JP3117937B2 - Antibacterial finishing agent for mild fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial treatment agent for fibers, and more particularly to a treatment agent having low irritation, excellent antibacterial activity and low corrosiveness.

[0002]

2. Description of the Related Art Clothes, bedding, curtains, carpets, etc.
There are many textile products around us. These are contaminated by fungi, bacteria, etc., which are not individually visible, apart from visible dirt and dust. Sterilization and disinfection of these fungi and bacteria are required to maintain the living environment in a sanitary manner. However, it is extremely complicated and impractical to constantly sterilize and disinfect the living environment. Therefore, materials having antimicrobial properties are desired for those used in situations where microorganisms such as fungi and bacteria are easily propagated. The places where these are used are not particularly limited, and the target microorganisms are numerous such as fungi and bacteria (gram-positive bacteria and gram-negative bacteria), and any of them is expected to be effective. As a conventional treating agent for imparting antibacterial properties to fibers, for example, JP-A-2-6489 discloses an organic silicone quaternary ammonium salt, and JP-B-1-33589 discloses an alkyl phosphate quaternary. Ammonium salts and the like are known. However, these are not effective enough for fungi, and fungicides, gram-positive bacteria,
None of the Gram-negative bacteria is effective. In addition, when the anion of the quaternary ammonium salt is a halogen atom, there is a problem that a metal antibacterial fiber knitting machine or a spinning machine is corroded. Many of the antibacterial fibers are in direct contact with the skin, such as clothes, bedding, curtains, carpets, etc., and are desired to have low irritation to the skin. In manufacturing facilities,
What does not corrode the equipment is desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antibacterial effect excellent against fungi, gram-positive bacteria and gram-negative bacteria. The purpose is to obtain an antibacterial processing agent having a high acidity.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have reached the present invention.

That is, the present invention provides a low-irritant antibacterial finishing agent for fibers, which comprises a quaternary ammonium salt represented by the general formula (1); A hypoallergenic antibacterial processing agent for fibers, characterized by containing an ammonium salt; and a hypoallergenic antibacterial fiber obtained by applying the antiirritant antibacterial agent for fibers to fibers. General formula (1) (Wherein, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is a linear or branched alkyl group having 1 to 22 carbon atoms; m is a number of 1 to 4; X ^m- is an organic carboxylic acid Of the general formula (2). (Wherein R ₅ , R ₆ and R ₇ are a linear or branched alkyl group having 1 to 22 carbon atoms; m is a number of 1 to 4; and X ^m− is an anion of an organic carboxylic acid.)

According to the present invention, there is provided a low-irritant antibacterial processing agent having an excellent antibacterial effect against any of fungi, gram-positive bacteria and gram-negative bacteria by solving the above problems.

In the general formula (1), the quaternary ammonium group is represented by the following general formula (3). Specifically, [1] R ₁ and R ₂ are linear or branched alkyl group having 8 to 12 carbon atoms, R ₃ and R ₄ is an alkyl group having 1 to 3 carbon atoms, preferably an R ₁ R ₂ is a linear or branched alkyl group having 8 to 12 carbon atoms, and R ₃ and R ₄ are quaternary ammonium groups such as methyl groups. [2] R ₁ is a linear or branched alkyl group having 8 to 12 carbon atoms, and R ₂ , R ₃ and R ₄ are alkyl groups having 1 to 3 carbon atoms, and preferably, R ₁ is 8 carbon atoms. ~ 12 linear or branched alkyl groups,
R ₂ , R ₃ and R ₄ are quaternary ammonium groups of a methyl group. The following are specific examples of the quaternary ammonium group. [1] dimethyl octyl decyl ammonium, dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl didodecyl ammonium, etc. [2] trimethyl dodecyl ammonium, trimethyl tetradecyl ammonium, trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, trimethyl coco oil alkyl ammonium, methyl Diethyl dodecyl ammonium, methyl diethyl tetradecyl ammonium, methyl diethyl hexadecyl ammonium,
Methyl diethyl octadecyl ammonium, methyl diethyl coconut oil alkyl ammonium, 2-ethylhexyl trimethyl ammonium, bis (2-ethylhexyl)
Dimethylammonium, isostearyltrimethylammonium, dimethylethyldodecylammonium, dimethylethyltetradecylammonium, dimethylethylhexadecylammonium, dimethylethyloctadecylammonium, dimethylethyl coconut oil alkylammonium, etc. Among these, preferred is [1] dimethyloctyl. They are decyl ammonium, dimethyl dioctyl ammonium, and dimethyl didecylammonium, and in [2], they are trimethyl dodecyl ammonium, trimethyl tetradecyl ammonium, and trimethyl hexadecyl ammonium. Particularly preferred is [1] dimethyldidecylammonium and [2] trimethylhexadecylammonium.

In the general formula (2), the quaternary ammonium group is represented by the following general formula (4). Specifically, R ₅ , R ₆ and R ₇ are linear or branched alkyl groups having 1 to 22 carbon atoms, and preferably, R ₅ is a linear or branched alkyl group having 8 to 18 carbon atoms. , R ₆ and R ₇
Is an alkyl group having 1 to 3 carbon atoms. More preferably, R ₅ is a linear or branched alkyl group having 8 to 18 carbon atoms, and R ₆ and R ₇ are methyl groups. Specific examples of the quaternary ammonium group include dimethyldecylbenzylammonium, dimethyldodecylbenzylammonium, dimethyltetradecylbenzylammonium, dimethylhexadecylbenzylammonium, and coconut oil alkyldimethylbenzylammonium. Of these, preferred are dimethyldodecylbenzylammonium and dimethyltetradecylbenzylammonium.

The organic carboxylic acids constituting the m-valent anion of the organic carboxylic acid represented by X ^m- in the general formulas (1) and (2) include the following. <1> Aliphatic monocarboxylic acid ・ Saturated monocarboxylic acid (acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, velargonic acid, lauric acid, myristic acid, stearic acid, behenic acid , 2-ethylhexanoic acid, etc.)-Unsaturated monocarboxylic acid (oleic acid, etc.)-Aliphatic oxycarboxylic acid (glycolic acid, lactic acid, tartaric acid, gluconic acid, etc.) <2> Polycarboxylic acid-2- to 4-valent Polycarboxylic acids of aliphatic polycarboxylic acids [saturated polycarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.); unsaturated polycarboxylic acids ( Maleic acid, fumaric acid, itaconic acid, etc.)]; aromatic polycarboxylic acids [phthalic acid, isophthalic acid, terephthalic acid, trimellitic Acid,
Pyromellitic acid, etc.]-S-containing polycarboxylic acid (thiodipropionic acid, etc.) <3> Aromatic / heterocyclic monocarboxylic acid Benzoic acid, cinnamic acid, naphthoic acid, pyrrolidone carboxylic acid, etc.

Of these, preferred are those having a molecular weight of 60
~ 600 organic carboxylic acids, and <1> to <3>
Among them, preferred are <1> aliphatic monocarboxylic acids and <2> di- to tetravalent polycarboxylic acids, such as gluconic acid, adipic acid, sebacic acid, acetic acid, and lactic acid;
More preferred are gluconic acid and adipic acid.

The fourth compound represented by the general formula (1) or (2)
The quaternary ammonium organic carboxylate can be usually produced by the following method. A dialkyl carbonate of at least equimolar to one mole of a tertiary amine is reacted with or without a solvent at a reaction temperature of 80 to 200 ° C, preferably 100 ° C.
An alkylation reaction is performed at ~ 150 ° C, and an organic carboxylic acid and water are added to the reaction product to obtain a quaternary ammonium organic carboxylate solution.

The antibacterial processing agent of the present invention can be applied to known fibers. That is, natural fibers such as cotton and wool,
Or acrylic, nylon, synthetic fibers such as polyester,
Alternatively, it can be applied to these blended fibers. There is no particular limitation on the processing method for imparting antibacterial properties to these fibers, and antibacterial processing can be performed by a processing method suitable for the characteristics of each fiber. The amount is usually 0.01 to 5% by weight based on the antibacterial effect and the texture of the fiber, based on the fiber.
Preferably it is 0.1 to 2% by weight.

[0013]

The present invention will be further described with reference to the following production examples and examples, but the present invention is not limited thereto. % In Examples shows% by weight.

Production Example 1 157 g of a 50% gluconic acid aqueous solution and 300 g of water were
While maintaining the temperature at 90 ° C., 230 g of a methanol solution of didecyldimethylammonium methyl carbonate (containing 69 g of methanol) was gradually added over 2 hours, and the carbon dioxide and methanol generated were distilled off. A 36% aqueous solution of decyldimethylammonium gluconate was obtained. [1] is a transparent liquid, pH 5 (1
% Aqueous solution).

Production Example 2 While maintaining 100 g of 90% lactic acid and 390 g of water at 80 to 90 ° C., 573 g of a methanol solution of didecyldimethylammonium methyl carbonate (containing 172 g of methanol) was gradually added over 2 hours, and the carbon dioxide and methanol generated were gradually added. Was distilled off to obtain a 51% aqueous solution of the antibacterial composition [2] didecyldimethylammonium lactate of the present invention.
[2] was liquid and had a pH of 4 (1% aqueous solution).

Production Example 3 101 g of adipic acid was added to 594 g of a methanol solution of didecyldimethylammonium methyl carbonate (containing 89 g of methanol) at 40 to 80 ° C., 500 g of water was added, and methanol was distilled off. Composition [3] Didecyldimethylammonium adipate 5
A 0% aqueous solution was obtained. [3] was liquid and had a pH of 5.5 (1% aqueous solution).

Production Example 4 517 g of a methanol solution of hexadecyltrimethylammonium methyl carbonate (containing 77 g of methanol)
100 g of adipic acid at 40-80 ° C.
After adding g, methanol was distilled off to obtain a 50% aqueous solution of the antibacterial agent composition [4] hexadecyltrimethylammonium adipate of the present invention. [4] is liquid and has a pH of 5.6
(1% aqueous solution).

Production Example 5 100 g of adipic acid was added to 555 g of a methanol solution of dimethyldodecylbenzylammonium methyl carbonate (containing 470 g of methanol) at 40 to 80 ° C., and water 5
After adding 00 g, methanol was distilled off to obtain a 50% aqueous solution of the antibacterial agent composition [5] dimethyldodecylbenzyltrimethylammonium adipate of the present invention. [5] was liquid and had a pH of 5.5 (1% aqueous solution).

Example 1 Cotton broth (No. 40) was immersed in a 0.5% by weight aqueous solution of didecyldimethylammonium gluconate obtained in Production Example 1, and then squeezed with a mangle (100% squeezing ratio). ),
After drying at 100 ° C. for 10 minutes, an antibacterial cotton blade was obtained.

Example 2 Cotton broth (No. 40) was immersed in a 0.5% by weight aqueous solution of didecyldimethylammonium lactate obtained in Production Example 2, and immersed with a mangle after immersion (100% squeezing ratio). , 100
Drying at 10 ° C. for 10 minutes gave antibacterial cotton broth.

Example 3 Cotton broth (No. 40) was immersed in a 0.5% by weight aqueous solution of the didecyldimethylammonium adipate obtained in Production Example 3, and then squeezed with a mangle (squeezing rate 100%). ),
After drying at 100 ° C. for 10 minutes, an antibacterial cotton blade was obtained.

Example 4 Cotton broth (No. 40) was prepared by adding 0.5% by weight of hexadecyltrimethylammonium adipate obtained in Production Example 4.
Immerse in an aqueous solution and squeeze with a mangle after immersion
%) And dried at 100 ° C. for 10 minutes to obtain an antibacterial cotton blade.

Example 5 A cotton broth (No. 40) was immersed in a 0.5% by weight aqueous solution of dimethyldodecylbenzylammonium adipate obtained in Production Example 5, squeezed with a mangle after immersion (squeezing rate 10).
0%) and dried at 100 ° C. for 10 minutes to obtain an antibacterial cotton blade.

Comparative Example 1 Cotton broth (No. 40) was immersed in a 0.5% by weight aqueous solution of dimethyl-2 (dimethylamino) ethyl-3 (trimethoxysilyl) propylammonium chloride, squeezed with a mangle after immersion. Squeezing rate 100%), 10 at 100 ° C
After drying for minutes, an antibacterial cotton blade was obtained.

COMPARATIVE EXAMPLE 2 Cotton broth (No. 40) was immersed in a 0.5% by weight aqueous solution of lauryl dimethylhydroxyethylammonium butyl phosphate and squeezed with a mangle after immersion.
0%) and dried at 100 ° C. for 10 minutes to obtain an antibacterial cotton blade.

Comparative Example 3 Cotton broth (No. 40) was immersed in a 0.5% by weight aqueous solution of didecyldimethylammonium chloride, squeezed with a mangle (squeezing ratio 100%), and dried at 100 ° C. for 10 minutes. Thus, an antibacterial cotton blade was obtained.

<Evaluation of antibacterial activity> Table 1 shows the results of evaluating the antibacterial activity of the samples (antibacterial cotton broad) obtained in Examples 1 to 5 and the samples obtained in Comparative Examples 1, 2 and 3. Indicated. Evaluation of antibacterial properties was performed as follows. <Evaluation of antibacterial activity against fungi> A test sample was placed on an agar medium mixed with fungi such as blue mold and black mold spores, and the growth state of the bacteria around the sample was determined after culturing at 25 ° C for one week. (Judgment criteria) ：: Halo occurs around the sample. Δ: No halo was generated around the sample, but no fungal growth was observed on the sample surface. X: Fungal growth is observed on the sample surface. <Evaluation of antibacterial activity against Gram-negative bacteria> A test sample was placed on an agar medium mixed with Escherichia coli as a Gram-negative bacterium, and the growth state of the bacteria around the sample was determined after culturing at 36 ° C for 24 hours. (Judgment criteria) ：: Halo occurs around the sample. Δ: No halo was generated around the sample, but no bacterial growth was observed on the sample surface. X: Bacterial growth is observed on the sample surface. <Evaluation of antibacterial activity against Gram-positive bacteria> A test sample was placed on an agar medium mixed with Staphylococcus aureus, a Gram-positive bacterium, and the growth state of the bacteria around the sample was determined after culturing at 36 ° C for 24 hours. (Judgment criteria) ：: Halo occurs around the sample. Δ: No halo was generated around the sample, but no bacterial growth was observed on the sample surface. X: Bacterial growth is observed on the sample surface.

[0028]

[Table 1]

From Table 1, it can be seen that the fiber treated with the antibacterial processing agent of the present invention has an antibacterial effect on all of fungi, gram-positive bacteria and gram-negative bacteria.

<Evaluation of Skin Irritation> Using the samples (antibacterial cotton broad) obtained in Examples 1 to 5 and Comparative Examples 1 to 3, the skin irritation was measured by a closed patch test (4) by five men and women.
Eight hours later, the upper arm was evaluated) and evaluated according to the following criteria. The total value is shown in Table 2. The evaluation criteria for the intensity of the stimulus response are as follows.

[0031]

[Table 2]

From Table 2, it can be seen that the fibers treated with the antibacterial processing agent of the present invention have low skin irritancy and are excellent, whereas all of the comparative examples have problems.

<Evaluation of Corrosion to Metal> Production Examples 1 to 5
A 1% aqueous solution of the antibacterial processing agent of Example 1 and a 1% aqueous solution of the antibacterial processing agent used in Comparative Examples 1 to 3 were prepared. The steel sheet was half-immersed and sealed in a glass container. Expression was determined visually. The results are shown in Table 3.

[0034]

[Table 3]

Table 3 shows that the antibacterial processing agent of the present invention has no corrosiveness to metals.

[0036]

The antimicrobial treatment agent of the present invention has the following effects. (1) A high antibacterial effect can be imparted to fibers against any of fungi, gram-positive bacteria, and gram-negative bacteria. (2) The antibacterial processed fiber is hypoallergenic to the skin. (3) Less corrosive to metals such as equipment and containers.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI A01N 37:36) (72) Inventor Yoshimi Kataoka 11 Sanyo Kasei Kogyo Co., Ltd. Examiner, Sanyo Kasei Kogyo Co., Ltd. Kazuko (56) Reference JP-A-55-149367 (JP, A) JP-A-59-227842 (JP, A) JP-A-5-339107 (JP, A) JP-A-5-105603 (JP, A) JP-A-5-97606 (JP, A) JP-A-9-132504 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 33/12 101 D06M 13/463 A01N 37 / 04 A01N 37/36

Claims (8)

(57) [Claims] 1. A low-irritant antibacterial finishing agent for fibers, comprising a quaternary ammonium salt represented by the general formula (1). General formula (1) (Wherein, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is a linear or branched alkyl group having 1 to 22 carbon atoms; m is a number of 1 to 4; X ^m- is an organic carboxylic acid Is an anion.) 2. A general formula (1), R ₁ and R ₂ are linear or branched alkyl group having 8 to 12 carbon atoms, R ₃
And R ₄ is textile hypoallergenic antibacterial processing agent according to claim 1, wherein an alkyl group having 1 to 3 carbon atoms. 3. In the general formula (1), R ₁ has ₁ carbon atom.
2 to 18 linear or branched alkyl groups, R ₂ ,
R ₃ and R ₄ are textile hypoallergenic antibacterial processing agent according to claim 1, wherein an alkyl group having 1 to 3 carbon atoms. 4. A low-irritant antibacterial finishing agent for fibers, comprising a quaternary ammonium salt represented by the general formula (2). General formula (2) (Wherein R ₅ , R ₆ and R ₇ are a linear or branched alkyl group having 1 to 22 carbon atoms; m is a number of 1 to 4; and X ^m− is an anion of an organic carboxylic acid.) 5. In the general formula (2), R ₅ has 8 carbon atoms.
To 18 linear or branched alkyl groups, R ₆ and R ₇
The low-irritant antibacterial processing agent for fibers according to claim 4, wherein is an alkyl group having 1 to 3 carbon atoms. 6. The anti-microbial treating agent for fibers according to claim 1, wherein X ^m- is an anion of an organic carboxylic acid having a molecular weight of 60 to 600. 7. The hypoallergenic antibacterial treatment for fibers according to claim 1, wherein X ^m- is an anion of at least one organic carboxylic acid selected from gluconic acid, adipic acid, sebacic acid and lactic acid. Agent. 8. A hypoallergenic antibacterial fiber obtained by adding the hypoallergenic antibacterial processing agent for fibers according to any one of claims 1 to 7 to the fiber in an amount of 0.01 to 5% by weight.