JPH04351672A - Antibacterial compound and antibacterial polymeric structure - Google Patents

Abstract

PURPOSE:To obtain the title compound which is added to a natural or synthetic polymeric structure to give an antibacterial polymeric structure excellent in antibacterial properties and washing resistance. CONSTITUTION:Heavy metal ions (e.g. silver ions) are arranged in a polymeric compound having a sulfide bond in the side chain (e.g. 4-vinylphenyl methyl sulfide polymer).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to antibacterial compounds and antibacterial polymer structures such as textile products, films, and resin molded products using the same.

0002

BACKGROUND OF THE INVENTION Various types of microorganisms such as molds and bacteria live in the atmosphere and have harmful effects on textile products and the human body. For example, human sweat, food and beverages, etc. adhere to polymeric structures such as a wide range of textile products, including clothing, bedding, interior products, and exterior products, and these components act as nutrients and cause mold. and bacteria are cultured. These microorganisms and their discharged substances cause discoloration, embrittlement of the fibers themselves, and the generation of bad odors, resulting in serious hygienic problems. Especially socks, underwear, casual wear, bedding sheets, covers, etc.
It goes without saying that the growth, reproduction, and spread of bacteria attached to polymeric structures such as interior materials of aircraft, ships, vehicles, etc. are harmful to human health.

[0003] Conventionally, in order to solve such problems, there have been methods of post-processing with organic tin compounds, organic mercury compounds, halogenated phenolic compounds, etc., and methods of treatment with cationic surfactants containing quaternary ammonium bases. , 4th
A method of treatment with an organic silicone compound having a grade ammonium base is known. In addition, organic compounds such as trichlorocarbanide, polyhexamethylene biguanide hydrochloride, octadecyldimethyl-3-trimethoxysilylpropylammonium chloride, copper sulfide, and copper are used in the manufacturing process of fibers, films, resin molded products, resin paints, etc. A method of adding an inorganic compound such as powder or silver powder is known.

0004

[Problems to be Solved by the Invention] Conventionally known treatment methods using organometallic compounds or halogenated phenolic compounds have problems such as toxicity to the human body and pollution of treatment waste liquid, and they also contain quaternary ammonium bases. Methods of treatment with cationic surfactants and methods of treatment with organic silicone compounds containing quaternary ammonium bases are not durable, such as when washing with anionic detergents, the quaternary ammonium bases are blocked and the antibacterial properties are reduced. There's a problem. In the method of adding organic antibacterial compounds in the manufacturing process of polymeric structures such as fibers, films, resin molded products, and processing agents and processing agents for polymeric structures such as resin paints and resin processing agents, the antibacterial compound itself is Due to its volatility, in the manufacturing process of antibacterial fibers, antibacterial compounds tend to dissipate, making the expression of antibacterial properties unstable, and antibacterial polymer structures are exposed to high temperatures during the manufacturing process. When exposed, there is a problem in that it often reacts with the polymer that is to become the matrix, significantly inhibiting the original properties of the polymer. When an inorganic metal compound is added, due to its high specific gravity, precipitation tends to occur before the antibacterial polymer structure is manufactured, which is not only inconvenient to handle, but also requires a large amount to be added. There is a problem from the side.

[0005] The present invention aims to solve the above problems, and provides an antibacterial polymer structure that is highly safe and has excellent durability.

[0006]

[Means for Solving the Problems] As a result of intensive research to solve the above problems, the present inventors have found that a complex polymer in which a heavy metal ion is coordinated to a polymer compound containing a sulfide bond in the side chain is superior. They discovered that it has antibacterial properties. The coordination amount of heavy metal ions per mole of sulfide bonds in this complex polymer is preferably 0.01 to 5 moles, and more preferably 0.1 to 1 mole of heavy metal ions per mole of sulfide bonds. The backbone polymer of the polymer compound in the present invention is not particularly limited, but preferably includes polymers and copolymers of styrene derivatives. These polymers and copolymers are preferably polymers of monomers containing sulfide bonds in their side chains, or copolymers of the above monomers and other vinyl monomers. Furthermore, the present invention is a polymer structure obtained by adding the above-described complex polymer to a natural or synthetic polymer structure.

Examples of the complex polymer in which a heavy metal ion is coordinated to a polymer compound containing a sulfide group in the side chain used in the present invention include, but are not necessarily limited to, those shown below. Examples include polymers of styrene type monomers having sulfide groups such as 4-vinylbenzylmethyl sulfide and 4-vinylphenylmethyl sulfide, or copolymers of these with styrene or other vinyl monomers.

The amount of coordination of heavy metal ions is sulfide bond 1
Preferably 0.01 mol to 5 mol, more preferably 0.1 mol to 1 mol is required per mole. Heavy metals in the present invention include silver, copper, zinc, tin, lead, bismuth, cadmium, chromium, mercury, etc., but from the viewpoint of antibacterial activity and hygiene, silver and copper are preferable, and silver is more preferable. .

[0009] As the polymer structure in the present invention, organic polymer compounds such as polyester, polyamide, polyacrylonitrile, polyvinyl type, polyolefin type, polyvinyl chloride, polyvinylidene chloride, polyurethane, polybutyral, polyphenyl ether, polycarbonate, etc. and polymer compounds made of modified polymers thereof, composite structures thereof, recycled fibers such as rayon, all other man-made fibers, and natural fibers such as cotton, wool, and silk. These polymer structures include staple fibers, filament fibers, and loose hair made of them.
It may be of any shape, such as yarn, woven fabric, knitted fabric, nonwoven fabric, or products made of these, film products, and molded products.

[0010] As a method for imparting a complex polymer in which a heavy metal ion is coordinated to a polymer compound containing a sulfide group in a side chain to a polymer structure, it is possible to add a complex polymer in which heavy metal ions are coordinated to a polymer compound containing a sulfide group in the side chain. After dissolving or dispersing and kneading, or after forming a polymer structure,
In other words, a method in which a complex polymer is added to loose wool, yarn, woven fabric, knitted fabric, non-woven fabric, or products, films, molded articles, etc. made of these, by a post-processing method, and a compound containing sulfide is added to the side chain, and then polymerized. Any method such as forming a complex with a metal may be used.

[0011] The amount of the complex polymer, in which a heavy metal ion is coordinated to a polymer compound containing a sulfide group in its side chain, applied to the polymer structure is preferably 0.0001 to 10% by weight, more preferably 0.01% by weight. ~1% by weight.

0012

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. In addition, prior to the examples, the evaluation methods of antibacterial properties, mildew resistance, and washing durability used in the examples will be shown.

<Antibacterial property> Evaluation was made based on the difference in bacterial count increase/decrease of Staphylococcus aureus according to the bacterial count measurement method of the Processing Evaluation Manual for Antibacterial and Deodorizing Processed Products (Textile Sanitary Processing Council, 1988). The larger this value is, the stronger the antibacterial property is, and a value of 1.6 or higher is certified as having antibacterial properties. Bacteria count increase/decrease value difference = Bacteria count increase/decrease value of unprocessed sample - Bacteria count increase/decrease value of processed sample Bacteria count increase/decrease value = log10 (number of viable bacteria on test piece after culture/
Number of viable bacteria immediately before culturing)

<Mold resistance> Black mold, blue mold, etc. were evaluated according to JIS Z-2911.

<Washing durability> JIS L-0217
The antibacterial properties and mold resistance after washing 50 times using the 103 method were evaluated.

Production Example 1 4-vinylphenylmethyl sulfide was synthesized according to Chemical Formula 1, polymerized by a conventional method, dissolved in methylene chloride, and coordinated with silver ions in a two-phase system with water in which silver ions were dissolved. Ta. The silver ion content of this polymer is 5.6 x 10-4 mo
It was l/g.

[0017]

[Chemical formula 1]

Production Example 2 7-(4'-vinylbenzyloxy)-2,
5,9,12-tetrathiotridecane was synthesized and copolymerized with styrene according to a conventional method. The molar ratio of this copolymer was 12:88. Silver ions were coordinated to this copolymer in the same manner as in Example 1. The silver ion content of this copolymer was 13.2 x 10-4 mol/g.

[0019]

[Chemical 2]

Example 1 The silver ion-coordinated complex polymer obtained in Production Example 1 was dissolved in chloroform to form a polyester filament fabric (
It was applied to the attached white cloth for color fastness test) by the pad method. The amount applied was 0.4% by weight based on the weight of the fabric. Table 1 shows the results of antibacterial properties, mold resistance, and washing durability.

Comparative Example 1 The sulfide group-containing polymer obtained in Production Example 1 was applied to a sample cloth in the same manner as in Example 1 without coordinating silver ions. Table 1 shows the results of antibacterial properties, mold resistance, and washing durability.

Example 2 The silver ion-coordinated copolymer obtained in Production Example 2 was applied to a polyester filament fabric in the same manner as in Example 1. The amount applied was 0.04% by weight based on the weight of the fabric. Table 1 shows the results of antibacterial properties, mold resistance, and washing durability.

Comparative Example 2 The sulfide group-containing copolymer obtained in Production Example 2 was applied to a sample cloth in the same manner as in Example 2 without being coordinated with silver ions. However, the amount of copolymer applied is 0 per weight of fabric.
．． It was 4% by weight. Table 1 shows the results of antibacterial properties, mold resistance, and washing durability.

Comparative Examples 3 and 4 Samples were prepared in the same manner as in Example 1 for the aqueous treatment of polyoxyalkylene realkylammonium salt and the copper sulfide treatment solution (containing a synthetic resin binder), and their performance was evaluated. . The results are shown in Table 1.

[0025]

[Table 1] As is clear from Table 1, the textile fabric to which the antibacterial compound of the present invention has been added has excellent antibacterial properties and mold resistance, and the washing durability of the antibacterial and mold resistant antibacterial properties. It turns out that it is also excellent.

[0026]

[Effects of the Invention] According to the present invention, an antibacterial agent having stable antibacterial properties and excellent safety can be provided, and a polymer structure to which the antibacterial agent is applied has excellent washing durability. Has excellent advanced antibacterial performance.

Claims (2)

[Claims] 1. An antibacterial compound characterized in that it is a complex polymer in which a heavy metal ion is coordinated to a polymer compound containing a sulfide bond in a side chain. 2. An antibacterial polymer structure obtained by adding the complex polymer of claim 1 to a natural or synthetic polymer structure.