JP5916965B2 - Organosilane aqueous solution and storage method thereof - Google Patents

Description

  The present invention relates to an aqueous organosilane solution and a storage method thereof.

  In recent years, hygiene and antibacterial intentions for living environments such as household goods and clothing are increasing. In particular, with the advent of an aging society, antibacterial and antiviral treatment is applied to articles surrounding the living environment, such as towels and masks, as an environmental improvement in nursing care sites and as a simple inactivation measure against pathogen viruses such as influenza and norovirus Therefore, it is desired to reduce the risk of infection and secondary infection, and many antibacterial agents in the form of easy-to-use spray types and the like are on the market.

  In response to such needs, antibacterial agent compositions and antiviral agent compositions containing a silicon-containing compound that is a silane coupling agent have been developed (see Patent Documents 1 to 4). When these compositions diluted with ethanol and water are applied to an object, the silane coupling agent in the composition is immobilized on the object and can exhibit antibacterial and antiviral effects for a long period of time. Compared to conventional antibacterial agents, it is extremely superior and has been put into practical use.

  However, silane coupling agents generally have a disadvantage that the solution becomes cloudy or gels because it is condensed and precipitated through hydrolysis. When the silane coupling agent is in such a state, in addition to not being able to exhibit the expected effect, there is a concern that in the product form such as the spray type, there is a problem such as clogging of the injection port. In consideration of the storage period from manufacture to use, it is necessary to suppress the cloudiness or gelation for a long period of several months in a storage temperature environment that can be assumed.

  For such a problem, both pH / cationic surfactants are added to the antibacterial agent composition solution (see Patent Documents 1 and 2), and the pH is adjusted to a range of 2.0 to 3.5 (patent) Add a water-soluble organic quaternary ammonium compound and a cationic surfactant (see Patent Document 4), adjust the pH to 2.0 to 3.0 with an acid such as hydrochloric acid or acetic acid. Measures such as adding a glycol ether and a cationic surfactant (see Patent Document 5) have been taken.

JP 2011-98976 A International Publication No. 2010/073825 JP 2007-31290 A Japanese National Patent Publication No. 06-505036 Special table 2009-528326

  However, these measures are insufficient to suppress long-term cloudiness or gelation for several months, and it is difficult to obtain an effect particularly in a high temperature or low temperature region. Moreover, it can not be said that the conditions of pH 2.0-3.5 are preferable on use environment, when the possibility of corrosion of a target object, the influence on a human body, etc. is considered. Accordingly, an object of the present invention is to provide an organosilane aqueous solution that can suppress white turbidity or gelation in units of several months under a temperature environment that can be assumed in normal storage or the like, that is, an organosilane aqueous solution excellent in long-term storage stability, and a method for storing the same. Is to provide.

（式中、ｎは、１〜１０の整数であり、Ｒ^１は、炭素数１０〜３０のアルキル基であり、Ｒ^２及びＲ^３は、それぞれ独立して炭素数１〜６のアルキル基であり、Ｘ⁻は、ハロゲンイオンである。）The present invention completed to solve the above problems
<1> An organosilane aqueous solution containing a compound represented by the following general formula (1); at least one acid selected from the group consisting of lactic acid and acetic acid; and ethanol.
General formula (1):

(In the formula, n is an integer of 1 to 10, R ¹ is an alkyl group having 10 to 30 carbon atoms, and R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms. And X ⁻ is a halogen ion.)

<2> The organosilane aqueous solution according to <1>, wherein the content of the compound represented by the general formula (1) is 0.001% by mass to 0.8% by mass.

<3> The organosilane aqueous solution according to <1> or <2>, wherein the pH is 4.0 to 7.0.

<4> The organosilane aqueous solution according to any one of <1> to <3>, wherein the acid content is 10 ppm to 100 ppm with respect to the mass of the total organosilane aqueous solution.

<5> The organosilane aqueous solution according to any one of <1> to <4>, wherein the acid is lactic acid.

<6> The organosilane aqueous solution according to any one of <1> to <5>, which is stable for 6 months or more under a temperature condition of −30 ° C. to 50 ° C.

<7> The organosilane aqueous solution according to any one of <1> to <6>, wherein the compound represented by the general formula (1) is octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride.

（式中、ｎは、１〜１０の整数であり、Ｒ^１は、炭素数１０〜３０のアルキル基であるり、Ｒ^２及びＲ^３は、それぞれ独立して炭素数１〜６のアルキル基であり、Ｘ⁻は、ハロゲンイオンである。）<8> A mixture containing a compound represented by the following general formula (1), ethanol and water contains at least one acid selected from the group consisting of lactic acid and acetic acid, and a temperature of −30 ° C. to 50 ° C. The preservation | save method of the organosilane aqueous solution in any one of <1>-<7> preserve | saved under conditions.
General formula (1):

(In the formula, n is an integer of 1 to 10, R ¹ is an alkyl group having 10 to 30 carbon atoms, or R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms. And X ⁻ is a halogen ion.)

  The organosilane aqueous solution of the present invention can suppress white turbidity or gelation over a long period from production to use, and is excellent in long-term storage stability, so when used as an antibacterial agent, antiviral agent, etc. Performance can be maintained for a long time.

  Hereinafter, the present invention will be described in detail.

<Aqueous organosilane solution>
The organosilane aqueous solution of the present invention (hereinafter also referred to as “the aqueous solution”) has the following general formula (1):

（式中、ｎは、１〜１０の整数であり、Ｒ^１は、炭素数１０〜３０のアルキル基であり、Ｒ^２及びＲ^３は、それぞれ独立して炭素数１〜６のアルキル基であり、Ｘ⁻は、ハロゲンイオンである。）
で表される化合物（以下、「当該オルガノシラン化合物」ともいう）、乳酸及び酢酸からなる群より選択される少なくとも１種の酸、並びにエタノールを必須成分として含む。当該水溶液は、溶媒である水中に、当該オルガノシラン化合物、乳酸及び／又は酢酸、並びにエタノールを含むことで、想定されうる保存温度環境下、即ち、冷凍・冷蔵温度、室温、ある程度の高温条件等において長期間保存しても、白濁、ゲル化を起こしにくく、長期保存安定性に優れる。

(In the formula, n is an integer of 1 to 10, R ¹ is an alkyl group having 10 to 30 carbon atoms, and R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms. And X ⁻ is a halogen ion.)
And at least one acid selected from the group consisting of lactic acid and acetic acid, and ethanol as essential components. The aqueous solution contains the organosilane compound, lactic acid and / or acetic acid, and ethanol in water as a solvent, so that it can be assumed at a storage temperature environment, that is, freezing / refrigeration temperature, room temperature, some high temperature conditions, etc. Even when stored for a long period of time, white turbidity and gelation are unlikely to occur, and excellent long-term storage stability.

  Here, “excellent in long-term storage stability” means that the aqueous solution in a sealed container is stored at −30 ° C. to 50 ° C., preferably −16 ° C. to 40 ° C. for 3 months or more, preferably It means 6 months or more, more preferably 1 year or more, and even more preferably 2 years or more, a state in which white turbidity or gelation does not occur, or a state in which the resulting white turbidity or gelled component is not precipitated. In addition, about storage temperature conditions, the said aqueous solution should just be stable for said period at the temperature in any one of the said temperature range. Compared to the conventional solution, the aqueous solution can dramatically extend the storage stability period, and the effect is effective in the wide temperature range described above. , Can prevent product quality deterioration over a long period of time.

  Each component contained in the aqueous solution will be described below.

[Organosilane compound]
The organosilane compound contained in the aqueous solution is represented by the above formula (1). In said formula (1), n is an integer of 1-10. R ¹ is an alkyl group having 10 to 30 carbon atoms. R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms. X ⁻ is a halogen ion.

  The organosilane compound represented by the formula (1) includes a triethoxysilane structure and a quaternary ammonium salt structure. This quaternary ammonium salt structure is the same structure as the quaternary ammonium salt contained in general hand antiseptics, and has antibacterial and antiviral effects. On the other hand, since this triethoxysilane structure portion is chemically bonded and fixed to a material (glass, wood, metal, fiber, etc.), the object coated with the aqueous solution has the antibacterial / antiviral effect described above. The surface is covered with a structural part having the above, and the antibacterial / antiviral effect for a certain period can be maintained. Here, “antibacterial” means sterilization or damage of bacteria and fungi, or prevention of their growth, and “antiviral” means inactivation of pathogen virus. In addition, “immobilization” means that when the aqueous solution is applied to an object to which antibacterial / antiviral properties are desired, the organosilane compound is chemically bonded by the action of the silane coupling agent of the organosilane compound. Means that.

  In said formula (1), n is an integer of 1-10, it is preferable that it is 1-6, and it is more preferable that it is 2-4.

In said formula (1), R < ¹ > is a C10-C30 alkyl group, and it is a C12-C24 alkyl group from the said antibacterial and antiviral viewpoint which the said organosilane compound has. Preferably, it is a C15-20 alkyl group, and more preferably an octadecyl group. The alkyl group may be a linear or branched chain alkyl group or a cycloalkyl group, but a chain alkyl group is preferred from the viewpoint of antibacterial and antiviral properties.

In the above formula (1), R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms, from the viewpoint of the antibacterial and antiviral which the organosilane compound has, carbons 1-4 The alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group.

In the above formula (1), X ⁻ is a halogen ion, preferably F ⁻ , Cl ⁻ , Br ⁻ or I ⁻ , and more preferably Cl ⁻ .

  As the organosilane compound represented by the above formula (1), octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride is preferable.

  As content of the said organosilane compound in the said aqueous solution, 0.0001 mass%-0.9 mass% are preferable, 0.001 mass%-0.8 mass% are more preferable, 0.005 mass%-0 More preferably, 6% by mass. By setting the content of the organosilane compound within the above numerical range, it is possible to achieve both long-term storage stability and antibacterial / antiviral properties of the aqueous solution.

[acid]
The aqueous solution contains at least one acid selected from the group consisting of lactic acid and acetic acid. When the aqueous solution contains the acid, white turbidity and gelation are suppressed even during long-term storage, and the long-term storage stability is excellent. In the prior art in which the pH is adjusted to 2 to 3 using hydrochloric acid or the like, there are concerns such as corrosion of the coated surface and influence on the human body. Even if the aqueous solution containing lactic acid and / or acetic acid is adjusted to a pH of weakly acidic to near neutral, specifically pH 4.0 to 7.0, it can be kept at a freezing / refrigeration temperature condition to a certain high temperature condition. Over a wide temperature range, it exhibits a sufficient cloudiness and gelation suppressing effect and is excellent in long-term storage stability. On the other hand, an organosilane aqueous solution to which citric acid or the like is added as an acid other than lactic acid and acetic acid has a disadvantage that white turbidity and gelation are likely to occur particularly when stored for a long time under freezing temperature conditions. Further, when boric acid was added, white turbidity and gelation occurred in about two months, and there was a problem in stability particularly in a high temperature region. Since the aqueous solution exhibits sufficient long-term storage stability even when the pH is weakly acidic to near neutral, the aqueous solution also has an advantage of less concern about the corrosion of the coated surface and the influence on the human body. .

  The aqueous solution may contain either lactic acid or acetic acid, or may contain both. From the viewpoint that the storage stability under various temperature conditions can be maintained for a longer period of time, only lactic acid is used. It is preferable to include.

  The concentration of the acid in the aqueous solution is not particularly limited, but a long-term storage stability effect can be obtained by containing a very small amount. The concentration is preferably 5 ppm to 200 ppm, preferably 10 ppm to 100 ppm, and more preferably 15 ppm to 50 ppm with respect to the total mass of the aqueous solution.

[ethanol]
The aqueous solution contains ethanol. The ratio of ethanol and water in the aqueous solution is not particularly limited, and the mass ratio is ethanol: water = 40: 60 to 80:20, which is said to have the highest sterilization / disinfection performance. Ethanol: water = 70: 30 Is preferred. Here, the “water” in the aqueous solution is not particularly limited. For example, normal water such as tap water, industrial water such as industrial water, ion exchange water, pure water, and the like can be used. Among these, ion exchange water is preferable.

  The aqueous solution contains, in addition to the essential components described above, if necessary, for example, an additive (for example, methanol, isopropanol, a fragrance, etc.) defined by the Alcohol Business Law, or a salt corresponding to the acid to be added. Can be added to obtain a pH buffer solution.

  The pH of the aqueous solution is preferably 4.0 to 7.0, from the viewpoint of improving long-term storage stability in a wide temperature range, and from the viewpoint of less concern about corrosion of the coated surface and influence on the human body. 0-6.8 are more preferable, and 4.3-6.6 are still more preferable.

<Method for producing organosilane aqueous solution>
The method for producing the organosilane aqueous solution of the present invention is not particularly limited, and the organosilane compound of the present invention is mixed and dissolved in any order in the order of the organosilane compound, ethanol, lactic acid and / or acetic acid, and water. An aqueous solution can be obtained. As the above production method, for example, lactic acid and / or acetic acid is added to ethanol and water mixed and stirred at room temperature, and the organosilane compound is further added. The organosilane aqueous solution of the present invention can be obtained by continuing stirring until all the raw materials are mixed and dissolved sufficiently uniformly.

（式中、ｎは、１〜１０の整数である。Ｒ^１は、炭素数１０〜３０のアルキル基である。Ｒ^２及びＲ^３は、それぞれ独立して炭素数１〜６のアルキル基である。Ｘ⁻は、ハロゲンイオンである。）<Preservation method of organosilane aqueous solution>
The method for preserving an aqueous organosilane solution of the present invention comprises a mixture comprising a compound represented by the following general formula (1), ethanol and water containing at least one acid selected from the group consisting of lactic acid and acetic acid, It is stored under a temperature condition of −30 ° C. to 50 ° C.
General formula (1):

(In the formula, n is an integer of 1 to 10. R ¹ is an alkyl group having 10 to 30 carbon atoms. R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms. there .X ^- is a halogen ion).

Examples of the present invention are specifically shown below, but the present invention is not limited to the contents of the examples. The abbreviations in the examples are as follows.
ESi-QAC: compound represented by the above formula (1), compound name: octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride

[Examples 1 to 15]
An organosilane aqueous solution was prepared according to the following operation. In addition, the usage-amount of each component, the mass ratio of ethanol: ion-exchange water, the ESi-QAC density | concentration and acid concentration of produced aqueous solution, and pH of produced aqueous solution are shown to Tables 1-3.

  Ethanol (Wako Pure Chemical Industries, Ltd.) and ion-exchanged water were placed in a beaker at room temperature, and stirred and mixed with a magnetic stirrer. While continuing mixing, lactic acid or acetic acid (all Wako Pure Chemical Industries, Ltd.) was added, and then ESi-QAC (Manac Co., Ltd.) was added, followed by stirring and mixing for about 1 hour. A silane aqueous solution was obtained.

[Comparative Examples 1-5]
An organosilane aqueous solution was prepared according to the following operation. In addition, Table 2-3 shows the usage-amount of each component, the mass ratio of ethanol: ion-exchange water, the ESi-QAC density | concentration and acid density | concentration in the produced composition, and pH of the produced aqueous solution.

  Ethanol (Wako Pure Chemical Industries, Ltd.) and ion-exchanged water were placed in a beaker at room temperature, and stirred and mixed with a magnetic stirrer. While continuing the mixing, ESi-QAC (Manac Co., Ltd.) was added and then stirred and mixed for about 1 hour to obtain a colorless and clear organosilane aqueous solution. In Comparative Examples 2 to 4, a predetermined amount of acid was added before adding ESi-QAC.

[Storage stability test]
The storage stability test was implemented about the organosilane aqueous solution obtained in Examples 1-15 and Comparative Examples 1-5. The test method and test conditions will be described. Each test sample was filled with about 20 ml of a colorless transparent glass screw cap bottle of about 20 ml capacity, and the lid was closed and sealed. During filling, natural filtration was performed with a 200 mesh filter cloth in order to remove dust in the liquid. The test sample was stored under the temperature conditions of −16 ° C., 4 ° C., room temperature (variable between 10 ° C. and 30 ° C.), and 40 ° C., and the appearance change was visually observed. Test results are shown in Tables 4-6. The test results were evaluated by the following method and listed in the table. Moreover, nd in the table indicates that it has not been measured.
○: Clear x: cloudiness or gelation or precipitation of those components

  The organosilane aqueous solutions of Examples 1 and 5 were subjected to a storage stability test over a longer period of time, and all temperature conditions of −16 ° C., 4 ° C., room temperature, and 40 ° C. were observed even after 2 years. It was clear below.

  As shown in Tables 4-6, it can be seen that the organosilane aqueous solution according to the present invention is extremely excellent in long-term storage stability under each storage temperature condition. As shown in Table 6, the organosilane aqueous solution of the present invention has a longer storage stability than that of the comparative example organosilane aqueous solution to which acids other than acetic acid and lactic acid are added, particularly storage under freezing temperature conditions. It turns out that it is excellent in stability.

  The organosilane aqueous solution of the present invention can suppress white turbidity or gelation over a long period from production to use, and is excellent in long-term storage stability. Therefore, the organosilane aqueous solution of the present invention is suitably used as an antibacterial agent, an antiviral agent, etc. in the form of a particularly convenient spray type. The organosilane aqueous solution of the present invention can impart antibacterial and antiviral properties to the surface of various materials such as metals, glass, ceramics, resins, fibers, etc., with a simple treatment without environmental pollution. Therefore, it can be particularly suitably used in fields requiring antibacterial and antiviral effects such as in the medical field and food field.

Claims (8)

An organosilane aqueous solution containing a compound represented by the following general formula (1); at least one acid selected from the group consisting of lactic acid and acetic acid; and ethanol.
General formula (1):

(In the formula, n is an integer of 1 to 10, R ¹ is an alkyl group having 10 to 30 carbon atoms, and R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms. And X ⁻ is a halogen ion.) The content of the compound represented by the general formula (1) is 0.001% by mass to 0.8% by mass,
The organosilane aqueous solution according to claim 1. the pH is 4.0-7.0,
The organosilane aqueous solution according to claim 1 or 2. The acid content is 10 ppm to 100 ppm with respect to the mass of the total organosilane aqueous solution.
The organosilane aqueous solution according to any one of claims 1 to 3. The acid is lactic acid,
The organosilane aqueous solution according to any one of claims 1 to 4. It is stable for 6 months or more under the temperature condition of -30 ° C to 50 ° C.
The organosilane aqueous solution according to any one of claims 1 to 5. The compound represented by the general formula (1) is octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride.
The organosilane aqueous solution according to any one of claims 1 to 6. In a mixture containing a compound represented by the following general formula (1), ethanol and water, at least one acid selected from the group consisting of lactic acid and acetic acid is contained, and under a temperature condition of −30 ° C. to 50 ° C. save,
The storage method of the organosilane aqueous solution of any one of Claims 1-7.
General formula (1):

(In the formula, n is an integer of 1 to 10, R ¹ is an alkyl group having 10 to 30 carbon atoms, and R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms. And X ⁻ is a halogen ion.)