Composition comprising organosilicon compound

Abstract

To provide a composition in which an organosilicon compound containing a ureido group is dissolved in a solvent containing water.SOLUTION: There is provided a composition in which a ureido group-containing organosilicon compound represented by the following formula (1) and an amino group-containing organosilicon compound represented by the following formula (3) are dissolved in a solvent containing alcohol and water. (In the formulae, R1 represents a hydrogen atom, an alkyl group or an aryl group, R2 represents a hydrogen atom, an alkyl group or a functional group represented by formula (2), R3 represents a hydrogen atom, an alkyl group or an aryl group, R4 represents a hydrogen atom, an alkyl group or a functional group represented by formula (4), a represents an integer of 1 to 3, m represents an integer of 1 to 12, b represents an integer of 1 to 3, n represents an integer of 1 to 12, p represents an integer of 1 to 12 and q represents an integer of 1 to 12.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition containing an organosilicon compound, and more specifically to a composition in which a ureido group-containing organosilicon compound and an amino group-containing organosilicon compound are dissolved in a solvent containing alcohol and water. [Background technology]

[0002] 2. Description of the Related Art Ureido group-containing organosilicon compounds, typified by 3-ureidopropyltriethoxysilane, have been widely used as surface treatment agents for inorganic substances and adhesion promoters for compositions. Known methods for producing such ureido group-containing organosilicon compounds include reacting an amino group-containing organosilicon compound with urea (Patent Documents 1 to 5). The ureido group-containing organosilicon compounds obtained by this method have the advantage of being of good quality, having a low content of carbamic acid ester compounds, which are impurities, and not containing metal catalysts.

[0003] On the other hand, ureido group-containing organosilicon compounds have insufficient water solubility, and although products in which 3-ureidopropyltriethoxysilane is diluted with alcohol such as methanol are widely used, there is a demand for improved water solubility. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 63-188688 [Patent Document 2] JP 2020-045304 A [Patent Document 3] DE 102006018500 [Patent Document 4] China Patent Application Publication No. 104262382 [Patent Document 5] China Patent Publication No. 104628760 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 has as its object to provide a composition in which a ureido group-containing organosilicon compound is dissolved in a solvent containing water. [Means for solving the problem]

[0006] As a result of intensive research aimed at solving the above problems, the present inventors have discovered that by using a specific ureido group-containing organosilicon compound in combination with a specific amino group-containing organosilicon compound, the ureido group-containing organosilicon compound dissolves in a solvent containing alcohol and water, thereby obtaining a composition with excellent water solubility, and have completed the present invention.

[0007] That is, the present invention provides 1. A composition comprising a ureido group-containing organosilicon compound represented by the following formula (1) and an amino group-containing organosilicon compound represented by the following formula (3) dissolved in a solvent containing alcohol and water. [ka] [In the formula, R 1 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms; R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by the following formula (2): [ka] (In the formula, the asterisk * represents a bond to an adjacent atom, and p represents an integer of 1 to 12.) where Me represents a methyl group, a represents an integer of 1 to 3, and m represents an integer of 1 to 12. [ka] [In the formula, R 3each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms; R 4 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by the following formula (4): [ka] (In the formula, the asterisk * represents a bond to an adjacent atom, and q represents an integer of 1 to 12.) where Me represents a methyl group, b represents an integer of 1 to 3, and n represents an integer of 1 to 12. 2. The composition according to 1, wherein the content of the amino group-containing organosilicon compound represented by the above formula (3) is 0.0001 to 10 parts by mass per 100 parts by mass of the ureido group-containing organosilicon compound represented by the above formula (1). 3. The composition according to 1 or 2, wherein the alcohol is represented by the following formula (5): R 5 OH (5) (In the formula, R 5 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. 4. The composition according to any one of 1 to 3, wherein the content of the alcohol is 10 to 1,000 parts by mass per 100 parts by mass of the ureido group-containing organosilicon compound represented by the above formula (1). 5. The composition according to any one of 1 to 4, wherein the content of water is 1,000 to 30,000 parts by mass per 100 parts by mass of the ureido group-containing organosilicon compound represented by the above formula (1). 6. The composition according to any one of 1 to 5, wherein the content ratio of alcohol to water is 1 / 1 to 1 / 300 by mass ratio. 7. The composition according to any one of 1 to 6, wherein the water is adjusted to be acidic. to provide. Effect of the Invention

[0008] The composition of the present invention is useful as a surface treatment agent for inorganic substances or as an additive to aqueous compositions, since the ureido group-containing organosilicon compound is dissolved in a solvent containing water. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention will be specifically described below. The composition of the present invention is characterized in that a ureido group-containing organosilicon compound represented by the following formula (1) (hereinafter referred to as compound (1)) and an amino group-containing organosilicon compound represented by the following formula (3) (hereinafter referred to as compound (3)) are dissolved in a solvent containing alcohol and water.

[0010] [ka]

[0011] The ureido group-containing organosilicon compound in the composition of the present invention is represented by the following formula (1).

[0012] [ka]

[0013] In formula (1), R 1 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R 1 The alkyl group having 1 to 10 carbon atoms preferably has 1 to 8 carbon atoms, and more preferably has 1 to 6 carbon atoms, and may be linear, cyclic, or branched. Specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. R 1 The aryl group having 6 to 10 carbon atoms is preferably an aryl group having 6 to 8 carbon atoms, and specific examples thereof include phenyl, α-naphthyl, and β-naphthyl groups. Among these, R 1is preferably a hydrogen atom, a methyl group, or an ethyl group.

[0014] a represents an integer of 1 to 3, preferably 2 or 3, and m represents an integer of 1 to 12, preferably 1 to 8, more preferably 3, from the viewpoint of raw material procurement.

[0015] R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a functional group represented by the following formula (2). The alkyl group having 1 to 10 carbon atoms preferably has 1 to 8 carbon atoms, more preferably has 1 to 6 carbon atoms. Specific examples thereof include the above-mentioned R 1 Examples of the alkyl group include the same groups as those exemplified in 1., but a straight-chain alkyl group is preferred, and a methyl group or an ethyl group is more preferred. Me represents a methyl group.

[0016] [ka] (In the formula, the asterisk * has the same meaning as above.)

[0017] In formula (2), p represents an integer of 1 to 12, preferably an integer of 1 to 8, and more preferably 2, from the viewpoint of availability of raw materials.

[0018] Specific examples of compound (1) include, but are not limited to, compounds represented by the following formulas (6) to (10). Among these, the compound represented by the following formula (6) is preferred.

[0019] [ka] (In the formula, R 1 , Me and a have the same meanings as above, and Bu represents an n-butyl group.

[0020] These compounds may be commercially available or may be manufactured. When manufactured, the manufacturing method is not particularly limited, and a conventionally known manufacturing method can be adopted. For example, according to the method described in JP-A-2020-045304, it can be obtained by reacting an amino group-containing organosilicon compound with urea.

[0021] On the other hand, the amino group-containing organosilicon compound in the composition of the present invention is represented by the following formula (3).

[0022] [ka]

[0023] In formula (3), R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R 3 The alkyl group having 1 to 10 carbon atoms preferably has 1 to 8 carbon atoms, more preferably has 1 to 6 carbon atoms, and may be linear, cyclic, or branched. The aryl group having 6 to 10 carbon atoms preferably has 6 to 8 carbon atoms. Specific examples of these alkyl and aryl groups include R 1 Among them, R 3 is preferably a hydrogen atom, a methyl group, or an ethyl group.

[0024] b represents an integer of 1 to 3, preferably 2 or 3, and n represents an integer of 1 to 12, preferably 1 to 8, more preferably 3, from the viewpoint of raw material procurement.

[0025] R 4 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a functional group represented by the following formula (4). The alkyl group having 1 to 10 carbon atoms preferably has 1 to 8 carbon atoms, more preferably has 1 to 6 carbon atoms. Specific examples thereof include the above R 1 Examples of the groups include the same as those exemplified in the above, and a methyl group and an ethyl group are preferred.

[0026] [ka] (In the formula, the asterisk * has the same meaning as above.)

[0027] In the formula (4), q represents an integer of 1 to 12, preferably an integer of 1 to 8, and more preferably 2, from the viewpoint of easy availability of raw materials.

[0028] Specific examples of the compound (3) include, but are not limited to, those represented by the following formulas (11) to (14). Among these, the compound represented by the following formula (11) is preferred.

[0029] [ka] (In the formula, R 3 , Me, Bu and b have the same meanings as above.)

[0030] These compounds are commercially available. For example, compounds represented by the above formula (11) include KBM-903 and KBE-903 (both manufactured by Shin-Etsu Chemical Co., Ltd.), and compounds represented by the above formula (12) include KBM-602 and KBM-603 (both manufactured by Shin-Etsu Chemical Co., Ltd.).

[0031] The content of compound (3) in the composition of the present invention is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 3 parts by mass, and even more preferably 0.001 to 1 part by mass, relative to 100 parts by mass of compound (1).

[0032] The alcohol in the composition of the present invention includes those represented by the following formula (5). R 5 OH (5)

[0033] In formula (5), R 5each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. R 5 The alkyl group having 1 to 10 carbon atoms preferably has 1 to 8 carbon atoms, more preferably has 1 to 6 carbon atoms, and may be linear, cyclic, or branched. The aryl group having 6 to 10 carbon atoms preferably has 6 to 8 carbon atoms. Specific examples of these alkyl and aryl groups include R 1 Among them, R 5 is preferably a methyl group.

[0034] The content of the alcohol in the composition of the present invention is preferably from 10 to 1,000 parts by mass, more preferably from 50 to 300 parts by mass, and even more preferably from 50 to 200 parts by mass, relative to 100 parts by mass of compound (1). The content of water in the composition of the present invention is preferably from 1,000 to 30,000 parts by mass, more preferably from 5,000 to 20,000 parts by mass, and even more preferably from 5,000 to 10,000 parts by mass, relative to 100 parts by mass of compound (1). The content ratio of alcohol and water in the composition of the present invention, alcohol / water, is preferably 1 / 1 to 1 / 300, more preferably 1 / 10 to 1 / 200, and even more preferably 1 / 10 to 1 / 100, by mass ratio.

[0035] The method for producing the water-containing composition of the present invention is not particularly limited. For example, the composition can be prepared by mixing a previously prepared alcohol solution of compound (1) and compound (3) (water-free composition) with water. Specifically, first, compound (1), compound (3) and alcohol are mixed, but the order of mixing is not particularly limited. Compound (1) and alcohol may be mixed and then compound (2) may be added, or compound (2) and alcohol may be mixed and then compound (1) may be added, or compound (1) and compound (2) may be mixed together with alcohol, but it is preferable to mix compound (1) and alcohol, then add compound (3) and further mix. When mixing, the entire amount of compound (1) or compound (2) may be added at once, or may be added gradually by dropwise addition, etc. The temperature during mixing is preferably 10 to 50°C, more preferably 15 to 40°C, and the mixing time is preferably 0.5 to 3 hours, more preferably 0.5 to 2 hours. After mixing, the resulting solution is filtered as necessary, and left to stand at preferably 10 to 50°C, more preferably 15 to 40°C, for preferably 1 to 10 days, more preferably 3 to 10 days, and then the resulting alcohol solution and water are mixed. When mixing the alcohol solution and water, water may be added to the alcohol solution, or the alcohol solution may be added to water, and the entire amount may be added at once or in portions. The temperature and time when mixing the alcohol solution and water are the same as the above-mentioned mixing temperature and time.

[0036] From the viewpoint of stability, the composition of the present invention preferably uses water adjusted to be acidic. Examples of acids for adjusting the acidity include organic acids such as formic acid, acetic acid, and citric acid, and inorganic acids such as hydrochloric acid. When an acid is used, the amount of the acid added is preferably 0.001 to 0.5 mass % of the total composition, and more preferably 0.01 to 0.1 mass %. When an acid is used, the water may be adjusted to be acidic in advance by mixing the acid and water, or the composition of the present invention may be adjusted to be acidic by adding the acid.

[0037] The content of compound (1) in the composition of the present invention is preferably from 0.05 to 2.0 mass %, more preferably from 0.05 to 1.5 mass %, and even more preferably from 0.1 to 1 mass %. EXAMPLES

[0038] The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following, "parts" means parts by mass. 1 It was determined by H-NMR measurement.

[0039] [1] Synthesis of ureido group-containing organosilicon compounds [Synthesis Example 1] Into a 10 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 901 g (15 mol) of urea and 996 g (4.5 mol) of 3-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) were placed and stirred at 117° C. for 20 hours. 1 The reaction rate was 95 mol% according to H-NMR. Then, 2,324 g (10.5 mol) of 3-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 10 hours at 120°C while stirring. After the dropwise addition was completed, the mixture was stirred at 117°C for 5 hours. 1 The reaction rate was 100 mol % as measured by 1 H-NMR. After completion of the reaction, the reaction mixture was distilled under reduced pressure to obtain an organosilicon compound containing a ureido group represented by the following formula (15).

[0040] [ka]

[0041] [2] Preparation of composition and solubility evaluation [Examples 1 to 3, Comparative Example 1] The ureido group-containing organosilicon compound obtained in Synthesis Example 1 and methanol were mixed at 25°C in the ratio shown in Table 1 below, and 3-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise, followed by stirring for 1 hour. The solution was filtered and allowed to stand at 25°C for 7 days, after which it was mixed with 0.05% by mass of acetic acid in water to obtain a composition. The appearance of the resulting composition after 5 minutes was visually checked, and it was rated as ◯ when it was completely dissolved, and x when it was not dissolved and cloudy.

[0042]

Table 1

Claims

1. A composition comprising a ureido group-containing organosilicon compound represented by the following formula (1) and an amino group-containing organosilicon compound represented by the following formula (3) dissolved in a solvent containing alcohol and water. 【Chemistry 1】 [In the formula, R 1 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms; R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by the following formula (2): 【Chemistry 2】 (In the formula, the asterisk * represents a bond to an adjacent atom, and p represents an integer of 1 to 12.) where Me represents a methyl group, a represents an integer of 1 to 3, and m represents an integer of 1 to 12. 【Chemistry 3】 [In the formula, R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms; R 4 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by the following formula (4): 【Chemistry 4】 (In the formula, the asterisk * represents a bond to an adjacent atom, and q represents an integer of 1 to 12.) where Me represents a methyl group, b represents an integer of 1 to 3, and n represents an integer of 1 to 12.

2. 2. The composition according to claim 1, wherein the content of the amino group-containing organosilicon compound represented by the formula (3) is 0.0001 to 10 parts by mass per 100 parts by mass of the ureido group-containing organosilicon compound represented by the formula (1).

3. 2. The composition according to claim 1, wherein the alcohol is represented by the following formula (5): R 5 OH (5) (In the formula, R 5 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.

4. 2. The composition according to claim 1, wherein the content of the alcohol is 10 to 1,000 parts by mass per 100 parts by mass of the ureido group-containing organosilicon compound represented by the formula (1) above.

5. 2. The composition according to claim 1, wherein the content of water is 1,000 to 30,000 parts by mass per 100 parts by mass of the ureido group-containing organosilicon compound represented by formula (1) above.

6. 2. The composition according to claim 1, wherein the content ratio of alcohol to water is 1 / 1 to 1 / 300 by mass ratio.

7. 2. The composition according to claim 1, wherein said water is water adjusted to be acidic.