KR20070071337A - Wet tissue product having a good antimicrobial property - Google Patents

Abstract

A wet tissue product is provided to improve the initial fungicide activity and the fungicide maintenance, and realize a wet tissue unharmful to a human body and without skin irritation. A wet tissue product contains a fungicide composition, wherein the fungicide composition includes polyalkylene guandine salt and 2-bromo-2-nitro-1,3-propanediol in the ratio of 1-65:1. The wet tissue product is manufactured by spraying a wet tissue composition including the fungicide composition and water on an absorption sheet or immersing the absorption sheet in the wet tissue composition.

Description

Wet tissue product having a good antimicrobial property

The present invention relates to water tissues, and more particularly, to water tissue products having excellent sterilizing power for hygienic purposes.

Water tissue products in the present invention is used for hygienic purposes, for example, means a product that can be used to wipe the other parts of the human body, such as hands in hospitals, restaurants and public places. In general, water tissue products are prepared by adding water, surfactants, fragrances, ethanol, etc. to paper or textiles, and in order to give bactericidal power to water tissues, a synthetic disinfectant or a bactericidal active material extracted from a plant is further added. Since water tissue products are used directly on the skin of the human body, the safety of the skin should be excellent, and at the same time, the ability to remove foreign substances and pathogenic microorganisms remaining on the skin should be excellent. Thus, disinfectants applied to water tissue products should: a) be soluble in solvents which do not irritate the skin, for example water, b) have a pH of 5 to 6.5 (weakly acidic) that is similar to the skin itself, and c) It should show bactericidal activity at the pH, d) very low toxicity to the human body, and e) sustained bactericidal activity.

As an active ingredient of a wide range of antimicrobial agents, it is used for various purposes such as detergents, deodorants, liquid and powder soaps, food preservatives, animal feed preservatives, wood preservatives, dyes, metal processing solutions, paper treatment, petrochemicals, adhesives, nonwovens, and cosmetics. Since widely used methyl CG (Kathon CG) has methylchloroisothiazoline / methylisothiazoline (CMIT / MIT) as an active ingredient, it exhibits antimicrobial activity or antiseptic activity in acid and weakness in neutrality. Have. In order to solve this problem, it is possible to keep the pH acidic by using a pH adjusting agent, but this method may cause another skin irritation by the pH adjusting agent, which is economically undesirable.

Water tissue products are also commonly used to treat feces when the baby discharges feces at home, especially outdoors or on the go. Because of the hygiene and ease of use of today's babies, the use of disposable diaper products is increasing, but due to the skin irritation of ammonia derived from feces and chemical and physical skin irritation by diapers, diaper rash, red It has a problem of causing redness, dermatitis, and the like. The root cause of this is known as the hydration of the stratum corneum by the moisture generated during body fluid excretion, the continuous friction between the diaper and the skin, the secondary infection by microorganisms. Among these causes, the secondary infection by the microorganism, in particular, is a major cause of worsening the condition such as expanding the site of infection and causing inflammation, and therefore, it is important to prevent and treat infection by the microorganism. However, the development of such a product is urgent, since no water tissue product containing a fungicide with good bactericidal activity has yet been developed without skin irritation.

Accordingly, it is an object of the present invention to provide a water tissue product having excellent initial sterilization activity and long-lasting sterilization.

It is another object of the present invention to provide a water tissue product which is harmless to the human body and has no skin irritation.

Still another object of the present invention is to provide a water tissue product which can be manufactured by a simple and economical method because it has an excellent bactericidal effect with only minimal use of a disinfectant and does not undergo additional pH adjustment.

In order to achieve the above object, the present invention provides a polyalkyleneguanidine salt represented by the following formula (1) and 2-bromo-2-nitro-1,3-propanediol represented by the following formula (2) of 1 to 65: 1 It provides a water tissue product containing the sterilizing agent composition in a weight ratio.

[Formula 1]

In Formula 1, Y is independently HCl, HBr, HI, HNO ₃ , carbonic acid, sulfuric acid, phosphoric acid, acetic acid, benzoic acid, dehydroacetic acid, propionic acid, gluconic acid, sorbic acid, fumaric acid, maleic acid, lactic acid, malic acid, citric acid , Succinic acid, oxalic acid, tartaric acid, formic acid, glycolic acid and epichlorohydric acid, X is a bridging group having 3 to 17 carbon atoms in total, n is an integer of 1 or more, m Is the number of moles of salt Y, n / m is 0.1 to 100.

 [Formula 2]

Here, the water tissue product may be prepared by spraying or immersing the water tissue composition containing the sterilant composition and water on the absorbent sheet, the concentration of the sterilant composition in the water tissue composition is 1 to 100,000ppm. .

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

The present invention is a disinfectant composition comprising a polyalkyleneguanidine salt represented by the following formula (1) and 2-bromo-2-nitro-1,3-propanediol represented by the following formula (2) in a weight ratio of 1 to 65: 1. It provides a water tissue product containing.

In Formula 1, Y is independently HCl, HBr, HI, HNO ₃ , carbonic acid, sulfuric acid, phosphoric acid, acetic acid, benzoic acid, dehydroacetic acid, propionic acid, gluconic acid, sorbic acid, fumaric acid, maleic acid, lactic acid, malic acid, citric acid , Succinic acid, oxalic acid, tartaric acid, formic acid, glycolic acid and epichlorohydric acid, X is a bridging group having 3 to 17 carbon atoms in total, n is an integer of 1 or more, m Is the number of moles of salt Y, n / m is 0.1 to 100.

2-Bromo-2-nitro-1,3-propanediol represented by Chemical Formula 2 (2-Bromo-2-nitro-1,3-propane diol, hereinafter referred to as "bronopol") is a white crystalline powder As a solvent, it is well soluble in water, alcohol, and ethyl acetate, but insoluble in chloroform, acetone, and ether. The bronopol is used in small amounts for pharmaceutical use, is used for preservatives in the manufacture of paper or cosmetics, and is widely used for water treatment. When the bronopol alone is used, the sterilization sustainability is excellent, but the initial sterilization effect is somewhat weak, and if the concentration is increased to increase the sterilization effect, an odor may occur and the manufacturing cost may increase. In order to solve the problem of the bronopol, in the present invention, by adding a predetermined ratio of the polyalkyleneguanidine salt represented by the formula (1) to the bronopol, synergistic effect (synergy effect of sterilization synergistic effect, initial sterilization and improvement of sterilization sustainability) Disinfectant composition was prepared. The sterilization synergistic effect of the disinfectant composition means that a better sterilization effect can be obtained even at a much lower concentration than the sum of the respective disinfectants when the two disinfectants are used in combination, than when each disinfectant is used independently. The polyalkyleneguanidine salt represented by Chemical Formula 1 is a compound having excellent bactericidal activity against various microorganisms such as bacteria, fungi and algae, and does not contain heavy metals and volatile organic compounds (VOCs), thereby causing skin irritation. There is no environmentally friendly characteristics.

In the fungicide composition, the mixing of the polyalkyleneguanidine salt represented by the formula (1) and 2-bromo-2-nitro-1,3-propanediol represented by the formula (2) comprises a weight ratio of 1 to 65: 1. It is preferable. If the weight ratio of the polyalkyleneguanidine salt to the 2-bromo-2-nitro-1,3-propanediol is less than 1 or more than 65, the synergistic effect of the bactericidal power does not appear or becomes very weak. have. The disinfectant composition according to the present invention is well dissolved in water, which is a solvent that does not irritate the skin, has a very low toxicity to the human body, and is mixed with a neutral polyalkyleneguanidine salt and an acid bronopol to have a pH similar to that of the skin. It has a range of 5 to 6.5 (weakly acidic), so there is no need to use a separate pH adjuster. Usually, citric acid, triethanolamine and the like are used to adjust the pH of the fungicide, and these may cause skin irritation and increase the manufacturing cost, so it is preferable not to use them. Therefore, the disinfectant composition according to the present invention satisfies all desirable conditions of the disinfectant applied to the water tissue product, and also has excellent initial disinfection effect and disinfection duration. In addition, the fungicide composition comprises a solvent for dissolving the fungicide, the solvent is preferably used pure water, ultrapure water, purified water and the like.

The water tissue product according to the present invention may be prepared by spraying or immersing a water tissue composition including the sterilant composition and water on an absorbent sheet. The water tissue composition may further include additives such as a moisturizer, a surfactant, and a perfume, as necessary. As the moisturizing agent, propylene glycol, natural extracts, glycerol, and sorbitol may be used alone or in combination. As the surfactant, benzalkonium chloride, sodium phosphate, ethanol (emulsifier) and polyethylene glycol may be used alone or in combination. As the fragrance, synthetic fragrance, natural fragrance, or the like may be used. In addition, the absorbent sheet may be a nonwoven fabric, a pulp, or the like, and the nonwoven fabric may be formed in a paper-like shape without weaving cotton, cellulose, synthetic fiber, or the like. Examples thereof include spun lace, airlaid, chemical bonding, melt blown, thermal bonding such as thermal bonding, synthetic fibers such as polypropylene, and the like. The pulp may be used natural pulp and the like.

The concentration of the disinfectant composition in the water tissue composition is preferably 1 to 100,000 ppm. If the concentration of the disinfectant composition is less than 1 ppm there is a problem that does not have sufficient sterilizing power, if it exceeds 100,000 ppm there is an economic problem. In addition, the water tissue product according to the present invention preferably contains 50 to 500 parts by weight of the water tissue composition based on 100 parts by weight of the absorbent sheet. When the content of the water tissue composition is less than 50 parts by weight, not only does not achieve the desired sterilization effect, but also is not suitable for use in water tissues due to lack of water, if not more than 500 parts by weight economical problems, There is a risk of inconvenience when using.

Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by these examples.

Example 1 Sterile Synergistic Effects of Fungicide Compositions

Polyhexamethyleneguanidine phosphate (hereinafter referred to as 'PHMG', SKYBIO 1100 ^™ , manufactured by SK Chemical Co., Ltd.) and bronopol were mixed and dissolved in pure water to prepare a disinfectant composition. The fungicide composition was diluted according to the Two fold dilution method using Tryptic Soy Broth (Difco, Inc.), and then the culture medium containing the fungicide and the mixed strain was incubated at 30 ° C. for 3 days. Afterwards, the lowest concentration of turbidity that inhibited growth was visually observed to determine the minimum growth inhibition concentration (MIC), and then the synergistic effect of the fungicide was calculated. The synergy of fungicides is described by Kull, FC et al. According to the method published in the article ( Appl . Microbiol. 9: 538-544 (1961)), it was measured using the ratio measured by the following equation (1). At this time, when the sum of Qa / QA and Qb / QB is less than 1, it was determined that the synergy appeared, the results are shown in Table 1 below. In this case, the strains used were Staphylococcus aureus (ATCC 6538), Escherichia coli (ATCC 11229), Pseudomonas aeruginosa (ATCC 15442), Klebsiella pneumoniae Klebsiella pneumonia (ATCC 1560).

SI = (QA / Qa + QB / Qb)

In Equation 1, Qa is PHMG alone MIC, Qb is bronopol alone MIC, QA is MIC of PHMG when PHMG and bronopol are used together, and QB is MIC of bronopol when both PHMG and bronopol are used together. to be. Here, SI (Synergy Index)> 1 indicates antagonism, and SI (Synergy Index) <1 indicates synergy.

Qa (ppm) Qb (ppm) QA (ppm) QB (ppm) SI (QA / Qa + QB / Qb) 625 39 312 5 0.63 625 39 156 5 0.38 625 39 78 5 0.25 625 39 39 5 0.19 625 39 19 5 0.16

From Table 1, it can be seen that the synergistic effect of PHMG and bronopol occurs in the weight ratio range of 1 ~ 65: 1.

[Example 2 and Comparative Examples 1 to 3] Comparison of fast-acting and sterilization sustainability of PHMG and bronopol

100 mL of four microbial mixtures with a concentration of 5.8 × 10 ⁶ CFU / mL were treated with no fungicide (blank, Comparative Example 1) and 25% fungicide composition in which PHMG and bronopol were mixed in a weight ratio of 4: 1 ( Example 2), the treatment group to which 100ppm of each of the existing water-soluble fungicide, katon CG (Comparative Example 2) and 25% PHMG (Comparative Example 3) was added, was incubated at 37 ° C for 2 hours after treatment with the disinfectant. The bactericidal effect was measured every 8 hours, 24 hours and 72 hours. The bactericidal effect was measured based on Equation 2 below, and the results are shown in Table 2 below.

Bactericidal effect (%) = {(Blank viable cell concentration-biocide concentration of fungicide treatment group) / Blank viable cell concentration} × 100

Elapsed time disinfectant Blank 0 ppm (Comparative Example 1) Catton CG 100ppm (Comparative Example 2) PHMG + Bronopol 100ppm (Example 2) PHMG only 100ppm (Comparative Example 3) Inoculation concentration (0 hours) 5.8 × 10 ⁶ CFU / mL 5.8 × 10 ⁶ CFU / mL 5.8 × 10 ⁶ CFU / mL 5.8 × 10 ⁶ CFU / mL 2 hours later - 28% 100% 100% 8 hours later - 42% 100% 100% 24 hours later - 88% 100% 100% After 72 hours - 84% 100% 82%

From Table 2, the conventional fungicide (Comparative Example 2) is low in the sterilization effect, while the effect is expressed late, while PHMG (Comparative Example 3) was excellent in the sterilization effect after only 2 hours, PHMG and bro Nopol's mixed composition (Example 2) also showed excellent sterilization effect in 2 hours. PHMG alone (Comparative Example 3) showed a disadvantage that the bacteria are generated after 72 hours in terms of sustaining sterilization power, which may cause a problem that the sterilization power is lowered during transportation and storage of water tissue. On the other hand, it can be seen that the mixed composition of PHMG and bronopol (Example 2) shows an excellent bactericidal effect even after 72 hours.

[Examples 3 to 5 and Comparative Examples 4 to 5] Preparation of the composition for water tissue and pH comparison of the composition

For final application to water tissue products, according to the composition of Table 3, after preparing a composition for water tissue comprising purified water, propylene glycol, polyethylene glycol, lavender flavor, fungicide composition, pH was measured. Comparative Examples 4 and 5, in which the pH was not in the range of 5 to 6.5, were adjusted to pH 6.5 using triethanolamine (TEA).

Furtherance(%) Example Comparative Example 4 Comparative Example 5 Purified water 91.4 91.4 91.6 Propylene glycol 5 5 5 Polyethylene glycol 3 3 3 Lavender 0.2 0.2 0.2 Fungicide composition PHMG: Bronopol Catton CG 0.4 Catton CG 0.2 Example 3 0.4 (1: 1) Example 4 0.4 (4: 1) Example 5 0.4 (30: 1) pH regulator - - - TEA TEA Final pH 5.8 6.0 6.3 6.5 6.5

From Table 3, the PHMG and bronopol mixed fungicide composition of Examples 3 to 5 have a weak acidity similar to that of human skin, but do not use a separate pH adjuster, Comparative Example 4 and using acidic catone CG as a fungicide 5 shows that the pH was adjusted using triethanolamine (TEA).

[Examples 6 to 8 and Comparative Examples 6 to 7] Preparation of Water Tissue Products and Comparison of Effects

350 parts by weight of the water tissue compositions prepared in Examples 3 to 5 and Comparative Examples 4 to 5 were absorbed with respect to 100 parts by weight of spanlace (150 × 200 mm) to prepare a water tissue product. The effect on diaper rash and dermatitis of the prepared water tissue product was measured as follows.

Water tissues prepared in the above Examples and Comparative Examples were selected for 100 infants each of about 12 months without diaper rash and diaper dermatitis, and when using a disposable disposable diaper for 24 hours, or when changing diapers. After using the diaper wearing part 3 times / day as a product, the degree of diaper rash and diaper dermatitis was examined after one month, and the results are shown in Table 4 below.

Skin grade Percentage above level 1 (%) 0 One 2 3 4 Comparative Example 4 72% 11% 8% 6% 3% 28% Comparative Example 5 84% 9% 5% 2% 0% 16% Example 3 89% 7% 4% 0% 0% 11% Example 4 92% 7% One% 0% 0% 8% Example 5 95% 5% 0% 0% 0% 5%

[By skin grade]

0: no gross skin lesion

1: Weak Sores

2: moderate sore state

3: medium or higher sores and weak cracks

4: severe soreness and moderate cracking

From Table 4, the incidence of diaper rash and diaper rash of Comparative Examples 4 and 5 (skin grade 1 or higher) were 28% and 16%, respectively, and Examples 3 to 5 were 11%, 8%, and 5%, respectively. It can be seen that it represents%. This can be seen as a result of the skin stability of PHMG and the small use of bronopol in the PHMG and bronopol mixed fungicide compositions.

As described above, the water tissue product according to the present invention not only has excellent initial disinfection activity and disinfection persistence, but also has no merits to the human body, has no skin irritation, and has an excellent disinfection effect with a minimum amount of disinfectant. It can be produced simply and economically without additional pH adjustment.

Claims (4)

Water containing a sterilizing agent composition comprising a polyalkyleneguanidine salt represented by the following formula (1) and 2-bromo-2-nitro-1,3-propanediol represented by the following formula (2) in a weight ratio of 1 to 65: 1. Tissue products. [Formula 1]

In Formula 1, Y is independently HCl, HBr, HI, HNO ₃ , carbonic acid, sulfuric acid, phosphoric acid, acetic acid, benzoic acid, dehydroacetic acid, propionic acid, gluconic acid, sorbic acid, fumaric acid, maleic acid, lactic acid, malic acid, citric acid , Succinic acid, oxalic acid, tartaric acid, formic acid, glycolic acid and epichlorohydric acid, X is a bridging group having 3 to 17 carbon atoms in total, n is an integer of 1 or more, m Is the number of moles of salt Y, n / m is 0.1 to 100.  [Formula 2]

The water tissue product of claim 1, wherein the water tissue product is prepared by spraying or dipping a composition for water tissue comprising the fungicide composition and water on an absorbent sheet. The water tissue product of claim 2 wherein the concentration of the fungicide composition in the water tissue composition is 1 to 100,000 ppm. The water tissue product according to claim 2, wherein the water tissue product contains 50 to 500 parts by weight of the composition for water tissue, based on 100 parts by weight of the absorbent sheet.