Aldimine-modified silicone and moisture curable silicone resin composition containing the same, and method for producing the aldimine-modified silicone

Abstract

To provide aldimine-modified silicone which enables long-term one-liquid storage of a silicone resin composition without chemically modifying a polyamine compound, and a method for producing the same.SOLUTION: Aldimine-modified silicone is represented by the following formula (1). Formula (1): (AR12SiO1 / 2)a(R12SiO2 / 2)b(R1SiO3 / 2)c(SiO4 / 2)d. In the formula, A is an aldimine group represented by the following formula (2), R1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, a satisfies 2≤a≤5, b satisfies 0<b≤200, c satisfies 0≤c≤1, and d satisfies 0≤d≤1. Where, 2≤a+b+c+d≤200 is satisfied. Formula (2): -Q1-CH=N-R2. In the formula, Q1 is a divalent hydrocarbon group having 2 to 10 carbon atoms, and R2 is a monovalent hydrocarbon group having 1 to 10 carbon atoms.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an aldimine-modified silicone and a moisture-curable silicone resin composition containing the same, as well as a method for producing the aldimine-modified silicone. [Background technology]

[0002] Silicone resin compositions are known that use modified silicones containing reactive functional groups such as aldehydes, acid anhydrides, acrylics, maleimides, and epoxy groups, and polyamine compounds as crosslinkers. However, the reaction rate of the above compositions is fast, so that long-term storage is difficult in the form of a mixture called a one-liquid composition.

[0003] A method is known in which the storage stability of the one-liquid composition is improved by reacting the polyamine compound with a ketone compound to form a polyketimine compound (Patent Documents 1 and 2). However, the polyketimine compound is not suitable for long-term storage over several months to several years because the nitrogen atom on the ketimine group still has nucleophilicity. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 5-271389 [Patent Document 2] Japanese Patent Application Publication No. 10-060227 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an aldimine-modified silicone that enables long-term storage of a one-part silicone resin composition without chemically modifying a polyamine compound, and a method for producing the same. [Means for solving the problem]

[0006] In order to solve the above problems, the present invention provides the following aldimine-modified silicone and a moisture-curable silicone resin composition containing the same, as well as a method for producing the aldimine-modified silicone.

[0007] That is, the present invention provides an aldimine-modified silicone represented by the following formula (1). (AR 1 2SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 )c(SiO 4 / 2 )d (1) (In the formula, A is an aldimine group represented by the following formula (2), and R 1 are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, a is 2≦a≦5, and b is 0. <b≦200であり、cは0≦c≦1であり、dは0≦d≦1である。ただし、2≦a+b+c+d≦200である。) -Q 1 -CH=NR 2 (2) (In the formula, Q 1 is a divalent hydrocarbon group having 2 to 10 carbon atoms, R 2 is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0008] The aldimine-modified silicone of the above formula (1) is preferably represented by the following formula (3). [ka] (Wherein, A and R 1 is the same as the above formula (1), and e is a number from 1 to 150.

[0009] These aldimine-modified silicones have excellent storage stability when made into moisture-curable silicone resin compositions containing polyamine compounds, and are well balanced with the moisture-induced curing rate.

[0010] The present invention provides a moisture-curable silicone resin composition comprising the aldimine-modified silicone of the present invention and a polyamine compound.

[0011] In the moisture-curable silicone resin composition of the present invention, the polyamine compound is preferably an amino-modified silicone represented by the following formula (7). [ka] (In the formula, R 1 are independently the same as in formula (1) above, and R A is an amino group represented by the following formula (8), f is a number from 1 to 200, and g is a number from 2 to 50. [ka] (In the formula, Q 2 is an alkylene group having 1 to 8 carbon atoms, and h is an integer of 0 to 4.

[0012] The moisture-curable silicone resin composition of the present invention has the property of curing in the atmosphere, yet can remain liquid at room temperature in a sealed container.

[0013] The present invention provides a method for producing an aldimine-modified silicone of the present invention represented by the above formula (1) below, which is characterized by reacting an aldehyde-modified silicone represented by the following formula (4) with a primary amine compound represented by the following formula (6). (A'R 1 2SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 )c(SiO 4 / 2 )d (4) (In the formula, R 1 are independently the same as those in the formula (1), a, b, c and d are also the same as those in the formula (1), and A′ is represented by the following formula (5) (wherein, Q 1is the same as the above formula (2). -Q 1 -CH=O (5) H2N-R 2 (6) (In the formula, R 2 is a divalent hydrocarbon group having 2 to 10 carbon atoms.

[0014] The above-described production method makes it possible to produce an aldimine-modified silicone suitable for use in the moisture-curable silicone resin composition of the present invention. Effect of the Invention

[0015] The aldimine-modified silicone of the present invention has excellent storage stability when made into a moisture-curable silicone resin composition containing a polyamine compound, and has a good balance with the moisture-induced curing rate. The moisture-curable silicone resin composition can be used as a resin modifier, a sealing material, a pressure-sensitive adhesive, an adhesive, etc. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] As described above, there has been a demand for the development of a moisture-curable silicone resin composition that enables long-term storage of the silicone resin composition in one liquid form without chemically modifying the polyamine compound.

[0017] Means for Solving the Problems The present inventors conducted extensive research to solve the above problems and discovered that an aldimine-modified silicone obtained from an aldehyde-modified silicone and a primary amine can be stored for long periods as a one-part solution when combined with a polyamine compound, thereby completing the present invention.

[0018] That is, the present invention relates to an aldimine-modified silicone represented by the above formula (1), a moisture-curable silicone resin composition containing the same, and a method for producing the aldimine-modified silicone.

[0019] The present invention will be described in detail below, but the present invention is not limited thereto.

[0020] [Aldimine-modified silicone] The aldimine-modified silicone of the present invention is represented by the following formula (1). (AR 1 2SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 )c(SiO 4 / 2 )d (1)

[0021] In the above formula (1), R 1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group, etc. Examples of the aryl group having 6 to 10 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group, etc. Examples of the aralkyl group having 7 to 10 carbon atoms include benzyl group, phenethyl group, etc. Among these, a methyl group, a butyl group, a phenyl group or a benzyl group is preferable, and a methyl group or a butyl group is more preferable.

[0022] In the above formula (1), a is 2 ≤ a ≤ 5, preferably 2; b is 0 < b ≤ 200, preferably 1 ≤ b ≤ 100, more preferably 5 ≤ b ≤ 60; c is 0 ≤ c ≤ 1, preferably 0; d is 0 ≤ d ≤ 1, preferably 0. However, 2 ≤ a + b + c + d ≤ 200, preferably 2 ≤ a + b + c + d ≤ 100, more preferably 2 ≤ a + b + c + d ≤ 60.

[0023] In the above formula (1), when a is less than 2, the moisture curability of the silicone resin composition is insufficient; when it exceeds 5, the stability of the raw material aldehyde-modified silicone (4) deteriorates, making the preparation difficult and thus not preferable. Also, when b exceeds 200, the compatibility with the polyamine compound deteriorates, and when c and d exceed 1, the handleability deteriorates due to an increase in viscosity, so it is not preferable.

[0024] Furthermore, in the above formula (1), if a+b+c+d is less than 2, the number of siloxane bonds will be less than the minimum required number, and if it exceeds 200, compatibility with the polyamine compound will be insufficient and handleability will be impaired due to an increase in viscosity, which is not preferable.

[0025] A in the above formula (1) is an aldimine group represented by the following formula (2). -Q 1 -CH=NR 2 (2)

[0026] In the above formula (2), Q 1 is a divalent hydrocarbon group having 2 to 10 carbon atoms, and is preferably an alkylene group having 2 to 10 carbon atoms. Examples of the alkylene group having 2 to 10 carbon atoms include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group. Among these, an ethylene group and a heptamethylene group are preferred, and a heptamethylene group is more preferred.

[0027] In the above formula (2), R 2 is a monovalent hydrocarbon group having 2 to 10 carbon atoms, and is preferably an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; and cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group.

[0028] Furthermore, a linear aldimine-modified silicone represented by the following formula (3), in which c=d=0 in the above formula (1), is preferred. [ka] (Wherein, A and R 1 is the same as the above formula (1), and e is a number from 1 to 150. In the above formula (3), e is a number from 1 to 150, preferably from 1 to 100, and more preferably from 5 to 60. When e is in the range of 1 to 150, it is preferable because it provides excellent compatibility with many polyamine compounds and a viscosity that is easy to handle.

[0029] [Moisture-curable silicone resin composition] The moisture-curable silicone resin composition of the present invention is characterized by containing the above-mentioned aldimine-modified silicone and a polyamine compound.

[0030] The polyamine compound used in the moisture-curable silicone resin composition of the present invention has a structure containing three or more primary or secondary amines, and may be any compound that is compatible with the aldimine-modified silicone. For example, an amino-modified silicone represented by the following formula (7) may be mentioned. Here, R A is an amino group represented by the following formula (8). [ka] (In the formula, R A is an amino group represented by the following formula (8). [ka]

[0031] In the above formula (7), f is a number from 1 to 200, preferably 1 to 100, and more preferably 20 to 80. Also, g is a number from 2 to 50, preferably 2 to 25, and more preferably 2 to 10. When f is in the range of 1 or more and 200 or less, the viscosity becomes easy to handle, which is preferable. Furthermore, when g is in the range of 2 or more and 50 or less, the compatibility with the aldimine-modified silicone becomes good, which is preferable.

[0032] In the above formula (8), Q 2 is an alkylene group having 1 to 8 carbon atoms, and is preferably a propylene group. Furthermore, h is a number from 0 to 4, and preferably from 0 to 1. When h is 4 or less, compatibility with the aldimine-modified silicone becomes good, which is preferable.

[0033] In addition to the above-mentioned main components, the moisture-curable silicone resin composition of the present invention may contain various additives such as antioxidants such as titanium oxide, pigments such as carbon, fillers such as calcium carbonate, ultraviolet absorbers, plasticizers, etc. These additives may be added in any amount and in various combinations depending on the application of the silicone composition.

[0034] The moisture-curable silicone resin composition of the present invention contains the aldimine-modified silicone of the present invention and a polyamine compound, and therefore, in the presence of moisture, an aldehyde-modified silicone is generated from the aldimine-modified silicone within the system, which exhibits addition reactivity with the polyamine compound and thus exhibits a curing action, and the aldimine-modified silicone blocks moisture, thereby suppressing the generation of the aldehyde-modified silicone, thereby improving storage stability.

[0035] [Method of manufacturing aldimine-modified silicone] The method for producing an aldimine-modified silicone of the present invention (hereinafter sometimes abbreviated as "the production method of the present invention") is characterized by having a production step of reacting an aldehyde group of an aldehyde-modified silicone represented by the following formula (4) with a primary amine represented by the following formula (6). (A'R 1 2SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 )c(SiO 4 / 2 )d (4) H2N-R 2 (6) (In the formula, R 2 is a divalent hydrocarbon group having 2 to 10 carbon atoms.

[0036] In the above formula (4), R 1is the same as R’ in the formula (1), and is preferably a group independently selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group. Examples of the aryl group having 6 to 10 carbon atoms include phenyl group, tolyl group, xylyl group, and naphthyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include benzyl group and phenethyl group. Among these, methyl group, butyl group, phenyl group or benzyl group is preferable, and methyl group or butyl group is more preferable.

[0037] In the above formula (4), a satisfies 2 ≦ a ≦ 5, preferably a = 2; b satisfies 0 < b ≦ 200, preferably 1 ≦ b ≦ 100, more preferably 5 ≦ b ≦ 60; c satisfies 0 ≦ c ≦ 1, preferably c = 0; d satisfies 0 ≦ d ≦ 1, preferably d = 0. However, 2 ≦ a + b + c + d ≦ 200, preferably 2 ≦ a + b + c + d ≦ 100, more preferably 2 ≦ a + b + c + d ≦ 60.

[0038] In the above formula (6), R 2 is a divalent hydrocarbon group having 2 to 10 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group. Among them, butyl group, hexyl group, and octyl group are preferable, and octyl group is more preferable.

[0039] A’ in the above formula (4) is an aldehyde group represented by the following formula (5). -Q 1 -CH=O (5)

[0040] In the above formula (5), Q 1is a divalent hydrocarbon group having 2 to 10 carbon atoms, and is preferably an alkylene group having 2 to 10 carbon atoms. Examples of the alkylene group having 2 to 10 carbon atoms include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group. Among these, an ethylene group and a heptamethylene group are preferred, and a heptamethylene group is more preferred.

[0041] The manufacturing method of the present invention is characterized in that an aldimine-modified silicone is obtained by reacting an aldehyde-modified silicone with a primary amine. Here, the mixed molar ratio of the aldehyde-modified silicone and the primary amine is preferably in the range of 1.0 to 5.0 moles of the primary amine per mole of the aminoaldehyde-modified silicone, and more preferably in the range of 1.0 to 2.0 moles. This is because if the number of moles of the primary amine per mole of the aldehyde-modified silicone is less than the above range, the highly reactive aldehyde group derived from the raw material aldehyde-modified silicone is likely to remain in the final product, and if it exceeds the above range, the pot yield during production becomes too low, which is disadvantageous in terms of cost.

[0042] The reaction between the aldehyde-modified silicone and the primary amine proceeds without heating, but may be carried out under heating. The temperature is usually in the range of 10°C to 120°C, and more preferably in the range of 10°C to 60°C.

[0043] In the production method of the present invention, the reaction time is not particularly limited, but is preferably 1 to 24 hours, more preferably 2 to 12 hours, and most preferably 2 to 4 hours. EXAMPLES

[0044] The present invention will be described in more detail below with reference to examples and comparative examples, but they can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited to the specific examples shown below.

[0045] < 1 H-NMR> As described in the examples 1 H-NMR was measured using AVANCE-III 400 MHz (manufactured by BRUKER) with deuterated chloroform as a solvent and TMS (tetramethylsilane) as a standard substance.

[0046] <Example 1-1> An aldimine-modified silicone represented by the following formula (10) was produced. Specifically, 10.0 g (4.5 mmol) of the aldehyde-modified silicone represented by the following formula (9) was charged, and then 0.59 g (1.0 equivalent) of octylamine was added under a nitrogen atmosphere at 25°C while stirring, and the reaction was carried out at 23°C for 2 hours. 1 H-NMR revealed that the peak at 9.8 ppm derived from the aldehyde group disappeared and a new peak derived from the aldimine group appeared at 7.7 ppm, confirming the production of the aldimine-modified silicone represented by the following formula (10). [ka] [ka]

[0047] <Example 1-2> To the aldimine-modified silicone (formula (10)) obtained in Example 1-1, 3.83 g (1.0 equivalent) of an amino-modified silicone represented by the following formula (11) was added and stirred for 10 minutes at 23° C. to obtain a moisture-curable silicone resin composition. The obtained moisture-curable silicone resin composition had the property of curing in 24 hours in the atmosphere, but could remain liquid for more than a year at room temperature (25° C.) in a sealed container. [ka]

[0048] <Example 2-1> In the above Example 1-1, the aldehyde-modified silicone (formula (9)) was changed to an aldehyde-modified silicone represented by the following formula (12), and an aldimine-modified silicone represented by the following formula (13) was obtained by the method described in the above Example 1-1. [ka] [ka]

[0049] <Example 2-2> A moisture-curable silicone resin composition was obtained from aldimine-modified silicone (formula (13)) and amino-modified silicone (formula (11)) by the method described in Example 1-2. The obtained silicone resin composition had the property of curing in 24 hours in the atmosphere, but could remain liquid for more than one year at room temperature in a sealed container.

[0050] <Example 3-1> In the above Example 1-1, the aldehyde-modified silicone (formula (9)) was changed to the aldehyde-modified silicone represented by the following formula (14), and the aldimine-modified silicone represented by the following formula (15) was obtained by the method described in the above Example 1-1. [ka] [ka]

[0051] <Example 3-2> A moisture-curable silicone resin composition was obtained from aldimine-modified silicone (15) and amino-modified silicone (11) by the method described in Example 1-2. The obtained silicone resin composition had the property of curing in 24 hours in the atmosphere, but could remain liquid for more than a year at room temperature in a sealed container.

[0052] <Comparative Example 1> In the above Example 1-2, the aldimine-modified silicone (formula (10)) was changed to an aldehyde-modified silicone (formula (9)), and a silicone resin composition was obtained by the method described in the above Example 1-2. The obtained silicone resin composition gelled after 1 minute in a closed container at room temperature.

[0053] <Comparative Example 2> In the above Example 1-2, the aldimine-modified silicone (formula (10)) was changed to the acid anhydride-modified silicone (16) shown below in formula (16), and a silicone resin composition was obtained by the method described in the above Example 1-2. The obtained silicone resin composition gelled after 1 minute in a closed container at room temperature. [ka]

[0054] <Comparative Example 3> In the above Example 1-2, the aldimine-modified silicone (formula (10)) was changed to the acrylic-modified silicone (17) of the following formula (17), and a silicone resin composition was obtained by the method described in the above Example 1-2. The obtained silicone resin composition gelled after 10 minutes in a closed container at room temperature. [ka]

[0055] <Comparative Example 4> In the above Example 1-2, the aldimine-modified silicone (formula (10)) was changed to the maleimide-modified silicone (18) of the following formula (18), and a silicone resin composition was obtained by the method described in the above Example 1-2. The obtained silicone resin composition gelled after 10 minutes in a closed container at room temperature. [ka]

[0056] <Comparative Example 5> In the above Example 1-2, the aldimine-modified silicone (formula (10)) was changed to the epoxy-modified silicone (19) of the following formula (19), and a silicone resin composition was obtained by the method described in the above Example 1-2. The obtained silicone resin composition gelled after 7 days in a closed container at room temperature. [ka]

[0057] <Comparative Example 6> In the above Example 1-2, the aldimine-modified silicone (formula (10)) was changed to the aldimine-modified silicone (20) of the following formula (20), and a silicone resin composition was obtained by the method described in the above Example 1-2. The obtained silicone resin composition did not cure in the air. [ka]

[0058] <Comparative Example 7> In the above Example 1-2, the aldimine-modified silicone (formula (10)) was changed to the aldehyde-modified silicone (formula (9)), and the amino-modified silicone (formula (11)) was changed to the ketimine-modified silicone represented by the following formula (21), and a silicone resin composition was obtained by the method described in the above Example 1-2. The obtained silicone resin composition gelled after 1 minute in a closed container at room temperature. [ka]

[0059] As shown in Examples 1-2 to 3-2, the moisture-curable silicone resin composition containing the aldimine-modified silicone of the present invention was able to remain liquid for more than one year in a closed container at room temperature, while having the property of curing in 24 hours in the atmosphere. On the other hand, as shown in Comparative Examples 1 to 7, the silicone resin composition lacking the aldimine-modified silicone of the present invention either gelled in a short time in a closed container at room temperature or did not cure in the atmosphere.

[0060] Thus, the aldimine-modified silicone of the present invention has excellent storage stability when made into a moisture-curable silicone resin composition containing a polyamine compound, and has a good balance with the moisture-induced curing rate. Furthermore, the present invention has made it possible to obtain a moisture-curable silicone resin composition containing an aldimine-modified silicone that allows long-term storage of the silicone resin composition in one liquid form without chemically modifying the polyamine compound.

[0061] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention.

Claims

1. An aldimine-modified silicone represented by the following formula (1): (AR) １ ２ Yes １／２ ) ａ (R １ ２ Yes ２／２ ) ｂ (R １ Yes ３／２ )c(SiO ４／２ )d (1) (In the formula, A is an aldimine group represented by the following formula (2), and R １ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, a is 2≦a≦5, b is 0<b≦200, c is 0≦c≦1, and d is 0≦d≦1, provided that 2≦a+b+c+d≦200. -Q １ -CH=N-R ２ (2) (In the formula, Q １ is a divalent hydrocarbon group having 2 to 10 carbon atoms, R ２ is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

2. 2. The aldimine-modified silicone according to claim 1, wherein the aldimine-modified silicone of the formula (1) is represented by the following formula (3): 【Chemistry 1】 (Wherein, A and R １ is the same as in formula (1), and e is a number from 1 to 150.

3. A moisture-curable silicone resin composition comprising the aldimine-modified silicone according to claim 1 and a polyamine compound.

4. 4. The moisture-curable silicone resin composition according to claim 3, wherein the polyamine compound is an amino-modified silicone represented by the following formula (7): 【Chemistry 2】 (In the formula, R １ are independently the same as those in formula (1), and R Ａ is an amino group represented by the following formula (8), f is a number from 1 to 200, and g is a number from 2 to 50. 【Chemistry 3】 (In the formula, Q ２ is an alkylene group having 1 to 8 carbon atoms, and h is an integer of 0 to 4.

5. A method for producing the aldimine-modified silicone represented by formula (1) of claim 1, comprising the steps of: A method for producing an aldimine-modified silicone, comprising reacting an aldehyde-modified silicone represented by the following formula (4) with a primary amine compound represented by the following formula (6): (A’R １ ２ SiO １／２ ) ａ (R １ ２ SiO ２／２ ) ｂ (R １ SiO ３／２ )c(SiO ４／２ )d (4) (In the formula, R １ are independently the same as those in the formula (1), a, b, c and d are also the same as those in the formula (1), and A′ is represented by the following formula (5) (wherein, Q １ is the same as the above formula (2). -Q １ -CH=O (5) H ２ N-R ２ (6) (In the formula, R ２ is a divalent hydrocarbon group having 2 to 10 carbon atoms.

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