Organosilicon compound, production method thereof, and curable composition

Abstract

An organosilicon compound represented by general formula (1) can reduce odor problems while having high hydrolyzability. In the formula, R1 represents a monovalent hydrocarbon group, NHR5 or an alkoxy group; R2 represents an oxygen atom or a divalent hydrocarbon group; R3 represents an oxygen atom or a divalent hydrocarbon group, wherein the divalent hydrocarbon group may have a sulfur atom or 1-5 silicon atoms and / or siloxane bonds intervening therein; R4 represents a monovalent hydrocarbon group; R5 represents a monovalent hydrocarbon group terminated with any of an alkoxy group, a dialkylamino group and an alkoxysilyl group; R6 and R7 each represent a monovalent hydrocarbon group and may be linked to each other to form a cyclic structure together with a nitrogen atom; n is an integer of 0-1,000; p is 0 or 1; q is 2 or 3; and X represents -R3-SiR4 p(NHR5)q(NR6R7)3-p-q group or a monovalent hydrocarbon group.

Description

Organosilicon compounds, methods for producing the same, and curable compositions

[0001] This invention relates to organosilicon compounds, methods for producing the same, and curable compositions.

[0002] Silicone oil is a polymer composed of linked dimethylsiloxane units, and its properties are exhibited through a combination of the characteristics of inorganic siloxane bonds, organic methyl groups, and the three-dimensional structure of the polymer. Such properties include heat resistance, cold resistance, electrical properties, water resistance, chemical resistance, mold release properties, water repellency, and defoaming properties.

[0003] Conventional silicone oils do not form a film because they do not possess hydrolyzable groups. Therefore, even when silicone oil is mixed with a film-forming silicone compound that has hydrolyzable groups, the molecules do not integrate, and the aforementioned characteristics cannot be imparted to the film-forming silicone compound, nor can they be maintained over a long period. For this reason, silicone oils having hydrolyzable groups such as trimethoxysilyl groups and triethoxysilyl groups at their ends have been developed (Patent Document 1).

[0004] Furthermore, Patent Document 2 reports a compound having an alkoxysilyl group at the end of the molecule via a sylalkylene bond. Compared to the compound in Patent Document 1, this compound is more susceptible to hydrolysis because the distance between the silicone oil and the hydrolyzable group is greater. Patent Document 3 reports a silicone oil in which the silicone oil structure and the alkoxysilyl group are linked by a sulfide-methylene bond. Due to the effect of the sulfide-methylene bond, this compound has higher reactivity compared to the compounds in Patent Documents 1 and 2, and hydrolysis proceeds even more easily.

[0005] Furthermore, Patent Document 4 reports disiloxane compounds having silazane structures at both ends of the molecule, such as 1,3-bis(bis(dimethylamino)methyl)silylethyl-1,1,3,3-tetramethyldisiloxane and 1,3-bis(bis(diethylamino)methyl)silylethyl-1,1,3,3-tetramethyldisiloxane. Compositions of these compounds with silanol-modified silicone oils at both ends are prepared, and the physical properties of cured products obtained from these compositions are evaluated. Generally, the Si-N bond in silazane compounds is more reactive than the alkoxysilyl group (Si-OR, where R is a monovalent hydrocarbon group) and readily reacts with moisture, alcohol, and silanol in the air. For this reason, it is said that by mixing silanol-modified silicone oils at both ends with the above compounds, silazane-modified silicone oils at both ends are produced, exhibiting excellent hydrolytic and curable properties.

[0006] Japanese Patent Publication No. 7-196946, Japanese Patent Publication No. 2002-1665069, Japanese Patent Publication No. 2017-203025, Chinese Patent No. 103183814

[0007] However, the compounds described in Patent Documents 1 and 2 are silicone oils having alkoxysilyl groups, but alkoxysilyl groups generally have low reactivity. Therefore, there is a problem in that it takes a long time for the film to form.

[0008] The compound described in Patent Document 3 exhibits higher hydrolysis properties compared to the compounds described in Patent Documents 1 and 2, allowing for the formation of a cured film in a short time. However, due to its high reactivity, the generally stable siloxane structure is easily hydrolyzed. For example, if a cured film formed from the compound described in Patent Document 3 is exposed to high temperature and high humidity conditions, the film may soften and deteriorate. There are also issues regarding odors derived from sulfide bonds.

[0009] The composition obtained from the compound described in Patent Document 4 and the silanol-modified silicone oil at both ends contains a highly reactive silazane bond, allowing for the production of a cured film in a short time. However, compounds containing a secondary amine-derived structure in the silazane portion exhibit poor reactivity with the silanol-modified silicone oil at both ends due to steric hindrance. This presents a challenge in obtaining a uniform composition, particularly when incorporating metal catalysts. Furthermore, the generation of amine components with low boiling points and high volatility during hydrolysis poses an odor problem. To improve the odor, it is thought that a silazane compound derived from a high-boiling-point amine compound could be used. However, using such an amine compound increases the molecular weight of the substituent on the nitrogen atom, making it less compatible with water and further worsening the hydrolyzability, creating a new problem.

[0010] This invention has been made in view of the above circumstances, and aims to provide an organosilicon compound that has high hydrolytic properties while improving odor problems, a method for producing the same, and a curable composition thereof.

[0011] As a result of diligent research to solve the above problems, the inventors of the present invention have found that an organosilicon compound using an amine with a highly water-soluble substituent in the silazane moiety can improve odor problems while exhibiting high hydrolysis properties. Furthermore, they have found that the cured film obtained from a curable composition containing this organosilicon compound does not have an unstable structure, and therefore its degradation is suppressed even under high temperature and high humidity conditions, thus completing the present invention.

[0012] In other words, the present invention relates to: 1. An organosilicon compound represented by the following general formula (1), [In the formula, R 1 These are, independently, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, NHR 5 , or represents an alkoxy group having 1 to 3 carbon atoms, R 2 R represents an oxygen atom or an unsubstituted divalent hydrocarbon group having 2 to 20 carbon atoms. 3each independently represents an oxygen atom or a substituted or unsubstituted divalent hydrocarbon group having 2 to 20 carbon atoms, and this divalent hydrocarbon group may have a sulfur atom or 1 to 5 silicon atoms and / or a siloxane bond intervening therein, R 4 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, R 5 each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms and having a group selected from an alkoxy group, a dialkylamino group, and an alkoxysilyl group at the terminal, R 6 and R 7 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms, and these may combine with each other to form a ring structure together with a nitrogen atom, n is an integer of 0 to 1000, p is 0 or 1, q is 2 or 3, X is -R 3 -SiR 4 p (NHR 5 ) q (NR 6 R 7 ) 3-p-q (wherein R 3 to R 7 , p, and q have the same meanings as described above.) group, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. ] 2. The following general formula (2) (wherein R 1 , R 2 , and n have the same meanings as described above, and Y represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms.) and a Si-H-containing compound represented by the following general formula (3) (wherein R 8 represents a single bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms, and this divalent hydrocarbon group may have 1 to 5 silicon atoms and / or a siloxane bond intervening therein, r is 0 or 1, R 4 , R 6 , and R 7 have the same meanings as described above.) a silazane compound having an alkenyl group at the terminal is reacted in the presence of a platinum catalyst, and then the following general formula (4) (wherein R5 ) represents the same meaning as above. 3. A method for producing an organosilicon compound, comprising the step of performing an amine exchange reaction on an amine compound represented by ) in the presence of an acidic compound with a pKa of 4 to 12 and an aprotic polar solvent. 4. The following general formula (5) (In the formula, R 9 R represents a single bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms. 1 , R 2 , R 8 And n have the same meaning as above, and Z is R 9 -CH=CH2 or represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms.) A terminally unsaturated bond-containing compound represented by the following general formula (6) (In the formula, R 4 The above has the same meaning as above, and m is 0 or 1.) After reacting a hydrogen chlorosilane compound represented by ) in the presence of a platinum catalyst, the following general formula (4) (In the formula, R 5) has the same meaning as above. ) A method for producing an organosilicon compound 1, comprising the steps of reacting an amine compound represented by the general formula (1) in the presence of an aprotic polar solvent, liquefying the hydrochloride salt of the resulting amine compound in the presence of an aprotic polar solvent, performing liquid-liquid separation of a layer containing the organosilicon compound represented by the general formula (1) and a layer containing the hydrochloride salt of the amine compound and an aprotic polar solvent, and removing the layer containing the hydrochloride salt of the amine compound and an aprotic polar solvent by liquid-liquid separation; 5. A method for producing an organosilicon compound 4, wherein the aprotic polar solvent is a nitrile solvent; 6. A method for producing an organosilicon compound 4 or 5, comprising the step of neutralizing the layer containing the organosilicon compound with a solid basic compound after the step of removal by liquid-liquid separation; 7. A curable composition containing the organosilicon compound 1; 8. A curable composition 7 containing a curing catalyst; 9. A curable composition 8 where the curing catalyst is an aminosilane compound; 10. A cured product of the organosilicon compound 1; 11. 12. A coated substrate having a cured product of any of the curable compositions 7 to 9, and a coating film formed thereon, wherein the coating film is made of the cured product of 10 or 11.

[0013] The organosilicon compound of the present invention is highly compatible with water, has high hydrolytic properties, produces little odor even when amine components are generated during hydrolysis, and provides a cured film that exhibits excellent stability even under high temperature and high humidity conditions.

[0014] This figure shows the IR spectrum of the compound obtained in Example 1-1. 1 This figure shows the 1H-NMR spectrum. This figure shows the IR spectrum of the compound obtained in Example 1-2. 1 This figure shows the 1H-NMR spectrum. This figure shows the IR spectrum of the compounds obtained in Examples 1-3. 1 This figure shows the 1H-NMR spectrum. This figure shows the IR spectrum of the compounds obtained in Examples 1-4. 1This figure shows the 1H-NMR spectrum. This figure shows the IR spectrum of the compounds obtained in Examples 1-5. 1 This figure shows the 1H-NMR spectrum. This figure shows the IR spectrum of the compounds obtained in Examples 1-6. 1 This figure shows the 1H-NMR spectrum. This figure shows the IR spectrum of the compounds obtained in Examples 1-7. 1 This figure shows the 1H-NMR spectrum. This figure shows the IR spectrum of the compounds obtained in Examples 1-8. 1 This figure shows the 1H-NMR spectrum. This figure shows the IR spectrum of the compounds obtained in Examples 1-9. 1 This figure shows the 1H-NMR spectrum. This figure shows the IR spectrum of the compounds obtained in Examples 1-10. 1 This is a diagram showing the 1H-NMR spectrum.

[0015] The present invention will be described in detail below. [1] Organosilicon compound The organosilicon compound of the present invention (hereinafter referred to as "compound (1)") is represented by the following general formula (1).

[0016]

[0017] In general formula (1), R 1 Each of these independently comprises 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, and NHR 5 R represents either a carbon-1 to carbon-3 alkoxy group. 1The 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, 1-propenyl, butenyl, and pentenyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenethyl groups. Among these, methyl, ethyl, propyl, and phenyl groups are preferred due to the ease of raw material procurement.

[0018] R 1 Specific examples of alkoxy groups having 1 to 3 carbon atoms include methoxy, ethoxy, n-propoxy, and isopropoxy groups. Among these, methoxy and ethoxy groups are preferred due to the ease of raw material procurement and the ability to shorten the touch-dry time.

[0019] Note R 1 The monovalent hydrocarbon group may have some or all of its hydrogen atoms substituted with fluorine atoms. Specific examples of monovalent hydrocarbon groups substituted with fluorine atoms include fluoroalkyl groups such as (3,3,3-trifluoro)propyl, (3,3,4,4,5,5,6,6,6)nonafluorohexyl, and (3,3,4,4,5,5,6,6,7,7,8,8,8)-tridecafluorooctyl.

[0020] In general formula (1), R 2 R represents an oxygen atom or an unsubstituted divalent hydrocarbon group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms. 2The divalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkylene groups such as ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, and decylene; branched alkylene groups such as methyltrimethylene and methyltetramethylene; cyclic alkylene groups such as cyclohexylene and methylenecyclohexylenemethylene; linear alkenylene groups such as butenylene, hexenylene, and octenylene; branched alkenylene groups such as isobutenylene; arylene groups such as phenylene; and aralkylene groups such as methylenephenylene, methylenephenylmethylene, and ethylenephenylethylene. Among these, linear alkylene groups and aralkylene groups having 2 to 10 carbon atoms are preferred due to the ease of obtaining raw materials and the hardness of the resulting coating.

[0021] In general formula (1), R 3 Each independently represents an oxygen atom or a substituted or unsubstituted divalent hydrocarbon group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and this divalent hydrocarbon group may have a sulfur atom or 1 to 5 silicon atoms and / or a siloxane bond interposed therein. 3 As for the divalent hydrocarbon group, R 2 Similar examples include the above.

[0022] R 3 Examples of divalent hydrocarbon groups that involve a sulfur atom include alkylentioalkylene groups, specifically methylenethioethylene, methylenethiooctylene, propylenethioethylene, propylenethiooctylene, octylenethioethylene, and octylenethiooctylene groups.

[0023] R 3Examples of divalent hydrocarbon groups when 1 to 5 silicon atoms are interposed include alkylenedialkylsilylalkylene, alkylenedialkylsilylalkylenedialkylsilylalkylene, ariadialkylsilylalkylene, alkylenedialkylsilylariadialkylsilylalkylene groups, and specifically, ethylenedimethylsilylethylene, ethylenedimethylsilylethylenedimethylsilylethylene, ethylenediphenylsilylethylene, phenylenedimethylsilylethylene, and ethylenedimethylsilylphenylenedimethylsilylethylene groups. 3 When 1 to 5 siloxane bonds are interposed, the divalent hydrocarbon group may have an oligodialkylsiloxanyl group represented by the following general formula (7), or a group containing a cyclic siloxane structure represented by the following general formula (8) or (9).

[0024] (In the formula, a is 1, 2, or 3, and b is 0, 1, or 2, preferably 1.)

[0025] In general formula (7), R 10 Each of these is independently 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. 10 As for the monovalent hydrocarbon group, R 1 Similar groups to those exemplified above can be cited, and among them, linear alkyl groups, alkenyl groups, and aryl groups are preferred from the viewpoint of ease of raw material procurement. 10 The monovalent hydrocarbon group may have some or all of its hydrogen atoms substituted with fluorine atoms. A specific example of a monovalent hydrocarbon group substituted with fluorine atoms is R 1 Similar substituents can be cited.

[0026] In general formulas (8) and (9), R 11 Each of these is independently 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. 11 As for the monovalent hydrocarbon group, R 10 Similar substituents can be cited.

[0027] In general formula (1), R 4 Each of these is independently an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. 4 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, and n-hexyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and texyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and pentenyl; and aryl groups such as phenyl. Among these, R 4 From the viewpoint of ease of raw material procurement, linear alkyl groups, alkenyl groups, and aryl groups are preferred, with methyl groups being the most preferred.

[0028] In general formula (1), R 5 Each of these is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 3 to 6 carbon atoms, each independently having one of the following at its terminus: an alkoxy group, a dialkylamino group, or an alkoxysilyl group. The above R is an example of this monovalent hydrocarbon group. 1 Examples of groups similar to those exemplified above include those with 1 to 6 carbon atoms, and more preferably those with 1 to 3 carbon atoms, as alkyl groups of the alkoxy group, dialkylamino group, and alkoxysilyl group. Examples of these alkyl groups include those with 1 to 6 carbon atoms. 4 Examples similar to the base exemplified above can be given.

[0029] R 5Specific examples include alkoxyalkyl groups such as methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, propoxypropyl, and isopropoxypropyl; dialkylaminoalkyl groups such as dimethylaminoethyl, dimethylaminopropyl, diethylaminoethyl, and diethylaminopropyl; trialkoxysilylalkyl groups such as trimethoxysilylmethyl, triethoxysilylmethyl, trimethoxysilylpropyl, triethoxysilylpropyl, trimethoxysilyloctyl, and triethoxysilyloctyl; and alkyldialkoxysilylalkyl groups such as methyldimethoxysilylmethyl, methyldiethoxysilylmethyl, methyldimethoxysilylpropyl, methyldiethoxysilylpropyl, methyldimethoxysilyloctyl, and methyldiethoxysilyloctyl. Examples include trialkoxysilylalkylaminoalkyl groups such as trimethoxysilylpropylaminoethyl, triethoxysilylpropylaminoethyl, trimethoxysilyloctylaminoethyl, and trimethoxysilylpropylamino(methyl)ethyl; trialkoxysilylalkylaminoalkylaminoalkyl groups such as trimethoxysilylpropylaminoethylaminoethyl; alkyldialkoxysilylalkylaminoalkyl groups such as methyldimethoxysilylpropylaminoethyl, methyldiethoxysilylpropylaminoethyl, methyldimethoxysilyloctylaminoethyl, and methyldimethoxysilylpropylamino(methyl)ethyl; and alkyldialkoxysilylalkylaminoalkylaminoalkyl groups such as methyldimethoxysilylpropylaminoethylaminoethyl. Among these, R 5 From the viewpoint of ease of raw material procurement, safety, and curability of the product, alkoxyalkyl groups, trialkoxysilylalkyl groups, and alkyldialkoxysilyl groups are preferred, and methoxypropyl groups, ethoxypropyl groups, trimethoxysilylpropyl groups, and triethoxysilylpropyl groups are more preferred.

[0030] In general formula (1), R 6 , R 7 Each of these independently represents an unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms. 6 , R7 The monovalent hydrocarbon group can be linear or branched, and specific examples include linear alkyl groups such as methyl, ethyl, n-propyl, and n-butyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and alkenyl groups such as allyl and butenyl. Among these, methyl and ethyl groups are preferred due to the ease of raw material procurement.

[0031] Note R 6 and R 7 These atoms may bond with each other to form a ring structure, preferably a ring structure having 2 to 10 carbon atoms, and this ring structure may contain at least one element selected from the group consisting of O and N in addition to the nitrogen atom in a part of the ring. Specific examples of such ring structures include pyrrolidine, piperidine, piperazine, N-methylpiperazine, and morpholine rings.

[0032] In general formula (1), n ​​is 0 to 1000, preferably 0 to 200, more preferably 0 to 100, and even more preferably 0 to 40. Furthermore, when compound (1) is used alone, n is preferably 3 to 200, more preferably 6 to 100, and even more preferably 8 to 40, in order to reduce curing shrinkage of the cured product obtained from the product while ensuring hardness and providing sufficient water repellency. On the other hand, when compound (1) is used as a crosslinking agent in a composition with other components, n is preferably 0 to 40, more preferably 0 to 10, and even more preferably 0 to 6, in order to increase the crosslinking density of the cured product obtained from the composition. p is independently 0 or 1, and q is independently 2 or 3.

[0033] In general formula (1), X is R 3 -SiR 4 p (NHR 5 ) q (NR 6 R 7 ) 3-p-q (In the formula, R 3 ~R 7n, p, and q have the same meanings as above.) represent a group, or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 6 carbon atoms. The monovalent hydrocarbon group of X is as above R 1 Examples of groups similar to those exemplified above include methyl, n-butyl, tert-butyl, and hexyl groups, which are preferred due to the ease of raw material procurement. Note that some or all of the hydrogen atoms in the above monovalent hydrocarbon groups may be substituted with fluorine atoms. Specific examples of monovalent hydrocarbon groups substituted with fluorine atoms include R 1 Similar substituents can be cited.

[0034] Specific examples of compounds represented by general formula (1) include, but are not limited to, those represented by the following formula. In the following formula, Me represents a methyl group, Et represents an ethyl group, Bu represents an n-butyl group, and TMS represents a trimethylsilyl group.

[0035] (In the formula, n has the same meaning as above.)

[0036] (In the formula, n has the same meaning as above.)

[0037] (In the formula, n has the same meaning as above.)

[0038] (In the formula, n has the same meaning as above.)

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

[0040] (In the formula, n has the same meaning as above.)

[0041] (In the formula, n has the same meaning as above.)

[0042] (In the formula, n has the same meaning as above.)

[0043] (In the formula, n has the same meaning as above.)

[0044] (In the formula, n represents the same meaning as described above.)

[0045] (In the formula, n represents the same meaning as described above.)

[0046] (In the formula, n represents the same meaning as described above.)

[0047] The organosilicon compound of the present invention uses an amine compound having high water solubility and low volatility at the silazane site, so that even if an amine component is generated during hydrolysis, it is difficult to feel an odor. Further, since the above organosilicon compound has a highly water-soluble site, it is easily miscible with water and has high hydrolyzability. Furthermore, since the above organosilicon compound does not have a characteristic structure in the main chain having a silazane structure, the cured film obtained using it exhibits excellent stability even under high-temperature and high-humidity conditions.

[0048] [2] Method for producing organosilicon compound The above compound (1) is, for example, an Si—H-containing compound represented by the following general formula (2) (hereinafter referred to as “compound (2)”) and a silazane compound having an alkenyl group at the terminal represented by the following general formula (3) (hereinafter referred to as “compound (3)”). After reacting in the presence of a platinum catalyst, an amine compound represented by the following general formula (4) (hereinafter referred to as “compound (4)”) is subjected to an amine exchange reaction in the presence of an acidic compound having a pKa of 4 to 12 and an aprotic polar solvent (hereinafter referred to as “production method A”), or a method in which a terminal unsaturated bond-containing compound represented by the following general formula (5) (hereinafter referred to as “compound (5)”) and a hydrogen chlorosilane compound represented by the following general formula (6) (hereinafter referred to as “compound (6)”) are reacted in the presence of a platinum catalyst, and then reacted with compound (4) in the presence of an aprotic polar solvent (hereinafter referred to as “production method B”).

[0049] (In the formula, R 1 , R 2 , R 4 ~ R 7 , and n represent the same meaning as described above, r is 0 or 1, and m is 0 or 1.)

[0050] (1) Manufacturing Method A First, manufacturing method A will be explained. Manufacturing method A is a method in which a Si-H-containing compound and a silazane compound having an alkenyl group at the terminal are reacted in the presence of a platinum catalyst, and then an amine compound is subjected to an amine exchange reaction in the presence of an acidic compound with a pKa of 4 to 12 and an aprotic polar solvent.

[0051] In general formula (2), Y represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. The monovalent hydrocarbon group of Y is R as described above. 1 Similar groups to those exemplified above can be cited, and among them, hydrogen atoms, methyl, n-butyl, tert-butyl, and hexyl groups are preferred due to the ease of raw material procurement.

[0052] Specific examples of compound (2) include pentamethyldisiloxane, 1,1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,1,3,3,5,5,7,7-nonamethyltetrasiloxane, 1,1,1,3,3,5,5,7,7,9,9-undecamethylpentasiloxane, 1-butyl-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1-hexyl-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1-octyl-1,1,3,3,5,5,7,7, Examples include 9,9-decamethylpentasiloxane, 1-phenylethyl-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1-tris(trimethylsiloxy)silylethyl-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, α-butyl-ω-hydro-polydimethylpolysiloxane, tetramethyldisiloxane, hexamethyltrisiloxane, octamethyltetrasiloxane, decamethylpentasiloxane, and α,ω-dihydropolydimethylpolysiloxane.

[0053] In general formula (3), R 8 R represents a single bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, and this divalent hydrocarbon group may have 1 to 5 silicon atoms and / or siloxane bonds interposed therein. 8 The divalent hydrocarbon group is the above R2 In addition to those similar to the groups exemplified above, a methylene group is also included. Among these, a single bond and an alkylene group are preferred from the viewpoint of ease of raw material procurement. R 8 When R is a sulfur atom, or when 1 to 5 silicon atoms and / or a siloxane bond are interposed, groups similar to the above R 3 are included.

[0054] Specific examples of compound (3) include bisdimethylaminomethylvinylsilane, bisdiethylaminomethylvinylsilane, bisdibutylaminomethylvinylsilane, bismorpholinomethylvinylsilane, bis-4-methylpiperazine-1-ylmethylvinylsilane, bisdimethylaminomethoxyvinylsilane, bisdiethylaminomethoxyvinylsilane, bisdibutylaminomethoxyvinylsilane, bismorpholinomethoxyvinylsilane, bis-4-methylpiperazine-1-ylmethoxyvinylsilane, bisdimethylaminoethoxyvinylsilane, and bisdiethyl Aminoethoxyvinylsilane, bis-dibutylaminoethoxyvinylsilane, bis-morpholinoethoxyvinylsilane, bis-4-methylpiperazine-1-ylethoxyvinylsilane, dimethylaminodimethylallylsilane, diethylaminodimethylallylsilane, dibutylaminodimethylallylsilane, morpholinodimethylallylsilane, 4-methylpiperazine-1-yldimethylallylsilane, dimethylaminomethoxymethylallylsilane, diethylaminomethoxymethylallylsilane, dibutylaminomethoxymethylallylsilane, morpholinomethoxymethyl Tylallylsilane, 4-methylpiperazine-1-ylmethoxymethylallylsilane, dimethylaminoethoxymethylallylsilane, diethylaminoethoxymethylallylsilane, dibutylaminoethoxymethylallylsilane, morpholinoethoxymethylallylsilane, 4-methylpiperazine-1-ylethoxymethylallylsilane, dimethylaminodimethoxyallylsilane, diethylaminodimethoxyallylsilane, dibutylaminodimethoxyallylsilane, morpholinodimethoxyallylsilane, 4-methylpiperazine-1-yldimethoxyallylsilane , bisdimethylaminomethylallylsilane, bisdiethylaminomethylallylsilane, bisdibutylaminomethylallylsilane, bismorpholinomethylallylsilane, bis-4-methylpiperazine-1-ylmethylallylsilane, bisdimethylaminomethoxyallylsilane, bisdiethylaminomethoxyallylsilane, bisdibutylaminomethoxyallylsilane, bismorpholinomethoxyallylsilane, bis-4-methylpiperazine-1-ylmethoxyallylsilane, bisdimethylaminoethoxyallylsilane, bisdiethylaminoethoxyallylsilane,Bis-dibutylaminoethoxyarylsilane, bismorpholinoethoxyarylsilane, bis-4-methylpiperazine-1-ylethoxyarylsilane, bisdimethylaminomethyloctenylsilane, bis-diethylaminomethyloctenylsilane, bis-dibutylaminomethyloctenylsilane, bismorpholinomethyloctenylsilane, bis-4-methylpiperazine-1-ylmethyloctenylsilane, bisdimethylaminomethoxyoctenylsilane, bis-diethylaminomethoxy Octenylsilane, bis-dibutylaminomethoxyoctenylsilane, bismorpholinomethoxyoctenylsilane, bis-4-methylpiperazine-1-ylmethoxyoctenylsilane, bisdimethylaminoethoxyoctenylsilane, bis-diethylaminoethoxyoctenylsilane, bis-dibutylaminoethoxyoctenylsilane, bismorpholinoethoxyoctenylsilane, bis-4-methylpiperazine-1-ylethoxyoctenylsilane, 1-vinyl-3-bisdiethylaminomethylaminoethoxyoctenylsilane Bis-dialkylaminoalkyl alkenyl methyl ethyl 1,1,3,3-tetramethyldisiloxane, 1-vinyl-5-bis-diethylaminomethylethyl 1,1,3,3,5,5-hexamethyltrisiloxane, 1-vinyl-7-bis-diethylaminomethylethyl 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-vinyl-9-bis-diethylaminomethylethyl 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, etc. Examples of tris(dialkylamino)alkenylsilanes include tris(dimethylamino)vinylsilane, tris(morpholino)vinylsilane, tris(hexamethyleneimino)vinylsilane, tris(dimethylamino)allylsilane, tris(morpholino)allylsilane, tris(hexamethyleneimino)allylsilane, tris(dimethylamino)octenylsilane, tris(morpholino)octenylsilane, tris(hexamethyleneimino)octenylsilane, and other tris(dialkylamino)alkenylsilanes.

[0055] The mixing ratio of compound (2) and compound (3) is not particularly limited, but from the viewpoint of productivity, the amount of compound (3) is preferably 1.0 to 1.5 moles, more preferably 1.0 to 1.2 moles, and even more preferably 1.0 to 1.05 moles, of compound (3) per mole of Si-H contained in compound (2).

[0056] When compound (2) and compound (3) are reacted, a platinum compound is used as a catalyst. Specific examples of this platinum compound include chloroplatinic acid, an alcoholic solution of chloroplatinic acid, a toluene or xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, platinum-activated carbon, and the like. The amount of platinum compound used is not particularly limited, but from the viewpoint of productivity, it is preferably 0.000001 to 0.2 moles, more preferably 0.00001 to 0.1 moles, per mole of unsaturated bonds contained in compound (3).

[0057] The temperature of the above reaction is not particularly limited, but from the viewpoint of product stability, it is preferably 0 to 200°C, more preferably 20 to 150°C. The reaction time is also not particularly limited, but from the viewpoint of product stability, it is preferably 1 to 40 hours, more preferably 1 to 20 hours. The above reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon in order to prevent deactivation of the catalyst and hydrolysis of compound (2) and compound (3).

[0058] The above reaction can proceed without a solvent, but a solvent may also be used. Specific examples of solvents include aliphatic hydrocarbon solvents with 5 to 20 carbon atoms such as pentane, hexane, cyclohexane, heptane, octane, nonane, decane, isooctane, and isododecane; aromatic hydrocarbon solvents with 6 to 10 carbon atoms such as benzene, toluene, and xylene; and nitrile solvents such as acetonitrile. These solvents may be used individually or in mixtures of two or more.

[0059] The mixing ratio of the reaction product of compound (2) and compound (3) to compound (4) is not particularly limited, but is preferably 0.5 to 1.2 moles, more preferably 0.75 to 1.0 mole, relative to the number of moles of amino groups contained in compound (3).

[0060] Specific examples of compound (4) include alkoxyalkylamines such as methoxyethylamine, methoxypropylamine, ethoxyethylamine, ethoxypropylamine, propoxypropylamine, and isopropoxypropylamine; dialkylaminoalkylamines such as dimethylaminoethylamine, dimethylaminopropylamine, diethylaminoethylamine, and diethylaminopropylamine; trialkoxysilylalkylamines such as trimethoxysilylmethylamine, triethoxysilylmethylamine, trimethoxysilylpropylamine, triethoxysilylpropylamine, trimethoxysilyloctylamine, and triethoxysilyloctylamine; and methyldimethoxysilylmethylamine, methyldiethoxysilylmethylamine, methyldimethoxysilylpropylamine, methyldiethoxysilylpropylamine, methyldimethoxysilyloctylamine, and methyldiethoxysilyloctylamine. Examples include quildialkoxysilylalkylamines; trialkoxysilylalkylaminoalkylamines such as trimethoxysilylpropylaminoethylamine, triethoxysilylpropylaminoethylamine, trimethoxysilyloctylaminoethylamine, and trimethoxysilylpropylamino(methyl)ethylamine; trialkoxysilylalkylaminoalkylaminoalkylamines such as trimethoxysilylpropylaminoethylaminoethylamine; alkyldialkoxysilylalkylaminoalkylamines such as methyldimethoxysilylpropylaminoethylamine, methyldiethoxysilylpropylaminoethylamine, methyldimethoxysilyloctylaminoethylamine, and methyldimethoxysilylpropylamino(methyl)ethylamine; and alkyldialkoxysilylalkylaminoalkylaminoalkylamines such as methyldimethoxysilylpropylaminoethylaminoethylamine. Among these, alkoxyalkylamines, trialkoxysilylalkylamines, and alkyldialkoxysilylalkylamines are preferred from the viewpoint of ease of raw material procurement, safety, and curability of the product, and methoxypropamine, ethoxypropylamine, trimethoxysilylpropylamine, triethoxysilylpropylamine, and methyldiethoxysilylpropylamine are more preferred.

[0061] The acidic compounds used in the amine exchange reaction are acidic compounds with a pKa of 4 to 12, preferably pKa of 7 to 10. By using such acidic compounds, side reactions can be reduced and the amount of compound (1) produced can be increased. Specific examples of acidic compounds with a pKa of 4 to 12 include carboxylic acids such as acetic acid, propionic acid, hexanoic acid, and octanoic acid; ammonium halides such as ammonium chloride and ammonium bromide; hydrogen halides of amines such as diethylamine hydrochloride and diethylamine hydrobromide; ammonium sulfates such as ammonium sulfate and ammonium amidosulfate; ammonium sulfonates such as ammonium methanesulfonate and ammonium dodecylbenzenesulfonate; and sulfonamides such as p-toluenesulfonamide and o-toluenesulfonamide. Among these, ammonium halides, hydrogen halides of amines, and ammonium sulfonates are preferred, with hydrogen halides of amines being more preferred, as they provide sufficient reaction acceleration and produce fewer by-products.

[0062] The amount of acidic compound with a pKa of 4 to 12 used is not particularly limited, but is preferably 0.000001 to 0.02 moles, more preferably 0.000005 to 0.01 moles, and even more preferably 0.00001 to 0.005 moles, relative to the number of moles of compound (3). The amine exchange reaction temperature is preferably 30 to 150°C, more preferably 50 to 110°C. The amine exchange reaction time is preferably 30 to 600 minutes, more preferably 60 to 600 minutes, and even more preferably 60 to 300 minutes.

[0063] In the manufacturing method of the present invention, compound (1) can be efficiently produced by using an aprotic polar solvent. Examples of solvents that can be used include nitrile compounds such as acetonitrile, propionitrile, butyronitrile, and isobutyronitrile; ether compounds such as tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 4-methyltetrahydropyran, and cyclopentyl methyl ether; and amide compounds such as N,N-dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Among these, nitrile compounds that have a high reaction-promoting effect and are less prone to side reactions are preferred, with acetonitrile being the most preferred.

[0064] The acidic compounds with pKa 4 to 12 described above can be neutralized after the reaction to increase the stability of compound (1). In this case, the basic compound used for neutralization is not particularly limited, but solid basic compounds are preferred. Specific examples of solid basic compounds include aluminum hydroxide, hydrosaltite, magnesium silicate, aluminum silicate, aluminum oxide, and magnesium oxide, which may be used individually or in combination of two or more. Commercially available solid basic compounds can be used, for example, as the Kyoward series (Kyoward 100, 200, 300, 500, 600, 700, 2000) manufactured by Kyowa Chemical Industry Co., Ltd.

[0065] The amount of solid basic compound used is not particularly limited, but is preferably 1.0 to 2.0 moles, more preferably 1.0 to 1.8 moles, and even more preferably 1.2 to 1.8 moles, relative to the number of moles of the pKa 4 to 12 acidic compound used.

[0066] It is preferable to separate the salts produced in the neutralization reaction and any excess solid basic compounds used. While the separation method is not particularly limited, separation by filtration is a convenient method.

[0067] (2) Manufacturing Method B Next, manufacturing method B will be described. Manufacturing method B involves reacting a terminally unsaturated bond-containing compound with a hydrogen chlorosilane compound in the presence of a platinum catalyst, then reacting an amine compound in the presence of an aprotic polar solvent, performing liquid-liquid separation between the layer containing compound (1) and the layer containing the hydrochloride salt of compound (4) and the aprotic polar solvent, and removing the layer containing the hydrochloride salt of compound (4) and the aprotic polar solvent by liquid-liquid separation.

[0068] In general formula (5), R 9 R represents a single bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms. 9 As for the divalent hydrocarbon group, R 2 In addition to the groups similar to those exemplified above, methylene groups can also be mentioned. Among these, single bonds or alkylene groups are preferred due to the ease of raw material procurement.

[0069] In general formula (5), Z is R 9 -CH = CH2 or represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. The monovalent hydrocarbon group of Z is as described above for R. 1 Examples similar to those exemplified above can be given. Among these, R is chosen due to the ease of raw material procurement. 9 -CH=CH2, methyl, n-butyl, tert-butyl, and hexyl groups are preferred.

[0070] Specific examples of compound (5) include 1-vinylpentamethyldisiloxane, 1-vinylheptamethyltrisiloxane, 1-vinylnonamethyltetrasiloxane, 1-vinylundecamethylpentasiloxane, 1-butyl-9-vinyldecamethylpentasiloxane, 1-hexyl-9-vinyldecamethylpentasiloxane, 1-octyl-9-vinyldecamethylpentasiloxane, and 1-phenylethyl-9-vinyldecameth Examples include dipentasiloxane, 1-tris(trimethylsiloxy)silylethyl-9-vinyl-decamethylpentasiloxane, α-butyl-ω-vinyl-polydimethylpolysiloxane, 1,3-divinyltetramethyldisiloxane, 1,5-divinylhexamethyltrisiloxane, 1,7-divinyloctamethyltetrasiloxane, 1,9-divinyldecamethylpentasiloxane, and α,ω-divinylpolydimethylpolysiloxane.

[0071] Specific examples of compound (6) include methyldichlorosilane and trichlorosilane.

[0072] The mixing ratio of compound (5) and compound (6) is not particularly limited, but from the viewpoint of productivity, the amount of compound (6) is preferably 1.0 to 1.5 moles, more preferably 1.0 to 1.2 moles, and even more preferably 1.0 to 1.05 moles per mole of unsaturated bonds contained in compound (5).

[0073] When compound (5) and compound (6) are reacted, a platinum compound is used as a catalyst. Specific examples of platinum compounds are those the same as those mentioned above. The amount of platinum compound used is not particularly limited, but from the viewpoint of productivity, it is preferably 0.000001 to 0.2 moles, more preferably 0.00001 to 0.1 moles, per mole of unsaturated bonds contained in compound (5). The reaction temperature, reaction time, and reaction atmosphere are the same as when compound (2) and compound (3) are reacted.

[0074] The above reaction can proceed without a solvent, but a solvent may also be used. Specific examples of solvents include aliphatic hydrocarbon solvents with 5 to 20 carbon atoms such as pentane, hexane, cyclohexane, heptane, octane, nonane, decane, isooctane, and isododecane; aromatic hydrocarbon solvents with 6 to 10 carbon atoms such as benzene, toluene, and xylene; and nitrile solvents such as acetonitrile. These solvents may be used individually or in mixtures of two or more.

[0075] Compound (1) is produced by adding compound (4) to the reaction product of compound (5) and compound (6). The mixing ratio of compound (4) is not particularly limited, but is preferably 2.0 to 3.0 moles, more preferably 2.0 to 2.5 moles, relative to the number of moles of chlorine atoms contained in compound (6).

[0076] In manufacturing method B, the hydrochloride salt of compound (4) produced by the above series of reactions is dissolved, and the layer containing compound (1) and the layer containing the hydrochloride salt of compound (4) and an aprotic polar solvent are separated into liquid-liquid layers, and the layer containing the hydrochloride salt of compound (4) and an aprotic polar solvent is removed by liquid-liquid separation.

[0077] The hydrochloride salt of compound (4) is often solid, and an aprotic polar solvent is used to dissolve it. Examples of solvents that can be used include nitrile solvents such as acetonitrile, propionitrile, butyronitrile, and isobutyronitrile; amide solvents such as dimethylformamide (DMF) and dimethylacetamide; urea solvents such as dimethylimidazolidinone (DMI) and dimethylpropylene urea (DMPU); and other aprotic polar solvents. These solvents may be used individually or in combination of two or more. Among these, nitrile solvents are preferred due to their excellent solubility of the hydrochloride salt of compound (4), and acetonitrile is the most preferred. The amount of solvent used is not particularly limited, but is preferably 50 to 300 g, more preferably 75 to 200 g, per mole of chlorine atoms contained in compound (6).

[0078] The solvent for dissolving the hydrochloride salt of compound (4) may be added at the time of the reaction between compound (5) and compound (6), or it may be added when the reactants of compound (5) and compound (6) and compound (4) are reacted.

[0079] In addition, (iso)paraffin compounds such as hexane, octane, isooctane, decane, dodecane, and isododecane; and aromatic hydrocarbon compounds such as toluene and xylene may be used in combination with the above solvent. By using these compounds, the polarity of the layer containing compound (3) is reduced, making it easier to separate it from the layer in which the hydrochloride salt of compound (4) is dissolved in the solvent.

[0080] After the above series of reactions, liquid-liquid separation is performed, separating the layer containing compound (1) from the layer in which the hydrochloride salt of compound (4) is dissolved in the solvent. In most cases, the former becomes the upper layer and the latter the lower layer. By removing this lower layer, the hydrochloride salt of compound (4) and the solvent used to dissolve it can be removed. To ensure that the hydrochloride salt is completely dissolved in the solvent, the lower layer may be removed by heating to, for example, 50°C or higher.

[0081] The layer containing compound (1) obtained as described above may contain trace amounts of the hydrochloride salt of compound (4). The stability of compound (1) can be increased by neutralizing this hydrochloride salt. In this case, the basic compound used for neutralization is the same as that used in production method A. The removal method is also the same. The amount of solid basic compound used is not particularly limited, but it is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, relative to the weight of the layer containing compound (1) obtained after removing the hydrochloride salt of compound (4) and the solvent used to dissolve it.

[0082] To isolate the target compound (1) from the reaction solution obtained in the above series of reactions, one of the usual purification methods in organic synthesis, such as filtration, distillation, vacuum stripping, various types of chromatography, and treatment with adsorbents, can be appropriately selected and used. Among these, purification by vacuum stripping or distillation is preferred from the viewpoint of production efficiency and the ability to achieve high purity of the target product.

[0083] [3] Curable composition and cured product The curable composition of the present invention contains compound (1). The amount of compound (1) in the curable composition is not particularly limited, but is preferably 1 to 90% by mass, more preferably 5 to 85% by mass, and even more preferably 10 to 80% by mass. The curable composition of the present invention may also optionally contain a curing catalyst, a solvent, a hydrolyzable group-containing silicone compound, etc.

[0084] As curing catalysts, metal compounds such as titanium compounds, aluminum compounds, zinc compounds, and tin compounds, as well as aminosilane compounds, can be used. Specific examples of titanium compounds include tetraalkyl orthotitanates such as tetrabutyl orthotitanate, tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, and tetraisopropyl orthotitanate, as well as their partially hydrolyzed condensates and titanium acylates. Specific examples of aluminum compounds include aluminum trihydrate, aluminum alkoxide, aluminum acylate, salts of aluminum acylate, aluminosiloxy compounds, and aluminum metal chelate compounds. Specific examples of zinc compounds include zinc octoate and zinc 2-ethylhexanoate. Specific examples of tin compounds include dioctyltine dioctate and dioctyltine dilaurate.

[0085] Specific examples of aminosilane compounds include trialkoxysilylalkylamines such as trimethoxysilylmethylamine, triethoxysilylmethylamine, trimethoxysilylpropylamine, triethoxysilylpropylamine, trimethoxysilyloctylamine, and triethoxysilyloctylamine; alkyldialkoxysilylalkylamines such as methyldimethoxysilylmethylamine, methyldiethoxysilylmethylamine, methyldimethoxysilylpropylamine, methyldiethoxysilylpropylamine, methyldimethoxysilyloctylamine, and methyldiethoxysilyloctylamine; and trimethoxysilylpropylaminoethylamine, triethoxysilylpropylaminoethylamine, and trimethoxysilyloctylamine. Examples include trialkoxysilylalkylaminoalkylamines such as noethylamine and trimethoxysilylpropylamino(methyl)ethylamine; trialkoxysilylalkylaminoalkylaminoalkylamines such as trimethoxysilylpropylaminoethylaminoethylamine; alkyldialkoxysilylalkylaminoalkylamines such as methyldimethoxysilylpropylaminoethylamine, methyldiethoxysilylpropylaminoethylamine, methyldimethoxysilyloctylaminoethylamine, and methyldimethoxysilylpropylamino(methyl)ethylamine; and alkyldialkoxysilylalkylaminoalkylaminoalkylamines such as methyldimethoxysilylpropylaminoethylaminoethylamine. Among these, aminosilane compounds are preferred from the viewpoint of compositional stability.

[0086] When a curing catalyst is used, the amount it is added is not particularly limited, but from the viewpoint of exhibiting the effect of the catalyst, it is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, relative to the mass of compound (1), or the total mass of compound (1) and the hydrolyzable group-containing silicone compound used as needed. The curing catalyst may be added to the curable composition later, or it may be dissolved in the solvent or hydrolyzable group-containing silicone compound used as needed and added as part of the mixture.

[0087] Furthermore, the NHR of compound (1) 5However, if the structure is derived from the aminosilane compound of the curing catalyst mentioned above, there is no need to specifically add the curing catalyst. This is because the aminosilane compound is generated when compound (1) undergoes hydrolysis.

[0088] Specific examples of solvents include aliphatic hydrocarbon solvents having 5 to 20 carbon atoms such as pentane, hexane, cyclohexane, heptane, octane, nonane, decane, isooctane, and isododecane; aromatic hydrocarbon solvents having 6 to 10 carbon atoms such as benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, and dipropylene glycol dimethyl ether; ester solvents such as ethyl acetate and butyl acetate; and silicone solvents such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tris(trimethylsiloxy)methylsilane, and 3,5-diethyl-octamethyltetrasiloxane. These solvents may be used individually or in mixtures of two or more. When using a solvent, the amount of solvent used is not particularly limited, but from the viewpoint of workability, it is preferably 10 to 99% by mass, more preferably 20 to 80% by mass, and even more preferably 20 to 60% by mass.

[0089] The hydrolyzable group-containing silicone compound may be the silane compound as is, a partially hydrolyzed condensate of the silane compound, or a mixture of the silane compound and its partially hydrolyzed product. Furthermore, the partially hydrolyzed condensate of the hydrolyzable group-containing silane compound may be the partially hydrolyzed condensate of one hydrolyzable group-containing silane compound, or it may be a partially hydrolyzed condensate composed of two or more compounds. When using the hydrolyzable group-containing silicone compound, the amount used is not particularly limited, but from the viewpoint of curability, it is preferably 10 to 89% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass.

[0090] The cured product of the present invention is obtained by curing the above-mentioned curable composition, and more specifically, it is a cured product obtained by the hydrolysis and condensation of the silazane structure contained in compound (1). If the curable composition contains a solvent, the solvent may or may not be evaporated before curing, or curing may be carried out while volatilizing the solvent.

[0091] The curing temperature can range from room temperature to heated. While there are no particular restrictions on the temperature as long as it does not adversely affect the substrate, to maintain reactivity, it is preferably 0 to 250°C, more preferably 20 to 180°C, and even more preferably 20 to 150°C. Furthermore, since it reacts with moisture in the air, the relative humidity is preferably 15 to 100%, more preferably 25 to 80%.

[0092] A coated substrate can also be obtained by coating the surface of a substrate such as an inorganic or organic material with the above-mentioned curable composition, and then curing it by reacting it with moisture in the air. Specific examples of inorganic materials include metals, glass, silica, alumina, talc, calcium carbonate, and carbon. The shape of these materials is not particularly limited, but they may be in the form of plates, sheets, fibers, or powders. As for the glass, commonly used types of glass such as E-glass, C-glass, and quartz glass can be used, and glass fibers may also be used. Glass fibers may be aggregates thereof, for example, bundles of glass-based (filament) fibers with a fiber diameter of 3 to 30 μm, twisted yarns, woven fabrics, etc.

[0093] Specific examples of organic materials include resin materials such as polyethylene, polypropylene, polystyrene, poly(meth)acrylic, polyvinyl chloride, polycarbonate, nylon, polyurethane, polybutylene terephthalate, polyethylene terephthalate, ABS (polymer of acrylonitrile, butadiene, and styrene), melamine, phenol, epoxy, and polyimide; elastomers and rubber materials such as polybutadiene rubber, polyisopropylene rubber, nitrile rubber, neoprene rubber, polysulfide, and urethane rubber. The shape of the base material is not particularly limited, but it may be in the form of a plate, sheet, fiber, or powder.

[0094] As for the application method to the substrate, known application methods can be used, such as brush application, sponge application, cloth application, spray coating, wire bar application, blade application, roll coating, dipping, and spin coating. In addition, for powdered materials such as silica, alumina, talc, and calcium carbonate, a mixing method may be used in which the curable composition is directly mixed with the substrate using a mixer or mill.

[0095] The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0096] [Example 1-1] (In the formula, Me represents a methyl group and Et represents an ethyl group. The same applies hereafter.)

[0097] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 64 g (0.30 mol) of bis(diethylamino)methylvinylsilane and 0.098 g (0.000015 mol as platinum atoms) of a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex were charged, and the temperature was adjusted to 80°C. To this, 107 g (0.300 mol as Si-H, n≈8) of Si-H modified siloxane at both ends was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 1 hour. To 57 g of the resulting reaction solution, 17.8 g (0.200 mol) of methoxypropylamine, 30 g of acetonitrile, 30 g of toluene, and 0.0088 g (0.080 mmol) of diethylamine hydrochloride were added, and the mixture was stirred under reflux for 3 hours. 0.2 g of Kyoward 500SH (manufactured by Kyowa Kogyo Kagaku Co., Ltd.) was added and stirred for 1 hour. The resulting diethylamine and the solvents acetonitrile and toluene were removed by stripping. The obtained residue was filtered to obtain 60 g of a colorless, transparent liquid. The IR of the obtained compound was analyzed. 1 1H-NMR was measured. The results are shown in Figures 1 and 2. From Figure 1, a peak originating from NH was confirmed, and from Figure 2, the peak originating from the diethylamino group decreased, and a new peak originating from methoxypropylamine was confirmed, thus confirming the formation of compound 1.

[0098] [Examples 1-2]

[0099] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 21.4 g (0.100 mol) of bis(diethylamino)methylvinylsilane and 0.033 g (0.000005 mol as platinum atoms) of a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex were charged, and the temperature was adjusted to 80°C. 149 g (0.100 mol as Si-H, n≈40) of Si-H modified siloxane at both ends was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 1 hour. To the resulting 64 g of reaction solution, 6.7 g (0.075 mol) of methoxypropylamine, 30 g of acetonitrile, 30 g of toluene, and 0.0033 g (0.030 mmol) of diethylamine hydrochloride were added, and the mixture was stirred under reflux for 3 hours. 0.03 g of Kyoward 500SH (manufactured by Kyowa Kogyo Kagaku Co., Ltd.) was added and stirred for 1 hour. The resulting diethylamine and the solvents acetonitrile and toluene were removed by stripping. The obtained residue was filtered to obtain 65 g of a colorless, transparent liquid. The IR of the obtained compound was... 1 1H-NMR was measured. The results are shown in Figures 3 and 4. From Figure 3, a peak originating from NH was confirmed, and from Figure 4, the peak originating from the diethylamino group decreased, and a new peak originating from methoxypropylamine was confirmed, thus confirming the formation of compound 2.

[0100] [Examples 1-3]

[0101] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen. 43.5 g of Si-vinyl modified siloxane (0.100 mol as vinyl groups, n ≈ 10) and 0.024 g of isopropanol solution of platinum-1,3-divinyltetramethyldisiloxane complex (0.0000025 mol as platinum atoms) were charged into the flask, and the temperature was adjusted to 80°C. 13.4 g of trichlorosilane (0.099 mol) was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 1 hour. 30 g of acetonitrile and 30 g of isooctane were added to the resulting reaction mixture, and 53.5 g of methoxypropylamine (0.600 mol) was added dropwise over 30 minutes while cooling with water, and the mixture was stirred at 50°C for 1 hour. At this point, the reaction mixture had separated into two layers. The reaction mixture was transferred to a separatory funnel, and the lower layer was removed. 2.3 g of Kyoward 500SH (manufactured by Kyowa Kogyo Kagaku Co., Ltd.) was added to the upper layer and stirred for 1 hour, after which the solvent was removed by stripping. The resulting residue was filtered to obtain 70 g of a colorless, transparent liquid. The IR of the obtained compound was analyzed. 1 1H-NMR was measured. The results are shown in Figures 5 and 6. From Figure 5, a peak originating from NH was confirmed, and from Figure 6, a peak originating from methoxypropylamine was confirmed, thus confirming the formation of compound 3.

[0102] [Examples 1-4]

[0103] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 129 g (0.600 mol) of bis(diethylamino)methylvinylsilane and 0.039 g (0.0000060 mol as platinum atoms) of a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex were charged, and the temperature was adjusted to 80°C. 40.3 g (0.600 mol as Si-H) of tetramethyldisiloxane was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 1 hour. To the resulting reaction mixture of 42.3 g, 26.7 g (0.300 mol) of methoxypropylamine, 60 g of acetonitrile, and 0.0033 g (0.030 mmol) of diethylamine hydrochloride were added, and the mixture was stirred under reflux for 5 hours. 0.024 g of Kyoward 500SH (manufactured by Kyowa Kogyo Kagaku Co., Ltd.) was added and stirred for 1 hour. The resulting diethylamine and the solvent acetonitrile were removed by stripping. The obtained residue was filtered to obtain 45 g of a colorless, transparent liquid. The IR of the obtained compound was... 1 1H-NMR was measured. The results are shown in Figures 7 and 8. From Figure 7, a peak originating from NH was confirmed, and from Figure 8, the peak originating from the diethylamino group decreased, and a new peak originating from methoxypropylamine was confirmed, thus confirming the formation of compound 4.

[0104] [Examples 1-5]

[0105] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 107 g (0.500 mol) of bis(diethylamino)methylvinylsilane and 0.16 g (0.000250 mol as platinum atoms) of a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex were charged, and the temperature was adjusted to 80°C. 48.6 g (0.500 mol as Si-H) of 1,4-bis(dimethylsilyl)benzene was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 1 hour. To the resulting reaction solution 46.8 g, 26.7 g (0.300 mol) of methoxypropylamine, 60 g of acetonitrile, and 0.003 g (0.030 mmol) of diethylamine hydrochloride were added, and the mixture was stirred under reflux for 3 hours. 0.024 g of Kyoward 500SH (manufactured by Kyowa Kogyo Kagaku Co., Ltd.) was added and stirred for 1 hour. The resulting diethylamine and the solvent acetonitrile were removed by stripping. The obtained residue was filtered to obtain 50 g of a colorless, transparent liquid. The IR of the obtained compound was analyzed. 1 1H-NMR was measured. The results are shown in Figures 9 and 10. From Figure 9, a peak originating from NH was confirmed, and from Figure 10, the peak originating from the diethylamino group decreased, and a new peak originating from methoxypropylamine was confirmed, thus confirming the formation of compound 5.

[0106] [Examples 1-6]

[0107] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 21.4 g (0.100 mol) of bis(diethylamino)methylvinylsilane and 0.033 g (0.0000050 mol as platinum atoms) of a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex were charged, and the temperature was adjusted to 80°C. 35.6 g (0.100 mol as Si-H, n≈8) of Si-H modified siloxane at both ends was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 1 hour. To the resulting reaction solution, 33.2 g (0.15 mol) of 3-aminopropyltriethoxysilane, 20 g of acetonitrile, and 0.0011 g (0.000010 mol) of diethylamine hydrochloride were added, and the mixture was stirred under reflux for 3 hours. 0.3 g of Kyoward 500SH (manufactured by Kyowa Kogyo Kagaku Co., Ltd.) was added and stirred for 1 hour. The resulting diethylamine and the solvent acetonitrile were removed by stripping. The obtained residue was filtered to obtain 70 g of a colorless, transparent liquid. The IR of the obtained compound was... 1 1H-NMR was measured. The results are shown in Figures 11 and 12. From Figure 11, a peak originating from NH was confirmed, and from Figure 12, the peak originating from the diethylamino group decreased, and a new peak originating from 3-aminopropyltriethoxysilane was confirmed, thus confirming the formation of compound 6.

[0108] [Examples 1-7]

[0109] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen. 10.7 g (0.0500 mol) of bis(diethylamino)methylvinylsilane and 0.016 g (0.0000025 mol as platinum atoms) of a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex were charged, and the temperature was adjusted to 80°C. 74.7 g (0.050 mol as Si-H, n≈40) of Si-H modified siloxane at both ends was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 1 hour. To the resulting reaction solution, 16.6 g (0.0750 mol) of 3-aminopropyltriethoxysilane, 20 g of acetonitrile, and 0.0055 g (0.050 mmol) of diethylamine hydrochloride were added, and the mixture was stirred under reflux for 3 hours. 0.1 g of Kyoward 500SH (manufactured by Kyowa Kogyo Kagaku Co., Ltd.) was added and stirred for 1 hour. The resulting diethylamine and the solvent acetonitrile were removed by stripping. The obtained residue was filtered to obtain 80 g of a colorless, transparent liquid. The IR of the obtained compound was... 1 1H-NMR was measured. The results are shown in Figures 13 and 14. From Figure 13, a peak originating from NH was confirmed, and from Figure 14, the peak originating from the diethylamino group decreased, and a new peak originating from methoxypropylamine was confirmed, thus confirming the formation of compound 7.

[0110] [Examples 1-8]

[0111] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 12.9 g (0.060 mol) of bis(diethylamino)methylvinylsilane and 0.020 g (0.0000030 mol as platinum atoms) of a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex were charged, and the temperature was adjusted to 80°C. 131 g (0.060 mol as Si-H, n≈30) of a one-ended Si-H modified siloxane was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 1 hour. To the resulting reaction solution of 59.8 g, 4.5 g (0.050 mol) of methoxypropylamine, 30 g of acetonitrile, 30 g of toluene, and 0.002 g (0.0020 mol) of diethylamine hydrochloride were added, and the mixture was stirred under reflux for 3 hours. 0.045 g of Kyoward 500SH (manufactured by Kyowa Kogyo Kagaku Co., Ltd.) was added and stirred for 1 hour. The resulting diethylamine and the solvents acetonitrile and toluene were removed by stripping. The obtained residue was filtered to obtain 60 g of a colorless, transparent liquid. The IR of the obtained compound was analyzed. 1 1H-NMR was measured. The results are shown in Figures 15 and 16. From Figure 15, a peak originating from NH was confirmed, and from Figure 16, the peak originating from the diethylamino group decreased, and a new peak originating from 3-aminopropyltriethoxysilane was confirmed, thus confirming the formation of compound 8.

[0112] [Examples 1-9]

[0113] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen. 80 g of one-ended Si-vinyl modified siloxane (0.10 mol as vinyl groups, n ≈ 8) and 0.049 g of isopropanol solution of chloroplatinic acid (0.0000050 mol as platinum atoms) were charged into the flask, and the temperature was adjusted to 80°C. 13.4 g of trichlorosilane (0.0990 mol) was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 1 hour. 50 g of acetonitrile and 100 g of isooctane were added to the resulting reaction mixture, and 56.2 g of methoxypropylamine (0.630 mol) was added dropwise over 30 minutes while cooling with water, and the mixture was stirred at 50°C for 1 hour. At this point, the reaction mixture had separated into two layers. The reaction mixture was transferred to a separatory funnel, and the lower layer was removed. 2.3 g of Kyoward 500SH (manufactured by Kyowa Kogyo Kagaku Co., Ltd.) was added to the upper layer and stirred for 1 hour, after which the solvent was removed by stripping. The resulting residue was filtered to obtain 90 g of a colorless, transparent liquid. The IR of the obtained compound was analyzed. 1 1H-NMR was measured. The results are shown in Figures 17 and 18. From Figure 17, a peak originating from NH was confirmed, and from Figure 18, a peak originating from methoxypropylamine was confirmed, thus confirming the formation of compound 9.

[0114] [Examples 1-10]

[0115] A four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 10.7 g (0.0500 mol) of bis(diethylamino)methylvinylsilane and 0.016 g (0.0000025 mol as platinum atoms) of a toluene solution of platinum-1,3-divinyltetramethyldisiloxane complex were charged, and the temperature was adjusted to 80°C. 109 g (0.0500 mol as Si-H, n≈30) of a one-ended Si-H modified siloxane was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 1 hour. To the resulting reaction solution, 16.6 g (0.0750 mol) of 3-aminopropyltriethoxysilane, 20 g of acetonitrile, 20 g of toluene, and 0.0027 g (0.0025 mmol) of diethylamine hydrochloride were added, and the mixture was stirred under reflux for 3 hours. 0.1 g of Kyoward 500SH (manufactured by Kyowa Kogyo Kagaku Co., Ltd.) was added and stirred for 1 hour. The resulting diethylamine and the solvents acetonitrile and toluene were removed by stripping. The obtained residue was filtered to obtain 110 g of a colorless, transparent liquid. The IR of the obtained compound was... 1 1H-NMR was measured. The results are shown in Figures 19 and 20. From Figure 19, a peak originating from NH was confirmed, and from Figure 20, the peak originating from the diethylamino group decreased, and a new peak originating from methoxypropylamine was confirmed, thus confirming the formation of compound 10.

[0116] [Examples 2-1 to 2-12, Comparative Examples 2-1 to 2-6] Compounds 1 to 7 obtained in the above examples and comparative compounds 1 to 3 shown below, along with a curing catalyst and silanol-modified oils at both ends as needed, were mixed in the ratios shown in Table 1 or Table 2 below, taking care to prevent moisture from entering, and the mixture was stirred in a vortex mixer to prepare a curable composition. The appearance, curing time, odor during film formation, and moisture resistance of the obtained curable composition were evaluated by the following methods. Note that in Table 2, the blending of silanol-modified oils at both ends and each compound was such that the molar ratio of the compound to the number of silanol groups in the silanol-modified oil at both ends was 1:1.

[0117] [Appearance] The compositions stirred in a vortex mixer were allowed to stand, and their appearance was visually judged. A composition that was uniformly transparent was marked with ○, and one that was not transparent or had insoluble matter was marked with ×. Compositions that received a × in appearance were not evaluated further. [Curing Time] Each curable composition was applied to a cleaned polished steel plate (10 cm x 15 cm) using a bar coater to a wet thickness of 30 μm. The test specimens were then left to stand in an environment of 25°C and 50% relative humidity, and the time until the coated material no longer adhered to the fingertips when the surface of the test specimen was touched (tack-free time) was measured according to the method specified in JIS K5600-1-1. If curing did not occur for more than 3 days, it was marked with ×, and no further evaluation was performed. [Odor] Each curable composition was applied to a soda glass plate (7 cm x 15 cm) using a bar coater to a wet thickness of 30 μm, and then left to stand in an environment of room temperature (23°C). Afterward, a finger was pressed against the coated surface, and it was checked whether an odor was generated while waiting for the fingerprint to disappear. A circle (○) was used if almost no odor was detected, and a cross (×) was used if an odor was detected. [Humidity resistance] The test pieces used for odor determination were left to stand at room temperature (23°C) for another day, and then left to stand for 8 hours in an environment of 85°C / 85% relative humidity. Afterward, the coating on the test piece was rubbed with a finger, and a circle (○) was used if there was no change, and a cross (×) was used if the coating softened or peeled off.

[0118]

[0119]

[0120]

[0121] [Examples 3-1 to 3-3, Comparative Examples 3-1 to 3-5] Compounds 8 to 10 and comparative compounds 4 and 5 obtained in the above examples, along with a curing catalyst and solvent as needed, were mixed in the ratios shown in Table 3 below, ensuring that no moisture entered, and the mixture was stirred in a vortex mixer to prepare a curable composition. 0.4 g of the prepared curable composition was dropped onto a cleaned polished steel plate (10 cm x 15 cm) and spread with a microfiber cloth. After standing for 2 minutes, excess liquid was wiped off with the same microfiber cloth, and the mixture was wiped until there were no visible irregularities, thus creating a cured film on the polished steel plate.

[0122] [Water Repellency] After leaving the above test specimens at room temperature (23°C) for one day, the contact angle of 2 μL of water was measured at room temperature using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) on the cured film, and judged according to the following criteria. The results are shown in Table 3. ○: Contact angle 100° or more △: Contact angle 90 to 99° ×: Contact angle 89° or less [Durability] The test specimens that underwent water repellency evaluation were hand-washed 50 times back and forth using a water-soaked urethane sponge (manufactured by Kikuron Co., Ltd., Kikuron A). The water repellency of the obtained test specimens was evaluated. The results are shown in Table 3. [Odor] It was checked whether an odor was generated during the series of operations to create the cured film on the polished steel plate, and ○ was used if almost no odor was detected, and × if an odor was detected.

[0123]

[0124] The results from Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-8 show that the organosilicon compounds of the present invention are colorless and transparent in appearance, either as compounds themselves or as curable compositions. In addition, when using a mildly reactive aminosilane compound as a catalyst, they can form a film in an extremely short time compared to conventional compounds, and they do not produce any odor during film formation and have good moisture resistance. Furthermore, the results from Examples 3-1 to 3-3 show that the organosilicon compounds of the present invention undergo hydrolysis condensation even when using a mildly reactive aminosilane compound, resulting in a film with excellent durability. In contrast, in Comparative Examples 3-1 and 3-2, where the hydrolyzable group is a methoxy group, hydrolysis does not proceed even without a catalyst or when using an aminosilane compound as a catalyst, and the film is wiped off in the durability test. Furthermore, the results from Comparative Examples 3-3 and 3-4 show that even silazane compounds containing structures derived from secondary amines have low hydrolysis properties due to steric hindrance and similarly poor durability. The results from Comparative Example 3-5 show that even structures derived from secondary amines can undergo hydrolysis using a highly active titanium catalyst, resulting in a durable coating. However, the progression of hydrolysis generates highly volatile amine compounds, which can cause an odor.

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