JP2003113004A - Combined agent for cationic antimicrobial processing and method for antimicrobial processing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both a combined agent capable of solving problems of foam in a treating bath and compatibility with other agents and further preventing a material to be treated from discoloring with an antimicrobial agent while maintaining antimicrobial effects of the antimicrobial agent and a method for processing the same. SOLUTION: This combined agent for cationic antimicrobial processing comprises an anionic compound represented by the following general formula (1) [wherein, R denotes hydrogen atom or methyl group; X<1> and X<2> denote each hydrogen atom or an anionic group (except that both of X<1> and X<2> are not hydrogen atoms); and n denotes an integer of 2-500]. The method for antimicrobial processing comprises using the cationic antimicrobial agent with the combined agent in combination and treating the material to be treated.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a concomitant agent used with a cationic antibacterial agent during antibacterial processing, and an antibacterial processing method using a cationic antibacterial agent.

[0002]

2. Description of the Related Art In recent years, many problems caused by microorganisms have occurred, and as the society as a whole has begun to revise the way of hygiene management, awareness of hygiene has increased and antibacterial textile products have been widely distributed in the market. There is. Antibacterial processing agents for textile products are roughly classified according to the step of antibacterial processing, and are generally inorganic antibacterial agents in the spinning / spinning step, and generally in the fourth step in the post-processing step such as finishing step. Cationic antibacterial agents represented by primary ammonium salt compounds are widely used. However, the cationic antibacterial agent has drawbacks such that it causes discoloration of the material to be treated and, in the case of a white cloth, it reduces whiteness. Also, when processing an antibacterial agent in the finishing process of textile products, it is common to use it together with a chemical agent that imparts other functionality,
Cationic antibacterial agents often have poor compatibility with other agents that impart functionality. Especially with cellulose fibers, there are many processes that use fluorescent dyes in combination to improve whiteness, but since this fluorescent dye is an anionic compound, it is not possible to use fluorescent dyes when processing with cationic antibacterial agents. Have a problem. As a method for solving such a problem, JP-A-2-112473 and JP-A-8-158258 disclose that a surfactant-type anionic compound having a long-chain alkyl group is used in combination, and a cationic agent is used. A processing method for suppressing discoloration by treating a fiber material with an antibacterial agent and then further treating with a surfactant type anionic compound is disclosed. However, with these conventional surfactant type anionic compounds, the bubbles in the processing bath become very large, and problems occur due to the bubbles in the processing step, and there is a problem that the washing durability of the antibacterial effect is reduced. Further, since the cationic group expressing antibacterial property is blocked by the anionic group, there is a problem that the antibacterial effect itself is lowered.

[0003]

DISCLOSURE OF THE INVENTION The present invention does not cause the above problems when treating a material such as paper or fiber with a cationic antibacterial agent, that is, retains the antibacterial effect of the antibacterial agent and its washing durability. At the same time, the treatment bath has a low foaming property, improves the compatibility with other chemicals, and can prevent the discoloration of the material to be treated due to the antibacterial agent treatment, and its processing method. It was made for the purpose.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that it is effective to use an anionic compound having a specific structure as a concomitant agent. The present invention has been completed based on this finding. That is, the present invention provides a concomitant agent for cationic antibacterial processing containing an anionic compound represented by the following general formula (1).

[Chemical 3] (In the formula, R represents a hydrogen atom or a methyl group, X ¹ and X ² each represent a hydrogen atom or an anion group (provided that both X ¹ and X ² are not hydrogen atoms), n Represents an integer of 2 to 500) Further, the present invention represents a cationic antibacterial agent and an anionic compound represented by the following general formula (1) at the same time, or a cationic antibacterial agent and the following general formula (1). A method for antibacterial treatment is characterized in that the anionic compound to be treated is separately attached to a material to be treated.

[Chemical 4] (In the formula, R represents a hydrogen atom or a methyl group, X ¹ and X ² each represent a hydrogen atom or an anion group (provided that both X ¹ and X ² are not hydrogen atoms), n Represents an integer of 2 to 500)

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The above general formula used in the present invention
The anionic compound represented by (1) is a polyalkylene.
Anion group was introduced at one or both ends of glycol
It is a compound. As the polyalkylene glycol,
Polyethylene glycol, polypropylene glycol, d
Block of Tylene Oxide and Propylene Oxide
Alternatively, a random copolymer may be used, and polyalkylene glycol may be used.
Cole having a weight average molecular weight of 100 to 20,000
Is preferred. Introduced into polyalkylene glycol
As a nonion group, -SO_ThreeH, -CH_TwoCOOH,-
PO (OH)_Two And these anionic groups
Is an alkali metal salt, alkaline earth metal salt or ammonium salt.
It may be um salt. Polyalkylene glycol
The method of introducing a nonion group is a conventionally known method.
, For example, -SO_ThreeIntroduction of H is polyalkylene
Obtained by dehydrochlorination reaction between recall and chlorosulfonic acid
-CH _TwoThe introduction of COOH is polyalkylene glycol
-P obtained by dehydrochlorination reaction of monochloroacetic acid with
O (OH)_TwoThe introduction of polyalkylene glycol and pentaacid
It can be easily obtained by phosphorylation reaction with diphosphorus chloride.
The anionic compound represented by the general formula (1) of the invention is
It is not limited by these production methods. And
These anionic compounds are used alone or in combination of two or more.
It is possible to use the same amount as the cationic antibacterial agent.
That is, the weight of the cationic antibacterial agent and the anionic compound.
The amount ratio is preferably 1: 0.1 to 1: 3, particularly
It is preferably 1: 0.3 to 1: 2. Anionization
If the amount of the compound used is less than 1: 0.1, the treatment bath will not
The compatibility of on-bacterial antibacterial agents with other drugs may be reduced or
It may not be possible to prevent discoloration of the material to be treated due to the ON antibacterial agent.
If the ratio exceeds 1: 3, the antibacterial effect may decrease.
There is.

The cationic antibacterial agent used in the antibacterial treatment of the present invention is not particularly limited, and examples thereof include benzalkonium chloride, cetylpyridinium chloride, didodecyldimethylammonium chloride, poly [oxyalkylene (dimethyliminio) alkylene ( Dimethyliminio) alkylene dihalide], polyhexamethylene biguanide, polyhexamethylene guanide, and quaternary ammonium salt compounds such as a reaction product of dimethylamine and epichlorohydrin. The treatment amount of the cationic antibacterial agent on the material to be treated is not particularly limited and can be appropriately selected depending on the type of the material to be treated and the degree of antibacterial effect.

The material to be treated to be subjected to the antibacterial treatment in the present invention includes paper and fiber, and the paper is one of broad leaf pulp, needle pulp, waste paper pulp, bagasse, kenaf, bamboo pulp, synthetic fiber or the like. Examples of the fibers include papers made by using two or more kinds. Fibers include natural fibers such as cotton, silk and wool, recycled fibers such as rayon, semi-synthetic fibers such as acetate and triacetate, polyester, nylon, polyacrylonitrile and polyurethane. Examples thereof include synthetic fibers, and composite fibers obtained by combining two or more of these. Examples of the form of the fiber include yarn, woven fabric, knitted fabric, non-woven fabric and the like, but the material to be treated used in the present invention is not limited by the types and forms of these paper and fiber materials.

The antibacterial processing method of the present invention includes a method of simultaneously adhering the cationic antibacterial agent and the anionic compound to a material to be treated, and a method of adhering the cationic antibacterial agent and then adhering the anionic compound. And a method of depositing the cationic antimicrobial agent after depositing the anionic compound. When the cationic antibacterial agent and the anionic compound are simultaneously attached, the cationic antibacterial agent and the anionic compound may be mixed in the treatment bath, or the cationic antibacterial agent and the anionic compound may be mixed in advance. You may use what was mixed. Further, there is no particular limitation on the method of treating these chemicals into the material to be treated, for example, in the case where the material to be treated is paper, a method of adding paper at the stage of preparation of the stock or making paper, or spray treatment to paper. And a method of adhering by a coating treatment. When the material to be treated is a fiber, conventionally used methods such as padding treatment, dipping treatment, spraying treatment and coating treatment can be used.
After these adhesion treatments, an antibacterial processed material can be obtained by drying and, if the material to be treated is a fiber, optionally curing.
The drying temperature and the curing temperature at this time may be the temperatures conventionally used for processing paper and fibers, and are not particularly limited.

[0009]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Example 1 A 20 wt% aqueous solution of a disulfate diammonium salt of polyethylene glycol (weight average molecular weight 1000). Example 2 A 20% by weight aqueous solution of dicarboxymethyl ether disodium salt of polyethylene glycol (weight average molecular weight 2000).

Comparative Example 1 20% by weight of monooleyl sulfosuccinic acid sodium salt
Aqueous solution. Comparative Example 2 20% by weight of dodecylbenzenesulfonic acid sodium salt
Aqueous solution.

The cationic antibacterial agents used in the test are as follows. Antibacterial agent 1 A 20% by weight aqueous solution of benzalkonium chloride. Antibacterial agent 2 20% by weight aqueous solution of poly [oxyethylene (dimethyliminio) propyl (dimethyliminio) ethylene dichloride] (weight average molecular weight 30,000). Antibacterial agent 3 A 20% by weight aqueous solution of polyhexamethylene biguanide hydrochloride (weight average molecular weight 2000).

The combination agents of Examples 1 and 2 and Comparative Examples 1 and 2 and the aqueous solution of the antibacterial agent 1, 2 or 3 were mixed at the compounding ratio shown in Table 1, and the total amount was 100 parts by weight. It used for the evaluation test of.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

Evaluation Test (1) Effect on Antibacterial Activity The effect on antibacterial activity was evaluated by measuring the minimum inhibitory concentration (hereinafter referred to as MIC). The MIC measurement method is as follows. Example 3 described in Table 1
14, the mixed solutions of Comparative Examples 3 to 16 were diluted with ion-exchanged water, and finally mixed with a soybean casein digest (hereinafter referred to as SCD) agar medium so as to be a 2 to 10-fold dilution series. , Make plate agar. SC in advance
Streaks of the bacterial solution cultivated at about 10 ⁶ cells / mL in D liquid medium were streaked on the SCD plate agar medium containing the drug solution (antibacterial agent and concomitant agent) of the predetermined concentration prepared above, and then at 37 ° C. for 4 hours.
The MIC (ppm) was defined as the minimum concentration at which no growth of bacteria was observed when the cells were cultured for 8 hours. As test bacteria, Staphylococcus aureu
s ATCC6538P; hereinafter referred to as bacterium 1), Klebsiella pneumoniae A
TCC4352; hereinafter referred to as fungus 2), E. coli (Esc
herichia coli IFO3301;
Bacteria 3) and Pseudomonase (Pseudomonase)
aeruginosa IFO3080; hereinafter referred to as fungus 4) was used. The stronger the antibacterial activity (the smaller the effect on the antibacterial activity), the smaller the MIC value.

(2) Foamability Test 100 mL of a 5 wt% aqueous solution of the mixed solution of Examples 3 to 14 and Comparative Examples 3 to 16 shown in Table 1 was placed in a 300 mL beaker and stirred with a homomixer at 10,000 rpm. Then, the time (seconds) until the bubbles overflowed from the beaker was measured. The longer the time, the lower the foaming property. The evaluation results of the effect test on antibacterial activity and the foaming test are summarized in Table 2.

[0018]

[Table 4]

(3) Compatibility Test with Fluorescent Dye Appearance of liquid when 5% by weight aqueous solution of the mixed liquid of Examples and Comparative Examples shown in Table 1 and 0.5% by weight fluorescent dye aqueous solution are mixed The compatibility was evaluated according to the following evaluation criteria. In addition,
The fluorescent dye is Hakkor BRK-L (Showa Chemical Industry Co., Ltd.)
Manufactured; hereinafter referred to as fluorescent dye 1. ) And Illuminar RFco
nc (Showa Kako Co., Ltd .; hereinafter referred to as fluorescent dye 2) was used. ◯: Good compatibility (maintains a transparent liquid or an emulsified state) Δ: Compatibility is acceptable (white turbid liquid, but no aggregates or layer separation is observed) ×: Compatibility is not possible (aggregates are formed) However, layer separation is recognized)

(4) Whiteness test A mixture of a fluorescent dye and an example or comparative example prepared in "(3) Compatibility test with fluorescent dye" was used as a processing bath, using a cotton broad white cloth as a treated sample. Using a padding process (pickup 60%), then drying at 120 ° C. for 2 minutes and then curing at 160 ° C. for 2 minutes, the hunter whiteness of cotton broad was measured by Minolta CM-3700.
It was measured at d. The whiter the item, the greater the whiteness value. In addition, without using a cationic antibacterial agent and a concomitant agent,
The whiteness of the cotton broad treated in the same manner as above with the treatment bath containing 0.5% by weight of fluorescent dye was 124.3 for fluorescent dye 1 and 132.0 for fluorescent dye 2.
The evaluation results of the compatibility test with the fluorescent dye and the whiteness test are summarized in Table 3.

[0021]

[Table 5]

(5) Antibacterial test Using a cotton broad cloth treated by the method of "(4) Whiteness test" as a test sample, fungi 1 (Staphylococcus aureus), fungus 2 (Klebsiella pneumoniae) as test bacteria ), JISL 190
2 (1998), the bactericidal activity value was obtained according to the antibacterial test method of the textile product, and evaluated according to the following evaluation criteria. The washing resistance was evaluated according to the washing method of the bacteriostatically treated textile product (general purpose) defined by the Textile Product New Function Evaluation Council, and the bactericidal activity value of the sample after 10 washings was evaluated. ◯: The bactericidal activity value is 1 or more and has a sufficient antibacterial effect Δ: The bactericidal activity value is 0 or more and less than 1 and suppresses the growth of bacteria ×: The bactericidal activity value is less than 0, Proliferation is observed and antibacterial activity is not found. In addition, the bactericidal activity value of 0 or more, that is, those evaluated as ○ or △ in the above evaluation, is based on the standard of antibacterial processing (general use) defined by the New Functional Evaluation Council It satisfies.
The evaluation results of the antibacterial test are shown in Table 4.

[0023]

[Table 6]

As can be seen from the above results, in the Examples, the problem of discoloration of the material to be treated due to the use of the cationic antibacterial agent could be improved while maintaining the antibacterial property. Further, there was no problem of foaming in the treatment bath, and there was no problem in compatibility with the fluorescent dye.

[0025]

According to the antibacterial processing method using the concomitant drug of the present invention, the antibacterial effect of the cationic antibacterial agent and the washing durability thereof are not impaired, and other agents such as foam in the treatment bath and fluorescent dye are used. The compatibility problem can be improved, and discoloration of the material to be treated due to the treatment with the cationic antibacterial agent can be prevented.

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Claims (2)

[Claims] 1. A combined use agent for cationic antibacterial processing containing an anionic compound represented by the following general formula (1). [Chemical 1] (In the formula, R represents a hydrogen atom or a methyl group, X ¹ and X ² each represent a hydrogen atom or an anion group (provided that both X ¹ and X ² are not hydrogen atoms), n Represents an integer of 2 to 500) 2. A cationic antibacterial agent and an anionic compound represented by the following general formula (1) at the same time, or a cationic antibacterial agent and an anionic compound represented by the following general formula (1) are separately provided. In addition, an antibacterial processing method characterized in that it is attached to a material to be treated. [Chemical 2] (In the formula, R represents a hydrogen atom or a methyl group, X ¹ and X ² each represent a hydrogen atom or an anion group (provided that both X ¹ and X ² are not hydrogen atoms), n Represents an integer of 2 to 500)