KR0137112B1 - Bactericidal and Antimicrobial Compositions Forming Water Resistant Coatings - Google Patents

Abstract

The present invention relates to bactericidal and antimicrobial compositions that form water resistant coatings.

Conventional disinfectants containing sodium hypochlorite are strongly alkaline and have high corrosiveness and can not expect long-term disinfection effects. In addition, disinfectants containing orthophenylphenol or chibendazole are weak and mildew resistant. There was a disadvantage that does not last.

The present invention sterilizes bacteria and molds quickly by synergistic action of iodine alkynyl carbamates and low alcohols, and after the low alcohol and water volatile components evaporate, the polymer material and the fungicide are uniformly mixed on the surface of the object. The film is formed so that the antimicrobial and antifungal effects last for a long time.

Description

[Name of invention]

Bactericidal and Antimicrobial Compositions Forming Water Resistant Coatings

Detailed description of the invention

[Purpose of invention]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to bactericidal and antimicrobial compositions that form water resistant coatings.

More specifically, (a) iodoalkynylcarbamate (b) lower alcohol and (c) general formula (II)

As (Y is OH or R ＇is prepared by mixing a polymer compound selected from poly (vinyl alkyl carboxylate) homopolymer and poly (vinyl alkyl carboxylate) -poly (vinyl alcohol) copolymer as a main component. It relates to a bactericidal and antimicrobial composition for forming a water-resistant coating, characterized in that.

In addition, the present invention by controlling the degree of polymerization of the poly (vinyl alkyl carboxylate) -poly (vinyl alcohol) copolymer, or by controlling the amount of additionally added water, to the water-resistant film-forming bactericidal and antimicrobial composition to which transparency is added It is about.

Microorganisms, such as fungi and bacteria, are present around life and grow on the surface of objects under moderate temperature and humidity conditions. This is not only aesthetically ugly, but also corrupts the object or causes physico-chemical changes that cause irreparable damage. In addition, if left untreated, it causes various diseases and odors, and may generate carcinogenic substances such as aflatoxin as a byproduct of metabolism. Therefore, these fungi or bacteria should be removed immediately after discovery. In particular, microorganisms which are by-products in the air reattach to the surface of the object and grow vigorously under conditions of moderate temperature and humidity.Because the growth of bacteria is vigorous in humid places, it is safe to sterilize the surface of the object. none. Therefore, in addition to sterilization on the surface of the object, continuous preventive measures are necessary.

Looking at the prior art, there are many products that can be mixed with surfactants and fragrance with sodium hypochlorite as a disinfectant, so that a large amount of foam is generated when the viscosity is increased or used, so that sterilization and washing can be performed simultaneously. (EP 0,233,666; US4,588,514; J63,198,006). Most of these products use the strong oxidizing power of sodium hypochlorite and can quickly remove the colony of bacteria or fungi attached to the surface of the object, but it is a strong alkaline chlorine oxidant with sodium hypochlorite pH of 12 or more. In particular, since the metal is rapidly corroded, it is disadvantageous to be washed off with excess water immediately after use. In addition, since it generates chlorine gas when it comes into contact with acid or when mixed with household powder detergent, it may cause acute poisoning when used in a narrow space such as a bathroom, and may cause discoloration or chemical damage when it comes into contact with clothing or wood. . Therefore, long-term prevention power cannot be expected because it must be washed out immediately with water.

Another conventional technique is to dissolve ortho phenylphenol (EP 0,308,786) or chibendazole (US 4,962,093; US 4,859,689) or salts of biguanides (EP 0,226,081; EP 0,293,761) in lower alcohols of C1 to C5. There are products in the form of sprays or aerosols that can be used to disinfect surfaces or skin. However, they have a weak bactericidal power, and in particular, since the protection against mold does not last, there is a disadvantage in that mold or bacteria are reattached to the coated surface immediately after treatment.

[Technical problem to be achieved]

The present invention is to solve the problems of the conventional disinfectant as described above, an object of the present invention, by being applied to the surface of the object that is contaminated or may be contaminated with microorganisms such as bacteria or fungi, microorganisms present on the coated surface In addition to sterilizing in a short time, to form a water-resistant and bactericidal polymer film in order to be able to be used in a lot of moisture for a long time to provide a bactericidal and antimicrobial composition that can maintain the antimicrobial activity. In another aspect, the present invention is to provide a transparent water-resistant film forming bactericidal and antimicrobial agent for maintaining the color of the object as it is applied to the object.

[Configuration and Function of Invention]

In order to achieve the above object, the present invention (a) iodoalkynyl carbamate represented by the general formula (I), the sterilizing power is strong as a main disinfectant, in particular, the sterilizing power against mold, excellent durability of performance, and ( b) C1 to C5 lower alcohol which is well volatilized at room temperature as a solvent and co-disinfectant that uniformly mixes iodoalkynylcarbamate and the following polymer compounds, and (c) a polymer having water resistance after evaporation of alcohol. A coating of poly (vinyl alkyl carboxylate) homopolymer and poly (vinyl alkyl carboxylate-vinyl alcohol) represented by general formula (II) and forming a coating so that the protection against microorganisms can be sustained for a long time. Water-soluble coating type, characterized in that the polymerization of vinyl alcohol is made of a polymer compound selected from the group of less than 90% by molar ratio as a main component Provides antiseptic and antimicrobial compositions.

In addition, the present invention provides a water-resistant film forming bactericidal and antimicrobial composition to which transparency is added by controlling the degree of polymerization of the poly (vinylalkyl carboxylate) -poly (vinyl alcohol) copolymer or by adjusting the amount of additionally added water. do.

Hereinafter will be described in detail the water-resistant film-forming bactericidal and antimicrobial composition of the present invention.

Iodoalkynyl carbamate is represented by the general formula (I), wherein m and n are 1,2 or 3, respectively, R is H and a hydrocarbon group having 1 to 20 carbon atoms, alkyl group, aryl group, alkyl An aryl group, an alkenyl group, a cyclic alkyl group, a cyclic alkenyl group, or an alkoxyaryl group is represented.

Since iodoalkynyl carbamate has excellent sterilizing power and durability, it has been used as a preservative for solutions and emulsions such as cutting oil and ink, or as a preservative for wood or paint. In addition, it exhibits excellent performance in protecting the inner and outer surfaces of the coating from the mold growing on the surface of the polymer coating.

The content of iodoalkynyl carbamate in the composition of the present invention is preferably 0.01 to 5.0% by weight based on the total composition, preferably 0.05 to 2%.

Lower alcohols in the compositions of the present invention include C1 to C5 carbonyl alcohol, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol normal alcohol and their isomers.

Lower alcohol acts as a solvent to uniformly mix iodoalkynyl carbamate and one of the constituents of the present invention, and also acts as an auxiliary disinfectant because it has excellent bactericidal power. In addition, in general, the surface of the mold has a small affinity with water, so that the application of the fungicide in the form of an aqueous solution does not penetrate into the colony of the fungus, so the drug efficacy is not rapid or sufficient. Therefore, the lower alcohol as a constituent of the present invention enhances the effect of sterilization by allowing the drug to penetrate into the fungal colony immediately after being applied to the surface of the contaminated object to exert its effect deeply and quickly. In addition, a solution in which iodoalkynylcarbamate is mixed with lower alcohol has a synergistic effect such as showing excellent sterilizing power against bacteria as well as mold. Lower alcohols, on the other hand, are highly volatile at room temperature and evaporate immediately after application on the surface of the object.

The content of the lower alcohol in the composition of the present invention is suitable as 70 to 99.8% by weight of the composition, preferably 85% or more.

In addition, as the length of the hydrocarbon chain increases, the odor increases and methyl alcohol is toxic when eaten, and ethyl alcohol and propyl alcohol are most preferable when the human body is concerned about contact. However, it is necessary to control the evaporation rate of the composition or depending on the application, one or more mixtures of the normal form of methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, and isomers thereof. It is used as a solvent main component in the composition.

The polymer compound in the composition of the present invention uses a poly (vinylalkyl carboxylate) homopolymer or a poly (vinylalkyl carboxylate) -poly (vinyl alcohol) copolymer as a material capable of forming a rigid thin film. In the case of the copolymer, random, block, and graft copolymers may be used.

The present invention provides a polymer compound capable of forming a water-resistant coating so that the high humidity, such as bathrooms, wash basins, sinks, basements, etc., may cause condensation water or maintain the prevention of mold in places where water is heavily used. Used as a constituent of the present invention. That is, when the composition according to the present invention is applied to the surface of the object to prevent mold contamination, various microorganisms present on the surface of the object are sterilized by synergistic action of iodoalkyl carbamate and alcohol, and lower alcohol After evaporation, a water-resistant polymer membrane containing iodoalkynylcarbamate component is formed on the surface of the object to prevent secondary microbial contamination from the outside.

The average molecular weight of the poly (vinylalkylcarboxylate) homopolymer or poly (vinylalkylcarboxylate) -poly (vinyl alcohol) copolymer, which is a high molecular compound in the composition of the present invention, is 30,000 to 1,000,000, and the higher the molecular weight, the stronger the film is formed. do. In the case of poly (vinylalkyl carboxylate) -poly (vinyl alcohol) copolymer, when the content of polyvinyl alcohol is high, it is difficult to dissolve in low alcohol, and it is difficult to obtain a transparent film even after application. Peeling off prevents microbial protection from continuing. Therefore, in order to obtain a solid transparent film that is not easily soluble in water, the content of vinyl alcohol in the degree of polymerization of the copolymer should be 90% or less in molar ratio, preferably 80% or less.

The content of the polymer compound in the composition of the present invention is preferably 0.01 to 25% by weight of the composition, preferably 0.1 to 10%. If the content of the polymer compound is too low, the coating on the coated surface may be too thin, resulting in a short duration.

The composition according to the present invention is applied to the bathroom or basement, around the washbasin, before and after wallpaper, building timber or sealing area of the building, and can be used for the purpose of killing mold or bacteria and preventing contamination of long-lasting microorganisms, the present invention The composition can be applied as it is, sprayed or sealed in a pressure vessel to be used in aerosol form. However, when using the composition of the present invention in the form of an aerosol, a small amount of water is required because of the pressure in the pressure vessel. The water content of the composition of the present invention is preferably 30% or less as the weight ratio of the composition, preferably 20% or less.

In particular, when made in the form of aerosol it is appropriate to fill the pressure vessel with a high pressure gas at a pressure of 2kg to 8kg. If the pressure is too low, the injection will not be smooth. If the pressure is too high, there is a risk of explosion. LPG, liquefied butane gas, and DME are relatively safer than Freon gas in terms of the environment, and the mixing ratio of these gases is 1:10 to 10: 1. 1: 5 to 5: 1 are good.

Recently, volatile organic compounds (VOCs) have been newly introduced to the environment, and CO ₂ may be used in areas where volatile organic matters such as liquefied natural gas, liquefied butane gas, and DME are problematic or injector fires are concerned. The high-pressure container can be filled at a pressure of 2 kg to 8 kg, preferably 3 kg to 5 kg.

Thus making the composition according to the invention in the form of an aerosol spray is particularly convenient for use at home.

In other words, when aerosol is sprayed, fine particles are spread evenly on the surface of the object to form a thin film, and evenly sprayed to the depths beyond the reach of the hand, effectively sterilizing the surface of the object and maintaining long-lasting sterilizing power. .

The composition of the present invention can be used by adding flavors, deodorants, surfactants and the like as necessary.

Next, it will be described in detail through experiments whether the composition according to the present invention serves as a fungicide to form a transparent and water-resistant coating.

Experimental Example 1

Antibacterial activity test against mold (compared with other fungicides)

1) Experimental Method: The bactericidal test for mold was conducted in accordance with KS K0692-92 fabric antibacterial test method. The strain used was black fungus (Aspargillus niger, KCCM11239).

Incubate the fungus in a solid medium, scrape the spores in sterile distilled water, filter it with gauze, count it to 10 ⁵ / mL, and drop the fungus spores into the nutrient medium and rub it evenly with a sterile rod. Now place a 0.8 mm paper disc in the center of the Petri dish and drop 100 microliters of sterilization solution into the paper ring. After a certain time has elapsed, the size of the growth-lowering ring that occurs around the paper ring is measured by bactericidal and antibacterial activity, and the formula is as follows.

Size of growth-lowering ring = (size of total low-ring ring-size of paper ring) / 2

2) bactericidal and antimicrobial activity of the Examples and Comparative Examples

According to the test method, the bactericidal and antimicrobial effects of the concentration of iodopropynylbutyl carbamate (IPBC) selected from the disinfectant iodoalkynylcarbamate (IPBC) and the composition ratio of the composition and the bactericidal and antimicrobial activities according to the types of fungicides Is shown in Table 1. In case of using blue mold (Penicillium chrysogenum, KCTC1262)

Similar results were obtained.

TABLE 1

Legend

IPBC: Iodoalkynylbutyl Carbamate

PVAc: Polyvinylacetate

PVA: Polyvinyl Alcohol

EtOH: ethyl alcohol

IPA: Isopropyl Alcohol

OPP: Orthophenylphenol

TBZ: Chiabendazole

As shown in Table 1, when compared with Example 6 and Comparative Examples 9 and 10, OPP (comparative to different germicidal ring size of the present invention (Example 6) containing iodoalkynylbutyl carbamate Example 9) and TBZ (Comparative Example 10) is significantly larger than the size of the growth-lowering ring, it can be seen that the bactericidal power of the composition of the present invention is superior to other fungicides. Furthermore, comparing the size of the growth-lowering ring after 50 days, the compositions according to the present invention (Examples 1, 2, 3, 4, 5 and 6), while maintaining the size of the growth-lowering ring, Since fungicides such as OPP and TBZ have disappeared growth-lowering ring, the composition of the present invention can be seen that the antimicrobial activity lasts for a long time.

Experimental Example 2

Experiment on transparency water resistance and film formation

1) Experimental method

5 ml of Examples and Comparative Examples listed in Table 2 were dropped on white tiles each 12 cm wide and vertical, rubbed with an applicator having a gap of 10 µm, and evaporated at room temperature for 3 hours. Observation was made by eye, and the firmness was observed by rubbing by hand. To determine the water resistance, the dried sample was kept at a humidity of 95% and a temperature of 25 ° C. in a thermo-hygrostat and tested for robustness after 96 hours.

2) transparency, water resistance and film formation of Examples and Comparative Examples

The experimental results are shown in Table 2.

TABLE 2

Legend: ◎ very good, ○ good, △ normal, bad

As shown in Table 2, other compositions (Examples 11, 12, 13, 14, and Comparative Example 16) of the present invention may form a water resistant coating. Therefore, looking at the results with Table 1, it can be seen that the compositions according to the present invention exhibits antimicrobial activity continuously with water-resistant film formation. In addition, when Example 11 is compared with Comparative Example 16, it can be seen that when the moisture content is large, transparency, film formation, and water resistance of the film forming bactericide are lowered. In addition, as the lower alcohol composition ratio increases, the lower alcohol uniformly mixes the iodoalkynyl carbamate and the polymer compound, thereby maintaining the firmness of the formation of the polymer film having bactericidal power and maintaining the transparency and the water resistance as well. It can be seen.

In addition, when comparing Examples 11 and 13 and Comparative Example 15, in the case of the poly (vinyl alkyl carboxylate) -poly (vinyl alcohol) copolymer, when the content of polyvinyl alcohol is increased, it is difficult to obtain a transparent film even after application, and the water resistance is also high. It can be seen that it is considerably degraded. Therefore, it can be seen that the degree of transparency, water resistance, and firmness of the film varies depending on which polymer is used as the polymer material.

[Effects of the Invention]

As described above, the present invention is (a) iodoalkynylcarbamate represented by the general formula (I), which has a strong disinfecting power as a main disinfectant, in particular, excellent disinfecting power against mold, excellent durability of performance, and (b) ) As a solvent and co-disinfectant that uniformly mixes the iodoalkyl carbamate and the following polymer compounds, C1 to C5 lower alcohol which is well volatilized at room temperature, and (c) a polymer film having a transparent water resistance after evaporation of alcohol. High molecular compounds selected from poly (vinylalkylcarboxylate) homopolymers and poly (vinylalkylcarboxylate-vinyl alcohol) copolymers represented by the general formula (II) to form long-lasting protection against microorganisms. It provides a water-resistant film-forming bactericidal and antimicrobial composition characterized in that it is prepared by mixing as a main component.

In addition, the present invention provides a water-resistant film forming bactericidal and antimicrobial composition to which transparency is added by controlling the degree of polymerization of the poly (vinylalkyl carboxylate) -poly (vinyl alcohol) copolymer or by adjusting the amount of additionally added water. do.

The composition of the present invention is applied to the surface of the object that is contaminated or may be contaminated with microorganisms such as bacteria or fungi, which not only sterilizes the microorganisms present on the coated surface in a short time, but also has a polymer film having water resistance and sterilizing power on the surface of the object. It can form and maintain antimicrobial activity continuously. In addition, the present invention, with a sterilization and antibacterial action in a certain composition state, when applied to the object can form a transparent water-resistant film to reveal the color of the object as it is.

Looking in detail, the present invention shows a synergistic effect of the bactericidal power against various fungi and bacteria present on the surface of the object by using a mixture of iodoalkynyl carbamate and lower alcohol. In addition, according to the composition of the present invention, since most of the fungicides do not maintain the protection against microorganisms such as molds for a long time, the surface of the object may be contaminated by the microorganisms by sterilizing the surface of the object. The problem can be solved. Moreover, the higher the humidity, the more proliferative the fertility is, and thus, the conventional technique cannot maintain its sustainability at a place where condensate is generated or water is used, and in the case of mold, the problem is more serious. By forming a water-resistant coating, it is possible to maintain long-term protection against microorganisms such as molds in a wet place.

In particular, the composition of the present invention can form a transparent film having sterilizing power while controlling the degree of polymerization or additionally added water content of poly (vinylalkylcarboxylate-vinyl alcohol) while revealing the surface color of the object to be coated such as tiles. Can be.

Claims (13)

(a) general formula (I), Wherein m and n are 1,2 or 3, respectively, and R is H and a hydrocarbon group having 1 to 20 carbon atoms, and represents alkyl, aryl, alkylaryl, alkenyl, cyclic alkyl, cyclic alkenyl, or alkoxyaryl 0.01 to 5.0% by weight of iodoalkynylcarbamate, indicated as (b) 70 to 99.8 weight percent of a lower alcohol selected from normal alcohols of methyl, ethyl, propyl, butyl, pentyl and isomeric alcohols of C1 to C5 hydrocarbon chains; (c) general formula (II) As (Y is OH or Marked with; R ′ is a poly (vinylalkylcarboxylate) homopolymer or poly (vinylalkylcarboxylate) -poly (vinylalcohol) copolymer (wherein the degree of polymerization of polyvinylalcohol is 90% in molar ratio). 0.01 to 25% by weight of the polymer compound selected from (d) Water-resistant film forming bactericidal and antimicrobial composition, characterized in that the mixture is prepared by the main component of 0 to 30% by weight of water. The water resistant film-forming bactericidal and antimicrobial composition according to claim 1, wherein the content of iodoalkynylcarbamate represented by the general formula (I) is 0.05 to 2.0% by weight. The antimicrobial composition according to claim 1, wherein the content of the polymer compound is 0.1 to 10.0% by weight. The water-resistant film-forming bactericidal and antimicrobial composition according to claim 1, wherein the water content is 20% or less by weight. The antimicrobial composition according to claim 1, wherein the polymer compound is a homopolymer containing vinyl alkyl carboxylate as a main component. 6. The water resistant film forming bactericidal and antimicrobial composition according to claim 5, wherein the vinyl alkyl carboxylate is vinyl acetate. The antimicrobial agent according to claim 1, wherein the polymer compound is a copolymer of poly (vinylalkylcarboxylate-vinyl alcohol), provided that the polymerization degree of polyvinyl alcohol is less than 90% in molar ratio. Composition The water-resistant film-forming bactericidal and antimicrobial composition according to claim 5, wherein the homopolymer having vinyl alkyl carboxylate as its main component has a molecular weight of 30,000 to 1,000,000. 6. The water-resistant film forming bactericidal and antimicrobial composition according to claim 5, wherein the homopolymer having vinylalkyl carboxylate as its main component has a molecular weight of 70,000 to 500,000. 8. The water resistant film forming bactericidal and antimicrobial composition according to claim 7, wherein the copolymer of poly (vinylalkylcarboxylate-vinyl alcohol) has a molecular weight of 30,000 to 1,000,000. 8. The water resistant film forming bactericidal and antimicrobial composition according to claim 7, wherein the copolymer of poly (vinylalkylcarboxylate-vinyl alcohol) has a molecular weight of 70,000 to 500,000. 8. The water resistant film forming bactericidal and antimicrobial composition according to claim 7, wherein the copolymer of poly (vinylalkyl carboxylate-vinyl alcohol) has a degree of polymerization of less than 80% in terms of molar ratio. 8. The water resistant film forming bactericidal and antimicrobial composition according to claim 7, wherein the copolymer of poly (vinylalkylcarboxylate-vinyl alcohol) is selected from random, block, and graft copolymers.