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 of general formula (1): ##STR00396## wherein in general formula (1), n11 is an integer of at least 1 but not more than 100, each of X.sup.11 and X.sup.12 is independently a residue obtained by removing a hydrogen atom from a terminal hydroxyl group of a monofunctional polyalkylene oxide polyether alcohol, Q.sup.11 is a group of general formula (1-a) shown below or a group of general formula (1-b) shown below, when n11 is 1, Q.sup.11 is a group of general formula (1-b) shown below, and when n11 is 2 or greater, plural Q.sup.11 may be identical to or different from each other, and each of R.sup.11 and R.sup.12 is independently a residue obtained by removing two isocyanate groups from a diisocyanate, ##STR00397## wherein in the formulas, each asterisk indicates a bonding site, in general formula (1-b), Y.sup.11 is a residue obtained by removing one isocyanate group from an isocyanate compound, and the diisocyanate and the isocyanate compound are different compounds.

2. 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.

3. The compound according to claim 1, wherein the monofunctional polyalkylene oxide polyether alcohol is a polyethylene glycol monoalkyl ether, a polypropylene glycol monoalkyl ether, or a copolymer thereof.

4. The compound according to claim 1, wherein each of X.sup.11 and X.sup.12 is independently a group of general formula (II-1) shown below or a group of general formula (II-2) shown below: ##STR00398## wherein in general formula (II-1), each of n21 and n22 is independently an integer of at least 1 but not more than 30, and R.sup.21 is 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 is independently an integer of at least 1 but not more than 30, and R.sup.22 is an alkyl group of at least 1 but not more than 12 carbon atoms that may contain a carbonyl group, and each asterisk indicates a bonding site.

5. The compound according to claim 1, wherein each of R.sup.11 and R.sup.12 is independently a group of general formula (III-1), a group of general formula (III-2), a group of general formula (III-3), a group of general formula (III-5), a group of general formula (III-6), or a group of general formula (VI): ##STR00399## wherein each asterisk indicates a bonding site, R.sup.61 is 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, and the alkylene group and the arylene group may each have at least one functional group selected from the group consisting of an isocyanurate group, an allophanate group, a biuret group, an uretdione group, an iminooxadiazinedione group and a urethane group.

6. The compound according to claim 5, wherein R.sup.11 and R.sup.12 are groups of the general formula (VI).

7. The compound according to claim 6, wherein each of R.sup.11 and R.sup.12 is independently at least one group selected from the group consisting of groups of general formula (VI-1) shown below, a group of general formula (VI-2) shown below and a group of general formula (VI-3) shown below: ##STR00400## wherein in the formulas, each asterisk indicates a bonding site, and in general formula (VI-1), n61 is an integer of at least 1 but not more than 10.

8. The compound according to claim 7, wherein each of R.sup.11 and R.sup.12 is independently a group of the general formula (VI-1), and the isocyanate compound is an aliphatic isocyanate compound.

9. The compound according to claim 8, wherein among a carbon atom that is bonded to the uretonimine group in Y.sup.11, and a carbon atom that is bonded to the uretonimine group in R.sup.11 or R.sup.12, 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.

10. The compound according to claim 1, wherein the isocyanate compound is at least one of an isocyanate derived from an amino acid and a trifunctional or higher isocyanate.

11. The compound according to claim 10, wherein the trifunctional or higher isocyanate is a trifunctional isocyanate.

12. The compound according to claim 11, wherein the trifunctional isocyanate is a compound of general formula (1-B)-3c shown below: ##STR00401## wherein in general formula (1-B)-3c, each of a plurality of R.sup.134b groups is independently 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 is a hydrogen atom or a monovalent hydrocarbon group of at least 1 but not more than 12 carbon atoms.

13. The compound according to claim 10, wherein the isocyanate having a group derived from an amino acid is an isocyanate having a group of formula (5) shown below: ##STR00402## wherein in formula (5), each asterisk indicates a bonding site.

14. A method for producing a compound of claim 1, the method comprising: producing a compound having an uretonimine group of general formula (1) by reacting a carbodiimide compound of general formula (2) shown below and an isocyanate compound of general formula (3) shown below: ##STR00403## wherein in general formula (1), n11 is an integer of at least 1 but not more than 100, each of X.sup.11 and X.sup.12 is independently a residue obtained by removing a hydrogen atom from a terminal hydroxyl group of a monofunctional polyalkylene oxide polyether alcohol, Q.sup.11 is a group of formula (1-b) shown below, when n11 is 1, Q.sup.11 is a general formula (1-b) shown below, and when n11 is 2 or greater, plural Q.sup.11 may be identical to or different from each other, and each of R.sup.11 and R.sup.12 is independently a residue obtained by removing two isocyanate groups from a diisocyanate, ##STR00404## wherein in the formulas, each asterisk indicates a bonding site, in general formula (1-b), Y.sup.11 is a residue obtained by removing one isocyanate group from an isocyanate compound, and the diisocyanate and the isocyanate compound are different compounds, ##STR00405## wherein in general formula (2), n13 is an integer of at least 1 but not more than 100, each of X.sup.15 and X.sup.16 is independently a group of general formula (VIII) shown below, each of R.sup.15 and R.sup.16 is independently a residue obtained by removing two isocyanate groups from a diisocyanate or a polyisocyanate derived from a diisocyanate, ##STR00406## wherein in general formula (VIII), Y.sup.81 is a carbodiimide group, a urea group or a urethane group, R.sup.81 is a monovalent hydrocarbon group of at least 1 but not more than 12 carbon atoms that may include a carbonyl group or an ester linkage, and an asterisk indicates a bonding site,
R.sup.3-NCO (3) wherein in general formula (3), R.sup.3 is a residue obtained by removing one isocyanate group from an isocyanate compound.

15. A curing agent composition, comprising a compound of claim 1.

16. A resin composition, comprising a curing agent composition of claim 15 and a compound having a carboxyl group.

17. A coating material composition, comprising a resin composition of claim 16.

18. A resin cured product, obtained by curing a coating material composition of claim 17.

Description

EXAMPLES

(1) 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 1-4

Reference Example 1-1

(2) 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

(3) 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.

(4) ##STR00065##

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

Example 1-2

(6) 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.

(7) ##STR00066##

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

Example 1-3

(9) 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.

(10) ##STR00067##

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

Example 1-4

(12) 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.

(13) ##STR00068##

(14) 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.

(15) ##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

(16) <Evaluation Method>

(17) [Evaluation 2-1] Storage Stability of Resin Composition

(18) Evaluations of the compounds obtained in the examples and comparative example were conducted using the method described below.

(19) 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.

(20) (Evaluation Criteria)

(21) Good: no gelling occurred Poor: gelling occurred
<Production of Uretonimine Group-Containing Compounds>

Example 2-1

(22) (Step 1)

(23) 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.

(24) (Step 2)

(25) 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.

(26) ##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

(27) 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.

(28) (Hydrophilic Group-Containing Compounds)

(29) MPEG220: polyethylene glycol monomethyl ether (number average molecular weight: 220)

(30) MPEG400: polyethylene glycol monomethyl ether (number average molecular weight: 400)

(31) MPEG550: polyethylene glycol monomethyl ether (number average molecular weight: 550)

(32) TABLE-US-00001 TABLE 1 Storage stability Hydrophilic of resin Isocyanate group-containing com- Diisocyanate A compound B compound x/y position Ex- ample 2-1 Compound (III-5)-1 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0.5 good Ex- ample 2-2 Compound (III-6)-1 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 1.0 good Ex- ample 2-3 Compound (III-5)-1 Pentamethylene diisocyanate (PDI) MPEG220 0 good Ex- ample 2-4 Compound (III-5)-1 HDI MPEG550 0 good Ex- ample 2-5 Compound (III-4)-1 0 MPEG400 0.5 good Ex- ample 2-6 Compound (III-4)-1 HDI Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0 good Ex- ample 2-7 Compound (III-2)-1 Diethylene glycol monomethyl ether 0.1 good Ex- ample 2-8 Compound (III-6)-1 Triethylene glycol monomethyl ether 0.5 good Ex- ample 2-9 Compound (III-6)-1 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 1.4 good Ex- ample 2-10 Compound (III-5)-1 0 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 Ex- ample 2-11 Compound (III-5)-1 MPEG550 0 good Ex- ample 2-12 Compound (III-5)-1 Diethylene glycol monomethyl ether 0.1 good Ex- ample 2-13 Compound (III-5)-1 Triethylene glycol monomethyl ether 0.2 good

(33) TABLE-US-00002 TABLE 2 Storage stability Hydrophilic of resin Isocyanate group- containing com- Diisocyanate A compound B compound x/y position Ex- ample 2-14 Compound (III-5)-1 Nonane triisocyanate (NTI) Triethylene glycol monomethyl ether 0.2 good Ex- ample 2-15 Compound (III-5)-1 00 Lysine triisocyanate (LTI) MPEG400 0 good Ex- ample 2-16 01 Compound (III-5)-1 02 Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 0 good Ex- ample 2-17 03 Compound (III-5)-1 04 Compound (III-2)-1 MPEG550 0.3 good Ex- ample 2-18 05 Compound (III-5)-1 06 Compound (III-6)-1 Triethylene glycol monomethyl ether 0.2 good Ex- ample 2-19 07 Compound (III-6)-1 08 MPEG550 0.3 good Ex- ample 2-20 09 Compound (III-6)-1 0 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0 good Ex- ample 2-21 Compound (III-6)-1 MPEG220 0 good Ex- ample 2-22 Compound (III-6)-1 MPEG400 0.3 good Ex- ample 2-23 Compound (III-6)-1 NTI Triethylene glycol monomethyl ether 0.5 good Ex- ample 2-24 Compound (III-6)-1 LTI Diethylene glycol monomethyl ether 0.1 good Ex- ample 2-25 Compound (III-6)-1 0 Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0 good Ex- ample 2-26 Compound (III-2)-1 Compound (III-6)-1 MPEG220 0 good

(34) TABLE-US-00003 TABLE 3 Storage stability Isocyanate Hydrophilic group- of resin Diisocyanate A compound B containing compound x/y composition Example 2-27 Compound (III-2)-1 Diethylene glycol monomethyl ether 0.1 good Example 2-28 Compound (III-2)-1 MPEG550 0.3 good Example 2-29 Compound (III-2)-1 Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 0 good Example 2-30 Compound (III-2)-1 0 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0 good Example 2-31 Compound (III-2)-1 NTI Triethylene glycol monomethyl ether 0.5 good Example 2-32 Compound (III-2)-1 LTI MPEG400 0.3 good Example 2-33 Compound (III-2)-1 Triethylene glycol monomethyl ether 0.5 good Example 2-34 Molar ratio Compound (III-2)-1: Compound (III-5)-1 = 1:1 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 Compound (III-6)-1 MPEG220 0.1 good Example 2-36 Molar ratio Compound (III-5)-1: Compound (III-6)-1 = 1:1 NTI Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0.1 good Example 2-37 Molar ratio Compound (III-5)-1: Compound (III-6)-1 = 1:1 0 MPEG550 0 good Example 2-38 Molar ratio Compound (III-5)-1: Compound (III-6)-1 = 1:1 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 Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0.2 good

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

(36) 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

(37) <Evaluation Method>

(38) [Evaluation 3-1] Storage Stability of Resin Composition

(39) Evaluations of the compounds obtained in the examples and comparative example were conducted using the method described below.

(40) 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.

(41) (Evaluation Criteria)

(42) Good: no gelling occurred Poor: gelling occurred
<Production of Uretonimine Group-Containing Compounds>

Example 3-1

(43) (Step 1)

(44) 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.

(45) (Step 2)

(46) 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.

(47) ##STR00147##
(In general formula (IV-2), the ratio of n421 relative to n422 is 1.)
(Step 3)

(48) 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

(49) 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.

(50) (Hydrophilic Group-Containing Compounds)

(51) MPEG220: polyethylene glycol monomethyl ether (number average molecular weight: 220)

(52) MPEG400: polyethylene glycol monomethyl ether (number average molecular weight: 400)

(53) MPEG550: polyethylene glycol monomethyl ether (number average molecular weight: 550)

(54) TABLE-US-00005 TABLE 5 Storage stability Isocyanate Hydrophilic group- of resin Diisocyanate A compound B containing compound x/y composition Example 3-1 Hexamethylene diisocyanate (HDI) Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0.3 good Example 3-2 0 Compound (VI-3)-1 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0.8 good Example 3-3 HDI MPEG220 0 good Example 3-4 HDI MPEG550 0 good Example 3-5 Tetramethylene diisocyanate MPEG400 0.1 good Example 3-6 Tetramethylene diisocyanate Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0 good Example 3-7 0 Compound (VI-2)-1 Diethylene glycol monomethyl ether 0.1 good Example 3-8 Compound (VI-3)-1 Triethylene glycol monomethyl ether 0.2 good Example 3-9 Compound (VI-3)-1 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0.5 good Example 3-10 HDI Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0 good Example 3-11 HDI MPEG550 0 good Example 3-12 0 HDI Diethylene glycol monomethyl ether 0 good Example 3-13 HDI Triethylene glycol monomethyl ether 0.3 good

(55) TABLE-US-00006 TABLE 6 Storage stability Isocyanate Hydrophilic group- of resin Diisocyanate A compound B containing compound x/y composition Example 3-14 HDI Nonane triisocyanate (NTI) Triethylene glycol monomethyl ether 0.2 good Example 3-15 HDI Lysine triisocyanate (LTI) MPEG400 0 good Example 3-16 HDI Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 0 good Example 3-17 0 HDI MPEG550 0.3 good Example 3-18 HDI Diphenylmethane-4,4- diisocyanate (MDI) Triethylene glycol monomethyl ether 0.2 good Example 3-19 Compound (VI-3)-1 MPEG550 0.2 good Example 3-20 Compound (VI-3)-1 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0 good Example 3-21 Compound (VI-3)-1 MPEG220 0 good Example 3-22 0 Compound (VI-3)-1 MPEG400 0.3 good Example 3-23 Compound (VI-3)-1 NTI Triethylene glycol monomethyl ether 0.5 good Example 3-24 Compound (VI-3)-1 LTI Diethylene glycol monomethyl ether 0.3 good Example 3-25 Compound (VI-3)-1 Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0 good Example 3-26 Compound (VI-2)-1 MDI MPEG220 0 good

(56) TABLE-US-00007 TABLE 7 Storage Hydrophilic stability group- of resin Isocyanate containing com- Diisocyanate A compound B compound x/y position Example 3-27 00 01 Diethylene glycol monomethyl ether 0.1 good Example 3-28 02 03 MPEG550 0.4 good Example 3-29 04 05 Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 0 good Example 3-30 06 07 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0 good Example 3-31 08 09 Triethylene glycol monomethyl ether 0.3 good Example 3-32 0 MPEG400 0.3 good Example 3-33 Compound (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 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 MPEG220 0.1 good Example 3-36 Molar ratio pentamethylene diisocyanate: HDI = 1:1 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 MPEG550 0 good Example 3-38 Molar ratio Compound (VI-2)-1: HDI = 1:1 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 Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 0.2 good

(57) TABLE-US-00008 TABLE 8 Storage Hydrophilic stability group- of resin Isocyanate containing com- Diisocyanate A compound B compound x/y position Example 3-40 Molar ratio Compound (VI-2)-1 : pentamethylene diisocyanate = 1:1 0 Triethylene glycol monomethyl ether 0.1 good Example 3-41 Molar ratio Compound (VI-2)-1 : pentamethylene diisocyanate = 1:1 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 MPEG550 0 good 3-42 Compound (VI-2)-1: (manufactured by Asahi Compound (VI-3)-1 = Kasei Corporation) 1:1 Example Molar ratio Mass ratio Compound (IV-2) 0 good 3-43 Compound (VI-2)-1: HDI : Number average Compound (VI-3)-1 = DURANATE TPA-100 molecular weight: 1:1 (manufactured by Asahi 300 Kasei Corporation) = Ratio of n421 to 0.9:0.1 n422 (n421/n422):1 Example Molar ratio Mass ratio Diethylene glycol 0 good 3-44 Compound (VI-2)-1: MDI:NTI = 0.9:0.1 monomethyl ether Compound (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: (manufactured by Asahi 500 Kasei Corporation) = Ratio of n421 to 0.9:0.1 n422 (n421/n422):1 (random copolymer) Com- parative Example 3-1 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 1.7 poor

(58) 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

(59) <Evaluation Method>

(60) [Evaluation 4-1] Storage Stability of Resin Composition

(61) Evaluations of the compounds obtained in the examples and comparative example were conducted using the method described below.

(62) 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.

(63) (Evaluation Criteria)

(64) Good: no gelling occurred Poor: gelling occurred
<Production of Carbodiimide Compounds>

Example 4-1

(65) (Step 1)

(66) 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.

(67) (Step 2)

(68) 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.

(69) ##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

(70) 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.

(71) (Hydrophilic Group-Containing Compound)

(72) MPEG400: polyethylene glycol monomethyl ether (number average molecular weight: 400)

Example 4-24

(73) 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.

(74) 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.

(75) TABLE-US-00009 TABLE 9 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 4-1 Hexamethylene diisocyanate (HDI) Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 good Example 4-2 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 good Example 4-3 Tetramethylene diisocyanate Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 good Example 4-4 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 good Example 4-5 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 good Example 4-6 0 Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 good Example 4-7 Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 good Example 4-8 HDI Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 good Example 4-9 Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 good Example 4-10 Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 good Example 4-11 Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 good Example 4-12 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 good

(76) TABLE-US-00010 TABLE 10 Storage stability Hydrophilic group-containing of resin Diisocyanate 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 Number average molecular weight: 510 (VI-3)-1 = 1:1 Ratio of n421 to n422 (n421/n422):1 Example Molar ratio Compound (IV-2) good 4-16 Compound (III-6)-1:Compound Number average molecular weight: 300 (VI-3)-1 = 1:1 Ratio of n421 to n422 (n421/n422):1 Example Molar ratio Compound (IV-2) good 4-17 Compound (III-5)-1:Compound Number average molecular weight: 300 (VI-2)-1 = 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 Number average molecular weight: 500 (III-6)-1 = 1:1 Ratio of n421 to n422 (n421/n422):1 (random copolymer) Example Molar ratio Compound (IV-2) good 4-19 Compound (III-2)-1: Number average molecular weight: 510 HDI = 1:1 Ratio of n421 to n422 (n421/n422):1 Example Mass ratio Compound (IV-2) good 4-20 DURANATE TPA-100 (manufactured Number average molecular weight: 1800 by Asahi Kasei Corporation): Ratio of n421 to n422 (n421/n422):1 Compound (III-5)-1 = 0.1:0.9 Example Molar ratio Compound (IV-2) good 4-21 pentamethylene diisocyanate: Number average molecular weight: 1800 HDI = 1:1 Ratio of n421 to n422 (n421/n422):1 Example Mass ratio Compound (IV-2) good 4-22 DURANATE TPA-100 (manufactured Number average molecular weight: 500 by Asahi Kasei Corporation): Ratio of n421 to n422 (n421/n422):1 HDI = 0.1:0.9 (random copolymer) Example Mass ratio Compound (IV-2) good 4-23 DURANATE TPA-100 (manufactured Number average molecular weight: 1800 by Asahi Kasei Corporation): Ratio of n421 to n422 (n421/n422):1 pentamethylene diisocyanate = 0.1:0.9 Example Molar ratio Compound (IV-2) good 4-24 Compound (III-6)-1:Compound Number average molecular weight: 300 (VI-2)-1 = 1:1 Ratio of n421 to n422 (n421/n422):1 Comparative Example 4-1 MPEG400 poor

(77) 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

(78) <Evaluation Method>

(79) [Evaluation 5-1] Storage Stability of Resin Composition

(80) Evaluations of the compounds obtained in the examples were conducted using the method described below.

(81) 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.

(82) (Evaluation Criteria)

(83) Good: the viscosity after storage at 40 C. for 10 days was less than 1.5 times the viscosity immediately after production 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

(84) 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.

(85) 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

(86) 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.

(87) TABLE-US-00011 TABLE 11 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-1 Hexamethylene diisocyanate (HDI) good Example 5-2 0 Hexamethylene diisocyanate (HDI) good Example 5-3 Hexamethylene diisocyanate (HDI) good Example 5-4 Hexamethylene diisocyanate (HDI) good Example 5-5 Hexamethylene diisocyanate (HDI) good Example 5-6 Hexamethylene diisocyanate (HDI) good Example 5-7 0 Hexamethylene diisocyanate (HDI) good Example 5-8 Hexamethylene diisocyanate (HDI) good Example 5-9 Hexamethylene diisocyanate (HDI) good

(88) TABLE-US-00012 TABLE 12 Hydrophilic group- Storage stability of Diisocyanate containing compound resin composition Example 5-10 Tetramethylene diisocyanate good Example 5-11 good Example 5-12 0 good Example 5-13 good Example 5-14 good Example 5-15 good Example 5-16 Molar ratio Pentamethylene diisocyanate: HDI = 1:1 good Example 5-17 Molar ratio Hydrogenated XDI: Hydrogenated MDI = 1:1 good Example 5-18 Molar ratio XDI:HDI = 1:1 0 good Example 5-19 Molar ratio Hydrogenated XDI:XDI = 1:1 1-hexyl isocyanate good

(89) 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 good Example 5-21 Molar ratio MDI:XDI = 1:1 good Example 5-22 Molar ratio Hydrogenated XDI:MDI = 1:1 good Example 5-23 Molar ratio TMXDI:MDI = 1:1 good Example 5-24 Molar ratio IPDI:HDI = 1:1 good Example 5-25 Mass ratio DURANATE TPA-100 (manufactured by Asahi Kasei Corporation):HDI = 0.1:0.9 good Example 5-26 Mass ratio DURANATE TPA-100 (manufactured by Asahi Kasei Corporation): pentamethylene diisocyanate = 0.1:0.9 good Example 5-27 Mass ratio DURANATE TPA-100 (manufactured by Asahi Kasei Corporation): Hydrogenated MDI = 0.1:0.9 good

(90) TABLE-US-00014 TABLE 14 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-28 0 Hexamethylene diisocyanate (HDI) good Example 5-29 Hexamethylene diisocyanate (HDI) good Example 5-30 Hexamethylene diisocyanate (HDI) good Example 5-31 Hexamethylene diisocyanate (HDI) good Example 5-32 Hexamethylene diisocyanate (HDI) good Example 5-33 0 Hexamethylene diisocyanate (HDI) good Example 5-34 Hexamethylene diisocyanate (HDI) good Example 5-35 Hexamethylene diisocyanate (HDI) good Example 5-36 Hexamethylene diisocyanate (HDI) good

(91) TABLE-US-00015 TABLE 15 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-37 Tetramethylene diisocyanate good Example 5-38 00 IPDI 01 good Example 5-39 02 Hydrogenated MDI 03 good Example 5-40 04 XDI 05 good Example 5-41 06 TMXDI 07 good Example 5-42 08 MDI 09 good Example 5-43 Molar ratio Pentamethylene diisocyanate: HDI = 1:1 0 good Example 5-44 Molar ratio Hydrogenated XDI: Hydrogenated MDI = 1:1 good Example 5-45 Molar ratio XDI:HDI = 1:1 good Example 5-46 Molar ratio Hydrogenated XDI:XDI = 1:1 good

(92) 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 good Example 5-48 Molar ratio MDI:XDI = 1:1 good Example 5-49 Molar ratio Hydrogenated XDI:MDI = 1:1 good Example 5-50 Molar ratio TMXDI:MDI = 1:1 good Example 5-51 Molar ratio IPDI:HDI = 1:1 good Example 5-52 Mass ratio DURANATE TPA-100 (manufactured by Asahi Kasei Corporation):HDI = 0.1:0.9 good Example 5-53 Mass ratio DURANATE TPA-100 (manufactured by Asahi Kasei Corporation): pentamethylene diisocyanate = 0.1:0.9 0 good Example 5-54 Mass ratio DURANATE TPA-100 (manufactured by Asahi Kasei Corporation): Hydrogenated MDI = 0.1:0.9 good

(93) TABLE-US-00017 TABLE 17 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-55 Hexamethylene diisocyanate (HDI) good Example 5-56 Hexamethylene diisocyanate (HDI) good Example 5-57 Hexamethylene diisocyanate (HDI) good Example 5-58 Hexamethylene diisocyanate (HDI) good Example 5-59 0 Hexamethylene diisocyanate (HDI) good Example 5-60 Hexamethylene diisocyanate (HDI) good Example 5-61 Hexamethylene diisocyanate (HDI) good

(94) TABLE-US-00018 TABLE 18 Hydrophilic group-containing Storage stability of Diisocyanate compound resin composition Example 5-62 Tetramethylene diisocyanate good Example 5-63 good Example 5-64 0 good Example 5-65 good Example 5-66 good Example 5-67 good Example 5-68 Molar ratio Pentamethylene diisocyanate: HDI = 1:1 good Example 5-69 Molar ratio Hydrogenated XDI: Hydrogenated MIDI = 1:1 good Example 5-70 Molar ratio XDI:HDI = 1:1 0 good Example 5-71 Molar ratio Hydrogenated XDI:XDI = 1:1 good

(95) 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

(96) <Evaluation Methods>

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

(98) 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.

(99) 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.

(100) (Evaluation Criteria)

(101) Good: gelling time of 10 hours or longer Poor: gelling time of less than 10 hours
[Evaluation 6-2] Evaluation of Reactivity with Main Agent (Resin Composition Evaluation 2)

(102) 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.

(103) 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.

(104) 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.

(105) (Evaluation Criteria)

(106) Good: increase in gel fraction of at least 10% Poor: increase in gel fraction of less than 10%
[Evaluation 6-3] Water Resistance of Coating Film (Coating Film Evaluation 1)

(107) 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.

(108) 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.

(109) (Evaluation Criteria)

(110) Good: the degree of whitening was less than the reference, indicating superior water resistance Poor: the degree of whitening was at least as great as the reference, indicating low water resistance

Comparative Example 6-1

(111) (Step 1)

(112) 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.

(113) (Step 2)

(114) 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.

(115) ##STR00352##
(In general formula (IV-2), the ratio of n421 relative to n422 is 1.)
(Step 3)

(116) 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

(117) 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.

(118) (Isocyanate Compound B)

(119) 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.

(120) ##STR00353##
(In formula (X), R.sup.101 is a group represented by formula (X-1) shown below.)

(121) ##STR00354##
(In general formula (X-1), the ratio of n111 relative to n112 is 1.)
(Hydrophilic Group-Containing Compounds)

(122) MPEG220: polyethylene glycol monomethyl ether (number average molecular weight: 220)

(123) MPEG550: polyethylene glycol monomethyl ether (number average molecular weight: 550)

(124) TABLE-US-00019 TABLE 19 Storage Re- Cur- stability activity ability Hydrophilic of resin with of Isocyanate group-containing x/y com- main coating Diisocyanate A compound B compound position agent film Ex- ample 6-1 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0.0 good good good Ex- ample 6-2 Compound (IV-2) Number average molecular weight: 970 Ratio of n421 to n422 (n421/n422):1 0.0 good good good Ex- ample 6-3 0 Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 0.0 good good good Ex- ample 6-4 MPEG550 0.0 good good good Ex- ample 6-5 MPEG220 0.0 good good good Ex- ample 6-6 Triethylene glycol monomethyl ether 0.0 good good good Ex- ample 6-7 Diethylene glycol monomethyl ether 0.0 good good good Ex- ample 6-8 Tetramethylene diisocyanate 0 Compound (IV-2) Number average molecular weight: 300 Ratio of n421 to n422 (n421/n422):1 0.0 good good good Ex- ample 6-9 Compound (IV-2) Number average molecular weight: 970 Ratio of n421 to n422 (n421/n422):1 0.0 good good good Ex- ample 6-10 Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0.1 good good good

(125) TABLE-US-00020 TABLE 20 Storage Re- Cur- stability activity ability Hydrophilic of resin with of Isocyanate group-containing com- main coating Diisocyanate A compound B compound x/y position agent film Example 6-11 Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 0.0 good good good Example 6-12 Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0.1 good good good Example 6-13 0 MPEG550 0.2 good good good Example 6-14 Compound (IV-2) Number average molecular weight: 970 Ratio of n421 to n422 (n421/n422):1 0.0 good good good Example 6-15 Compound (IV-2) Number average molecular weight: 970 Ratio of n421 to n422 (n421/n422):1 0.2 good good good Example 6-16 Isophorone diisocyanate (IPDI) Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0.1 good good good Example 6-17 Molar ratio Pentamethylene diisocyanate: HDI = 1:1 Compound (IV-2) Number average molecular weight: 970 Ratio of n421 to n422 (n421/n422):1 0.2 good good good Example 6-18 Compound (IV-2) Number average molecular weight: 970 Ratio of n421 to n422 (n421/n422):1 0.0 good good good Example 6-19 0 Compound (IV-2) Number average molecular weight: 510 Ratio of n421 to n422 (n421/n422):1 0.1 good good good Example 6-20 Molar ratio Hydrogenated MDI: Hydrogenated XDI = 1:1 Compound (IV-2) Number average molecular weight: 1800 Ratio of n421 to n422 (n421/n422):1 0.1 good good good Com- parative Example 6-1 Compound (IV-2) Number average molecular weight: 970 Ratio of n421 to n422 (n421/n422):1 0.3 poor good good Com- parative Example 6-2 Compound (X) Compound (IV-2) Number average molecular weight: 970 Ratio of n421 to n422 (n421/n422):1 0.0 good poor poor

(126) 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

(127) 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.