WO2013047642A1 - Article comprising immobilized antibacterial agent and method for producing same - Google Patents

Abstract

The problem is to provide an article having durability against abrasion and laundering wherein an antibacterial agent comprising an ethoxysilane quaternary ammonium salt is immobilized on the surface, and to provide a method for the inexpensive production of an antibacterial article having long-lasting (durable) antibacterial capability. The present invention is an antibacterial article, characterized in that at least the surface comprises a resin component having carboxyl groups and is imparted with antibacterial agent comprising an ethoxysilane quaternary ammonium salt. The resin component having carboxyl groups can be contained in the substrate of the article or it can be imparted as a binder to the surface of the article.

Description

Article having antibacterial agent immobilized thereon and method for producing the same

The present invention relates to an article having an antibacterial agent immobilized on its surface and a method for producing the same. In particular, the present invention relates to an article in which an antibacterial agent containing an ethoxysilane-based quaternary ammonium salt is applied and immobilized on the surface, and a method for producing the same.

In recent years, many antibacterial agents and materials to which antibacterial agents have been added have been developed in connection with increasing awareness of environmental sanitation. Among these, ethoxysilane quaternary ammonium salts are known as antibacterial agents that can be immobilized on the surface of the material (Patent Document 1). Specifically, octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride is disclosed as the ethoxysilane-based quaternary ammonium salt. This antibacterial agent has in its molecule an ammonium group having a relatively long-chain alkyl group that exhibits antibacterial properties, and an alkoxysilyl group that can form a covalent bond with the surface of the material. Since a covalent bond is formed by reacting with a hydroxyl group or the like present on the surface of an inorganic material or the like, it can be firmly fixed on the surface of the inorganic material or the like.

Patent Document 1 discloses that the antibacterial agent is immobilized on an article having an oxygen-containing functional group on the surface. Specifically, as the oxygen-containing functional group, —OH group (hydroxyl group), —O -Groups are illustrated. Moreover, in order to provide an oxygen-containing functional group on the article surface, it is disclosed that the article is subjected to ozone water treatment before the antibacterial agent is imparted.
However, a method for immobilizing the antibacterial agent has not been known so as to be efficient and excellent in durability with respect to articles of any material. Specifically, the antibacterial agent can be immobilized relatively easily on inorganic materials such as glass and metal, and materials having hydroxyl groups on the surface, whereas synthetic fibers such as polyester fibers, polypropylene, etc. Articles having no hydroxyl group on the surface, such as resin materials, are not suitable for immobilizing the antibacterial agent.

In Patent Document 2, in order to immobilize the above antibacterial agent on a synthetic resin, plasma treatment is performed on the synthetic resin prior to the immobilization treatment of the antibacterial agent, so that polymethylmethacrylate resin or polyethylene terephthalate can be used. It is disclosed that immobilization can be performed efficiently. According to the invention of Patent Document 2, an antibacterial agent can be suitably imparted to dental resins such as dentures and dentures.
However, in the present invention, it is necessary to perform a plasma treatment, and a plasma treatment apparatus is indispensable in equipment for producing a resin having an antibacterial agent immobilized thereon.

Patent Document 3 describes performing microwave irradiation in addition to ozone water treatment in order to immobilize the antibacterial agent on the surface of the article.
Both the ozone water treatment and the microwave irradiation are aimed at generating an —OH group (hydroxyl group), —CHO group (aldehyde group), —O— group or the like on the surface of the article. This is because, if these groups are present on the surface of the article, they can react with the alkoxysilyl group of the antibacterial agent molecule, and the antibacterial agent can be immobilized on the surface of the article.
However, in order to perform the ozone water treatment, it is necessary to provide an ozone water generation facility for supplying ozone water used for the treatment. Also, when performing microwave irradiation, a dedicated facility for generating microwaves is required.

As described above, conventionally, there is no known method for easily applying an antibacterial agent containing an ethoxysilane-based quaternary ammonium salt to an article made of a resin material or the like without requiring a special treatment apparatus. It was.
In addition, in order to put the antibacterial agent-immobilized article into practical use, the antibacterial agent is maintained on the surface without losing the antibacterial agent against the friction due to use and the many washings (durability) ) Is required, however, sufficient studies have not been made on durability.

JP 2011-98976 A JP 2007-126557 A WO2009 / 136561

Therefore, an object of the present invention is to provide an article in which an antibacterial agent containing an ethoxysilane-based quaternary ammonium salt is immobilized on the surface, and a method for producing such an article. Furthermore, this invention makes it a subject to provide the articles | goods by which this antimicrobial agent is fixed so that it may have durability, and an antimicrobial effect is maintained.

As the inventors proceeded with the study of immobilizing an antibacterial agent containing an ethoxysilane-based quaternary ammonium salt, a carboxyl group was formed on the surface instead of the hydroxyl group that was conventionally considered suitable for immobilization. It is possible to effectively fix the antibacterial agent to the article by a simple method and to obtain an article having antibacterial properties with excellent durability by using a binder having a carboxyl group. The present invention has been completed.
In the present specification, “having a carboxyl group” means not only a case where a carboxyl group present on the surface of an article exists as a free carboxyl group (—COOH) that is not dissociated, but also a terminal hydrogen atom. In the case where is released to form a carboxylate anion or the carboxylate anion and the antibacterial molecule are chemically bonded, unless otherwise specified.
In addition, in this specification, the “base material of an article” means a portion that is a main body that defines the structure and form of an article among elements constituting an article to which an antibacterial agent is applied.

That is, the present invention relates to an antibacterial article characterized in that it contains a resin component having a carboxyl group at least on its surface and is provided with an antibacterial agent containing an ethoxysilane quaternary ammonium salt.

The resin component having a carboxyl group preferably contains a polymer obtained by polymerizing a monomer containing at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid and carboxymethylcellulose.

The resin component having a carboxyl group used in the present invention more preferably contains at least one of an acrylic polymer, a polyester polymer, a polyolefin polymer and / or a urethane polymer. These polymers may be used as a mixture.
When such a polymer is used as a resin component having a carboxyl group or together with a resin component having a carboxyl group, the antibacterial agent can be efficiently immobilized on the surface, and physical properties such as desired flexibility and strength Therefore, an article having both antibacterial properties and desired physical properties can be obtained. In addition, selecting an appropriate resin is advantageous in terms of cost.

As an antibacterial agent containing an ethoxysilane-based quaternary ammonium salt, the following formula (1)

(Wherein R ¹ represents an alkyl group having 12 to 24 carbon atoms, R ² and R ³ represent the same or different lower alkyl groups having 1 to 6 carbon atoms, and X represents a halogen ion or An antibacterial agent represented by an organic carbonyloxy ion (which represents an organic carboxylic acid ion) is preferred, and octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride is more preferred.

In the present invention, the resin component having a carboxyl group constitutes at least the surface of the substrate of the article itself, and the article having the antibacterial agent applied to the surface of the substrate or the surface of the article substrate The present invention relates to an article to which the antibacterial agent is applied via a binder, and the binder includes a resin component having the carboxyl group.
The binder having a carboxyl group is more preferably a binder containing an acrylic polymer obtained by polymerizing acrylic acid and / or methacrylic acid, and the article is more preferably a fabric.
An article having a binder having a carboxyl group on its surface can obtain a carboxyl group on its surface even if the article itself does not contain a carboxyl group. Therefore, the antibacterial agent can be attached to the article by attaching the antibacterial agent via the binder. In addition, a binder containing a polymer obtained by polymerizing acrylic acid and / or methacrylic acid is generally easy to handle, and further has an advantage that it is relatively inexpensive and easily available.
When the article is a fabric, an ethoxysilane-based quaternary ammonium salt can be immobilized on fabrics of various materials including natural fibers and synthetic fibers using a binder having a carboxyl group. For example, in the past, it was difficult to fix an ethoxysilane-based quaternary ammonium salt to a fabric made of polyester and to have excellent washing durability, but by combining with a binder having a carboxyl group, antibacterial properties, A fabric made of polyester fiber having washing durability and friction durability can be obtained at low cost.

The article of the present invention is considered to have an antibacterial agent containing an ethoxysilane quaternary ammonium salt immobilized on the surface of the article via a carboxyl group. The article of the present invention has high antibacterial properties due to the immobilized antibacterial agent. By using a resin component having a carboxyl group, the antibacterial agent can be immobilized on the surface of the article efficiently and reliably, and the material of the article is natural fibers such as cotton, wool, silk, hemp, Even natural products such as paper, wood, and metal are synthetic fibers such as polyester, polyurethane, polyamide, rayon, acrylic, and other synthetic fibers, polyethylene, polypropylene, vinyl chloride, nitrile rubber, acrylic resin, and polycarbonate resin. However, the surface of the article is composed of a resin component having a carboxyl group, or the binder has a carboxyl group on the surface of the article so that the antibacterial agent does not easily fall off the article surface and has high durability. become. In addition, an article having an antibacterial agent immobilized thereon can be obtained at low cost by using ordinary equipment without requiring a special treatment apparatus.

In addition, the present invention provides an article containing at least a resin component having a carboxyl group on the surface thereof in contact with a solution of a composition containing an antibacterial agent containing an ethoxysilane quaternary ammonium salt, so that the surface of the article has an ethoxysilane series. The present invention relates to a method for producing an article having antibacterial properties, comprising a step of imparting a quaternary ammonium salt.

According to the production method of the present invention, an antibacterial agent containing an ethoxysilane-based quaternary ammonium salt can be immobilized on an article using conventional equipment used for the treatment of the article. The production method of the present invention is advantageous in terms of cost, friction fastness and light fastness, and can be suitably applied with an antibacterial agent even in a relatively low temperature range. Even so, the antibacterial agent can be immobilized.

Furthermore, the production method of the present invention may include a step of attaching a binder having a carboxyl group to the surface of the article. When a binder having a carboxyl group is attached to the surface of the article, the antibacterial agent can be immobilized even on an article which does not contain a carboxyl group on the surface as the material of the article itself.

The antibacterial article of the present invention is excellent in antibacterial property and durability (sustainability of antibacterial effect) since an antibacterial agent is immobilized on the surface. In addition, no special pretreatment is required for production, and an article having antibacterial properties can be produced at low cost using a conventional apparatus. Furthermore, in the case of an article having a carboxyl group on the surface as the material of the article itself, even if the antibacterial agent is reapplied or additionally applied, it does not require any special pretreatment and is in contact with the antibacterial agent. It is possible to easily apply antibacterial agents simply by making them.
Moreover, the antibacterial agent containing an ethoxysilane type | system | group quaternary ammonium salt is also provided with respect to the article | item which does not have a carboxyl group on the surface as a material of article | item itself by providing the binder which has a carboxyl group to the article | item surface. Can be immobilized.

(Antimicrobial agent)
The antibacterial agent immobilized on the article of the present invention is an antibacterial agent containing an ethoxysilane quaternary ammonium salt, and the ethoxysilane quaternary ammonium salt is a relatively long-chain alkyl group that exhibits antibacterial properties. And an alkoxysilyl group capable of forming a covalent bond with the material surface of the article. Specifically as an ethoxysilane type | system | group quaternary ammonium salt, following General formula (1)

(Wherein R ¹ represents an alkyl group having 12 to 24 carbon atoms, R ² and R ³ represent the same or different lower alkyl groups having 1 to 6 carbon atoms, and X represents a halogen ion or There is a compound represented by an organic carbonyloxy ion (an organic carboxylate ion).

X in the formula (1) is a halogen ion such as chlorine ion or bromine ion, methylcarbonyloxy ion (acetate ion), ethylcarbonyloxy ion (propionate ion), phenylcarbonyloxy ion (benzoate ion), etc. An organic carbonyloxy ion (organic carboxylate ion) can be exemplified.

Examples of the alkyl group having 12 to 24 carbon atoms of R ¹ in the formula (1) include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, and uneicosyl group. , Doeicosyl group, trieicosyl group, tetraeicosyl group and the like.

Examples of the lower alkyl group having 1 to 6 carbon atoms, which may be the same or different as R ² and R ³ in the formula (1), include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl Examples thereof include a group, a hexyl group, and a cyclohexyl group.

Specific examples of the silicon-containing compound represented by the general formula (1) include octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride, dodecyldimethyl (3-triethoxysilylpropyl) ammonium chloride, dodecyldiisopropyl (3- Triethoxysilylpropyl) ammonium chloride, tetradecyldimethyl (3-triethoxysilylpropyl) ammonium chloride, tetradecyldiethyl (3-triethoxysilylpropyl) ammonium chloride, tetradecyldi-n-propyl (3-triethoxysilylpropyl) ammonium Chloride, pentadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride, pentadecyldiethyl (3-triethoxysilylpropyl) Ammonium chloride, pentadecyl di-n-propyl (3-triethoxysilylpropyl) ammonium chloride, hexadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride, hexadecyl diethyl (3-triethoxysilylpropyl) ammonium chloride, hexadecyl di-n -Propyl (3-triethoxysilylpropyl) ammonium chloride, octadecyl diethyl (3-triethoxysilylpropyl) ammonium chloride, octadecyl di-n-propyl (3-triethoxysilylpropyl) ammonium chloride, and the like. , Octadecyldimethyl (3-triethoxysilylpropyl) ammonium with less biotoxicity, environmental impact during use, and environmental impact of waste liquid Roraido is preferable.

The antibacterial agent imparted to the article of the present invention may be one or more of the above ethoxysilane quaternary ammonium salts, and may be used in combination with other antibacterial agents.
The above ethoxysilane quaternary ammonium salts have antibacterial (antibacterial) effects against gram-positive and gram-negative bacteria, and have antiviral effects against envelope viruses such as influenza virus and measles virus. (The antibacterial effect and the antiviral effect are collectively called antibacterial effect). Furthermore, in addition to the antibacterial effect, it is considered to have an antistatic effect and a deodorizing effect at the same time.

(Goods)
The article to which the antibacterial agent of the present invention is immobilized is an article having a resin component having a carboxyl group on at least the surface of the article, a part of the article, or the entire article.
The article of the present invention
1) At least the surface of the substrate itself of the article is made of a resin component having a carboxyl group 2) Any of those obtained by adding a binder (resin component) having a carboxyl group to the surface of the substrate of the article. In the case of 1), only the surface of the base material may be composed of a resin having a carboxyl group, or the entire base material may be composed of a resin having a carboxyl group.
If the resin component having a carboxyl group is on the surface, the antibacterial agent can be effectively immobilized. Parts other than the surface, for example, parts where bacteria and viruses do not adhere in normal use, and the inside of articles where bacteria and viruses do not become a problem are made of materials other than resins containing carboxyl groups Also good.

(When the base material of the article itself contains a carboxyl group)
When a resin component having a carboxyl group is included in the substrate of the article itself, the resin component having a carboxyl group includes a resin component including a polymer having a carboxyl group in a side chain bonded to the main chain. Examples of the monomer having a carboxyl group that gives such a polymer include known compounds such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and carboxymethylcellulose. Among these, a resin component containing a polymer obtained by polymerizing a monomer containing acrylic acid and / or methacrylic acid is preferable.

The monomer having a carboxyl group exemplified above may be polymerized by itself, or may be a copolymer of a monomer having the carboxyl group and a monomer having no carboxyl group. Also good. Moreover, the mixture (polymer alloy) by which the polymer which has a carboxyl group, and the polymer which does not have a carboxyl group may be mixed.

The monomer copolymerized with the monomer having a carboxyl group is not particularly limited as long as the effect of the present invention is not impaired. For example, when obtaining an acrylic acid polymer, methyl acrylate, ethyl acrylate, n-butyl acrylate is used. And alkyl acrylates such as isobutyl acrylate and pentyl acrylate, and alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and pentyl methacrylate.

Moreover, when obtaining a vinyl polymer, as a monomer copolymerized with the monomer containing a carboxyl group, in addition to the acrylic acid monomer, a vinyl monomer, for example, a glycidyl group-containing vinyl monomer, an aromatic vinyl Monomers, vinyl cyanide monomers, ethylenically unsaturated ether monomers, ethylenically unsaturated amine monomers, ethylenically unsaturated silane monomers, aliphatic conjugated diene monomers, polyether polyols, and the like can be used.

When a polyester polymer having a carboxyl group is used, an acid anhydride and a polyester polyol can be used as monomers. Examples of such acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimetic anhydride, succinic anhydride, and the like. Polyester polyols include condensates of dicarboxylic acid and diol, and open lactones. Examples thereof include a ring polymer.
When a polyolefin-based polymer having a carboxyl group is used, an acid-modified polyethylene, polypropylene, or the like can be used. Examples of such a polymer include unsaturated carboxylic acid-modified polyolefin, specifically, maleic anhydride-modified polypropylene.

When obtaining a urethane polymer having a carboxyl group, a compound having a carboxyl group and active hydrogen and a polyfunctional isocyanate are used as monomers. Examples of such carboxyl group-containing monomers include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid, tartaric acid, and lysine. Examples of the polyfunctional isocyanate include 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), ethylene diisocyanate, tetramethylene diisocyanate, Hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, and the like.

As the resin component having a carboxyl group that constitutes the surface of the article of the present invention, a resin in which a polymer having a carboxyl group and a polymer having no carboxyl group are mixed can be used. As a polymer used in combination with a polymer having a carboxyl group, for example, one or more of a polyester-based polymer and a urethane-based polymer not having a carboxyl group can be used. Further, it may be a functional group other than a carboxyl group, for example, a polymer having a hydroxyl group, a polymer having an amino group, or the like, or polyethylene glycol or polypropylene glycol having no functional group.

When a resin component containing a carboxyl group is present on the surface of the substrate of the article itself, the layer of the resin component having a carboxyl group may be a part of the article body or a coating film that covers the surface of the article Or a laminated film or the like. From the viewpoint of maintaining the immobilization of the antibacterial agent, the thickness of the resin component layer having a carboxyl group may have a certain thickness or more so that the resin layer containing the carboxyl group is not lost with use. Preferably, for example, it is 3 μm or more, preferably 30 μm or more.

The proportion of the carboxyl group-containing monomer in the resin component having a carboxyl group is not particularly limited as long as a desired amount of the antibacterial agent can be immobilized on the surface of the article, but for example, 5 wt% to 95 wt%, preferably 20 wt%. % To 60% by weight.
Adhesion amount of the antimicrobial agent to an article of the present invention is not particularly limited as long as the effects of the present invention is obtained, for example ^{0.0005g / m 2 ~ 10g / m} 2 with respect to the article, preferably 0.001 g / ^{m 2} Up to 3 g / m ² .

(When using a binder)
When a binder having a carboxyl group is applied to an article, the article on which the antibacterial agent is immobilized is not particularly limited as long as the binder adheres, and can be appropriately selected depending on the application and purpose. For example, a thread | yarn, a fabric, a plastic molding, a film, a touch panel, a decorative plate, a plywood etc. are mentioned. The material of the article is not particularly limited as long as it is a material to which the binder adheres. For example, polyester, polypropylene, acrylic, vinyl chloride, rayon, polycarbonate, synthetic rubber, natural rubber, various natural fibers, various wood, various metals, etc. Selected.

When the article of the present invention is a fabric, the fabric to which the antibacterial agent is immobilized may be a woven fabric, a knitted fabric, or a nonwoven fabric, and can be appropriately selected depending on the application and purpose. The material of the fabric may be natural fiber, chemical fiber, or a combination thereof. Examples of the natural fiber include cotton, wool, silk, hemp, etc., and examples of the chemical fiber include polyester, polyurethane, polyamide, rayon, and acrylic. A fabric combining these alone or in combination can be selected. Furthermore, from the viewpoints of use and design, other fibers, for example, inorganic fibers such as metal fibers and glass fibers may be included. Moreover, the cloth by which various processes, for example, a flame-retardant process, an antifouling process, etc. were given with respect to these fabrics, may be sufficient. For example, polyester-based fabrics are mainly selected for vehicle interior applications such as automobile seats.

Among the fabrics, for example, fibers having hydroxyl groups on the surface thereof such as cotton and wool are relatively easy to immobilize the above antibacterial agent. However, when a binder containing a carboxyl group is used, the antibacterial agent can be antibacterial even after many washings. It is possible to obtain a fabric that does not drop off and has excellent washing durability.

When a binder having a carboxyl group is given to the article, as the binder having a carboxyl group, for example, if the article is a fabric, a binder containing a component having a carboxyl group is used among binders for ordinary fiber processing. For example, an acrylic binder, a polyester binder, a polyolefin binder, or a urethane binder containing a component having a carboxyl group can be selected.
The component having a carboxyl group means a component having a carboxyl group in a side chain bonded to the main chain of a polymer (homopolymer and / or copolymer) which is a component of the binder. Specific examples of the monomer component having a carboxyl group that constitutes such a polymer include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, carboxymethylcellulose, and the like. Acid and methacrylic acid are preferable, and methacrylic acid is more preferable.
When a polyolefin-based binder is used, an acid-modified polyethylene, polypropylene, or the like can be used. Examples of such a binder include unsaturated carboxylic acid-modified polyolefin, specifically, maleic anhydride-modified polypropylene.
When the proportion of the monomer containing a carboxyl group in the polymer exceeds 65%, the water resistance of the binder is lowered, so that it is preferably 65% or less with respect to the solid content of the binder component.

The monomer copolymerized with the monomer containing a carboxyl group is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include the acrylic acid monomers (acrylic acid esters) described above.
In the case of polyester polymers and urethane polymers, monomers copolymerized with monomers containing carboxyl groups include vinyl monomers such as glycidyl group-containing vinyl monomers, aromatic vinyl monomers, and vinyl cyanide monomers. , Ethylenically unsaturated ether monomers, ethylenically unsaturated amine monomers, ethylenically unsaturated silane monomers, aliphatic conjugated diene monomers, polyether polyols, and the like.

Depending on the material of the article to which the binder is applied, the skeleton of the polymer contained in the binder can be appropriately selected. For example, in addition to polyacrylate, urethane acrylate, epoxy acrylate, polyester acrylate, and the like can be selected. The antibacterial agent can be immobilized on various articles by appropriately selecting a polymer that is copolymerized with the binder skeleton.
Further, for example, when the article is a polypropylene resin product, it is more preferable to use a binder having a polypropylene polymer skeleton because the adhesiveness between the article and the binder is improved. That is, when the antibacterial agent is applied after the polypropylene polymer having a carboxyl group described above is applied to the polypropylene resin product, the adhesion between the binder and the article is further improved, and as a result, the antibacterial agent is easily held on the surface of the article. Therefore, it is preferable.
When the article is a fabric, among these, from the viewpoints of film-forming properties of the binder, adhesion to the fabric surface, and softness of the fabric when adhered to the fabric surface, methyl acrylate, acrylic An acrylic binder containing an acrylic polymer containing an alkyl acrylate ester such as ethyl acrylate, n-butyl acrylate, isobutyl acrylate, or pentyl acrylate as a monomer is more preferable.

A mixture of a polymer having a carboxyl group and a polymer having no carboxyl group can also be used as a binder. In this case, the substance used in combination with the polymer having a carboxyl group may be a polymer having a functional group other than a carboxyl group (for example, a polymer having a hydroxyl group, a polymer having an amino group, etc.) Polyethylene glycol, polypropylene glycol, etc. that do not have may be used.

Adhesion amount of the binder having a carboxyl group to an article of the present invention is not particularly limited as long as the effects of the present invention is ^{obtained, 0.0005g / m 2 ~ 50g /} m 2 with respect to the article, preferably 0.001 g / m ² to 30 g / m ² . For example, when the article is a fabric, if the adhesion amount of the binder having a carboxyl group is too small, it is difficult to ensure sufficient performance for washing durability, and the adhesion amount of the binder having a carboxyl group is large. If it is too high, the softness of the material is impaired, so that it is preferably 0.2 g / m ² to 10 g / m ² .

Adhesion amount of the antimicrobial agent to an article of the present invention is not particularly limited as long as the effects can be obtained the present ^{invention, 0.0005g / m 2 ~ 10g /} m 2 with respect to the article, preferably 0.001 g ^{/ m} 2 ~ It can be 3 g / m ² . For example, when the article is a fabric, it is 0.01 to 10 g / m ² , preferably 0.01 to 3 g / m ² , and preferably 0.01 to 1 g / m ² with respect to the fabric. Is more preferable. The fabric of the present invention is characterized in that the immobilized antibacterial agent is retained with little peeling even after repeated washing, for example, JIS L0217 No. 32 When the washing test is performed by the washing method of item 2, the antimicrobial agent retention after 3 washings is 30% or more, preferably the antimicrobial retention after 10 washings is 30% or more.

(Production method)
The antibacterial article of the present invention is manufactured by a manufacturing method including a step of applying and fixing an antibacterial agent containing an ethoxysilane-based quaternary ammonium salt to an article containing a resin component having a carboxyl group on at least the surface. can do.
When the material itself contains a carboxyl group, the resin containing the carboxyl group may be molded into a desired form, and an antibacterial agent may be applied to the molded product, or an already molded article is obtained. An antibacterial agent can be applied.
The application of the antibacterial agent does not require any special pretreatment, and can be manufactured with equipment and processing conditions in a range that is commonly used for various articles, and thus can be manufactured at low cost.

The specific method can be appropriately selected depending on the material and shape of the article. For example, when the article is a relatively small resin molded product, the resin molded product may be washed as necessary and then immersed in a solution containing an antibacterial agent containing an ethoxysilane quaternary ammonium salt. . In addition to dipping, it can be performed by spraying, coating, or the like, and another appropriate processing method may be selected and used.

The concentration of the treatment liquid when the article is treated with the antibacterial agent can be, for example, 0.0002 wt% to 4.2 wt% (active ingredient concentration of the antibacterial agent). It is preferable that the content be 004 wt% to 1.3 wt%. As the treatment liquid, water and / or an organic solvent (for example, ethanol, propanol, acetone, acetonitrile), or a mixture thereof can be used as a solvent. The treatment liquid may contain a dispersant, a pH adjuster, a buffering agent, a solvent and the like as necessary.
The treatment temperature in particular when processing an antibacterial agent to articles | goods is not restrict | limited, It can carry out in the temperature range including normal temperature. For example, the treatment is performed at 110 ° C. to 180 ° C.
The ethoxysilane quaternary ammonium salt is considered to be immobilized on the surface of the article in a relatively short time, and the treatment time is 30 seconds to 10 minutes, preferably 1 minute to 3 minutes. it can.

After the antibacterial agent has been treated on the article, it may be washed as necessary and naturally dried, or may be heat-dried. In the case of heat drying, for example, a heat drying apparatus such as a dryer, a gear oven, or a tenter can be used for drying.

In the case of applying a binder having a carboxyl group to the surface of the article, a step of attaching the binder having a carboxyl group to the surface of the article, and an ethoxysilane quaternary ammonium salt is included in the article having the binder fixed to the surface. And immobilizing an antibacterial agent. This manufacturing method does not require special equipment or complicated processing conditions, and can be manufactured with equipment and processing conditions in a range that is commonly used for various articles, so it can be manufactured at low cost. It is.

The detailed method can be appropriately selected depending on the material and shape of the article. For example, when the article is a three-dimensional molded article such as a resin molded article or a metal molded article, first, the desired molded article is immersed in a solution containing a binder having a carboxyl group, and then an ethoxysilane quaternary ammonium salt. There is a so-called dipping method in which the sample is immersed in a solution containing an antibacterial agent.
Alternatively, first, a solution containing a binder having a carboxyl group may be sprayed on a desired molded article, followed by spraying a solution containing an antibacterial agent containing an ethoxysilane-based quaternary ammonium salt. Alternatively, first, a solution containing a binder having a carboxyl group may be applied to a desired molded article, and then a solution containing an antibacterial agent containing an ethoxysilane quaternary ammonium salt may be applied.
Moreover, these immersion, spraying, and application may be used in combination, and another appropriate surface treatment method may be selected and used.

For example, when the article is a fabric, examples of the method for producing the fabric include a Dip-Nip method, an exhaust method, a coating method, and the like.
In the case of performing the treatment by the Dip-Nip method, first, the fabric is immersed in a binder solution, squeezed with a mangle or the like, and then dried by heating to adhere the binder to the fabric. Subsequently, the antibacterial agent can be immobilized by immersing the fabric in an antibacterial agent having a desired concentration and squeezing with a mangle or the like, followed by heat drying treatment.

When the treatment is performed by the exhaust method, the fabric is immersed in a solution containing 80 to 140 ° C. containing a binder, squeezed with a mangle, and then dried by heating to adhere the binder to the fabric. Subsequently, the antibacterial agent can be immobilized by immersing the fabric in an antibacterial agent having a desired concentration and squeezing with a mangle or the like, followed by heat drying treatment.

When the coating method is used, the fabric is coated with a binder having a carboxyl group and then dried.Subsequently, the fabric is immersed in an antibacterial agent having a desired concentration, and after being squeezed with mangle or the like, a heat drying treatment is performed, Antibacterial agent can be immobilized. The coating method is not particularly limited, and examples thereof include gravure roll processing, spray processing, roll coater processing, jet printing processing, transfer printing processing, and screen printing processing.

The drying and heat treatment temperature of the fabric to which the binder and the antibacterial agent are applied can be 100 to 190 ° C, and preferably 110 to 160 ° C.
The drying / heat treatment time can be appropriately selected depending on the material of the fabric to be produced, the basis weight, and the use, but is preferably 1 to 5 minutes. For drying and heat treatment, devices such as a loop dryer, a net dryer, an oven, and a heat setter can be used.

The application of the binder and the antibacterial agent to the fabric may be performed as separate steps, or a treatment solution for performing the treatment in one step may be prepared and applied. In order to provide a more stable fabric with excellent washing durability, the binder and antibacterial agent are applied to the fabric as separate steps. First, the binder is fixed to the fabric, and then the binder is fixed. It is preferable to apply an antibacterial agent to the finished fabric.

The treatment liquid of the binder having a carboxyl group and the antibacterial agent may contain other components in addition to the binder and the antibacterial agent. For example, ethanol, isopropyl alcohol, lignin sulfonic acid, linear sodium alkylbenzene sulfonate and the like can be mentioned.

Next, examples relating to the antibacterial article according to the present invention will be shown, but the present invention is not limited to these examples.

<Test series 1: When binder treatment is performed>
[material]
1. Antibacterial agent: Ethanolic quaternary ammonium salt octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride in ethanol solution (manufactured by EAC-QAC, manufactured by Manac Co., Ltd.) with water to a predetermined concentration Was used.
2. Binders: Binders a to d containing a hydroxyl group (not containing a carboxyl group) and binders 1 to 5 containing a carboxyl group shown in Table 1 below were used.
3. Articles: Fabrics (polyester fabrics, wool fabrics, flame retardant (Zapro processing) wool fabrics, cotton fabrics, basis weight etc. are described in each example), polypropylene resin molded products, and nitrile rubber films were used.

[Test method]
1. Detection of antibacterial agent: Cationic color reaction between bromophenol blue and ammonium salt was used to detect the antibacterial agent attached to the fabric.
Specifically, a 2.5 cm × 5 cm sample piece was cut out of the fabric after the antibacterial agent fixing treatment or the fabric after the fabric was washed a predetermined number of times, and a color reaction of bromophenol blue (reagent concentration) : 0.03% sol, reaction time: 30 seconds or 180 seconds), and after drying, the brightness and ΔE of the test cloth after coloring were measured with an SM color computer (manufactured by Suga Test Instruments Co., Ltd.) Calculated. The measurement and calculation method conformed to JIS Z 8729. The retention rate of the antibacterial agent is calculated by calculating the ratio of the value of ΔE after washing a predetermined number of times, assuming that ΔE of the fabric after the antibacterial agent is fixed (that is, the number of times of washing is 0) is 100. did.
2. Cleaning method A: JIS L 0217 No. 103 Conforms to item 2 (ordinary) cleaning method. As the detergent, Attack ALLin (manufactured by Kao Corporation) was used.
3. Cleaning method B: JIS L 0217 No. 103 Conforms to item 2 (ordinary) cleaning method. As the detergent, JAFET standard detergent was used.
4). Antibacterial performance test: Conforms to JIS L 1902, bacterial liquid absorption method.

[Test 1: Immobilization of antibacterial agent on polyester fabric (durability)]
(Test 1-1)
Antibacterial agents were immobilized on the polyester fabric using binders a to d containing hydroxyl groups (not containing carboxyl groups) shown in Table 1.
Fabrics with an antibacterial agent immobilized thereon were prepared as follows. A piece of fabric of 20 cm in length and width was cut out from a polyester base fabric A having a mass of 390 g / m ² , immersed in a predetermined binder solution, and then squeezed with a mangle. The fabric pickup rate at this time was 70%. Then, it dried at the preset temperature of 150 degreeC using the heat setter. The amount of binder attached to each fabric at this time is shown in Table 2.
Then, after dipping in an antibacterial agent solution prepared so that octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride, which is an active ingredient of the antibacterial agent, is 0.3%, it is dried at a set temperature of 150 ° C. using a heat setter. did. The amount of the antibacterial agent attached to each fabric at this time was 0.82 g / m ² .
For washing, the above-described washing method A was used, and the amount of the antibacterial agent adhered was measured for each fabric after 0 times, 1 time and 3 times of washing. The antibacterial agent was detected using the color reaction described above, and the coloration time of bromophenol blue was 30 seconds. The results are shown in Table 2.

As shown in Table 2, when binders a to d that are hydroxyl group-containing (carboxyl group-free) binders are used, the antibacterial agent retention after three washings is 6.9 to 10.3%. Thus, a sufficient antimicrobial agent retention rate could not be obtained.

(Test 1-2)
An antibacterial agent was immobilized on the polyester fabric using binders a and d containing hydroxyl groups (not containing carboxyl groups) and binder 1 having hydroxyl groups and carboxyl groups shown in Table 1.
The antibacterial agent was immobilized on the fabric except that the active ingredient of the antibacterial agent (octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride) was adjusted to a concentration of 0.03 to 0.3% (shown in Table 3). Were performed under the same conditions as in Test 1-1. For washing, the above-described washing method A was used, and the amount of the antibacterial agent adhered was measured for each fabric after 0 times, 1 time and 3 times of washing. The amount of antibacterial agent attached was detected using the method described above, and the coloration time of bromophenol blue was 180 seconds. The results are shown in Table 3.

As shown in Table 3, in Examples 1 to 3 using the binder 1 containing a hydroxyl group and a carboxyl group, the antibacterial agent retention after 3 times of washing was 31.6 to 46.5%. The retention rate was higher than those of Comparative Examples 5 to 10 using the binder having the above. In addition, with respect to the amount of adhesion at the time of application of the antibacterial agent (in the case of 0 washings), the lightness of the fabric is 57.88 to 71.03 in the comparative example, while 57.94 to 68.96 in Example 1. No significant difference was observed.

(Test 1-3)
The antibacterial agent was adhered to the polyester fabric A in the same manner as in Test 1-2 using binders 2 to 5 containing carboxyl groups. The active ingredient concentration of the antibacterial agent was 0.3% sol. For washing, the above-described washing method A was used, and the amount of the antibacterial agent adhered was measured for each fabric after 0 times, 1 time and 3 times of washing. The amount of antibacterial agent attached was detected using the method described above, and the coloration time of bromophenol blue was 180 seconds. The results are shown in Table 4.

As shown in Table 4, in Examples 4 to 7 using the binders 2 to 5 containing a carboxyl group, the antibacterial agent retention after 3 times of washing was 46.4 to 73.6%, and had hydroxyl groups. The antibacterial agent retention rate is higher than that of binders a to d, and the washing durability is excellent. Especially, in Example 4 using the binder 2 which is a binder containing methacrylic acid, a high antimicrobial agent retention was obtained.

(Test 1-4)
The antibacterial agent was attached to the polyester fabric A in the same manner as in Test 1-2 without using the binder 2 having a carboxyl group, the binders a and d having a hydroxyl group, and the binder. The active ingredient concentration of the antibacterial agent was 0.3%. For washing, the washing method B was used, and the adhesion amount of the antibacterial agent was measured for each fabric after washing 0 times, once, and 3 times. The amount of antibacterial agent attached was detected using the method described above, and the coloration time of bromophenol blue was 180 seconds. The results are shown in Table 5.

As shown in Table 5, the retention rate of the antibacterial agent after 3 washings was 8. in either case of binders a and d having hydroxyl groups (Comparative Examples 11 and 12) and no binder (Comparative Example 13). It was 2 to 16.0%. On the other hand, when the binder 2 containing a carboxyl group (methacrylic acid) was used (Example 8), the antibacterial agent retention after 3 washes was as high as 76.6%.

[Test 2: Immobilization of antibacterial agent to fabric of each material (washing durability)]
The antibacterial agent was fixed to each fabric of cotton, polyester, wool, and flame retardant (zapro) wool, and the amount of the antibacterial agent adhered after 10 washings (7 washings for wool and flame retardant wool) was confirmed. . About each fabric, when not using a binder, it tested about each when using the binder (binder 2) containing a carboxyl group.
When a binder is not used, the antibacterial agent is fixed to the cotton raw fabric by cutting out a piece of fabric of 20 cm in length and width from a cotton raw fabric having a mass of 84 g / m ² and immersing it in a predetermined antibacterial agent solution. Squeezed at. The fabric pickup rate at this time was 89%. Then, it dried at the preset temperature of 150 degreeC using the heat setter. The amount of the antibacterial agent attached to the fabric at this time was 0.22 g / m ² .
When using a binder, it was first dipped in a predetermined binder solution and then squeezed with mangle. The fabric pickup rate at this time was 70%. Then, it dried at the preset temperature of 150 degreeC using the heat setter. Table 6 shows the amount of binder attached to the fabric. Then, after being immersed in a predetermined antibacterial agent solution (active ingredient concentration of antibacterial agent 0.3%), it was dried at a set temperature of 150 ° C. using a heat setter.
The antibacterial agent was immobilized on the polyester base fabric in the same manner as the cotton base fabric, except that the polyester fabric A having a mass of 390 g / m ² was used as the polyester base fabric. The pickup rate was 70%.
The antibacterial agent was immobilized on the wool base cloth in the same manner as the cotton base cloth except that a wool base cloth having a mass of 118 g / m ² was used. The pickup rate was 63%.
The antibacterial agent was immobilized on the flame-retardant processed wool in the same manner as the cotton raw fabric except that the flame-retardant processed raw fabric having a mass of 366 g / m ² was used. The pickup rate was 58%.
Washing was performed using washing method B, and the amount of antibacterial agent was measured on each fabric after washing 0 times, 1, 3, 5, and 10 times (however, wool and flame-retardant processed wool was 7 times). . The amount of antibacterial agent attached was detected using the method described above, and the coloration time of bromophenol blue was 180 seconds. The results are shown in Table 6.

As shown in Table 6, in any of cotton, polyester, wool, and flame-retardant processed wool, the use of the binder 2 having a carboxyl group significantly improved the washing durability as compared with the case where no binder was used. .

[Test 3: Treatment temperature of antibacterial agent]
The antibacterial agent was immobilized on the polyester fabric A by using the binder 2 having a carboxyl group and setting the drying temperature after the immersion treatment to each temperature of 110 to 180 ° C. Conditions other than the treatment temperature were the same as in Test 1-2. For washing, the washing method B was used, and the adhesion amount of the antibacterial agent was measured for each fabric after washing 0 times, once, three times, and five times. The amount of antibacterial agent attached was detected using the method described above, and the coloration time of bromophenol blue was 180 seconds. The results are shown in Table 7 below.

As shown in Table 7, at any temperature of 110 to 180 ° C., the antibacterial retention rate after 5 washes was as good as 71.0 to 80.5%. This result shows that the treatment can be performed without any problem at any temperature. In other words, it is shown that the treatment can be suitably performed even at a drying temperature in a relatively low temperature range (110 to 130 ° C.), and the antibacterial agent can be more suitably immobilized in the range of 110 to 160 ° C. .

[Test 4: Antibacterial performance test]
Antibacterial properties of polyester fabric A with antibacterial agent immobilized using binder 2 having a carboxyl group, polyester fabric A treated with antibacterial agent without using a binder (both washed 10 times), and untreated cotton fabric The performance was confirmed. The treatment method and washing method of the fabric were the same as in Test 1-2. The antibacterial performance test method was performed according to JIS L 1902 and the bacterial solution absorption method. The results are shown in Table 8.

As shown in Table 8, the polyester fabric A (Example 21) in which the antibacterial agent was immobilized using the binder 2 having a carboxyl group showed a good bacteriostatic activity value. On the other hand, polyester fabric A (Comparative Example 18) that did not use a binder did not have sufficient bacteriostatic activity, and the untreated cotton fabric (Comparative Example 19) did not show bacteriostatic activity.

[Test 5: Friction durability test]
The friction durability of the antibacterial agent was confirmed for the polyester fabric A in which the antibacterial agent was immobilized using the binder 2 having a carboxyl group and the polyester fabric A treated with the antibacterial agent without using the binder.
As a test piece, a polyester fabric A having a length of 230 mm and a width of 30 mm (treated with a binder and an antibacterial agent, treated with only an antibacterial agent) was prepared.
Using a friction tester II specified in JIS L 0849, cotton canvas No. 10 (50 mm square) of JIS L 0803 was attached to a friction piece having a load of 500 g. Thereafter, in accordance with JIS L 0849, the test piece is attached to the testing machine, and is rubbed at a speed of 30 reciprocations per minute on the test piece at a rate of 10 to 1000 times (described in the table). After each number of frictions, the cotton canvas was removed and a color reaction of bromophenol blue was performed on the cotton canvas to detect the antibacterial agent that had fallen from the polyester to the cotton canvas.
Evaluation was read with brightness, ΔE (amount of deterioration of ΔE based on the value at the time of friction 10 times), and a series (coloring reaction result of cotton canvas on a gray scale for contamination color (conforming to JIS L 0805)). Value). The results are shown in Table 9.

As shown in Table 9, the polyester fabric A (Example 22) in which the antibacterial agent was immobilized using the binder 2 having a carboxyl group was one that did not use the binder at any time of 10 to 1000 times ( Compared with Comparative Example 20), the brightness was high, ΔE was low, and the series was less reduced. This indicates that the migration of the antibacterial agent from the polyester fabric to the cotton fabric due to friction is small, that is, the polyester fabric using the binder 2 having a carboxyl group has little antibacterial agent falling off and has excellent friction resistance. ing.

[Test 6-1: Immobilization of antibacterial agent to polypropylene resin molded product 1]
The adhesion of the antibacterial agent was confirmed for the plastic molded product in which the antibacterial agent was immobilized using the binder 2 having a carboxyl group and the plastic molded product treated with the antibacterial agent without using the binder.
A polypropylene plastic molded product was prepared as a test piece.
The polypropylene plastic molded article was immersed in the binder 2 solution for 1 minute, then taken out and dried in hot air with a dryer. Then, after being immersed for 1 minute in an antibacterial agent solution (active ingredient concentration 0.3% solution), it was taken out and dried in hot air with a dryer. As a comparative example, a test piece was prepared in which only the antibacterial agent treatment was performed without the binder treatment.
Test piece treated with binder and antibacterial agent (Example 23), Test piece not treated with binder or antibacterial agent (Comparative Example 21), Test piece treated only with antibacterial agent without binder treatment (Comparative Example) The color reaction of bromophenol blue was conducted for 22), and the antibacterial agent adhering to each test piece was detected. The results are shown in Table 10. ΔE represents the amount of change with respect to the value of an untested product (no bromophenol blue color reaction) of a plastic molded product made of polypropylene.

As shown in Table 10, in Example 23 in which the antibacterial agent was immobilized using a binder, the brightness was lower than that of Comparative Examples 21 and 22, the value of ΔE was large, and the antibacterial agent was adhered. Showed that. In addition, although there is no remarkable difference in the result of the comparative example 21 and the comparative example 22, this has shown that an antibacterial agent does not adhere to a polypropylene without a binder, and an ethoxysilane type | system | group 4th class conventionally. This is consistent with the fact that it has been considered difficult to fix ammonium salts in polypropylene products.

[Test 6-2: Immobilization of antibacterial agent on polypropylene resin molded product 2]
Using maleic anhydride-modified polypropylene (acid number 3.0), which is a polyolefin-based binder having a carboxyl group, as a binder, the adhesion of the antibacterial agent to the polypropylene film and the adhesion of the binder to the molded product were confirmed.
A polypropylene film (thickness 0.20 mm) was prepared as a test piece.
The binder was applied onto a polypropylene film with a doctor knife and dried at 90 ° C. for 10 minutes, and then the amount applied to the film was measured. This film was cut into a size of 70 mm in width and 300 mm in length.
A sample of urethane foam of the same size as the film was attached to the bottom, and the sample was fixed to both ends of the flat wear machine. The friction element was rubbed 50 times back and forth between 140 mm at a speed of 60 ± 10 with a load of 1 kgf. . The flat wear machine is manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd. E9660 was used.
The polypropylene film after friction was cut, and antibacterial agent treatment and antibacterial agent detection were performed.
The antibacterial treatment was immersed in a predetermined antibacterial agent solution (active ingredient concentration: 0.3%) and then dried at a set temperature of 90 ° C. using a gear oven. The antibacterial agent was detected by the aforementioned color reaction of bromophenol blue (reaction time 180 seconds). Color measurement was performed by using a SM color computer manufactured by Suga Test Instruments Co., Ltd. and measuring each sample by overlaying a white plate and measuring ΔE for a blank film to which neither a binder nor an antibacterial agent was applied. The results are shown in the table below.

As shown in Table 11, the examples (Examples 201 and 202) using maleic anhydride-modified polypropylene as a binder with respect to the polypropylene film had an antibacterial agent attached even after surface abrasion, High adhesion was shown.

[Test 7: Immobilization of antibacterial agent on film product and friction durability]
The antibacterial agent antibacterial agent friction durability was confirmed about the thick film nitrile rubber film which fixed the antibacterial agent using the binder 2 which has a carboxyl group, and the thick film nitrile rubber film which processed the antibacterial agent without using the binder.
A thick nitrile rubber film having a length of 50 mm, a width of 50 mm, and a thickness of 90 μm was prepared as a test piece.
The nitrile rubber film was immersed in the binder 2 solution for 1 minute, then taken out and dried with hot air with a dryer. Then, after being immersed for 1 minute in an antibacterial agent solution (active ingredient concentration 0.3% solution), it was taken out and dried in hot air with a dryer. As a comparative example, a test piece was prepared in which only the antibacterial agent treatment was performed without the binder treatment.
The test piece treated with the binder and antibacterial agent and the test piece treated only with the antibacterial agent without being treated with the binder were subjected to a color reaction of bromophenol blue (reaction time: 180 seconds), dried, and then rubbed A durability test was conducted.
In the friction durability test, a friction tester type II specified in JIS L 0849 was used, and cotton canvas No. 10 (50 mm square) of JIS L 0803 was attached to a friction element having a load of 500 g. Furthermore, a test piece which is a nitrile rubber film is attached thereto, and a cotton canvas No. 10 of JIS L 0803 is cut into a length of 230 mm in length and 30 mm in width and attached to a testing machine defined in JIS L 0849, and 100 mm on the cotton canvas. Friction was made 50 times at a speed of 30 reciprocations per minute. After rubbing 50 times, the test piece attached to the friction piece was removed, and the antibacterial agent transferred from the test piece to the cotton canvas by friction was measured.
The retention rate of the antibacterial agent is calculated by calculating the ratio of the ΔE value after the friction endurance test by setting the ΔE of the nitrile rubber film after the immobilization treatment of the antibacterial agent (that is, before the friction endurance test) to 100. Rate. The results are shown in Table 12.

As shown in Table 12, the retention rate of the antibacterial agent is higher than that of the nitrile rubber film (Comparative Example 23) subjected to only the antibacterial agent treatment in the nitrile rubber film (Example 24) subjected to the binder 2 and antibacterial agent treatment. . That is, it was shown that the antibacterial agent did not fall off and was excellent in friction durability.

[Test 8-1: Immobilization of antibacterial agent on polyester fabric 2 (further examination of binder composition)]
Various binders other than those described above were used as the binder having a carboxyl group, and the effect of the carboxyl group was confirmed.
[material]
1. Antibacterial agent: Ethanolic quaternary ammonium salt octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride in ethanol solution (manufactured by EAC-QAC, manufactured by Manac Co., Ltd.) with water to a predetermined concentration Was used.
2. Binder: Binders 6 to 9 containing a carboxyl group shown in Table 13 below and a binder e containing no carboxyl group were used as a comparison.
3. Article: The same polyester fabric A as used in Test Example 1 was used.

[Test method]
Application of the antibacterial agent, detection, and washing of the fabric were performed in the same manner as in Test Example 1. The coloration time of bromophenol blue in the detection of the antibacterial agent was 180 seconds, and the washing method A was used for washing the fabric.

The following table shows the detection results of the antibacterial agent remaining on the fabric from the first washing to the tenth washing of the fabric to which the various binders and the antibacterial agent are applied.

As shown in Table 14, examples using binders 6 to 9 which are binders containing carboxyl groups (Examples 101 to 104) are examples using binder e which is a binder having no carboxyl group (Comparative Examples). 101) and the example using no binder (Comparative Example 102), the lightness after one wash was lower. This indicates that all of the fabrics of the Examples have more antibacterial agents attached to the fabric.
Further, the ratio of ΔE after 10 washes and after 1 wash was 0.76 to 1.00 in Examples 101 to 104, and the decrease in ΔE value was small, while Comparative Example 101 and In 102, it was 0.42 to 0.52, and the ΔE value was significantly reduced. This indicates that all of the fabrics of the Examples have less antibacterial agent dropout and have washing durability.

[Test 8-2: Immobilization of antibacterial agent on polyester fabric 3 (further examination of binder composition)]
Various binders other than those described above were used as the binder having a carboxyl group, and the effect of the carboxyl group was confirmed.
[material]
1. Antibacterial agent: Ethanolic quaternary ammonium salt octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride in ethanol solution (manufactured by EAC-QAC, manufactured by Manac Co., Ltd.) with water to a predetermined concentration Was used.
2. Binder: Binder 2 (acid value 250) as described above, a maleic anhydride-modified polypropylene resin (acid value 3.0) binder (binder 10), which is a binder containing a carboxyl group, and a urethane-based resin having a carboxyl group (Acid value 40) A binder (binder 11) was used.
3. Article: Another type of polyester fabric B (weight per unit area: 350 g / m ² ) having a structure different from that of the polyester fabric A used in Test Example 1 was used.

[Test method]
After applying various binders to the fabric in the same manner as in the test method described above, an antibacterial agent was applied.
Application of the antibacterial agent was performed by drying at 150 ° C. for 180 seconds after the dip-nip method. The working fluid was adjusted so that the active ingredient of the antibacterial agent applied to the fabric was 0.63 g / m ² .
Detection of the antibacterial agent and washing of the fabric were performed in the same manner as in Test Example 1. The coloration time of bromophenol blue in the detection of the antibacterial agent was 180 seconds, and the washing method B was used for washing the fabric.

The following table shows the detection results of the antibacterial agent remaining on the fabric from the first washing to the fifth washing of the fabric to which the various binders and the antibacterial agent are applied.

As shown in Table 15, the examples using the polyester polymer binder 2, the polypropylene binder 10, and the polyurethane binder 11 (Examples 105 to 108) are all more than the examples using no binder (Comparative Example 103). The lightness was 0 after washing. This suggests that there is much adhesion of an antibacterial agent. In addition, in all of Examples 105 to 108, the antibacterial agent retention after 5 washes was higher than that of Comparative Example 103.

<Test Series 2: When antibacterial agent is added to resin product containing carboxyl group without binder treatment>
[Test 9: Immobilization of antibacterial agent to resin product]
[material]
1. Antibacterial agent: Ethanolic quaternary ammonium salt octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride in ethanol solution (manufactured by EAC-QAC, manufactured by Manac Co., Ltd.) with water to a predetermined concentration Was used.
2. Article: A resin film formed by combining the polymers shown in the table below was used.

[Production of resin film]
(No. 1)
100 g of urethane polymer A was poured into a glass plate (1.35 cm × 9.0 cm) at room temperature and allowed to stand at room temperature for 2 days, and then dried at 100 ° C. for 10 minutes and subsequently at 150 ° C. for 5 minutes. After allowing to cool to room temperature, each sample was peeled off from the glass plate to obtain a molded resin film having a thickness of 0.71 mm.
(No. 2)
No. 1 except that urethane polymer B100 g was used instead of urethane polymer A100 g. In the same manner as in Example 1, a resin film was obtained.

(No. 3)
In place of the urethane polymer A 100 g, No. 1 except that the urethane polymer A 90 g and the carboxyl group-containing polymer 10 g were uniformly mixed. In the same manner as in Example 1, a resin film was obtained.
(No. 4)
It changed to urethane polymer A100g, and it was No. except having used what mixed urethane polymer B90g and the carboxyl group-containing polymer 10g uniformly. In the same manner as in Example 1, a resin film was obtained.
(No. 5)
In place of 100 g of urethane polymer A, no. Except that a polymer obtained by uniformly mixing 90 g of an acrylate polymer and 10 g of a carboxyl group-containing polymer was used. In the same manner as in Example 1, a resin film was obtained.

[Immobilization and detection of antibacterial agents]
1. Application of antibacterial agent: No. above. 1-No. Each 5 resin film was cut into 5 cm × 5 cm, dipped in a 0.3% (antibacterial agent active ingredient concentration) solution for 60 seconds, then pulled up and air-dried.
2. Detection of antibacterial agent: Cationic color reaction between bromophenol blue and ammonium salt was used to detect the antibacterial agent adhering to each resin film.
The resin film (5 cm × 5 cm) provided with the antibacterial agent was immersed in a bromophenol blue solution (reactant concentration: 0.03% sol) for 60 seconds. Subsequently, it was washed with water and air-dried. For this sample, the brightness and ΔE were measured and calculated with an SM color computer (manufactured by Suga Test Instruments Co., Ltd.).
The detection results of the antibacterial agent attached to each resin film are shown in the table below.

As shown in Table 17, the film composed only of the urethane polymer (Comparative Examples 24 and 25) had little change in brightness before and after coloring, and ΔE was a low value of around 3.0. That is, the antibacterial agent did not adhere to the resin film made only of the urethane polymer. On the other hand, the resin films (Examples 25, 26, and 27) containing a polymer containing a carboxyl group had low brightness after coloring compared to before coloring, and ΔE was 12.97 to 22.84. That is, it was shown that an antibacterial agent adheres to the resin film containing the polymer containing a carboxyl group.

Claims (11)

1. An antibacterial article comprising an antibacterial agent containing at least a resin component having a carboxyl group on the surface and containing an ethoxysilane-based quaternary ammonium salt.
2. The resin component having a carboxyl group includes a polymer obtained by polymerizing a monomer containing at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and carboxymethylcellulose. The article of claim 1.
3. The resin component having a carboxyl group includes at least one polymer selected from the group consisting of an acrylic polymer, a polyester polymer, a polyolefin polymer, and a urethane polymer. The article described.
4. The antibacterial agent containing the ethoxysilane quaternary ammonium salt is represented by the following formula (1):
   

   

   (Wherein R ¹ represents an alkyl group having 12 to 24 carbon atoms, R ² and R ³ represent the same or different lower alkyl groups having 1 to 6 carbon atoms, and X represents a halogen ion or The article according to any one of claims 1 to 3, which is an antibacterial agent represented by an organic carbonyloxy ion (which represents an organic carboxylate ion).
5. The article according to any one of claims 1 to 4, wherein the antibacterial agent containing the ethoxysilane-based quaternary ammonium salt is octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride.
6. The resin component having a carboxyl group constitutes at least the surface of the substrate itself of the article, and the antibacterial agent is applied to the surface of the substrate. Article according to item.
7. The antibacterial agent is applied to the surface of the base material of the article through a binder, and the binder includes a resin component having the carboxyl group. Article according to item 1.
8. The article according to claim 7, wherein the binder having a carboxyl group is a binder containing an acrylic polymer obtained by polymerizing acrylic acid and / or methacrylic acid.
9. The article according to claim 7 or 8, wherein the article is a fabric.
10. An article containing a resin component having a carboxyl group on at least the surface of the article substrate itself is brought into contact with a solution of a composition containing an antibacterial agent containing an ethoxysilane-based quaternary ammonium salt, so that the surface of the article has ethoxysilane. A method for producing an antibacterial article comprising the step of providing a quaternary ammonium salt.
11. Contacting a binder having a carboxyl group on the surface of a substrate of the article; and contacting the article to which the binder has adhered with a solution of a composition containing an antibacterial agent containing an ethoxysilane-based quaternary ammonium salt, And a step of applying an ethoxysilane-based quaternary ammonium salt to the surface of the article.