JP2019099577A - Selective antibacterial member suppressing increase of bad bacteria and selective antibacterial product using the member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To use antibacterial materials in various fields such as cosmetics, face masks, underwear, and bedding. However, antibacterial agents eliminate not only bad bacteria such as Staphylococcus aureus that cause skin infections and food poisoning, but also good bacteria such as Staphylococcus epidermidis that keeps the skin healthy. For this reason, it is necessary to suppress the action of bad bacteria among the indigenous bacteria and to be non-toxic to good bacteria, which was difficult with the conventional techniques. The present invention was created in view of the current state of the art, and an object thereof is to provide a selective antibacterial product that suppresses the growth of bad bacteria among the indigenous bacteria of the skin. SOLUTION: In a member containing a material having an H-type carboxyl group, the amount of H-type carboxyl group is 0.2 to 3.0 mmol/g, and a salt having a divalent or higher valent metal ion as a counter ion. A selective antibacterial member for suppressing the growth of bad bacteria, characterized in that the amount of type carboxyl groups is less than 0.5 mmol/g. [Selection diagram] None

Description

The present invention relates to a selective anti-microbial product that reduces the growth of bad bacteria.

BACKGROUND ART In recent years, development of materials for antibacterial agents has been required due to rising of health consciousness, and the fields include cosmetics, face masks, underwear, bedding, etc.

However, the antimicrobial agent is pointed out such as skin irritation (Non-Patent Document 1), and is particularly concerned with use in applications that contact the skin, such as cosmetics, face masks, underwear, and bedding. In addition, these antibacterial agents are representative of bad bacteria among the indigenous bacteria of the skin and help eliminate S. aureus and Malassezia bacteria that cause skin infections and food poisoning, but also keep the skin healthy Since good bacteria such as staphylococci and acne bacteria are also excluded, this also has an adverse effect on the skin.

Kaniwa Masaaki, "Health hazards and safety measures for chemicals used in household products," National Institute of Health Sciences, National Institute of Health Sciences, 2006, No. 124, p. 1-20

As described above, since the antibacterial agent has an effect of eliminating bacteria but does not have selectivity of bacteria, there is a disadvantage that even useful bacteria are eliminated. This is a particular concern in applications that come in contact with the skin, and among the indigenous bacteria, the function of the bad bacteria is suppressed, and non-toxic products are required for good bacteria, but it is difficult with conventional techniques. there were. The present invention has been made in view of the current state of the prior art, and an object thereof is to provide a selective antibacterial product which suppresses the growth of bad bacteria among skin-resident bacteria.

As a result of intensive studies to achieve the above-mentioned purpose, the inventor of the present invention has found that in a member having an H-type carboxyl group, the amount of H-type carboxyl group in the member is in the range of 0.2 to 3.0 mmol / g. By controlling the amount of salt type carboxyl group whose counter ion is a metal ion having a valence of 2 or more as less than 0.5 mmol / g, it is possible to selectively suppress the growth of only the bad bacteria among the indigenous bacteria of the skin. The inventors have found that the product is an antibacterial product and reached the present invention.

That is, the present invention is achieved by the following means.
(1) A member containing a material having an H-type carboxyl group, wherein the amount of the H-type carboxyl group is 0.2 to 3.0 mmol / g, and a salt type wherein a divalent or higher metal ion is used as a counter ion A member for selective antibacterial which suppresses the growth of bad bacteria, characterized in that the amount of carboxyl group is less than 0.5 mmol / g.
(2) The selective antibacterial member according to (1), wherein the material having an H-type carboxyl group is fibrous.
(3) A product for selective antibacterial which contains the member for selective antibacterial as described in (1) or (2) in the part which contacts skin.
(4) The selective antibacterial product according to (3), which is an underwear, a sock, a glove, a side of a bedding, a face mask, a cosmetic cotton or a wet tissue.

A notable effect of the present invention is a salt having an amount of H-type carboxyl group of 0.2 to 3.0 mmol / g and a divalent or higher metal ion as a counter ion in the skin contacting part of the product. By using a member having a type carboxyl group content of less than 0.5 mmol / g, it has been found out that the product becomes a selective antibacterial product that suppresses the growth of bad bacteria among the resident bacteria of the skin. Such a selective antibacterial product of the present invention can selectively suppress the growth of bad bacteria while preserving good bacteria, so that the skin can be kept healthy, and underwear, bedding, face masks, etc. It can be suitably used as a product that contacts the skin of

The present invention provides a member containing a material having an H-type carboxyl group, wherein the amount of H-type carboxyl group is 0.2 to 3.0 mmol / g, and a salt type wherein a divalent or higher metal ion is used as a counter ion It is a member for selective antibacterial which suppresses the growth of the bad bacteria characterized by the quantity of a carboxyl group being less than 0.5 mmol / g.

First, the material having an H-type carboxyl group employed in the present invention is not limited as long as it has the functional group, and low molecular to high molecular materials can be used. Further, the shape thereof is not limited as it is liquid or solid (for example, fibrous, particulate, coating, film, etc.), and is not limited, and which one is selected is processability, durability, It can be selected in consideration of applications and the like.

Among the materials having the H-type carboxyl group, examples of low molecular weight materials include acetic acid, butyric acid, tartaric acid, citric acid, oxalic acid, benzoic acid and the like.

Moreover, as a polymeric material, a copolymer of polyacrylic acid, polymethacrylic acid, polymaleic acid and acrylic acid, methacrylic acid and maleic acid, and the like can be mentioned.

As a fibrous material, a fiber obtained by acid treatment of a crosslinked acrylate fiber obtained by subjecting a crosslinking introduction treatment with a crosslinking agent such as hydrazine and a hydrolysis treatment with an alkaline compound or the like is described in JP-A 2013-147774 There are fibers that can be obtained by the method. The fibrous material can be suitably used for the selective antibacterial member of the present invention which is used for underwear, which places importance on durability and feeling, side of bedding, and the like.

As the above-mentioned crosslinked acrylate fiber, for example, as described in JP-A-2000-314082, a nitrogen-containing compound introduced by crosslinking treatment of an acrylic fiber having an acrylonitrile content of 85 to 95% by weight with a hydrazine compound A cross-linked acrylate fiber having an increase in the amount of 1.0 to 5.0% by weight, wherein a part of the remaining nitrile group is hydrolyzed to 3.0 to 6.0 meq / g of alkali metal salt type carboxyl group Fibers that have been converted into groups are mentioned. What converted the salt type carboxyl group into the H type carboxyl group by immersing such a crosslinked acrylate type fiber in nitric acid aqueous solution etc. can be employ | adopted as a fibrous material which has the H type carboxyl group in this invention. The amount of H-type carboxyl group can be adjusted by changing the drug concentration, reaction time, reaction temperature and the like in the hydrolysis treatment.

Moreover, as a particulate-form raw material, the crosslinked particle etc. which have a H type carboxyl group which can be manufactured by the method described in the cation exchange resin and Unexamined-Japanese-Patent No. 2013-147473 etc. are mentioned.

The bad bacteria referred to in the present invention are bacteria which cause inflammation and roughening of the skin by proliferation, and include Staphylococcus aureus, Malassezia bacteria, Trichophyton bacteria, Candida bacteria etc., among which Staphylococcus aureus is particularly problematic. There are many things. Also, good bacteria are bacteria that work to prevent skin dryness and protect from external stimuli, and epidermidis staphylococci, acne bacteria, etc. are applicable.

The member for selective antibacterial of the present invention has the H-type carboxyl group described above so as to have an amount of H-type carboxyl group of 0.2 to 3.0 mmol / g, preferably 0.5 to 2.0 mmol / g. Containing the material having When the amount of H-type carboxyl group is less than 0.2 mmol / g, it is difficult to suppress the growth of bad bacteria, and conversely, when it exceeds 3.0 mmol / g, not only bad bacteria but also good bacteria It will also reduce proliferation.

It is not clear why the growth of bad bacteria can be selectively suppressed by setting the H-type carboxyl group to the above range, but bad bacteria and good bacteria have different environments suitable for growth, and bad bacteria The resistance to the H-type carboxyl group may be weak, or the presence of the functional group may easily suppress the growth.

Further, in the selective antibacterial member of the present invention, it is desirable to reduce the amount of salt type carboxyl group as much as possible. In particular, it is important that the amount of the salt type carboxyl group whose counter ion is a divalent or higher metal ion be less than 0.5 mmol / g. When the amount of salt type carboxyl group of the divalent metal ion exceeds 0.5 mmol / g, it is not possible to grow good bacteria such as acne bacteria. In addition, the salt type carboxyl group having a monovalent metal ion as a counter ion also has the effect of suppressing the growth of a good bacteria, although not to the extent of the salt type carboxyl group of the divalent metal ion. It is preferably 0 mmol / g or less, more preferably 1.0 mmol / g or less.

The member for selective antimicrobial of the present invention is a resin molding such as a film, a coating, a bead, an injection molded body, a yarn, a yarn (including a wrap yarn), a filament, a woven fabric, a knitted fabric, a non-woven fabric, a paper-like material, Examples thereof include sheet-like materials, laminates, and fibrous structures such as cotton-like materials (including spherical and massive materials). In addition, the selective antibacterial member of the present invention may be constituted of a material having an H-type carboxyl group alone, as long as it satisfies the above-mentioned H-type carboxyl group weight, or it is combined with other materials It may be one.

As a specific example, a sheet obtained by applying a material having an H-type carboxyl group dissolved in a liquid or solvent to a solution form to a film or a fabric, or a material having a fibrous H-type carboxyl group And fiber structures such as yarn mixed with other fibrous materials, knitted fabric, non-woven fabric and the like.

There is no particular limitation on other fibrous materials that can be used together in the above fiber structure, and commonly used natural fibers, organic fibers, semi-synthetic fibers, synthetic fibers are used, and inorganic fibers, glass fibers, etc. are also used. It may be adopted depending on the application. Specific examples include cotton, hemp, silk, wool, nylon, rayon, polyester, acrylic fiber and the like.

Further, the selective antibacterial product of the present invention comprises the above-mentioned selective antibacterial member of the present invention in a portion in contact with the skin such as a surface layer of the product. The selective antibacterial product of the present invention has an effect of being able to selectively suppress the growth of bad bacteria while preserving good bacteria. From this, it is suitable as a product which contacts skin for a long time or a large area. Specific products include underwear, socks, gloves, woven or non-woven bedding, and non-woven fabric on the face using the knitted fabric of the selective antibacterial member of the present invention in various forms described above. Such as a face mask used on the side to be used, cotton for makeup, and a wet tissue using a non-woven fabric.

Examples are given below to facilitate understanding of the present invention, but these are merely illustrative, and the scope of the present invention is not limited by these. In the examples, parts and percentages are indicated on a weight basis unless otherwise noted.

<Measurement of H-type carboxyl group content and salt-type carboxyl group content>
Approximately 1 g of a sufficiently dried sample is precisely weighed (W 1 g), 200 ml of 1 mol / L aqueous hydrochloric acid solution is added thereto, and the sample is immersed and allowed to stand for 30 minutes. . After repeating this treatment three times, the solution is thoroughly washed with water until the pH of the filtrate reaches 5 or more. Next, this material is put into 200 ml of pure water, and 1 mol / L aqueous hydrochloric acid solution is added to adjust to pH 2, and then a titration curve is determined according to the information with 0.1 mol / L aqueous sodium hydroxide solution. From the titration curve, the consumed amount (V ml) of the aqueous sodium hydroxide solution consumed for all carboxyl groups is determined, and the total amount of carboxyl groups is determined by the following equation.
Total amount of carboxyl groups (mmol / g) = (0.1 × V) / W1
Next, the amount of H-type carboxyl groups is calculated in the same manner as in the above-described method for measuring the total amount of carboxyl groups, except that the first immersion in 1 mol / L hydrochloric acid aqueous solution and the subsequent water washing are not performed. Furthermore, the amount of salt-type carboxyl groups is calculated by subtracting the amount of H-type carboxyl groups from the total amount of carboxyl groups described above.

<Antibacterial test>
After suspending the bacteria precultured at 37 ° C. for about 20 hours in sterile physiological saline, the OD630 nm was adjusted to about 0.12. Thereafter, it was diluted about 100 times with 1⁄2 nutrient culture medium to prepare a test solution. After sufficiently spraying ethanol for sterilization into a sterilized vial (volume of 30 mL), 0.4 g of each test sample (control: cotton fiber) dried in a safety cabinet was added to the bottom of the vial. After 0.2 mL each of the test solution was added, it was precultured at 37 ° C. for 18 hours. Immediately after incubation and after 18 hours at 37 ° C., 20 mL of buffered saline was added to each vial and shaken vigorously 30 times (100 ×). It was diluted 10 ¹ to 10 ⁵ times with saline. The stock solution and 1 mL of each diluted solution were added to each of 2 pieces of sterile plastic petri dishes, and about 20 mL of nutrient agar medium kept at about 50 ° C. after sterilization was added and mixed. After cooling and culturing for about 48 hours at 37 ° C., the number of emerging bacteria was counted, and the bacterial growth value was calculated by the following equation.
Fungal growth value = LOG (number of bacteria after culture) -LOG (number of bacteria before culture)
If the bacterial growth value is a positive value, it indicates that the bacterial growth is occurring, and if it is a negative value, it indicates that the bacterial growth is decreasing.

Example 1
An acrylic fiber was obtained by spinning in the usual way using a spinning solution prepared by dissolving 10 parts of an acrylonitrile polymer consisting of 90% acrylonitrile and 10% methyl acrylate in 90 parts of a 48% aqueous sodium thiocyanate solution. The obtained acrylic fiber was subjected to a crosslinking introduction treatment in a 15% aqueous hydrazine solution at 110 ° C. for 3 hours, and washed with water. Next, it was acid-treated in an 8% nitric acid aqueous solution at 110 ° C. for 1 hour and washed with water. Subsequently, hydrolysis treatment was performed at 90 ° C. for 1 hour in a 5% aqueous sodium hydroxide solution, followed by washing with water to obtain a crosslinked acrylate fiber having a salt type carboxyl group. Thereafter, acid treatment was carried out in a 3% nitric acid aqueous solution at 110 ° C. for 1 hour, followed by washing with water to obtain a fiber having an H-type carboxyl group. The results of evaluating the antibacterial performance of the obtained fiber are shown in the table.

Examples 2 to 5
The same procedure as Example 1 was repeated except that the time of hydrolysis treatment with an aqueous solution of sodium hydroxide was changed to 40 minutes in Example 2, 20 minutes in Example 3, 10 minutes in Example 4, and 5 minutes in Example 5. To obtain a fiber having an H-type carboxyl group. The results of evaluating the antibacterial performance of the obtained fiber are shown in the table.

Example 6
The fiber having H-type carboxyl group obtained in Comparative Example 1 below was mixed at a ratio of 30% and polyester at a ratio of 70% to form a carded web, and a nonwoven fabric with a fabric weight of 50 g / m ² was formed by a needle punch method. The result of having evaluated the antimicrobial performance of the obtained nonwoven fabric is shown in a table | surface.

Example 7
In Example 1, the time of hydrolysis treatment with aqueous sodium hydroxide solution was changed to 30 minutes, and instead of acid treatment in aqueous 3% nitric acid solution, pH = 7.0 with sodium phosphate buffer solution A fiber having an H-type carboxyl group and a Na salt-type carboxyl group was obtained in the same manner except that the adjustment treatment to The results of evaluating the antibacterial performance of the obtained fiber are shown in the table.

Example 8
In Example 1, the same procedure is followed until water washing after acid treatment in 8% nitric acid aqueous solution, followed by hydrolysis treatment in 5% sodium hydroxide aqueous solution at 90 ° C. for 15 minutes, and then water washing, then 5 % Aqueous solution of magnesium sulfate and treated with water for 1 hour at 80.degree. The obtained fiber was added to pure water, and adjusted to pH 5.0 by adding a 3% nitric acid aqueous solution to obtain a fiber having an H-type carboxyl group and an Mg salt-type carboxyl group. The results of evaluating the antibacterial performance of the obtained fiber are shown in the table.

Example 9
A fiber having an H-type carboxyl group and a Ca salt-type carboxyl group was obtained in the same manner as in Example 8 except that a 5% aqueous solution of calcium sulfate was used instead of the 5% aqueous solution of magnesium sulfate. The results of evaluating the antibacterial performance of the obtained fiber are shown in the table.

Comparative Example 1
A fiber having an H-type carboxyl group was obtained in the same manner as in Example 1 except that the time of hydrolysis treatment with an aqueous sodium hydroxide solution was changed to 70 minutes. The results of evaluating the antibacterial performance of the obtained fiber are shown in the table.

Comparative Example 2
A fiber having an H-type carboxyl group was obtained in the same manner as in Example 1 except that the time of hydrolysis treatment with an aqueous solution of sodium hydroxide was changed to 1 minute. The results of evaluating the antibacterial performance of the obtained fiber are shown in the table.

Comparative Example 3
The result of having evaluated the antimicrobial performance of the fiber obtained by giving 0.2 weight% of quaternary ammonium antimicrobial agents to the acrylic fiber of the raw material obtained in Example 1 is shown in a table | surface.

Comparative Example 4
The results obtained by evaluating the antibacterial performance of the fiber to which 0.2% by weight of silver was imparted by immersing the acrylic fiber of the raw material obtained in Example 1 in an aqueous solution of silver nitrate and drying by heating are shown in the table.

Comparative Example 5
In Example 1, the same procedure is followed until water washing after acid treatment in an 8% nitric acid aqueous solution, followed by hydrolysis treatment in a 5% aqueous sodium hydroxide solution at 90 ° C. for 30 minutes, and then water washing, then 5 % Aqueous solution of magnesium sulfate and treated with water for 1 hour at 80.degree. The obtained fiber was added to pure water, and adjusted to pH 7.0 by adding a 3% nitric acid aqueous solution to obtain a fiber having an H-type carboxyl group and an Mg salt-type carboxyl group. The results of evaluating the antibacterial performance of the obtained fiber are shown in the table.

Comparative Example 6
A fiber having an H-type carboxyl group and a Ca salt-type carboxyl group was obtained in the same manner as in Comparative Example 5 except that a 5% aqueous solution of calcium sulfate was used instead of the 5% aqueous solution of magnesium sulfate. The results of evaluating the antibacterial performance of the obtained fiber are shown in the table.

In the fibers of Examples 1 to 5 having the amount of H-type carboxyl group specified in the present invention, no decrease in the number of good bacteria is observed, and only bad bacteria can be selectively reduced. Moreover, although the member of Example 6 is a member containing the fiber of Comparative Example 1, since the amount of H-type carboxyl group as a member is within the range specified in the present invention, only the bad bacteria are selectively selected. Can be reduced to

Furthermore, only the bad bacteria were able to be selectively reduced also about the fiber of Examples 7-9. However, since the fibers of Examples 7 to 9 have a salt type carboxyl group, the growth value of good bacteria is reduced compared to the member of Example 4 having an equivalent H-type carboxyl group, and The reduction effect is also smaller.

On the other hand, in the member of Comparative Example 1 having more H-type carboxyl groups than the present invention, the growth of good bacteria is suppressed, and in the member of Comparative Example 2 having less H-type carboxyl groups than the present invention, the growth of bad bacteria can not be suppressed. I understand that. In addition, the fiber to which the quaternary ammonium antibacterial agent of Comparative Example 3 is added and the fiber to which the silver-based antibacterial agent of Comparative Example 4 is applied are more reduced in good bacteria than bad bacteria, and the materials of these Comparative Examples Is found to adversely affect the skin. Furthermore, in the members of Comparative Examples 5 and 6, since many salt type carboxyl groups having a divalent metal ion as a counter ion are contained, it is a result that acne bacteria which are good bacteria are decreased.

Claims (4)

A member containing a material having an H-type carboxyl group, wherein the amount of the H-type carboxyl group is 0.2 to 3.0 mmol / g, and a salt type carboxyl group having a divalent or higher metal ion as a counter ion A member for selective antibacterial which suppresses the growth of bad bacteria characterized in that the amount is less than 0.5 mmol / g. The selective antibacterial member according to claim 1, wherein the material having an H-type carboxyl group is fibrous. A product for selective antibacterial which contains the member for selective antibacterial according to claim 1 or 2 in the part which contacts skin. The selective antibacterial product according to claim 3, which is an underwear, a sock, a glove, a side of a bed, a face mask, a cosmetic cotton or a wet tissue.