COMPOUND, CURING AGENT COMPOSITION, RESIN COMPOSITION, COATING COMPOSITION AND RESIN CURED PRODUCT

Abstract

A compound having an uretonimine group contains, as a structural unit, a carbodiimide compound derived from at least one of an aliphatic diisocyanate and an aromatic diisocyanate, and also contains an isocyanate compound as a structural unit, wherein the residue obtained by removing an isocyanate group from the isocyanate compound and the residue obtained by removing a carbodiimide group from the carbodiimide compound are different.

Claims

1. A compound having an uretonimine group, the compound containing, as a structural unit, a carbodiimide compound derived from at least one of an aliphatic diisocyanate and an aromatic diisocyanate, and also containing an isocyanate compound as a structural unit, wherein a residue obtained by removing an isocyanate group from the isocyanate compound and a residue obtained by removing a carbodiimide group from the carbodiimide compound are different.

2. The compound according to claim 1, represented by general formula (1) shown below:
[Chemical formula 1]
Q.sup.1-X.sup.1—Y.sup.1-Q.sup.2  (1) wherein in general formula (1), X.sup.1 represents a group containing at least one group represented by general formula (1-1) shown below, and in those cases where X.sup.1 contains two or more groups represented by general formula (1-1) shown below, a plurality of groups represented by general formula (1-1) shown below may be identical or different, Y.sup.1 is a group represented by general formula (1-2) shown below, and each of Q.sup.1 and Q.sup.2 independently represents a hydrogen atom, a group represented by general formula (1-3) shown below, a group represented by general formula (1-4) shown below, or a group represented by general formula (1-5) shown below: ##STR00396## wherein in general formula (1-1) to general formula (1-5), each asterisk represents a bonding site, each of X.sup.2 and Y.sup.2 independently represents a residue obtained by removing two isocyanate groups from at least one diisocyanate among an aliphatic diisocyanate and an aromatic diisocyanate, Q.sup.3 represents a hydrogen atom or a monovalent organic group of at least 1 but not more than 15 carbon atoms, Z.sup.1 is a group represented by general formula (1-a) shown below or a group represented by general formula (1-b) shown below, Z.sup.2 is a group represented by general formula (1-a) shown below, a group represented by general formula (1-b) shown below, a group represented by general formula (1-c) shown below, or a group represented by general formula (1-d) shown below, X.sup.2 contains at least one group represented by general formula (1-b) shown below, and R.sup.1 represents a residue obtained by removing a hydrogen atom from a terminal hydroxyl group of a monofunctional polyalkylene oxide polyether alcohol: ##STR00397## wherein in general formula (1-a), general formula (1-b), general formula (1-c) and general formula (1-d), each asterisk represents a bonding site, and Y.sup.11 represents a residue obtained by removing one isocyanate group from an isocyanate compound.

3. The compound according to claim 1, wherein in a spectrum measured by infrared spectroscopy, a ratio of an absorbance attributable to carbodiimide groups relative to an absorbance attributable to uretonimine groups and urethane groups is at least 0 but less than 1.5.

4. The compound according to claim 2, wherein the monofunctional polyalkylene oxide polyether alcohol is a polyethylene glycol monoalkyl ether, a polypropylene glycol monoalkyl ether, or a copolymer thereof.

5. The compound according to claim 2, wherein R.sup.1 is a group represented by general formula (II-1) shown below or a group represented by general formula (II-2) shown below: ##STR00398## wherein in general formula (II-1), each of n21 and n22 independently represents an integer of at least 1 but not more than 30, and R.sup.21 represents an alkyl group of at least 1 but not more than 12 carbon atoms that may contain a carbonyl group, in general formula (II-2), each of n23 and n24 independently represents an integer of at least 1 but not more than 30, and R.sup.22 represents an alkyl group of at least 1 but not more than 12 carbon atoms that may contain a carbonyl group, and each asterisk represents a bonding site.

6. The compound according to claim 2, wherein X.sup.1 is a group containing one or more of at least one type of group selected from the group consisting of groups represented by general formula (III-1-1) shown below, groups represented by general formula (III-2-1) shown below, groups represented by general formula (III-2-2) shown below, groups represented by general formula (III-3-1) shown below, groups represented by general formula (III-5-1) shown below, groups represented by general formula (III-6-1) shown below, groups represented by general formula (VI-1-1) shown below, groups represented by general formula (VI-2-1) shown below, and groups represented by general formula (VI-3-1) shown below, and Y.sup.1 is a group represented by general formula (III-1) shown below, a group represented by general formula (III-2) shown below, a group represented by general formula (III-3) shown below, a group represented by general formula (III-5) shown below, a group represented by general formula (III-6) shown below, a group represented by general formula (VI-1) shown below, a group represented by general formula (VI-2) shown below, or a group represented by general formula (VI-3) shown below: ##STR00399## wherein in the formulas, each asterisk represents a bonding site, n62 represents an integer of at least 1 but not more than 10, and Z.sup.3 represents a group represented by the general formula (1-a) or a group represented by the general formula (1-b): ##STR00400## wherein in the formulas, each asterisk represents a bonding site, and n61 represents an integer of at least 1 but not more than 10.

7. The compound according to claim 5, wherein X.sup.2 and Y.sup.2 are groups represented by general formula (VI) shown below:
[Chemical formula 7]
*—CH.sub.2—R.sup.61—CH.sub.2—*  (V) wherein in general formula (VI), R.sup.61 represents an alkylene group of at least 1 but not more than 18 carbon atoms or an arylene group of at least 6 but not more than 18 carbon atoms, the alkylene group and the arylene group may each have at least one functional group selected from the group consisting of an isocyanurate group, allophanate group, biuret group, uretdione group, iminooxadiazinedione group and urethane group, and each asterisk represents a bonding site.

8. The compound according to claim 7, wherein each of X.sup.2 and Y.sup.2 independently represents at least one group selected from the group consisting of groups represented by general formula (VI-1) shown below, groups represented by general formula (VI-2) shown below and groups represented by general formula (VI-3) shown below: ##STR00401## wherein in the formulas, each asterisk represents a bonding site, and in general formula (VI-1), n61 represents an integer of at least 1 but not more than 10.

9. The compound according to claim 1, wherein the carbodiimide compound is a carbodiimide compound derived from an aliphatic diisocyanate, and the isocyanate compound is an aliphatic isocyanate compound.

10. The compound according to claim 9, wherein among a carbon atom that is bonded to the uretonimine group in a residue obtained by removing an isocyanate group from the isocyanate compound, and a carbon atom that is bonded to the uretonimine group in a residue obtained by removing a carbodiimide group from the carbodiimide compound, one carbon atom is a primary carbon atom or a primary carbon atom to which an electron-withdrawing group is bonded, and another carbon atom is a secondary carbon atom, or one carbon atom is a primary carbon atom to which an electron-withdrawing group is bonded, and another carbon atom is a primary carbon atom to which an electron-withdrawing group is not bonded.

11. The compound according to claim 2, wherein the isocyanate compound is at least one of an isocyanate derived from an amino acid and a trifunctional or higher isocyanate.

12. The compound according to claim 11, wherein the trifunctional or higher isocyanate is a trifunctional isocyanate.

13. The compound according to claim 12, wherein the trifunctional isocyanate is a compound represented by general formula (1-B)-3c shown below: ##STR00402## wherein in general formula (1-B)-3c, each of a plurality of R.sup.134b groups independently represents a single bond, or a divalent hydrocarbon group of at least 1 but not more than 20 carbon atoms that may contain at least one group selected from the group consisting of an ester group and an ether group, and R.sup.135b represents a hydrogen atom or a monovalent hydrocarbon group of at least 1 but not more than 12 carbon atoms.

14. The compound according to claim 11, wherein the isocyanate having a group derived from an amino acid is an isocyanate having a group represented by formula (5) shown below: ##STR00403## wherein in formula (5), each asterisk represents a bonding site.

15. A carbodiimide compound, represented by general formula (2) shown below:
[Chemical formula 11]
Q.sup.21-X.sup.21—Y.sup.21-Q.sup.22  (2) wherein in general formula (2), X.sup.21 is a group containing at least one group represented by general formula (2-1) shown below, and in those cases where X.sup.21 contains two or more groups represented by general formula (2-1) shown below, a plurality of groups represented by general formula (2-1) shown below may be identical or different, Y.sup.21 is a group represented by general formula (1-2) shown below, and each of Q.sup.21 and Q.sup.22 independently represents a hydrogen atom, a group represented by general formula (1-3) shown below, a group represented by general formula (1-4) shown below, or a group represented by general formula (1-5) shown below:
[Chemical formula 12]
*—X.sup.22—N═C═N—*  (2-1) wherein in general formula (2-1), X.sup.22 represents a residue obtained by removing two isocyanate groups from at least one diisocyanate among an aliphatic diisocyanate and an aromatic diisocyanate, ##STR00404## wherein in general formula (1-2) to general formula (1-5), each asterisk represents a bonding site, Y.sup.2 represents a residue obtained by removing two isocyanate groups from at least one diisocyanate among an aliphatic diisocyanate and an aromatic diisocyanate, Q.sup.3 represents a hydrogen atom or a monovalent organic group of at least 1 but not more than 15 carbon atoms, Z.sup.2 is a group represented by general formula (1-a) shown below, a group represented by general formula (1-c) shown below, or a group represented by general formula (1-d) shown below, and R.sup.1 represents a residue obtained by removing a hydrogen atom from a terminal hydroxyl group of a monofunctional polyalkylene oxide polyether alcohol: ##STR00405## wherein in general formula (1-a), general formula (1-c) and general formula (1-d), each asterisk represents a bonding site.

16. The compound according to claim 15, wherein X.sup.21 is a group containing one or more of at least one type of group selected from the group consisting of groups represented by general formula (III-1-2) shown below, groups represented by general formula (III-2-3) shown below, groups represented by general formula (III-2-4) shown below, groups represented by general formula (III-3-2) shown below, groups represented by general formula (III-5-2) shown below, groups represented by general formula (III-6-2) shown below, groups represented by general formula (VI-1-2) shown below, groups represented by general formula (VI-2-2) shown below, and groups represented by general formula (VI-3-2) shown below, and Y.sup.21 is a group represented by general formula (III-1) shown below, a group represented by general formula (III-2) shown below, a group represented by general formula (III-3) shown below, a group represented by general formula (III-5) shown below, a group represented by general formula (III-6) shown below, a group represented by general formula (VI-1) shown below, a group represented by general formula (VI-2) shown below, or a group represented by general formula (VI-3) shown below: ##STR00406## wherein in the formulas, each asterisk represents a bonding site, and n63 represents an integer of at least 1 but not more than 10, ##STR00407## wherein in the formulas, each asterisk represents a bonding site, and n61 represents an integer of at least 1 but not more than 10.

17. The compound according to claim 16, wherein each of X.sup.22 and Y.sup.21 independently represents a group represented by general formula (VI) shown below:
[Chemical formula 17]
*—CH.sub.2—R.sup.61—CH.sub.2—*  (V) wherein in general formula (VI), R.sup.61 represents an alkylene group of at least 1 but not more than 18 carbon atoms or an arylene group of at least 6 but not more than 18 carbon atoms, the alkylene group and the arylene group may each have at least one functional group selected from the group consisting of an isocyanurate group, allophanate group, biuret group, uretdione group, iminooxadiazinedione group and urethane group, and each asterisk represents a bonding site.

18. The compound according to claim 17, wherein each of X.sup.22 and Y.sup.21 independently represents at least one group selected from the group consisting of groups represented by general formula (VI-1) shown below, groups represented by general formula (VI-2) shown below and groups represented by general formula (VI-3) shown below: ##STR00408## wherein in the formulas, each asterisk represents a bonding site, and in general formula (VI-1), n61 represents an integer of at least 1 but not more than 10.

19. A method for producing the compound according to claim 2, the method comprising: producing a compound having an uretonimine group represented by the general formula (1) by reacting a carbodiimide compound represented by general formula (2) shown below and an isocyanate compound represented by general formula (3) shown below:
[Chemical formula 19]
Q.sup.21-X.sup.21—Y.sup.21-Q.sup.22  (2) wherein in general formula (2), X.sup.21 is a group containing at least one group represented by general formula (2-1) shown below, and in those cases where X.sup.21 contains two or more groups represented by general formula (2-1) shown below, a plurality of groups represented by general formula (2-1) shown below may be identical or different, Y.sup.21 is a group represented by general formula (1-2) shown below, and each of Q.sup.21 and Q.sup.22 independently represents a hydrogen atom, a group represented by general formula (1-3) shown below, a group represented by general formula (1-4) shown below, or a group represented by general formula (1-5) shown below,
[Chemical formula 20]
*—X.sup.22—N═C═N—*  (2-1) wherein in general formula (2-1), X.sup.22 represents a residue obtained by removing two isocyanate groups from at least one diisocyanate among an aliphatic diisocyanate and an aromatic diisocyanate, ##STR00409## wherein in general formula (1-2) to general formula (1-5), each asterisk represents a bonding site, Y.sup.2 represents a residue obtained by removing two isocyanate groups from at least one diisocyanate among an aliphatic diisocyanate and an aromatic diisocyanate, Q.sup.3 represents a hydrogen atom or a monovalent organic group of at least 1 but not more than 15 carbon atoms, Z.sup.2 is a group represented by general formula (1-a) shown below, a group represented by general formula (1-c) shown below, or a group represented by general formula (1-d) shown below, and R.sup.1 represents a residue obtained by removing a hydrogen atom from a terminal hydroxyl group of a monofunctional polyalkylene oxide polyether alcohol, ##STR00410## wherein in general formula (1-a), general formula (1-c) and general formula (1-d), each asterisk represents a bonding site,
[Chemical formula 23]
R.sup.3—NCO  (3) wherein in general formula (3), R.sup.3 represents a residue obtained by removing one isocyanate group from an isocyanate compound.

20. A curing agent composition, comprising the compound according to claim 1.

21. A resin composition, comprising the curing agent composition according to claim 20 and a compound having a carboxyl group.

22. A coating material composition, comprising the resin composition according to claim 21.

23. A resin cured product, obtained by curing the coating material composition according to claim 22.

Description

EXAMPLES

[0417] Embodiments of the present invention are described below in further detail using specific examples, but embodiments of the present invention are in no way limited by the following examples, provided they do not exceed the scope of the present invention.

Reference Example 1-1, Examples 1-1 to l-4

Reference Example 1-1

[0418] An SUS316 stirred tank with an internal capacity of 1 L was charged with 300 g of xylene and 500 g of an isocyanate compound, and the mixture was heated to 140° C. Subsequently, 1 g of 1-phenyl-2-phospholene-1-oxide was added to the tank and stirred for 5 hours. The xylene and any excess isocyanate compound were removed by distillation to obtain a polycarbodiimide.

Example 1-1

[0419] Using hexamethylene diisocyanate as the isocyanate compound, a carbodiimide compound was produced using the same method as Reference Example 1-1. Subsequently, the obtained carbodiimide compound and phenyl isocyanate were mixed such that the stoichiometric ratio of the isocyanate group of the phenyl isocyanate relative to the carbodiimide group of the carbodiimide compound was 1.05-fold, and the mixture was then heated at 80° C. for 5 hours. Analysis of the reaction product revealed that a compound represented by formula (E-1) shown below had been produced.

##STR00065##

[0420] In formula (E-1), the average degree of polymerization E1 was 10.

Example 1-2

[0421] Using diphenylmethane diisocyanate as the isocyanate compound, a carbodiimide compound was produced using the same method as Reference Example 1-1. Subsequently, the obtained carbodiimide compound and cyclohexyl isocyanate were mixed such that the stoichiometric ratio of the isocyanate group of the cyclohexyl isocyanate relative to the carbodiimide group of the carbodiimide compound was 1.05-fold, and the mixture was then heated at 80° C. for 5 hours. Analysis of the reaction product revealed that a compound represented by formula (E-2) shown below had been produced.

##STR00066##

[0422] In formula (E-2), the average degree of polymerization E2 was 3.

Example 1-3

[0423] Using dicyclohexylmethane diisocyanate as the isocyanate compound, a carbodiimide compound was produced using the same method as Reference Example 1-1. Subsequently, the obtained carbodiimide compound and methyl 2-isocyanato-4-methylvalerate were mixed such that the stoichiometric ratio of the isocyanate group of the methyl 2-isocyanato-4-methylvalerate relative to the carbodiimide group of the carbodiimide compound was 1.05-fold, and the mixture was then heated at 80° C. for 5 hours. Analysis of the reaction product revealed that a compound represented by formula (E-3) shown below had been produced.

##STR00067##

[0424] In formula (E-3), the average degree of polymerization E3 was 8.

Example 1-4

[0425] Using hydrogenated xylylene diisocyanate as the isocyanate compound, a carbodiimide compound was produced using the same method as Reference Example 1-1. Subsequently, the obtained carbodiimide compound and 1,8-diisocyanato-4-isocyanatomethyloctane were mixed such that the stoichiometric ratio of the isocyanate groups of the 1,8-diisocyanato-4-isocyanatomethyloctane relative to the carbodiimide group of the carbodiimide compound was 3.15-fold, toluene was then added to adjust the substrate concentration to 5% by mass, and the mixture was then heated at 80° C. for 5 hours. Analysis of the reaction product revealed that a compound represented by general formula (E-4) shown below had been produced.

##STR00068##

[0426] In general formula (E-4), R.sup.e represents a residue obtained by removing one isocyanate group from 1,8-diisocyanato-4-isocyanatomethyloctane (namely, a group represented by formula (E-4-1) shown below, a group represented by formula (E-4-2) shown below, or a group represented by formula (E-4-3) shown below), and the average degree of polymerization E4 was 4.

##STR00069##

(In formulas (E-4-1) to (E-4-3), each asterisk represents a bonding site.)

Examples 2-1 to 2-45, and Comparative Example 2-1

<Evaluation Method>

[Evaluation 2-1] Storage Stability of Resin Composition

[0427] Evaluations of the compounds obtained in the examples and comparative example were conducted using the method described below.

[0428] Specifically, 1 g of each of the compounds obtained in the examples and comparative example was first dispersed in 10 g of water, and 15 g of an acrylic polyol (SETAQUA 6515 manufactured by Allnex Group) was added and stirred to form a uniform solution (resin composition). This uniform solution (resin composition) was stored at 40° C. for 10 days, and the contents were then inspected visually. The storage stability was evaluated against the following evaluation criteria.

(Evaluation Criteria)

[0429] Good: no gelling occurred

[0430] Poor: gelling occurred

<Production of Uretonimine Group-Containing Compounds>

[Example 2-1]

(Step 1)

[0431] Dicyclohexylmethane diisocyanate was used as the diisocyanate (hereafter sometimes referred to as “diisocyanate A”) for producing a carbodiimide compound. An SUS316 stirred tank with an internal capacity of 1 L was charged with 300 g of xylene and 500 g of the diisocyanate A, and the mixture was heated to 140° C. Subsequently, 1 g of 1-phenyl-2-phospholene-1-oxide was added to the tank and stirred for 5 hours. The obtained reaction liquid was supplied to a thin-film evaporator, the interior of which had been heated to 180° C. and evacuated to a pressure of 0.1 kPa (absolute pressure), thereby removing the xylene and excess isocyanate compound by evaporation to obtain a carbodiimide compound. The average degree of polymerization of the obtained carbodiimide compound was 5. Subsequently, using phenyl isocyanate as the isocyanate compound (hereafter sometimes referred to as “isocyanate compound B”) to be reacted with the carbodiimide compound, the carbodiimide compound and the isocyanate compound B were mixed so as to achieve a stoichiometric ratio of the isocyanate group of the isocyanate compound B relative to the carbodiimide group of the carbodiimide compound was 1.05-fold, and the mixture was then heated at 80° C. for 5 hours. Analysis of the reaction product by infrared spectroscopy confirmed absorption near 1720 cm.sup.−1 attributable to the stretching vibration of uretonimine groups and urethane groups.

(Step 2)

[0432] Subsequently, 700 g of a poly(oxyethylene-oxypropylene) glycol monobutyl ether (number average molecular weight: 300, a compound represented by formula (IV-2) shown below (hereafter sometimes referred to as “compound (IV-2)”) was added as a compound having a hydrophilic group (hereafter sometimes referred to as the “hydrophilic group-containing compound”) to the reaction product obtained above in step 1, and the mixture was heated under stirring at 120° C. for 2 hours. The obtained compound was a compound which, in an infrared spectroscopy spectrum, exhibited a value for the absorbance x near 2020 cm.sup.−1 attributable to the stretching vibration of carbodiimide groups relative to the absorbance y near 1720 cm.sup.−1 attributable to the stretching vibration of uretonimine groups and urethane groups, namely a value represented by x/y, of 0.5. Further, evaluation of the resin composition storage stability for the obtained compound using the evaluation method described above yielded a good result.

##STR00070##

(In general formula (IV-2), the ratio of n421 relative to n422 is 1.)

Examples 2-2 to 2-45 and Comparative Example 2-1

[0433] With the exceptions of using the combinations of the diisocyanate A, the isocyanate compound B and the hydrophilic group-containing compound shown below in Tables 1 to 4, the same method as that described for Example 2-1 was used to produce compounds, and then evaluate the storage stability when used as resin compositions. The results are shown below in Tables 1 to 4. In Tables 1 to 4, the abbreviations used for the hydrophilic group-containing compounds represent the compounds described below. Further, for the compound (IV-2), compounds having different number average molecular weights of 300, 510 and 1800 (compounds having different degrees of polymerization) were used as appropriate. Further, for the compound (IV-2), random copolymers having number average molecular weights of 300 and 500 were also used as appropriate.

(Hydrophilic Group-Containing Compounds)

[0434] MPEG220: polyethylene glycol monomethyl ether (number average molecular weight: 220)

[0435] MPEG400: polyethylene glycol monomethyl ether (number average molecular weight: 400)

[0436] MPEG550: polyethylene glycol monomethyl ether (number average molecular weight: 550)

TABLE-US-00001 TABLE 1 Storage stability Isocyanate Hydrophilic group- of resin Diisocyanate A compound B containing compound x/y composition Example 2-1 [00071]   Compound (III-5)-1 [00072] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 0.5 good Example 2-2 [00073]   Compound (III-6)-1 [00074] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 1.0 good Example 2-3 [00075]   Compound (III-5)-1 [00076] Pentamethylene diisocyanate (PDI) MPEG220 0   good Example 2-4 [00077]   Compound (III-5)-1 [00078] HDI MPEG550 0   good Example 2-5 [00079]   Compound (III-4)-1 [00080] MPEG400 0.5 good Example 2-6 [00081]   [00082] HDI Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422): 1 0   good Compound (III-4)-1 Example 2-7 [00083] [00084] Diethylene glycol monomethyl ether 0.1 good Compound (III-2)-1 Example 2-8 [00085]   Compound (III-6)-1 [00086] Triethylene glycol monomethyl ether 0.5 good Example 2-9 [00087]   Compound (III-6)-1 [00088] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 1.4 good Example 2-10 [00089]   Compound (III-5)-1 [00090] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 0   good Example 2-11 [00091]   Compound (III-5)-1 [00092] MPEG550 0   good Example 2-12 [00093]   Compound (III-5)-1 [00094] Diethylene glycol monomethyl ether 0.1 good Example 2-13 [00095]   Compound (III-5)-1 [00096] Triethylene glycol monmethyl ether 0.2 good

TABLE-US-00002 TABLE 2 Hydrophilic Storage group- stability Isocyanate containing of resin Diisocyanate A compound B compound x/y composition Example 2-14 [00097]   Compound (III-5)-1 [00098]   Nonane triisocyanate (NTI) Triethylene glycol monomethyl ether 0.2 good Example 2-15 [00099]   Compound (III-5)-1 [00100]   Lysine triisocyanate (LTI) MPEG400 0   good Example 2-16 [00101]   Compound (III-5)-1 [00102] Compound (IV-2) Number average molecular weight: 1800 ratio of n421 to n422 (n421/n422): 1 0   good Example 2-17 [00103]   Compound (III-5)-1 [00104]   Compound (III-2)-1 MPEG550 0.3 good Example 2-18 [00105]   Compound (III-5)-1 [00106]   Compound (III-6)-1 Triethylene glycol monomethyl ether 0.2 good Example 2-19 [00107]   Compound (III-6)-1 [00108] MPEG550 0.3 good Example 2-20 [00109]   Compound (III-6)-1 [00110] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 0   good Example 2-21 [00111]   Compound (III-6)-1 [00112] MPEG220 0   good Example 2-22 [00113]   Compound (III-6)-1 [00114] MPEG400 0.3 good Example 2-23 [00115]   Compound (III-6)-1 [00116]   NTI Triethylene glycol monomethyl ether 0.5 good Example 2-24 [00117]   Compound (III-6)-1 [00118] Diethylene glycol monomethyl ether 0.1 good Example 2-25 [00119]   Compound (III-6)-1 [00120] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422): 1 0   good Example 2-26 [00121] [00122]   Compound (III-6)-1 MPEG220 0   good Compound (III-2)-1

TABLE-US-00003 TABLE 3 Storage stability Isocyanate Hydrophilic group- of resin Diisocyanate A compound B containing compound x/y composition Example 2-27 [00123] [00124] Diethylene glycol monomethyl ether 0.1 good Compound (III-2)-1 Example 2-28 [00125] [00126] MPEG550 0.3 good Compound (III-2)-1 Example 2-29 [00127] [00128] Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422): 1 0 good Compound (III-2)-1 Example 2-30 [00129] [00130] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 0   good Compound (III-2)-1 Example 2-31 [00131] [00132]   NTI Triethylene glycol monomethyl ether 0.5 good Compound (III-2)-1 Example 2-32 [00133] [00134]   LTI MPEG400 0.3 good Compound (III-2)-1 Example 2-33 [00135] [00136] Triethylene glycol monomethyl ether 0.5 good Compound (III-2)-1 Example 2-34 Molar ratio Compound (III-2)-1: Compound (III-5)-1 = 1:1 [00137] Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422): 1 0.3 good Example 2-35 Molar ratio Compound (III-2)-1: Compound (III-5)-1 = 1:1 [00138]   Compound (III-6)-1 MPEG220 0.1 good Example 2-36 Molar ratio Compound (III-5)-1: Compound (III-6)-1 = 1:1 [00139] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422): 1 0.1 good NTI Example 2-37 Molar ratio Compound (III-5)-1: Compound (III-6)-1 = 1:1 [00140] MPEG550 0   good Example 2-38 Molar ratio Compound (III-5)-1: Compound (III-6)-1 = 1:1 [00141] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 0.1 good Example 2-39 Molar ratio Compound (III-5)-1 : Compound (III-6)-1 = 1:1 [00142] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422): 1 0.2 good

TABLE-US-00004 TABLE 4 Storage stability Isocyanate Hydrophilic group- of resin Diisocyanate A compound B containing compound x/y composition Example 2-40 Molar ratio Compound (III-5)-1: Compound (III-6)-1 = 1:1 [00143] Triethylene glycol monomethyl ether 0.1 good Lysine triisocyanate (LTI) Example 2-41 Molar ratio Compound (III-4)-1: Compound (III-6)-1 = 1:1 [00144] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 (random copolymer) 0   good Compound (III-2)-1 Example Molar ratio DURANATE TPA-100 MPEG550 0   good 2-42 Compound (III-3)-1: (manufactured by Asahi Compound (III-6)-1 = Kasei Corporation) 1:1 Example Molar ratio Mass ratio Compound (IV-2) 0   good 2-43 Compound (III-3)-1: HDI: Number average Compound (III-4)-1 = DURANATE TPA-100 molecular weight: 300 1:1 (manufactured by Asabi Ratio of n421 to n422 Kasei Corporation) = (n421/n422): 1 0.9:0.1 Example Molar ratio Mass ratio Diethylene glycol 0   good 2-44 Compound (III-2)-1: HDI:NTI = 0.9:0.1 monomethyl ether Compound (III-6)-1 = 1:1 Example Molar ratio Mass ratio Compound (IV-2) 0   good 2-45 Compound (III-2)-1: Compound (III-5)-1:NTI = Number average Compound (III-6)-1 = 0.9:0.1 molecular weight: 500 1:1 Ratio of n421 to n422 (n421/n422): 1 (random copolymer) Compara- tive Example 2-1 [00145]   Compound (III-6)-1 [00146] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 2.0 poor 2,6-xylyl isocyanate

[0437] Based on Tables 1 to 4, it was evident that whereas the compounds produced in Examples 2-1 to 2-45 all exhibited good storage stability when used as resin compositions, the compound produced in Comparative Example 2-1 exhibited poor storage stability when used as a resin composition.

Examples 3-1 to 3-45 and Comparative Example 3-1

<Evaluation Method>

[Evaluation 3-1] Storage Stability of Resin Composition

[0438] Evaluations of the compounds obtained in the examples and comparative example were conducted using the method described below.

[0439] Specifically, 1 g of each of the compounds obtained in the examples and comparative example was first dispersed in 10 g of water, and 15 g of an acrylic polyol (SETAQUA 6515 manufactured by Allnex Group) was added and stirred to form a uniform solution (resin composition). This uniform solution (resin composition) was stored at 40° C. for 10 days, and the contents were then inspected visually. The storage stability was evaluated against the following evaluation criteria.

(Evaluation Criteria)

[0440] Good: no gelling occurred

[0441] Poor: gelling occurred

<Production of Uretonimine Group-Containing Compounds>

Example 3-1

(Step 1)

[0442] An SUS316 stirred tank with an internal capacity of 1 L was charged with 300 g of xylene and 500 g of hexamethylene diisocyanate, and the mixture was heated to 140° C. Subsequently, 1 g of 1-phenyl-2-phospholene-1-oxide was added to the tank and stirred for 5 hours. The obtained reaction liquid was supplied to a thin-film evaporator, the interior of which had been heated to 180° C. and evacuated to a pressure of 0.1 kPa (absolute pressure), thereby removing the xylene and excess isocyanate compound by evaporation to obtain a compound. Analysis of the obtained compound by infrared spectroscopy confirmed absorption peaks attributable to an uretonimine group and a carbodiimide group.

(Step 2)

[0443] Subsequently, 890 g of a poly(oxyethylene-oxypropylene) glycol monobutyl ether (number average molecular weight: 300, a compound represented by formula (IV-2) shown below (hereafter sometimes referred to as “compound (IV-2)”) was added as a compound having a hydrophilic group (hereafter sometimes referred to as the “hydrophilic group-containing compound”) to the compound obtained above in step 1, and the mixture was heated under stirring at 150° C. for 8 hours. When the obtained compound was analyzed by .sup.13C-NMR spectroscopy, no peak was observed at a chemical shift corresponding with an uretonimine group.

##STR00147##

(In general formula (IV-2), the ratio of n421 relative to n422 is 1.)

(Step 3)

[0444] Using phenyl isocyanate as the isocyanate compound (hereafter sometimes referred to as “isocyanate compound B”) for reaction with the carbodiimide compound, the isocyanate compound B was mixed with the compound obtained above in step 2 such that the stoichiometric ratio of the isocyanate group of the isocyanate compound B relative to the carbodiimide group of the carbodiimide compound was 1.05-fold, and the mixture was then heated at 80° C. for 5 hours. The obtained compound was a compound which, in an infrared spectroscopy spectrum, exhibited a value for the absorbance x near 2020 cm.sup.−1 attributable to the stretching vibration of carbodiimide groups relative to the absorbance y near 1720 cm.sup.−1 attributable to the stretching vibration of uretonimine groups and urethane groups, namely a value represented by x/y, of 0.3. Further, evaluation of the resin composition storage stability for the obtained compound using the evaluation method described above yielded a good result.

Examples 3-2 to 3-45 and Comparative Example 3-1

[0445] With the exceptions of using the combinations of the diisocyanate A, the isocyanate compound B and the hydrophilic group-containing compound shown below in Tables 5 to 8, the same method as that described for Example 3-1 was used to produce compounds, and then evaluate the storage stability when used as resin compositions. The results are shown below in Tables 5 to 8. In Tables 5 to 8, the abbreviations used for the hydrophilic group-containing compounds represent the compounds described below. Further, for the compound (IV-2), compounds having different number average molecular weights of 300, 510 and 1800 (compounds having different degrees of polymerization) were used as appropriate. Further, for the compound (IV-2), random copolymers having number average molecular weights of 300 and 500 were also used as appropriate.

(Hydrophilic Group-Containing Compounds)

[0446] MPEG220: polyethylene glycol monomethyl ether (number average molecular weight: 220)

[0447] MPEG400: polyethylene glycol monomethyl ether (number average molecular weight: 400)

[0448] MPEG550: polyethylene glycol monomethyl ether (number average molecular weight: 550)

TABLE-US-00005 TABLE 5 Storage stability Isocyanate Hydrophilic group- of resin Diisocyanate A compound B containing compound x/y composition Example 3-1  [00148] Hexamethylene diisocyanate (HDI) [00149] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 0.3 good Example 3-2  [00150] [00151] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 0.8 good Compound (VI-3)-1 Example 3-3  [00152] HDI [00153] MPEG220 0   good Example 3-4  [00154] HDI [00155] MPEG550 0   good Example 3-5  [00156] Tetramethylene diisocyanate [00157] MPEG400 0.1 good Example 3-6  [00158] Tetramethylene diisocyanate [00159] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422): 1 0   good Example 3-7  [00160] [00161] Diethylene glycol monomethyl ether 0.1 good Compound (VI-2)-1 Example 3-8  [00162] [00163] Triethylene glycol monomethyl ether 0.2 good Compound (VI-3)-1 Example 3-9  [00164] [00165] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 0.5 good Compound (VI-3)-1 Example 3-10 [00166] HDI [00167] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 0   good Example 3-11 [00168] HDI [00169] MPEG550 0   good Example 3-12 [00170] HDI [00171] Diethylene glycol monomethyl ether 0   good Example 3-13 [00172] HDI [00173] Triethylene glycol monomethyl ether 0.3 good

TABLE-US-00006 TABLE 6 Storage stability of resin Isocyanate Hydrophilic group- compo- Diisocyanate A compound B containing compound x/y sition Example 3-14 [00174] HDI [00175]   Nonane triisocyanate (NTI) Triethylene glycol monomethyl ether 0.2 good Example 3-15 [00176] HDI [00177]   Lysine triisocyanate (LTI) MPEG400 0   good Example 3-16 [00178] HDI [00179] Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422): 1 0   good Example 3-17 [00180] HDI [00181] MPEG550 0.3 good Example 3-18 [00182] HDI [00183]   Diphenylmethane-4,4′- diisocyanate (MDI) Triethylene glycol monomethyl ether 0.2 good Example 3-19 [00184] [00185] MPEG550 0.2 good Compound (VI-3)-1 Example 3-20 [00186]   Compound (VI-3)-1 [00187] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422): 1 0   good Example 3-21 [00188] [00189] MPEG220 0   good Compound (VI-3)-1 Example 3-22 [00190] [00191] MPEG400 0.3 good Compound (VI-3)-1 Example 3-23 [00192]   Compound (VI-3)-1 [00193]   NTI Triethylene glycol monomethyl ether 0.5 good Example 3-24 [00194]   Compound (VI-3)-1 [00195]   LTI Diethylene glycol monomethyl ether 0.3 good Example 3-25 [00196] [00197] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422): 1 0   good Compound (VI-3)-1 Example 3-26 [00198] [00199]   MDI MPEG220 0   good Compound (VI-2)-1

TABLE-US-00007 TABLE 7 Storage stability Isocyanate Hydrophilic group- of resin Diisocyanate A compound B containing compound x/y composition Example 3-27 [00200] [00201] Diethylene glycol monomethyl ether 0.1 good Example 3-28 [00202] [00203] MPEG550 0.4 good Example 3-29 [00204] [00205] Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 0 good Example 3-30 [00206] [00207] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0 good Example 3-31 [00208] [00209] Triethylene glycol monomethyl ether 0.3 good Example 3-32 [00210] [00211] MPEG400 0.3 good Example 3-33 [00212] [00213] Compond (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0.4 good Example 3-34 Molar ratio pentamethylene diisocyanate:HDI = 1:1 [00214] Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 0.3 good Example 3-35 Molar ratio pentamethylene diisocyanate:HDI = 1:1 [00215] MPEG220 0.1 good Example 3-36 Molar ratio pentamethylene diisocyanate:HDI = 1:1 [00216] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0.1 good Example 3-37 Molar ratio pentamethylene diisocyanate:HDI = 1:1 [00217] MPEG550 0 good Example 3-38 Molar ratio Compound (VI-2)-1:HDI = 1:1 [00218] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0.1 good Example 3-39 Molar ratio Compound (VI-2)-1:HDI = 1:1 [00219] Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 0.2 good

TABLE-US-00008 TABLE 8 Storage stability Isocyanate Hydrophilic group- of resin Diisocyanate A compound B containing compound x/y composition Example 3-40 Molar ratio Compound (VI-2)-1:penta- methylene diisocyanate = 1:1 [00220] Triethylene glycol monomethyl ether 0.1 good Example 3-41 Molar raito Compound (VI-2)-1:penta- methylene diisocyanate = 1:1 [00221] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 (random copolymer) 0 good Example Molar ratio DURANATE TPA-100 MPEG500 0 good 3-42 Compound (VI-2)-1:Com- (manufactured by Asahi pound (VI-3)-1 = Kasei Corporation) 1:1 Example Molar ratio Mass ratio Compound (IV-2) 0 good 3-43 Compound (VI-2)-1:Com- HDI: Number average pound (VI-3)-1 = DURANATE TPA-100 molecular weight: 300 1:1 (manufactured by Asahi Ratio of n421 to n422 Kasei Corporation) = (n421/n422): 1 0.9:0.1 Example Molar ratio Mass ratio Diethylene glycol 0 good 3-44 Compound (VI-2)-1:Com- MDI:NTI = 0.9:0.1 monomethyl ether pound (VI-3)-1 = 1:1 Example Mass ratio Mass ratio Compound (IV-2) 0 good 3-45 Compound (VI-2)-1: MDI:NTI = 0.9:0.1 Number average DURANATE TPA-100 molecular weight: 500 (manufactured by Asahi Ratio of n421 to n422 Kasei Corporation) = (n421/n422):1 0.9:0.1 (random copolymer) Com- parative Example 3-1 [00222] [00223] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/422):1 1.7 poor

[0449] Based on Tables 5 to 8, it was evident that whereas the compounds produced in Examples 3-1 to 3-45 all exhibited good storage stability when used as resin compositions, the compound produced in Comparative Example 3-1 exhibited poor storage stability when used as a resin composition.

Examples 4-1 to 4-24 and Comparative Example 4-1

<Evaluation Method>

[Evaluation 4-1] Storage Stability of Resin Composition

[0450] Evaluations of the compounds obtained in the examples and comparative example were conducted using the method described below.

[0451] Specifically, 1 g of each of the compounds obtained in the examples and comparative example was first dispersed in 10 g of water, and 15 g of an acrylic polyol (SETAQUA 6515 manufactured by Allnex Group) was added and stirred to form a uniform solution (resin composition). This uniform solution (resin composition) was stored at 40° C. for 10 days, and the contents were then inspected visually. The storage stability was evaluated against the following evaluation criteria.

(Evaluation Criteria)

[0452] Good: no gelling occurred

[0453] Poor: gelling occurred

<Production of Carbodiimide Compounds>

Example 4-1

(Step 1)

[0454] An SUS316 stirred tank with an internal capacity of 1 L was charged with 300 g of xylene and 500 g of hexamethylene diisocyanate, and the mixture was heated to 140° C. Subsequently, 1 g of 1-phenyl-2-phospholene-1-oxide was added to the tank and stirred for 5 hours. The obtained reaction liquid was supplied to a thin-film evaporator, the interior of which had been heated to 180° C. and evacuated to a pressure of 0.1 kPa (absolute pressure), thereby removing the xylene and excess isocyanate compound by evaporation to obtain a compound. Analysis of the obtained compound by infrared spectroscopy confirmed absorption peaks attributable to an uretonimine group and a carbodiimide group.

(Step 2)

[0455] Subsequently, 890 g of a poly(oxyethylene-oxypropylene) glycol monobutyl ether (number average molecular weight: 300, a compound represented by formula (IV-2) shown below (hereafter sometimes referred to as “compound (IV-2)”) was added as a compound having a hydrophilic group (hereafter sometimes referred to as the “hydrophilic group-containing compound”) to the compound obtained above in step 1, and the mixture was heated under stirring at 150° C. for 8 hours. When the obtained compound was analyzed by .sup.13C-NMR spectroscopy, no peak was observed at a chemical shift corresponding with an uretonimine group.

##STR00224##

(In general formula (IV-2), the ratio of n421 relative to n422 is 1.)

Examples 4-2 to 4-23, and Comparative Example 4-1

[0456] With the exceptions of using the combinations of the diisocyanate and the hydrophilic group-containing compound shown below in Tables 9 and 10, the same method as that described for Example 4-1 was used to produce compounds, and then evaluate the storage stability when used as resin compositions. The results are shown below in Tables 9 and 10. In Tables 9 and 10, the abbreviation used for the hydrophilic group-containing compound represents the compounds described below. Further, for the compound (IV-2), compounds having different number average molecular weights of 300, 510 and 1800 (compounds having different degrees of polymerization) were used as appropriate. Further, for the compound (IV-2), random copolymers having number average molecular weights of 300 and 500 were also used as appropriate.

(Hydrophilic Group-Containing Compound)

[0457] MPEG400: polyethylene glycol monomethyl ether (number average molecular weight: 400)

Example 4-24

[0458] An SUS316 stirred tank with an internal capacity of 1 L was charged with 84.1 g of hydrogenated XDI (the compound (VI-2)-1) and 82.5 g of the compound (IV-2) (number average molecular weight: 300, ratio of n421 to n422 in general formula (IV-2) of 1), the mixture was stirred at 120° C. for one hour, 13.1 g of 4,4′-diphenylmethane diisocyanate (the compound (III-6)-1) and 1.94 g of 3-methyl-1-phenyl-2-phospholene-1-oxide were added, and the resulting mixture was stirred under a stream of nitrogen at 185° C. for a further 5 hours, thus obtaining a compound. Analysis of the reaction liquid using an infrared spectrometer revealed that the isocyanate group absorption at 2200 cm.sup.−1 to 2300 cm.sup.−1 had disappeared.

[0459] Further, when the obtained compound was analyzed by .sup.13C-NMR spectroscopy, no peak was observed at a chemical shift corresponding with an uretonimine group.

TABLE-US-00009 TABLE 9 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 4-1 [00225] Compound (IV-2) Number average molecular weight: 300 Ratio of 421 to 422 (n421/n422):1 good Example 4-2 [00226] Compound (IV-2) Number average molecular weight: 300 Ratio of 421 to n422 (n421/n422):1 good Example 4-3 [00227] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 good Example 4-4 [00228] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 good Example 4-5 [00229] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 good Example 4-6 [00230] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 good Example 4-7 [00231] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 good Example 4-8 [00232] Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 good Example 4-9 [00233] Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 good Example 4-10 [00234] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 good Example 4-11 [00235] Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 good Example 4-12 [00236] Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 good

TABLE-US-00010 TABLE 10 Storage stability Hydrophilic group-containing of resin Diiocyanate compound composition Example Molar ratio Compound (IV-2) good 4-13 pentamethylene diisocyanate:HDI = Number average molecular weight: 300 1:1 Ratio of n421 to n422 (n421/n422):1 Example Molar ratio Compound (IV-2) good 4-14 Compound (VI-3)-1:HDI = Number average molecular weight: 300 1:1 Ratio of n421 to n422 (n421/n422):1 Example Molar ratio Compound (IV-2) good 4-15 Compound (VI-2)-1:Compound (VI-3)-1 = Number average molecular weight: 510 1:1 Ratio of n421 to n422 (n421/n422):1 Example Molar ratio Compound (IV-2) good 4-16 Compound (III-6)-1:Compound (VI-3)-1 = Number average molecular weight: 300 1:1 Ratio of n421 to n422 (n421/n422):1 Example Molar ratio Compound (IV-2) good 4-17 Compound (III-5)-1:Compound (VI-2)-1 = Number average molecular weight: 300 1:1 Ratio of n421 to n422 (n421/n422):1 (random copolymer) Example Molar ratio Compound (IV-2) good 4-18 Compound (III-4)-1:Compound (III-6)-1 = Number average molecular weight: 500 1:1 Ratio of n421 to n422 (N421/n422):1 (random coppolymer) Example Molar ratio Compound (IV-2) good 4-19 Compound (III-2)-1:HDI = Number average molecular weight: 510 1:1 Ratio of n421 to n422 (n421/n422):1 Example Mass ratio Compound (IV-2) good 4-20 DURANATE TPA-100 (manufactured by Number average molecular weight: 1800 Asahi Kasei Corporation):Com- Ratio of n421 to n422 (n421/n422):1 pound (III-5)-1 = 0.1:0.9 Example Molar ratio Compound (IV-2) good 4-21 pentamethylene diisocyanate:HDI = Number average molecular weight: 1800 1:1 Ratio of n421 to n422 (N421/n422):1 Example Mass ratio Compound (IV-2) good 4-22 DURANATE TPA-100 (manufactured by Number average molecular weight: 500 Asahi Kasei Corporation):HDI = 0.1:0.9 Ratio of n421 to n422 (n421/n422):1 (random copolymer) Example Mass ratio Compound (IV-2) good 4-23 DURANATE TPA-100 (manufactured by Number average molecular weight: 1800 Asahi Kasei Corporation):penta- Ratio of n421 to n422 (n421/n422):1 methylene diisocyanate = 0.1:0.9 Example Molar ratio Compound (IV-2) good 4-24 Compound (III-6)-1:Compound (VI-2)-1 = Number average molecular weight: 300 1:1 Ratio of n421 to n422 (n421/n422 ):1 Comparative Example 4-1 [00237] MPEG400 poor

[0460] Based on Tables 9 and 10, it was evident that whereas the compounds produced in Examples 4-1 to 4-24 all exhibited good storage stability when used as resin compositions, the compound produced in Comparative Example 4-1 exhibited poor storage stability when used as a resin composition.

Examples 5-1 to 5-71

<Evaluation Method>

[Evaluation 5-1] Storage Stability of Resin Composition

[0461] Evaluations of the compounds obtained in the examples were conducted using the method described below.

[0462] Specifically, 1 g of each of the compounds obtained in the examples was first dispersed in 10 g of butyl acetate, and 15 g of an acrylic polyol (STALAX 1152 manufactured by Allnex Group) was added and stirred to form a uniform solution (resin composition). This uniform solution (resin composition) was stored at 40° C. for 10 days, and the contents were then inspected visually. The storage stability was evaluated against the following evaluation criteria.

(Evaluation Criteria)

[0463] Good: the viscosity after storage at 40° C. for 10 days was less than 1.5 times the viscosity immediately after production

[0464] Poor: the viscosity after storage at 40° C. for 10 days was at least 1.5 times the viscosity immediately after production

<Production of Carbodiimide Group-Containing Compound>

Example 5-1

[0465] An SUS316 stirred tank with an internal capacity of 2 L and fitted with a reflux condenser was charged with 600 g of xylene, 500 g of hexamethylene diisocyanate and 118 g of tert-butyl isocyanate, and the mixture was heated to 140° C. Subsequently, 1 g of 1-phenyl-2-phospholene-1-oxide was added to the tank and stirred for 30 hours. The obtained reaction liquid was supplied to a thin-film evaporator, the interior of which had been heated to 180° C. and evacuated to a pressure of 0.1 kPa (absolute pressure), thereby removing the xylene by evaporation to obtain a compound. Analysis of the obtained compound by infrared spectroscopy confirmed an absorption peak attributable to a carbodiimide group.

[0466] Evaluation of the resin composition storage stability for the obtained compound using the evaluation method described above yielded a good result.

Examples 5-2 to 5-71

[0467] With the exceptions of using the combinations of diisocyanates and hydrophilic group-containing compounds shown below in Tables 11 to 18, the same method as that described for Example 5-1 was used to produce compounds, and then evaluate the storage stability when used as resin compositions.

TABLE-US-00011 TABLE 11 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-1 [00238] [00239] good Example 5-2 [00240] [00241] good Example 5-3 [00242] [00243] good Example 5-4 [00244] [00245] good Example 5-5 [00246] [00247] good Example 5-6 [00248] [00249] good Example 5-7 [00250] [00251] good Example 5-8 [00252] [00253] good Example 5-9 [00254] [00255] good Methyl (S)-(−)-2-isocyanatoacetate

TABLE-US-00012 TABLE 12 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-10 [00256] [00257] good Example 5-11 [00258] [00259] good Example 5-12 [00260] [00261] good Example 5-13 [00262] [00263] good Example 5-14 [00264] [00265] good Example 5-15 [00266] [00267] good Example 5-16 Molar ratio Pentamethylene diisocyanate:HDI = 1:1 [00268] good Example 5-17 Molar ratio Hydrogenated XDI:Hydro- genated MDI = 1:1 [00269] good Example 5-18 Molar ratio XDI:HDI = 1:1 [00270] good Example 5-19 Molar ratio Hydrogenated XI:XDI = 1:1 [00271] good

TABLE-US-00013 TABLE 13 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-20 Molar ratio Hydrogenated XDI:TMXDI = 1:1 [00272] good Example 5-21 Molar ratio MDI:XDI = 1:1 [00273] good Example 5-22 Molar ratio Hydrogenated XDI:MDI = 1:1 [00274] good Example 5-23 Molar ratio TMXDI:MDI = 1:1 [00275] good Example 5-24 Molar ratio IPDI:HDI = 1:1 [00276] good Example 5-25 Mass ratio DURANATE TPA-100 (manufactured by Asahi Kasei Corporation):HDI = 0.1:0.9 [00277] good Example 5-26 Mass ratio DURANATE TPA-100 (manufactured by Asahi Kasei Corporation):penta- methylene diisocyanate = 0.1:0.9 [00278] good Example 5-27 Mass ratio DURANATE TPA-100 (manufactured by Asahi Kasei Corporation):Hydro- genated MDI = 0.1:0.9 [00279] good

TABLE-US-00014 TABLE 14 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-28 [00280] [00281] good Example 5-29 [00282] [00283] good Example 5-30 [00284] [00285] good Example 5-31 [00286] [00287] good Example 5-32 [00288] [00289] good Example 5-33 [00290] [00291] good Example 5-34 [00292] [00293] good Example 5-35 [00294] [00295] good Example 5-36 [00296] [00297] good

TABLE-US-00015 TABLE 15 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-37 [00298] [00299] good Example 5-38 [00300] [00301] good Example 5-39 [00302] [00303] good Example 5-40 [00304] [00305] good Example 5-41 [00306] [00307] good Example 5-42 [00308] [00309] good Example 5-43 Molar ratio Pentamethylene diisocyanate:HDI = 1:1 [00310] good Example 5-44 Molar ratio Hydrogenated XDI:Hydro- genated MDI = 1:1 [00311] good Example 5-45 Molar ratio XDI:HDI = 1:1 [00312] good Example 5-46 Molar ratio Hydrogenated XDI:XDI = 1:1 [00313] good

TABLE-US-00016 TABLE 16 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-47 Molar ratio Hydrogenated XDI:TMXDI = 1:1 [00314] good Example 5-48 Molar ratio MDI:XDI = 1:1 [00315] good Example 5-49 Molar ratio Hydrogenated XDI:MDI = 1:1 [00316] good Example 5-50 Molar ratio TMXDI:MDI = 1:1 [00317] good Example 5-51 Molar ratio IPDI:HDI = 1:1 [00318] good Example 5-52 Mass ratio DURANATE TPA-100 (manufactured by Asahi Kasei Corporation):HDI = 0.1:0.9 [00319] good Example 5-53 Mass ratio DURANATE TPA-100 (manufactured by Asahi Kasei Corporation):penta- methylene diisocyanate = 0.1:0.9 [00320] good Example 5-54 Mass ratio DURANATE TPA-100 (manufactured by Asahi Kasei Corporation):Hydro- genated MDI = 0.1:0.9 [00321] good

TABLE-US-00017 TABLE 17 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-55 [00322] [00323] good Example 5-56 [00324] [00325] good Example 5-57 [00326] [00327] good Example 5-58 [00328] [00329] good Example 5-59 [00330] [00331] good Example 5-60 [00332] [00333] good Example 5-61 [00334] [00335] good

TABLE-US-00018 TABLE 18 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-62 [00336] [00337] good Example 5-63 [00338] [00339] good Example 5-64 [00340] [00341] good Example 5-65 [00342] [00343] good Example 5-66 [00344] [00345] good Example 5-67 [00346] [00347] good Example 5-68 Molar ratio Pentamethylene diisocyanate:HDI = 1:1 [00348] good Example 5-69 Molar ratio Hydrogenated XDI:Hydro- genated MDI = 1:1 [00349] good Example 5-70 Molar ratio XI:HDI = 1:1 [00350] good Example 5-71 Molar ratio Hydrogenated XDI:XDI = 1:1 [00351] good

[0468] Based on Tables 11 to 18, it was evident that the compounds produced in Examples 5-1 to 5-71 all exhibited good storage stability when used as resin compositions.

Examples 6-1 to 6-21, Comparative Examples 6-1 and 6-2

<Evaluation Methods>

[Evaluation 6-1] Storage Stability Evaluation (Resin Composition Evaluation 1)

[0469] Using the method described below, the storage stability was evaluated by measuring the gelling time of the resin compositions that used the compounds obtained in the examples and comparative examples.

[0470] Specifically, 2 g of each of the compounds obtained in the examples and comparative examples was first dispersed in 5 g of water, and the resulting dispersion was added to 20 g of a polyurethane water dispersion (SUPERFLEX 150, manufactured by DKS Co., Ltd.) to form a uniform solution (resin composition). This uniform solution (resin composition) was heated to 40° C., the contents were inspected visually every 5 hours to confirm the presence or absence of gelling, and the time elapsed until gelling was confirmed was recorded as the gelling time. Subsequently, using the obtained gelling time, the storage stability was evaluated against the following evaluation criteria.

(Evaluation Criteria)

[0471] Good: gelling time of 10 hours or longer

[0472] Poor: gelling time of less than 10 hours

[Evaluation 6-2] Evaluation of Reactivity with Main Agent (Resin Composition Evaluation 2)

[0473] Evaluations of the reactivity with the main agent were conducted by measuring the increase in the gel fraction of the resin composition formed using each of the compounds obtained in the examples and comparative examples using the method described below.

[0474] Specifically, 5 g of water was first added to 20 g of a polyurethane water dispersion (SUPERFLEX 150, manufactured by DKS Co., Ltd.) and stirred to obtain a uniform solution. This uniform solution was coated onto a polypropylene sheet (hereafter sometimes abbreviated as “PP sheet”) and cured inside a dryer at 100° C. Subsequently, the coating film was cut from the PP sheet, placed in a woven wire mesh and immersed in an acetone solution for 16 hours, and the coating film and the woven wire mesh were then removed from the acetone and dried using a dryer. The change in the mass of the coating film from before immersion to after immersion in the acetone solution was measured, and the value obtained by dividing the change in the mass of the coating film by the mass of the coating film before immersion was calculated as the reference gel fraction.

[0475] Subsequently, 2 g of each of the compounds obtained in the examples and comparative examples was dispersed in 5 g of water, and the resulting dispersion was added to 20 g of a polyurethane water dispersion (SUPERFLEX 150, manufactured by DKS Co., Ltd.) and stirred to form a uniform solution (resin composition). This uniform solution (resin composition) was coated onto a PP sheet and cured in the same manner as described above, the gel fraction was then measured in the same manner as described above, and the increase in the gel fraction was determined from the difference relative to the reference gel fraction. Based on the thus obtained increase in the gel fraction, the reactivity with the main agent was evaluated against the following evaluation criteria.

(Evaluation Criteria)

[0476] Good: increase in gel fraction of at least 10%

[0477] Poor: increase in gel fraction of less than 10%

[Evaluation 6-3] Water Resistance of Coating Film (Coating Film Evaluation 1)

[0478] Evaluations of the water resistance of the coating films formed using the compounds obtained in the examples and comparative examples were conducted using the method described below. Specifically, 5 g of water was first added to 20 g of a polyurethane water dispersion (SUPERFLEX 150, manufactured by DKS Co., Ltd.) and stirred to obtain a uniform solution. This uniform solution (resin composition) was coated onto a PP sheet and cured in a dryer at 100° C. Subsequently, an O-ring (inner diameter: 1.78 mm, wire diameter: 1.78 mm) was placed on top of the coating film, and 1 mL of ion-exchanged water was dripped inside the O-ring. Subsequently, the coating film was left to stand for 5 hours at room temperature, and the degree of whitening of the coating film was then confirmed visually as a reference.

[0479] Subsequently, 2 g of each of the compounds obtained in the examples and comparative examples was dispersed in 5 g of water, and the resulting dispersion was added to 20 g of a polyurethane water dispersion (SUPERFLEX 150, manufactured by DKS Co., Ltd.) and stirred to form a uniform solution (resin composition). This uniform solution (resin composition) was coated onto a PP sheet and cured in the same manner as described above, and the degree of whitening of the coating film was confirmed visually using the same method as described above and compared with the reference. Based on the obtained visual results, the water resistance of the coating film was evaluated against the following evaluation criteria.

(Evaluation Criteria)

[0480] Good: the degree of whitening was less than the reference, indicating superior water resistance

[0481] Poor: the degree of whitening was at least as great as the reference, indicating low water resistance

Comparative Example 6-1

(Step 1)

[0482] Hexamethylene diisocyanate was used as the diisocyanate (hereafter sometimes referred to as “diisocyanate A”) for producing a carbodiimide compound. An SUS316 stirred tank with an internal capacity of 1 L was charged with 300 g of xylene and 500 g of the diisocyanate A, and the mixture was heated to 140° C. Subsequently, 1 g of 1-phenyl-2-phospholene-1-oxide was added to the tank and stirred for 5 hours. The xylene and excess isocyanate compound were removed from the reaction liquid by evaporation using a thin-film evaporator, thus obtaining a compound. Analysis of the obtained compound by infrared spectroscopy confirmed absorption peaks attributable to an uretonimine group and a carbodiimide group.

(Step 2)

[0483] Subsequently, 890 g of a poly(oxyethylene-oxypropylene) glycol monobutyl ether (number average molecular weight: 970, a compound represented by formula (IV-2) shown below (hereafter sometimes referred to as “compound (IV-2)”) was added as a compound having a hydrophilic group (hereafter sometimes referred to as the “hydrophilic group-containing compound”) to the compound obtained above in step 1, and the mixture was heated under stirring at 150° C. for 8 hours. When the obtained compound was analyzed by .sup.13C-NMR spectroscopy, no peak was observed at a chemical shift corresponding with an uretonimine group.

##STR00352##

(In general formula (IV-2), the ratio of n421 relative to n422 is 1.)

(Step 3)

[0484] Using phenyl isocyanate as the isocyanate compound (hereafter sometimes referred to as “isocyanate compound B”) reacted with the carbodiimide group, the compound obtained above in step 2 and phenyl isocyanate were mixed such that the stoichiometric ratio of the isocyanate group of the isocyanate compound B relative to the carbodiimide group of the carbodiimide compound was 1.05-fold, and the mixture was then heated at 80° C. for 5 hours. The obtained compound was a compound which, in an infrared spectroscopy spectrum, exhibited a value for the absorbance x near 2020 cm.sup.−1 attributable to the stretching vibration of carbodiimide groups relative to the absorbance y near 1720 cm.sup.−1 attributable to the stretching vibration of uretonimine groups and urethane groups, namely a value represented by x/y, of 0.3.

Comparative Example 6-2, Examples 6-1 to 6-20

[0485] With the exceptions of using the combinations of the diisocyanate A, the isocyanate compound B and the hydrophilic group-containing compound shown below in Tables 19 and 20, the same method as that described for Comparative Example 6-1 was used to produce compounds, and then evaluate the storage stability when used as a resin composition, the reactivity with the main agent, and the water resistance when used to form a coating film. In Tables 19 and 20, the compound X among the isocyanate compounds B is shown below. Further, the abbreviations used for the hydrophilic group-containing compounds represent the compounds described below. Furthermore, for the compound (IV-2), compounds having different number average molecular weights of 300, 510, 970 and 1800 (compounds having different degrees of polymerization) were used as appropriate.

(Isocyanate Compound B)

[0486] The compound X is a compound represented by formula (X) shown below, and represents a compound obtained by conventional methods in which one terminal isocyanate group of hexamethylene diisocyanate has been modified with a monofunctional polyalkylene oxide poly ether alcohol.

##STR00353##

(In formula (X), R.sup.101 is a group represented by formula (X-1) shown below.)

##STR00354##

(In general formula (X-1), the ratio of n111 relative to n112 is 1.)

(Hydrophilic Group-Containing Compounds)

[0487] MPEG220: polyethylene glycol monomethyl ether (number average molecular weight: 220)

[0488] MPEG550: polyethylene glycol monomethyl ether (number average molecular weight: 550)

TABLE-US-00019 TABLE 19 Storage Reactivity Curability Hydrophilic stability of with of Isocyanate group- resin main coating Diisocyanate A compound B containing compound x/y composition agent film Ex- am- ple 6-1 [00355] [00356] Compound (IV-2) Number average molecular weight: 300 0.0 good good good Ratio of n421 to n422 (n421/n422):1 Ex- am- ple 6-2 [00357] [00358] Compound (IV-2) Number average molecular weight: 970 0.0 good good good Ratio of n421 to n422 (n421/n422):1 Ex- am- ple 6-3 [00359] [00360] Compound (IV-2) Number average molecular weight: 1800 0.0 good good good Ratio of n421 to n422 (n421/n422):1 Ex- am- ple 6-4 [00361] [00362] MPEG550 0.0 good good good Ex- am- ple 6-5 [00363] [00364] MPEG220 0.0 good good good Ex- am- ple 6-6 [00365] [00366] Triethylene glycol monomethyl ether 0.0 good good good Ex- am- ple 6-7 [00367] [00368] Diethylene glycol monomethyl ether 0.0 good good good Ex- am- ple 6-8 [00369] [00370] Compound (IV-2) Number average molecular weight: 300 0.0 good good good Ratio of n421 to n422 (n421/n422):1 Ex- am- ple 6-9 [00371] [00372] Compound (IV-2) Number average molecular weight: 970 Ratio of n421 to 0.0 good good good n422 (n421/n422):1 Ex- am- ple 6-10 [00373] [00374] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0.1 good good good

TABLE-US-00020 TABLE 20 Storage Reac- Cura- stability of tivity bility Hydrophilic resin with of Isocyanate group-containing composi- main coating Diisocyanate A compound B compound x/y tion agent film Ex- ample 6-11 [00375] [00376] Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 0.0 good good good Ex- ample 6-12 [00377] [00378] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 0.1 good good good (n421/n422):1 Ex- ample 6-13 [00379] [00380] MPEG550 0.2 good good good Ex- ample 6-14 [00381] [00382] Compound (IV-2) Number average molecular weight: 970 Ratio of n421 to n422 0.0 good good good (n421/n422):1 Ex- ample 6-15 [00383] [00384] Compound (IV-2) Number average molecular weight: 970 Ratio of n421 to n422 (n421/n422):1 0.2 good good good Ex- ample 6-16 [00385] [00386] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0.1 good good good isophorone diisocyanate (IPDI) Ex- ample 6-17 Molar ratio Pentamethyl diisocyanate:HCl = 1:1 [00387] Compound (IV-2) Number average molecular weight: 970 Ratio of n421 to n422 (n421/n422):1 0.2 good good good Ex- ample 6-18 [00388] [00389] Compound (IV-2) Number average molecular weight: 970 Ratio of 0.0 good good good n421 to n422 (n421/n422):1 Ex- ample 6-19 [00390] [00391] Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0.1 good good good Ex- ample 6-20 Molar ratio Hydrogenated MDI:Hydro- genated XDI = 1:1 [00392] Compound (IV-2) Number average molecular weight: 1800 0.1 good good good Ratio of n421 to n422 (n421/n422):1 Com- para- tive Ex- ample 6-1 [00393] [00394] Compound (IV-2) Number average molecular weight: 9.70 Ratio of n421 to n422 (n421/n422):1 0.3 good good good Com- para- tive [00395] Compound (X) Compound (IV-2) Number average molecular 0.0 good good good Ex- weight: 970 ample Ratio of 6-2 n421 to n422 (n421/n422):1

[0489] Based on Tables 19 and 20, it was evident that the compounds produced in Examples 6-1 to 6-20 all exhibited good results for the storage stability when used as a resin composition, the reactivity with the main agent, and the water resistance when used to form a coating film. In contrast, although the compound produced in Comparative Example 6-1 exhibited good results for the reactivity with the main agent and the water resistance when used to form a coating film, the storage stability when used as a resin composition was poor. Further, although the compound produced in Comparative Example 6-2 exhibited good storage stability when used as a resin composition, the reactivity with the main agent and the water resistance when used to form a coating film were poor.

INDUSTRIAL APPLICABILITY

[0490] The compound of an embodiment of the present invention is able to provide a novel compound having an uretonimine group. Further, the compound of an embodiment of the present invention is able to provide a novel carbodiimide compound. The compounds of embodiments of the present invention exhibit excellent water dispersibility, and can be used favorably as curing agent components for water-based resin compositions.