Polyisocyanate composition and method for producing isocyanate compound

Abstract

Disclosed is a polyisocyanate composition which contains at least one compound represented by any one of general formulae (I), (II), and (III), and a polyisocyanate compound. Also disclosed is a method for producing an isocyanate compound, the method including a reaction step for decomposing a blocked isocyanate compound into a blocking agent and an isocyanate compound by a heat treatment in the presence of a compound which has a structure that is represented by one or both of general formulae (I) and (II), thereby obtaining an isocyanate compound.

Description

Polyisocyanate composition and method for producing isocyanate compound

[0001] The present invention relates to a polyisocyanate composition and a method for producing an isocyanate compound. This application claims priority to 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.

[0002] Polyisocyanate compounds are used in polyurethane synthesis and as curing agents, and are utilized in a wide range of fields, including flexible foams, rigid foams, elastomers, adhesives, paints, and binders.

[0003] For example, Patent Document 1 describes an isocyanate composition containing a tri- or higher functional isocyanate compound and a compound having at least one unsaturated bond other than an unsaturated bond constituting an aromatic ring.

[0004] Patent Document 2 describes a polyisocyanate composition containing a polyisocyanate and a compound having an unsaturated bond, or at least one inactive compound 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.

[0005] Isocyanates are also widely used as raw materials for the production of polyurethane foams, paints, adhesives, etc. The main industrial method for producing isocyanates is the reaction of an amine compound with phosgene (the phosgene process), and almost all of the isocyanates produced worldwide are produced by the phosgene process. However, the phosgene process has many problems related to the raw material phosgene and the by-product hydrogen chloride.

[0006] In light of this background, a method for producing an isocyanate without using phosgene is desired. For example, Patent Document 3 describes a method for producing 1,6-hexamethylene diisocyanate by thermally decomposing a 1,6-hexamethylene dicarbamate ester in the presence of a specific catalyst. Furthermore, Patent Document 4 describes a method for producing a diisocyanate compound by reacting a diamine with dimethyl carbonate in the presence of an alkali catalyst to synthesize a urethane compound, and then thermally decomposing the urethane compound in the presence of a catalyst.

[0007] In addition, isocyanates are highly reactive and react easily with compounds such as water. Therefore, to improve stability, they are sometimes converted to blocked isocyanates, and when used, the blocking agent is dissociated by heating to regenerate the isocyanate. Blocked isocyanates have low reactivity with active hydrogen compounds, can be stored stably, and are less toxic than isocyanates, making them useful as one-component paints, adhesives, and molding compounds.

[0008] In addition, blocked isocyanates have the property of dissociating into an isocyanate and a blocking agent upon thermal decomposition. Therefore, blocked isocyanates can be decomposed into an isocyanate and a blocking agent by thermal decomposition, and the resulting isocyanate and blocking agent can be separated after or simultaneously with the thermal decomposition. The separated isocyanate and blocking agent are useful because they can also be used as raw materials in the production of isocyanates.

[0009] Various methods for producing blocked isocyanates are known, including, for example, a method of producing a blocked isocyanate by directly reacting an isocyanate with a blocking agent, a method of producing a blocked isocyanate by reacting a carbamic acid chloride obtained by reacting an amine with phosgene with the blocking agent, a method of producing a blocked isocyanate by reacting a carbamic acid with a blocking agent and a condensing agent, a method of producing a blocked isocyanate by reacting an amine with a carbonic acid derivative to produce a blocked isocyanate containing a compound derived from the carbonic acid derivative, and a method of producing a blocked isocyanate by reacting an amine with a carbonic acid derivative and a blocking agent.

[0010] In particular, when a blocked isocyanate is produced using an amine as a raw material, as described in Patent Document 5, a side reaction may occur in which the resulting blocked isocyanate and a ureylene group are produced.

[0011] When an isocyanate is produced by thermally decomposing such a blocked isocyanate composition containing a ureylene group into an isocyanate and a blocking agent and separating the resulting isocyanate and blocking agent after or simultaneously with the thermal decomposition, the resulting isocyanate may react with the ureylene group to form a biuret, which may result in an increase in the amount of by-products produced.

[0012] International Publication No. 2018 / 070539 International Publication No. 2014 / 069605 JP-A-6-239826 JP-A-64-85956 JP-A-2022-180170

[0013] When polyisocyanate compounds are used in fields where high appearance quality is required, such as as raw materials for polyurethane, it is important that the polyisocyanate compounds are little discolored. However, isocyanates generally tend to be easily oxidized by oxygen in the air, resulting in deterioration or discoloration. Furthermore, when an isocyanate polymer is produced by polymerization of a diisocyanate, the isocyanate tends to easily become discolored due to the catalyst or solvent used in the polymerization reaction.

[0014] Furthermore, in a method for producing an isocyanate compound, when an isocyanate compound is obtained by thermally decomposing a blocked isocyanate compound in the presence of a catalyst, improving the thermal decomposition rate may be accompanied by an increase in the amount of by-products produced.

[0015] One aspect of the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyisocyanate composition that is excellent in storage stability and coloration suppression.

[0016] One aspect of the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing an isocyanate compound that can improve the thermal decomposition rate of a blocked isocyanate compound without increasing the amount of by-products produced.

[0017] That is, the present invention includes the following aspects: [1] A polyisocyanate composition containing at least one compound represented by any one of the following general formulas (I), (II), and (III) and a polyisocyanate compound: (In general formula (I), R １ and R ２ are each independently a monovalent organic group. １ and R ２ may each independently form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. ３ is a hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group. (In general formula (II), R ２１０ is a monovalent organic group, and R ２２０ , R ２３０ , R ２４０ and R ２５０ R is each independently a monovalent organic group or hydrogen. ２１０ and R ２２０ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.) (In general formula (III), R ３１０ is an (n+m)-valent organic group, n is an integer of 0 to 12, m is an integer of 1 to 12, and n+m is an integer of 13 or less; R ３２０ and R ３３０ are each independently a monovalent organic group. ３２０ and R ３３０ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. ３２０ and R ３３０ At least one of them has an aromatic group.) [2] 1.0 ppm by mass or more and 1.0 × 10 based on the total mass of the polyisocyanate compound. ４The polyisocyanate composition according to [1], which contains at least one compound represented by any one of general formulas (I), (II), and (III) in an amount of not more than ppm by mass. [3] A method for producing an isocyanate compound, which comprises a reaction step of decomposing a blocked isocyanate compound into a blocking agent and an isocyanate compound by heat treatment in the presence of a compound having a structure represented by either or both of the following general formulas (I) and (II), thereby obtaining the isocyanate compound. (In general formula (I), R １ and R ２ are each independently a monovalent organic group. １ and R ２ may each independently form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. ３ is a hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group. (In general formula (II), R ２１０ is a monovalent organic group, and R ２２０ , R ２３０ , R ２４０ and R ２５０ R is each independently a monovalent organic group or hydrogen. ２１０ and R ２２０ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.) [4] The method for producing an isocyanate compound according to [3], wherein the blocking agent contains one or more compounds selected from the group consisting of hydroxy compounds, amine compounds, and ammonia. [5] The method for producing an isocyanate compound according to [3] or [4], wherein the isocyanate compound is an isocyanate compound represented by the following general formula (IV): (In general formula (IV), R ２１ is an n21-valent organic group, where n21 is an integer of 1 or more and 12 or less. [6] The method for producing an isocyanate compound according to [3] or [4], wherein the blocking agent is an aromatic hydroxy compound represented by the following general formula (V): (In general formula (V), ring A ３１ is an aromatic hydrocarbon ring having 6 to 20 carbon atoms. ３１is a hydrogen atom, a halogen atom, a carboxy group, an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an alkyloxycarbonyl group having from 1 to 20 carbon atoms, an alkylcarbonyloxy group having from 1 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, an aryloxy group having from 6 to 20 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms, or an aralkyloxy group having from 7 to 20 carbon atoms. ３１ is ring A ３１ and n31 may bond to form a ring structure. In addition, n31 is an integer of 1 or more and 10 or less. [7] The method for producing an isocyanate compound according to [3] or [4], wherein the blocking agent is an aliphatic hydroxy compound represented by the following general formula (VI): (In general formula (VI), R ４１ is a substituted or unsubstituted aliphatic hydrocarbon group having from 1 to 24 carbon atoms, which may have an ether group, a carbonyl group, or an ester group. [8] The method for producing an isocyanate compound according to [3] or [4], wherein the blocking agent is a secondary amine compound represented by the following general formula (VII): (In general formula (VII), R ５１ and R ５２ are each independently a monovalent organic group. ５１ and R ５２ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.) [9] The method for producing an isocyanate compound according to [3] or [4], wherein in the reaction step, the amount of the compound having a structure represented by either or both of general formulas (I) and (II) is 1 ppm by mass or more relative to the blocked isocyanate compound.

[0018] The polyisocyanate composition of the above aspect can provide a polyisocyanate composition that is excellent in storage stability and coloration suppression. The method for producing an isocyanate compound of the above aspect can provide a method for producing an isocyanate compound that can improve the thermal decomposition rate of a blocked isocyanate compound without increasing the amount of by-products produced.

[0019] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an example for explaining the present invention, and the present invention is not limited to the following present embodiment. The present invention can be carried out by appropriately modifying it within the scope of its gist.

[0020] In this specification, the term "active hydrogen" refers to a hydrogen atom bonded to an oxygen atom, a sulfur atom, or a nitrogen atom, and a hydrogen atom of an active methylene group. For example, an -OH group, a -C(=O)OH group, a -SH group, a -NH ２ group, -NH- group, -C(=O)-C(-H) ２ It is a hydrogen atom contained in an atomic group such as a —C(═O)— group.

[0021] <Polyisocyanate Composition> The polyisocyanate composition of the present embodiment contains at least one compound represented by any one of general formulas (I), (II), and (III) and a polyisocyanate compound.

[0022] The polyisocyanate composition of the present embodiment may contain optional components other than the compounds (I), (II), and (III) and the polyisocyanate compound depending on the application, purpose, and the like.

[0023] The polyisocyanate composition of the present embodiment can be used as a polyurethane synthesis material, a curing agent, etc. The polyisocyanate composition of the present embodiment can be used in a wide range of fields, such as flexible foams, rigid foams, elastomers, adhesives, paints, and binders.

[0024] The polyisocyanate composition 1 of the present embodiment contains a compound represented by general formula (I) and a polyisocyanate compound. Hereinafter, the "compound represented by general formula (I)" may be referred to as "compound (I)."

[0025] The polyisocyanate composition 2 of the present embodiment contains a compound represented by general formula (II) and a polyisocyanate compound. Hereinafter, the "compound represented by general formula (II)" may be referred to as "compound (II)."

[0026] The polyisocyanate composition 3 of the present embodiment contains a compound represented by general formula (III) and a polyisocyanate compound. Hereinafter, the "compound represented by general formula (III)" may be referred to as "compound (III)."

[0027] The polyisocyanate composition 4 of the present embodiment contains two or more compounds selected from the compounds represented by general formulas (I), (II), and (III), and a polyisocyanate compound. One aspect of the polyisocyanate composition 4 contains the compounds represented by general formulas (I), (II), and (III), and a polyisocyanate compound.

[0028] <Polyisocyanate Composition 1> Polyisocyanate composition 1 of the present embodiment contains compound (I) and a polyisocyanate compound.

[0029] [Compound (I)] Compound (I) is represented by the following general formula (I).

[0030] (In general formula (I), R １ and R ２ are each independently a monovalent organic group. １ and R ２ may each independently form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. ３ is a hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group.

[0031] [R １ and R ２ In the above general formula (I), R １ and R ２ are each independently a monovalent organic group. １ and R ２ may each independently form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.

[0032] Among them, R １ and R ２are each independently preferably a monovalent aliphatic hydrocarbon group having from 1 to 70 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having from 6 to 70 carbon atoms which may have a substituent.

[0033] R １ and R ２ When an aliphatic hydrocarbon group is selected for at least one of R, the number of carbon atoms is preferably 1 or more and 70 or less, more preferably 1 or more and 20 or less, even more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 10 or less. １ and R ２ Examples of the aliphatic hydrocarbon group in the formula (I) include linear alkyl groups, branched alkyl groups, and cycloalkyl groups, which may be unsubstituted or substituted. Examples of the substituents on these aliphatic hydrocarbon groups include hydroxyl groups, cyano groups, and halogen atoms. Examples of the halogen atoms in the substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0034] R １ and R ２ Specific examples of the aliphatic hydrocarbon group in include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, cyclohexyl, etc. Among these, unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl is preferred.

[0035] R １ and R ２ When an aromatic hydrocarbon group is selected for at least one of R, the number of carbon atoms is preferably 6 to 70, more preferably 6 to 20, even more preferably 6 to 12, and particularly preferably 6 to 10. １ and R ２Examples of the aromatic hydrocarbon group in R include an aryl group, an aralkyl group, etc., which may be unsubstituted or substituted. Examples of the substituent of these aromatic hydrocarbon groups include an aliphatic hydrocarbon group, a hydroxyl group, a cyano group, a halogen atom, etc. １ and R ２ The aliphatic hydrocarbon group selected as a substituent of the aromatic hydrocarbon group in R １ and R ２ Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0036] R １ and R ２ Specific examples of the aromatic hydrocarbon group in include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a benzyl group, and a phenethyl group.

[0037] R １ and R ２ When they are bonded to each other to form a ring structure, R １ and R ２ The group formed by bonding R to each other is a divalent organic group. １ and R ２ The group in which the groups are bonded to each other is preferably a divalent aliphatic hydrocarbon group having from 1 to 70 carbon atoms or a divalent aromatic hydrocarbon group having from 6 to 70 carbon atoms, which may have a substituted or unsubstituted ether group, carbonyl group, ester group, imino group (—NH—), amide group, or imide group.

[0038] [R ３ ] In general formula (I), R ３ is a hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group. ３Specific examples of the aliphatic hydrocarbon group in include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, cyclohexyl, etc. Among these, unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl is preferred.

[0039] R ３ In the case where 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. ３ Examples of the aromatic hydrocarbon group in R include an aryl group, an aralkyl group, etc., which may be unsubstituted or substituted. Examples of the substituent of these aromatic hydrocarbon groups include an aliphatic hydrocarbon group, a hydroxyl group, a cyano group, a halogen atom, etc. ３ The aliphatic hydrocarbon group selected as a substituent of the aromatic hydrocarbon group in R ３ Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0040] R ３ Specific examples of the aromatic hydrocarbon group in include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a benzyl group, and a phenethyl group.

[0041] Compound (I) is preferably a compound represented by the following general formula (I-1):

[0042] [In general formula (I-1), R １１ is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having from 1 to 70 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group having from 6 to 70 carbon atoms, R １２R is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 70 carbon atoms. １３ is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 70 carbon atoms.

[0043] [R １１ ] In general formula (I-1), R １１ R is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having from 1 to 70 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group having from 6 to 70 carbon atoms. １１ Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, etc. Among these, unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl is preferred.

[0044] [R １２ ] In general formula (I-1), R １２ R is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 70 carbon atoms. １２ Specific examples of the alkyl group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, each isomer of a pentyl group, each isomer of a hexyl group, each isomer of a heptyl group, each isomer of an octyl group, each isomer of a nonyl group, each isomer of a decyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, etc. Among these, an unsubstituted aliphatic hydrocarbon group having from 1 to 12 carbon atoms is preferred, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group is preferred.

[0045] [R １３ ] In general formula (I-1), R １３ R is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 70 carbon atoms. １３ Examples of R include substituted or unsubstituted monovalent aliphatic hydrocarbon groups having from 1 to 12 carbon atoms and monovalent aromatic hydrocarbon groups having from 6 to 12 carbon atoms. １３ Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, etc. Among these, unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl is preferred.

[0046] In general formula (I-1), R １３ When R is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, it is preferably a phenyl group which may have a substituent. １３ Examples of the substituent that the phenyl group may have include an aliphatic hydrocarbon group or an aromatic hydrocarbon group, such as an alkyl group having from 1 to 12 carbon atoms, an aryl group having from 6 to 12 carbon atoms, or an aralkyl group having from 7 to 12 carbon atoms. When the substituent on the benzene ring has an ether group, examples of the substituent on the benzene ring include an alkoxy group having from 1 to 12 carbon atoms, an aryloxy group having from 6 to 12 carbon atoms, or an aralkyloxy group having from 7 to 12 carbon atoms. When the substituent on the benzene ring has a carbonyl group, examples of the substituent on the benzene ring include an alkylcarbonyl group having from 1 to 12 carbon atoms, an arylcarbonyl group having from 6 to 12 carbon atoms, or an aralkylcarbonyl group having from 7 to 12 carbon atoms.

[0047] When the substituent on the benzene ring has an ester group, examples of the ester group include an alkoxycarbonyl group or an alkylcarbonyloxy group having from 1 to 12 carbon atoms, an aryloxycarbonyl group or an arylcarbonyloxy group having from 6 to 12 carbon atoms, and an aralkyloxycarbonyl group or an aralkylcarbonyloxy group having from 7 to 12 carbon atoms.

[0048] Specific examples of the substituent on the benzene ring include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, cumyl, etc. Among these, unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl is preferred.

[0049] Compound (I) is preferably a compound represented by the following general formula (I-2):

[0050] [In general formula (I-2), R ２２ R is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 70 carbon atoms. ２３ is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 70 carbon atoms.

[0051] [R ２２ ] In general formula (I-2), R ２２ is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 70 carbon atoms, and specific descriptions are given in the above R １２ In general formula (I-2), R ２２ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or an unsubstituted phenyl group.

[0052] [R ２３ ] In general formula (I-2), R ２３ is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 70 carbon atoms, and specific descriptions are given in the above R １３ In general formula (I-2), R ２３ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenyl group. ２３ When is a phenyl group having a substituent, examples of the substituent include a linear or branched alkyl group having 1 to 10 carbon atoms.

[0053] Compound (I) acts as an ultraviolet absorber, and therefore, a polyisocyanate composition containing compound (I) can reduce the coloration and denaturation of the polyisocyanate compound due to ultraviolet light, even when stored outdoors.

[0054] Compound (I) suppresses the excitation of the chromophore by light, so that radicals are less likely to be generated when irradiated with light. Compound (I) acts as a stabilizer during storage, so that polyisocyanate compositions containing compound (I) have excellent storage stability.

[0055] In order to improve the storage stability and coloration 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, this may affect the production cost, applications, etc. of the polyisocyanate composition.

[0056] The polyisocyanate composition 1 has a content of 1.0 mass ppm or more and 5.0 × 10 based on the total mass of the polyisocyanate compound. ４ It is preferable that the compound (I) is contained in an amount of 1.0 ppm by mass or less, and 1.0 x 10 ppm by mass or more. ４ It is more preferable that the compound (I) is contained in an amount of not more than ppm by mass.

[0057] Compound (I) may be a commercially available product, or may be a compound synthesized by a known production method. Examples of commercially available products of Compound (I) include Angene International Limited, product number: AG00AJDF, product name: N-methylcarbanilic acid phenyl ester 95%, CAS number: 13599-69-4.

[0058] Compound (I) can be synthesized by stirring the corresponding chloroformate and the corresponding amine in a suitable solvent in the presence of a neutralizer for the by-produced hydrochloric acid, such as triethylamine, at room temperature to reflux. Alternatively, the corresponding carbamoyl chloride and the corresponding alcohol can be stirred in a suitable solvent in the presence of a neutralizer for the by-produced hydrochloric acid, such as triethylamine, at room temperature to reflux. If necessary, a catalyst such as N,N-dimethyl-4-aminopyridine (DMAP) may be used. The resulting compound (I) is isolated and purified by known methods.

[0059] <Polyisocyanate Composition 2> Polyisocyanate composition 2 of the present embodiment contains compound (II) and a polyisocyanate compound.

[0060] [Compound (II)] Compound (II) is represented by the following general formula (II): Compound (II) may be referred to as "quinazolinedione compound (II)."

[0061] (In general formula (II), R ２１０ is a monovalent organic group, and R ２２０ , R ２３０ , R ２４０ and R ２５０ R is each independently a monovalent organic group or hydrogen. ２１０ and R ２２０ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.)

[0062] The quinazolinedione compound (II) has a quinazoline-2,4(1H,3H)-dione structure (hereinafter, sometimes referred to as a "quinazolinedione structure"), which contains an active hydrogen atom in the -C(=O)-NH-C(=O)- group.

[0063] However, the -C(=O)-NH-C(=O)- group contained in the quinazolinedione structure may exhibit tautomerism represented by -C(-OH)=N-C(=O)- or -C(=O)-N=C(-OH)-.

[0064] The inventors have found that the problems of thermal denaturation and coloration can be solved by producing a blocked isocyanate in the presence of a specific amine compound having an aromatic group, and have completed the present invention.

[0065] Conventionally, compounds having an amino group bonded to an aromatic carbon atom have been known to be easily oxidized and cause discoloration, and therefore, although they have been used in products where discoloration is not an issue, such as rubber deterioration inhibitors, they have not been used in products where discoloration is an issue.

[0066] On the other hand, it has now been surprisingly revealed for the first time that polyisocyanate composition 2 of the present embodiment, even when a specific amine compound having an aromatic group is used, does not cause the problem of coloration, but rather exhibits an especially remarkable effect of improving (suppressing) thermal denaturation and coloration.

[0067] [R ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０ In the above general formula (II), R ２１０ is a monovalent organic group, and R ２２０ , R ２３０ , R ２４０ and R ２５０ R is each independently a monovalent organic group or hydrogen. ２１０ and R ２２０may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.

[0068] Among them, R ２１０ is preferably a monovalent aliphatic hydrocarbon group having 1 to 70 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 70 carbon atoms, which may have a substituted or unsubstituted ether group, carbonyl group, ester group, imino group (—NH—), amide group, or imide group. ２２０ , R ２３０ , R ２４０ and R ２５０ are each independently preferably a substituted or unsubstituted monovalent aliphatic hydrocarbon group having from 1 to 70 carbon atoms, a monovalent aromatic hydrocarbon group having from 6 to 70 carbon atoms, or hydrogen, which may have an ether group, a carbonyl group, an ester group, an imino group (—NH—), an amide group, or an imide group.

[0069] R ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０ When an aliphatic hydrocarbon group is selected for at least one of R, the number of carbon atoms is preferably 1 or more and 70 or less, more preferably 1 or more and 20 or less, even more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 10 or less. ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０ Examples of the aliphatic hydrocarbon group in the formula (I) include linear alkyl groups, branched alkyl groups, and cycloalkyl groups, which may be unsubstituted or substituted. Examples of the substituents on these aliphatic hydrocarbon groups include hydroxyl groups, cyano groups, and halogen atoms. Examples of the halogen atoms in the substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0070] R ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０Specific examples of the aliphatic hydrocarbon group in include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, cyclohexyl, etc. Among these, unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl is preferred.

[0071] R ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０ When an aromatic hydrocarbon group is selected for at least one of R, the number of carbon atoms is preferably 6 to 70, more preferably 6 to 20, even more preferably 6 to 12, and particularly preferably 6 to 10. ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０ Examples of the aromatic hydrocarbon group in R include an aryl group, an aralkyl group, etc., which may be unsubstituted or substituted. Examples of the substituent of these aromatic hydrocarbon groups include an aliphatic hydrocarbon group, a hydroxyl group, a cyano group, a halogen atom, etc. ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０ The aliphatic hydrocarbon group selected as a substituent of the aromatic hydrocarbon group in R ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０ Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0072] R ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０Specific examples of the aromatic hydrocarbon group in include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a benzyl group, and a phenethyl group.

[0073] R ２１０ and R ２２０ When they are bonded to each other to form a ring structure, R ２１０ and R ２２０ The group formed by bonding together is a divalent organic group. ２１０ and R ２２０ The group formed by bonding together is preferably a divalent aliphatic hydrocarbon group having from 1 to 70 carbon atoms or a divalent aromatic hydrocarbon group having from 6 to 70 carbon atoms, which may have a substituted or unsubstituted ether group, carbonyl group, ester group, imino group (—NH—), amide group, or imide group.

[0074] R ２１０ and R ２２０ In the group formed by bonding together, examples of the divalent aliphatic hydrocarbon group include alkylene groups such as methylene, ethylene, propylene, and trimethylene. ２１０ and R ２２０ In the group formed by bonding together, examples of the divalent aromatic hydrocarbon group include arylene groups such as phenylene and naphthylene.

[0075] R ２１０ is R ２１０ and R ２２０ Regardless of whether or not R are bonded to each other to form a ring structure, it is preferable that R has a carbon atom at the position where it is bonded to the nitrogen atom of the quinazolinedione structure. ２１０ is bonded to the nitrogen atom of the quinazolinedione structure, ２１０ The carbon atom is preferably a primary carbon atom, a secondary carbon atom, a tertiary carbon atom, a carbon atom having aromaticity, or a carbonyl carbon atom.

[0076] Preferred quinazolinedione compounds (II) include the following (II-1), (II-2) and (II-3):

[0077] (II-1) is the same as R in the above general formula (II). ２１０ is a monovalent organic group, and R ２２０ , R ２３０ , R ２４０ and R ２５０ are each independently a monovalent organic group or hydrogen.

[0078] In (II-1), R ２１０ Examples of R include substituted or unsubstituted monovalent aliphatic hydrocarbon groups having from 1 to 12 carbon atoms and monovalent aromatic hydrocarbon groups having from 6 to 12 carbon atoms. ２１０ Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, etc. Among these, unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl is preferred.

[0079] In (II-1), R ２２０ , R ２３０ , R ２４０ and R ２５０ The number of R that becomes a monovalent organic group is an integer of 0 to 4, more preferably 0 or 1, and even more preferably 0. ２２０ , R ２３０ , R ２４０ and R ２５０ When one or more of the above is a monovalent organic group, they become substituents on the benzene ring in the quinazolinedione structure (hereinafter may be referred to as "benzene ring substituents"). Examples of the substituent on the benzene ring include substituted or unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms or aromatic hydrocarbon groups having from 6 to 12 carbon atoms. The substituent on the benzene ring may have an ether group, a carbonyl group, or an ester group.

[0080] When the substituent on the benzene ring is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, examples of the substituent include an alkyl group having from 1 to 12 carbon atoms, an aryl group having from 6 to 12 carbon atoms, or an aralkyl group having from 7 to 12 carbon atoms. When the substituent on the benzene ring has an ether group, examples of the substituent include an alkoxy group having from 1 to 12 carbon atoms, an aryloxy group having from 6 to 12 carbon atoms, or an aralkyloxy group having from 7 to 12 carbon atoms. When the substituent on the benzene ring has a carbonyl group, examples of the substituent include an alkylcarbonyl group having from 1 to 12 carbon atoms, an arylcarbonyl group having from 6 to 12 carbon atoms, or an aralkylcarbonyl group having from 7 to 12 carbon atoms. When the substituent on the benzene ring has an ester group, examples of the substituent on the benzene ring include an alkoxycarbonyl group or alkylcarbonyloxy group having from 1 to 12 carbon atoms, an aryloxycarbonyl group or arylcarbonyloxy group having from 6 to 12 carbon atoms, or an aralkyloxycarbonyl group or aralkylcarbonyloxy group having from 7 to 12 carbon atoms.

[0081] Specific examples of the substituent on the benzene ring include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, etc. Among these, unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl is preferred.

[0082] (II-2) is the same as R in the above general formula (II). ２１０ and R ２２０ are bonded to each other to form a ring structure via a carbon-carbon bond, and R ２３０ , R ２４０ and R ２５０ R is each independently a monovalent organic group or hydrogen. ２１０ and R ２２０The group formed by bonding together is a substituted or unsubstituted divalent aliphatic hydrocarbon group having from 1 to 12 carbon atoms or a divalent aromatic hydrocarbon group having from 6 to 12 carbon atoms.

[0083] R ２１０ and R ２２０ Specific examples of the group formed by bonding R include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a phenylene group. ２３０ , R ２４０ and R ２５０ The number of substituents on the benzene ring is an integer of 0 to 3, preferably 0 or 1, and even more preferably 0. ２３０ , R ２４０ and R ２５０ Specific examples of the substituent on the benzene ring include the same as those exemplified as the substituent on the benzene ring in (II-1).

[0084] (II-3) is the same as R in the above general formula (II). ２１０ and R ２２０ are bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond, and R ２３０ , R ２４０ and R ２５０ R is each independently a monovalent organic group or hydrogen. ２１０ and R ２２０ are bonded to each other, the group represented by the general formula -R ３１１ -Z ３１１ - is a divalent organic group represented by the formula: ３１１ is R ２１０ is bonded to the same nitrogen atom as ３１１ is R ２２０ Attaches to the same carbon atom as Z. ３１１ is —O—, —NH—, or —C(═O)—. ３１１ is a substituted or unsubstituted divalent aliphatic hydrocarbon group having from 1 to 12 carbon atoms or a divalent aromatic hydrocarbon group having from 6 to 12 carbon atoms.

[0085] R ３１１Specific examples of R include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a phenylene group. ２３０ , R ２４０ and R ２５０ The number of substituents on the benzene ring is an integer of 0 to 3, preferably 0 or 1, and even more preferably 0. ２３０ , R ２４０ and R ２５０ Specific examples of the substituent on the benzene ring include the same as those exemplified as the substituent on the benzene ring in (II-1).

[0086] Among the above general formulas (II), (II-1), (II-2) and (II-3), R ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０ and R ２１０ and R ２２０ Preferably, the group formed by bonding R to each other does not contain an olefinic or acetylenic unsaturated carbon-carbon bond. ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０ and R ２１０ and R ２２０ The hydrocarbon group contained in the group formed by bonding together is preferably a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0087] In addition, from the viewpoint of thermal stability, R ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０ and R ２１０ and R ２２０ The group formed by bonding together is Z in (II-3). ３１１ It is preferable that the structure is composed only of carbon atoms and hydrogen atoms, excluding the following:

[0088] In (II-1), R ２１０ is a monovalent aliphatic hydrocarbon group, and R ２２０ , R ２３０ , R２４０ and R ２５０ three or more of R ２２０ , R ２３０ , R ２４０ and R ２５０ Preferably, at most one of the groups is an unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. ２１０ is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ２２０ , R ２３０ , R ２４０ and R ２５０ three or more of R ２２０ , R ２３０ , R ２４０ and R ２５０ It is preferred that at most one of the groups be a methyl group or an ethyl group.

[0089] In (II-2), R ２１０ and R ２２０ are bonded to each other to form a divalent aliphatic hydrocarbon group, and R ２３０ , R ２４０ and R ２５０ two or more of R ２３０ , R ２４０ and R ２５０ Preferably, at most one of the groups is an unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. ２１０ and R ２２０ are bonded to each other to form a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ２３０ , R ２４０ and R ２５０ two or more of R ２３０ , R ２４０ and R ２５０ It is preferred that at most one of the groups be a methyl group or an ethyl group.

[0090] In (II-3), R ３１０ is a divalent aliphatic hydrocarbon group, and R ２３０ , R ２４０ and R ２５０ two or more of R２３０ , R ２４０ and R ２５０ Preferably, at most one of the groups is an unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. ３１０ is a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ２３０ , R ２４０ and R ２５０ two or more of R ２３０ , R ２４０ and R ２５０ It is preferred that at most one of the groups be a methyl group or an ethyl group.

[0091] [Method for Producing Quinazolinedione Compound (II)] The quinazolinedione compound (II) can be synthesized by a known production method. As a method for synthesizing the quinazolinedione compound (II), a method of reacting an aniline compound with a carbonic acid derivative can be mentioned. The carbonic acid derivative used in the synthesis of the quinazolinedione compound (II) may be one type or two or more types.

[0092] The aniline compound used in the synthesis of quinazolinedione compound (II) has an unsubstituted or monosubstituted nitrogen atom, and at least one of the carbon atoms in the ortho position relative to the nitrogen atom of the benzene ring is unsubstituted. The quinazolinedione compound (II) is obtained by forming a -C(=O)-NH-C(=O)- group between the nitrogen atom of the aniline compound and one of the carbon atoms in the ortho position.

[0093] The aniline compound may be an unsubstituted aniline or a quinazolinedione compound (II) having R ２１０ , R ２２０ , R ２３０ , R ２４０ and R ２５０ and substituted anilines having the same organic group as at least one of R ２１０ and R ２２０ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.

[0094] The carbonic acid derivative is not particularly limited, but a compound represented by the following general formula (A) (hereinafter, sometimes referred to as "carbonic acid derivative (A)") is preferably used because of its ready availability.

[0095] R ６１ -C(=O)-R ６２ (A)

[0096] In the above general formula (A), R ６１ and R ６２ are each independently an amino group, a substituted or unsubstituted alkoxy group having from 1 to 20 carbon atoms, or an aryloxy group having from 6 to 20 carbon atoms, or a substituted or unsubstituted alkylamino group having from 1 to 20 carbon atoms, or an arylamino group having from 6 to 20 carbon atoms.

[0097] R ６１ and R ６２ may be the same or different. The alkylamino group may be a monoalkylamino group or a dialkylamino group. The arylamino group may be a monoarylamino group, a diarylamino group, or an alkyl(aryl)amino group.

[0098] R ６１ and R ６２ Examples of the alkoxy group having 1 to 20 carbon atoms in R include a methoxy group, an ethoxy group, each isomer of a propoxy group, each isomer of a butoxy group, and each isomer of a hexyloxy group. ６１ and R ６２ Examples of the aryloxy group having 6 to 20 carbon atoms in R include a phenoxy group and a naphthyloxy group. ６１ and R ６２ Examples of the alkylamino group having 1 to 20 carbon atoms in R include a methylamino group, an ethylamino group, each isomer of a propylamino group, each isomer of a butylamino group, and each isomer of a hexylamino group. ６１ and R ６２ Examples of the arylamino group having 6 to 20 carbon atoms in the formula (I) include a phenylamino group and a naphthylamino group.

[0099] Examples of the substituents that the alkoxy group, aryloxy group, alkylamino group, and arylamino group have include alkyl groups and alkoxy groups. ６１ and R ６２ is preferably each independently an amino group, a substituted or unsubstituted aryloxy group having from 6 to 20 carbon atoms, or a substituted or unsubstituted arylamino group having from 6 to 20 carbon atoms.

[0100] Preferred examples of the carbonic acid derivative (A) include urea compounds, carbamic acid esters, and carbonic acid esters.

[0101] [Urea Compound] Urea compounds include those represented by the general formula (A) above, ６１ and R ６２ are each independently a substituted or unsubstituted alkylamino group or arylamino group. Among urea compounds, compounds represented by the following general formula (A-1) are preferred.

[0102] R ６１１ - (R ６１２ -)N-C(=O)-N(-R ６１３ )-R ６１４ (A-1)

[0103] In the above general formula (A-1), R ６１１ , R ６１２ , R ６１３ and R ６１４ R are each 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. ６１１ and R ６１２ The total number of carbon atoms constituting R is an integer of 0 to 20, ６１３ and R ６１４ The total number of carbon atoms constituting the group is an integer of 0 to 20.

[0104] Examples of the urea compound include unsubstituted urea compounds, monosubstituted urea compounds, N,N-disubstituted urea compounds, N,N'-disubstituted urea compounds, trisubstituted urea compounds, and tetrasubstituted urea compounds.

[0105] [Carbamic acid ester] The carbamic acid ester is a compound represented by the general formula (A) above, wherein R ６１ and R ６２ is an amino group, or a substituted or unsubstituted alkylamino group or arylamino group, and R ６１ and R ６２ Among the carbamic acid esters, compounds represented by the following general formula (A-2) are preferred:

[0106] R ６２２ - (R ６２３ -)NC(=O)-OR ６２１ (A-2)

[0107] In the above general formula (A-2), R ６２１ is 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. ６２２ and R ６２３ are each 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.

[0108] Examples of carbamic acid esters include N-unsubstituted carbamic acid esters, N-monosubstituted carbamic acid esters, and N,N-disubstituted carbamic acid esters.

[0109] [Carbonate] The carbonate is a compound represented by the general formula (A) in which R ６１ and R ６２ are each independently a substituted or unsubstituted alkoxy group or an aryloxy group. Among carbonate esters, the compound represented by the following general formula (A-3) is preferred.

[0110] R ６３１ -OC(=O)-OR ６３２ (A-3)

[0111] In the above general formula (A-3), R ６３１ and R ６３２are each independently an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0112] The quinazolinedione compound (II) has active hydrogen and is excellent in storage stability and coloration inhibition of the polyisocyanate composition 2. The quinazolinedione compound (II) inhibits the formation of a 1-nylon structure, which is a "compound having UV absorption in the region of an isocyanate decamer or higher in GPC" described below, and acts as a stabilizer during storage.

[0113] Since the quinazolinedione compound (II) has a benzene ring in the quinazolinedione structure, the active hydrogen contained in the quinazolinedione structure is bulky, and addition reaction with an isocyanate group does not occur or occurs only slightly. Furthermore, since the benzene ring has electron-withdrawing properties, the anion generated when the active hydrogen contained in the quinazolinedione structure is abstracted by a base is stabilized, and the formation of a 1-nylon structure can be suppressed.

[0114] In order to improve the storage stability and coloration inhibition of the polyisocyanate composition 2, it is preferable to increase the content of the quinazolinedione compound (II). However, if the content of the quinazolinedione compound (II) is too high, this may affect the production costs, applications, etc. of the polyisocyanate composition 2.

[0115] The polyisocyanate composition 2 has a content of 1.0 mass ppm or more and 5.0 × 10 based on the total mass of the polyisocyanate compound. ４ It is preferable that the quinazolinedione compound (II) is contained in an amount of not more than ppm by mass, and more preferably in an amount of not less than 1.0 ppm by mass and not more than 1.0 x 10 ４ It is more preferable that the quinazolinedione compound (II) is contained in an amount of not more than ppm by mass.

[0116] The polyisocyanate composition 2 of the present embodiment may contain optional components other than the quinazolinedione compound (II) and the polyisocyanate compound depending on the application, purpose, and the like.

[0117] The polyisocyanate composition 2 of the present embodiment can be used as a polyurethane synthesis material, a curing agent, etc. The polyisocyanate composition 2 of the present embodiment can be used in a wide range of fields, such as flexible foams, rigid foams, elastomers, adhesives, paints, and binders.

[0118] [Compound Having UV Absorption in the Region of Isocyanate Decamer or Higher in GPC] In gel permeation chromatography (hereinafter, sometimes referred to as "GPC"), the compound having UV absorption in the region of isocyanate decamer or higher in GPC is preferably a compound having a 1-nylon structure represented by the following general formula (W) as its main skeleton:

[0119] -[N(-R Ｗ )-C(=O)] Ｗ - (W)

[0120] In the above general formula (W), R Ｗ represents a residue obtained by removing one isocyanate group from a polyisocyanate compound, and W represents an integer of 1 or more. Terminal groups are not described.

[0121] In a spectrum measured by GPC, the isocyanate constituting the compound having UV absorption in the isocyanate decamer or higher region may be the same isocyanate as the isocyanate compound constituting the isocyanate composition of this embodiment, or a different isocyanate. The compound is defined by GPC measurement. Specifically, in GPC using tetrahydrofuran as the developing solvent and polystyrene as the molecular weight standard, the compound exhibits a peak with UV absorption at a wavelength of 254 nm in the isocyanate decamer or higher region. In a spectrum measured by GPC, the concentration of the compound having UV absorption in the isocyanate decamer or higher region can be determined from the value calculated by (B) / (A), where A is the area of ​​the peak corresponding to a bifunctional or higher isocyanate in UV absorption (wavelength 210 nm) measured by a PDA detector, and B is the area of ​​the peak corresponding to a compound having UV absorption (wavelength 254 nm) in the isocyanate decamer or higher region.

[0122] <Polyisocyanate Composition 3> Polyisocyanate composition 3 of the present embodiment contains a tri-substituted urea compound (III) and a polyisocyanate compound.

[0123] [Compound (III)] Compound (III) is represented by the following general formula (III): The compound represented by the following general formula (III) may be hereinafter referred to as a "tri-substituted urea compound (III)."

[0124] (In general formula (III), R ３１０ is an (n+m)-valent organic group, n is an integer of 0 to 12, m is an integer of 1 to 12, and n+m is an integer of 13 or less; R ３２０ and R ３３０ are each independently a monovalent organic group. ３２０ and R ３３０ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. ３２０ and R ３３０ At least one of the groups has an aromatic group.

[0125] The trisubstituted urea compound (III) is ２ N—CO—NH ２ The urea molecule represented by (OCN) ｎ -R ３１０ - group, R ３２０ Groups and R ３３０ The trisubstituted urea structure has a structure in which a group is bonded (hereinafter, this may be referred to as a "trisubstituted urea structure"). The trisubstituted urea structure is a structure in which a group is bonded to a —NH—C(═O)—N(—R ３３０ )-R ３２０ It is a monovalent group represented by the formula:

[0126] The trisubstituted urea structure contains an active hydrogen atom in the —NH—C(═O)—N< group. However, the —NH—C(═O)—N< group contained in the trisubstituted urea structure may exhibit tautomerism represented by —N═C(—OH)—N<.

[0127] The inventors have found that the problems of thermal denaturation and coloration can be solved by producing a blocked isocyanate in the presence of a specific amine compound having an aromatic group, and have completed the present invention.

[0128] Conventionally, compounds having an amino group bonded to an aromatic carbon atom have been known to be easily oxidized and cause discoloration, and therefore, although they have been used in products where discoloration is not an issue, such as rubber deterioration inhibitors, they have not been used in products where discoloration is an issue.

[0129] On the other hand, it has now been revealed for the first time that the polyisocyanate composition of the present embodiment surprisingly exhibits an especially remarkable effect of improving (suppressing) thermal denaturation and coloration, far from causing the problem of coloration, even when a specific amine compound having an aromatic group is used.

[0130] [R ３１０ In the above general formula (III), R ３１０ is an (n+m)-valent organic group, n is an integer of 0 or more and 12 or less, m is an integer of 1 or more and 12 or less, and n+m is an integer of 13 or less.

[0131] n is R ３１０ m represents the number of isocyanate groups (OCN-) bonded to R ３１０ represents the number of trisubstituted urea structures bonded to the aryl group. Since n is an integer of 0 or more and m is an integer of 1 or more, n+m is an integer of 1 or more.

[0132] The trisubstituted urea compound (III) is a compound having n isocyanate groups. ３１０ is an organic group that does not contain an isocyanate group. The trisubstituted urea compound (III) is a compound having m trisubstituted urea structures. ３１０ is an organic group that does not contain a trisubstituted urea structure.

[0133] The trisubstituted urea compound (III) may be a compound that does not have a blocked isocyanate group, except when the trisubstituted urea structure corresponds to a blocked isocyanate group. ３１０ is an organic group that does not contain a blocked isocyanate group.

[0134] The blocked isocyanate group is a group shown on the left side of the following reaction formula (K), and is a group that can be thermally dissociated into an isocyanate group and a blocking agent represented by the general formula BL-H, as shown on the right side of reaction formula (K).

[0135] -NH-C(=O)-BL → -N=C=O + BL-H (K)

[0136] In the above reaction formula (K), the blocking agent represented by BL-H is a compound having active hydrogen. Examples of the blocking agent include phenol-based blocking agents, alcohol-based blocking agents, thiol-based blocking agents, amine-based blocking agents, ammonia-based blocking agents, oxime-based blocking agents, hydroxylamine-based blocking agents, and active methylene-based blocking agents.

[0137] Phenol-based blocking agents include organic compounds having an -OH group bonded to an aromatic carbon atom. Alcohol-based blocking agents include organic compounds having an -OH group bonded to a non-aromatic carbon atom. Thiol-based blocking agents include organic compounds having an -SH group. Amine-based blocking agents include organic compounds having an -NH ２ Examples of the blocking agents include organic compounds having an -NH- group or an -NH- group. Triazole compounds, pyrazole compounds, etc. are also included in the amine-based blocking agents having an -NH- group. An example of the blocking agent is ammonia. An example of the blocking agent is an organic compound having an =N-OH group bonded to one carbon atom. An example of the blocking agent is a hydroxylamine-based organic compound having >N-OH groups bonded to two carbon atoms. An example of the blocking agent is an active methylene-based organic compound is -C(=O)-C(-H) ２Examples of organic compounds containing an atomic group such as a -C(=O)- group include acetoacetic acid ester compounds, malonic acid diester compounds, and acetylacetone.

[0138] The trisubstituted urea compound (III) may be a compound that does not have a unit constituting an isocyanate polymer. In this case, R ３１０ is an organic group that does not contain a unit that constitutes an isocyanate polymer.

[0139] The units constituting the isocyanate polymer refer to, among units containing nitrogen atoms derived from one or more isocyanate groups, an isocyanurate group, a biuret group, an iminooxadiazinedione group, a ureylene group (—NH—C(═O)—NH—), an allophanate group, a uretdione group, and a urethane group.

[0140] R ３１０ is preferably an (n+m)-valent aliphatic hydrocarbon group having from 1 to 70 carbon atoms, or an (n+m)-valent aromatic hydrocarbon group having from 6 to 70 carbon atoms, which may have a substituted or unsubstituted ether group, carbonyl group, ester group, imino group (—NH—), amide group, or imide group.

[0141] R ３１０ Examples of the monovalent aliphatic hydrocarbon group in R include substituted or unsubstituted alkyl groups and cycloalkyl groups. ３１０ Examples of the divalent aliphatic hydrocarbon group in R include a substituted or unsubstituted alkylene group and a cycloalkylene group. ３１０ Examples of the trivalent aliphatic hydrocarbon group in R include a substituted or unsubstituted alkanetriyl group and a cycloalkanetriyl group. ３１０ Examples of the tetravalent aliphatic hydrocarbon group in R include a substituted or unsubstituted alkanetetrayl group and a cycloalkanetetrayl group. ３１０ Examples of the pentavalent aliphatic hydrocarbon group in R include substituted or unsubstituted alkanpentyl groups and cycloalkanpentyl groups. ３１０ Examples of the hexavalent aliphatic hydrocarbon group in R include a substituted or unsubstituted alkanehexyl group and a cycloalkanehexyl group.３１０ Examples of the heptavalent aliphatic hydrocarbon group in R include substituted or unsubstituted alkaneheptyl groups and cycloalkaneheptyl groups. ３１０ Examples of the octavalent aliphatic hydrocarbon group in R include a substituted or unsubstituted alkane octyl group and a cycloalkane octyl group. ３１０ Examples of the nonavalent aliphatic hydrocarbon group in R include a substituted or unsubstituted alkannonyl group and a cycloalkanoyl group. ３１０ Examples of the decavalent aliphatic hydrocarbon group in R include a substituted or unsubstituted alkanedecyl group and a cycloalkanedecyl group. ３１０ Examples of the 11-valent aliphatic hydrocarbon group in R include a substituted or unsubstituted alkane undecyl group and a cycloalkane undecyl group. ３１０ Examples of the dodecavalent aliphatic hydrocarbon group in R include a substituted or unsubstituted alkanedodecyl group and a cycloalkanedodecyl group. ３１０ Examples of the 13-valent aliphatic hydrocarbon group in the formula include a substituted or unsubstituted alkane tridecyl group and a cycloalkane tridecyl group.

[0142] R ３１０ In the case where an aliphatic hydrocarbon group is selected, the number of carbon atoms is preferably 1 or more and 70 or less, more preferably 1 or more and 20 or less, even more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 10 or less. ３１０ Examples of the substituent of the aliphatic hydrocarbon group in the formula (I) include a hydroxyl group, a cyano group, and a halogen atom. Examples of the halogen atom of the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The number of the substituents is not particularly limited, but is preferably 0 to 10.

[0143] R ３１０Specific examples of the aliphatic hydrocarbon group in include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, cyclohexyl, etc. Among these, unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl is preferred.

[0144] R ３１０ Examples of the monovalent aromatic hydrocarbon group in R include substituted or unsubstituted aryl groups. ３１０ Examples of the divalent aromatic hydrocarbon group in R include a substituted or unsubstituted arylene group. ３１０ Examples of the trivalent aromatic hydrocarbon group in R include a substituted or unsubstituted arenetriyl group. ３１０ Examples of the tetravalent aromatic hydrocarbon group in R include a substituted or unsubstituted arenetetrayl group. ３１０ Examples of the pentavalent aromatic hydrocarbon group in R include substituted or unsubstituted arenepentyl groups. ３１０ Examples of the hexavalent aromatic hydrocarbon group in R include a substituted or unsubstituted arenehexyl group. ３１０ Examples of the heptavalent aromatic hydrocarbon group in R include substituted or unsubstituted arene heptile groups. ３１０ The octavalent aromatic hydrocarbon group in R may be a substituted or unsubstituted arene octyl group. ３１０ Examples of the nonavalent aromatic hydrocarbon group in R include a substituted or unsubstituted arenenonyl group. ３１０ Examples of the decavalent aromatic hydrocarbon group in R include a substituted or unsubstituted arenedecyl group. ３１０ Examples of the 11-valent aromatic hydrocarbon group in R include a substituted or unsubstituted arene undecyl group. ３１０Examples of the dodecavalent aromatic hydrocarbon group in R include a substituted or unsubstituted arendodecayl group. ３１０ Examples of the trivalent aromatic hydrocarbon group in the formula include a substituted or unsubstituted arenetridecayl group.

[0145] R ３１０ In the case where 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. ３１０ Examples of the aryl group in R include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, and a phenanthryl group. ３１０ Examples of the arylene group in R include a phenylene group, a naphthylene group, an anthrylene group, a pyrenylene group, and a phenanthrylene group. ３１０ Examples of the arene ring contained in the aromatic hydrocarbon group having a valence of 3 to 13 in the above formula include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, and a phenanthrene ring.

[0146] R ３１０ Examples of the substituent of the aromatic hydrocarbon group in R include an aliphatic hydrocarbon group, a hydroxyl group, a cyano group, and a halogen atom. ３１０ The aliphatic hydrocarbon group selected as a substituent of the aromatic hydrocarbon group in R ３１０ Examples of the aliphatic hydrocarbon group include the same groups as those exemplified above. Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The number of substituents is not particularly limited, but is preferably 0 to 10.

[0147] R ３１０ R preferably has a carbon atom at a position bonding to the isocyanate group or the nitrogen atom of the trisubstituted urea structure. ３１０ is bonded to the nitrogen atom of the isocyanate group or the trisubstituted urea structure, ３１０ The carbon atom is preferably a primary carbon atom, a secondary carbon atom, a tertiary carbon atom, a carbon atom having aromaticity, or a carbonyl carbon atom.

[0148] The trisubstituted urea compound (III) may be a compound represented by the following general formula (III-a):

[0149] (Z ３１１ -) ｋ１ -R ４１０ -L ３１１ -R ４２０ -(-Z ３１２ ) ｋ２ ...(III-a)

[0150] In the above general formula (III-a), R ４１０ is a (k1+1)-valent cycloaliphatic hydrocarbon group or aromatic hydrocarbon group, and L ３１１ is a single bond or a divalent acyclic aliphatic hydrocarbon group, and R ４２０ is a (k2+1)-valent cycloaliphatic hydrocarbon group or aromatic hydrocarbon group. ３１１ and Z ３１２ are each independently an isocyanate group or a trisubstituted urea structure. ３１１ and Z ３１２ The number of isocyanate groups is within the range of n in general formula (III), and Z ３１１ and Z ３１２ The number of trisubstituted urea structures is within the range of m in the general formula (III), k1+k2 is within the range of n+m, and k1 and k2 are each an integer of 1 or more.

[0151] -R in general formula (III-a) ４１０ -L ３１１ -R ４２０ - group is R in general formula (III) ３１０ This applies to: ４１０ , R ４２０ and L ３１１ In general formula (III), the cyclic or acyclic aliphatic hydrocarbon group or aromatic hydrocarbon group is, for example, ３１０ Examples of the aliphatic hydrocarbon group or aromatic hydrocarbon group include the same as those exemplified above.

[0152] The trisubstituted urea compound (III) may be a compound represented by the following general formula (III-b):

[0153] (Z３１３ -) ｋ３ -R ３１３ -L ３１３ -R ３１４ -(-Z ３１４ ) ｋ４ ...(III-b)

[0154] In the above general formula (III-b), R ３１３ is a (k3+1)-valent aliphatic hydrocarbon group or aromatic hydrocarbon group, and L ３１３ is an ether group, a carbonyl group, an ester group, an imino group (—NH—), an amide group, or an imide group, and R ３１４ is a (k4+1)-valent aliphatic hydrocarbon group or aromatic hydrocarbon group. ３１３ and Z ３１４ are each independently an isocyanate group or a trisubstituted urea structure. ３１３ and Z ３１４ The number of isocyanate groups is within the range of n in general formula (III), and Z ３１３ and Z ３１４ The number of trisubstituted urea structures is within the range of m in the general formula (III), k3+k4 is within the range of n+m, and k3 and k4 are each an integer of 0 or more.

[0155] -R in general formula (III-b) ３１３ -L ３１３ -R ３１４ - group is R in general formula (III) ３１０ This applies to: ３１３ and R ３１４ In general formula (III), the aliphatic hydrocarbon group or aromatic hydrocarbon group is R ３１０ Examples of the aliphatic hydrocarbon group or aromatic hydrocarbon group include the same as those exemplified above.

[0156] In the trisubstituted urea compound (III), R ３１０ Specific examples of the compound represented by the general formulas (1) to (10) below can be given.

[0157]

[0158] In the above general formula (1), Z １ａ and Z１ｂ are each independently an isocyanate group or a trisubstituted urea structure. １ａ and Z １ｂ isocyanate group is 0 or 1, Z １ａ and Z １ｂ is a trisubstituted urea structure, and Z １ａ and Z １ｂ The total number of isocyanate groups or trisubstituted urea structures is 2.

[0159]

[0160] In the above general formula (2), Z ２ａ and Z ２ｂ are each independently an isocyanate group or a trisubstituted urea structure. ２ａ and Z ２ｂ isocyanate group is 0 or 1, Z ２ａ and Z ２ｂ is a trisubstituted urea structure, and Z ２ａ and Z ２ｂ The total number of isocyanate groups or trisubstituted urea structures is 2.

[0161]

[0162] In the general formula (3), Z ３ａ and Z ３ｂ are each independently an isocyanate group or a trisubstituted urea structure. ３ａ and Z ３ｂ isocyanate group is 0 or 1, Z ３ａ and Z ３ｂ is a trisubstituted urea structure, and Z ３ａ and Z ３ｂ The total number of isocyanate groups or trisubstituted urea structures is 2.

[0163]

[0164] In the general formula (4), Z ４ａ and Z ４ｂ are each independently an isocyanate group or a trisubstituted urea structure. ４ａ and Z ４ｂ isocyanate group is 0 or 1, Z４ａ and Z ４ｂ is a trisubstituted urea structure, and Z ４ａ and Z ４ｂ is an isocyanate group or a trisubstituted urea structure, the total number of which is 2. The compound represented by general formula (4) may be a mixture of isomers.

[0165]

[0166] In the above general formula (5), Z ５ａ and Z ５ｂ are each independently an isocyanate group or a trisubstituted urea structure. ５ａ and Z ５ｂ isocyanate group is 0 or 1, Z ５ａ and Z ５ｂ is a trisubstituted urea structure, and Z ５ａ and Z ５ｂ The total number of isocyanate groups or trisubstituted urea structures is 2.

[0167]

[0168] In the above general formula (6), Z ６ａ and Z ６ｂ are each independently an isocyanate group or a trisubstituted urea structure. ６ａ and Z ６ｂ isocyanate group is 0 or 1, Z ６ａ and Z ６ｂ is a trisubstituted urea structure, and Z ６ａ and Z ６ｂ The total number of isocyanate groups or trisubstituted urea structures is 2.

[0169]

[0170] In the above general formula (7), Z ７ａ and Z ７ｂ are each independently an isocyanate group or a trisubstituted urea structure. ７ａ and Z ７ｂ isocyanate group is 0 or 1, Z ７ａ and Z ７ｂ is a trisubstituted urea structure, and Z ７ａ and Z７ｂ The total number of isocyanate groups or trisubstituted urea structures is 2.

[0171]

[0172] In the general formula (8), Z ８ａ , Z ８ｂ and Z ８ｃ are each independently an isocyanate group or a trisubstituted urea structure. ８ａ , Z ８ｂ and Z ８ｃ isocyanate group is 0, 1 or 2, Z ８ａ , Z ８ｂ and Z ８ｃ is a trisubstituted urea structure, and Z ８ａ , Z ８ｂ and Z ８ｃ The total number of isocyanate groups or tri-substituted urea structures is 3.

[0173]

[0174] In the above general formula (9), Z ９ａ , Z ９ｂ and Z ９ｃ are each independently an isocyanate group or a trisubstituted urea structure. ９ａ , Z ９ｂ and Z ９ｃ isocyanate group is 0, 1 or 2, Z ９ａ , Z ９ｂ and Z ９ｃ is a trisubstituted urea structure, and Z ９ａ , Z ９ｂ and Z ９ｃ The total number of isocyanate groups or tri-substituted urea structures is 3.

[0175]

[0176] In the general formula (10), Z １０ａ and Z １０ｂ are each independently an isocyanate group or a trisubstituted urea structure. １０ａ and Z １０ｂ isocyanate group is 0 or 1, Z １０ａ and Z １０ｂis a trisubstituted urea structure, and Z １０ａ and Z １０ｂ The total number of isocyanate groups or trisubstituted urea structures is 2.

[0177] [R ３２０ and R ３３０ In the above general formula (III), R ２ and R ３ are each independently a monovalent organic group. ３２０ and R ３３０ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. ３２０ and R ３３０ At least one of the groups has an aromatic group.

[0178] Among them, R ３２０ and R ３３０ are each independently a substituted or unsubstituted monovalent aliphatic hydrocarbon group having from 1 to 70 carbon atoms or a monovalent aromatic hydrocarbon group having from 6 to 70 carbon atoms, which may have an ether group, a carbonyl group, an ester group, an imino group (—NH—), an amide group, or an imide group.

[0179] R ３２０ and R ３３０ When an aliphatic hydrocarbon group is selected for at least one of R, the number of carbon atoms is preferably 1 or more and 70 or less, more preferably 1 or more and 20 or less, even more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 10 or less. ３２０ and R ３３０ Examples of the aliphatic hydrocarbon group in the formula (I) include linear alkyl groups, branched alkyl groups, and cycloalkyl groups, which may be unsubstituted or substituted. Examples of the substituents on these aliphatic hydrocarbon groups include hydroxyl groups, cyano groups, and halogen atoms. Examples of the halogen atoms in the substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0180] R ３２０ and R ３３０Specific examples of the aliphatic hydrocarbon group in include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, cyclohexyl, etc. Among these, unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl is preferred.

[0181] R ３２０ and R ３３０ When an aromatic hydrocarbon group is selected for at least one of R, the number of carbon atoms is preferably 6 to 70, more preferably 6 to 20, even more preferably 6 to 12, and particularly preferably 6 to 10. ３２０ and R ３３０ Examples of the aromatic hydrocarbon group in R include an aryl group, an aralkyl group, etc., which may be unsubstituted or substituted. Examples of the substituent of these aromatic hydrocarbon groups include an aliphatic hydrocarbon group, a hydroxyl group, a cyano group, a halogen atom, etc. ３２０ and R ３３０ The aliphatic hydrocarbon group selected as a substituent of the aromatic hydrocarbon group in R ３２０ and R ３３０ Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0182] R ３２０ and R ３３０ Specific examples of the aromatic hydrocarbon group in include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a benzyl group, and a phenethyl group.

[0183] R ３２０ and R ３３０ When they are bonded to each other to form a ring structure, R ３２０ and R ３３０The group formed by bonding together is a divalent organic group. ３２０ and R ３３０ The group formed by bonding together is preferably a divalent group having from 7 to 70 carbon atoms, which may have a substituted or unsubstituted ether group, carbonyl group, ester group, imino group (—NH—), amide group, or imide group, and which includes a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group.

[0184] R ３２０ and R ３３０ In the group formed by bonding together, examples of the divalent aliphatic hydrocarbon group include alkylene groups such as methylene, ethylene, propylene, and trimethylene. ３２０ and R ３３０ In the group formed by bonding together, examples of the divalent aromatic hydrocarbon group include arylene groups such as phenylene and naphthylene.

[0185] R ３２０ and R ３３０ is R ３２０ and R ３３０ Regardless of whether or not R are bonded to each other to form a ring structure, it is preferable that R has a carbon atom at a position bonded to the nitrogen atom of the trisubstituted urea structure. ３２０ and R ３３０ is bonded to the nitrogen atom of the trisubstituted urea structure, ３２０ and R ３３０ The carbon atom is preferably a primary carbon atom, a secondary carbon atom, a tertiary carbon atom, a carbon atom having aromaticity, or a carbonyl carbon atom.

[0186] R ３２０ and R ３３０ The aromatic group contained in at least one of the above preferably has an aromatic carbon atom at a position bonding 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 the aromatic group having an aromatic carbon atom at a position bonding to an external atom include aryl groups such as a phenyl group and arylene groups such as a phenylene group.

[0187] Preferred trisubstituted urea compounds (III) include the following (III-1), (III-2) and (III-3):

[0188] (III-1) is the same as R in the above general formula (III). ３２０ and R ３３０ At most one of R is a monovalent organic group having no aromatic group, and at least one is a substituted or unsubstituted phenyl group. ３２０ and R ３３０ One of R may be a substituted or unsubstituted phenyl group and the other may be a monovalent aliphatic hydrocarbon group. ３２０ and R ３３０ may each independently be a substituted or unsubstituted phenyl group.

[0189] In (III-1), R ３２０ and R ３３０ Examples of the monovalent organic group having no aromatic group, which is one or more of the above, include substituted or unsubstituted monovalent aliphatic hydrocarbon groups having from 1 to 12 carbon atoms. Specific examples of the monovalent organic group having no aromatic group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, and cyclohexyl. Among these, unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl is preferred.

[0190] In (III-1), R ３２０ and R ３３０ The number of substituents of the phenyl group, which is at least one of R, is an integer of 0 to 5, more preferably 0 or 1, and even more preferably 0. ３２０ and R ３３０When at least one of the groups is a substituted phenyl group, the substituent (hereinafter, may be referred to as "substituent on the benzene ring") may be a substituted or unsubstituted aliphatic hydrocarbon group having from 1 to 12 carbon atoms or an aromatic hydrocarbon group having from 6 to 12 carbon atoms. The substituent on the benzene ring may have an ether group, a carbonyl group, or an ester group.

[0191] When the substituent on the benzene ring is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, examples of the substituent include an alkyl group having from 1 to 12 carbon atoms, an aryl group having from 6 to 12 carbon atoms, or an aralkyl group having from 7 to 12 carbon atoms. When the substituent on the benzene ring has an ether group, examples of the substituent include an alkoxy group having from 1 to 12 carbon atoms, an aryloxy group having from 6 to 12 carbon atoms, or an aralkyloxy group having from 7 to 12 carbon atoms. When the substituent on the benzene ring has a carbonyl group, examples of the substituent include an alkylcarbonyl group having from 1 to 12 carbon atoms, an arylcarbonyl group having from 6 to 12 carbon atoms, or an aralkylcarbonyl group having from 7 to 12 carbon atoms. When the substituent on the benzene ring has an ester group, examples of the substituent on the benzene ring include an alkoxycarbonyl group or alkylcarbonyloxy group having from 1 to 12 carbon atoms, an aryloxycarbonyl group or arylcarbonyloxy group having from 6 to 12 carbon atoms, or an aralkyloxycarbonyl group or aralkylcarbonyloxy group having from 7 to 12 carbon atoms.

[0192] Specific examples of the substituent on the benzene ring include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, each isomer of pentyl, each isomer of hexyl, each isomer of heptyl, each isomer of octyl, each isomer of nonyl, each isomer of decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, etc. Among these, unsubstituted aliphatic hydrocarbon groups having from 1 to 12 carbon atoms are preferred, and methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl is preferred.

[0193] (III-2) is the same as R in the above general formula (III). ３２０and R ３３０ are bonded to each other to form a ring structure via a carbon-carbon bond, and the general formula -R ３２１ -R ３２２ R is a divalent organic group represented by the formula: ３２１ and R ３２２ at most one of R is a substituted or unsubstituted divalent aliphatic hydrocarbon group having from 1 to 12 carbon atoms, ３２１ and R ３２２ At least one of R is a substituted or unsubstituted o-phenylene group. ３２１ and R ３２２ One of R may be a substituted or unsubstituted o-phenylene group and the other may be a divalent aliphatic hydrocarbon group. ３２１ and R ３２２ may each independently be a substituted or unsubstituted o-phenylene group.

[0194] R ３２１ and R ３２２ Specific examples of the divalent aliphatic hydrocarbon group that is one or less of the above include a methylene group, an ethylene group, a propylene group, and a trimethylene group. ３２１ and R ３２２ The number of substituents of the o-phenylene group, which is at least one of R, is an integer of 0 to 4, more preferably 0 or 1, and even more preferably 0. ３２１ and R ３２２ Examples of the substituent on the o-phenylene group, which is at least one of the above, include the same substituents as those exemplified as the substituent on the benzene ring in (III-1).

[0195] (III-3) is the same as R in the above general formula (III). ３２０ and R ３３０ are bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond, and are represented by the general formula -R ３３１ -Z ３３１ -R ３３２ Z is a divalent organic group represented by the formula: ３３１ is —O—, —NH—, or —C(═O)—. ３３１ and R ３３２at most one of R is a substituted or unsubstituted divalent aliphatic hydrocarbon group having from 1 to 12 carbon atoms, ３３１ and R ３３２ At least one of R is a substituted or unsubstituted o-phenylene group. ３３１ and R ３３２ One of R may be a substituted or unsubstituted o-phenylene group and the other may be a divalent aliphatic hydrocarbon group. ３３１ and R ３３２ may each independently be a substituted or unsubstituted o-phenylene group.

[0196] R ３３１ and R ３３２ Specific examples of the divalent aliphatic hydrocarbon group that is one or less of the above include a methylene group, an ethylene group, a propylene group, and a trimethylene group. ３３１ and R ３３２ The number of substituents of the o-phenylene group, which is at least one of R, is an integer of 0 to 4, more preferably 0 or 1, and even more preferably 0. ３３１ and R ３３２ Examples of the substituent on the o-phenylene group, which is at least one of the above, include the same substituents as those exemplified as the substituent on the benzene ring in (III-1).

[0197] Among the above general formulas (III), (III-1), (III-2) and (III-3), R ３２０ and R ３３０ and R ３２１ , R ３２２ , R ３３１ and R ３３２ Preferably, R does not contain any olefinic or acetylenic unsaturated carbon-carbon bonds. ３２０ and R ３３０ and R ３２１ , R ３２２ , R ３３１ and R ３３２ The hydrocarbon group contained in is preferably a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0198] In addition, from the viewpoint of thermal stability, R ３２０ and R ３３０and R ３２１ , R ３２２ , R ３３１ and R ３３２ is Z in (III-3). ３３１ It is preferable that the structure is composed only of carbon atoms and hydrogen atoms, excluding the following:

[0199] In (III-1), R ３２０ and R ３３０ at most one of R is a monovalent aliphatic hydrocarbon group; ３２０ and R ３３０ At least one of the groups is an unsubstituted or monosubstituted phenyl group, and the substituent of the phenyl group is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. ３２０ and R ３３０ at most one of R is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms; ３２０ and R ３３０ At least one of the groups is preferably an unsubstituted or monosubstituted phenyl group, and the substituent of the phenyl group is preferably a methyl group or an ethyl group.

[0200] In (III-2), R ３２１ and R ３２２ at most one of R is a divalent aliphatic hydrocarbon group; ３２１ and R ３２２ At least one of the groups is an unsubstituted or monosubstituted o-phenylene group, and the substituent of the o-phenylene group is preferably an unsubstituted aliphatic hydrocarbon group having from 1 to 12 carbon atoms or an aromatic hydrocarbon group having from 6 to 12 carbon atoms. ３２１ and R ３２２ at most one of R is a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms; ３２１ and R ３２２ At least one of the groups is an unsubstituted or monosubstituted o-phenylene group, and the substituent of the o-phenylene group is preferably a methyl group or an ethyl group.

[0201] In (III-3), R ３３１ and R ３３２at most one of R is a divalent aliphatic hydrocarbon group; ３３１ and R ３３２ At least one of the groups is an unsubstituted or monosubstituted o-phenylene group, and the substituent of the o-phenylene group is preferably an unsubstituted aliphatic hydrocarbon group having from 1 to 12 carbon atoms or an aromatic hydrocarbon group having from 6 to 12 carbon atoms. ３３１ and R ３３２ at most one of R is a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms; ３３１ and R ３３２ At least one of the groups is an unsubstituted or monosubstituted o-phenylene group, and the substituent of the o-phenylene group is preferably a methyl group or an ethyl group.

[0202] [Method for Producing Tri-Substituted Urea Compound (III)] The tri-substituted urea compound (III) can be synthesized by a known production method, for example, a method in which an isocyanate group blocked with a secondary amine compound is produced in a production process of a blocked isocyanate compound.

[0203] The secondary amine compound used in the synthesis of the trisubstituted urea compound (III) includes a compound represented by the following general formula (B).

[0204] H-N (-R ３５３ )-R ３５２ (B)

[0205] In the above general formula (B), R ３５２ and R ３５３ are respectively represented by R ３２０ and R ３３０ It is the same as that listed above.

[0206] The tri-substituted urea compound (III) has an active hydrogen and is excellent in the storage stability and coloration suppression of the polyisocyanate composition. The tri-substituted urea compound (III) suppresses the formation of the 1-nylon structure, which is the aforementioned [compound having UV absorption in the region of isocyanate decamers or higher in GPC], and acts as a stabilizer during storage.

[0207] The trisubstituted urea compound (III) is R ３２０ and R ３３０ Since at least one of the groups has an aromatic group, the active hydrogen contained in the tri-substituted urea structure is bulky, preventing addition reactions with the isocyanate group. Furthermore, since the aromatic group has electron-withdrawing properties, the anion generated when the active hydrogen contained in the tri-substituted urea structure is abstracted by a base is stabilized, thereby suppressing the formation of a 1-nylon structure.

[0208] In order to improve the storage stability and coloration inhibition of the polyisocyanate composition 3, it is preferable to increase the content of the tri-substituted urea compound (III). However, if the content of the tri-substituted urea compound (III) is too high, this may affect the production cost, applications, etc. of the polyisocyanate composition.

[0209] The polyisocyanate composition 3 has a polyisocyanate content of 1.0 ppm by mass or more and 1.0 x 10 based on the total mass of the polyisocyanate compound. ４ It is preferred that the tri-substituted urea compound (III) is contained in an amount of not more than ppm by mass.

[0210] The polyisocyanate composition 3 of the present embodiment may contain optional components other than the tri-substituted urea compound (III) and the polyisocyanate compound depending on the application, purpose, etc.

[0211] The polyisocyanate composition 3 of this embodiment can be used as a polyurethane synthesis material, a curing agent, etc. The polyisocyanate composition of this embodiment can be used in a wide range of fields, such as flexible foams, rigid foams, elastomers, adhesives, paints, and binders.

[0212] Polyisocyanate Composition 4 Polyisocyanate composition 4 of the present embodiment contains two or more compounds selected from the compounds represented by general formulas (I), (II), and (III), and a polyisocyanate compound. The forms of the compounds represented by general formulas (I), (II), and (III) are the same as those of the polyisocyanate compositions 1 to 3 described above.

[0213] Polyisocyanate composition 4 is more preferred because it can provide a polyisocyanate that is more excellent in storage stability and coloration inhibition than the above-mentioned polyisocyanate compositions 1 to 3. Among polyisocyanate compositions 4, those containing compounds represented by general formulas (I), (II), and (III) and a polyisocyanate compound are even more preferred because they can provide a polyisocyanate that is even more excellent in storage stability and coloration inhibition.

[0214] The polyisocyanate composition 4 has a content of compound (I), compound (II), or compound (III) based on the total mass of the polyisocyanate compound of 1.0 mass ppm or more and 5.0 × 10 ４ Preferably, it is 1.0 ppm by mass or more and 1.0 x 10 ４ Furthermore, when the polyisocyanate composition 4 contains all of the compounds represented by the general formulas (I), (II), and (III), the total amount of the compounds represented by the general formulas (I), (II), and (III) is 1.0 ppm by mass or more and 15.0 × 10 ppm by mass or less, based on the total mass of the polyisocyanate compounds. ４ Preferably, it is 1.0 ppm by mass or more and 3.0 × 10 ４ It is more preferably ppm by mass or less.

[0215] [Polyisocyanate Compound] The polyisocyanate compound contained 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), but it may be a compound having two or more isocyanate groups (-NCO). Examples of the polyisocyanate compound include a compound represented by the following general formula (P) (hereinafter, sometimes referred to as "polyisocyanate compound (P)"):

[0216] R ７０ -(-NCO) ｐ (P)

[0217] In the above general formula (P), R ７０ is a p-valent organic group that does not contain an isocyanate group, and p is an integer of 2 or more and 12 or less.

[0218] R ７０is preferably a p-valent aliphatic hydrocarbon group having from 1 to 70 carbon atoms or a p-valent aromatic hydrocarbon group having from 6 to 70 carbon atoms, which may have a substituted or unsubstituted ether group, carbonyl group, ester group, imino group (—NH—), amide group or imide group. p is preferably 2 or 3.

[0219] R ７０ In the case where an aliphatic hydrocarbon group is selected, the number of carbon atoms is preferably 1 or more and 70 or less, more preferably 1 or more and 20 or less, even more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 10 or less.

[0220] R ７０ In the case where an aromatic hydrocarbon group is selected, the number of carbon atoms is preferably 6 to 70, more preferably 6 to 20, even more preferably 6 to 12, and particularly preferably 6 to 10.

[0221] The polyisocyanate compound (P) may be a compound that does not have a blocked isocyanate group. ７０ is an organic group that does not contain a blocked isocyanate group.

[0222] The blocked isocyanate group is a group that can be thermally dissociated into an isocyanate group and a blocking agent represented by the general formula BL-H. The blocking agent is a compound having active hydrogen. Examples of the blocking agent include phenol-based blocking agents, alcohol-based blocking agents, thiol-based blocking agents, amine-based blocking agents, ammonia-based blocking agents, oxime-based blocking agents, hydroxylamine-based blocking agents, and active methylene-based blocking agents.

[0223] The polyisocyanate compound (P) is R ７０ The units constituting an isocyanate polymer may or may not be included in the above-mentioned copolymer. The units constituting an isocyanate polymer refer to units containing nitrogen atoms derived from one or more isocyanate groups, such as an isocyanurate group, a biuret group, an iminooxadiazinedione group, a ureylene group, an allophanate group, a uretdione group, and a urethane group.

[0224] The polyisocyanate compound (P) may be a compound represented by the following general formula (Pa):

[0225] (OCN-) ｐ１ -R ７１ -L ７１ -R ７２ -(-NCO) ｐ２ (P-a)

[0226] In the above general formula (Pa), R ７１ is a (p+1)-valent cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group, and L ７１ is a single bond or a divalent acyclic aliphatic hydrocarbon group, and R ７２ is a (p2+1)-valent cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group, where p1 and p2 are each an integer of 1 or greater, provided that p1+p2 is an integer of 2 or greater and 12 or less.

[0227] The polyisocyanate compound (P) may be a compound represented by the following general formula (Pb):

[0228] (OCN-) ｐ３ -R ７３ -L ７３ -R ７４ -(-NCO) ｐ４ (P-b)

[0229] In the above general formula (Pb), R ７３ is a (p+1)-valent aliphatic hydrocarbon group or aromatic hydrocarbon group, and L ７３ is an ether group, a carbonyl group, an ester group, an imino group (—NH—), an amide group, or an imide group, and R ７４ is a (p4+1)-valent aliphatic hydrocarbon group or aromatic hydrocarbon group, and p3 and p4 are each an integer of 0 or greater, provided that p3+p4 is an integer of 2 or greater and 12 or less.

[0230] R ７１ , R ７２ , R ７３ , R ７４ and L ７１ The aliphatic hydrocarbon group or aromatic hydrocarbon group in R ７０ Examples of the aliphatic hydrocarbon group or aromatic hydrocarbon group include the same groups as those exemplified above.

[0231] Specific 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(cyclohexane isocyanate) (hereinafter sometimes referred to as "MBCI"), diisocyanatotoluene (hereinafter sometimes referred to as "TDI"), 4,4'-diphenylmethane diisocyanate (hereinafter sometimes referred to as "MDI"), 4-isocyanatomethyl-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").

[0232] <Method for Producing Isocyanate Compound> The method for producing an isocyanate compound of the present embodiment includes a reaction step of decomposing a blocked isocyanate compound into a blocking agent and an isocyanate compound by heat treatment in the presence of a compound having a structure represented by either or both of the following general formulas (I) and (II), thereby obtaining the isocyanate compound.

[0233] (In general formula (I), R １ and R ２ are each independently a monovalent organic group. １ and R ２ may each independently form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. ３ is a hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group.

[0234] (In general formula (II), R ２１０ is a monovalent organic group, and R ２２０ , R ２３０ , R ２４０ and R ２５０ R is each independently a monovalent organic group or hydrogen. ２１０ and R ２２０may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.)

[0235] <<Isocyanate Compound Production Method 1>> The isocyanate compound production method 1 includes a reaction step of decomposing a blocked isocyanate compound into a blocking agent and an isocyanate compound by heat treatment in the presence of a compound having a structure represented by general formula (I) above, to obtain the isocyanate compound.

[0236] The present inventors have discovered that a method for producing an isocyanate compound in high yield without increasing the amount of by-products produced can be achieved by heat-treating a blocked isocyanate compound in the presence of compound (I) to decompose it into a blocking agent and an isocyanate compound, thereby completing the present invention. The production method of the present invention will now be described.

[0237] In the reaction step in the method for producing an isocyanate compound according to this embodiment, a blocked isocyanate compound is decomposed into a blocking agent and an isocyanate compound by heat treatment in the presence of compound (I), thereby obtaining an isocyanate compound.

[0238] The compound (I) is a compound (I) represented by the above general formula (I). ３ When is an aromatic hydrocarbon group, the reactivity of the organic amine generated by decomposition of the ureylene group with compound (I) is improved, and the ureylene group can be efficiently reduced, which is more preferable.

[0239] The compound (I) used in the method for producing an isocyanate compound 1 is R ３ When an aromatic hydrocarbon group is selected as R, 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. ３ Examples of the aromatic hydrocarbon group in R include an aryl group, an aralkyl group, etc., which may be unsubstituted or substituted. Examples of the substituent of these aromatic hydrocarbon groups include an aliphatic hydrocarbon group, a hydroxyl group, a cyano group, a halogen atom, etc. ３The aliphatic hydrocarbon group selected as a substituent of the aromatic hydrocarbon group in R ３ Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0240] R ３ Specific examples of the aromatic hydrocarbon group in include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a benzyl group, and a phenethyl group.

[0241] The ureylene group reacts with isocyanate, for example, according to the reactions represented by the following formulas (70), (71), and (72), to produce by-products.

[0242]

[0243] Compound (I) reacts with a ureylene group to suppress the generation of by-products due to the ureylene group. The reaction between compound (I) and a ureylene group is represented by either or both of the following general formula A and general formula B. Here, it is presumed that the ureylene group decomposes into an amino group and an isocyanate group by thermal dissociation, and the generated amino group reacts with compound (I), thereby causing either or both of the reactions of general formula A and general formula B to proceed. Whether the reaction of general formula A or the reaction of general formula B is dominant depends on the leaving ability of the group bonded to the carbonyl, and therefore the reaction of general formula A is dominant.

[0244]

[0245] Here, when the reaction of general formula B proceeds, the obtained carbamic acid ester reacts with isocyanate according to the reaction represented by the following general formula C, and reactions such as those shown in (67), (68), and (69) proceed.

[0246]

[0247] On the other hand, when the reaction of general formula A proceeds, the reaction of the obtained tri-substituted urea group with the above-mentioned isocyanate is slight or not observed. Although the reason for this is not clear, it is presumed that the resulting tri-substituted urea group has a large steric hindrance.

[0248] In the reaction step, the amount of compound (I) present is preferably large from the viewpoint of improving the thermal decomposition rate. Specifically, the amount of compound (I) present is preferably 1 mass ppm or more, more preferably 100 mass ppm or more, even more preferably 1000 mass ppm or more, and particularly preferably 10,000 mass ppm or more relative to the blocked isocyanate compound. Furthermore, from the viewpoint of suppressing the generation of by-products due to ureylene groups, the amount of compound (I) present is preferably 0.1 mol% or more relative to the ureylene groups, more preferably 1 mol% or more, even more preferably 10 mol% or more, and particularly preferably 100 mol% or more.

[0249] The reaction temperature in the reaction step (thermal decomposition temperature of the blocked isocyanate compound) is not particularly limited and is appropriately selected depending on the rate at which the blocked isocyanate compound decomposes into a blocking agent and an isocyanate compound, and the degree of thermal denaturation and coloration. From the viewpoint of suppressing denaturation 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, if the reaction temperature is low, it may be necessary to set the condenser temperature at a low temperature, which may require new equipment. From this viewpoint, the reaction temperature is preferably 50°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher.

[0250] The reaction pressure in the reaction step varies depending on the type of compound used and the reaction temperature, but may be reduced pressure, normal pressure, or increased pressure. The absolute pressure is usually 20 Pa or more and 2×10 ７ The temperature is set within a range of 0.1 Pa or less.

[0251] The reaction step may be carried out in the presence of oxygen. When the reaction step is carried out in the presence of oxygen, the amount of oxygen present in the thermal decomposition apparatus for the blocked isocyanate compound is preferably reduced because thermal denaturation and coloration of the isocyanate compound may occur. On the other hand, when considering a large-scale production facility, in order to reduce the amount of oxygen present in the thermal decomposition apparatus for the blocked isocyanate compound, it is necessary to reduce air leakage into the production facility, which results in stricter design standards for the facility and increased facility costs. From this perspective, the oxygen concentration in the gas supplied to the reaction step is preferably controlled at a high condition, preferably greater than 0% by volume, more preferably greater than 0.0001% by volume, and even more preferably greater than 0.001% by volume.

[0252] In the reaction step, any solvent may be used in any proportion. The solvent is preferably an inert solvent that does not have reactivity with the blocked isocyanate compound, etc. Such a solvent is preferably an ester solvent, an ether solvent, a phosphate ester solvent, a hydrocarbon solvent, an aromatic hydrocarbon solvent, or a carbonic acid derivative solvent.

[0253] In the reaction step, the reaction solution may contain any metal in any proportion. The metal may be in the form of a complex or a solid. While the metal reduces the thermal decomposition temperature of the blocked isocyanate compound, it may cause thermal denaturation, deterioration, and coloration. The metal content 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, relative to the mass of the blocked isocyanate compound.

[0254] In the reaction step, the reaction solution may contain an organic acid, an inorganic acid, an organic base, or an inorganic base. These acids and bases act as catalysts in the thermal decomposition of the blocked isocyanate, thereby reducing the temperature required for thermal decomposition. On the other hand, these acids and bases also act as catalysts for side reactions in the thermal decomposition of the blocked isocyanate. From these viewpoints, the content of these organic acids, inorganic acids, organic bases, and inorganic bases is preferably less than 10% by mass, more preferably less than 1% by mass, even more preferably less than 0.1% by mass, and particularly preferably less than 1 ppb by mass, relative to the mass of the blocked isocyanate compound.

[0255] The thermal decomposition apparatus for the blocked isocyanate compound is not particularly limited, and known thermal decomposition apparatuses can be used. For example, an apparatus that places a composition containing a blocked isocyanate compound in a container connected to a condenser, heats the container to thermally decompose the blocked isocyanate compound, and then introduces vapor containing a blocking agent produced thereafter or simultaneously with the thermal decomposition into a condenser to separate the isocyanate compound and the blocking agent in a batchwise manner; an apparatus that continuously introduces a composition containing a blocked isocyanate compound into a distillation column heated to a temperature equal to or higher than the thermal decomposition temperature of the blocked isocyanate compound, and then separates the blocking agent and the isocyanate compound produced simultaneously with the thermal decomposition of the blocked isocyanate compound, thereby continuously obtaining free isocyanate compound and the blocking agent; an apparatus that introduces a blocked isocyanate compound into an evaporator or thin film heated to a temperature equal to or higher than the thermal decomposition temperature of the blocked isocyanate compound, introduces vapor containing the blocking agent and the isocyanate compound produced by thermal decomposition into a distillation column, and separates the blocking agent and the isocyanate compound in the distillation column.

[0256] In the thermal decomposition apparatus for a blocked isocyanate compound, the material of the portion that comes into contact with the composition containing the blocked isocyanate compound and the blocking agent, isocyanate compound, and other components that are generated during thermal decomposition may be any known material as long as it does not adversely affect the denaturation of the blocked isocyanate compound, the blocking agent, the isocyanate compound, and other components. Specific examples of such materials include steel, stainless steel, ceramic, carbon, and materials lined with these materials.

[0257] [Blocked Isocyanate Compound] The blocked isocyanate compound is a compound that can be dissociated into a blocking agent and an isocyanate compound by heat, as shown in the following reaction formula.

[0258] R ａ -(NH-C(=O)-BL) ｎａ → BL-H + R ａ -(N=C=O) ｎａ

[0259] In the above reaction formula, BL-H is a blocking agent having active hydrogen. ａ is an organic group with a valence of n a, where n a is an integer of 1 or more. BL- is a residue obtained by removing active hydrogen from a blocking agent.

[0260] [Isocyanate Compound] As the isocyanate compound in the reaction step, an isocyanate compound represented by the following general formula (IV) (hereinafter, sometimes referred to as "isocyanate compound (IV)") is preferably used.

[0261]

[0262] (In general formula (IV), R ２１ is an n21-valent organic group, where n21 is an integer of 1 or more and 12 or less.

[0263] R ２１ Although R is not particularly limited as long as it is an organic group having a valence of 1 to 12, it is preferably an organic group (hydrocarbon group) consisting of carbon atoms and hydrogen atoms or an organic group consisting of carbon atoms, oxygen atoms, and hydrogen atoms, and more preferably an organic group having no active hydrogen. ２１The oxygen atom contained in preferably constitutes an ether group or an ester group.

[0264] R ２１ The aliphatic hydrocarbon group in is preferably an alkyl group, an alkylene group, an alkanetriyl group, a cycloalkyl group, a cycloalkylene group, a cycloalkanetriyl group, or a group composed of two or more of these.

[0265] R ２１ The aromatic hydrocarbon group in is preferably a substituted or unsubstituted group having an aromatic ring with 6 to 13 carbon atoms. Examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, and an alkylcarbonyloxy group.

[0266] The isocyanate compound (IV) may be a monofunctional isocyanate compound, a bifunctional isocyanate compound, or a polyfunctional isocyanate compound.

[0267] In the monofunctional isocyanate compound, R ２１ Examples of the monovalent organic group include a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, and aryl group.

[0268] In the bifunctional isocyanate compound, R ２１ Examples of the divalent organic group include a substituted or unsubstituted alkylene group, a cycloalkylene group, an arylene group, an arylene dialkylene group, an alkylenediarylene group, an alkylenedicycloalkylene group, etc. The bifunctional isocyanate compound may be a compound having an isocyanatoalkyl group such as isophorone diisocyanate, a compound having an isocyanatocycloalkyl group such as dicyclohexylmethane 4,4'-diisocyanate, a compound having an isocyanatoaryl group such as diphenylmethane diisocyanate, or a compound having a carbonyl group such as lysine diisocyanate.

[0269] In the polyfunctional isocyanate compound, R ２１Examples of the polyvalent organic group include a substituted or unsubstituted alkanetriyl group, a cycloalkanetriyl group, an arenetriyl group, etc. The polyfunctional isocyanate compound may be a compound having an isocyanatoalkyl group such as 4-isocyanatomethyl-1,8-octamethylene diisocyanate, or a compound having a carbonyl group such as lysine triisocyanate.

[0270] [Blocking Agent] The blocking agent is a compound having active hydrogen. The blocking agent used in the reaction step preferably contains one or more compounds selected from the group consisting of hydroxy compounds, amine compounds, and ammonia. The hydroxy compound may be one or more compounds selected from the group consisting of aromatic hydroxy compounds and aliphatic hydroxy compounds.

[0271] (Blocking Agent as Aromatic Hydroxy Compound) Aromatic hydroxy compounds preferred as blocking agents include aromatic hydroxy compounds represented by the following general formula (V).

[0272]

[0273] (In general formula (V), ring A ３１ is an aromatic hydrocarbon ring having 6 to 20 carbon atoms. ３１ is a hydrogen atom, a halogen atom, a carboxy group, an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an alkyloxycarbonyl group having from 1 to 20 carbon atoms, an alkylcarbonyloxy group having from 1 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, an aryloxy group having from 6 to 20 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms, or an aralkyloxy group having from 7 to 20 carbon atoms. ３１ is ring A ３１ may bond to form a ring structure. n31 is an integer of 1 or more and 10 or less.

[0274] Ring A ３１ may be a monocyclic ring or a polycyclic ring such as a condensed ring. ３１Specific examples of the ring A include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a naphthacene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a pentalene ring, an azulene ring, a heptalene ring, an indacene ring, a biphenylene ring, an acenaphthylene ring, an aceanthrylene ring, and an acephenanthrylene ring. ３１ As the ring, a benzene ring, a naphthalene ring, or an anthracene ring is preferable, and a benzene ring is more preferable.

[0275] The hydroxy group shown in general formula (V) is ３１ and has phenolic properties. ３１ and n31 R ３１ The aromatic hydrocarbon group having the formula may be a substituted or unsubstituted monovalent aromatic hydrocarbon group such as an aryl group.

[0276] R ３１ is a ring A except for hydrogen atoms. ３１ is a substituent of the formula: ３１ As shown in general formula (V), it is a group consisting of one hydroxy group and n31 R ３１ n31 R ３１ are each independently R ３１ Different rings may be selected from the group exemplified in the above, or two or more of the same rings may be selected. ３１ is the above R ３１ Besides, Ring A ３１ The ring A may have a hydrogen atom and / or a substituent bonded to the carbon atom constituting the ring. ３１ The hydrogen atoms, substituents, and functional groups bonded to the carbon atoms constituting the general formula (V) are one hydroxy group and n31 R ３１ Only this is acceptable.

[0277] (Blocking Agent as Aliphatic Hydroxy Compound) Examples of aliphatic hydroxy compounds preferred as blocking agents include aliphatic hydroxy compounds represented by the following general formula (VI).

[0278]

[0279] (In general formula (VI), R ４１represents a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 24 carbon atoms, which may have an ether group, a carbonyl group, or an ester group.

[0280] R ４１ is a monovalent aliphatic hydrocarbon group. ４１ The number of carbon atoms in the aliphatic hydrocarbon group in R is 1 or more and 24 or less, preferably 1 or more and 20 or less, and more preferably 1 or more and 12 or less. ４１ The aliphatic hydrocarbon group in the general formula (VI) may be saturated or unsaturated. ４１ It is bonded to a saturated carbon atom in and has alcoholic properties.

[0281] (Blocking Agent as Secondary Amine Compound) Preferred secondary amine compounds as blocking agents include secondary amine compounds represented by the following general formula (VII).

[0282]

[0283] (In general formula (VII), R ５１ and R ５２ are each independently a monovalent organic group. ５１ and R ５２ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.)

[0284] Among them, R ５１ and R ５２ is preferably a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 70 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 70 carbon atoms, which may have an ether group, a carbonyl group, or an ester group. ５１ and R ５２ is preferably an organic group that does not contain active hydrogen, and more preferably an organic group that does not contain a substituted or unsubstituted amino group.

[0285] R ５１ and R ５２ Examples of the aliphatic hydrocarbon group in R include an alkyl group and a cycloalkyl group. ５１ and R ５２The number of carbon atoms in the aliphatic hydrocarbon group in R is preferably 1 or more and 70 or less, more preferably 1 or more and 20 or less, even more preferably 1 or more and 12 or less, and particularly preferably 1 or more and 10 or less. ５１ and R ５２ Examples of the substituent on the aliphatic hydrocarbon group in the formula include a hydroxyl group, a cyano group, and a halogen atom.

[0286] R ５１ and R ５２ Examples of the aromatic hydrocarbon group in R include an aryl group and an aralkyl group. ５１ and R ５２ The number of carbon atoms in the aromatic hydrocarbon group in R 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. ５１ and R ５２ Examples of the substituent on the aromatic hydrocarbon group in the formula (I) include an aliphatic hydrocarbon group, a hydroxyl group, a cyano group, and a halogen atom.

[0287] R ５１ and R ５２ When they are bonded to each other to form a ring structure, R ５１ and R ５２ The group formed by bonding together is a divalent organic group. ５１ and R ５２ Examples of the group formed by bonding together include a substituted or unsubstituted ether group, a carbonyl group, an ester group, a substituted imino group (-N(-R ５３ )-), —CH═N— group, substituted amide group (—C(═O)—N(—R ５４ )-) or a substituted imido group (-C(=O)-N(-R ５５ )-C(=O)-), and a divalent aliphatic hydrocarbon group having 1 to 70 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 70 carbon atoms. ５３ , R ５４ and R ５５ Examples of the alkyl group include monovalent aliphatic hydrocarbon groups and aromatic hydrocarbon groups.

[0288] <<Isocyanate Compound Production Method 2>> The isocyanate compound production method according to the present embodiment includes a reaction step of decomposing a blocked isocyanate compound into a blocking agent and an isocyanate compound by heat treatment in the presence of a compound having a structure represented by general formula (II) above (hereinafter, may be referred to as a “quinazolinedione structure (II)”), thereby obtaining the isocyanate compound.

[0289] The inventors have found that the problem of the thermal decomposition rate can be solved without increasing the amount of by-products produced by heat-treating a blocked isocyanate compound in the presence of a compound having a quinazolinedione structure (II) to decompose the compound into a blocking agent and an isocyanate compound, thereby completing the present invention.

[0290] [Reaction Step] In the reaction step in the method for producing an isocyanate compound according to the present embodiment, a blocked isocyanate compound is decomposed into a blocking agent and an isocyanate compound by heat treatment in the presence of a compound having a quinazolinedione structure (II), thereby obtaining an isocyanate compound.

[0291] In the reaction step, the amount of the compound having the quinazolinedione structure (II) present is preferably large from the viewpoint of improving the thermal decomposition rate. Specifically, the amount of the compound having the quinazolinedione structure (II) present is preferably 1 ppm by mass or more, more preferably 100 ppm by mass or more, even more preferably 1,000 ppm by mass or more, and particularly preferably 10,000 ppm by mass or more, relative to the blocked isocyanate compound.

[0292] The descriptions regarding the blocked isocyanate compound, isocyanate compound, and blocking agent in the method for producing an isocyanate compound 2 are the same as the descriptions regarding the blocked isocyanate compound, isocyanate compound, and blocking agent in the method for producing an isocyanate compound 1 described above.

[0293] The reaction temperature in the reaction step (thermal decomposition temperature of the blocked isocyanate compound) is not particularly limited and is appropriately selected depending on the rate at which the blocked isocyanate compound decomposes into a blocking agent and an isocyanate compound, and the degree of thermal denaturation and coloration. From the viewpoint of suppressing denaturation 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, if the reaction temperature is low, it may be necessary to set the condenser temperature at a low temperature, which may require new equipment. From this viewpoint, the reaction temperature is preferably 50°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher.

[0294] The reaction pressure in the reaction step varies depending on the type of compound used and the reaction temperature, but may be reduced pressure, normal pressure, or increased pressure. The reaction pressure is usually 20 Pa or more and 2×10 ７ The temperature is set within a range of 0.1 Pa or less.

[0295] In the reaction step, any solvent may be used in any proportion. The solvent is preferably an inert solvent that does not have reactivity with the blocked isocyanate compound, etc. Such a solvent is preferably an ester solvent, an ether solvent, a phosphate ester solvent, a hydrocarbon solvent, an aromatic hydrocarbon solvent, or a carbonic acid derivative solvent.

[0296] In the reaction step, the reaction solution may contain any metal in any proportion. The metal may be in the form of a complex or a solid. While the metal reduces the thermal decomposition temperature of the blocked isocyanate compound, it may cause thermal denaturation, deterioration, and coloration. The metal content 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, relative to the mass of the blocked isocyanate compound.

[0297] In the reaction step, the reaction solution may contain an organic acid, an inorganic acid, an organic base, or an inorganic base. These acids and bases act as catalysts in the thermal decomposition of the blocked isocyanate, thereby reducing the temperature required for thermal decomposition. On the other hand, these acids and bases also act as catalysts for side reactions in the thermal decomposition of the blocked isocyanate. From these viewpoints, the content of these organic acids, inorganic acids, organic bases, and inorganic bases is preferably less than 10% by mass, more preferably less than 1% by mass, even more preferably less than 0.1% by mass, and particularly preferably less than 1 ppb by mass, relative to the mass of the blocked isocyanate compound.

[0298] The thermal decomposition apparatus for the blocked isocyanate compound is not particularly limited, and known thermal decomposition apparatuses can be used. For example, an apparatus that places a composition containing a blocked isocyanate compound in a container connected to a condenser, heats the container to thermally decompose the blocked isocyanate compound, and then introduces vapor containing a blocking agent produced thereafter or simultaneously with the thermal decomposition into a condenser to separate the isocyanate compound and the blocking agent in a batchwise manner; an apparatus that continuously introduces a composition containing a blocked isocyanate compound into a distillation column heated to a temperature equal to or higher than the thermal decomposition temperature of the blocked isocyanate compound, and then separates the blocking agent and the isocyanate compound produced simultaneously with the thermal decomposition of the blocked isocyanate compound, thereby continuously obtaining free isocyanate compound and the blocking agent; an apparatus that introduces a blocked isocyanate compound into an evaporator or thin film heated to a temperature equal to or higher than the thermal decomposition temperature of the blocked isocyanate compound, introduces vapor containing the blocking agent and the isocyanate compound produced by thermal decomposition into a distillation column, and separates the blocking agent and the isocyanate compound in the distillation column.

[0299] In the thermal decomposition apparatus for a blocked isocyanate compound, the material of the portion that comes into contact with the composition containing the blocked isocyanate compound and the blocking agent, isocyanate compound, and other components that are generated during thermal decomposition may be any known material as long as it does not adversely affect the denaturation of the blocked isocyanate compound, the blocking agent, the isocyanate compound, and other components. Specific examples of such materials include steel, stainless steel, ceramic, carbon, and materials lined with these materials.

[0300] <<Isocyanate Compound Production Method 3>> The isocyanate compound production method 3 of the present embodiment includes a reaction step of decomposing a blocked isocyanate compound into a blocking agent and an isocyanate compound by heat treatment in the presence of a compound having a structure represented by both of the general formulas (I) and (II) above, thereby obtaining the isocyanate compound.

[0301] In a reaction step in which a blocked isocyanate compound is decomposed into a blocking agent and an isocyanate compound by heat treatment in the presence of a compound having a structure represented by both general formulas (I) and (II) to obtain an isocyanate compound, the amount of compound (I) or (II) present is preferably 1 ppm by mass or more relative to the blocked isocyanate compound, more preferably 100 ppm by mass or more, even more preferably 1,000 ppm by mass or more, and particularly preferably 10,000 ppm by mass or more. Furthermore, from the viewpoint of suppressing the generation of by-products due to ureylene groups, the amount of compound (I) present is preferably 0.1 mol% or more relative to the ureylene groups, more preferably 1 mol% or more, even more preferably 10 mol% or more, and particularly preferably 100 mol% or more.

[0302] The descriptions regarding the blocked isocyanate compound, the isocyanate compound, and the blocking agent in the method for producing an isocyanate compound 3 are the same as the descriptions regarding the blocked isocyanate compound, the isocyanate compound, and the blocking agent in the method for producing an isocyanate compound 1 described above.

[0303] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. All of the reagents used as raw materials were purified products.

[0304] <Production of Polyisocyanate Composition 1> A polyisocyanate compound, compound (I), and a reaction terminator were mixed to produce polyisocyanate compositions of Examples 1 to 26 and Comparative Examples 1 and 2. The amounts of each component mixed and specific materials are shown in Tables 1 and 2.

[0305] As the polyisocyanate compound, any one of HDI, IPDI, PDI, MBCI, TDI, MDI, TTI, LTI, and LDI was used.

[0306] Dibutyl phosphate (DBP) was used as the reaction terminator.

[0307] The following compounds (I)-1 to (I)-11 were used as compound (I). In the following chemical formula, each symbol represents the following group: Me: methyl group Et: ethyl group n-Bu: n-butyl group i-Pr: isopropyl group Oc: octyl group Cumyl: cumyl group

[0308]

[0309]

[0310]

[0311] <Evaluation of Color Suppression> The polyisocyanate compositions before and after storage were subjected to a color test using Hazen color scale (APHA rank) to evaluate color suppression. Specifically, the APHA rank before storage was measured using a sample prepared by dissolving 1 g of the obtained polyisocyanate composition in 2 g of benzyl toluene. Based on the values ​​measured with the Hazen meter, the samples were ranked according to the following evaluation criteria.

[0312] (Evaluation criteria) Rank 1: APHA 0 or more and less than 5 Rank 2: APHA 5 or more and less than 10 Rank 3: APHA 10 or more and less than 15 Rank 4: APHA 15 or more and less than 20 Rank 5: APHA 20 or more and less than 25 Rank 6: APHA 25 or more and less than 30 Rank 7: APHA 30 or more and less than 35 Rank 8: APHA 35 or more and less than 40 Rank 9: APHA 40 or more and less than 45 Rank 10: APHA 45 or more and less than 50

[0313] The APHA rank after 300 days of storage was measured using a sample prepared by dissolving 1 g of the polyisocyanate composition after 300 days of storage in 2 g of benzyltoluene. Based on the value measured with a Hazen meter, the APHA rank was determined using the same evaluation criteria as in Evaluation 1.

[0314] <Evaluation of Storage Stability> The storage stability was measured by GPC using a polyisocyanate composition sample after a 300-day storage period, and evaluated using the following area ratio: Area ratio (B) / (A) (In the above area ratio, (A) is the area of ​​the peak corresponding to a difunctional or higher functional isocyanate in UV absorption (210 nm), and (B) is the area of ​​the peak corresponding to a compound having UV absorption (wavelength 254 nm) in the region of an isocyanate decamer or higher.)

[0315] Compounds that have UV absorption (wavelength 254 nm) in the region of isocyanate decamers or higher are high-boiling impurity components, and when the production of such compounds is small, it can be evaluated that storage stability is improved.

[0316] The peak area ratio (%) after 300 days of storage was measured by GPC using the polyisocyanate composition after the storage period as a sample. The storage method was a method in which 300 g of the polyisocyanate composition obtained above was placed in a 500 mL SUS storage container, the atmosphere was substituted with nitrogen, and the composition was stored in a storage environment in Kojima district, Kurashiki city, Okayama prefecture, Japan for 300 days. In Example 18 and Comparative Example 2, the storage container was changed to a glass bottle, and the storage location was changed to outdoors.

[0317] (GPC measurement method) Instrument used: HLC-8120 (manufactured by Tosoh Corporation) Columns used: TSK GEL Super H1000, TSK GEL Super H2000, TSK GEL Super H3000 (all manufactured by Tosoh Corporation) Sample concentration: 5 wt / vol% (50 mg of sample was dissolved in 1 mL of tetrahydrofuran (THF)) Carrier: THF Detection method: PDA detector Outlet rate: 0.6 mL / min Column temperature: 30°C Polystyrene with a molecular weight of 1,000 to 20,000 was used to create a calibration curve.

[0318]

[0319]

[0320] As can be seen from Tables 1 and 2, polyisocyanate composition 1 containing a compound selected from the group consisting of compounds (I) was excellent in storage stability and coloration inhibition.

[0321] The polyisocyanate composition not containing Compound (I) gelled during the 300-day storage period, making it impossible to perform GPC measurement.

[0322] <Production of Polyisocyanate Composition 2> Polyisocyanate composition 2 containing a quinazolinedione compound and a polyisocyanate compound was produced. Specifically, as shown in Table 3, polyisocyanate composition 2 was prepared using any one of HDI, IPDI, PDI, MBCI, TDI, MDI, TTI, LTI, and LDI as the polyisocyanate compound.

[0323] The quinazolinedione compound used was a compound obtained by reacting a secondary amine compound with a carbonic acid derivative, and was any one of a compound derived from N-methylaniline (NMA), a compound derived from N-ethylaniline (NEA), a compound derived from N-butylaniline (NBA), and a compound derived from N-isopropylaniline (NiPA).

[0324] The compound derived from NMA is a compound represented by the general formula (II) above, wherein R ２１０ is a methyl group, and R ２２０ , R ２３０ , R ２４０ and R ２５０is hydrogen. The compound derived from NEA is a compound having R ２１０ is an ethyl group, and R ２２０ , R ２３０ , R ２４０ and R ２５０ is hydrogen. The compound derived from NBA is a compound having R ２１０ is an n-butyl group, and R ２２０ , R ２３０ , R ２４０ and R ２５０ is hydrogen. The compound derived from NiPA is a compound having R ２１０ is an isopropyl group, and R ２２０ , R ２３０ , R ２４０ and R ２５０ is hydrogen.

[0325] APHA ranking before storage was carried out in the same manner as described above in <Evaluation of color inhibition>. Storage stability was evaluated in the same manner as described above in <Evaluation of storage stability>.

[0326] <Evaluation of APHA Rank after Storage> The APHA rank after 300 days of storage was measured using a sample prepared by dissolving 1 g of the polyisocyanate composition after 300 days of storage in 2 g of benzyltoluene, according to the method described above in <Evaluation of Coloration Inhibition>. Based on the value measured with a Hazen meter, ranking was performed using the same evaluation criteria as in the above <Evaluation of Coloration Inhibition>.

[0327]

[0328] From Table 3, it can be seen that polyisocyanate composition 2 containing a compound selected from the group consisting of quinazolinedione compounds (II) was excellent in storage stability and coloration inhibition.

[0329] The polyisocyanate composition not containing the quinazolinedione compound (II) gelled during the 300-day storage period, making it impossible to perform GPC measurement.

[0330] <Production of Polyisocyanate Composition 3> Polyisocyanate composition 3 containing a tri-substituted urea compound and a polyisocyanate compound was produced. Specifically, as shown in Table 4, polyisocyanate composition 3 was prepared using any one of HDI, IPDI, PDI, MBCI, TDI, MDI, TTI, LTI, and LDI as the polyisocyanate compound.

[0331] The tri-substituted urea compound used was a compound obtained by reacting at least one isocyanate group of a polyisocyanate compound with a secondary amine compound, which was any one of N-methylaniline (NMA), N-ethylaniline (NEA), N-butylaniline (NBA), N-isopropylaniline (NiPA), diethylamine (DEA), and diphenylamine (DPA).

[0332] Tri-substituted urea compounds obtained using HDI are represented by the above general formula (1). Tri-substituted urea compounds obtained using IPDI are represented by the above general formula (2). Tri-substituted urea compounds obtained using PDI are represented by the above general formula (3). Tri-substituted urea compounds obtained using MBCI are represented by the above general formula (4). Tri-substituted urea compounds obtained using TDI are represented by the above general formulas (5) and (6). Tri-substituted urea compounds obtained using MDI are represented by the above general formula (7). Tri-substituted urea compounds obtained using TTI are represented by the above general formula (8). Tri-substituted urea compounds obtained using LTI are represented by the above general formula (9). Tri-substituted urea compounds obtained using LDI are represented by the above general formula (10).

[0333] The tri-substituted urea compound obtained by reacting a polyisocyanate compound with NMA is represented by the general formula (III) above, ３２０ and R ３３０ The tri-substituted urea compound obtained by reacting a polyisocyanate compound with NEA is represented by the general formula (III) above, where R ３２０ and R ３３０The tri-substituted urea compound obtained by reacting a polyisocyanate compound with NBA is represented by the general formula (III) above, where R ３２０ and R ３３０ One of the groups is an n-butyl group and the other is a phenyl group. The tri-substituted urea compound obtained by reacting a polyisocyanate compound with NiPA is represented by the general formula (III) above, ３２０ and R ３３０ The tri-substituted urea compound obtained by reacting a polyisocyanate compound with DEA ​​is represented by the general formula (III) above, wherein one of R is an isopropyl group and the other is a phenyl group. ３２０ and R ３３０ The tri-substituted urea compound obtained by reacting a polyisocyanate compound with DPA is represented by the general formula (III) above, ３２０ and R ３３０ are all phenyl groups.

[0334] APHA ranking before storage was carried out in the same manner as described above in <Evaluation of color inhibition>. Storage stability was evaluated in the same manner as described above in <Evaluation of storage stability>.

[0335] <Evaluation of APHA Rank after Storage> The APHA rank after 300 days of storage was measured using a sample prepared by dissolving 1 g of the polyisocyanate composition after 300 days of storage in 2 g of benzyltoluene, according to the method described above in <Evaluation of Coloration Inhibition>. Based on the value measured with a Hazen meter, ranking was performed using the same evaluation criteria as in the above <Evaluation of Coloration Inhibition>.

[0336]

[0337] From Table 4, R ３２０ and R ３３０ Polyisocyanate composition 3 containing a compound selected from the group consisting of tri-substituted urea compounds (III), at least one of which has an aromatic group, was excellent in storage stability and coloration inhibition.

[0338] The polyisocyanate composition containing no tri-substituted urea compound (III) gelled during the 300-day storage period, making GPC measurement impossible.

[0339] R ３２０ and R ３３０ Polyisocyanate compositions containing tri-substituted urea compounds in which none of the groups is an aromatic group have poor storage stability.

[0340] <Preparation of Polyisocyanate Composition 4> Polyisocyanate composition 4 containing two or more of compound (I), quinazolinedione compound (II) and tri-substituted urea compound (III) was prepared.

[0341] 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. Compound (I), the quinazolinedione compound, and the tri-substituted urea compound were prepared in the same manner as in the production of polyisocyanate compositions 1 to 3.

[0342] APHA ranking before storage was carried out in the same manner as described above in <Evaluation of color inhibition>. Storage stability was evaluated in the same manner as described above in <Evaluation of storage stability>.

[0343] <Evaluation of APHA Rank after Storage> The APHA rank after 300 days of storage was measured using a sample prepared by dissolving 1 g of the polyisocyanate composition after 300 days of storage in 2 g of benzyltoluene, according to the method described above in <Evaluation of Coloration Inhibition>. Based on the value measured with a Hazen meter, ranking was performed using the same evaluation criteria as in the above <Evaluation of Coloration Inhibition>.

[0344]

[0345] As can be seen from Table 5, polyisocyanate composition 4 containing two or more of compound (I), quinazolinedione compound (II), and tri-substituted urea compound (III) was excellent in storage stability and coloration inhibition. In particular, Examples 4-IV to 10-IV containing compound (I), quinazolinedione compound (II), and tri-substituted urea compound (III) had peak area ratios (%) of 3 or less and APHA ranks of 2 or less, and were therefore particularly excellent in storage stability and coloration inhibition.

[0346] The polyisocyanate composition (Comparative Example 19-IV) containing none of the compound (I), the quinazolinedione compound (II), and the tri-substituted urea compound (III) gelled during the 300-day storage period, making GPC measurement impossible.

[0347] <Method 1 for Producing Isocyanate Compound> An isocyanate compound was produced in the presence of compound (I).

[0348] [Production Example of Blocked Isocyanate Compound] 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-diyldicarbamate. Subsequently, excess phenol was distilled off under reduced pressure at 100°C and 1 Pa. As a result of 1H NMR analysis, blocked isocyanate composition BL-1 containing 5 mol% of ureylene groups and 95 mol% of blocked isocyanate groups was obtained.

[0349] Table 6 shows the abbreviations of the obtained blocked isocyanate compounds, the contents of ureylene (-NHCONH-) groups, and blocked isocyanate (BL-NCO) groups.

[0350] Examples 1A to 15A The blocked isocyanate compound of the above-described Production Example, Compound (I), and a solvent were added to 300 mL glass vessels equipped with pressure reducing devices at the ends of condenser tube 1 (the condensate from condenser tube 1 enters a 300 mL glass vessel) and condenser tube 2 (the condensate from condenser tube 2 does not enter the 300 mL glass vessel but is recovered as a TOP liquid), each filled with a filler. The temperature inside the 300 mL glass vessel (reaction temperature), the degree of vacuum, the temperature of condenser tube 1, and the temperature of condenser tube 2 were then set as shown in the reaction conditions in Table 2. The absolute pressure inside the reaction vessel was adjusted to 380 mmHg using the pressure reducing device, and the reaction was then carried out for 3 hours.

[0351] The yield of isocyanate groups (NCO group mol %) and the residual rate of ureylene groups (ureylene group mol %) contained in the resulting reaction solution were determined.

[0352] Comparative Examples 1A to 11A Blocked isocyanate compounds were heat-treated in the same manner as in Examples 1A to 15A, except that, as shown in Table 8, compound (I) was not added, and the blocked isocyanate compound and a solvent were added to a glass container, and the reaction conditions were set.

[0353] In the following table, the abbreviations represent the following compounds.

[0354] (Isocyanate compounds) HDI: 1,6-hexamethylene diisocyanate IPDI: isophorone diisocyanate (mixture of isomers) TDI: diisocyanatotoluene (mixture of isomers) MDI: diphenylmethane diisocyanate (mixture of isomers) HMDI: dicyclohexylmethane 4,4'-diisocyanate

[0355] (Blocking agent) PhOH: Phenol o-cresol: o-cresol m-cresol: m-cresol p-cresol: p-cresol n-BuOH: n-butanol DBA: dibutylamine NMA: N-methylaniline (Solvent) Naphthene: naphthenic solvent (EXXOL ＴＭ D80)

[0356] In Table 6 below, the structure of compound (I) is as follows:

[0357]

[0358]

[0359]

[0360]

[0361] As can be seen from Table 7, when the blocked isocyanate compound was thermally decomposed in the presence of compound (I), the residual rate of ureylene groups (ureylene group mol %) decreased and the yield of isocyanate groups (NCO group mol %) improved.

[0362] On the other hand, as can be seen from Table 8, when the blocked isocyanate compound was thermally decomposed without the presence of compound (I), the residual rate of ureylene groups did not change and the yield of isocyanate groups decreased.

[0363] <Method 2 for Producing Isocyanate Compound> An isocyanate compound was produced in the presence of compound (II).

[0364] [Production Example of Blocked Isocyanate Compound] 1 part by mass of an isocyanate compound and 9 parts by mass of a blocking agent were placed in an SUS pressure vessel and reacted for 20 hours at 150° C. The free blocking agent contained in the resulting reaction liquid was distilled off under reduced pressure to obtain a blocked isocyanate composition.

[0365] Table 9 shows the abbreviations of the obtained blocked isocyanate compounds and the content of blocked isocyanate (BL-NCO) groups.

[0366] Examples 1B to 17B To 300 mL glass vessels equipped with pressure reducing devices at the ends of condenser tubes 1 (structured so that the condensate from condenser tube 1 enters a 300 mL glass vessel) and 2 (condensate from condenser tube 2 does not enter the 300 mL glass vessel but is recovered as a TOP liquid) filled with a filler, the blocked isocyanate compound of the aforementioned Production Example, a catalyst corresponding to compound (II), and a solvent were added as shown in Table 10. Next, the internal temperature of the 300 mL glass vessel (reaction temperature), the degree of vacuum, the temperature of condenser tube 1, and the temperature of condenser tube 2 were set as shown in the reaction conditions in Table 2, and the mixture was allowed to react for 3 hours.

[0367] The yield of isocyanate groups (NCO group mol%) and the residual rate of blocked isocyanate groups (BL-NCO group mol%) contained in the resulting reaction solution were determined. The sum of the yield of isocyanate groups and the residual rate of blocked isocyanate groups was calculated as the mass balance (MB mol%).

[0368] Comparative Examples 1B to 13B As shown in Table 11, blocked isocyanate compounds were heat-treated in the same manner as in Examples 1B to 17B, except that the blocked isocyanate compounds and solvents were added to a glass container without adding a catalyst, and the reaction conditions were set.

[0369] Comparative Example 14B A blocked isocyanate compound was heat-treated in the same manner as in Examples 1B to 17B, except that the blocked isocyanate compound, catalyst, and solvent were added to a glass container and the reaction conditions were set as shown in Table 11.

[0370] In the following table, the abbreviations represent the following compounds.

[0371] (Isocyanate compounds) HDI: 1,6-hexamethylene diisocyanate IPDI: isophorone diisocyanate (mixture of isomers) TDI: diisocyanatotoluene (mixture of isomers) MDI: diphenylmethane diisocyanate (mixture of isomers) HMDI: dicyclohexylmethane 4,4'-diisocyanate

[0372] (Blocking agent) PhOH: Phenol o-cresol: o-cresol m-cresol: m-cresol p-cresol: p-cresol n-BuOH: n-butanol DBA: dibutylamine NMA: N-methylaniline

[0373] (Catalyst: Compound (II)) MQD: 1-methyl-2,4(1H,3H)-quinazolinedione BQD: 1-butyl-2,4(1H,3H)-quinazolinedione PQD: 1-phenyl-2,4(1H,3H)-quinazolinedione

[0374] (Solvent) DBT: dibenzyltoluene

[0375]

[0376]

[0377]

[0378] As can be seen from Table 10, when a blocked isocyanate compound was thermally decomposed in the presence of a compound having a quinazolinedione structure (II), the residual rate of blocked isocyanate groups (BL-NCO group mol %) decreased and the yield of isocyanate groups (NCO group mol %) improved.

[0379] According to the polyisocyanate compositions 1 to 4 of the present embodiment, it is possible to provide polyisocyanate compositions that are excellent in storage stability and coloration inhibition.

[0380] According to the isocyanate compound production methods 1 and 2 of the present embodiment, it is possible to provide a production method for an isocyanate compound that can improve the thermal decomposition rate of a blocked isocyanate compound without increasing the amount of by-products produced.

Claims

1. A polyisocyanate composition containing 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 are each independently a monovalent organic group. １ and R ２ may each independently form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. ３ is a hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group. 【Chemistry 2】 (In general formula (II), R ２１０ is a monovalent organic group, and R ２２０ , R ２３０ , R ２４０ and R ２５０ R is each independently a monovalent organic group or hydrogen. ２１０ and R ２２０ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.) 【Transformation 3】 (In general formula (III), R ３１０ is an (n+m)-valent organic group, n is an integer of 0 to 12, m is an integer of 1 to 12, and n+m is an integer of 13 or less; R ３２０ and R ３３０ are each independently a monovalent organic group. ３２０ and R ３３０ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. ３２０ and R ３３０ At least one of the groups has an aromatic group.

2. 1.0 ppm by mass or more 1.0 × 10 based on the total mass of the polyisocyanate compound ４ The polyisocyanate composition according to claim 1, comprising at least one compound represented by any one of general formulas (I), (II), and (III) in an amount of not more than ppm by mass.

3. A method for producing an isocyanate compound, comprising a reaction step of decomposing a blocked isocyanate compound into a blocking agent and an isocyanate compound by heat treatment in the presence of a compound having a structure represented by either or both of the following general formulas (I) and (II), thereby obtaining the isocyanate compound: 【Chemistry 4】 (In general formula (I), R １ and R ２ are each independently a monovalent organic group. １ and R ２ may each independently form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond. ３ is a hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group. 【Transformation 5】 (In general formula (II), R ２１０ is a monovalent organic group, and R ２２０ , R ２３０ , R ２４０ and R ２５０ R is each independently a monovalent organic group or hydrogen. ２１０ and R ２２０ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.)

4. The method for producing an isocyanate compound according to claim 3, wherein the blocking agent comprises one or more compounds selected from the group consisting of hydroxy compounds, amine compounds, and ammonia.

5. The method for producing an isocyanate compound according to claim 3 or 4, wherein the isocyanate compound is an isocyanate compound represented by the following general formula (IV): 【Transformation 6】 (In general formula (IV), R ２１ is an n21-valent organic group, where n21 is an integer of 1 or more and 12 or less.

6. The method for producing an isocyanate compound according to claim 3 or 4, wherein the blocking agent is an aromatic hydroxy compound represented by the following general formula (V): 【Transformation 7】 (In general formula (V), ring A ３１ is an aromatic hydrocarbon ring having 6 to 20 carbon atoms. ３１ is a hydrogen atom, a halogen atom, a carboxy group, an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an alkyloxycarbonyl group having from 1 to 20 carbon atoms, an alkylcarbonyloxy group having from 1 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, an aryloxy group having from 6 to 20 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms, or an aralkyloxy group having from 7 to 20 carbon atoms. ３１ is ring A ３１ may bond to form a ring structure. n31 is an integer of 1 or more and 10 or less.

7. The method for producing an isocyanate compound according to claim 3 or 4, wherein the blocking agent is an aliphatic hydroxy compound represented by the following general formula (VI): 【Transformation 8】 (In general formula (VI), R ４１ represents a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 24 carbon atoms, which may have an ether group, a carbonyl group, or an ester group.

8. The method for producing an isocyanate compound according to claim 3 or 4, wherein the blocking agent is a secondary amine compound represented by the following general formula (VII): 【Chemistry 9】 (In general formula (VII), R ５１ and R ５２ are each independently a monovalent organic group. ５１ and R ５２ may be bonded to each other to form a ring structure via a carbon-carbon bond, a carbon-oxygen-carbon bond, or a carbon-nitrogen-carbon bond.)

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

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