KR102371552B1 - Method for producing antibacterial and antiviral composition with improved formulation stability and antibacterial and antiviral composition using the same - Google Patents

Abstract

The present invention relates to a method for producing an antibacterial and antiviral composition with improved formulation stability and an antibacterial and antiviral composition using the same. The method for producing an antibacterial and antiviral composition of the present invention obtains a composition in which transparent formulation stability is secured without precipitation even after 10 days by adding an alkoxy silane stabilized at a temperature of 30 to 36℃ in a raw material composition containing an antibacterial and antiviral active ingredient in an alcohol solvent condition maintained at a temperature of 28℃ or higher and confirms improved antibacterial and antiviral performance by adding a specific siloxane or aluminum-based complex to the composition. The composition of the present invention can be applied in the form of coatings or sprays in various markets including personal care products, disposable products, etc. that require antibacterial and antiviral performance.

Description

Method for producing an antibacterial and antiviral composition with increased formulation stability and an antibacterial and antiviral composition using the same

The present invention relates to a method for preparing an antibacterial and antiviral composition with improved formulation stability and an antibacterial and antiviral composition using the same, and more particularly, to an antibacterial and antiviral activity in an alcohol solvent condition maintained at a temperature of 28° C. or higher. A composition in which formulation stability is secured by adding an alkoxysilane stabilized at a temperature of 30 to 36° C. to the raw material composition containing the raw material, and siloxane or aluminum-based complex compound is added thereto to improve antibacterial and antiviral performance. It relates to a method for producing an antibacterial and antiviral composition with increased stability and an antibacterial and antiviral composition using the same.

Since the 2000s, due to the outbreak of epidemics such as SARS and H1N1 flu, interest in harmful microorganisms to prevent bacterial and viral infections is increasing, and research has been steadily progressing.

In particular, in a situation where the spread of the coronavirus (COVID-19) infection does not subside, in addition to virus vaccine research, it is required to develop products with antiviral performance along with daily life prevention due to the nature of the virus transmitted by contact.

In general, the average human cell size is about 20 to 100 μm, and bacteria are smaller than this, at the level of 1 to 10 μm. Although the minimum size that can be distinguished with the naked eye is slightly different from person to person, since it is about 0.1 mm, bacteria cannot be seen with the naked eye, but the existence of bacteria can be sufficiently confirmed using an optical microscope.

However, since the average size of the virus is much smaller than this, about 10 to 300 nm, it cannot be observed with an optical microscope with a maximum magnification of only 1000 times. Therefore, the existence of viruses became possible after the development of electron microscopes with much greater magnification (maximum magnification of 1 million times).

Viruses are individuals with both living and non-living characteristics, and are basically a simple structure containing nucleic acids (DNA or RNA), which are genetic materials, in an envelope composed of proteins.

Therefore, unlike bacteria, viruses cannot metabolize alone and thus cannot carry out life activities. However, when introduced into a host cell, it parasitizes in the life activity of the host cell and reproduces the genetic material and protein envelope to multiply the population. make it

When viruses that exist in the form of protein crystals meet a host cell, they bind to the cell membrane of the host cell and then flow into it. After entering the host cell, the virus uses the host cell's function of replicating the genetic material and producing protein to make its own genetic material and protein envelope, and then reassembles them to proliferate virus cells resembling itself.

In particular, it is not possible to control the rapid mutation of RNA virus, which has been proven by the continuous spread of the recent coronavirus (COVID-19) infection. Alternatively, demand in various markets including disposable products is expected to continue.

As a recently reported prior document, Patent Document 1 discloses an antibacterial and antiviral composition containing hydroxyapatite, wherein the hydroxyapatite is represented by the formula Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ As a natural mineral form of expressed calcium apatite, the hydroxyapatite reacts with water to form hydroxyl radicals, thereby destroying the cell membrane of viruses or bacteria, denaturing proteins, and generating genes It is reported to have an antibacterial effect by destroying

As another example, Patent Document 2 reports on an antiviral and antibacterial composition comprising a copper-iron alloy nanopowder, and in particular, when the dispersibility and dispersion stability of copper in a solvent is low, layer separation or Nanopowder of copper-iron alloy; a solvent including polyethylene glycol, salicylic acid, glycolic acid, lower alcohol and purified water; and surfactant; and improved dispersibility and dispersion stability of the copper-iron alloy nanopowder in a solvent, thereby realizing significantly improved antiviral and antibacterial effects.

In addition, in Non-Patent Document 1, as a report on a case study of performance analysis of "antiviral copper film for glass window attachment" for responding to Corona 19, the performance analysis and scientific verification results of East and West for antimicrobial copper products are presented. . The antibacterial copper refers to copper that can receive a certification mark when it uses more than 65% of copper alloy with antibacterial effect to eradicate 99.9% of harmful bacteria within 2 hours from the International Copper Association.

According to the test results of the US NIH and CDC's "Corona 19 viability test according to the surface material" in March 2020, it inactivates up to 99.9% of the Corona 19 virus on the copper surface within 4 hours (loss of infectivity), and Corona 19 on the copper surface reported to survive up to 4 hours, 24 hours on a cardboard surface (similar to a delivery box), and up to 48 hours on a plastic surface.

In addition, in this report, in order to confirm the efficacy certification through performance test and analysis of antiviral copper film for attaching glass windows to buildings and automobiles to prevent the spread of COVID-19 infection, in 2020, “antibacterial copper As a result of the performance test of the antiviral performance evaluation of the film against COVID-19, compared to the control group (parafilm), it inactivated COVID-19 by 14.0% after 30 minutes, 38.1% after 120 minutes, and up to 97.2% after 24 hours. It suggests the effect of

However, in that the antiviral test is still the result of the laboratory ( In Vitro ) and the antimicrobial copper plays a role in reducing the survival time of the virus, the activity of bacteria or viruses in contact with the copper component is reduced. Antibacterial and antiviral effects are confirmed due to decreased survival time, but it takes about 4 hours to kill the virus.

Therefore, since the antibacterial film is attached to most objects or spaces in contact with the human body in daily life and is attached to the location where many people come into contact with it, it should be able to achieve faster and stronger antibacterial and antiviral effects.

Above all, based on materials that are not harmful or toxic to the human body, research on materials that can achieve antibacterial or antiviral effects, and verification of whether the effects can be achieved in a shorter time should be continuously conducted.

In particular, based on materials that are not harmful or toxic to the human body, search and development research on materials that can achieve antibacterial or antiviral effects, and verification of whether the effect can be achieved in a shorter time should be continuously performed. .

(Trihydroxysilyl) propyldimethyloctadecyl ammonium chloride [(Trihydroxysilyl) propyldimethyloctadecyl ammonium chloride, Cas No. 199111-50-7] is a compound whose human safety has been certified as an antibacterial and antiviral active ingredient through FDA approval and EPA registration (No.83019-1).

Formula 1

However, the antibacterial and antiviral active raw material has low solubility in water and has been pointed out a problem of limited application, and although it has limited solubility in methanol solvent, it is a field requiring antibacterial and antiviral due to the harmfulness of methanol. There are practically impossible points to apply.

Accordingly, the present inventors have tried to solve the problems of the antibacterial and antiviral active raw material represented by Formula 1 whose antibacterial and antiviral effects and safety are certified. Prepare a raw material composition in which the active raw material is dispersed, and add an alkoxysilane stabilized at a temperature of 30 to 36° C. to the raw material composition to obtain a composition in which formulation stability is ensured, and a specific siloxane or aluminum-based complex is added to the composition By confirming further improved antibacterial and antiviral performance, the present invention was completed.

Republic of Korea Patent Publication No. 2258923 (Announcement on May 31, 2021) Korean Patent Laid-Open Patent No. 2198915 (published on Jan. 06, 2021)

J Korean Soc Disaster Secur Vol. 14, No. 1, March 2021

It is an object of the present invention to include an active raw material whose antibacterial and antiviral effects and safety are certified, but overcome the low solubility of the compound in water and eliminate the use of a methanol solvent while increasing formulation stability. to provide a way

Another object of the present invention is to provide an antibacterial and antiviral composition that implements further improved performance by adding a siloxane or aluminum-based complex to the composition in which formulation stability is secured from the method for preparing the antibacterial and antiviral composition.

In order to achieve the above object, the present invention prepares a raw material composition containing the antibacterial and antiviral active raw material represented by the following formula (1) in an alcohol solvent condition maintained at a temperature of 28 ℃ or more,

It provides a method for producing an antibacterial and antiviral composition with improved formulation stability by adding an alkoxysilane monomer represented by the following Chemical Formula 2 to the raw material composition, which is stabilized at a temperature of 30 to 36°C.

Formula 1

Formula 2

(R _a ) _4-n -Si-(OR _b ) _n

In Formula 2, R _a is a C ₁ to C ₈ alkyl group, a C ₃ to C ₈ allyl group, a C ₁ to C ₈ fluorinated alkyl group substituted with 3 to 6 fluorine elements, and 3 to 6 C substituted with a fluorine element _{3 ~} C ₈ At least one selected from allyl fluorinated group, R _b is a C ₂ ~ C ₈ alkyl group, n is an integer of 1 to 3.

In the above, the alcohol solvent is preferably a linear alcohol of CH ₃ (CH ₂ ) _n+1 -OH, n is 1 to 3, and more preferably 1-propanol.

In the above manufacturing method, the alkoxy silane monomer is added under the condition that the raw material composition is maintained through stirring at 28 to 45°C.

The present invention relates to 100 parts by weight of a raw material composition in which the antibacterial and antiviral active raw material represented by Formula 1 is contained in an alcohol solvent, obtained from a method for preparing an antibacterial and antiviral composition with improved dosage form stability, a dosage form stabilizer alkoxysilane It provides an antibacterial and antiviral composition in which 40 to 60 parts by weight of a monomer is added.

Specifically, the raw material composition contains 0.1 to 1% by weight of an antibacterial and antiviral active raw material, 40 to 75% by weight of an alkoxysilane-based binder polymer represented by the following Chemical Formula 3, 0.1 to 5% by weight of a metal alkoxide catalyst, and the remaining amount of an alcohol solvent. will be.

Formula 3

In Formula 3, n is represented by A-2, wherein A is a natural number selected from 1 to 100 that is a multiple of 4, m is a natural number selected from 1 to 100, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently at least one hydrocarbon group selected from C _1-16 alkyl, C _2-16 alkynyl, C _2-16 alkenyl and C _3-16 allyl am.

In addition, the antibacterial and antiviral composition of the present invention is added with 5 to 50 parts by weight of a siloxane having a hydroxyl group (-OH) at the terminal or both terminals as a functional enhancer, based on 100 parts by weight of the raw material composition. An antibacterial and antiviral composition with improved virality is provided.

In addition, the antibacterial and antiviral composition can provide a composition with improved antibacterial and antiviral properties by adding 0.01 to 0.5 parts by weight of an aluminum-based complex as a functional enhancer with respect to 100 parts by weight of the raw material composition.

According to the manufacturing method of the present invention, the active raw material certified for antibacterial and antiviral effects and safety reduces compatibility due to low solubility in water and solves the problem of toxicity caused by methanol when dissolved in methanol, even after 10 days It is possible to provide an antibacterial and antiviral composition with formulation stability that is preserved transparently without precipitation.

In addition, by adding a specific siloxane or aluminum-based complex compound to confirm the effect of further improved antibacterial and antiviral performance, the composition of the present invention can be coated or It can be applied in the form of a spray.

1 is a comparison of the formulation stability of the composition according to the alcohol solvent in the preparation step of the raw material composition in the manufacturing method of the present invention,
Figure 2 is a comparison of the formulation stability of the composition according to the alkoxy silane monomer to the raw material composition of Figure 1,
3 is an antibacterial test result of the composition prepared in Example 1 (using methyltriethoxysilane as an alkoxysilane monomer) of the present invention against E. coli after 24 hours;
4 is an antibacterial test result of the composition prepared in Example 1 of the present invention after 24 hours against pneumococcus,
5 is an antibacterial test result after 24 hours against E. coli of the composition prepared in Comparative Example 1 (methyltrimethoxysilane as an alkoxysilane monomer) of the present invention;
6 is an antibacterial test result after 24 hours against Staphylococcus aureus of the composition prepared in Comparative Example 1 of the present invention;
7 is a control result for a general cover glass for antiviral performance evaluation using the TCID50 assay of the present invention;
8 is a result of the antiviral performance of Example 7 for the evaluation of the antiviral performance using the TCID50 analysis of FIG.

Hereinafter, the present invention will be described in detail.

The present invention prepares a raw material composition containing an antibacterial and antiviral active raw material represented by the following formula (1) in an alcohol solvent maintained at a temperature of 28 ℃ or more,

It provides a method for producing an antibacterial and antiviral composition with improved formulation stability by adding an alkoxysilane monomer represented by the following Chemical Formula 2 to the raw material composition, which is stabilized at a temperature of 30 to 36°C.

Formula 1

Formula 2

(R _a ) _4-n -Si-(OR _b ) _n

In Formula 2, R _a is a C ₁ to C ₈ alkyl group, a C ₃ to C ₈ allyl group, a C ₁ to C ₈ fluorinated alkyl group substituted with 3 to 6 fluorine elements, and 3 to 6 C substituted with a fluorine element _{3 ~} C ₈ At least one selected from allyl fluorinated group, R _b is a C ₂ ~ C ₈ alkyl group, n is an integer of 1 to 3.

In the manufacturing method, the raw material composition containing the active raw material is to be added to the alkoxysilane monomer under the condition that the temperature is maintained through stirring in an alcohol solvent maintained at a temperature of 28 ℃ or more. At this time, the stirring temperature is preferably carried out under conditions maintained at 28 to 45 ℃.

The alcohol solvent is preferably a linear alcohol, and more specifically, a linear alcohol of CH ₃ (CH ₂ ) _n+1 -OH, wherein n is 1 to 3.

1 is a comparison of the formulation stability of the composition according to the alcohol solvent selection in the preparation step of the raw material composition in the preparation method of the present invention, (a) is a 1-propanol solvent, (b) is a composition according to 2-propanol present the form of

As a result, in the case of (a) 1-propanol solvent, a clear and transparent state, but (b) 2-propanol solvent, no precipitate was observed, but a non-transparent state can be confirmed.

Therefore, in order to increase the formulation stability of the present invention, 1-propanol is used as the most preferable alcohol solvent in the embodiment of the present invention.

The manufacturing method of the present invention is characterized in that formulation stability is improved by adding an alkoxysilane monomer represented by Formula 2 stabilized at a temperature of 30 to 36° C. to the raw material composition. At this time, when the alkoxy silane monomer is used at a temperature of less than 30° C., there is a problem in that precipitation occurs.

The present invention uses an alkoxy silane monomer represented by the following formula (2).

Formula 2

(R _a ) _4-n -Si-(OR _b ) _n

In Formula 2, R _a is a C ₁ to C ₈ alkyl group, a C ₃ to C ₈ allyl group, a C ₁ to C ₈ fluorinated alkyl group substituted with 3 to 6 fluorine elements, and 3 to 6 C substituted with a fluorine element _{3 ~} C ₈ At least one selected from allyl fluorinated group, R _b is a C ₂ ~ C ₈ alkyl group, n is an integer of 1 to 3.

More specifically, the terminal group (R _b ) of the alkoxy silane monomer is selected and used in a range that excludes a methyl group (-CH ₃ ) and does not exceed an octyl group for room temperature curing. At this time, when the terminal group (R _b ) is a methoxy group, the reactivity is high, which is disadvantageous to formulation stability, and when it exceeds the octyl group, there is a problem in that the hardness is soft and peeled off. On the other hand, when the terminal group of the alkoxysilane monomer is ethoxy (-OC ₂ H ₅ ) of triethoxymethylsilane, 3H hardness can be confirmed in a curing test at room temperature for 12 hours.

Preferred embodiments of the alkoxy silane monomer used in the present invention are trimethoxy (octyl) silane, triethoxy (octyl) silane, isobutyl (trimethoxy) Isobutyl(trimethoxy)silane, Isobutyl(triethoxy)silane, n-Propyltriethoxysilane, Trimethoxy(propyl) silane), triethoxy(ethyl)silane, triethoxymethylsilane, trimethoxymethylsilane, trimethoxy(3,3,3-trifluoropropyl) ) silane (Trimethoxy(3,3,3-trifluoropropyl)silane) and triethoxy(1H, 2H, 2H, 2H-perfluoro-1-octyl) silane At least one selected from 1-octyl)silane) or one or more types may be used.

2 is a comparison of the formulation stability of the composition according to the selection of the alkoxy silane monomer by adding an alkoxy silane monomer to the raw material composition.

In the case of (a), methyltriethoxysilane (MTES) was observed after 10 days and remained transparent, whereas (b) methyltrimethoxysilane (MTMS) was observed under the same conditions after 10 days. Precipitation due to particle formation can be confirmed.

In addition, FIGS. 3 and 4 are the antibacterial test results of the composition of Example 1 using methyltriethoxysilane (MTES) as an alkoxysilane monomer 24 hours after E. coli and pneumococcus, and FIGS . 5 and 6 are alkoxysilane The composition of Comparative Example 1 using methyltrimethoxysilane (MTMS) as a monomer is the result of an antibacterial test for E. coli and Staphylococcus aureus after 24 hours.

As a result, the composition of Example 1 prepared by adding methyltriethoxysilane (MTES) as the alkoxysilane monomer showed antibacterial performance of 94.7%, 99.6%, and 15.2% as a result of antibacterial tests against Escherichia coli, pneumoniae, and MASR. While [Table 2] was shown, the composition prepared by adding methyltrimethoxysilane (MTMS) was confirmed to be 61.3% and 18.4% [Table 3], respectively, as a result of the antibacterial test for E. coli and Staphylococcus aureus in the experiment under the same conditions. do.

In addition, Figure 7 is a control result for the general cover glass for antiviral performance evaluation using the TCID50 assay of the present invention, and Figure 8 is the antiviral composition of the composition prepared in Example 7 for antiviral performance evaluation using the TCID50 assay. As a result of the performance, it can be confirmed that the antiviral performance is superior to that of the control group. In addition, as a result of calculation through TCID50 analysis, the composition prepared in Example 7 showed a 74.88% virus reduction rate within 10 minutes of reaction time for the cat coronavirus (Pelin coronavirus).

From the above, in the preparation method of the antibacterial and antiviral composition with improved formulation stability of the present invention, by optimizing the operating conditions when selecting an alcohol solvent and selecting an alkoxysilane monomer and adding it, the antibacterial and antiviral performance expression can also be optimized accordingly. there is.

Furthermore, the present invention provides an antibacterial and antiviral composition in which formulation stability is secured from a manufacturing method.

More specifically, with respect to 100 parts by weight of the raw material composition contained in the alcohol solvent maintained at a temperature of 28 ° C. or higher, the antibacterial and antiviral active raw material represented by the following formula (1), the formulation stabilizer alkoxy silane monomer represented by the following formula (2) It provides an antibacterial and antiviral composition in which 40 to 60 parts by weight are added.

Formula 1

Formula 2

(R _a ) _4-n -Si-(OR _b ) _n

In Formula 2, R _a , R _b and n are as defined above.

More specifically, the raw material composition contains 0.1 to 1% by weight of an antibacterial and antiviral active raw material, 30 to 70% by weight of an alkoxysilane-based binder polymer represented by the following Chemical Formula 3, 0.1 to 5% by weight of a metal alkoxide catalyst, and the remaining amount of an alcohol solvent includes

Formula 3

In Formula 3, n is represented by A-2, wherein A is a natural number selected from 1 to 100 that is a multiple of 4, m is a natural number selected from 1 to 100, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently at least one hydrocarbon group selected from C _1-16 alkyl, C _2-16 alkynyl, C _2-16 alkenyl and C _3-16 allyl am.

Since the antibacterial and antiviral active ingredients and alcohol solvent constituting the raw material composition are the same as described above, a detailed description thereof will be omitted.

Since the alkoxysilane-based binder polymer represented by Chemical Formula 3 includes hydroxyl groups at both ends of the chain and an aliphatic hydrocarbon group and an alkoxy group therebetween, it has excellent compatibility with the hydrophobic material and the hydrophilic material.

In Formula 3, n is represented by A-2, wherein A is at least one selected from 1 to 100, which is any one of a multiple of 3, a multiple of 4, a multiple of 5, a multiple of 6, and a multiple of 7. is a natural number. For example, in Formula 1, A may be a multiple of 4 or a multiple of 5, preferably, A is a multiple of 4, and m is at least one natural number selected from 1 to 100.

In addition, in the alkoxysilane-based binder polymer comprising an alkoxy group, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently C _1-16 alkyl, C At least one hydrocarbon group selected from _2-16 alkynyl, C _2-16 alkenyl and C _3-16 allyl, in particular, R ₃ is a C _1-16 alkyl group, preferably R ₃ is a C _1-8 alkyl group, more Preferably, R ₃ may be a C _1-2 alkyl group, and most preferably R ₃ is methyl (methyl).

The alkoxysilane-based binder polymer can be obtained by ring-opening polymerization of cyclic siloxane and alkoxysilane, and is manufactured according to the applicant's Patent No. 2229794, and the method for preparing the siloxane does not require a high temperature heat treatment process. , it is possible to control the degree of hydrophobicity, hardness, oil repellency, etc. by changing the monomer, so that siloxanes with various properties can be synthesized at low temperature.

The alkoxysilane-based binder polymer contained as one composition in the raw material composition of the present invention is contained in an amount of 0 to 70% by weight, more preferably 30 to 70% by weight, not to exceed 70% by weight.

In addition, 0.1 to 5% by weight of the metal alkoxide catalyst contained in the raw material composition of the present invention is contained.

Specifically, the metal alkoxide catalyst is tantalum ethoxide, germanium ethoxide, titanium ethoxide, zirconium ethoxide, zirconium propoxide, titanium isopropoxide, germanium isopropoxide, titanium iso At least one selected from the group consisting of propoxide, zirconium isopropoxide, tantalum butoxide, titanium butoxide, titanium t-butoxide, zirconium butoxide and zirconium t-butoxide is used.

The present invention provides an antibacterial and antiviral composition in which 40 to 60 parts by weight of an alkoxysilane monomer is added to the above raw material composition to ensure formulation stability, and thereby preserve excellent antibacterial activity against Escherichia coli and pneumoniae.

Furthermore, the present invention can further improve antibacterial and antiviral properties by adding siloxane having a hydroxyl group (-OH) to the terminal or both terminals to the antibacterial and antiviral composition.

Therefore, the siloxane having a hydroxyl group (-OH) at the terminal or both terminals used as a function improver has a hydroxyl value (OH Value) of 1.5 to 5, and a viscosity of 15 to 50 mm2/s. .

In an embodiment of the present invention, as an example thereof, 5 to 50 parts by weight, preferably 5 to 35 parts by weight, of PDMS-OH (Polydimethylsiloxane hydroxy-terminated) based on 100 parts by weight of the raw material composition is used, but is not limited thereto. will be. At this time, if the content of the functional enhancer containing PDMS-OH is less than 5% by weight, the degree of antibacterial and antiviral improvement is insignificant, and if it exceeds 50% by weight, there is a problem in compatibility between the compositions rather than the performance improvement effect.

In addition, the present invention can further improve the antibacterial and antiviral properties by adding an aluminum-based complex compound as another function-improving agent to the antibacterial and antiviral composition, preferably based on 100 parts by weight of the raw material composition, 0.01 to 0.5 parts by weight is added.

As the aluminum complex, preferably aluminum ethoxide, aluminum isopropoxide, aluminum tributoxide, aluminum t-butoxide, aluminum n-butoxide, aluminum acetylatetonate, aluminum L-lactate and Any one or more selected from the group consisting of aluminum-tri-sec-butoxide may be used.

Hereinafter, the present invention will be described in more detail through examples.

These examples are for explaining the present invention in more detail, and the scope of the present invention is not limited to these examples.

<Example 1>

Prepare 1-propanol by keeping it at 28°C or higher in a sealed double-jacket container, and add an antibacterial and antiviral active ingredient ((Trihydroxysilyl) propyldimethyloctadecyl ammonium chloride, Cas No. 199111-50-7) to 0.3 weight of the total composition % was added and uniformly stirred to prepare a dispersion solution. At this time, the stirring temperature was carried out in a range not exceeding 28°C to 45°C, and stirring was performed to a clear and transparent state while checking whether the formulation of the solution was transparent during the process.

Methyltriethoxysilane (MTES) as an alkoxysilane monomer is slowly added dropwise dropwise to the dispersion solution, and at this time, a precipitation phenomenon occurs at a temperature of less than 30 ° C., and the alkoxy silane monomer is stabilized at a temperature of 30 to 36 ° C. After addition, transparency was maintained to prepare an antibacterial and antiviral composition.

<Example 2>

An antibacterial and antiviral composition was prepared in the same manner as in Example 1, except that octyltriethoxysilane (OTES) was used as the alkoxysilane monomer.

<Comparative Example 1>

An antibacterial and antiviral composition was prepared in the same manner as in Example 1, except that methyltrimethoxysilane (MTMS) was used as the alkoxysilane monomer.

<Comparative Example 2>

An antibacterial and antiviral composition was prepared in the same manner as in Example 1, except that dodecyltriethoxysilane (DDTES) was used as the alkoxysilane monomer.

<Experimental Example 1> Formulation stability evaluation

1. Evaluation of formulation stability according to alcohol solvent

For the case of using 1-propanol as an alcohol solvent in the preparation step of the raw material composition of Example 1 and the case of using 1-propanol in Comparative Example 1, the formulation stability was evaluated by visually observing during stirring.

As can be seen from the results of FIG. 1 , (a) the 1-propanol solvent was in a clear and transparent state, but (b) the 2-propanol solvent showed no precipitate, but was not transparent.

2. Formulation stability evaluation according to alkoxy silane monomer

After the preparation step of the raw material composition of Example 1, as the alkoxysilane monomer, for the case of using methyltriethoxysilane (MTES) and the case of using methyltrimethoxysilane (MTMS) in Comparative Example 1, the composition of the composition after addition Formulation stability was visually evaluated.

As a result, as shown in FIG. 2 , in the case of (a) methyltriethoxysilane (MTES), it remained transparent as a result of observation after 10 days, whereas (b) methyltrimethoxysilane (MTMS) was 10 After one day, as a result of observation under the same conditions, particles were formed.

In addition, the preparation of antibacterial and antiviral compositions and the results of evaluation of physical properties thereof are described in Table 1 below.

From the results of Table 1, the evaluation of the formulation stability of FIGS. 1 and 2 was described, and the composition using dodecyltriethoxysilane (DDTES) as an alkoxysilane monomer was cured at room temperature for 12 hours using a pencil hardness meter. As a result of measuring the hardness after maintaining the time, the composition of Example 1 showed 3H hardness, whereas the composition of Comparative Example 2 was judged to be too soft to measure.

<Experimental Example 2> Antibacterial performance evaluation

For the antibacterial and antiviral compositions prepared in Example 1 and Comparative Example 1, an antibacterial test was requested and evaluated (Korea Institute of Construction and Living Environment).

The specimen was sampled with a size of 5 cm × 5 cm, and the control specimen was prepared with 5 cm × 5 cm of Stomacher film, and the target strains used were E. coli ( Eschrichia coli ATCC 8739 ), Klebsiella pneumoniae ATCC 4352), MASR subsp. aureus ATCC 33591) and Staphylococcus aureus ATCC 6538P were used, and the results according to each concentration, test method and test environment are described in Tables 2 and 3 below.

From the results of Table 2, the composition according to the preparation method of the antibacterial and antiviral composition of Example 1 showed antibacterial performance of 94.7%, 99.6%, and 15.2% as a result of the antibacterial test against E. coli, pneumococcus, and MASR. , 3 and 4 show the results of the antibacterial test for E. coli and pneumococcus by the composition of Example 1 after 24 hours.

On the other hand, as shown in the results of Table 3, in the case of the composition of Comparative Example 1, when comparing the results for E. coli, it was 61.3%, showing a relatively low antibacterial performance compared to Example 1.

5 and 6, the composition of Comparative Example 1 presented the antibacterial test results after 24 hours against E. coli and Staphylococcus aureus.

<Example 3>

Prepare 1-propanol by keeping it at 28°C or higher in a sealed double-jacket container, and add an antibacterial and antiviral active ingredient ((Trihydroxysilyl) propyldimethyloctadecyl ammonium chloride, Cas No. 199111-50-7) to 0.3 weight of the total composition % was added and uniformly stirred to prepare a dispersion solution. At this time, the stirring temperature was carried out in a range not exceeding 28°C to 45°C, and stirring was performed to a clear and transparent state while checking whether the formulation of the solution was transparent during the process.

Methyltriethoxysilane (MTES) as an alkoxysilane monomer stabilized at a temperature of 30 to 36° C. to the dispersion solution was slowly added dropwise dropwise to prepare a composition having a transparent formulation.

In the above, with respect to 100 parts by weight of the raw material composition, 33 parts by weight of PDMS-OH (Polydimethylsiloxane hydroxy-terminated) as a function improving agent was added to prepare an antibacterial and antiviral composition.

<Examples 4 to 8>

Antibacterial and antiviral compositions were prepared by adding the compositions and contents shown in Table 4 below.

<Experimental Example 3> ATP measurement

For the compositions prepared in Examples 1 to 8 shown in Table 4, the antibacterial activity was evaluated by measuring the contamination level using an ATP (Adenosine Tri-Phosphate) contamination level meter.

General bacteria and mold were collected from the microbial medium, diluted in water, and the average contamination level of the contaminated water was measured as 1004 through an ATP contamination meter. The contaminated water was applied to the surface of the slide glass coated with the composition prepared in Examples 1 to 8, and ATP on the surface was measured 1 minute after spraying, and the results are shown in Table 4.

The number of bacteria is a CFU (Colony Form Unit) unit, and by adding PDMS-OH (Polydimethylsiloxane hydroxy-terminated) to the antibacterial and antiviral compositions of Examples 1 and 2, the number of bacteria was reduced as a result of ATP measurement.

In addition, when the aluminum-based complex compound was added to the antibacterial and antiviral compositions of Examples 1 and 2, the number of bacteria was also reduced as a result of ATP measurement. Furthermore, in the case of Examples 7 and 8 in which the antibacterial and antiviral compositions of Examples 1 and 2 were mixed with PDMS-OH (Polydimethylsiloxane hydroxy-terminated) and an aluminum-based complex compound, the number of bacteria was significantly reduced. By doing so, it showed excellent antibacterial properties.

<Experimental Example 4> Antiviral test evaluation

In Example 7, an inactivation test for coronavirus was performed through the tissue culture infection dose (TCID50) method [conducted by the Korea Institute of Medical Sciences].

TCID50 analysis shows the titer of the dilution factor of the virus that infects 50% by inoculating 5 or more (usually 8-10 test units) animal cells for each multiple of the virus suspension diluted 10 times. By observing the cell monolayer inoculated with the virus for each fold, the presence or absence of CPE is determined, and the percentage of infected wells is calculated. The 50% endpoint was calculated by the Reed-Muench method.

The experimental conditions and experimental results are described in Table 5 below. In addition, the antiviral test results for the experimental group of the present invention are shown in FIG. 7 in comparison with the control group.

As confirmed in Table 5 above, the antibacterial and antiviral composition of the present invention showed a 74.88% virus reduction rate within a short time of 10 minutes of reaction time for cat coronavirus (Pelin coronavirus).

In addition, in the antiviral performance evaluation using the TCID50 analysis, FIG. 7 is a control result for a general cover glass, and FIG. 8 is a result for the composition prepared in Example 7, showing superior antiviral performance compared to the control.

From the above, in the present invention, excellent antibacterial and antiviral performance was confirmed as a result of adding PDMS-OH (Polydimethylsiloxane hydroxy-terminated) and an aluminum-based complex compound to a composition in which formulation stability was secured and the composition. Therefore, the composition of the present invention having excellent antibacterial and antiviral performance can be applied in the form of coatings or sprays in various markets including personal care products and disposable products that require antibacterial and antiviral performance.

In the above, the present invention has been described in detail only with respect to the described embodiments, but it is obvious to those skilled in the art that various changes and modifications are possible within the scope of the technical spirit of the present invention, and it is natural that such variations and modifications belong to the appended claims.

Claims (11)

Prepare a raw material composition containing the antibacterial and antiviral active raw material represented by the following formula (1) in an alcohol solvent condition maintained at a temperature of 28 ℃ or more,
An alkoxysilane monomer represented by the following formula (2) is added to the raw material composition, which is stabilized at a temperature of 30 to 36°C,
The raw material composition contains 0.1 to 1% by weight of an antibacterial and antiviral active raw material, 30 to 70% by weight of an alkoxysilane-based binder polymer represented by the following Chemical Formula 3, 0.1 to 5% by weight of a metal alkoxide catalyst, and the remaining amount of an alcohol solvent,
The alcohol solvent is a linear alcohol of CH ₃ (CH ₂ ) _n+1 -OH, and the n is 1 to 3 Method for producing an antibacterial and antiviral composition with improved formulation stability:
Formula 1

Formula 2
(R _a ) _4-n -Si-(OR _b ) _n
In Formula 2, R _a is a C ₁ to C ₈ alkyl group, a C ₃ to C ₈ allyl group, a C ₁ to C ₈ fluorinated alkyl group substituted with 3 to 6 fluorine elements, and 3 to 6 C substituted with a fluorine element _{3 ~} C ₈ at least one selected from allyl fluorinated group, R _b is a C ₂ ~ C ₈ alkyl group, n is an integer of 1 to 3,
Formula 3

In Formula 3, n is represented by A-2, wherein A is a natural number selected from 1 to 100 that is a multiple of 4, m is a natural number selected from 1 to 100, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently at least one hydrocarbon group selected from C _1-16 alkyl, C _2-16 alkynyl, C _2-16 alkenyl and C _3-16 allyl am. delete The method according to claim 1, wherein the alcohol solvent is 1-propanol. The method according to claim 1, wherein the alkoxysilane monomer is added while the raw material composition is stirred under a condition maintained at 28 to 45°C. Formulation stability is secured from the manufacturing method of any one of claims 1, 3 and 4,
With respect to 100 parts by weight of the raw material composition containing the antibacterial and antiviral active raw material represented by the following formula (1) in an alcohol solvent maintained at a temperature of 28 ° C. or higher,
40 to 60 parts by weight of the formulation stabilizer alkoxy silane monomer represented by the following formula (2) is added,
The raw material composition is antibacterial and antiviral active raw material 0.1 to 1% by weight,
30 to 70 wt% of an alkoxysilane-based binder polymer represented by the following formula (3);
0.1 to 5 wt% of a metal alkoxide catalyst, and
An antibacterial and antiviral composition comprising a residual amount of an alcohol solvent:
Formula 1

Formula 2
(R _a ) _4-n -Si-(OR _b ) _n
In Formula 2, R _a , R _b and n are as defined in claim 1,
Formula 3

In Formula 3, n, m, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are as defined in claim 1. delete The method of claim 5, wherein the metal alkoxide catalyst is tantalum ethoxide, germanium ethoxide, titanium ethoxide, zirconium ethoxide, zirconium propoxide, titanium isopropoxide, germanium isopropoxide , titanium isopropoxide, zirconium isopropoxide, tantalum butoxide, titanium butoxide, titanium t-butoxide, zirconium butoxide and zirconium t-butoxide, characterized in that at least one selected from the group consisting of antibacterial and antiviral compositions. The method according to claim 5, wherein 5 to 50 parts by weight of a siloxane having a hydroxyl group (-OH) at the terminal or both terminals as a functional enhancer is added to 100 parts by weight of the raw material composition to improve antibacterial and antiviral properties. An antibacterial and antiviral composition. The antibacterial and antiviral composition according to claim 8, wherein the siloxane has a hydroxyl value (OH Value) of 1.5 to 5 and a viscosity of 15 to 50 mm 2 /s. [Claim 6] The antibacterial and antiviral composition according to claim 5, wherein 0.01 to 0.5 parts by weight of an aluminum-based complex is added as a functional enhancer to 100 parts by weight of the raw material composition to improve antibacterial and antiviral properties. 11. The method of claim 10, wherein the aluminum-based The complexes are aluminum ethoxide, aluminum isopropoxide, aluminum tributoxide, aluminum t-butoxide, aluminum n-butoxide, aluminum acetylatetonate, aluminum L-lactate and aluminum-tri-sec-butoxide. Antibacterial and antiviral composition, characterized in that any one or more selected from the group consisting of side.

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