Compounds having a silyl ester structure of amidic acid, methods for producing the same, and curable compositions and cured products containing the same.

Abstract

To provide a compound having an amido acid silyl ester structure that has good solubility in resins and solvents, gives a neutral and stable composition, and can be used as a curing agent for various resins. 【Solution means】 A compound having an amido acid silyl ester structure represented by the following general formula (1). TIFF2026089313000024.tif3157[In the formula, R 1 represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be intervened by an oxygen, nitrogen, silicon, sulfur atom or a siloxane bond, and R 2 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 3 each independently represents a hydrogen atom, CO2SiR 2 3, OSiR 2 3 (wherein R 2 represents the same meaning as described above), but at least one of R 3 represents CO2SiR 2 3 or OSiR 2 3, and A represents a benzene ring or a cyclohexane ring.]

Description

Technical Field

[0001] The present invention relates to a compound having an amido acid silyl ester structure, a method for producing the same, and a curable composition and a cured product containing the same.

Background Art

[0002] Amido acids and amido acid silyl ester compounds, particularly 1,2-amido acids and 1,2-amido acid silyl ester compounds, are known as precursors of cyclic imide compounds that can be induced into cyclic imide compounds by intramolecular dehydration or desilanol by heating. Among them, amido acid silyl ester compounds have the advantage that the carboxylic acid moiety is protected by a silyl group, so they have lower polarity than amido acids, good solubility in various organic solvents, and excellent handling properties.

[0003] Among the imide compounds derived from the above compounds, N-alkylimide compounds do not have nucleophilic reactive groups. Therefore, there is a problem that compounds having only an N-alkylimide structure, or N-alkylamido acids and N-alkylamido acid silyl esters, which are their precursors, cannot be used as resin modifiers or the like.

[0004] In order to solve this problem, Patent Document 1 reports a diimide dicarboxylic acid-based compound obtained by inducing an amido acid obtained by reacting an aromatic diamine with trimellitic anhydride into an imide compound. Since this compound has a carboxylic acid structure in addition to an imide group, the carboxylic acid moiety can be used as a reactive group. For example, in Patent Document 1, the obtained compound is used as a curing agent for an epoxy resin to obtain a cured product having high heat resistance derived from the imide group.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

[0006] However, although the diimidodicarboxylic acid compounds described in Patent Document 1 have a carboxylic acid structure that can be used as curing agents for epoxy resins, they are highly polar because they are carboxylic acid compounds, and have poor compatibility with various resins, especially epoxy resins, making them difficult to mix with resins.

[0007] The present invention has been made in view of the above, and aims to provide a compound having a silyl ester structure of amidic acid that has good solubility in resins and solvents, gives a neutral and stable composition, and can be used as a curing agent for various resins, as well as a method for producing the same, and a curable composition and cured product containing the same. [Means for solving the problem]

[0008] As a result of diligent research to solve the above problems, the present inventors have found that compounds having a silyl ester structure of amidic acid and a carboxylic acid or hydroxyl group protected by a silyl group provide a composition with good solubility, neutrality, and stability, and can be suitably used as a curing agent for various resins, especially epoxy resins, thus completing the present invention.

[0009] In other words, the present invention 1. Compounds having a silyl ester structure of an amide acid represented by the following general formula (1), [ka] [In the formula, R 1 R represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be interposed by a hydrogen atom, or an oxygen, nitrogen, silicon, sulfur atom, or siloxane bond. 2 Each of these independently represents an unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, and R 3 These are, independently, hydrogen atoms and CO2SiR. 2 3. OSiR2 3 (wherein, R 2 represents the same meaning as described above.) represents, but R 3 at least one of which is CO2SiR 2 3 or OSiR 2 3 represents, and A represents a benzene ring or a cyclohexane ring.] 2. A composition containing a compound having an amido acid silyl ester structure of 1 and an aprotic solvent, 3. A curable composition containing a compound having an amido acid silyl ester structure of 1 and an epoxy compound, 4. Further, a curable composition of 3 containing a cyclic acid anhydride, 5. Further, a curable composition of 4 containing an aprotic solvent, 6. Further, a curable composition according to any one of 3 to 5 containing a curing catalyst selected from the group consisting of an amine compound, a salt of an amine compound, a phosphine compound, a phosphonium salt, a sulfonium salt, an iodonium salt and a urea compound, 7. A cured product obtained by curing the curable composition of 3 or 4, 8. The following general formula (2)

Chemical formula

Chemical formula

[0010] The compounds of the present invention are useful not only as curing agents for various resins, particularly epoxy resins, because they provide a neutral and stable composition with good solubility, but also because they can be cured while introducing imide groups by heat curing, thereby imparting imide-derived functions to the resulting cured product. [Brief explanation of the drawing]

[0011] [Figure 1] This figure shows the IR spectrum of compound 1 obtained in Example 1-1. [Figure 2] This figure shows the 1H-NMR spectrum of compound 1 obtained in Example 1-1. [Figure 3] This figure shows the IR spectrum of compound 2 obtained in Example 1-2. [Figure 4] This figure shows the 1H-NMR spectrum of compound 2 obtained in Examples 1-2. [Figure 5] This figure shows the IR spectrum of compound 3 obtained in Examples 1-3. [Figure 6] This figure shows the 1H-NMR spectrum of compound 3 obtained in Examples 1-3. [Figure 7] This figure shows the IR spectrum of compound 4 obtained in Examples 1-4. [Figure 8] This figure shows the 1H-NMR spectrum of compound 4 obtained in Examples 1-4. [Figure 9] This figure shows the IR spectrum of compound 5 obtained in Examples 1-5. [Figure 10] This figure shows the 1H-NMR spectrum of compound 5 obtained in Examples 1-5. [Modes for carrying out the invention]

[0012] The present invention will be described in detail below. [1] Compounds having a silyl ester structure of amic acid The compound having a silyl ester structure of the present invention is represented by the following general formula (1) (hereinafter referred to as "compound (1)").

[0013] [ka]

[0014] In general formula (1), R 1 This represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, which may be interposed by a hydrogen atom, or an oxygen, nitrogen, silicon, sulfur atom, or siloxane bond. R 1 The monovalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, tetradecyl, hexadecyl, and octadecyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, texyl, and 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and pentenyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenethyl groups. Among these, linear alkyl groups and alkenyl groups are preferred from the viewpoint of ease of raw material procurement.

[0015] Also, R 1The monovalent hydrocarbon group may have some or all of its hydrogen atoms substituted with substituents, such substituents include, for example, alkoxy groups having 1 to 3 carbon atoms; halogen atoms such as chlorine, bromine, and iodine atoms; aryl groups having 6 to 10 carbon atoms; aralkyl groups having 7 to 10 carbon atoms; cyano groups, amino groups, acyl groups, carboxyl groups, alkoxyalkyl groups having 1 to 6 carbon atoms, alkoxycarbonyl groups having 1 to 3 carbon atoms, trialkoxysilyl groups having 3 to 9 carbon atoms, alkyldialkoxysilyl groups having 3 to 12 carbon atoms, dialkylalkoxysilyl groups having 3 to 15 carbon atoms, trialkylsilyl groups having 3 to 18 carbon atoms, and the group represented by X below.

[0016] [ka] (In the formula, *- represents R 1 (This represents the bonding site with the carbon atom.)

[0017] R 1 If a siloxane bond is present, it may have a polydialkylsiloxanyl group represented by the following general formula (4) or a group containing a cyclic siloxane structure represented by the following general formula (5).

[0018] [ka] (In equation (5), the dashed line represents R 8 (This represents the bond arrangement when it is a divalent hydrocarbon group.)

[0019] In general formula (4), R 6 Each of these independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. R 6The monovalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and decyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, texyl, and 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and pentenyl groups; aryl groups such as phenyl and tolyl groups; aralkyl groups such as benzyl and phenethyl groups; and alkoxy groups such as methoxy, ethoxy, n-propoxy, and isopropoxy groups. Among these, R 6 From the viewpoint of ease of raw material procurement, linear alkyl groups, alkenyl groups, aryl groups, and alkoxy groups are preferred. Note, R 6 The monovalent hydrocarbon group may have some or all of its hydrogen atoms substituted with substituents, such as R 1 Similar substituents can be cited.

[0020] In general formula (4), q represents any integer, but from the viewpoint of the hardness of the hardened product obtained from the product, it preferably represents an integer between 0 and 100, more preferably between 0 and 40, and even more preferably between 0 and 10.

[0021] Specific examples of polydialkylsiloxanyl groups represented by general formula (4) include the following substituents. Note that q 1 +q 2 = q, and q 1 +q 2 +q 3 = q

[0022] [ka] (In the formula, Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and Vi represents a vinyl group. The same applies hereafter.)

[0023] In general formula (5), R 7 Each of these independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. 7 As for the monovalent hydrocarbon group, R 6 Similar substituents can be cited. Note, R 7 The monovalent hydrocarbon group may have some or all of its hydrogen atoms substituted with substituents, such substituents include, for example, alkoxy groups having 1 to 3 carbon atoms; halogen atoms such as chlorine, bromine, and iodine atoms; aryl groups having 6 to 10 carbon atoms; aralkyl groups having 7 to 10 carbon atoms; cyano groups, amino groups, alkoxy groups, acyl groups, carboxyl groups, alkoxyalkyl groups having 1 to 6 carbon atoms, alkoxycarbonyl groups having 1 to 3 carbon atoms, trialkoxysilyl groups having 3 to 9 carbon atoms, alkyldialkoxysilyl groups having 3 to 12 carbon atoms, dialkylalkoxysilyl groups having 3 to 15 carbon atoms, and trialkylsilyl groups having 3 to 18 carbon atoms.

[0024] In general formula (5), R 8 Each of these independently represents a substituted or unsubstituted monovalent hydrocarbon group or divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, but R 8 At least one of them represents a divalent hydrocarbon group. 8 As for the monovalent hydrocarbon group, R 6 Similar substituents can be cited. Note, R 8 The monovalent hydrocarbon group may have some or all of its hydrogen atoms substituted, and the substituent may be R 1 Similar substituents can be cited. R 8 Specific examples of divalent hydrocarbon groups include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and desilene groups. In general formula (5), r represents 0, 1, or 2.

[0025] Specific examples of substituents containing a cyclic siloxane structure represented by general formula (5) include the following:

[0026] [ka]

[0027] The above R 2 Each of these independently represents an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 carbon atom. R 2 The monovalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and decyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, texyl, and 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and pentenyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenethyl groups. Among these, the methyl group is preferred from the viewpoint of ease of raw material procurement.

[0028] The above R 3 These are, independently, hydrogen atoms and CO2SiR 2 3, or OSiR 2 3 (wherein, R 2 This represents the same meaning as above. ) but R 3 At least one of them, based on the structure of the raw material, is CO2SiR 2 3 or OSiR 2 It represents the number 3. In the above, A represents a benzene ring or a cyclohexane ring. Of these, a benzene ring is preferred due to the ease of procuring the raw materials.

[0029] Specific examples of compounds represented by general formula (1) include 2,4-bis(trimethylsilyl)-1-(aminocarbonyl)-2,4-benzenedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(allylaminocarbonyl)-2,4-benzenedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(octenylaminocarbonyl)-2,4-benzenedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(trimethoxysilylpropylaminocarbonyl)-2,4-benzenedicarboxylic acid, and 2,4-bis(trimethylsilyl)-1-(triethylsilyl Sisilylpropylaminocarbonyl)-2,4-benzenedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(methyldiethoxysilylpropylaminocarbonyl)-2,4-benzenedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(methyldiethoxysilylpropylaminocarbonyl)-2,4-benzenedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(dimethylmethoxysilylpropylaminocarbonyl)-2,4-benzenedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(dimethylethoxysilylpropylaminocarbonyl) Nocarbonyl)-2,4-benzenedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(trimethoxysilylpropylthiopropylaminocarbonyl)-2,4-benzenedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(trimethoxysilylmethylthiopropylaminocarbonyl)-2,4-benzenedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(trimethoxysilylethyldimethylsiloxydimethylsilylpropylaminocarbonyl)-2,4-benzenedicarboxylic acid, bis(trimethylsilyl)-2-((3-(2,4, 4,6,6,8,8-Heptamethyl-1,3,5,7,2,4,6,8-Tetraoxatetrasilocan-2-yl)propyl)carbamoyl)terephthalic acid, Bis(trimethylsilyl)-2-((3-(2,4,6,8-Tetramethyl-2,4,6-Tripropyl-1,3,5,7,2,4,6,8-Tetraoxatetrasilocan-2-yl)propyl)carbamoyl)terephthalic acid, Bis(trimethylsilyl)-2-((3-(2,4,6,8-Tetramethyl-4,6,8-Tris(3,3,3-Trifluoropropyl)-1,3,5,7,2,4,6,8-Tetraoxatetrasilocan-2-yl)propyl)carbamoyl)terephthalic acid, bis(trimethylsilyl)-2-((3-(2,4,6,8-tetramethyl-4,6,8-tris(trimethoxysilylethyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl)propyl)carbamoyl)terephthalic acid, bis(trimethylsilyl)-2-((3-(2,4,6,8-tetramethyl-4,6,8-tris(trimethoxysilyloctyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl )Propyl)carbamoyl)terephthalic acid, 2,4-bis(trimethylsilyl)-1-(aminocarbonyl)-2,4-cyclohexanedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(allylaminocarbonyl)-2,4-cyclohexanedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(octenylaminocarbonyl)-2,4-cyclohexanedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(trimethoxysilylpropylaminocarbonyl)-2,4-cyclohexanedicarboxylic acid, 2,4-bis(trimethylsilyl 2,4-Bis(trimethylsilyl)-1-(triethoxysilylpropylaminocarbonyl)-2,4-cyclohexanedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(methyldiethoxysilylpropylaminocarbonyl)-2,4-cyclohexanedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(methyldiethoxysilylpropylaminocarbonyl)-2,4-cyclohexanedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(dimethylmethoxysilylpropylaminocarbonyl)-2,4-cyclohexanedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(dimethylmethoxysilylpropylaminocarbonyl)-2,4-cyclohexanedicarboxylic acid, 2,4-bis(trimethyl Lucilyl)-1-(dimethylethoxysilylpropylaminocarbonyl)-2,4-cyclohexanedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(trimethoxysilylpropylthiopropylaminocarbonyl)-2,4-cyclohexanedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(trimethoxysilylmethylthiopropylaminocarbonyl)-2,4-cyclohexanedicarboxylic acid, 2,4-bis(trimethylsilyl)-1-(trimethoxysilylethyldimethylsiloxydimethylsilylpropylaminocarbonyl)-2,4-Cyclohexanedicarboxylic acid, bis(trimethylsilyl)-2-((3-(2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl)propyl)carbamoyl)cyclohexanedicarboxylic acid, bis(trimethylsilyl)-2-((3-(2,4,6,8-tetramethyl-2,4,6-tripropyl-1,3,5,7,2,4,6,8-tetramethyl Traoxatetrasilocan-2-yl)propyl)carbamoyl)cyclohexanedicarboxylic acid, bis(trimethylsilyl)-2-((3-(2,4,6,8-tetramethyl-4,6,8-tris(3,3,3-trifluoropropyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl)propyl)carbamoyl)cyclohexanedicarboxylic acid, bis(trimethylsilyl)-2- ((3-(2,4,6,8-tetramethyl-4,6,8-tris(trimethoxysilylethyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilokano-2-yl)propyl)carbamoyl)cyclohexanedicarboxylic acid, bis(trimethylsilyl)-2-((3-(2,4,6,8-tetramethyl-4,6,8-tris(trimethoxysilyloctyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilokano-2-yl)propyl)carbamoyl)cyclohexanedicarboxylic acid, trimethylsilyl-2-carbamoyl-3-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(methylcarbamoyl)-3-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(allylcarbamoyl)-3-(trimethylsilyloxy)benzenecarboxylic acid, , Trimethylsilyl-2-(trimethoxysilylpropylcarbamoyl)-3-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(methyldiethoxysilylpropylcarbamoyl)-3-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(dimethylmethoxysilylpropylcarbamoyl)-3-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(triethoxysilylpropylcarbamoyl)-3-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(die Toxymethylsilylpropylcarbamoyl)-3-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(dimethylethoxysilylpropylcarbamoyl)-3-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-carbamoyl-3-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(methylcarbamoyl)-4-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(allylcarbamoyl)-4-(trimethylsilyloxy)benzenecarboxylic acid, trimethyl Silyl-2-(trimethoxysilylpropylcarbamoyl)-4-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(methyldiethoxysilylpropylcarbamoyl)-4-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(dimethylmethoxysilylpropylcarbamoyl)-4-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(triethoxysilylpropylcarbamoyl)-4-(trimethylsilyloxy)benzenecarboxylic acid, trimethylsilyl-2-(diethoxymethyl Compounds having one group represented by X in the molecule, such as lusilylpropylcarbamoyl)-4-(trimethylsilyloxy)benzenecarboxylic acid and trimethylsilyl-2-(dimethylethoxysilylpropylcarbamoyl)-4-(trimethylsilyloxy)benzenecarboxylic acid; tetrakis(trimethylsilyl)-2,2'-((((1,1,3,3-tetramethyldisiloxane-1,3-diyl)-bis(propane-3,1-diyl))bis(azandiyl))bis(carbonyl))diterephthalic acid, tetrakis(trimethylsilyl)-2,2'-((((1,1,3,3-Tetramethyldisiloxane-1,3-diyl)-bis(hexane-3,1-diyl))bis(azandiyl))bis(carbonyl))diterephthalic acid, tetrakis(trimethylsilyl)-2,2'-((((1,1,3,3-Tetramethyldisiloxane-1,3-diyl)-bis(octane-3,1-diyl))bis(azandiyl))bis(carbonyl))diterephthalic acid, tetrakis(trimethylsilyl)-2,2'-((((1,1,3,3,5,5-Hexamethyltrisiloxane-1,5-diyl)-bis(propane- 5,1-diyl))bis(azandiyl))bis(carbonyl))diterephthalic acid, tetrakis(trimethylsilyl)-2,2'-((((1,1,3,3,5,5,7,7-octamethyltetrasiloxane-1,7-diyl)-bis(propane-7,1-diyl))bis(azandiyl))bis(carbonyl))diterephthalic acid, tetrakis(trimethylsilyl)-2,2'-((((polymethylpolysiloxane-α,ω-diyl)-bis(propane-ω,α-diyl))bis(azandiyl))bis(carbonyl))diterephthalic acid, tetra Tetrakis(trimethylsilyl)-2,2'-((((2,4,4,6,8,8-hexamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,6-diyl)bis(propane-3,1-diyl))bis(azandiyl))bis(carbonyl))diterephthalic acid, Tetrakis(trimethylsilyl)-2,2'-((((2,4,6,6,8,8-hexamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,4-diyl)bis(propane-3,1-diyl))bis(azandiyl))bis(carbonyl )) Diterephthalic acid, tetrakis(trimethylsilyl)-2,2'-((((2,4,6,8-tetramethyl-4,8-dipropyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,6-diyl)bis(propane-3,1-diyl))bis(azandiyl))bis(carbonyl)) Diterephthalic acid, tetrakis(trimethylsilyl)-2,2'-((((2,4,6,8-tetramethyl-6,8-dipropyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,4-diyl)bis(propane-3,1-Diyl))Bis(Azandiyl))Bis(Carbonyl))Diterephthalic acid, Tetrakis(trimethylsilyl)-2,2'-((((2,4,6,8-Tetramethyl-4,8-Bis(trimethoxysilylethyl)-1,3,5,7,2,4,6,8-Tetraoxatetrasilocane-2,6-Diyl)Bis(propane-3,1-Diyl))Bis(Azandiyl))Bis(Carbonyl))Diterephthalic acid, Tetrakis(trimethylsilyl)-2,2'-((((2,4,6,8-Tetramethyl-6,8-Bis(trimethoxysilyl) (Tyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,4-diyl)bis(propane-3,1-diyl)bis(azandiyl)bis(carbonyl))diterephthalic acid, tetrakis(trimethylsilyl)-2,2'-((((1,1,3,3-tetramethyldisiloxane-1,3-diyl)-bis(propane-3,1-diyl)bis(azandiyl)bis(carbonyl))bis(cyclohexanedicarboxylic acid, tetrakis(trimethylsilyl)-2,2'-((((1,1,3,3-tetramethyl Disiloxane-1,3-diyl)-bis(hexane-3,1-diyl))bis(azandiyl))bis(carbonyl))bis(cyclohexanedicarboxylic acid), tetrakis(trimethylsilyl)-2,2'-((((1,1,3,3-tetramethyldisiloxane-1,3-diyl)-bis(octane-3,1-diyl))bis(azandiyl))bis(carbonyl))bis(cyclohexanedicarboxylic acid, tetrakis(trimethylsilyl)-2,2'-((((1,1,3,3,5,5-hexamethyltrisiloxane-1,5- Diyl)-bis(propane-5,1-diyl))bis(azandiyl))bis(carbonyl))bis(cyclohexanedicarboxylic acid), tetrakis(trimethylsilyl)-2,2'-((((1,1,3,3,5,5,7,7-octamethyltetrasiloxane-1,7-diyl)-bis(propane-7,1-diyl))bis(azandiyl))bis(carbonyl))bis(cyclohexanedicarboxylic acid, tetrakis(trimethylsilyl)-2,2'-((((polymethylpolysiloxane-α,ω-diyl)-bis(propane-ω,α-diyl))bis(azandiyl))bis(carbonyl))bis(cyclohexanedicarboxylic acid), tetrakis(trimethylsilyl)-2,2'-((((2,4,4,6,8,8-hexamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,6-diyl)bis(propane-3,1-diyl))bis(azandiyl))bis(carbonyl))bis(cyclohexanedicarboxylic acid, tetrakis(trimethylsilyl)-2,2'-((((2,4,6,6,8,8-hexamethyl-1,3,5,7,2,4,6,8-tetrao Xatetrasilocane-2,4-diyl)bis(propane-3,1-diyl))bis(azandiyl))bis(carbonyl))bis(cyclohexanedicarboxylic acid), tetrakis(trimethylsilyl)-2,2'-((((2,4,6,8-tetramethyl-4,8-dipropyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,6-diyl)bis(propane-3,1-diyl))bis(azandiyl))bis(carbonyl))bis(cyclohexanedicarboxylic acid, tetrakis(trimethylsilyl)-2,2'-((((2,4,6 ,8-tetramethyl-6,8-dipropyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,4-diyl)bis(propane-3,1-diyl)bis(azandiyl)bis(carbonyl)bis(cyclohexanedicarboxylic acid), tetrakis(trimethylsilyl)-2,2'-((((2,4,6,8-tetramethyl-4,8-bis(trimethoxysilylethyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,6-diyl)bis(propane-3,1-diyl)bis(azandiyl)bis(carbonyl Compounds having two groups represented by X in the molecule, such as bis(cyclohexanedicarboxylic acid), tetrakis(trimethylsilyl)-2,2'-((((2,4,6,8-tetramethyl-6,8-bis(trimethoxysilylethyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,4-diyl)bis(propane-3,1-diyl))bis(azandiyl))bis(carbonyl))bis(cyclohexanedicarboxylic acid; hexakis(trimethylsilyl)-2,2',2''-((((2,4,6-trimethyl-1,3,5,2,4,6-Trioxatrisilocane-2,4,6-triyl)-tris(propane-3,1-diyl))tris(azandiyl))tris(carbonyl))triterephthalic acid, hexakis(trimethylsilyl)-2,2',2''-((((2,4,6,8-tetramethyl-8-propyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,4,6-triyl)-tris(propane-3,1-diyl))bis(azandiyl))tris(carbonyl))triterephthalic acid, hexakis(trimethylsilyl)-2,2',2 ''-((((2,4,6,8-tetramethyl-8-(trimethoxysilylethyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,4,6-triyl)-tris(propane-3,1-diyl))bis(azandiyl))tris(carbonyl))triterephthalic acid, hexakis(trimethylsilyl)-2,2',2''-((((2,4,6-trimethyl-2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilocane-2,4,6-triyl)-tris(propane-3,1-diyl))tris( Azandiyl))tris(carbonyl))tris(cyclohexanedicarboxylic acid),hexakis(trimethylsilyl)-2,2',2''-((((2,4,6,8-tetramethyl-8-(trimethoxysilylethyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,4,6-triyl)-tris(propane-3,1-diyl))bis(azandiyl))tris(carbonyl))tris(cyclohexanedicarboxylic acid),hexakis(trimethylsilyl)-2,2',2''-((((2,4,6,8-tetra Compounds having three X-represented groups in the molecule, such as methyl-8-propyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,4,6-triyl)-tris(propane-3,1-diyl))bis(azandiyl))tris(carbonyl))tris(cyclohexanedicarboxylic acid); octakis(trimethylsilyl)-2,2',2'',2'''-((((2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,4,6,8-tetrayl)-tetrakis(propane-3,Examples include compounds having four groups represented by X in the molecule, such as 1-diyl))tetrakis(azandiyl))tetrakis(carbonyl))tetraphthalic acid and octakis(trimethylsilyl)-2,2',2'',2'''-((((2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2,4,6,8-tetrayl)-tetrakis(propane-3,1-diyl))tetrakis(azandiyl))tetrakis(carbonyl))tetrakis(cyclohexanedicarboxylic acid).

[0030] [2] Compositions containing compounds with a silyl ester structure of amidate The compound (1) of the present invention described above can be used alone, but it may also be used as part of a composition containing an aprotic solvent (hereinafter referred to as "composition 1"), for example, as long as it does not affect compound (1). Specific examples of aprotic solvents include aliphatic hydrocarbon compounds with 5 to 20 carbon atoms such as pentane, hexane, cyclohexane, octane, isooctane, nonane, decane, dodecane, and isododecane; aromatic hydrocarbon compounds with 6 to 10 carbon atoms such as benzene, toluene, and xylene; ether compounds such as diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyltetrahydropyran, cyclopentyl methyl ether, dioxane, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, and dipropylene glycol dialkyl ether; ester compounds such as ethyl acetate, isopropyl acetate, butyl acetate, and γ-butyrolactone; and Examples include nitrile compounds such as cetonitrile, propionitrile, butyronitrile, and isobutyronitrile; amide compounds such as N,N-dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and organosilicon compounds with 1 to 10 silicon elements such as tetraethylsilane, hexamethyldisiloxane, octamethyltrisiloxane, tris(trimethylsiloxy)methylsilane, 3,5-diethyl-1,1,1,3,5,7,7,7-octamethyltetrasiloxane, octamethylcyclotetrasiloxane, decamethyltetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylpentasiloxane. These may be used individually or in combination of two or more. Among these, amide compounds, ether compounds, and ester compounds are preferred in terms of solubility.

[0031] The amount of aprotic solvent used is not particularly limited, but is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass, relative to the mass of compound (1).

[0032] Furthermore, compound (1) of the present invention can also be used, for example, as a curable composition containing an epoxy compound (hereinafter referred to as "composition 2"). The epoxy compound used in composition 2 of the present invention is not particularly limited, and conventionally known compounds can be used. Specific examples include bisphenol-type epoxy compounds, dicyclopentadiene-type epoxy compounds, diaminodiphenylmethane-type epoxy compounds, aminophenol-type epoxy compounds, naphthalene-type epoxy compounds, phenol novolac-type epoxy compounds, biphenyl-type epoxy compounds; hydrogenated biphenol-type epoxy resins, polyfunctional epoxy resins, glycidylamine-type epoxy resins, alicyclic epoxy resins, and heterocyclic-containing epoxy resins, which may be used individually or in combination of two or more. Among these, alicyclic epoxy resins, which exhibit less curing shrinkage when used in heat curing, are preferred. The amount of epoxy compound used is not particularly limited, however, the CO2SiR contained in compound (1) 2 3 or OSiR 2 For a given number of moles of 3, the amount is preferably 0.1 to 20 equivalents, more preferably 0.5 to 20 equivalents, and even more preferably 1 to 10 equivalents.

[0033] Furthermore, the above-mentioned composition 2 can also be used as a curable composition (hereinafter referred to as "composition 3") that includes any or all of a cyclic acid anhydride, a curing catalyst, and an aprotic solvent.

[0034] The cyclic acid anhydride is not particularly limited, and conventionally known cyclic acid anhydrides can be used. Specific examples include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, maleic anhydride, tetrahydrophthalic anhydride, tetrahydromethylphthalic anhydride, hexahydrophthalic anhydride, methylcyclohexane-1,2-dicarboxylic acid anhydride, hymic anhydride, methylhymic anhydride, allyl succinic anhydride, and dodecenyl succinic anhydride, and these may be used individually or in combination of two or more. Among these, methyltetrahydrophthalic anhydride, methylcyclohexane-1,2-dicarboxylic acid anhydride, and Hymic anhydride, which are cyclic acid anhydrides that are liquid at room temperature, are preferred. The amount of cyclic acid anhydride compound used is not particularly limited, but the number of moles of acid anhydride in the cyclic acid anhydride compound is preferably 0.1 to 5.0 equivalents, more preferably 0.5 to 3.0 equivalents, and even more preferably 1.0 to 3.0 equivalents, relative to the number of moles of epoxy groups in compound (1) or the epoxy compound.

[0035] Composition 3 of the present invention cures even without a catalyst, but the curing temperature can be lowered by adding a curing catalyst. The curing catalyst used is not particularly limited, and conventionally known curing catalysts for epoxy resins can be used. For example, amine compounds such as diazabicycloundecene, diazabicyclononene, tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, and salts of these amine compounds; phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium-tetraphenylborate; hexafluoroantimony acid, triphenylsulfonium diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimony acid, hexafluorophosphate triphenylsulfonium diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, and sulfonium salts such as tri-p-tolylsulfonium hexafluorophosphate; [4-(o Examples of iodonium salts include culoxy)phenyl](phenyl)iodonium hexafluoroantimonate, [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium hexafluoroantimonate, bis(4-tert-butylphenyl)iodonium hexafluoroantimonate, 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl) borate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, (4-isobutylphenyl)(p-tolyl)iodonium hexafluorophosphate, and urea compounds such as 3-phenyl-1,1-dimethylurea. These may be used individually or in combination of two or more. The amount of curing catalyst used is not particularly limited, but is 0.1 to 10% by mass, preferably 0.2 to 5% by mass, and more preferably 1 to 5% by mass, relative to the total mass of each component of composition 3.

[0036] Examples of aprotic solvents used in composition 3 of the present invention include those the same as those used in composition 1. The amount of aprotic solvent used is not particularly limited, but is preferably 10 to 90% by mass, more preferably 15 to 85% by mass, and even more preferably 20 to 85% by mass, relative to the total mass of each component of composition 3 excluding the aprotic solvent.

[0037] [3] Method for producing compounds having a silyl ester structure of amidic acid Next, we will describe the method for producing compound (1). Compound (1) of the present invention can be obtained, for example, by reacting a compound having a bissilylamino group represented by the following general formula (2) (hereinafter referred to as "compound (2)") with an acid anhydride compound represented by the following general formula (3) (hereinafter referred to as "compound (3)").

[0038] [ka] (In the formula, R 2 (This expresses the same meaning as above.)

[0039] [ka] (In the formula, A has the same meaning as above.)

[0040] In general formula (2), R 4 This represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 3 to 20, more preferably 3 to 10, which may be interposed by a hydrogen atom, or an oxygen, nitrogen, silicon, sulfur atom, or siloxane bond. R 4 The monovalent hydrocarbon group is the above R 1 Similar substituents can be cited.

[0041] Note, R 4 The monovalent hydrocarbon group may have some or all of its hydrogen atoms substituted with substituents, such substituents include, for example, alkoxy groups having 1 to 3 carbon atoms; halogen atoms such as chlorine, bromine, and iodine atoms; aryl groups having 6 to 10 carbon atoms; aralkyl groups having 7 to 10 carbon atoms; cyano groups, amino groups, acyl groups, carboxyl groups, alkoxyalkyl groups having 1 to 6 carbon atoms, alkoxycarbonyl groups having 1 to 3 carbon atoms, trialkoxysilyl groups having 3 to 9 carbon atoms, alkyldialkoxysilyl groups having 3 to 12 carbon atoms, dialkylalkoxysilyl groups having 3 to 15 carbon atoms, trialkylsilyl groups having 3 to 18 carbon atoms, and the group represented by Y below. R 4 If a siloxane bond is present, it may have a polydialkylsiloxanyl group represented by the general formula (4) described above, or a group containing a cyclic siloxane structure represented by the general formula (5).

[0042] [ka] (In the formula, R 2 * represents the same meaning as above, and *- represents R 4 (This represents the bonding site with the carbon atom.)

[0043] Specific examples of compound (2) include hexamethyldisilazane, heptamethyldisilazane, N,N-bis(trimethylsilyl)allylamine, N,N-bis(trimethylsilyl)octenylamine, N,N-bis(trimethylsilyl)decenylamine, N,N-bis(trimethylsilyl)butylamine, N,N-bis(trimethylsilyl)hexylamine, N,N-bis(trimethylsilyl)octylamine, N,N-bis(trimethylsilyl)aniline, and N,N-bis(trimethylsilyl)aminopropyltrimethoxysylamine. N,N-bis(trimethylsilyl)aminopropylmethyldimethoxysilane, N,N-bis(trimethylsilyl)aminopropyldimethylmethoxysilane, N,N-bis(trimethylsilyl)aminopropyltriethoxysilane, N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane, N,N-bis(trimethylsilyl)aminopropyldimethylethoxysilane, N,N-bis(trimethylsilyl)aminooctyltrimethoxysilane, N,N-bis(trimethylsilyl)aminooctyl N,N-Bis(trimethylsilyl)aminooctyldimethylmethoxysilane, N,N-Bis(trimethylsilyl)aminooctyltriethoxysilane, N,N-Bis(trimethylsilyl)aminooctylmethyldiethoxysilane, N,N-Bis(trimethylsilyl)aminooctyldimethylethoxysilane, N,N-Bis(trimethylsilyl)aminopropylthiopropyltrimethoxysilane, N,N-Bis(trimethylsilyl)aminopropylthiopropylmethyldimethoxysilane, N,N- Bis(trimethylsilyl)aminopropylthiopropyldimethylmethoxysilane, N,N-bis(trimethylsilyl)aminopropylthiomethyltrimethoxysilane, N,N-bis(trimethylsilyl)aminopropylthiomethylmethyldimethoxysilane, N,N-bis(trimethylsilyl)aminopropylthiomethyldimethylmethoxysilane, o-(N,N-bistrimethylsilylamino)(trimethoxysilyl)benzene, m-(N,N-bistrimethylsilylamino)(trimethoxysilyl)benzene, p-(N,Compounds having one bissilylamino group in the molecule, such as N-bistrimethylsilylamino)(trimethoxysilyl)benzene, 1-(N,N-bistrimethylsilylaminopropyl)-3-trimethoxysilylethyl-1,1,3,3-tetramethyldisiloxane, 1-(N,N-bistrimethylsilylaminopropyl)-3-methyldimethoxysilylethyl-1,1,3,3-tetramethyldisiloxane, and 1-(N,N-bistrimethylsilylaminopropyl)-3-trimethoxysilyloctyl-1,1,3,3-tetramethyldisiloxane; N, N,N'N'-Tetrakis(trimethylsilyl)aminoethane, N,N,N'N'-Tetrakis(trimethylsilyl)aminopropane, N,N,N'N'-Tetrakis(trimethylsilyl)aminobutane, N,N,N'N'-Tetrakis(trimethylsilyl)aminohexane, N,N,N'N'-Tetrakis(trimethylsilyl)aminooctane, 1,3-Bis(N,N-bistrimethylsilylaminopropyl)-1,1,3,3-tetramethyldisiloxane, 1,5-Bis(N,N-bistrimethylsilylaminopropyl)-1,1,3,3,5,5- Hexamethyltrisiloxane, 1,7-bis(N,N-bistrimethylsilylaminopropyl)-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,9-bis(N,N-bistrimethylsilylaminopropyl)-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, α,ω-bis(N,N-bistrimethylsilylaminopropyl)-polydimethylpolysiloxane, 1,3-bis(N,N-bistrimethylsilylaminopropyl)-5,7-dipropyl-1,3,5,7-tetramethylcyclotetrasiloxane, Compounds having two bissilylamino groups in their molecule, such as 1,5-bis(N,N-bistrimethylsilylaminopropyl)-3,7-dipropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-bis(N,N-bistrimethylsilylaminopropyl)-5,7-bis(trimethoxysilylethyl)-1,3,5,7-tetramethylcyclotetrasiloxane, and 1,5-bis(N,N-bistrimethylsilylaminopropyl)-3,7-bis(trimethoxysilylethyl)-1,3,5,7-tetramethylcyclotetrasiloxane; 1,3,Examples include compounds having three bissilylamino groups in their molecule, such as 5-tris(N,N-bistrimethylsilylaminopropyl)-1,3,5-trimethylcyclotrisiloxane and 1,3,5-tris(N,N-bistrimethylsilylaminopropyl)-7-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane; compounds having four bissilylamino groups in their molecule, such as 1,3,5,7-tetrakis(N,N-bistrimethylsilylaminopropyl)-1,3,5,7-tetramethylcyclotetrasiloxane; and compounds having numerous bissilylamino groups in their molecule, such as α,ω-dimethoxy-poly(N,N-bistrimethylsilylaminopropyl)(methyl)polysiloxane and α,ω-diethoxy-poly(N,N-bistrimethylsilylaminopropyl)(methyl)polysiloxane.

[0044] Compound (2) may be a commercially available product or may be manufactured. When manufactured, conventionally known methods may be followed. For example, it can be obtained by silylation of an amine compound having a primary amino group with a trialkylchlorosilane compound such as chlorotrimethylsilane, or by hydrosilylation of an alkenyl compound having a bistrimethylsilylamino group with a hydrosilane, hydrosiloxane, etc.

[0045] In general formula (3), R 5 Each of these independently represents a hydrogen atom, a carboxyl group, or a hydroxyl group, but R 5 At least one of these represents a carboxyl group or a hydroxyl group.

[0046] Specific examples of compound (3) include acid anhydrides having a carboxyl group, such as trimellitic anhydride and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride; and acid anhydrides having a hydroxyl group, such as 3-hydroxyphthalic anhydride and 4-hydroxyphthalic anhydride. Among these, acid anhydrides having a carboxyl group are preferred due to the ease of raw material procurement, and trimellitic anhydride is more preferred.

[0047] Compound (3) may be a commercially available product or may be manufactured. If manufactured, conventionally known methods may be followed, for example, by intramolecular dehydration of a tricarboxylic acid compound.

[0048] In the manufacturing method of the present invention, the reaction method of compound (2) and compound (3) is not particularly limited, and compound (3) may be added to compound (2), or compound (2) may be added to compound (3). In this case, the ratio of compound (2) to compound (3) used is not particularly limited, but the amount of compound (3) is preferably 0.8 to 1.2 equivalents, more preferably 0.9 to 1.1 equivalents, and even more preferably 1 equivalent, relative to the number of moles of bissilylamino groups in compound (2).

[0049] The reaction temperature is not particularly limited, but from the viewpoint of product stability, it is preferably -10 to 70°C, more preferably 0 to 50°C, and even more preferably 0 to 40°C. Furthermore, while the reaction time is not particularly limited, from the viewpoint of product stability, it is preferably 1 to 40 hours, more preferably 1 to 20 hours. Furthermore, the above reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon in order to prevent hydrolysis of the product compound (1).

[0050] The above reaction proceeds even without a solvent, but an aprotic solvent can also be used. Suitable solvents are those similar to those exemplified in Composition 1. Among these, amide compounds, ester compounds, and ether compounds are preferred in terms of solubility, and among them, those with a boiling point of 100 to 220°C are preferred.

[0051] Compound (1) can be isolated and purified using any of the standard purification methods in organic synthesis, such as vacuum stripping, various chromatography techniques, treatment with adsorbents, filtration, and distillation. Furthermore, in the manufacturing method of the present invention, since no compounds other than the target product (1) are produced in principle, they may be used without particular isolation or purification. [Examples]

[0052] The present invention will be described more specifically below with reference to examples, comparative examples, and synthesis examples, but the present invention is not limited to the following examples.

[0053] [Example 1-1] Synthesis of Compound 1 [ka] (In the formula, TMS represents a trimethylsilyl group (the same applies hereafter.))

[0054] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 4.8 g (0.025 mol) of trimellitic anhydride and 39.2 g of N-methylpyrrolidone (hereinafter referred to as "NMP") were charged in. The mixture was heated to 60°C to dissolve the trimellitic anhydride. The obtained solution was cooled to 5°C, and 5.0 g (0.025 mol) of N,N-bistrimethylsilylallylamine was added dropwise while cooling in a water bath so as not to exceed 20°C. After the addition was complete, the mixture was stirred at room temperature for 1 hour to obtain liquid compound 1. The infrared absorption spectrum (hereinafter referred to as "IR spectrum") chart of the obtained compound 1 is shown in Figure 1. 1 The H-NMR chart is shown in Figure 2. 1 1H-NMR analysis confirmed the disappearance of the peak around 3.3 ppm originating from the methylene group to which the bissilylamino group is attached. IR analysis revealed the presence of a peak at 1800 cm², characteristic of cyclic acid anhydrides. -1 Nearby stretching vibration peak, 920 cm, characteristic of the bissilylamino group. -1 The nearby stretching vibration peak disappears, and the 1264 cm⁻¹ peak originates from the trimethylsilyl carboxylate. -1 The formation of compound 1 was confirmed by the generation of a stretching vibration peak, and it was obtained as a 20% by mass NMP solution.

[0055] [Examples 1-2] Synthesis of Compound 2 [ka]

[0056] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 7.7 g (0.040 mol) of trimellitic anhydride and 21 g of dipropylene glycol dimethyl ether (hereinafter referred to as "DPGDME") were charged in. The mixture was heated to 60°C to dissolve the trimellitic anhydride. The obtained solution was cooled to 5°C, and 13.6 g (0.041 mol) of N,N-bistrimethylsilylaminopropylmethyldiethoxysilane was added dropwise while cooling in a water bath so as not to exceed 20°C. After the addition was complete, the mixture was stirred at room temperature for 1 hour to obtain liquid compound 2. The IR spectrum chart of the obtained compound 2 is shown in Figure 3. 1 The H-NMR chart is shown in Figure 4. 1 1H-NMR analysis confirmed the disappearance of the peak around 2.7 ppm originating from the methylene group to which the bissilylamino group is attached. IR analysis revealed the presence of a peak at 1800 cm², characteristic of cyclic acid anhydrides. -1 Nearby peak, 920 cm, characteristic of the bissilylamino group. -1 The nearby peak disappears, and the 3307 cm peak originates from the amide group. -1 And 1254 cm derived from trimethylsilyl carboxylate. -1 The formation of compound 2 was confirmed by the presence of a peak, and it was obtained as a 50% by mass DPGDME solution.

[0057] [Examples 1-3] Synthesis of Compound 3 [ka]

[0058] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 7.7 g (0.040 mol) of trimellitic anhydride and 21 g of DPGDME were added. The mixture was heated to 60°C to dissolve the trimellitic anhydride. The obtained solution was cooled to 5°C, and 13.6 g (0.041 mol) of N,N-bistrimethylsilylaminopropyltrimethoxysilane was added dropwise while cooling in a water bath so as not to exceed 20°C. After the addition was complete, the mixture was stirred at room temperature for 1 hour to obtain liquid compound 3. The IR spectral chart of the obtained compound 3 is shown in Figure 5. 1 The 1H-NMR chart is shown in Figure 6. 1 1H-NMR analysis confirmed the disappearance of the peak around 2.7 ppm originating from the methylene group to which the bissilylamino group is attached. IR analysis revealed the presence of a peak at 1800 cm², characteristic of cyclic acid anhydrides. -1 Nearby peak, 920 cm, characteristic of the bissilylamino group. -1 The nearby peak disappears, and the 3469 cm peak originates from the amide group. -1 And 1252 cm derived from trimethylsilyl carboxylate. -1 The formation of compound 3 was confirmed by the presence of a peak, and it was obtained as a 50% by mass DPGDME solution.

[0059] [Examples 1-4] Synthesis of Compound 4 [ka]

[0060] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 19.2 g (0.100 mol) of trimellitic anhydride and 46.1 g of γ-butyrolactone (hereinafter referred to as "GBL") were charged in. The mixture was heated to 90°C to dissolve the trimellitic anhydride. The obtained solution was cooled to 5°C, and 26.9 g (0.0500 mol) of 1,3-bis(N,N-bistrimethylsilylaminopropyl)-1,1,3,3-tetramethyldisiloxane was added dropwise while cooling in a water bath so as not to exceed 20°C. After the addition was complete, the mixture was stirred at room temperature for 1 hour to obtain liquid compound 4. The IR spectrum chart of the obtained compound 4 is shown in Figure 7. 1 The 1H-NMR chart is shown in Figure 8. 1¹H-NMR analysis confirmed the disappearance of the peak around 2.7 ppm originating from the methylene group to which the bissilylamino group is attached. IR analysis revealed the presence of a peak at 1800 cm², characteristic of cyclic acid anhydrides. -1 Nearby peak, 920 cm, characteristic of the bissilylamino group. -1 The nearby peak has disappeared, and the 3366 cm peak originates from the amide group. -1 The peak is derived from trimethylsilyl carboxylate and 1253 cm². -1 The formation of compound 4 was confirmed by the presence of a peak, and it was obtained as a 50% by mass GBL solution.

[0061] [Examples 1-5] Synthesis of Compound 5 [ka]

[0062] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 7.7 g (0.040 mol) of trimellitic anhydride and 42 g of N,N-dimethylformamide (hereinafter referred to as "DMF") were charged in. The mixture was heated to 60°C to dissolve the trimellitic anhydride. The obtained solution was cooled to 5°C, and 10.5 g (0.010 mol) of 1,3,5,7-tetrakis(N,N-bistrimethylsilylaminopropyl)-1,3,5,7-tetramethylcyclotetrasiloxane was added dropwise while cooling in a water bath so as not to exceed 20°C. After the addition was complete, the mixture was stirred at 40°C for 1 hour to obtain liquid compound 5. The IR spectrum chart of the obtained compound 5 is shown in Figure 9. 1 The H-NMR chart is shown in Figure 10. 1 1H-NMR analysis confirmed the disappearance of the peak around 2.7 ppm originating from the methylene group to which the bissilylamino group is attached. IR analysis revealed the presence of a peak at 1800 cm², characteristic of cyclic acid anhydrides. -1 Nearby peak, 920 cm, characteristic of the bissilylamino group. -1 The nearby peak disappears, and the 1255 cm peak originates from trimethylsilyl carboxylate. -1The formation of compound 5 was confirmed by the presence of a peak, and it was obtained as a 30% by mass DMF solution.

[0063] [Examples 2-1 to 2-12] The compounds used in Examples 2-1 to 2-12 are shown below. (1) Compounds containing a silyl ester structure of amidate Compounds 1-5 synthesized in Examples 1-1 to 1-5 above

[0064] (2) Epoxy compounds 3,4-Epoxycyclohexylmethyl-3'4'-Epoxycyclohexanecarboxylate

[0065] [ka]

[0066] (3) Cyclic acid anhydrides Methylcyclohexane-1,2-dicarboxylic acid anhydride [ka]

[0067] (4) Curing catalyst 2-Ethylimidazole [ka]

[0068] (5) Aprotic solvents NMP DPGDME GBL DMF

[0069] A curable composition was prepared by blending compounds 1-5, epoxy compounds, cyclic acid anhydrides, aprotic solvents, and, if necessary, a curing catalyst in the proportions shown in Table 1 below. The appearance of the prepared curable composition was evaluated as follows: "○" if it was colorless and transparent, and "×" if there were undissolved particles or turbidity. Next, 5g samples of each curable composition were placed on a fluororesin petri dish and heated at 120°C for 1 hour, followed by 180°C for 2 hours to cure. A "○" was used if the composition cured, and a "×" was used if it did not. "Not curing" refers to a state where the composition remained fluid. These results are also shown in Table 1.

[0070] [Table 1]

[0071] As shown in Table 1, the curable compositions containing compounds with the silyl ester structure of the amidoic acid of the present invention obtained in Examples 1-1 to 1-5 are neutral and stable compositions with excellent solubility. Furthermore, the compositions of the present invention can be cured by heating them while introducing imide groups into epoxy compounds.

Claims

1. A compound having a silyl ester structure of amidoic acid represented by the following general formula (1). 【Chemistry 1】 [wherein, R 1 represents a hydrogen atom, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms which may have an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom or a siloxane bond interposed therebetween, and R 2 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 3 each independently represents a hydrogen atom, CO 2 SiR 2 3 , OSiR 2 3 (wherein, R 2 represents the same meaning as described above.), but at least one of R 3 represents CO 2 SiR 2 3 or OSiR 2 3 represents, and A represents a benzene ring or a cyclohexane ring.]

2. A composition comprising a compound having a silyl ester structure of an amidic acid as described in claim 1, and an aprotic solvent.

3. A curable composition comprising a compound having a silyl ester structure of an amide acid as described in claim 1 and an epoxy compound.

4. Furthermore, the curable composition according to claim 3, further comprising a cyclic acid anhydride.

5. Furthermore, the curable composition according to claim 4, further comprising an aprotic solvent.

6. Furthermore, the curable composition according to any one of claims 3 to 5 further comprises a curing catalyst selected from the group consisting of amine compounds, salts of amine compounds, phosphine compounds, phosphonium salts, sulfonium salts, iodonium salts, and urea compounds.

7. A cured product obtained by curing the curable composition according to claim 3 or claim 4.

8. The following general formula (2) 【Chemistry 2】 (In the formula, R 4 R represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hydrogen atom, or an oxygen, nitrogen, silicon, sulfur atom, or siloxane bond interposed therein. 2 (This expresses the same meaning as above.) A compound having a bissilylamino group represented by the following general formula (3) 【Transformation 3】 (In the formula, A has the same meaning as above, R 5 Each of these independently represents a hydrogen atom, a carboxyl group, or a hydroxyl group, but R 5 At least one of them represents a carboxyl group or a hydroxyl group. A method for producing a compound having an amidic acid silyl ester structure according to claim 1, comprising reacting an acid anhydride compound represented by [the specified formula].

9. A method for producing a compound having a silyl ester structure of an amidic acid according to claim 8, wherein the reaction is carried out in an aprotic polar solvent.

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