Compositions comprising organosilicon compounds

Abstract

Provided is a composition in which a urea 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 an 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

Technical Field

[0001] This invention relates to compositions comprising organosilicon compounds, and more specifically, to compositions comprising organosilicon compounds containing urea groups and organosilicon compounds containing amino groups dissolved in a solvent comprising alcohol and water. Background Technology

[0002] Previously, organosilicon compounds containing urea groups, such as 3-ureopropyltriethoxysilane, were widely used as surface treatment agents for inorganic materials and adhesive additives for compositions.

[0003] As a method for manufacturing the urea-containing organosilicon compound, a method of reacting an amino-containing organosilicon compound with urea is known (Patent Documents 1-5). The urea-containing organosilicon compound obtained by this method has the following advantages: the content of urethane compounds as impurities is low, and in addition, it has good quality in terms of not containing metal catalysts.

[0004] On the other hand, organosilicon compounds containing urea groups have insufficient water solubility. Products made by diluting 3-ureopropyltriethoxysilane with alcohols such as methanol are already common, but improvements in water solubility are needed.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 63-188688

[0008] Patent Document 2: Japanese Patent Application Publication No. 2020-045304

[0009] Patent Document 3: German Patent Application Publication No. 102006018500

[0010] Patent Document 4: Description of Chinese Patent Application Publication No. 104262382

[0011] Patent Document 5: Description of Chinese Patent Application Publication No. 104628760 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] The present invention was made in view of the above-mentioned circumstances, and its object is to provide a composition of an organosilicon compound containing a urea group that is dissolved in a solvent containing water.

[0014] Methods for solving problems

[0015] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by using a specific organosilicon compound containing a urea group and a specific organosilicon compound containing an amino group in combination, the organosilicon compound containing the urea group is dissolved in a solvent containing alcohol and water, thereby obtaining a composition with excellent water solubility, thus completing the present invention.

[0016] That is, the present invention provides:

[0017] 1. A composition comprising an organosilicon compound containing a urea group represented by formula (1) and an organosilicon compound containing an amino group represented by formula (3) dissolved in a solvent containing an alcohol and water.

[0018] [Chemistry 1]

[0019]

[0020] 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 The expression represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a functional group represented by the following formula (2), where Me represents a methyl group, a represents an integer from 1 to 3, and m represents an integer from 1 to 12.

[0021] [Chemistry 2]

[0022]

[0023] In the formula, the asterisk * indicates bonding with adjacent atoms, and p represents an integer from 1 to 12.

[0024] [Chemistry 3]

[0025]

[0026] 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 The expression represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a functional group represented by the following formula (4), where Me represents a methyl group, b represents an integer from 1 to 3, and n represents an integer from 1 to 12.

[0027] [Chemistry 4]

[0028]

[0029] In the formula, the asterisk * indicates the combination with adjacent atoms, and q represents an integer from 1 to 12;

[0030] 2. The composition according to 1, wherein the content of the amino-containing organosilicon compound of formula (3) is 0.0001 to 10 parts by mass relative to 100 parts by mass of the urea-containing organosilicon compound of formula (1);

[0031] 3. The composition according to 1 or 2, wherein the alcohol is represented by the following formula (5),

[0032] R 5 OH (5)

[0033] In the formula, R 5 It is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms;

[0034] 4. The composition according to any one of 1 to 3, wherein the content of alcohol is 10 to 1000 parts by mass relative to 100 parts by mass of the organosilicon compound containing a urea group shown in formula (1);

[0035] 5. The composition according to any one of 1 to 4, wherein the water content is 1,000 to 30,000 parts by mass relative to 100 parts by mass of the organosilicon compound containing a urea group as shown in formula (1);

[0036] 6. The composition according to any one of 1 to 5, wherein the ratio of alcohol to water, expressed as a mass ratio, is 1 / 1 to 1 / 300;

[0037] 7. The composition according to any one of 1 to 6, wherein the water is water adjusted to be acidic.

[0038] The effects of the invention

[0039] The compositions of the present invention are formed by dissolving organosilicon compounds containing urea groups in a solvent containing water, and therefore can be used as surface treatment agents for inorganic materials and additives for aqueous compositions. Detailed Implementation

[0040] The present invention will now be described in detail.

[0041] The composition of the present invention is characterized in that it is formed by dissolving an organosilicon compound containing a urea group (hereinafter referred to as compound (1)) represented by the following formula (1) and an organosilicon compound containing an amino group (hereinafter referred to as compound (3)) represented by the following formula (3) in a solvent containing alcohol and water.

[0042] [Chemistry 5]

[0043]

[0044] The urea-containing organosilicon compounds in the compositions of the present invention are represented by the following formula (1).

[0045] [Chemistry 6]

[0046]

[0047] In equation (1), R 1 Each can independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0048] As R 1 Alkyl groups having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, can be linear, cyclic, or branched. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0049] As R 1 The aryl group has 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. Specific examples include phenyl, α-naphthyl, β-naphthyl, etc.

[0050] Among these, as R 1 The preferred atoms are hydrogen atoms, methyl groups, and ethyl groups.

[0051] a represents an integer from 1 to 3, preferably 2 or 3, and m represents an integer from 1 to 12. From the perspective of raw material procurement, an integer from 1 to 8 is preferred, and 3 is even more preferred.

[0052] R 2 The alkyl group representing a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a functional group represented by the following formula (2), preferably having 1 to 8 carbon atoms, more preferably having 1 to 6 carbon atoms, is an example of the alkyl group having 1 to 10 carbon atoms. 1 The same group as the group illustrated herein is preferred, preferably a straight-chain alkyl group, and more preferably methyl or ethyl.

[0053] Me represents methyl.

[0054] [Chemistry 7]

[0055]

[0056] (In the formula, the asterisk * indicates the same meaning as above.)

[0057] In formula (2), p represents an integer from 1 to 12. From the viewpoint of easy availability of raw materials, an integer from 1 to 8 is preferred, and 2 is more preferred.

[0058] As specific examples of compound (1), compounds represented by the following formulas (6) to (10) can be listed, but are not limited to these. Among these, compounds represented by the following formula (6) are preferred.

[0059] [Chemistry 8]

[0060]

[0061] (where R) 1 Me and a represent the same meaning as above, and Bu refers to n-butyl.

[0062] These compounds can be commercially available or manufactured. In the case of manufacture, there are no particular limitations on the manufacturing method, and conventionally known manufacturing methods can be used, such as the method described in Japanese Patent Application Publication No. 2020-045304, which involves reacting an amino-containing organosilicon compound with urea.

[0063] On the other hand, the amino-containing organosilicon compounds in the compositions of the present invention are represented by the following formula (3).

[0064] [Chemistry 9]

[0065]

[0066] In equation (3), R 3 Each can independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0067] As R 3 Alkyl groups having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, can be linear, cyclic, or branched. Aryl groups having 6 to 10 carbon atoms are preferred, having 6 to 8 carbon atoms. Specific examples of these alkyl and aryl groups include those with R... 1 The same group as the group illustrated in the example, wherein, as R 3 The preferred atoms are hydrogen atoms, methyl groups, and ethyl groups.

[0068] b represents an integer from 1 to 3, preferably 2 or 3, and n represents an integer from 1 to 12. From the perspective of raw material procurement, an integer from 1 to 8 is preferred, and 3 is even more preferred.

[0069] R 4 The alkyl group representing a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a functional group represented by the following formula (4), preferably having 1 to 8 carbon atoms, more preferably having 1 to 6 carbon atoms, is an alkyl group having 1 to 10 carbon atoms. Specific examples can be listed that are related to the above-mentioned R. 1 The same group as the group shown in the example is preferred, such as methyl or ethyl.

[0070] [Chemistry 10]

[0071]

[0072] (In the formula, the asterisk * indicates the same meaning as above.)

[0073] In equation (4), q represents an integer from 1 to 12. From the viewpoint of easy availability of raw materials, an integer from 1 to 8 is preferred, and 2 is more preferred.

[0074] As specific examples of compound (3), compounds represented by the following formulas (11) to (14) can be listed, but are not limited to these. Among these, compounds represented by the following formula (11) are preferred.

[0075] [Chemistry 11]

[0076]

[0077] (where R) 3 Me, Bu, and b have the same meaning as above.

[0078] These compounds are available as commercially available products. For example, KBM-903 and KBE-903 (both manufactured by Shin-Etsu Chemical Co., Ltd.) are examples of compounds represented by the above formula (11). KBM-602 and KBM-603 (both manufactured by Shin-Etsu Chemical Co., Ltd.) are examples of compounds represented by the above formula (12).

[0079] The content of compound (3) in the composition of the present invention is preferably 0.0001 to 10 parts by mass relative to 100 parts by mass of compound (1), more preferably 0.001 to 3 parts by mass, and even more preferably 0.001 to 1 part by mass.

[0080] Alcohols that can be used in the compositions of the present invention include those represented by the following formula (5).

[0081] R 5 OH (5)

[0082] In equation (5), R 5 Each can be independently represented as an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0083] As R 5 Alkyl groups having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, can be linear, cyclic, or branched. Aryl groups having 6 to 10 carbon atoms are preferred, having 6 to 8 carbon atoms. Specific examples of these alkyl and aryl groups include those with R... 1 The same group as the group illustrated in the example, wherein R 5 Methyl group is preferred.

[0084] The alcohol content in the composition of the present invention is preferably 10 to 1000 parts by mass relative to 100 parts by mass of compound (1), more preferably 50 to 300 parts by mass, and even more preferably 50 to 200 parts by mass.

[0085] The water content in the composition of the present invention is preferably 1,000 to 30,000 parts by mass relative to 100 parts by mass of compound (1), more preferably 5,000 to 20,000 parts by mass, and even more preferably 5,000 to 10,000 parts by mass.

[0086] Furthermore, the alcohol to water content ratio in the composition of the present invention, i.e., alcohol / water ratio, is expressed as a mass ratio, preferably 1 / 1 to 1 / 300, more preferably 1 / 10 to 1 / 200, and even more preferably 1 / 10 to 1 / 100.

[0087] There is no particular limitation on the method of manufacturing the water-containing composition of the present invention. For example, it can be prepared by mixing an alcoholic solution (an anhydrous composition) of a pre-prepared compound (1) and compound (3) with water.

[0088] Specifically, first, compound (1), compound (3), and alcohol are mixed. The order of mixing is not particularly important; compound (1) and alcohol can be mixed before adding compound (2), compound (2) can be mixed before adding compound (1), or compound (1) and compound (2) can be mixed together with the alcohol. Preferably, compound (1) and alcohol are mixed, followed by the addition of compound (3), and further mixing is performed. During mixing, the entire amount of compound (1) or compound (2) can be added at once, or it can be added slowly by dropping. The mixing temperature is preferably 10–50°C, more preferably 15–40°C, and the mixing time is preferably 0.5–3 hours, more preferably 0.5–2 hours.

[0089] After mixing, the resulting solution is filtered as needed. It is preferably left to stand at 10–50°C, more preferably 15–40°C, preferably for 1–10 days, more preferably for 3–10 days, before mixing the resulting alcohol solution with water. When mixing the alcohol solution and water, water can be added to the alcohol solution or vice versa; the entire amount can be added at once or in portions. The temperature and time for mixing the alcohol solution and water are the same as those described above.

[0090] From a stability viewpoint, the composition of the present invention preferably uses water that has been adjusted to be acidic. Examples of acids used for adjusting to acidity include organic acids such as formic acid, acetic acid, and citric acid, and inorganic acids such as hydrochloric acid. When using an acid, its addition amount is preferably 0.001 to 0.5% by mass of the total composition, more preferably 0.01 to 0.1% by mass. Furthermore, when using an acid, water that has been pre-mixed with acid and water to adjust to acidity can be used, or the acid can be added to the composition of the present invention to adjust it to acidity.

[0091] 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.

[0092] Example

[0093] The following examples and comparative examples illustrate the present invention in more detail, but the present invention is not limited to these examples.

[0094] Furthermore, in the following text, "parts" refers to parts by mass. The reaction rate is determined by... 1 Obtained by H-NMR determination.

[0095] [1] Synthesis of organosilicon compounds containing urea groups

[0096] [Synthesis example 1]

[0097] 901 g (15 mol) of urea and 996 g (4.5 mol) of 3-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-903) were placed in a 10 L detachable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer. The mixture was stirred at 117 °C for 20 hours. 1 The reaction rate obtained by H-NMR was 95 mol%. Then, 2324 g (10.5 mol) of 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) was added dropwise at 120°C for 10 hours with stirring. After the addition was complete, stirring was carried out at 117°C for 5 hours. According to... 1 The reaction rate was 100 mol% as determined by H-NMR. After the reaction was completed, the product was removed by vacuum distillation to obtain an organosilicon compound containing a urea group, represented by the following formula (15).

[0098] [Chemistry 12]

[0099]

[0100] [2] Preparation and solubility evaluation of the composition

[0101] [Examples 1-3, Comparative Example 1]

[0102] The urea-containing organosilicon compound obtained in Synthesis Example 1 was mixed with methanol at 25°C according to the proportions shown in Table 1 below. 3-Aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBE-903) was then added dropwise, and the mixture was stirred for 1 hour. The solution was filtered, allowed to stand at 25°C for 7 days, and then mixed with 0.05% (w / w) acetic acid water to obtain the composition.

[0103] The appearance of the composition after 5 minutes is visually confirmed. If it is completely dissolved, it is rated as 0; if it is not dissolved and appears cloudy, it is rated as ×.

[0104] [Table 1]

[0105]

Claims

1. A composition comprising an organosilicon compound containing a urea group represented by formula (1) and an organosilicon compound containing an amino group represented by formula (3) dissolved in a solvent containing an 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 The expression represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a functional group represented by the following formula (2), where Me represents a methyl group, a represents an integer from 1 to 3, and m represents an integer from 1 to 12. [Chemistry 2] In the formula, the asterisk * indicates bonding with adjacent atoms, and p represents an integer from 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 The expression represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a functional group represented by the following formula (4), where Me represents a methyl group, b represents an integer from 1 to 3, and n represents an integer from 1 to 12. [Chemistry 4] In the formula, the asterisk * indicates the combination with adjacent atoms, and q represents an integer from 1 to 12.

2. The composition according to claim 1, wherein, The content of the amino-containing organosilicon compound shown in formula (3) is 0.0001 to 10 parts by mass relative to 100 parts by mass of the urea-containing organosilicon compound shown in formula (1).

3. The composition according to claim 1 or 2, wherein, Alcohols are represented by the following formula (5), R 5 OH (5) In the formula, R 5 It 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 alcohol content is 10 to 1000 parts by mass relative to 100 parts by mass of the organosilicon compound containing urea group shown in 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 relative to 100 parts by mass of the organosilicon compound containing urea group shown in formula (1).

6. The composition according to any one of claims 1 to 5, wherein, The ratio of alcohol to water is expressed as a mass ratio, ranging from 1 / 1 to 1 / 300.

7. The composition according to any one of claims 1 to 6, wherein, The water is acidic.

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