JPH0543409A - Antibacterial sheet - Google Patents

Abstract

PURPOSE:To provide an antibacterial sheet having excellent antibacterial activity and usable as cleaning goods, medical supplies and building materials. CONSTITUTION:A carboxymethyl cellulose quaternary ammonium salt or a carboxymethyl cellulose chlorhexidine salt is used as an antibacterial material to be included in the objective sheet. The immobilization force of the antibacterial ammonium salt or to the sheet is improved by the use of the above compound. The sheet is resistant to the dissolution of the antibacterial component even by repeated wetting with water, etc., and has lasting activity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an antibacterial cleaning article,
The present invention relates to a sheet that can be used for medical supplies, building materials, etc.

[0002]

2. Description of the Related Art A conventional antibacterial sheet has a sheet impregnated with an antibacterial agent for the purpose of retaining the antibacterial property, a sheet surface coated with the antibacterial agent, and an antibacterial fiber internally added. There is a papermaking one. However, the antibacterial agent is not strongly fixed to the sheet in the sheet simply impregnated with the antibacterial agent, and the antibacterial agent is eluted and the effect is reduced when the sheet is repeatedly wet with water. In addition, a sheet having a surface coated with an antibacterial agent may not be able to exhibit its function sufficiently because the antibacterial agent is coated with the binder at the time of coating. A sheet containing antibacterial fibers internally can be expected to have a relatively excellent effect, but it is necessary to internally add a large amount of expensive antibacterial fibers in order to uniformly exert antibacterial properties on the sheet.
Not very practical.

[0003]

DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of the prior art and provides a practical sheet having excellent antibacterial properties.

[0004]

Means for Solving the Problems As means for solving the above problems, the present inventor has found that a carboxymethylcellulose quaternary ammonium salt (hereinafter abbreviated as CMC quaternary ammonium salt) and a carboxymethylcellulose chlorhexidine salt ( In the following, the inventors have found that a sheet containing CMC chlorhexidine salt) has excellent antibacterial properties and that the antibacterial agent does not elute even after repeated wetting with water and the effect continues, leading to the present invention. ..

The present invention will be described in detail below. The CMC quaternary ammonium salt used in the present invention is one in which a carboxymethyl group is partially or completely neutralized with a quaternary ammonium that is an antibacterial component, and carboxy that is not neutralized with a quaternary ammonium. The methyl group may be in any salt form such as chlorhexidine salt, sodium salt and calcium salt. The CMC chlorhexidine salt is a carboxymethyl group partially or completely neutralized with chlorhexidine which is an antibacterial component, and the carboxymethyl group not neutralized with chlorhexidine is a quaternary ammonium salt, sodium salt, It may be in the form of any salt such as calcium salt. As the quaternary ammonium which is an antibacterial component, any substance having bactericidal properties can be used, especially benzalkonium, benzethonium,
Salts such as dodecyltrimethylammonium are preferred.

The degree of substitution is preferably in the range of 0.05 to 1.50. If it is lower than this, the contents of quaternary ammonium and chlorhexidine, which are antibacterial components, are reduced and the antibacterial effect is reduced. If it is higher than this, the hydrophilicity will increase and it will dissolve and flow out from the sheet due to water wetting, etc.Also, if the sheet production is carried out by a general wet papermaking method, it will elute during papermaking and the yield will decrease significantly, so to make it water insoluble The degree of substitution is preferably 1.50 or less. The raw material CMC is not particularly limited and may be one that is commercially available in general, but considering that it is efficiently contained in the sheet, it is preferable that it has a fibrous form.

CMC quaternary ammonium salt and CMC
The method for producing the chlorhexidine salt is not particularly limited, and the carboxymethyl group of CMC is directly neutralized with a quaternary ammonium salt such as benzalkonium chloride or chlorhexidine gluconate, and the carboxymethyl group is temporarily separated. There is a method of neutralizing with a salt such as sodium salt or calcium salt, and then resubstituting with a quaternary ammonium salt such as benzalkonium chloride or chlorhexidine gluconate.

CMC quaternary ammonium salt or CMC
There are two possible methods for producing the chlorhexidine salt-containing sheet. One is a pre-manufactured CMC
A method of forming a quaternary ammonium salt or CMC chlorhexidine salt and a fiber material into a mixed sheet, and another method is to add a quaternary ammonium salt such as benzalkonium chloride or chlorhexidine gluconate to a sheet containing ordinary CMC. It is a method of impregnating and neutralizing the carboxymethyl group, and consequently containing it in the form of CMC quaternary ammonium salt or CMC chlorhexidine salt. As a method for producing the sheet, a conventionally known method may be used, and a wet papermaking method is generally suitable.

The fiber material constituting the sheet is not particularly limited, and a suitable material may be selected from wood pulp, non-wood pulp, rayon fiber, synthetic fiber, carbon fiber and the like depending on the purpose of use.

CMC quaternary ammonium salt or CMC
The mixing ratio of the chlorhexidine salt and the fiber material is not particularly limited, and it may be determined depending on the purpose of use and the content ratio of the CMC quaternary ammonium salt or the antibacterial component in the CMC chlorhexidine salt, but usually 0.5: 99. It is effective if the weight ratio is 5 or more.

[0011]

The important point in the present invention is that the sheet contains CMC quaternary ammonium salt or CMC chlorhexidine salt as an antibacterial material. For example, when a sheet simply impregnated with an antibacterial agent is repeatedly wet with water, the antibacterial agent elutes and the effect is reduced. However, a sheet containing a CMC quaternary ammonium salt or a CMC chlorhexidine salt has an antibacterial component and is itself a fiber. Sheet-like CMC
Because it is strongly bound to, the effect does not elute and the effect continues. Further, since the salt of the present invention is a cellulosic material, when it is formed into a sheet by a wet papermaking method, it can be easily fibrillated in the ordinary beating and disaggregation steps and can be uniformly internally added to the entire sheet, so that even a small mixing ratio is large. You can expect an effect.

[0012]

EXAMPLES Examples will be shown below, but the present invention is not limited thereto.

[0013]

EXAMPLE 1 DS0.40 fibrous wet CMC (water content 75%) was neutralized with an equivalent amount of sodium carbonate, and a predetermined amount of benzalkonium chloride was added to the obtained CMC sodium salt to obtain CMC benzalco A nium salt (mixed salt with sodium salt) was obtained. This CMC benzalkonium salt (nitrogen content 7.9 × 10 ^{−4 mol} / _g ) and pulp were ^mixed at a predetermined ratio to obtain a paper having a basis weight of 50 g. After adding a liquid in which miscellaneous bacteria were suspended by infiltrating an agar solution for culture medium to this paper, the bacteria were cultured in a thermostat bath at 40 ° C. and the breeding state was observed. The results are shown in Table 1.

[0014]

[Table 1]

[0015]

Example 2 5 g of CMC benzalkonium salt of Example 1
After washing the sample with 100 ml of deionized water a predetermined number of times,
Replace the water with 00 ml of methanol and dry at 100 ° C. for 3 hours. The nitrogen content of the CMC benzalkonium salt treated in this way was measured by the Kjeldahl method, and the nitrogen loss was investigated. The results are shown in Table 2.

[0016]

[Table 2]

[0017]

Example 3 and Comparative Example 1 CMC chlorhexidine salt (DS0.65) obtained in the same manner as in Example 1 was mixed with 5
% Basis weight paper having a basis weight of 50 g was obtained. Next, after soaking the paper in ion-exchanged water, it is lightly pressed with a dry filter paper. This operation was repeated a predetermined number of times, and after adding a liquid in which agar solution for medium was infiltrated to suspend miscellaneous bacteria, the bacteria were cultured in a constant temperature bath at 40 ° C. and the breeding state was observed. For comparison,
A paper having a basis weight of 50 g made of pulp was impregnated with a chlorhexidine gluconate aqueous solution and then dried to obtain a paper containing the same amount of chlorhexidine as in Example 3. This paper was treated in the same manner as in Example 3 and the reproduction state of bacteria was observed. These results are shown in Table 3.
Shown in.

[0018]

[Table 3]

[0019]

Example 4 and Comparative Example 2 DS 0.35 fibrous wet C
MC (water content 72%) was neutralized with an equivalent amount of sodium carbonate, and an equivalent amount of benzethonium chloride was added to the obtained CMC sodium salt to obtain a CMC benzethonium salt. For comparison, a DS 1.60 CMC benzethonium salt was similarly prepared. Paper was prepared by mixing these CMC benzethonium salt and pulp at a predetermined ratio, and the amount of CMC benzethonium salt eluted at the time of papermaking was measured from the weight. The results are shown in Table 4.

[0020]

[Table 4]

[0021]

INDUSTRIAL APPLICABILITY As described above, the sheet of the present invention has excellent antibacterial properties, and the antibacterial agent does not elute even if it is repeatedly wet with water, and the effect continues.
It can be used for underlays such as tatami mats, building materials such as wallpaper, and agricultural paper such as fruit bags.

Claims (5)

[Claims] 1. A sheet comprising at least one of a carboxymethyl cellulose quaternary ammonium salt or a carboxymethyl cellulose chlorhexidine salt. 2. The sheet according to claim 1, wherein the carboxymethyl cellulose quaternary ammonium salt and the carboxymethyl cellulose chlorhexidine salt have a degree of substitution of 0.05 to 1.50 and are insoluble in water. 3. The sheet according to claim 1, wherein the quaternary ammonium salt of carboxymethyl cellulose is a single salt of quaternary ammonium or a mixed salt with a salt other than quaternary ammonium. 4. The sheet according to claim 1, wherein the carboxymethyl cellulose chlorhexidine salt is a single salt of chlorhexidine or a mixed salt with a salt other than chlorhexidine. 5. The quaternary ammonium salt of quaternary ammonium salt of carboxymethyl cellulose is benzalkonium,
The sheet according to claim 1, which is benzethonium or dodecyltrimethylammonium.