WO2011148950A1 - Antibacterial and antifungal agent, and antibacterial and antifungal product - Google Patents

Abstract

Disclosed is an antibacterial and antifungal agent which contains a cationic polymer that is represented by general formula (1) and has a weight average molecular weight of 1,000 or more. (In general formula (1), R¹ represents a hydrogen atom, an alkyl group, a hydroxyalkyl group or an alkenyl group; R² represents an oxyalkylene group represented by general formula (2) below; R³ represents an alkylene group; R⁴ represents a hydrogen atom, an alkyl group, a hydroxyalkyl group or an alkenyl group; Y represents an oxygen atom or a sulfur atom; n represents a positive integer; and X^m- represents an m-valent anion.) -(CH₂)_a-(OR⁵)_b-O(CH₂)_a- (2) (In general formula (2), R⁵ represents an alkylene group; a represents an integer of 2 or more; and b represents an integer of 0 or more.)

Description

Antibacterial and antifungal agents and antibacterial and antifungal products

The present invention relates to an antibacterial and antifungal agent and an antibacterial and antifungal product. More specifically, the present invention relates to an antibacterial and antifungal agent containing a cationic polymer having antibacterial and antifungal properties, and an antibacterial and antifungal product to which antibacterial and antifungal properties are imparted.

In recent years, accidents caused by bacteria such as nosocomial infections caused by methicillin-resistant Staphylococcus aureus (MRSA) and food poisoning caused by pathogenic Escherichia coli O-157, etc., have become a social problem. In general households, molds are easy to propagate due to the increase in airtightness of living spaces and the spread of air conditioning equipment, and problems such as allergic diseases caused by molds and discoloration of daily necessities are increasing. In order to deal with these problems, for example, antibacterial agents for imparting antibacterial properties to the surface of desired members, and fiber products and resin products that have been antibacterial processed with an antibacterial agent in advance have been put on the market.

Antibacterial agents include low molecular organic antibacterial agents such as benzalkonium chloride, cetylpyridinium chloride, chlorhexidine gluconate, and 5-chloro-2- (2,4-dichlorophenoxy) phenol, and for example, the following patent documents High molecular organic systems such as polyhexamethylene biguanide hydrochloride, poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride] and condensation reaction products of cyanoguanidine and polyethylene polyamine as described in 1 to 3 Antibacterial agents have been used for a long time. In addition, inorganic antibacterial agents carrying silver, zinc, copper, etc., which are metals having antibacterial properties, such as zeolite and silica gel are also frequently used.

Japanese Examined Patent Publication No. 62-60509 JP-A-5-310505 JP-A-9-195171

Although the above conventional low molecular weight organic antibacterial agents show excellent antibacterial and antifungal properties, they have low water resistance, and even if they adhere to the surface of the member, they were easily removed by water. Therefore, it is said that the antibacterial and antifungal properties that have been imparted cannot be sustained over a long period of time for water products (places where water is used) such as kitchens, bathrooms, toilets, and toilets, and textile products that are repeatedly washed. There was a problem.

On the other hand, the above-mentioned conventional polymer organic antibacterial agents have excellent water resistance and antibacterial properties, but have insufficient antifungal properties. In addition, it has a problem that it cannot prevent off-flavors and the like.

Further, the above conventional high molecular organic antibacterial agent is a cationic polymer and has a problem that it is easily discolored by heat, an antioxidant such as BHT (dibutylhydroxytoluene) and a gas such as NOx. Therefore, in fiber products and resin products that have been antibacterial processed with the above-mentioned antibacterial agents, the BHT / NOx gas discoloration resistance is deteriorated, or the appearance is impaired due to heat during product processing and heat during product use. There was a case.

The present invention has been made in view of the above circumstances, and has an antibacterial and antifungal property, an antibacterial and antifungal agent excellent in water resistance, heat discoloration resistance and BHT / NOx gas discoloration, and the same An object of the present invention is to provide an antibacterial and antifungal product obtained by using.

As a result of intensive studies to solve the above problems, the present inventors have found that a cationic polymer having a specific structure and a specific weight average molecular weight has a wide antibacterial spectrum and has sufficient antibacterial and antifungal properties. It has been found that the fiber and the resin film having the cationic polymer attached thereto and having excellent water resistance exhibit sufficient antibacterial and antifungal properties even after the washing test and the water resistance test. Furthermore, the present inventors have found that such a cationic polymer is less discolored by heat and BHT / NOx gas. And based on these knowledge, it came to complete this invention.

That is, this invention provides the antibacterial antifungal agent containing the cationic polymer whose weight average molecular weight is 1000 or more represented by following General formula (1).

In formula (1), each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, or an alkenyl group having 2 to 4 carbon atoms, and R ² represents the following general formula (2 And R ³ independently represents an alkylene group having 2 to 10 carbon atoms, and each R ⁴ independently represents a hydrogen atom, 1 to carbon atoms. 4 represents an alkyl group or hydroxyalkyl group or an alkenyl group having 2 to 4 carbon atoms, Y represents an oxygen atom or a sulfur atom, n represents a positive integer, and X ^m− represents an m-valent anion.

In formula (2), R ⁵ represents an alkylene group having 1 or more carbon atoms, a independently represents an integer of 2 or more, and b represents an integer of 0 or more.

The antibacterial and antifungal agent of the present invention has sufficiently high antibacterial and antifungal properties due to the cationic polymer having the structure described above, and has water resistance, heat discoloration resistance, and BHT / NOx gas discoloration resistance. The effect of being excellent can be produced.

According to the antibacterial and antifungal agent of the present invention, sufficient antibacterial and antifungal properties can be imparted to the surface of water-related parts and resin products and fiber products used in the vicinity of water, and this can be sustained over a long period of time. Color change and off-flavor caused by bacteria or fungi can be suppressed.

Further, by using the antibacterial and antifungal agent of the present invention as a fiber treatment agent, a fiber product subjected to antibacterial and antifungal processing (providing antibacterial and antifungal properties) can be obtained. Such a textile product can suppress discoloration and off-flavor caused by bacteria or mold even after repeated washing. In addition, the textile product can be less likely to be discolored by heat and BHT / NOx gas as compared to the case where a conventional high molecular weight organic antibacterial agent is used.

Further, the antibacterial and antifungal agent of the present invention is excellent in processability because the cationic polymer has an advantage of low odor in addition to excellent heat discoloration.

The weight average molecular weight of the cationic polymer is preferably 1000 to 50000.

The present invention also provides an antibacterial and antifungal product to which antibacterial and antifungal properties are imparted by the antibacterial and antifungal agent of the present invention.

According to the present invention, an antibacterial and antifungal agent having sufficient antibacterial and antifungal properties, and excellent in water resistance, heat discoloration resistance and BHT / NOx gas discoloration property, and antibacterial and antifungal properties obtained by using the same Products can be provided.

Hereinafter, preferred embodiments of the present invention will be described.

The antibacterial and antifungal agent of the present embodiment contains a cationic polymer having a weight average molecular weight of 1000 or more represented by the following general formula (1).

In formula (1), each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, or an alkenyl group having 2 to 4 carbon atoms, and R ² represents the following general formula (2 And R ³ independently represents an alkylene group having 2 to 10 carbon atoms, and each R ⁴ independently represents a hydrogen atom, 1 to carbon atoms. 4 represents an alkyl group or hydroxyalkyl group or an alkenyl group having 2 to 4 carbon atoms, Y represents an oxygen atom or a sulfur atom, n represents a positive integer, and X ^m− represents an m-valent anion. In addition, n means the degree of polymerization when the cationic site in the parentheses is a repeating unit.

In formula (2), R ⁵ represents an alkylene group having 1 or more carbon atoms, a independently represents an integer of 2 or more, and b represents an integer of 0 or more.

Here, examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Examples of the hydroxyalkyl group having 1 to 4 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a 1-methyl-1-hydroxyethyl group, and a 1-methyl-2-hydroxyethyl group. . Examples of the alkenyl group having 2 to 4 carbon atoms include a vinyl group and an allyl group. In the present embodiment, R ¹ is preferably a methyl group or an ethyl group from the viewpoint of water resistance, and more preferably a methyl group.

The oxyalkylene group having 4 to 8 carbon atoms represented by R ² is represented by the general formula (2).

R ⁵ may be linear or branched as long as it is an alkylene group having 1 or more carbon atoms. If a is independently an integer of 2 or more and b is an integer of 0 or more, a, b and R ⁵ are appropriately adjusted so that the total number of carbon atoms is 4 to 8 in the general formula (2). do it. From the viewpoint of water resistance, preferably, a is the same integer, and a = 2 to 4 and b = 0.

Examples of the oxyalkylene group having 4 to 8 carbon atoms represented by R ² include an ethyleneoxyethylene group, a propyleneoxypropylene group, a butyleneoxybutylene group, an ethyleneoxymethyleneoxyethylene group, and an ethyleneoxyethyleneoxyethylene group. Can do. In the present embodiment, R ² is preferably an ethyleneoxyethylene group from the viewpoint of water resistance.

As the alkylene group having 2 to 10 carbon atoms represented by R ³ , either a linear alkylene group or a branched alkylene group can be used. Examples of such an alkylene group include an ethylene group, a propylene group, a trimethylene group, a butylene group, a tetramethylene group, a hexamethylene group, a 2-ethylhexamethylene group, an octamethylene group, and a decamethylene group. In the present embodiment, R ³ is preferably an alkylene group having 2 to 6 carbon atoms from the viewpoint of water resistance.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Examples of the hydroxyalkyl group having 1 to 4 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a 1-methyl-1-hydroxyethyl group, and a 1-methyl-2-hydroxyethyl group. . Examples of the alkenyl group having 2 to 4 carbon atoms include a vinyl group and an allyl group. In the present embodiment, R ⁴ is preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoint of water resistance, and more preferably a hydrogen atom.

The anion represented by X ^m- is not particularly limited as long as it is an anion capable of forming a counter ion with a quaternary ammonium compound. Formic acid, acetic acid, propionic acid, gluconic acid, lactic acid, fumaric acid, maleic acid And an anion derived from a monovalent or polyvalent carboxylic acid such as adipic acid, an alkyl phosphate ester anion, an alkyl sulfate anion, a halogen anion, a sulfate anion, a nitrate anion, and a phosphate anion. Of these anions, chlorine ions and bromine ions are preferred.

The cationic polymer according to this embodiment can be synthesized by, for example, the following two-stage reaction.
First stage: A diamine compound represented by the following general formula (3) and urea or thiourea are subjected to deammonia reaction at a molar ratio of 2: 0.8 to 2: 1.2 at 150 to 200 ° C. Then, a compound represented by the following general formula (4) is synthesized.
Second stage: a compound represented by the following general formula (4) and a dihalide represented by the following general formula (5) in a molar ratio of 1: 0.8 to 1: 1.2 in a ratio of 35 to By polymerizing at 120 ° C., the cationic polymer represented by the general formula (1) is synthesized.

In formula (3), R ¹ , R ³ and R ⁴ have the same meaning as described above.

In formula (4), R ¹ , R ³ , R ⁴ and Y have the same meaning as described above.

Z— (CH ₂ ) _a — (OR ⁵ ) _b —O (CH ₂ ) _a —Z (5)
In formula (5), Z represents a halogen atom, and a, b and R ⁵ have the same meaning as described above.

In the first stage reaction, the molar ratio of the diamine compound represented by the general formula (3) to urea or thiourea is 2: 0.8 to 2: 1.2. From the viewpoint of water resistance of the cationic polymer represented by (1), it is preferably 2: 0.9 to 2: 1.1, more preferably 2: 0.95 to 2: 1.05, Preferably it is 2: 1.

In the second stage reaction, the molar ratio of the compound represented by the general formula (4) and the dihalide represented by the general formula (5) is 1: 0.8 to 1: 1.2. However, from the viewpoint of water resistance of the cationic polymer represented by the general formula (1), it is preferably 1: 0.9 to 1: 1.1, more preferably 1: 0.95 to 1: 1. .05, more preferably 1: 1.

Examples of the diamine compound represented by the general formula (3) include N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N , N-dibutylaminopropylamine, N, N-dimethylaminohexylamine and N, N-di (2-hydroxyethyl) aminopropylamine. These compounds can be used individually by 1 type or in combination of 2 or more types. Among these, N, N-dimethylaminoethylamine and N, N-dimethylaminopropylamine are preferable from the viewpoint of water resistance of the cationic polymer represented by the general formula (1).

Examples of the dihalide represented by the general formula (5) include bis (2-chloroethyl) ether, bis (3-chloropropyl) ether, bis (4-chlorobutyl) ether, 1,2-bis (2- Chloroethyloxy) ethane, bis (2-bromoethyl) ether, bis (2-chloroethyl) formal and bis [2- (2-chloroethyloxy) ethyl] ether. These compounds can be used individually by 1 type or in combination of 2 or more types. Among these, bis (2-chloroethyl) ether, bis (2-bromoethyl) ether, bis (3-chloropropyl) ether and bis (2) from the viewpoint of water resistance of the cationic polymer represented by the general formula (1). 4-Chlorobutyl) ether is preferred.

Examples of the cationic polymer represented by the general formula (1) include bis (2-chloroethyl) ether-1,3-bis [3- (dimethylamino) propyl] urea copolymer and bis (2-chloroethyl). ) Ether-1,3-bis [2- (dimethylamino) ethyl] urea copolymer, bis (2-chloroethyloxy) ethane-1,3-bis [3- (dimethylamino) propyl] urea copolymer Bis (2-chloroethyl) ether-1,3-bis [3- (dimethylamino) propyl] thiourea copolymer, bis (2-chloroethyl) formal-1,3-bis [3- (dimethylamino) propyl ] Urea copolymer, bis (2-chloroethyl) ether-1,3-bis [6- (dimethylamino) hexyl] urea copolymer, bis (4-chlorobutyl) ether 1,3-bis [3- (dimethylamino) propyl] urea copolymer, bis (2-chloroethyl) ether-1,3-bis [3- (diethylamino) propyl] urea copolymer, bis (2- Chloroethyl) ether-1,3-bis [3- (dibutylamino) propyl] urea copolymer and bis (2-chloroethyl) ether-1,3-bis [3- (di (2-hydroxyethyl) amino) propyl ] A urea copolymer is mentioned.

The weight average molecular weight of the cationic polymer represented by the general formula (1) is 1000 or more, preferably 1000 to 50000, and more preferably 3000 to 20000. When the weight average molecular weight is less than 1000, an amine odor tends to remain, and water resistance tends to be insufficient. On the other hand, when the weight average molecular weight exceeds 50000, the polymerization time for obtaining the cationic polymer becomes longer, and the polymer tends to be extremely difficult to handle because it becomes a highly viscous polymer. The weight average molecular weight of the cationic polymer represented by the general formula (1) can be measured by gel permeation chromatography using polyethylene glycol having a known molecular weight as a standard substance.

The weight average molecular weight of the cationic polymer represented by the general formula (1) can be adjusted by the reaction time, the reaction temperature, and the reaction molar ratio.

The antibacterial and antifungal agent of the present embodiment exhibits sufficient antibacterial and antifungal properties even with the cationic polymer represented by the general formula (1) alone, but in addition to the cationic polymer represented by the general formula (1) A conventionally known antibacterial and antifungal compound can be contained. Examples of such compounds include low molecular organic antibacterial agents such as benzalkonium chloride and cetylpyridinium chloride, 5-chloro-2- [2,4-dichlorophenoxyl] phenol, and 3,4,4′- Examples include halogen antibacterial agents such as trichlorocarbanilide, inorganic antibacterial agents such as silver and zinc, and natural product antibacterial agents such as chitosan and polylysine.

The antibacterial and antifungal agent of the present embodiment is a surfactant such as a nonionic active agent, an anionic active agent, and a cationic active agent, a softener component, a smoothing agent component, a penetrating agent component, and a leveling agent component, depending on the application. Further, an antistatic agent, a chelating agent, an antioxidant, an antifoaming agent, a solvent, a binder resin, a thickener, a crosslinking agent, and the like can be further contained.

The antibacterial and antifungal agent of the present embodiment can exhibit antibacterial and antifungal properties effective against various bacteria and fungi. According to the antibacterial and antifungal agent of this embodiment, antibacterial and antifungal properties can be imparted to various products, and an antibacterial and antifungal product can be obtained. Such an antibacterial and antifungal product may be used for applying an antibacterial and antifungal process to a desired object.

Antibacterial and antifungal products include liquid detergents, liquid soaps, spraying liquids, other liquid products, gel products, coating agents, resin additives, textile products, resin products, and the like.

The liquid detergent of the present embodiment can contain the antibacterial and antifungal agent of the present embodiment in a proportion such that the content of the cationic polymer according to the present embodiment is 0.1 to 5% by mass based on the total amount of the liquid detergent. . When the content is less than 0.1% by mass, a sufficient antibacterial and antifungal effect is hardly exhibited, and even when used in excess of 5% by mass, the effect of further improving the antibacterial and antifungal property is small and not economical. The liquid detergent of this embodiment has antibacterial and antifungal properties effective against various bacteria and fungi, and is used in kitchens, bathrooms, toilets, toilets, etc., and washing machines. Discoloration and off-flavor caused by bacteria or mold can be suppressed. Moreover, when a liquid detergent is a detergent for textiles, the discoloration and nasty smell resulting from the bacteria or mold | fungi in a fiber can be suppressed. Other components contained in the liquid detergent include, for example, a softener and a bleaching agent, in addition to the detergent component including the surfactant described above and the antibacterial and antifungal component such as the antibacterial and antifungal agent according to the present embodiment. It is done.

The liquid soap of the present embodiment can contain the antibacterial and antifungal agent of the present embodiment in such a ratio that the content of the cationic polymer according to the present embodiment is 0.1 to 5% by mass based on the total amount of the liquid soap. . When the content is less than 0.1% by mass, a sufficient antibacterial and antifungal effect is hardly exhibited, and even when used in excess of 5% by mass, the effect of further improving the antibacterial and antifungal property is small and not economical. The liquid soap of this embodiment has antibacterial and antifungal properties effective against various bacteria and fungi, and can suppress discoloration and off-flavor caused by the bacteria or fungi in the object to be cleaned. Examples of the use of liquid soap include household laundry, industrial laundry, face washing, hand washing, body washing (body soap, etc.) and the like. As other components contained in the liquid soap, in addition to the soap component and the antibacterial and antifungal component such as the antibacterial and antifungal agent according to the present embodiment, for example, a moisturizing agent and a stabilizer are exemplified.

The spray liquid of the present embodiment contains the antibacterial and antifungal agent of the present embodiment in a proportion such that the content of the cationic polymer according to the present embodiment is 0.1 to 90% by mass based on the total amount of the spray liquid. Can do. Such a spraying liquid can be obtained by diluting the cationic polymer according to the present embodiment with water, a lower alcohol such as ethanol or isopropanol, or a mixed solvent thereof. The spray liquid of this embodiment may be contaminated by microorganisms such as kitchens, bathrooms, toilets and toilets, bedding, furniture, clothing, carpets, shoes, plastic products, ceramics, and filters. By spraying an appropriate amount onto the place, discoloration and off-flavor caused by bacteria or mold can be suppressed. Moreover, according to the liquid for spraying of this embodiment, an antibacterial and antifungal process can be given to a target object.

The spray liquid of this embodiment can be used as, for example, a fiber treatment agent, a deodorant, a resin treatment agent, an antibacterial agent, and an antifungal agent.

In addition, examples of liquid products other than those described above include machine oils, adhesives, and fiber treatment agents. These liquid products can contain the antibacterial and antifungal agent of the present embodiment in a proportion such that the content of the cationic polymer according to the present embodiment is 0.01 to 1% by mass based on the total amount of the liquid product. When the content is less than 0.01% by mass, a sufficient antibacterial and antifungal effect is hardly exhibited, and even if it is used in excess of 1% by mass, the effect of further improving the antibacterial and antifungal property is small and not economical. The liquid product of the present embodiment has antibacterial and antifungal properties effective against various bacteria and fungi, and can be unlikely to cause discoloration and off-flavor due to bacteria or fungi.

Examples of the gel product containing the antibacterial and antifungal agent of the present embodiment include a gel fragrance, a gel deodorant, a poultice, and a gel soap. These gel-like products can contain the antibacterial and antifungal agent of the present embodiment in a proportion such that the content of the cationic polymer according to the present embodiment is 0.01 to 1% by mass based on the total amount of the product. If the content is less than 0.01% by mass, sufficient antibacterial and antifungal effect (antibacterial and antifungal effect) is difficult to be exerted. Less economical. The gel-like product of this embodiment has antibacterial and antifungal properties effective against various bacteria and fungi, and can be less likely to cause discoloration and off-flavor due to bacteria or fungi.

The coating agent of this embodiment can contain the antibacterial and antifungal agent of this embodiment in a proportion such that the content of the cationic polymer according to this embodiment is 0.1 to 10% by mass based on the total amount of the coating agent. . According to the coating agent of the present embodiment, antibacterial and antifungal treatment can be applied to an object by coating the surface of a hard material such as textiles and plastics and ceramics (for example, roll coating and brushing). Color change and off-flavor caused by bacteria or fungi can be suppressed. Examples of other components contained in the coating agent include an antistatic agent, an antioxidant, and a dispersing agent in addition to a binder such as an acrylic resin and a urethane resin, and a thickener.

The coating and spraying conditions are preferably such that the amount of the cationic polymer attached to the fiber or hard material surface is 0.1 to 20 g / m ^{2 in} terms of nonvolatile content. If it is less than 0.1 g / m ² , a sufficient antibacterial and antifungal effect is hardly exhibited, and even if it is used in excess of 20 g / m ² , it is difficult to further improve the antibacterial and antifungal properties, which is not economical.

The coating agent of this embodiment can be used as, for example, a fiber treatment agent and a resin treatment agent.

The additive for resin of the present embodiment may contain the antibacterial and antifungal agent of the present embodiment at a ratio of 0.01 to 1% by mass of the cationic polymer according to the present embodiment with respect to the added resin. it can. According to the additive for resin of this embodiment, antibacterial and antifungal processing can be applied to a resin product by a method such as kneading into a resin composition containing resins. Examples of other components contained in the resin additive include antistatic agents, antioxidants, and dispersants.

Examples of the antibacterial and antifungal fiber product of the present embodiment include various materials and various forms of fiber products. For example, the raw materials for textile products include natural fibers such as cotton, hemp, wool and silk, regenerated cellulose fibers such as rayon, cupra and tencel (trademark), semi-synthetic fibers such as acetate and promix, polyamide fibers and polyester fibers. And synthetic fibers such as acrylic fiber, polyolefin fiber, polyvinyl chloride fiber, polyimide fiber and polyurethane fiber, and various materials of composite fibers of these fibers. Moreover, as a form of a textile product, a short fiber, a long fiber, a thread | yarn, a textile fabric, a knitted fabric, a nonwoven fabric, a cotton, a sliver, and a top are mentioned, for example.

The antibacterial and antifungal fiber product of the present embodiment is prepared by attaching the antibacterial and antifungal agent of the present embodiment to the fiber by a known method such as coating, spraying, dipping treatment, padding (dip-nip) treatment or the like. It can be manufactured by processing.

When the antibacterial and antifungal process is a coating, for example, a fiber treatment agent in which a cationic polymer is mixed with a binder such as an acrylic resin and a urethane resin, and a thickener can be used. In this case, the concentration of the cationic polymer in the fiber treatment agent is preferably 0.1 to 10% by mass based on the total amount of the fiber treatment agent. In the case of spraying, it is preferable to perform spraying using a solution having a cationic polymer concentration of 10 to 90% by mass. Examples of the solvent at this time include water, alcohols having 1 to 4 carbon atoms such as ethanol and isopropanol, ketones such as glycol, acetone and methyl ethyl ketone.

When the fiber product is coated or sprayed, the amount of the cationic polymer attached to the fiber is preferably 0.1 to 20 g / m ^{2 in} terms of nonvolatile content. If it is less than 0.1 g / m ² , a sufficient antibacterial and antifungal effect is hardly exhibited, and even if it is used in excess of 20 g / m ² , it is difficult to further improve the antibacterial and antifungal properties, which is not economical.

Also, when the textile product is dipped, the concentration of the cationic polymer in the treatment bath is 0.01 to 10% o. w. f. In the case of padding treatment, the concentration of the cationic polymer is preferably 0.01 to 10% by mass with respect to the fiber mass.

When the fiber product is dipped or padded, the cationic polymer is preferably 0.1 to 5% by mass based on the mass of the fiber. If it is less than 0.1% by mass, a sufficient antibacterial and antifungal effect is hardly exhibited, and even if it exceeds 5% by mass, it is difficult to further improve the antibacterial and antifungal properties, which is not economical.

The antibacterial and antifungal resin product of the present embodiment was formed from a resin composition containing the antibacterial and antifungal agent and resins according to the present embodiment, in addition to the resin product whose surface was processed by the coating agent described above. Things. Examples of the resins include acrylic resin, styrene resin, melamine resin, urethane resin, phenol resin, polyethylene resin, polypropylene resin, polyacetal, fluororesin, silicone resin, vinyl acetate resin, vinyl chloride resin, epoxy resin, polyester resin, polyamide Examples thereof include resins, ABS resins, polycarbonate resins, and cellulose acetate.

The antibacterial and antifungal resin product according to the present embodiment can be produced by a method such as kneading the antibacterial and antifungal agent according to the present embodiment into a resin composition containing resins. In this case, kneading can be carried out at a ratio such that the concentration of the cationic polymer is 0.01 to 1% by mass with respect to the resins. When the concentration of the cationic polymer is less than 0.01% by mass, a sufficient antibacterial and antifungal effect is hardly exhibited, and even when used in excess of 1% by mass, it is difficult to further improve the antibacterial and antifungal properties, which is not economical.

As described above, according to this embodiment, various antibacterial and antifungal products such as an antibacterial and antifungal fiber product and an antibacterial and antifungal resin product to which antibacterial and antifungal properties are imparted by the antibacterial and antifungal agent of the present embodiment. Can be provided.

Hereinafter, the present invention will be further described with reference to examples. However, the present invention is not limited to these examples.

(Example 1) <Preparation of 50% aqueous solution of bis (2-chloroethyl) ether-1,3-bis [3- (dimethylamino) propyl] urea copolymer>
A reaction vessel was charged with 204 g (2 mol) of N, N-dimethylaminopropylamine and 60 g (1 mol) of urea, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170 to 180 ° C. for about 5 hours. . Thereafter, the mixture was cooled, 143 g (1 mol) of bis (2-chloroethyl) ether was added, and the mixture was reacted at 95 ° C. for 10 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 8,000.

(Example 2) <Preparation of 50% aqueous solution of bis (2-chloroethyl) ether-1,3-bis [2- (dimethylamino) ethyl] urea copolymer>
176 g (2 mol) of N, N-dimethylaminoethylamine and 60 g (1 mol) of urea were charged into a reaction vessel, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170 to 180 ° C. for about 5 hours. Thereafter, the mixture was cooled, 143 g (1 mol) of bis (2-chloroethyl) ether was added, and the mixture was reacted at 95 ° C. for 5 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 5000.

(Example 3) <Preparation of 50% aqueous solution of bis (2-chloroethyloxy) ethane-1,3-bis [3- (dimethylamino) propyl] urea copolymer>
A reaction vessel was charged with 204 g (2 mol) of N, N-dimethylaminopropylamine and 60 g (1 mol) of urea, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170 to 180 ° C. for about 5 hours. . After cooling, 187 g (1 mol) of bis (2-chloroethyloxy) ethane was added and reacted at 95 ° C. for 10 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 7000.

(Example 4) <Preparation of 50% aqueous solution of bis (2-chloroethyl) formal-1,3-bis [3- (dimethylamino) propyl] urea copolymer>
204 g (2 mol) of N, N-dimethylaminopropylamine and 60 g (1 mol) of urea were charged in a reaction vessel, heated to a temperature in a nitrogen gas stream, and subjected to deammonia reaction at 170 to 180 ° C. for about 5 hours. Thereafter, the mixture was cooled, 173 g (1 mol) of bis (2-chloroethyl) formal was added, and the mixture was reacted at 95 ° C. for 12 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 7500.

(Example 5) <Preparation of 50% aqueous solution of bis (4-chlorobutyl) ether-1,3-bis [3- (dimethylamino) propyl] urea copolymer>
A reaction vessel was charged with 204 g (2 mol) of N, N-dimethylaminopropylamine and 60 g (1 mol) of urea, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170 to 180 ° C. for about 5 hours. . Thereafter, the mixture was cooled, and 199 g (1 mol) of bis (4-chlorobutyl) ether was added, followed by reaction at 95 ° C. for 12 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 7000.

(Example 6) <Preparation of 50% aqueous solution of bis (2-chloroethyl) ether-1,3-bis [3- (diethylamino) propyl] urea copolymer>
N, N-diethylaminopropylamine (260 g, 2 mol) and urea (60 g, 1 mol) were charged into a reaction vessel, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170-180 ° C. for about 5 hours. Thereafter, the mixture was cooled, 143 g (1 mol) of bis (2-chloroethyl) ether was added, and the mixture was reacted at 95 ° C. for 15 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 7200.

(Example 7) <Preparation of 50% aqueous solution of bis (2-chloroethyl) ether-1,3-bis [3- (dibutylamino) propyl] urea copolymer>
372 g (2 mol) of N, N-dibutylaminopropylamine and 60 g (1 mol) of urea were charged into a reaction vessel, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170 to 180 ° C. for about 5 hours. . Thereafter, the mixture was cooled, 143 g (1 mol) of bis (2-chloroethyl) ether was added, and the mixture was reacted at 95 ° C. for 15 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 6900.

(Example 8) <Preparation of 50% aqueous solution of bis (2-chloroethyl) ether-1,3-bis [3- (di (2-hydroxyethyl) amino) propyl] urea copolymer>
324 g (2 mol) of N, N-di (2-hydroxyethyl) aminopropylamine and 60 g (1 mol) of urea were charged into a reaction vessel, heated under a nitrogen gas stream and heated at 170 to 180 ° C. for about 5 Deammonia reaction was carried out for a time. Thereafter, the mixture was cooled, 143 g (1 mol) of bis (2-chloroethyl) ether was added, and the mixture was reacted at 95 ° C. for 15 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 6500.

(Example 9) <Preparation of 50% aqueous solution of bis (2-chloroethyl) ether-1,3-bis [3- (dimethylamino) propyl] thiourea copolymer>
A reaction vessel was charged with 204 g (2 mol) of N, N-dimethylaminopropylamine and 76 g (1 mol) of thiourea, heated under a nitrogen gas stream and heated at 170-180 ° C. for about 5 hours. did. Thereafter, the mixture was cooled, 143 g (1 mol) of bis (2-chloroethyl) ether was added, and the mixture was reacted at 95 ° C. for 10 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 7800.

(Example 10) <Preparation of 50% aqueous solution of bis (2-chloroethyl) ether-1,3-bis [6- (dimethylamino) hexyl] urea copolymer>
N, N-dimethylaminohexylamine (140 g, 2 mol) and urea (60 g, 1 mol) were charged into a reaction vessel, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170-180 ° C. for about 5 hours. . Thereafter, the mixture was cooled, 143 g (1 mol) of bis (2-chloroethyl) ether was added, and the mixture was reacted at 95 ° C. for 12 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 7400.

(Example 11) <Preparation of 50% IPA solution of bis (2-chloroethyl) ether-1,3-bis [3- (dimethylamino) propyl] urea copolymer>
A reaction vessel was charged with 204 g (2 mol) of N, N-dimethylaminopropylamine and 60 g (1 mol) of urea, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170 to 180 ° C. for about 5 hours. . Thereafter, the mixture was cooled, 143 g (1 mol) of bis (2-chloroethyl) ether was added, and the mixture was reacted at 95 ° C. for 10 hours. The reaction solution was diluted with isopropanol (IPA) to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 7500.

(Example 12) <Preparation of 50% aqueous solution of bis (2-chloroethyl) ether-1,3-bis [3- (dimethylamino) propyl] urea copolymer>
A reaction vessel was charged with 204 g (2 mol) of N, N-dimethylaminopropylamine and 60 g (1 mol) of urea, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170 to 180 ° C. for about 5 hours. . Thereafter, the mixture was cooled, 143 g (1 mol) of bis (2-chloroethyl) ether was added, and the mixture was reacted at 95 ° C. for 10 hours. By diluting the reaction solution with water, a yellow liquid composition containing 50% by mass of a cationic polymer was obtained. The weight average molecular weight of the cationic polymer was 45000.

(Comparative Example 1) <Preparation of 50% aqueous solution of bis (2-chloroethyl) ether-1,3-bis [3- (dimethylamino) propyl] urea copolymer (weight average molecular weight 800)>
A reaction vessel was charged with 204 g (2 mol) of N, N-dimethylaminopropylamine and 60 g (1 mol) of urea, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170 to 180 ° C. for about 5 hours. . Thereafter, the mixture was cooled, 143 g (1 mol) of bis (2-chloroethyl) ether was added, and the mixture was reacted at 95 ° C. for 1 hour. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 800.

(Comparative Example 2) <Preparation of 50% aqueous solution of poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride]>
116 g (1 mol) of N, N, N ′, N′-tetramethyl-1,2-ethylenediamine and 143 g of bis (2-chloroethyl) ether were added and reacted at 95 ° C. for 20 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 10,000.

(Comparative Example 3) <Preparation of 50% aqueous solution of dichlorohexane-1,3-bis [3- (dimethylamino) propyl] urea copolymer>
A reaction vessel was charged with 204 g (2 mol) of N, N-dimethylaminopropylamine and 60 g (1 mol) of urea, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170 to 180 ° C. for about 5 hours. . After cooling, 155 g (1 mol) of 1,6-dichlorohexane was added and reacted at 95 ° C. for 10 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 8,000.

(Comparative Example 4) <Preparation of 50% aqueous solution of bischloromethyl ether-1,3-bis [3- (dimethylamino) propyl] urea copolymer>
A reaction vessel was charged with 204 g (2 mol) of N, N-dimethylaminopropylamine and 60 g (1 mol) of urea, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170 to 180 ° C. for about 5 hours. . After cooling, 115 g (1 mol) of bischloromethyl ether was added and reacted at 95 ° C. for 10 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 8500.

(Comparative Example 5) <Preparation of 50% aqueous solution of bis (2-chloromethyloxy) ethane-1,3-bis [3- (dimethylamino) propyl] urea copolymer>
A reaction vessel was charged with 204 g (2 mol) of N, N-dimethylaminopropylamine and 60 g (1 mol) of urea, heated under a nitrogen gas stream, and subjected to deammonia reaction at 170 to 180 ° C. for about 5 hours. . Thereafter, the mixture was cooled, 159 g (1 mol) of bis (chloromethyloxy) ethane was added, and the mixture was reacted at 95 ° C. for 10 hours. The reaction solution was diluted with water to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 8300.

(Comparative Example 6)
Instead of the cationic polymer, a 50% by mass aqueous solution of benzalkonium chloride was prepared.

(Comparative Example 7)
No antibacterial antifungal agent was prepared.

(Comparative Example 8) <Preparation of 50% IPA solution of poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride]>
116 g (1 mol) of N, N, N ′, N′-tetramethyl-1,2-ethylenediamine and 143 g (1 mol) of bis (2-chloroethyl) ether were added and reacted at 95 ° C. for 20 hours. The reaction solution was diluted with IPA to obtain a slightly yellow liquid composition containing 50% by mass of a cationic polymer. The weight average molecular weight of the cationic polymer was 10,000.

[Molecular weight measurement conditions]
The weight average molecular weight of the cationic polymer was determined using gel permeation chromatography [Column: Tosoh Corporation, trade name: TSKgel G3000PW-CP], polyethylene glycol as a standard substance, and eluent with a sodium nitrate concentration of 0. It measured using 1M aqueous solution. Measurement conditions are as follows.
Flow rate: 0.70 mL / min
Sample concentration: 0.1 g / L
Filtration filter: 0.45μm-Millex-LH (Millipore)
Injection volume: 0.200 mL
Temperature: 23 ° C
Detector: Differential refractive index detector (product name: RI-8020, manufactured by Tosoh Corporation)

<Evaluation of antibacterial and antifungal agents>
The antibacterial and antifungal agents obtained above were subjected to the following evaluation tests. In the antibacterial and antifungal test, the following bacteria were used.

[Test bacteria]
Staphylococcus aureus ATCC 6538P: (abbreviated as Sa)
Klebsiella pneumoniae NBRC13277: (abbreviated as Kp)
Escherichia coli NBRC3301: (abbreviated E.c)
Pseudomonas aeruginosa NBRC3080: (abbreviated as Pa)
Methicillin-resistant Staphylococcus aureus IID1677: (abbreviated as MRSA)

[Test mold]
The following fungi were used in the antifungal evaluation test.
Black persimmon (Aspergillus niger NBRC105650): (abbreviated as A.n)
Black Spider (Cladosporium cladosporoides NBRC6348): (abbreviated C.c)
Blue 黴 (Penicillium citrinum NBRC6352): (abbreviated as P.c)
Trichophyton mentagrophytes NBRC32409: (abbreviated as T.m)

[Evaluation Test 1: Odor]
The odors of the cationic polymer aqueous solutions obtained in Examples 1 to 10 and 12 and Comparative Examples 1 to 5 and 8 were directly sniffed, and the case where there was almost no amine odor was designated as A, and the case where a strong amine odor was seen as B. did. In Comparative Examples 6 and 7, there was no amine odor.

[Evaluation Test 2: Minimum Growth Inhibitory Concentration Test]
For the cationic polymer aqueous solutions obtained in Examples 1 to 10 and 12, and Comparative Examples 1 to 5 and 8, and the benzalkonium chloride 50% by mass aqueous solution of Comparative Example 6, the “intelligible fungus test method” And anti-contamination measures (Techno System Co., Ltd.), Part II Easy-to-understand fungus test method, Chapter 6 Anti-fungal test, Section 4 Anti-fungal agent efficacy test " The minimum inhibitory concentration (mg / L) was measured.

The active ingredient concentration of the cationic polymer aqueous solution and the culture conditions for the test bacteria and test fungi were as follows. It was confirmed that the inoculated test bacterium or test fungus was a single culture, and the lowest active ingredient concentration at which growth was completely inhibited was defined as the minimum growth inhibitory concentration. It was determined that the smaller the value, the more antibacterial and antifungal effect.

Active ingredient concentration of cationic polymer aqueous solution: 2.5, 5, 10, 25, 50, 125, 250, 500, 1000 mg / L
Culture conditions Bacteria: 37 ° C x 48 hours Mold: 25 ° C x 2 or 7 days Medium Bacteria: Ordinary agar medium Mold: Potato dextrose agar medium

[Evaluation Test 3: Antibacterial and antifungal test of polyester film coated with antibacterial and antifungal agent]
Each of the aqueous solutions prepared in Examples and Comparative Examples was applied to a polyester film (Teijin Tetron Film, brand G2) by spraying so that the nonvolatile content was 0.5 g / m ² . The coated film was dried at 100 ° C. for 30 minutes to obtain a polyester film having antibacterial and antifungal properties. For Comparative Example 7, a polyester film without any application was prepared.

The antibacterial activity value and the antifungal activity value of the polyester film obtained above were determined according to the following methods.

(Measurement of antibacterial activity value)
Based on JIS Z 2801 (2006), the antibacterial activity value was determined using Staphylococcus aureus as a test bacterium. When the antibacterial activity value was larger than 2, it was determined to be effective.

(Measurement of antifungal activity value)
Black candy was tested as a test fungus in accordance with JIS CF301 “Anti-fungus processed fiber product certification standard” of the Japan Textile Evaluation Technology Council (hereinafter referred to as the Textile Technology Association). The antifungal activity value was calculated according to the following formula. When the antifungal activity value was larger than 2.0, it was determined that there was an effect. Antifungal activity value = (F _b −F _a ) − (F _c −F ₀ )
F _a : Average value of common logarithm values of the amount of ATP produced by the test mold immediately after inoculating the test mold on the standard polyester film (3 samples)
F _b : Average value of common logarithm of ATP amount produced by test fungi after inoculating test fungus on standard polyester film and culturing for 42 hours (3 samples)
F _c : Average value of the common logarithm of the amount of ATP produced by the test fungus after inoculating the test fungus on a polyester film having antibacterial and antifungal properties and culturing for 42 hours (3 samples)
F ₀ : Average value of common logarithm values of the amount of ATP produced by the test fungus immediately after inoculating the test fungus on the antimicrobial and antifungal polyester film (3 samples)
The amount of ATP was measured with Lumitester C-110 (Kikkoman Foods Co., Ltd.).

[Evaluation Test 4: Thermal Discoloration Test of Polyester Film Coated with Antibacterial Antifungal Agent]
The polyester film obtained in the same manner as in the evaluation test 3 was subjected to the following thermal discoloration test to evaluate heat discoloration.

(Thermal discoloration test)
The polyester film coated with the antibacterial and antifungal agent was heat-treated at 100 ° C. and 180 ° C. for 1 minute to perform color measurement. Based on Comparative Example 7, the difference in b value (Δb value) was determined under the following measurement conditions. It was determined that the greater the Δb value, the more yellow the color was changed.
Colorimetric conditions: Minolta colorimeter CM-3700d, light source D65, field of view 10 degrees

[Evaluation Test 5: Antibacterial and Antifungal Test of Cotton Fiber Products]
The aqueous solutions prepared in Examples and Comparative Examples were each applied to a cotton broad cloth by padding treatment so that the nonvolatile content was 0.5% by mass with respect to the fiber mass, dried at 120 ° C. for 2 minutes, A cotton fiber product having moldability was obtained. For Comparative Example 7, an untreated cotton fiber product was prepared.

The bacteriostatic and antifungal activity values before and after washing (L-0) and 10 times after washing (L-10) were determined for the cotton fiber product obtained above according to the following method.

(Measurement of bacteriostatic activity value)
Bacteriostatic activity values were measured for cotton fiber products before and after washing 10 times using Staphylococcus aureus as a test bacterium in accordance with the quantitative test method of JIS L 1902 (2008). Washing was performed according to JIS L 0217 (1995) Appendix 103, Method 103. When the bacteriostatic activity value was larger than 2.2, it was determined to be effective.

(Measurement of antifungal activity value)
The antifungal activity value was measured for cotton fiber products before washing and after 10 washings, using black candy as a test fungus, in accordance with JECF301 “Anti-fungus processed textile product certification standard”. When the antifungal activity value was larger than 2.0, it was determined that there was an effect.

[Evaluation Test 6: Thermal Discoloration Test of Cotton Fiber Products]
The following thermal discoloration test was performed on the cotton fiber product obtained in the same manner as in the evaluation test 5, and the heat discoloration property was evaluated.

(Thermal discoloration test)
The cotton fiber product treated with the antibacterial antifungal agent was heat-treated at 120 ° C. and 180 ° C. for 1 minute, and the whiteness was measured under the following measurement conditions. It was determined that there was discoloration as the whiteness was smaller than Comparative Example 7.
Whiteness measurement conditions: Minolta colorimeter CM-3700d, light source D65, field of view 10 degrees

[Evaluation Test 7: BHT / NOx Discoloration Test of Cotton Fiber Products]
The cotton fiber product obtained in the same manner as in the evaluation test 5 was subjected to the following BHT / NOx discoloration test to evaluate the BHT / NOx discoloration resistance.

(BHT / NOx discoloration test)
In accordance with JIS L 0855 (2005), a cotton fiber product was allowed to stand for 24 hours at 50 ° C. in a closed system in which 0.05 g of BHT coexisted in advance for 3 cycles. After the test The color of cotton fiber products was measured. Based on Comparative Example 7, the difference in b value (Δb value) was determined under the following measurement conditions. It was determined that the greater the Δb value, the more yellow the color was changed.
Measurement conditions: Minolta colorimeter CM-3700d, light source D65, field of view 10 degrees

[Evaluation Test 8: Antibacterial and antifungal test and evaluation of heat discoloration when kneaded into resins]
Polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumitomo Nobrene H-501) (100 parts by mass) and the cationic polymer (1 part by mass) obtained in Example 1, Comparative Example 2 or Comparative Example 7 After being kneaded for 5 minutes at 210 ° C. using a lab plast mill (trade name, Toyo Seiki Seisakusho Co., Ltd.), 150 mm (vertical) × 150 mm (horizontal) × 0.5 (thickness) with a small molding machine A resin product of mm was produced. The obtained resin product was evaluated for antibacterial and antifungal properties by the same method as in Evaluation Test 3. Moreover, the coloring of the resin product produced above was observed visually, and the heat discoloration was evaluated according to the following criteria.
A: Equivalent to resin without addition of cationic polymer B: Colored compared to resin without addition of cationic polymer

[Evaluation Test 9: Water Resistance Test]
The solution obtained in Example 11, Comparative Example 8, and Comparative Example 6 was applied to a polyester film (Teijin Tetron Film, Brand G2) by spraying so that the nonvolatile content was 0.5 g / m ^2, and the solution was brought to room temperature. And dried for 30 minutes to produce a plastic product for water resistance test. The plastic product for the water resistance test was immersed in water for 1 hour and then dried, and antibacterial and antifungal properties were evaluated by the same method as in Evaluation Test 3.

The results obtained in the above evaluation tests 1 to 9 are shown in Tables 1 to 6.

It was found that all of the antibacterial and antifungal agents containing the cationic polymer according to this example exhibited good antibacterial properties, antifungal properties and washing durability. Particularly, in the general formula (1), R ¹ is a methyl group, R ² is an ethyleneoxyethylene group, R ³ is a propylene group, and R ⁴ is a hydrogen atom. It was confirmed that good antibacterial and antifungal performance can be obtained. In addition, the cationic polymers of the examples all had less heat yellowing and less discoloration due to BHT / NOx gas than the cationic polymers of the comparative examples.

From the minimum growth inhibitory concentration test of Evaluation Test 2, it was confirmed that all of the cationic polymers obtained in the examples showed good antibacterial and antifungal properties. The antibacterial and antifungal agent of this example is an antibacterial and antifungal agent for liquid detergents, liquid soaps, spraying liquids and other liquid products, gel products, coating agents, resin additives, textile products, and resin products. It is possible to impart sex.

According to the antibacterial and antifungal test of the polyester film of evaluation test 3 and the thermal discoloration test of the polyester film coated with the antibacterial and antifungal agent of evaluation test 4, the cationic polymer obtained in the example is a hard material surface such as a polyester film. When used as an antibacterial and antifungal agent for antibacterial and antifungal processing, it was confirmed that it exhibits good antibacterial and antifungal properties with heat resistance.

Cationic polymer obtained in Examples by antibacterial and antifungal test of cotton fiber product of evaluation test 5, thermal discoloration test of cotton fiber product of evaluation test 6 and BHT / NOx discoloration test of cotton fiber product of evaluation test 7 When used as a treating agent for textiles, it was confirmed that the antibacterial and antifungal property with durability was excellent, thermal yellowing was small, and there was little discoloration due to BHT / NOx gas.

According to the antibacterial and antifungal test and the heat resistance test when kneaded into the resins of Evaluation Test 8, the cationic polymers obtained in the examples show good antibacterial and antifungal properties even when kneaded into the resin. It was confirmed that heat discoloration was also good.

The water resistance test of evaluation test 9 confirmed that the cationic polymer obtained in the example had better water resistance than the benzalkonium chloride of comparative example 6 and the cationic polymer of comparative example 8. .

On the other hand, as shown in Comparative Example 1, the cationic polymer compound having a low molecular weight had an amine odor. In addition, when applied to textile products, the antibacterial and antifungal durability against washing is poor.

As shown in Comparative Example 2, the cationic polymer having no urea group or thiourea group in the straight chain showed antibacterial properties but no antifungal properties.

As shown in Comparative Example 3, a cationic polymer having no oxyalkylene group in the straight chain showed antibacterial properties but no antifungal properties. Moreover, the antibacterial durability against washing was inferior.

As shown in Comparative Example 4, the cationic polymer having an oxyalkylene group having a carbon number of less than 4 in the straight chain showed antibacterial properties but no antifungal properties. Moreover, the antibacterial durability against washing was inferior.

As shown in Comparative Example 5, even when the straight chain has an oxyalkylene group having 4 or more carbon atoms, when the terminal of the oxyalkylene group is a methylene group, antibacterial property is recognized but antifungal property is recognized. There wasn't. Moreover, the antibacterial water resistance against washing was inferior.

As described above, the cationic polymer according to the present invention has a specific structure, thereby having both excellent antibacterial and antifungal properties against various bacteria and fungi, and water resistance and heat discoloration. It can be seen that the present invention has the effect of being excellent in heat resistance and BHT / NOx gas discoloration.

According to the present invention, it is possible to provide a new antibacterial and antifungal agent having a durable antifungal property as well as a durable antifungal property. This can prevent problems such as discoloration and off-flavor due to mold in recent years, in addition to the conventional antibacterial effect, in kitchens, bathrooms, toilets and toilets, and textile products. It becomes.

In addition, since the antibacterial and antifungal agent of the present invention has little discoloration due to heat and BHT / NOx gas, the discoloration problem can be reduced even when processed into a light-colored fiber or kneaded into a light-colored resin. be able to.

Claims (3)

1. An antibacterial antifungal agent containing a cationic polymer represented by the following general formula (1) having a weight average molecular weight of 1000 or more.
   

   

   [In Formula (1), each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, or an alkenyl group having 2 to 4 carbon atoms, and R ² represents the following general formula ( 2) represents an oxyalkylene group having 4 to 8 carbon atoms, R ³ independently represents an alkylene group having 2 to 10 carbon atoms, and R ⁴ each independently represents a hydrogen atom, a carbon number of 1 Represents an alkyl group or hydroxyalkyl group of ˜4, or an alkenyl group of 2 to 4 carbon atoms, Y represents an oxygen atom or a sulfur atom, n represents a positive integer, and X ^m− represents an m-valent anion. Show.
   

   

   In formula (2), R ⁵ represents an alkylene group having 1 or more carbon atoms, a independently represents an integer of 2 or more, and b represents an integer of 0 or more. ]
2. The antibacterial and antifungal agent according to claim 1, wherein the cationic polymer has a weight average molecular weight of 1,000 to 50,000.
3. An antibacterial and antifungal product to which antibacterial and antifungal properties are imparted by the antibacterial and antifungal agent according to claim 1 or 2.