Composition containing organosilicon compound

Abstract

Provided is a composition in which an ureido group-containing organosilicon compound represented by formula (1) and an amino group-containing organosilicon compound represented by formula (3) are dissolved in a solvent containing alcohol and water. (In the formula, 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, and R4 represents a hydrogen atom, an alkyl group, or a functional group represented by formula (4). a represents an integer of 1-3, m represents an integer of 1-12, b represents an integer of 1-3, n represents an integer of 1-12, p represents an integer of 1-12, and q represents an integer of 1-12.)

Description

Composition containing an organosilicon compound

[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.

[0002] Ureido group-containing organosilicon compounds, such as 3-ureidopropyltriethoxysilane, have been widely used as surface treatment agents for inorganic materials and as adhesion promoters for compositions. Known methods for producing these ureido group-containing organosilicon compounds include reacting an amino group-containing organosilicon compound with urea (see Patent Documents 1 to 5). The ureido group-containing organosilicon compounds obtained by this method have the advantage of being of high quality, with a low content of carbamate ester compounds as impurities and no 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 need for improved water solubility.

[0004] Japanese Patent Publication No. 63-188688 Japanese Patent Publication No. 2020-045304 German Patent Application Publication No. 102006018500 Chinese Patent Application Publication No. 104262382 Chinese Patent Application Publication No. 104628760

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition in which a ureido group-containing organosilicon compound is dissolved in a solvent containing water.

[0006] As a result of extensive 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 providing 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; [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): (wherein the asterisk * represents a bond to an adjacent atom, and p represents an integer of 1 to 12), Me represents a methyl group, a represents an integer of 1 to 3, and m represents an integer of 1 to 12.) [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): (wherein the asterisk * represents a bond to an adjacent atom, and q represents an integer of 1 to 12), 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 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. The composition according to 1 or 2, wherein the alcohol is represented by the following formula (5), R 5 OH (5) (wherein, R 5is 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 alcohol content 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 water content 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 alcohol to water content ratio is 1 / 1 to 1 / 300 by mass; 7. The composition according to any one of 1 to 6, wherein the water is water adjusted to be acidic.

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

[0009] The present invention will be described in detail 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]

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

[0012]

[0013] In formula (1), R 1 R 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. 1The alkyl group having 1 to 10 carbon atoms preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and may be linear, cyclic, or branched, and 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. 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. 1 is 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), and the alkyl group having 1 to 10 carbon atoms preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and specific examples thereof include the above-mentioned R 1 Although examples of the groups are the same as those exemplified above, a linear alkyl group is preferred, and a methyl group or an ethyl group is more preferred. Me represents a methyl group.

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

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

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

[0020] These compounds may be commercially available products 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 2020-045304 A, it can be obtained by a method of 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]

[0023] In formula (3), R 3 R 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. 3 The alkyl group having 1 to 10 carbon atoms preferably has 1 to 8 carbon atoms, more preferably 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; 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), and 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 specific examples thereof include the above-mentioned R 1 Examples of the groups include the same as those exemplified in 1 above, and a methyl group and an ethyl group are preferred.

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

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

[0028] Specific examples of 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] (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 formula (11) include KBM-903 and KBE-903 (both manufactured by Shin-Etsu Chemical Co., Ltd.), and compounds represented by the 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, per 100 parts by mass of compound (1).

[0032] The alcohol in the composition of the present invention may be one represented by the following formula (5): 5 OH (5)

[0033] In formula (5), R 5 R each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. 5 The alkyl group having 1 to 10 carbon atoms preferably has 1 to 8 carbon atoms, more preferably 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 alcohol in the composition of the present invention is preferably 10 to 1,000 parts by mass, more preferably 50 to 300 parts by mass, and even more preferably 50 to 200 parts by mass, per 100 parts by mass of compound (1). The content of water in the composition of the present invention is preferably 1,000 to 30,000 parts by mass, more preferably 5,000 to 20,000 parts by mass, and even more preferably 5,000 to 10,000 parts by mass, per 100 parts by mass of compound (1). Furthermore, the alcohol / water content ratio in the composition of the present invention 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.

[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) (a water-free composition) with water. Specifically, compound (1), compound (3), and alcohol are first mixed. 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. However, it is preferred 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 if necessary and allowed 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, before 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 mixing temperature and time described above.

[0036] From the viewpoint of stability, it is preferable to use water adjusted to an acidic state for the composition of the present invention. Examples of acids used to adjust the acidic state 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 added is preferably 0.001 to 0.5 mass %, more preferably 0.01 to 0.1 mass %, of the total mass of the composition. When an acid is used, water adjusted to an acidic state by mixing the acid and water in advance may be used, or the acid may be added to the composition of the present invention to adjust the acidic state.

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

[0038] The present invention will be described in more detail 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 compound [Synthesis Example 1] 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 in a 10 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, and the mixture was stirred at 117°C for 20 hours. 1 The reaction rate was 95 mol% according to H-NMR. Thereafter, 2,324 g (10.5 mol) of 3-aminopropyltriethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise at 120°C over 10 hours with stirring. After completion of the addition, the mixture was stirred at 117°C for 5 hours. 1 The reaction rate was 100 mol % as determined by H-NMR measurement. After completion of the reaction, the reaction mixture was distilled off under reduced pressure to obtain a ureido group-containing organosilicon compound represented by the following formula (15).

[0040]

[0041] [2] Preparation of Compositions and Evaluation of Solubility [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 blending ratios 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 aqueous acetic acid to obtain a composition. The appearance of the obtained composition was visually inspected after 5 minutes, and evaluation was performed with a ◯ for complete dissolution and an × for non-dissolution and turbidity.

[0042]

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. [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): (wherein, the asterisk * represents a bond to an adjacent atom, and p represents an integer of 1 to 12), Me represents a methyl group, a represents an integer of 1 to 3, and m represents an integer of 1 to 12.) [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): (wherein, the asterisk * represents a bond to an adjacent atom, and q represents an integer of 1 to 12), 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 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. The composition according to claim 1 or 2, wherein the alcohol is represented by the following formula (5): R 5 OH (5) (wherein, 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 claims 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 claims 1 to 4, wherein the water content 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 claims 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 claims 1 to 6, wherein the water is adjusted to be acidic.

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