KR100394429B1 - Synthesis of antimicrobial allylamine polymers and their application to textiles - Google Patents

Abstract

The present invention can be applied not only as an antimicrobial additive in various applications, but also as a blend of cotton (rayon), acetate, polyester / cotton or polyester / rayon, or a textile fabric mainly used as an innerwear and lining paper. The present invention relates to a cellulose-reactive fixed-type antimicrobial agent having laundry durability. To obtain polymer (II). Furthermore, the polymer (V) obtained by hydroxymethylating the dialkyl diallyl ammonium chloride / acrylamide copolymer (IV) which copolymerized the dialkyl diallyl ammonium chloride monomer (I) with acrylamide (III) is obtained. This polymer (V) is used as an antimicrobial processing agent for fabrics that greatly improves the durability of laundry without fear of bacterial resistance or human injury. The above-mentioned dialkyldiallylammonium chloride polymer (II) is excellent in various applications. It is characterized by its use as an antibacterial additive.

Description

Allylamine Antimicrobial Additives and Textile Antibacterial Agents, Manufacturing Method and Fabric Antibacterial Process {Synthesis of antimicrobial allylamine polymers and their application to textiles}

The present invention relates to a fixed-type antimicrobial agent of the fibrin reaction type, and more particularly, to cotton (rayon), acetate, polyester / cotton or polyester / rayon, which is mainly used as an antibacterial additive in various applications, as well as an innerwear and a lining paper. The present invention relates to a fixed-type antimicrobial agent of the fibrin reaction type that can be applied to blends or fabrics and has laundry durability for various detergents.

As the living environment is improved due to the recent development of science and technology, hygienic and comfortable health-oriented products are preferred from products that emphasized only the functionality of the past, the importance of antimicrobial processing of fibers using antimicrobial processing agents is also highlighted in the textile industry. .

Antimicrobial processing is a process that inhibits the growth and reproduction of microorganisms such as bacteria and molds on a fiber to protect users of textile products from harmful microorganisms that invade the human body through fibers and to prevent discoloration, embrittlement and contamination of the textile products. Say

The antimicrobial sterilization mechanism for microorganisms is divided into diffusion type and fixed type. Diffusion type inhibits or kills the growth of microorganisms as the antimicrobial agent is continuously released from the treated fiber. When the microorganism comes in contact with the fiber, the microorganisms are physically destroyed so that the microorganisms are killed. There are various types of diffusion-type antimicrobial agents, but there is a fear that antimicrobial activity may decrease due to the expression of bacteria having resistance, and there is a difficulty in that the harmfulness to the human body should be verified. In addition, in order to adhere to the fibers in the post-treatment, the binder is used in combination, so that the touch is damaged.

The present invention is to solve this problem, it is applied not only as an antimicrobial additive in various applications, but also used in cotton (rayon), acetate, polyester / cotton or polyester / rayon blends or fabrics mainly used as underwear and lining paper It is possible, and it is an object of the invention to provide a fibrin-reactive fixed-type antimicrobial agent having laundry durability for various detergents.

To achieve this purpose, a dialkyldiallylammonium chloride monomer (I) is synthesized from allyl chloride and dialkylamine, and a radical initiator (ammonium peroxodisulfate) is added to this monomer to obtain a polymer (II). Furthermore, the polymer (V) is obtained by hydroxymethylating the dialkyldiallylammonium chloride / acrylamide copolymer (IV) in which the dialkyldiallylammonium chloride monomer (I) is copolymerized with acrylamide (III). The dialkyl diallyl ammonium chloride polymer (II) is used as an additive for imparting antimicrobial properties to related products such as paper, plastics, water treatment agents, food preservation agents, and antibacterial detergents. It is characterized by its use as an antibacterial agent.

Referring to the synthesis of the antimicrobial processing agent of the present invention and the treatment method to the fabric as follows.

1. Synthesis of Antimicrobial Agents

1) Preparation of Dialkyldiallylammonium Chloride Polymer (II) from Dialkyldiallylammonium Chloride Monomer (I)

Nitrogen substitution by dialkyldiallylammonium chloride monomer (I) synthesized from allyl chloride and dialkylamine as a 30% aqueous solution and 0.1% of a radical initiator (ammonium peroxodisulfate) added to the monomer Sealed and polymerized at 80 ° C. for 3 hours. After the completion of the polymerization, the polymerization solution is precipitated in 10 cultured acetone and dried to obtain a white powdery polymer (II).

In the monomer (I) of the above formula, the substituents R ₁ , R ₂ represent methyl, ethyl, propyl, butyl, pentyl, hexyl groups,

In polymer (II), the minimum growth inhibitory concentration (MIC) values of polymers in which R ₁ and R ₂ are substituted with methyl, ethyl, propyl, and butyl are shown in Table 1 below.

TABLE 1 Minimum growth inhibitory concentration (MIC) values of polymers in which R ₁ and R ₂ of polymer (II) are substituted with methyl, ethyl, propyl, and butyl

R ₁ , R ₂ MIC (ppm) Staphylococcus aureus Klebsiella pneuminiae methyl 9 30 ethyl 9 20 profile 8 20 Butyl 8 20

2) Preparation of Dialkyldiallyl Ammonium Chloride / Acrylamide Copolymer (VI)

Dialkyldiallylammonium chloride monomer (I) and acrylamide (III) are dissolved in water at a ratio of 10: 1 to 1: 5 to form a 30% aqueous solution, and nitrogen is substituted by adding 0.1% of a radical initiator to shear monomers. Sealed and polymerized at 80 ° C. for 3 hours. After the completion of the polymerization, the polymerization solution is precipitated in 10 cultured acetone and dried to obtain a white powdery dialkyldiallylammonium chloride / acrylamide copolymer (IV).

In the copolymer (IV) of the above formula, the ratio of m / n has a value of 0.1 to 15.0,

When R ₁ and R ₂ are substituted by methyl, the minimum developmental concentration (MIC) for Staphylococcus aureus and Klebsiella pneumoniae according to the ratio of n and m is Is shown in Table 2.

<Table 2> Minimum growth inhibitory concentration (MIC) value according to the ratio of n and m when R ₁ and R ₂ of copolymer (IV) are substituted with methyl

n: m MIC (ppm) Staphylcoccus aureus Klebsiella pneumoniae 1.0: 0.22 8 30 1.0: 0.28 9 50 1.0: 0.55 9 50 1.0: 1.17 30 90 1.0: 2.29 70 100 1.0: 3.54 100 100 1.0: 4.65 200 200 1.0: 11.65 300 300

In the copolymer (IV), the minimum growth inhibitory concentration (MIC) value in the case where R ₁ and R ₂ are substituted with methyl, ethyl, propyl and butyl and the ratio n: m is 1: 1 is shown in Table 3 below. Same as

<Table 3> Minimum growth inhibitory concentration (MIC) value when R ₁ and R ₂ of copolymer (IV) are substituted with methyl, ethyl, propyl and butyl and the ratio n: m is 1: 1.

R ₁ , R ₂ MIC (ppm) Staphylococcus aureus Klebsiella pneumoniae methyl 30 90 ethyl 30 70 profile 30 60 Butyl 20 60

3) Preparation of Polymer (V) by Hydroxymethylation of Dialkyldiallylammonium Chloride / Acrylamide Copolymer (VI)

Formaldehyde corresponding to the amount of the dialkyldiallylammonium chloride / acrylimide copolymer (IV) and the acrylamide in the copolymer was dissolved in water to make a 25% aqueous solution, and then reacted at 60 DEG C for 1 hour. The antimicrobial processing agent of the polymer (V) which consists of is obtained.

Wherein R ₁ and R ₂ are methyl, propyl, butyl, pentyl, hexyl groups, respectively, and the ratio of m / n has a value of 0.1 to 2.0.

2. Textile treatment of antibacterial agent

The fabric (cotton, rayon, acetate, polyester / cotton, or a blend of polyester / rayon or a blended fabric, etc.) in an aqueous solution (0.3 to 3 wt%) of polymer (V) wherein R ₁ and R ₂ are substituted with methyl. After immersion, the resultant was wetted at an appropriate wet pick-up rate of 60 to 100 wt% and then preliminarily dried at a temperature of 100 ° C. or lower. The dried fabric is heat treated at 120 to 180 ° C. for 2 to 6 minutes to fix the antimicrobial agent on the fiber. Antimicrobial treatment agent treatment does not have a big difference in antimicrobial activity even if processed in a refined fabric or treated in a dyeing process.

<Example>

The cotton fabric is padded at a pick-up rate of 65% in a 0.5% aqueous solution of an antimicrobial agent which is a polymer (V) substituted with methyl and R ₁ and R ₂ , and then pre-dried at 95 ° C. for 3 minutes. The pre-dried cotton fabric is heat-treated at 150 ° C. for 5 minutes and washed with water.

The processed cotton fabric showed a 100% infection rate against the test strains Staphylococcus aureus and Klebsiella pneumoniae in the shake flask test, and KS K 430 According to method A-1, even after washing 30 times with an anionic detergent, the bactericidal rate is 70% or more.

The present invention can be applied not only as an antibacterial additive in various applications, but also as a blend of cotton (rayon), acetate, polyester / cotton or polyester / rayon or used in textiles mainly used as underwear and lining paper. It has washing durability against various detergents without fear of human harm. In addition, even after washing 30 times using an anionic detergent shows a sterilization rate of more than 70%.

Claims (7)

In the antibacterial agent, dialkyl diallyl ammonium chloride (I) and acrylamide (III) synthesized from allyl chloride and dialkylamine are dissolved in water at a ratio of 10: 1 to 1: 5 to obtain a 30% aqueous solution. Nitrogen-substituted by adding 0.1% of the radical initiator to the shear monomer, and then sealed and polymerized at 80 ° C. for 3 hours. The completed polymerization solution was precipitated in 10-fold acetone and dried to obtain a white powdery copolymer (IV). Formaldehyde corresponding to the amount of dialkyldiallylammonium chloride / acrylamide copolymer (IV) and acrylamide in the copolymer was dissolved in water to make a 25% aqueous solution, and then reacted at 60 ° C. for 1 hour for antibacterial processing on fabrics. Method for producing an allylamine fabric antimicrobial agent, characterized in that to obtain a polymer (V) consisting of the following formula. Wherein R ₁ and R ₂ are methyl, propyl, butyl, pentyl and hexyl groups, respectively, and the ratio of m / n of the copolymer (IV) has a value of 0.1 to 15.0, and m / n of the polymer (V). The ratio has a value of 0.1 to 2.0. In the antibacterial agent, the allylamine fabric antimicrobial agent, characterized in that the polymer (V) consisting of the following general formula. In the above formula, R ₁ and R ₂ of the polymer (V) are methyl, propyl, butyl, pentyl and hexyl groups, respectively, and the ratio of m / n has a value of 0.1 to 2.0. A fabric antimicrobial processing method, characterized in that the fabric is treated using an allylamine polymer (V) composed of the following general formula in whole or in part. In the above formula, R ₁ and R ₂ of the polymer (V) are methyl, propyl, butyl, pentyl and hexyl groups, respectively, and the ratio of m / n has a value of 0.1 to 2.0. delete delete The allylamine antimicrobial additive according to claim 1, which is a polymer (IV) consisting of the following general formula. In the above formula, R1 and R2 are methyl, propyl, butyl, pentyl and hexyl groups, respectively, and the ratio of m / n has a value of 0.1 to 15.0. A method for using an antimicrobial additive, wherein allylamine polymer (IV) consisting of all or part of the following general formula is used as an antimicrobial additive. In the above formula, R1 and R2 are methyl, propyl, butyl, pentyl and hexyl groups, respectively, and the ratio of m / n has a value of 0.1 to 15.0.