Z 2b The total number of isocyanate groups or trisubstituted urea structures is 2.

[0307] [Chemistry 17]

[0308]

[0309] In the above general formula (3), Z 3a and Z 3b Each is independently an isocyanate group or a trisubstituted urea structure. Z 3a and Z 3b The number of isocyanate groups is 0 or 1, Z 3a and Z 3bThe number of trisubstituted urea structures is 1 or 2, Z 3a and Z 3b The total number of isocyanate groups or trisubstituted urea structures is 2.

[0310] [Chemistry 18]

[0311]

[0312] In the above general formula (4), Z 4a and Z 4b Each is independently an isocyanate group or a trisubstituted urea structure. Z 4a and Z 4b The number of isocyanate groups is 0 or 1, Z 4a and Z 4b The number of trisubstituted urea structures is 1 or 2, Z 4a and Z 4b The total number of isocyanate groups or trisubstituted urea structures is 2. The compound represented by general formula (4) can be a mixture of isomers.

[0313] [Chemistry 19]

[0314]

[0315] In the above general formula (5), Z 5a and Z 5b Each is independently an isocyanate group or a trisubstituted urea structure. Z 5a and Z 5b The number of isocyanate groups is 0 or 1, Z 5a and Z 5b The number of trisubstituted urea structures is 1 or 2, Z 5a and Z 5b The total number of isocyanate groups or trisubstituted urea structures is 2.

[0316] [Chemistry 20]

[0317]

[0318] In the above general formula (6), Z 6a and Z 6b Each is independently an isocyanate group or a trisubstituted urea structure. Z 6a and Z 6b The number of isocyanate groups is 0 or 1, Z 6a and Z 6b The number of trisubstituted urea structures is 1 or 2, Z 6a and Z 6b The total number of isocyanate groups or trisubstituted urea structures is 2.

[0319] [Chemistry 21]

[0320]

[0321] In the above general formula (7), Z 7a and Z 7b Each is independently an isocyanate group or a trisubstituted urea structure. Z 7a and Z 7b The number of isocyanate groups is 0 or 1, Z 7a and Z 7b The number of trisubstituted urea structures is 1 or 2, Z 7a and Z 7b The total number of isocyanate groups or trisubstituted urea structures is 2.

[0322] [Chemistry 22]

[0323]

[0324] In the above general formula (8), Z 8a Z 8b and Z 8c Each is independently an isocyanate group or a trisubstituted urea structure. Z 8a Z 8b and Z 8c The number of isocyanate groups is 0, 1, or 2, Z 8a Z 8b and Z 8c The number of trisubstituted urea structures is 1, 2, or 3, Z 8a Z 8b and Z 8c The total number of isocyanate groups or trisubstituted urea structures is 3.

[0325] [Chemistry 23]

[0326]

[0327] In the above general formula (9), Z 9a Z 9b and Z 9c Each is independently an isocyanate group or a trisubstituted urea structure. Z 9a Z 9b and Z 9c The number of isocyanate groups is 0, 1, or 2, Z 9a Z 9b and Z 9c The number of trisubstituted urea structures is 1, 2, or 3, Z 9a Z 9b and Z 9c The total number of isocyanate groups or trisubstituted urea structures is 3.

[0328] [Chemistry 24]

[0329]

[0330] In the above general formula (10), Z 10a and Z 10b Each is independently an isocyanate group or a trisubstituted urea structure. Z 10a and Z 10b The number of isocyanate groups is 0 or 1, Z 10a and Z 10b The number of trisubstituted urea structures is 1 or 2, Z 10a and Z 10b The total number of isocyanate groups or trisubstituted urea structures is 2.

[0331] [R 320 and R 330 ]

[0332] In the above general formula (III), R 2 and R 3 Each is an independent monovalent organic group. R 320 and R 330 They can bond with each other and form ring structures from carbon-carbon, carbon-oxygen-carbon, or carbon-nitrogen-carbon bonds. R 320 and R 330 At least one of them has an aromatic group.

[0333] Among them, R 320 and R 330 Preferably, each group is a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group with 1 to 70 carbon atoms, and may be substituted or unsubstituted and may have an ether group, carbonyl group, ester group, imino (-NH-), amide group or imide group.

[0334] R 320 and R 330 When at least one of them is selected as an aliphatic hydrocarbon group, the number of carbon atoms is preferably 1 to 70 or less, more preferably 1 to 20 or less, even more preferably 1 to 12 or less, and particularly preferably 1 to 10 or less.

[0335] As R 320 and R 330 The aliphatic hydrocarbon groups in the text can be exemplified by straight-chain alkyl groups (without or with substituents), branched alkyl groups, cycloalkyl groups, etc. Substituents for these aliphatic hydrocarbon groups can include, for example, hydroxyl groups, cyano groups, and halogen atoms. Halogen atoms that can be substituents can include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0336] As R 320 and R 330The aliphatic hydrocarbon group in the formula can specifically include isomers of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, and cyclohexyl. Preferably, the aliphatic hydrocarbon group is unsubstituted and has 1 to 12 carbon atoms, and preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl.

[0337] R 320 and R 330 When an aromatic hydrocarbon group is selected from at least one of the groups, the number of carbon atoms is preferably 6 or more and 70 or less, more preferably 6 or more and 20 or less, even more preferably 6 or more and 12 or less, and particularly preferably 6 or more and 10 or less.

[0338] As R 320 and R 330 Aromatic hydrocarbon groups in R can include unsubstituted or substituted aryl and aralkyl groups. Substituents for these aromatic hydrocarbon groups can include aliphatic hydrocarbon groups, hydroxyl groups, cyano groups, and halogen atoms. 320 and R 330 Aliphatic hydrocarbon groups selected as substituents for aromatic hydrocarbon groups can be exemplified by those in R... 320 and R 330 The same group is exemplified as an aliphatic hydrocarbon group. Examples of halogen atoms that can be substituents include fluorine, chlorine, bromine, and iodine atoms.

[0339] As R 320 and R 330 The aromatic hydrocarbon groups in it, specifically, can include phenyl, naphthyl, anthraceneyl, pyrene, phenanthryl, o-tolyl, m-tolyl, p-tolyl, benzyl, phenethyl, etc.

[0340] R 320 and R 330 When they bond together to form a ring structure, R 320 and R 330 The groups formed by mutual bonding are divalent organic groups. As R 320 and R 330 The groups formed by mutual bonding preferably include divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon groups that are substituted or unsubstituted and may have ether, carbonyl, ester, imino (-NH-), amide or imide groups, and are divalent groups with 7 to 70 carbon atoms.

[0341] R 320 and R 330 Among the groups formed by mutual bonding, examples of divalent aliphatic hydrocarbon groups include methylene, ethylene, propylene, and trimethylene alkylene groups.

[0342] R 320 and R 330 Among the groups formed by mutual bonding, examples of divalent aromatic hydrocarbon groups include phenylene, naphthylene, and other arylene groups.

[0343] Regarding R 320 and R 330 Regardless of whether it is R 320 and R 330 In cases where mutual bonding forms a ring structure, a carbon atom is preferably present at the position where it bonds to the nitrogen atom in the trisubstituted urea structure. 320 and R 330 In the context, R is located at the position where it bonds to the nitrogen atom in the trisubstituted urea structure. 320 and R 330 The carbon atoms are preferably primary carbon atoms, secondary carbon atoms, tertiary carbon atoms, aromatic carbon atoms, or carbonyl carbon atoms.

[0344] R 320 and R 330 The aromatic group contained in at least one of the structures preferably contains an aromatic carbon atom at the position bonded to the nitrogen atom of the trisubstituted urea structure. The aromatic carbon atom is, for example, a carbon atom contained in a benzene ring. Examples of aromatic groups containing an aromatic carbon atom at the position bonded to an external location include aryl groups such as phenyl and arylene groups such as phenylene.

[0345] Preferred trisubstituted urea compounds (III) include (III-1), (III-2), and (III-3) described below.

[0346] Regarding (III-1), in the above general formula (III), R 320 and R 330 One or more of them are monovalent organic groups that do not have aromatic groups, and at least one of them is a substituted or unsubstituted phenyl group. R 320 and R 330 One of them can be a substituted or unsubstituted phenyl group, and the other can be a monovalent aliphatic hydrocarbon group. R 320 and R 330 Each can be a substituted or unsubstituted phenyl group, and each can be independently substituted or unsubstituted.

[0347] In (III-1), as R 320 and R 330One or less of the following monovalent organic groups that do not have an aromatic group can be included: monovalent aliphatic hydrocarbon groups with 1 to 12 carbon atoms, either substituted or unsubstituted. Specifically, examples of monovalent organic groups without an aromatic group include isomers of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, and cyclohexyl. Among these, unsubstituted aliphatic hydrocarbon groups with 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl are also preferred.

[0348] In (III-1), as R 320 and R 330 The number of substituents of the phenyl group in at least one of the components is an integer of 0 to 5, more preferably 0 or 1, and even more preferably 0.

[0349] As R 320 and R 330 When at least one of the components is a substituted phenyl group (hereinafter sometimes referred to as a "substituent of the benzene ring"), examples include aliphatic hydrocarbon groups with 1 to 12 carbon atoms or aromatic hydrocarbon groups with 6 to 12 carbon atoms, whether substituted or unsubstituted. Substituents of the benzene ring can be ether groups, carbonyl groups, or ester groups.

[0350] Examples of substituents on the benzene ring that are aliphatic or aromatic hydrocarbon groups include alkyl groups with 1 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, and aralkyl groups with 7 to 12 carbon atoms.

[0351] Examples of substituents on the benzene ring that have an ether group include alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 6 to 12 carbon atoms, or aralkyloxy groups with 7 to 12 carbon atoms.

[0352] Examples of carbonyl substituents on the benzene ring include alkyl carbonyl groups with 1 to 12 carbon atoms, aryl carbonyl groups with 6 to 12 carbon atoms, and aralkyl carbonyl groups with 7 to 12 carbon atoms.

[0353] Examples of substituents on the benzene ring that have an ester group include alkoxycarbonyl or alkylcarbonyloxy groups with 1 to 12 carbon atoms, aryloxycarbonyl or arylcarbonyloxy groups with 6 to 12 carbon atoms, or aralkyloxycarbonyl or aralkylcarbonyloxy groups with 7 to 12 carbon atoms.

[0354] Specifically, examples of substituents for the benzene ring include isomers of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, and p-tolyl. Among these, unsubstituted aliphatic hydrocarbon groups with 1 to 12 carbon atoms are preferred, with methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl being the most preferred.

[0355] Regarding (III-2), in the above general formula (III), R 320 and R 330 The bonds between the carbon atoms combine to form a ring structure, which has the general formula -R 321 -R 322 - represents a divalent organic group. R 321 and R 322 One of the following is a divalent aliphatic hydrocarbon group with 1 to 12 carbon atoms, either substituted or unsubstituted, R 321 and R 322 At least one of them is a substituted or unsubstituted o-phenylene. R 321 and R 322 One of them can be a substituted or unsubstituted o-phenylene group, and the other can be a divalent aliphatic hydrocarbon group. R 321 and R 322 Each can be an orthophenylene oxide, either substituted or unsubstituted, independently.

[0356] Regarding R 321 and R 322 One or more of the following divalent aliphatic hydrocarbon groups, specifically, methylene, ethylene, propylene, trimethylene, etc.

[0357] As R 321 and R 322 The number of substituents of at least one of the o-phenylene groups is an integer of 0 to 4, preferably 0 or 1, more preferably 0. Regarding R... 321 and R 322 The substituents of at least one of the orthophenylene groups can be the same groups exemplified as substituents of the benzene ring in (III-1).

[0358] Regarding (III-3), in the above general formula (III), R 320 and R 330 The bonds between the bonds form ring structures composed of carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds, with the general formula -R. 331 -Z 331 -R 332 - represents a divalent organic group. Z 331It can be -O-, -NH-, or -C(=O)-. R 331 and R 332 One of the following is a divalent aliphatic hydrocarbon group with 1 to 12 carbon atoms, either substituted or unsubstituted, R 331 and R 332 At least one of them is a substituted or unsubstituted o-phenylene. R 331 and R 332 One of them can be a substituted or unsubstituted o-phenylene group, and the other can be a divalent aliphatic hydrocarbon group. R 331 and R 332 Each can be an orthophenylene oxide, either substituted or unsubstituted, independently.

[0359] Regarding R 331 and R 332 One or more of the following divalent aliphatic hydrocarbon groups, specifically, methylene, ethylene, propylene, trimethylene, etc.

[0360] As R 331 and R 332 The number of substituents of at least one of the o-phenylene groups is an integer of 0 to 4, preferably 0 or 1, more preferably 0. Regarding R... 331 and R 332 The substituents of at least one of the orthophenylene groups can be the same groups exemplified as substituents of the benzene ring in (III-1).

[0361] In the above general formulas (III) and (III-1), (III-2) and (III-3), from the perspective of further improving the tinting reduction effect, R 320 and R 330 and R 321 R 322 R 331 and R 332 Preferably, it does not contain olefinic or acetyleneic unsaturated carbon-carbon bonds. 320 and R 330 and R 321 R 322 R 331 and R 332 The hydrocarbon groups contained therein are preferably saturated aliphatic hydrocarbon groups or aromatic hydrocarbon groups.

[0362] In addition, from the perspective of thermal stability, R 320 and R 330 and R 321 R 322 R 331 and R 332 Preferably, Z is the only one other than (III-3). 331Other than that, it is a structure composed only of carbon and hydrogen atoms.

[0363] In (III-1), R is preferred. 320 and R 330 One of them is an aliphatic hydrocarbon group with a valence of 1, R 320 and R 330 At least one of them is an unsubstituted or monosubstituted phenyl group, and the substituent of the phenyl group is an unsubstituted aliphatic hydrocarbon group with 1 to 12 carbon atoms or an aromatic hydrocarbon group with 6 to 12 carbon atoms.

[0364] As a more preferred option (III-1), R is preferred. 320 and R 330 One of them is a monovalent aliphatic hydrocarbon group with 1 to 12 carbon atoms, R 320 and R 330 At least one of them is an unsubstituted or monosubstituted phenyl group, and the substituent of the phenyl group is methyl or ethyl.

[0365] In (III-2), R is preferred. 321 and R 322 One of them is a divalent aliphatic hydrocarbon group, R 321 and R 322 At least one of them is an unsubstituted or monosubstituted o-phenylene, wherein the substituent of the o-phenylene is an unsubstituted aliphatic hydrocarbon group with 1 to 12 carbon atoms or an aromatic hydrocarbon group with 6 to 12 carbon atoms.

[0366] As a more preferred option (III-2), R is preferred. 321 and R 322 One of them is a divalent aliphatic hydrocarbon group with 1 to 12 carbon atoms, R 321 and R 322 At least one of them is an unsubstituted or monosubstituted o-phenylene, wherein the substituent of the o-phenylene is methyl or ethyl.

[0367] In (III-3), R is preferred. 331 and R 332 One of them is a divalent aliphatic hydrocarbon group, R 331 and R 332 At least one of them is an unsubstituted or monosubstituted o-phenylene, wherein the substituent of the o-phenylene is an unsubstituted aliphatic hydrocarbon group with 1 to 12 carbon atoms or an aromatic hydrocarbon group with 6 to 12 carbon atoms.

[0368] As a more preferred option (III-3), R is preferred. 331 and R 332 One of them is a divalent aliphatic hydrocarbon group with 1 to 12 carbon atoms, R 331 and R 332At least one of them is an unsubstituted or monosubstituted o-phenylene, wherein the substituent of the o-phenylene is methyl or ethyl.

[0369] [Method for manufacturing trisubstituted urea compound (III)]

[0370] Trisubstituted urea compounds (III) can be synthesized by known manufacturing methods. For example, a method for synthesizing trisubstituted urea compounds (III) can be described by generating isocyanate groups capped by a secondary amine compound during the manufacturing process of a capped isocyanate compound.

[0371] Examples of secondary amine compounds used in the synthesis of trisubstituted urea compounds (III) include compounds represented by the following general formula (B).

[0372] HN(-R 353 )-R 352 (B)

[0373] In the above general formula (B), R 352 and R 353 Respectively, as R in the above general formula (III) 320 and R 330 The groups listed are the same.

[0374] Trisubstituted urea compound (III) possesses active hydrogen, exhibits excellent storage stability of polyisocyanate compositions, and suppresses discoloration. Trisubstituted urea compound (III) inhibits the formation of the aforementioned [compounds with UV absorption in regions of the isocyanate decamer or higher in GPC], i.e., the 1-nylon body structure, thus acting as a storage stabilizer.

[0375] Regarding the trisubstituted urea compound (III), due to R 320 and R 330 At least one of the components contains an aromatic group, therefore the active hydrogen in the trisubstituted urea structure has a large surrounding volume, preventing addition reactions with the isocyanate group. Furthermore, due to the electron-withdrawing properties of the aromatic group, the active hydrogen in the trisubstituted urea structure is abstracted by the base, stabilizing the generated anion and inhibiting the formation of the 1-nylon body structure.

[0376] To improve the storage stability and color inhibition of polyisocyanate composition 3, it is preferable to increase the content of trisubstituted urea compound (III). However, if the content of trisubstituted urea compound (III) is too high, it may affect the manufacturing cost and application of the polyisocyanate composition.

[0377] In polyisocyanate composition 3, based on the total mass of the polyisocyanate compounds, it is preferable to contain 1.0 × 10⁻¹⁰ ppm or more. 4Trisubstituted urea compounds (III) with a mass of less than ppm.

[0378] The polyisocyanate composition 3 of this embodiment may contain optional components other than trisubstituted urea compound (III) and polyisocyanate compound, depending on the use, purpose, etc.

[0379] The polyisocyanate composition 3 of this embodiment can be used in polyurethane synthetic materials, curing agents, etc.

[0380] The polyisocyanate composition of this embodiment can be used in a wide range of fields such as flexible foams, rigid foams, elastomers, adhesives, coatings, and binders.

[0381] Polyisocyanate Composition 4

[0382] The polyisocyanate composition 4 of this embodiment contains two or more compounds represented by general formulas (I), (II), and (III), as well as a polyisocyanate compound. The compounds represented by general formulas (I), (II), and (III) have the same morphology as the polyisocyanate compositions 1 to 3 described above.

[0383] Compared with the above-mentioned polyisocyanate compositions 1 to 3, polyisocyanate composition 4 provides a polyisocyanate with superior storage stability and color inhibition, and is therefore preferred. In the case of polyisocyanate composition 4 containing compounds represented by general formulas (I), (II) and (III) and polyisocyanate compounds, a polyisocyanate with even better storage stability and color inhibition is provided, and is therefore further preferred.

[0384] In the polyisocyanate composition 4, the content of compound (I), compound (II), or compound (III), based on the total mass of the polyisocyanate compounds, is preferably 1.0 ppm or more and 5.0 × 10⁻⁶ ppm by mass, respectively. 4 Less than 1.0 ppm by mass, more preferably 1.0 ppm or more, 1.0 × 10⁻¹⁰ 4 The mass fraction is less than ppm. Furthermore, when the polyisocyanate composition 4 comprises all compounds represented by general formulas (I), (II), and (III), the total amount of compounds represented by general formulas (I), (II), and (III) is preferably 1.0 ppm or more (15.0 × 10⁻¹⁰ ppm), based on the total mass of the polyisocyanate compounds. 4 Less than ppm by mass, more preferably 1.0 ppm by mass or more, 3.0 × 10⁻⁶ 4 Mass below ppm.

[0385] [Polyisocyanate compounds]

[0386] The polyisocyanate compound included in polyisocyanate compositions 1 to 4 is not particularly limited as long as it is a compound different from the compounds represented by the above general formulas (I), (II) and (III), and is any compound having two or more isocyanate groups (-NCO). Examples of polyisocyanate compounds include compounds represented by the following general formula (P) (hereinafter sometimes referred to as "polyisocyanate compound (P)").

[0387] R 70 -(-NCO) p (P)

[0388] In the above general formula (P), R 70 It is a p-valent organic group that does not contain an isocyanate group, where p is an integer between 2 and 12.

[0389] As R 70 Preferably, it is a p-valent aliphatic hydrocarbon group with 1 to 70 carbon atoms or a p-valent aromatic hydrocarbon group with 6 to 70 carbon atoms, and may be substituted or unsubstituted and may have an ether group, carbonyl group, ester group, imino (-NH-), amide group or imide group. As p, 2 or 3 is preferred.

[0390] In R 70 When an aliphatic hydrocarbon group is selected, the number of carbon atoms is preferably 1 to 70 or less, more preferably 1 to 20 or less, even more preferably 1 to 12 or less, and particularly preferably 1 to 10 or less.

[0391] In R 70 When an aromatic hydrocarbon group is selected, the number of carbon atoms is preferably 6 or more and 70 or less, more preferably 6 or more and 20 or less, even more preferably 6 or more and 12 or less, and particularly preferably 6 or more and 10 or less.

[0392] Polyisocyanate compounds (P) can be compounds that do not have end-capped isocyanate groups. In this case, R... 70 It is an organic group that does not contain a capped isocyanate group.

[0393] The isocyanate group that has been capped is a thermally dissociable group that can form an isocyanate group and a capping agent represented by the general formula BL-H. Capping agents are compounds containing active hydrogen. Examples of capping agents include phenolic, alcoholic, thiol, amine, ammonia, oxime, hydroxylamine, and active methylene capping agents.

[0394] In polyisocyanate compounds (P), in R 70Whether or not it contains units that constitute isocyanate polymers is arbitrary. Units that constitute isocyanate polymers refer to isocyanurate groups, biuret groups, iminooxadiazine diketone groups, ureidyl groups, urethane groups, urea diketone groups, and carbamate groups in nitrogen-containing units that are derived from one or more isocyanate groups.

[0395] Polyisocyanate compounds (P) can be compounds represented by the following general formula (Pa).

[0396] (OCN-) p1 -R 71 -L 71 -R 72 -(-NCO) p2 (Pa)

[0397] In the above general formula (Pa), R 71 For cyclic aliphatic or aromatic hydrocarbon groups with a (p1+1) valence, L 71 R is a single bond or a divalent acyclic aliphatic hydrocarbon group. 72 A cyclic aliphatic or aromatic hydrocarbon group with a valence of (p2+1). Within the range where p1+p2 is an integer greater than 2 and less than 12, p1 and p2 are both integers greater than 1.

[0398] Polyisocyanate compounds (P) can be compounds represented by the following general formula (Pb).

[0399] (OCN-) p3 -R 73 -L 73 -R 74 -(-NCO) p4 (Pb)

[0400] In the above general formula (Pb), R 73 For aliphatic or aromatic hydrocarbon groups with a (p3+1) valence, L 73 It can be an ether group, carbonyl group, ester group, imino group (-NH-), amide group or imide group, R 74 It is an aliphatic or aromatic hydrocarbon group with a valence of (p4+1). p3+p4 is an integer between 2 and 12, where p3 and p4 are integers greater than or equal to 0.

[0401] As R 71 R 72 R 73 R 74 and L 71 Aliphatic or aromatic hydrocarbon groups in R can be cited as examples. 70 The aliphatic or aromatic hydrocarbon groups are the same groups shown in the example.

[0402] Specifically, examples of polyisocyanate compounds include pentamethylene diisocyanate (hereinafter sometimes referred to as "PDI"), hexamethylene diisocyanate (hereinafter sometimes referred to as "HDI"), isophorone diisocyanate (hereinafter sometimes referred to as "IPDI"), 4,4'-methylenebis(cyclohexaneisocyanate) (hereinafter sometimes referred to as "MBCI"), diisocyanate toluene (hereinafter sometimes referred to as "TDI"), 4,4'-diphenylmethane diisocyanate (hereinafter sometimes referred to as "MDI"), 4-isocyanate methyl-1,8-octamethylene diisocyanate (hereinafter sometimes referred to as "TTI"), lysine triisocyanate (hereinafter sometimes referred to as "LTI"), and lysine diisocyanate (hereinafter sometimes referred to as "LDI").

[0403] <Methods for manufacturing isocyanate compounds>

[0404] The method for manufacturing the isocyanate compound according to this embodiment includes the following reaction steps: in the presence of a compound having a structure represented by any one or both of the following general formulas (I) and (II), the end-capped isocyanate compound is decomposed into a capping agent and an isocyanate compound by heat treatment to obtain the isocyanate compound.

[0405] [Chemistry 25]

[0406]

[0407] (In general formula (I), R) 1 and R 2 Each is an independent monovalent organic group. R 1 and R 2 They can independently form ring structures from carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds. R 3 (It is an aliphatic hydrocarbon group or a hydrocarbon group containing an aromatic group.)

[0408] [Chemistry 26]

[0409]

[0410] (In general formula (II), R) 210 R is a monovalent organic group. 220 R 230 R 240 and R 250 Each is independently a monovalent organic group or hydrogen. R 210 and R 220 They can bond with each other and form ring structures from carbon-carbon, carbon-oxygen-carbon, or carbon-nitrogen-carbon bonds.

[0411] Methods for the manufacture of isocyanate compounds 1

[0412] Method 1 for manufacturing isocyanate compounds includes the following reaction steps: in the presence of a compound having the structure represented by the above general formula (I), the end-capped isocyanate compound is decomposed into a capping agent and an isocyanate compound by heat treatment to obtain the isocyanate compound.

[0413] The inventors discovered that by heat-treating a capped isocyanate compound in the presence of compound (I) to decompose it into a capping agent and an isocyanate compound, an isocyanate compound can be produced. This method can produce isocyanate compounds with high yields without increasing the amount of by-products, thus completing the present invention.

[0414] The manufacturing method of the present invention will be described below.

[0415] In the reaction step of the method for manufacturing the isocyanate compound in this embodiment, the isocyanate compound is decomposed into a capping agent and an isocyanate compound by heat treatment in the presence of compound (I).

[0416] Compound (I) uses the compound (I) represented by the above general formula (I). Wherein, in general formula (I), in R... 3 In the case of aromatic hydrocarbon groups, the reactivity of the organic amine generated by the decomposition of the ureidyl group with compound (I) is enhanced, which can effectively reduce the ureidyl group and is therefore more preferred.

[0417] In compound (I) used in method 1 of manufacturing isocyanate compounds, as R 3 When an aromatic hydrocarbon group is selected, the number of carbon atoms is preferably 6 or more and 70 or less, more preferably 6 or more and 20 or less, even more preferably 6 or more and 12 or less, and particularly preferably 6 or more and 10 or less.

[0418] As R 3 Aromatic hydrocarbon groups in R can include unsubstituted or substituted aryl and aralkyl groups. Substituents for these aromatic hydrocarbon groups can include aliphatic hydrocarbon groups, hydroxyl groups, cyano groups, and halogen atoms. 3 Aliphatic hydrocarbon groups selected as substituents for aromatic hydrocarbon groups can be exemplified by those in R... 3 The group is the same as the group exemplified as an aliphatic hydrocarbon group. Examples of halogen atoms that can be used as substituents include fluorine, chlorine, bromine, and iodine atoms.

[0419] As R 3 The aromatic hydrocarbon groups in it, specifically, can include phenyl, naphthyl, anthraceneyl, pyrene, phenanthryl, o-tolyl, m-tolyl, p-tolyl, benzyl, phenethyl, etc.

[0420] Urea groups react with isocyanates, for example, through the reactions shown in formulas (70), (71), and (72) below, to generate byproducts.

[0421] [Chemistry 27]

[0422]

[0423] Compound (I) inhibits the formation of byproducts caused by ureidyl groups by reacting with the ureidyl group. The reaction of compound (I) with the ureidyl group is represented by any one or both of the following general formulas A and B.

[0424] Here, it is presumed that the ureidyl group decomposes into an amino group and an isocyanate group via thermal dissociation. The resulting amino group reacts with compound (I) to carry out any or both of the following general formulas A and B. Which reaction of general formula A or general formula B is dominant depends on the decomposition ability of the group bonded to the carbonyl group; therefore, the reaction of general formula A is dominant.

[0425] [Chemistry 28]

[0426]

[0427] Here, after the reaction of general formula B is carried out, the resulting carbamate reacts with isocyanate by the reaction represented by general formula C below, for example, the reactions shown in (67), (68), and (69).

[0428] [Chemistry 29]

[0429]

[0430] On the other hand, when the reaction of general formula A was carried out, the reaction between the resulting trisubstituted urea group and the above-mentioned isocyanate was slight or not confirmed. The reason for this is not yet clear, but it is speculated that it is due to the large steric hindrance of the resulting trisubstituted urea group.

[0431] In the reaction process, from the perspective of increasing the thermal decomposition rate, it is preferable to have a high amount of compound (I). Specifically, relative to the capped isocyanate compound, the amount of compound (I) is preferably 1 ppm or more by mass, more preferably 100 ppm or more by mass, further preferably 1000 ppm or more by mass, and even more preferably 10000 ppm or more by mass. In addition, from the perspective of suppressing the formation of byproducts caused by ureite groups, the amount of compound (I) relative to ureite groups is preferably 0.1 mol% or more, more preferably 1 mol% or more, further preferably 10 mol% or more, and even more preferably 100 mol% or more.

[0432] There is no particular limitation on the reaction temperature (thermal decomposition temperature of the capped isocyanate compound) in the reaction process, and it can be appropriately selected according to the rate of decomposition of the capped isocyanate compound into the capping agent and the isocyanate compound, the degree of thermal modification, and the degree of coloring. From the perspective of suppressing the modification of the isocyanate compound, the reaction temperature is preferably 350°C or lower, more preferably 300°C or lower, and even more preferably 260°C or lower. On the other hand, when the reaction temperature is low, it is necessary to set the temperature of the condenser to a low temperature, and sometimes new equipment is required. Therefore, from this perspective, it is preferable to have a temperature of 50°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher.

[0433] The reaction pressure in the reaction process varies depending on the type of compound used and the reaction temperature. It can be any of reduced pressure, atmospheric pressure, or pressurized pressure, typically above 20 Pa and 2 × 10⁻⁶. 7 It is performed within the range below Pa.

[0434] The reaction process can be carried out in the presence of oxygen. When the reaction process is carried out in the presence of oxygen, it causes thermal modification and coloring of the isocyanate compound; therefore, it is preferable to reduce the amount of oxygen present in the terminal isocyanate compound within the pyrolysis apparatus. On the other hand, considering large-scale manufacturing equipment, reducing the amount of oxygen present in the terminal isocyanate compound within the pyrolysis apparatus requires minimizing air leakage into the manufacturing equipment, thus making the equipment design standards more stringent and increasing equipment costs. From this perspective, it is preferable to manage the conditions with a high oxygen concentration in the gas supplied to the reaction process, preferably greater than 0% by volume, more preferably greater than 0.0001% by volume, and even more preferably greater than 0.001% by volume.

[0435] In the reaction process, any solvent can be used in any proportion. As a solvent, an inert solvent that does not react with the terminal isocyanate compound is preferred. As such a solvent, ester solvents, ether solvents, phosphate ester solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, or carbonate derivative solvents are preferred.

[0436] In the reaction process, the reaction solution may contain any metal in any proportion. The metal may be a complex or a solid. The metal can lower the thermal decomposition temperature of the capped isocyanate compound; however, it may also cause thermal modification, degradation, and discoloration. The metal content relative to the mass of the capped isocyanate compound is preferably less than 10% by mass, more preferably less than 1% by mass, and even more preferably less than 0.1 ppm by mass.

[0437] In the reaction process, the reaction solution may contain organic acids, inorganic acids, organic bases, or inorganic bases. These acids and bases act as catalysts in the thermal decomposition of the terminal isocyanate, lowering the temperature required for thermal decomposition. Furthermore, these acids and bases also act as catalysts for side reactions in the thermal decomposition of the terminal isocyanate. From these perspectives, the content of these organic acids, inorganic acids, organic bases, and inorganic bases relative to the mass of the terminal isocyanate compound is preferably less than 10% by mass, more preferably less than 1% by mass, further preferably less than 0.1% by mass, and particularly preferably less than 1% by mass ppb.

[0438] There are no particular limitations on the thermal decomposition apparatus for the terminated isocyanate compound; known thermal decomposition apparatus can be used. For example, the following apparatus can be used: an apparatus in which a composition containing the terminated isocyanate compound is added to a container connected to a condenser, the container is heated to thermally decompose the terminated isocyanate compound, and then, either simultaneously with the thermal decomposition, the vapor containing the terminating agent is introduced into the condenser to separate the isocyanate compound and the terminating agent in batches; an apparatus in which a composition containing the terminated isocyanate compound is continuously introduced into a distillation column heated to above the thermal decomposition temperature of the terminated isocyanate compound to thermally decompose the terminated isocyanate compound and simultaneously separate the generated terminating agent from the isocyanate compound to continuously obtain free isocyanate compound and terminating agent; an apparatus in which the terminated isocyanate compound is introduced into an evaporator or thin film heated to above the thermal decomposition temperature of the terminated isocyanate compound, and the vapor containing the terminating agent and isocyanate compound generated by thermal decomposition is introduced into a distillation column to separate the terminating agent and isocyanate compound within the distillation column; and so on.

[0439] In the thermal decomposition apparatus for terminated isocyanate compounds, the material used for the parts that come into contact with the composition containing the terminated isocyanate compound and the terminating agent, isocyanate compound, and other components generated during thermal decomposition can be any known material, as long as it does not adversely affect the modification of the terminated isocyanate compound, terminating agent, isocyanate compound, or other components. Specifically, examples of such materials include steel, stainless steel, ceramics, carbon, and materials used as linings.

[0440] [Terminated isocyanate compounds]

[0441] As shown in the following reaction formula, a capped isocyanate compound is a compound that can be thermally dissociated into a capping agent and an isocyanate compound.

[0442] R a -(NH-C(=O)-BL) na → BL-H+ R a -(N=C=O)na

[0443] In the above reaction formula, BL-H is the capping agent and possesses active hydrogen. R a Organic groups with a valence of na, where na is an integer greater than or equal to 1. BL- represents the residue remaining after the active hydrogen has been removed from the end-capping agent.

[0444] [Isocyanate compounds]

[0445] As the isocyanate compound used in the reaction process, it is preferred to use an isocyanate compound represented by the following general formula (IV) (hereinafter sometimes referred to as "isocyanate compound (IV)").

[0446] [Chemistry 30]

[0447]

[0448] (In general formula (IV), R) 21 Organic groups with an n21 valence. (n21 is an integer between 1 and 12.)

[0449] As R 21 There are no particular limitations on the type of organic group, as long as it is 1-valent or 12-valent. Preferably, it is an organic group (hydrocarbon group) formed by carbon and hydrogen atoms or an organic group formed by carbon, oxygen and hydrogen atoms. More preferably, it is an organic group that does not have active hydrogen. 21 The oxygen atoms it contains preferably form ether or ester groups.

[0450] As R 21 The aliphatic hydrocarbon group in it is preferably an alkyl, alkylene, alkane trimethyl, cycloalkyl, cycloalkylene or cycloalkane trimethyl, or a group composed of two or more of them.

[0451] As R 21 The aromatic hydrocarbon group in the group is preferably a group having an aromatic ring with 6 to 13 carbon atoms, either substituted or unsubstituted. Examples of substituents include alkyl, aralkyl, aryl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, etc.

[0452] Examples of isocyanate compounds (IV) include monofunctional isocyanate compounds, difunctional isocyanate compounds, and polyfunctional isocyanate compounds.

[0453] In monofunctional isocyanate compounds, regarding R 21 Monovalent organic groups can include substituted or unsubstituted alkyl, cycloalkyl, aralkyl, aryl, etc.

[0454] In difunctional isocyanate compounds, regarding R 21The divalent organic group can be substituted or unsubstituted alkylene, cycloalkylene, arylene, aryldialkylene, alkyldiarylene, alkyldicycloalkylene, etc. The difunctional isocyanate compound can be a compound with an isocyanate alkyl group, such as isophorone diisocyanate; a compound with an isocyanate cycloalkyl group, such as dicyclohexylmethane 4,4'-diisocyanate; a compound with an isocyanate aryl group, such as diphenylmethane diisocyanate; or a compound with a carbonyl group, such as lysine diisocyanate.

[0455] In polyfunctional isocyanate compounds, regarding R 21 The polyvalent organic groups can include substituted or unsubstituted alkane trimethyl groups, cycloalkane trimethyl groups, and aromatic trimethyl groups. Polyfunctional isocyanate compounds can be compounds with isocyanate alkyl groups, such as 4-isocyanate methyl-1,8-octamethylene diisocyanate, or compounds with carbonyl groups, such as lysine triisocyanate.

[0456] [End-capping agent]

[0457] The capping agent is a compound containing active hydrogen. Preferably, the capping agent in the reaction step comprises one or more compounds selected from the group consisting of hydroxyl compounds, amine compounds, and ammonia. Furthermore, as hydroxyl compounds, one or more compounds selected from the group consisting of aromatic hydroxyl compounds and aliphatic hydroxyl compounds can be cited.

[0458] (As a capping agent for aromatic hydroxyl compounds)

[0459] Regarding the preferred aromatic hydroxyl compounds as capping agents, examples include aromatic hydroxyl compounds represented by the following general formula (V).

[0460] [Chemistry 31]

[0461]

[0462] (In general formula (V), ring A) 31 It is an aromatic hydrocarbon ring with 6 to 20 carbon atoms. 31 It can be a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, an alkoxycarbonyl group with 1 to 20 carbon atoms, an alkylcarbonyloxy group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aryloxy group with 6 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, or an arylalkyloxy group with 7 to 20 carbon atoms. R 31 Can be used with ring A 31 They bond together to form a ring structure. Additionally, n31 is an integer from 1 to 10.

[0463] Ring A 31 It can be a single ring, a fused ring, or other multiple rings. As ring A... 31 Specifically, examples include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, tetraphenylene rings, cyclophenylene rings, pyrene rings, triphenylene rings, cyclopentadiene rings, chamomile rings, heptane rings, indole rings, biphenylene rings, acenaphthene rings, acetylane rings, acetylane anthracene rings, and acetylane anthracene rings. Among these, ring A... 31 Preferably, it is a benzene ring, a naphthalene ring, or an anthracene ring, more preferably a benzene ring.

[0464] The hydroxyl group represented by general formula (V) and the ring A 31 The aromatic carbon atom bond in the middle exhibits phenolic properties. It has a ring A. 31 and n31 R 31 The aromatic hydrocarbon group can be a substituted or unsubstituted aryl group or a monovalent aromatic hydrocarbon group.

[0465] Regarding R 31 Apart from hydrogen atoms, it is a ring A. 31 Substituents. Regarding ring A 31 As shown in general formula (V), it has one hydroxyl group and n31 R groups. 31 n31 R 31 They can each independently originate from R 31 The groups shown in the examples can be selected from mutually distinct groups, or more than two identical groups can be selected. Cycle A 31 In addition to the aforementioned R 31 In addition, it can also have the same characteristics as the ring A. 31 The carbon atom is bonded to hydrogen atoms and / or substituents. These form the ring A. 31 The carbon atom bonded to the hydrogen atom, substituents, and functional groups can also be simply a hydroxyl group and n31 R atoms as shown in general formula (V). 31 .

[0466] (As a capping agent for aliphatic hydroxyl compounds)

[0467] Regarding aliphatic hydroxyl compounds preferred as capping agents, examples include aliphatic hydroxyl compounds represented by the following general formula (VI).

[0468] [Chemistry 32]

[0469]

[0470] (In general formula (VI), R) 41 (Aliphatic hydrocarbon group with 1 to 24 carbon atoms, which may be substituted or unsubstituted and may have an ether, carbonyl, or ester group.)

[0471] R 41 It is a monovalent aliphatic hydrocarbon group. R 41The aliphatic hydrocarbon group in the R has 1 to 24 carbon atoms, preferably 1 to 20, and more preferably 1 to 12. 41 The aliphatic hydrocarbon group in the formula can be saturated or unsaturated. A hydroxyl group in general formula (VI) is associated with R. 41 The saturated carbon atoms in it are bonded together, giving it alcoholic properties.

[0472] (As a capping agent for secondary amine compounds)

[0473] Regarding preferred secondary amine compounds as capping agents, examples include those represented by the following general formula (VII).

[0474] [Chemistry 33]

[0475]

[0476] (In general formula (VII), R) 51 and R 52 Each is an independent monovalent organic group. R 51 and R 52 They can bond with each other and form ring structures from carbon-carbon, carbon-oxygen-carbon, or carbon-nitrogen-carbon bonds.

[0477] Among them, R 51 and R 52 Preferably, it is a monovalent aliphatic hydrocarbon group with 1 to 70 carbon atoms, or a monovalent aromatic hydrocarbon group with 6 to 70 carbon atoms, and may be substituted or unsubstituted, having an ether group, a carbonyl group, or an ester group. 51 and R 52 Preferably, it is an organic group that does not contain active hydrogen, and more preferably, it is a substituted or unsubstituted organic group that does not contain amino groups.

[0478] As R 51 and R 52 Aliphatic hydrocarbon groups in R can be exemplified by alkyl and cycloalkyl groups. 51 and R 52 The aliphatic hydrocarbon group in the compound preferably has 1 to 70 carbon atoms, more preferably 1 to 20, further preferably 1 to 12, and particularly preferably 1 to 10. As R 51 and R 52 Substituents of aliphatic hydrocarbon groups, such as hydroxyl, cyano, and halogen atoms, can be used.

[0479] As R 51 and R 52 Aromatic hydrocarbon groups in R can be exemplified by aryl and aralkyl groups. 51 and R 52The aromatic hydrocarbon group in the aromatic hydrocarbon group preferably has 6 or more and 70 or less carbon atoms, more preferably 6 or more and 20 or less, even more preferably 6 or more and 12 or less, and particularly preferably 6 or more and 10 or less. As R 51 and R 52 Substituents of aromatic hydrocarbon groups in the group can include, for example, aliphatic hydrocarbon groups, hydroxyl groups, cyano groups, halogen atoms, etc.

[0480] In R 51 and R 52 When they bond together to form a ring structure, R 51 and R 52 The groups formed by mutual bonding are divalent organic groups. As R 51 and R 52 Examples of mutually bonded groups include substituted or unsubstituted groups having ether, carbonyl, ester, or substituted imino groups (-N(-R)). 53 )-), -CH=N- group, substituted amide group (-C(=O)-N(-R) 54 )-) or substituted imide group (-C(=O)-N(-R) 55 A divalent aliphatic hydrocarbon group with 1 to 70 carbon atoms or a divalent aromatic hydrocarbon group with 6 to 70 carbon atoms. As R 53 R 54 and R 55 Examples of 1-valent aliphatic or aromatic hydrocarbon groups can be given.

[0481] Methods for manufacturing isocyanate compounds 2

[0482] The method for manufacturing the isocyanate compound according to this embodiment includes the following reaction steps: in the presence of a compound having the structure represented by the above general formula (II) (hereinafter sometimes referred to as "quinazolinedione structure (II)"), the end-capped isocyanate compound is decomposed into a capping agent and an isocyanate compound by heat treatment to obtain the isocyanate compound.

[0483] The inventors discovered that by thermally treating a capped isocyanate compound in the presence of a compound having a quinazolinidone structure (II) to decompose it into a capping agent and an isocyanate compound, the problem of thermal decomposition rate can be solved without an increase in the amount of byproducts generated, thus completing the present invention.

[0484] [Reaction Process]

[0485] In the reaction step of the method for manufacturing the isocyanate compound in this embodiment, the isocyanate compound is decomposed into a capping agent and an isocyanate compound by heat treatment in the presence of a compound having a quinazolinidone structure (II), thereby obtaining the isocyanate compound.

[0486] In the reaction process, from the perspective of increasing the thermal decomposition rate, it is preferable to have a high amount of compounds having a quinazolinedione structure (II). Specifically, the amount of compounds having a quinazolinedione structure (II) relative to the capped isocyanate compound is preferably 1 ppm by mass or more, more preferably 100 ppm by mass or more, further preferably 1000 ppm by mass or more, and even more preferably 10000 ppm by mass or more.

[0487] The descriptions of the terminated isocyanate compound, isocyanate compound, and terminator in Method 2 for manufacturing isocyanate compound are the same as those in Method 1 for manufacturing isocyanate compound described above.

[0488] There is no particular limitation on the reaction temperature (thermal decomposition temperature of the capped isocyanate compound) in the reaction process; it is appropriately selected based on the rate at which the capped isocyanate compound decomposes into the capping agent and the isocyanate compound, the degree of thermal modification, and the degree of coloration. From the perspective of suppressing the modification of the isocyanate compound, the reaction temperature is preferably 350°C or lower, more preferably 300°C or lower, and even more preferably 260°C or lower. On the other hand, when the reaction temperature is low, it is necessary to set the temperature of the condenser to a low temperature, and sometimes new equipment is required. Therefore, from this perspective, it is preferable to have a temperature of 50°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher.

[0489] The reaction pressure in the reaction process varies depending on the type of compound used and the reaction temperature. It can be any of reduced pressure, atmospheric pressure, or pressurized pressure, typically above 20 Pa and 2 × 10⁻⁶. 7 It is performed within the range below Pa.

[0490] In the reaction process, any solvent can be used in any proportion. As a solvent, an inert solvent that does not react with the terminal isocyanate compound is preferred. As such a solvent, ester solvents, ether solvents, phosphate ester solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, or carbonate derivative solvents are preferred.

[0491] In the reaction process, the reaction solution may contain any metal in any proportion. The metal may be a complex or a solid. The metal can lower the thermal decomposition temperature of the capped isocyanate compound; however, it may also cause thermal modification, degradation, and discoloration. The metal content relative to the mass of the capped isocyanate compound is preferably less than 10% by mass, more preferably less than 1% by mass, and even more preferably less than 0.1 ppm by mass.

[0492] In the reaction process, the reaction solution may contain organic acids, inorganic acids, organic bases, or inorganic bases. These acids and bases act as catalysts in the thermal decomposition of the terminal isocyanate, lowering the temperature required for thermal decomposition. Furthermore, these acids and bases also act as catalysts for side reactions in the thermal decomposition of the terminal isocyanate. From these perspectives, the content of these organic acids, inorganic acids, organic bases, and inorganic bases relative to the mass of the terminal isocyanate compound is preferably less than 10% by mass, more preferably less than 1% by mass, further preferably less than 0.1% by mass, and particularly preferably less than 1% by mass ppb.

[0493] There are no particular limitations on the thermal decomposition apparatus for the terminated isocyanate compound; known thermal decomposition apparatus can be used. For example, the following apparatus can be used: an apparatus in which a composition containing the terminated isocyanate compound is added to a container connected to a condenser, the container is heated to thermally decompose the terminated isocyanate compound, and then, either simultaneously with the thermal decomposition, the vapor containing the terminating agent is introduced into the condenser to separate the isocyanate compound and the terminating agent in batches; an apparatus in which a composition containing the terminated isocyanate compound is continuously introduced into a distillation column heated to above the thermal decomposition temperature of the terminated isocyanate compound to thermally decompose the terminated isocyanate compound and simultaneously separate the generated terminating agent from the isocyanate compound to continuously obtain free isocyanate compound and terminating agent; an apparatus in which the terminated isocyanate compound is introduced into an evaporator or thin film heated to above the thermal decomposition temperature of the terminated isocyanate compound, and the vapor containing the terminating agent and isocyanate compound generated by thermal decomposition is introduced into a distillation column to separate the terminating agent and isocyanate compound within the distillation column; and so on.

[0494] In the thermal decomposition apparatus for terminated isocyanate compounds, the material used for the parts that come into contact with the composition containing the terminated isocyanate compound and the terminating agent, isocyanate compound, and other components generated during thermal decomposition can be any known material, as long as it does not adversely affect the modification of the terminated isocyanate compound, terminating agent, isocyanate compound, or other components. Specifically, examples of such materials include steel, stainless steel, ceramics, carbon, and materials used as linings.

[0495] Methods for manufacturing isocyanate compounds 3

[0496] The method 3 for manufacturing the isocyanate compound of this embodiment includes the following reaction steps: in the presence of a compound having the structure represented by the above general formulas (I) and (II), the end-capped isocyanate compound is decomposed into a capping agent and an isocyanate compound by heat treatment to obtain the isocyanate compound.

[0497] In the reaction step of obtaining an isocyanate compound by heat treatment of a capped isocyanate compound to decompose it into a capping agent and an isocyanate compound in the presence of compounds having structures represented by both general formulas (I) and (II), the amount of compound (I) or (II) relative to the capped isocyanate compound is preferably 1 ppm or more by mass, more preferably 100 ppm or more by mass, further preferably 1000 ppm or more by mass, and even more preferably 10000 ppm or more by mass, respectively. Furthermore, from the perspective of suppressing the formation of byproducts caused by ureite groups, the amount of compound (I) relative to ureite groups is preferably 0.1 mol% or more, more preferably 1 mol% or more, further preferably 10 mol% or more, and even more preferably 100 mol% or more.

[0498] The descriptions of the terminated isocyanate compound, isocyanate compound, and terminator in method 3 of manufacturing isocyanate compound are the same as those in method 1 of manufacturing isocyanate compound described above.

[0499] Example

[0500] The present invention will be described in more detail below through examples, but the present invention is not limited to the examples. It should be noted that all reagents used as raw materials are purified products.

[0501] <Preparation of Polyisocyanate Composition 1>

[0502] The polyisocyanate compound, compound (I), and reaction terminator were mixed to prepare the polyisocyanate compositions of Examples 1-26 and Comparative Examples 1-2.

[0503] The mixing amounts of each component and the specific materials are listed in Tables 1 and 2.

[0504] As a polyisocyanate compound, any one of HDI, IPDI, PDI, MBCI, TDI, MDI, TTI, LTI, and LDI is used.

[0505] Dibutyl phosphate (DBP) is used as a reaction terminator.

[0506] As compound (I), the following compounds (I)-1 to (I)-11 are used.

[0507] In the following chemical formulas, each symbol refers to one of the following groups.

[0508] •Me: Methyl

[0509] •Et: Ethyl

[0510] • n-Bu: n-Butyl

[0511] •i-Pr: Isopropyl

[0512] •Oc: sine

[0513] • Cumyl: Cumyl

[0514] [Chemistry 34]

[0515]

[0516] [Chemistry 35]

[0517]

[0518] [Chemistry 36]

[0519]

[0520] <Evaluation of coloring suppression>

[0521] For polyisocyanate compositions before and after storage, color tests based on Hazen unit chromaticity (APHA grade) were performed to evaluate color inhibition.

[0522] Specifically, regarding the APHA grade before storage, the test was performed using a sample prepared by dissolving 1 g of the obtained polyisocyanate composition in 2 g of benzyltoluene. The grade was based on the values ​​measured using a Hazen measuring instrument, according to the following evaluation criteria.

[0523] (Evaluation Criteria)

[0524] Level 1: APHA is 0 or higher and less than 5

[0525] Level 2: APHA is 5 or higher but less than 10

[0526] Level 3: APHA is 10 or higher but less than 15

[0527] Level 4: APHA is 15 or higher and less than 20

[0528] Level 5: APHA is 20 or higher but less than 25

[0529] Level 6: APHA is 25 or higher and less than 30

[0530] Level 7: APHA is 30 or higher but less than 35

[0531] Level 8: APHA is 35 or higher and less than 40

[0532] Level 9: APHA is 40 or higher but less than 45

[0533] Level 10: APHA score of 45 or higher but less than 50

[0534] Regarding the APHA grade after 300 days of storage, the test was performed using a sample prepared by dissolving 1 g of the aforementioned polyisocyanate composition after 300 days of storage in 2 g of benzyltoluene. The grade was based on the values ​​measured using a Hazen measuring instrument, according to the same evaluation criteria as Evaluation 1.

[0535] <Evaluation of storage stability>

[0536] Regarding storage stability, the polyisocyanate composition after a 300-day storage period was used as the sample, and the results were determined using GPC. The following area ratios were used for evaluation.

[0537] Area ratio... (B) / (A)

[0538] (In the above area ratios, (A) is the area of ​​the peak corresponding to isocyanates with more than two functions in the UV absorption (210nm), and (B) is the area of ​​the peak corresponding to the compound having UV absorption (wavelength 254nm) in the region of isocyanate decamer or more.)

[0539] Compounds exhibiting UV absorption (wavelength 254 nm) in regions above the isocyanate decamer are high-boiling-point impurities. When the formation of such compounds is low, storage stability can be assessed as improved.

[0540] Regarding the peak area ratio (%) after 300 days of storage, the polyisocyanate composition at the end of the storage period was used as a sample and determined using GPC. The storage method was as follows: 300g of the polyisocyanate composition obtained above was placed in a 500mL SUS storage container, nitrogen was purged, and the mixture was stored for 300 days under the storage conditions in Kojima area, Kurashiki City, Okayama Prefecture, Japan.

[0541] In Example 18 and Comparative Example 2, the storage container was changed to a glass bottle and the storage location was changed to outdoors for storage.

[0542] (GPC determination method)

[0543] Equipment used: HLC-8120 (manufactured by Tosoh Corporation)

[0544] Columns used: TSK GELSuperH1000, TSK GELSuperH2000, TSK GELSuperH3000 (all manufactured by Tosoh Corporation)

[0545] Sample concentration: 5 wt / vol% (50 mg of sample is dissolved in 1 mL of tetrahydrofuran (THF))

[0546] Carrier: THF

[0547] Detection method: PDA detector

[0548] Flow rate: 0.6 mL / min

[0549] Column temperature: 30℃

[0550] The calibration curves were prepared using polystyrene with a molecular weight of 1,000 to 20,000.

[0551] [Table 1]

[0552]

[0553] [Table 2]

[0554]

[0555] According to Tables 1 and 2, polyisocyanate composition 1 containing compounds selected from the group consisting of compound (I) exhibits excellent storage stability and color inhibition.

[0556] The polyisocyanate composition without compound (I) gelled during 300 days of storage and could not be subjected to GPC determination.

[0557] <Preparation of Polyisocyanate Composition 2>

[0558] A polyisocyanate composition 2 comprising a quinazolinidone compound and a polyisocyanate compound is prepared.

[0559] Specifically, as shown in Table 3, polyisocyanate composition 2 is prepared using any one of HDI, IPDI, PDI, MBCI, TDI, MDI, TTI, LTI, and LDI as the polyisocyanate compound.

[0560] As a quinazolinidone compound, it is a compound obtained by reacting a secondary amine compound with a carbonic acid derivative, using any one of the following: a compound derived from N-methylaniline (NMA), a compound derived from N-ethylaniline (NEA), a compound derived from N-butylaniline (NBA), or a compound derived from N-isopropylaniline (NiPA).

[0561] Regarding compounds derived from NMA, in the above general formula (II), R 210 For methyl, R 220 R 230 R 240 and R 250 It is hydrogen.

[0562] Regarding compounds from NEA, in the above general formula (II), R210 For ethyl, R 220 R 230 R 240 and R 250 It is hydrogen.

[0563] Regarding the compounds from the NBA, in the above general formula (II), R 210 It is n-butyl, R 220 R 230 R 240 and R 250 It is hydrogen.

[0564] Regarding compounds derived from NiPA, in the above general formula (II), R 210 It is isopropyl, R 220 R 230 R 240 and R 250 It is hydrogen.

[0565] APHA grading was performed before storage using the same method as described in the above-mentioned evaluation of colorimetric inhibition.

[0566] Storage stability was evaluated using the same method described in the above-mentioned evaluation of storage stability.

[0567] <APHA rating after storage>

[0568] Regarding the APHA grade after 300 days of storage, the test was conducted using a sample prepared by dissolving 1 g of the polyisocyanate composition stored for 300 days in 2 g of benzyltoluene, as described in the above-described evaluation of color inhibition. The grade was based on the values ​​measured using a Hazen measuring instrument, according to the same evaluation criteria as described in the above-described evaluation of color inhibition.

[0569] [Table 3]

[0570]

[0571] According to Table 3, polyisocyanate composition 2 containing compounds selected from the group consisting of quinazolinidone compounds (II) exhibits excellent storage stability and color inhibition.

[0572] The polyisocyanate composition without quinazolinidone compound (II) gelled during 300 days of storage and could not be subjected to GPC assays.

[0573] <Preparation of Polyisocyanate Composition 3>

[0574] 3. A polyisocyanate composition comprising a trisubstituted urea compound and a polyisocyanate compound is prepared.

[0575] Specifically, as shown in Table 4, polyisocyanate composition 3 is prepared using any one of HDI, IPDI, PDI, MBCI, TDI, MDI, TTI, LTI, and LDI as the polyisocyanate compound.

[0576] The trisubstituted urea compound is a compound obtained by reacting at least one of the isocyanate groups of a polyisocyanate compound with a secondary amine compound. The secondary amine compound is any one of N-methylaniline (NMA), N-ethylaniline (NEA), N-butylaniline (NBA), N-isopropylaniline (NiPA), diethylamine (DEA), and diphenylamine (DPA).

[0577] The trisubstituted urea compounds obtained using HDI are represented by the above general formula (1).

[0578] The trisubstituted urea compounds obtained using IPDI are represented by the above general formula (2).

[0579] The trisubstituted urea compounds obtained using PDI are represented by the above general formula (3).

[0580] The trisubstituted urea compounds obtained using MBCI are represented by the above general formula (4).

[0581] The trisubstituted urea compounds obtained using TDI are represented by the above general formulas (5) and (6).

[0582] The trisubstituted urea compounds obtained using MDI are represented by the above general formula (7).

[0583] The trisubstituted urea compounds obtained using TTI are represented by the above general formula (8).

[0584] The trisubstituted urea compounds obtained using LTI are represented by the above general formula (9).

[0585] The trisubstituted urea compounds obtained using LDI are represented by the above general formula (10).

[0586] Regarding the trisubstituted urea compounds obtained by reacting polyisocyanate compounds with NMA, in the above general formula (III), R 320 and R 330 One of them is methyl and the other is phenyl.

[0587] Regarding the trisubstituted urea compounds obtained by reacting polyisocyanate compounds with NEA, in the above general formula (III), R 320 and R 330 One of them is ethyl and the other is phenyl.

[0588] Regarding the trisubstituted urea compounds obtained by reacting polyisocyanate compounds with NBA, in the above general formula (III), R 320 and R 330 One of them is n-butyl and the other is phenyl.

[0589] Regarding the trisubstituted urea compounds obtained by reacting polyisocyanate compounds with NiPA, in the above general formula (III), R 320 and R 330 One of them is isopropyl and the other is phenyl.

[0590] Regarding the trisubstituted urea compounds obtained by reacting polyisocyanate compounds with DEA, in the above general formula (III), R 320 and R 330 All are ethyl.

[0591] Regarding the trisubstituted urea compounds obtained by reacting polyisocyanate compounds with DPA, in the above general formula (III), R 320 and R 330 All are phenyl.

[0592] APHA grading was performed before storage using the same method as described in the above-mentioned evaluation of colorimetric inhibition.

[0593] Storage stability was evaluated using the same method described in the above-mentioned evaluation of storage stability.

[0594] <APHA rating after storage>

[0595] Regarding the APHA grade after 300 days of storage, the test was conducted using a sample prepared by dissolving 1 g of the polyisocyanate composition stored for 300 days in 2 g of benzyltoluene, as described in the above-described evaluation of color inhibition. The grade was based on the values ​​measured using a Hazen measuring instrument, according to the same evaluation criteria as described in the above-described evaluation of color inhibition.

[0596] [Table 4]

[0597]

[0598] According to Table 4, the selection of R is included. 320 and R 330 The polyisocyanate composition 3, which consists of at least one of trisubstituted urea compounds (III) having an aromatic group, exhibits excellent storage stability and color inhibition.

[0599] Polyisocyanate compositions that do not contain trisubstituted urea compounds (III) gelled during 300 days of storage and could not be subjected to GPC assays.

[0600] Contains R 320 and R 330 Polyisocyanate compositions of trisubstituted urea compounds that are not aromatic groups have poor storage stability.

[0601] <Preparation of Polyisocyanate Composition 4>

[0602] 4. A polyisocyanate composition comprising two or more of compound (I), quinazolinidone compound (II), and trisubstituted urea compound (III).

[0603] As shown in Table 5, polyisocyanate composition 4 was prepared using any one of HDI, IPDI, PDI, MBCI, TDI, MDI, TTI, LTI, and LDI as the polyisocyanate compound. Here, compound (I), the quinazolinidone compound, and the trisubstituted urea compound were prepared using the same method as for the preparation of polyisocyanate compositions 1-3.

[0604] APHA grading was performed before storage using the same method as described in the above-mentioned evaluation of colorimetric inhibition.

[0605] Storage stability was evaluated using the same method described in the above-mentioned evaluation of storage stability.

[0606] <APHA rating after storage>

[0607] Regarding the APHA grade after 300 days of storage, the test was conducted using a sample prepared by dissolving 1 g of the polyisocyanate composition stored for 300 days in 2 g of benzyltoluene, as described in the above-described evaluation of color inhibition. The grade was based on the values ​​measured using a Hazen measuring instrument, according to the same evaluation criteria as described in the above-described evaluation of color inhibition.

[0608] [Table 5]

[0609]

[0610] According to Table 5, the polyisocyanate composition 4 containing two or more of compound (I), quinazolinedione compound (II), and trisubstituted urea compound (III) exhibits excellent storage stability and color inhibition. In particular, the peak area ratio (%) of Examples 4-IV to 10-IV containing compound (I), quinazolinedione compound (II), and trisubstituted urea compound (III) is 3 or less, and the APHA grade is 2 or less, resulting in even better storage stability and color inhibition.

[0611] The polyisocyanate composition (Comparative Examples 19-IV) that did not contain any of the compounds (I), quinazolinidone compounds (II), and trisubstituted urea compounds (III) gelled during 300 days of storage and could not be subjected to GPC determination.

[0612] <Method 1 for the manufacture of isocyanate compounds>

[0613] Isocyanate compounds are prepared in the presence of compound (I).

[0614] [Example of manufacturing end-capped isocyanate compounds]

[0615] 20 parts by mass of hexamethylene diisocyanate, 80 parts by mass of phenol, and 0.1 parts by mass of water were mixed and reacted at 150°C for 20 hours to synthesize diphenylhexane-1,6-dimethyldicarbamate. Excess phenol was then removed by vacuum distillation at 100°C and 1 Pa. 1H NMR analysis revealed a capped isocyanate composition BL-1 containing 5 mol% ureidyl groups and 95 mol% capped isocyanate groups.

[0616] Table 6 shows the abbreviations of the obtained capped isocyanate compounds, the content of ureidyl (-NHCONH-) groups, and the content of capped isocyanate (BL-NCO) groups.

[0617] [Examples 1A to 15A]

[0618] In a 300mL glass container equipped with a pressure-reducing device at the front end of condenser 1 (the condensate from condenser 1 flows into a 300mL glass container) and condenser 2 (the condensate from condenser 2 is recovered as TOP liquid instead of flowing into the 300mL glass container), the end-capped isocyanate compound, compound (I), and solvent of the above-described manufacturing example were added as shown in Table 7. Then, the internal temperature (reaction temperature), vacuum level, temperature of condenser 1, and temperature of condenser 2 were set as shown in Table 2. The pressure inside the reaction vessel was adjusted to an absolute pressure of 380mmHg using the pressure-reducing device, and the reaction was carried out for 3 hours.

[0619] Calculate the yield of isocyanate groups (NCO groups mol%) and the residual rate of urea groups (urea groups mol%) in the obtained reaction solution.

[0620] [Comparative Examples 1A to 11A]

[0621] As shown in Table 8, the capped isocyanate compound and solvent were added to a glass container without adding compound (I), and the reaction conditions were set. Otherwise, the capped isocyanate compound was heat-treated using the same method as in Examples 1A to 15A.

[0622] It should be noted that in the following table, each abbreviation refers to one of the following compounds.

[0623] (Isocyanate compounds)

[0624] HDI: 1,6-Hexamethylene diisocyanate

[0625] IPDI: Isophorone diisocyanate (mixture of isomers)

[0626] TDI: Toluene diisocyanate (mixture of isomers)

[0627] MDI: Diphenylmethane diisocyanate (mixture of isomers)

[0628] HMDI: Dicyclohexylmethane-4,4'-diisocyanate

[0629] (End-capping agent)

[0630] PhOH: Phenol

[0631] o-cresol: o-cresol

[0632] m-cresol: m-cresol

[0633] p-cresol: p-cresol

[0634] n-BuOH: n-Butanol

[0635] DBA: Dibutylamine

[0636] NMA: N-methylaniline

[0637] (solvent)

[0638] Cycloalkanes: Cycloalkan solvents (EXXOL) TM D80)

[0639] The structure of compound (I) is shown in Table 6 below.

[0640] [Chemistry 37]

[0641]

[0642] [Table 6]

[0643]

[0644] [Table 7]

[0645]

[0646] [Table 8]

[0647]

[0648] According to Table 7, when the end-capped isocyanate compound is thermally decomposed in the presence of compound (I), the residual rate of ureite groups (ureite group mol%) decreases and the yield of isocyanate groups (NCO group mol%) increases.

[0649] On the other hand, according to Table 8, when the capped isocyanate compound is thermally decomposed in the absence of compound (I), the residual rate of urea groups does not change, while the yield of isocyanate groups decreases.

[0650] <Method 2 for the manufacture of isocyanate compounds>

[0651] Isocyanate compounds are prepared in the presence of compound (II).

[0652] [Example of manufacturing end-capped isocyanate compounds]

[0653] One part by mass of isocyanate compound and nine parts by mass of end-capping agent were added to a pressure vessel made of SUS, and the mixture was reacted at 150°C for 20 hours. The free end-capping agent contained in the resulting reaction solution was removed by vacuum distillation to obtain a end-capped isocyanate composition.

[0654] Table 9 shows the abbreviations of the obtained capped isocyanate compounds and the content of the capped isocyanate (BL-NCO) groups.

[0655] [Examples 1B-17B]

[0656] In a 300mL glass container equipped with a pressure-reducing device at the front end of condenser 1 (the condensate from condenser 1 flows into a 300mL glass container) and condenser 2 (the condensate from condenser 2 is recovered as TOP liquid instead of flowing into the 300mL glass container), as shown in Table 10, the end-capped isocyanate compound of the above-described manufacturing example, a catalyst equivalent to compound (II), and a solvent were added. Then, the internal temperature (reaction temperature), vacuum level, temperature of condenser 1, and temperature of condenser 2 were set as shown in Table 2, and the reaction was carried out for 3 hours.

[0657] Calculate the yield of isocyanate groups in the resulting reaction solution (NCO group mol%) and the residual rate of end-capped isocyanate groups (BL-NCO group mol%). Additionally, calculate the sum of the isocyanate group yield and the residual rate of end-capped isocyanate groups in mass balance (MB mol%).

[0658] [Comparative Examples 1B-13B]

[0659] As shown in Table 11, the capped isocyanate compound and solvent were added to a glass container without a catalyst, and the reaction conditions were set. Otherwise, the capped isocyanate compound was heat-treated using the same method as in Examples 1B to 17B.

[0660] [Comparative Example 14B]

[0661] As shown in Table 11, the capped isocyanate compound, catalyst and solvent were added to a glass container and the reaction conditions were set. Otherwise, the capped isocyanate compound was heat-treated using the same method as in Examples 1B to 17B.

[0662] It should be noted that in the following table, each abbreviation refers to one of the following compounds.

[0663] (Isocyanate compounds)

[0664] HDI: 1,6-Hexamethylene diisocyanate

[0665] IPDI: Isophorone diisocyanate (mixture of isomers)

[0666] TDI: Toluene diisocyanate (mixture of isomers)

[0667] MDI: Diphenylmethane diisocyanate (mixture of isomers)

[0668] HMDI: Dicyclohexylmethane-4,4'-diisocyanate

[0669] (End-capping agent)

[0670] PhOH: Phenol

[0671] o-cresol: o-cresol

[0672] m-cresol: m-cresol

[0673] p-cresol: p-cresol

[0674] n-BuOH: n-Butanol

[0675] DBA: Dibutylamine

[0676] NMA: N-methylaniline

[0677] (Catalyst: Compound (II))

[0678] MQD: 1-Methyl-2,4(1H,3H)-quinazolinidone

[0679] BQD: 1-Butyl-2,4(1H,3H)-quinazolinidone

[0680] PQD: 1-Phenyl-2,4(1H,3H)-quinazolinidone

[0681] (solvent)

[0682] DBT: Dibenzyltoluene

[0683] [Table 9]

[0684]

[0685] [Table 10]

[0686]

[0687] [Table 11]

[0688]

[0689] According to Table 10, when the end-capped isocyanate compound is thermally decomposed in the presence of a compound with a quinazolinidone structure (II), the residual rate of the end-capped isocyanate group (BL-NCO group mol%) decreases and the yield of isocyanate group (NCO group mol%) increases.

[0690] Industrial applicability

[0691] The polyisocyanate compositions 1 to 4 according to this embodiment can provide polyisocyanate compositions with excellent storage stability and color inhibition.

[0692] According to the isocyanate compound manufacturing methods 1 to 2 of this embodiment, a method for manufacturing an isocyanate compound that can increase the thermal decomposition rate of the end-capped isocyanate compound without increasing the amount of by-products generated can be provided.

Claims

1. A polyisocyanate composition comprising at least one compound represented by any one of the following general formulas (I), (II), and (III), and a polyisocyanate compound. [Chemistry 1] In general formula (I), R 1 and R 2 Each is an independent monovalent organic group; R 1 and R 2 They can independently form ring structures from carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds; R 3 It is an aliphatic hydrocarbon group or a hydrocarbon group with an aromatic group; [Chemistry 2] In general formula (II), R 210 R is a monovalent organic group. 220 R 230 R 240 and R 250 Each is independently a monovalent organic group or hydrogen; R 210 and R 220 They can bond with each other and form ring structures from carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds; [Chemistry 3] In general formula (III), R 310 For (n+m) valence organic groups, n is an integer from 0 to 12, m is an integer from 1 to 12, n+m is an integer less than 13, R 320 and R 330 Each is an independent monovalent organic group; R 320 and R 330 They can bond together and form ring structures from carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds; R 320 and R 330 At least one of them has an aromatic group.

2. The polyisocyanate composition according to claim 1, wherein, Based on the total mass of the aforementioned polyisocyanate compounds, containing 1.0 ppm or more of 1.0 × 10⁻⁶ ppm. 4 At least one compound represented by any one of the general formulas (I), (II), and (III) in the mass fraction of ppm or less.

3. A method for producing an isocyanate compound, comprising the following reaction steps: in the presence of a compound having a structure represented by any one or both of the following general formulas (I) and (II), a capped isocyanate compound is decomposed into a capping agent and an isocyanate compound by heat treatment to obtain the isocyanate compound. [Chemistry 4] In general formula (I), R 1 and R 2 Each is an independent monovalent organic group; R 1 and R 2 They can independently form ring structures from carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds; R 3 It is an aliphatic hydrocarbon group or a hydrocarbon group with an aromatic group; [Chemistry 5] In general formula (II), R 210 R is a monovalent organic group. 220 R 230 R 240 and R 250 Each is independently a monovalent organic group or hydrogen; R 210 and R 220 They can bond with each other and form ring structures by carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds.

4. The method for manufacturing the isocyanate compound as described in claim 3, wherein, The capping agent comprises one or more compounds selected from the group consisting of hydroxyl compounds, amine compounds, and ammonia.

5. The method for manufacturing the isocyanate compound as described in claim 3 or 4, wherein, The isocyanate compound is an isocyanate compound represented by the following general formula (IV). [Chemistry 6] In general formula (IV), R 21 It is an organic group with an n21 valence; n21 is an integer greater than 1 and less than 12.

6. The method for producing the isocyanate compound as described in claim 3 or 4, wherein, The capping agent is an aromatic hydroxy compound represented by the following general formula (V). [Chemistry 7] In general formula (V), ring A 31 It is an aromatic hydrocarbon ring with 6 to 20 carbon atoms; R 31 It can be a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, an alkoxycarbonyl group with 1 to 20 carbon atoms, an alkylcarbonyloxy group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aryloxy group with 6 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, or an arylalkyloxy group with 7 to 20 carbon atoms; R 31 Can be used with ring A 31 The bonding forms a ring structure; in addition, n31 is an integer from 1 to 10.

7. The method for producing the isocyanate compound as described in claim 3 or 4, wherein, The capping agent is an aliphatic hydroxy compound represented by the following general formula (VI). [Chemistry 8] In general formula (VI), R 41 It is an aliphatic hydrocarbon group with 1 to 24 carbon atoms, which may be substituted or unsubstituted and may have an ether, carbonyl, or ester group.

8. The method for producing the isocyanate compound as described in claim 3 or 4, wherein, The capping agent is a secondary amine compound represented by the following general formula (VII). [Chemistry 9] In general formula (VII), R 51 and R 52 Each is an independent monovalent organic group; R 51 and R 52 They can bond with each other and form ring structures by carbon-carbon bonds, carbon-oxygen-carbon bonds, or carbon-nitrogen-carbon bonds.

9. The method for producing the isocyanate compound as described in claim 3 or 4, wherein, In the reaction step, the amount of a compound having the structure represented by either or both of the general formulas (I) and (II) is 1 ppm by mass or more relative to the capped isocyanate compound.

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