JP4993966B2 - Antibacterial agent - Google Patents

Description

  The present invention relates to an antibacterial agent capable of sustained release of an antibacterial component, and relates to an antibacterial agent containing benzotriazole silver as an antibacterial component, excellent in water resistance and heat resistance, and capable of maintaining an antibacterial effect for a long time. The present invention also relates to an antibacterial agent suitable for blending into cosmetics, resin molded products, paint products and the like.

  It has long been known that ions of metals such as silver, copper, and zinc have antibacterial properties. Conventionally used as antibacterial agents are those in which these antibacterial metal components are supported on inorganic particles, especially those introduced by ion exchange into zeolite, zirconium phosphate or the like. It has also been proposed to introduce into layered silicates and clay minerals by ion exchange.

  Conventionally, for example, an antibacterial composition (for example, see Patent Document 1) in which a metal component having an antibacterial property is supported on a powder such as zeolite, silica gel, or titanium oxide is known. However, the conventionally known powdery antibacterial composition has a big problem of discoloration. Several proposals have been made for such problems.

  Patent Document 2 below proposes an antibacterial composition obtained by ion exchange of a metal ion of an inorganic oxo acid salt with an antibacterial metal ion. Patent Document 3 below proposes an antibacterial agent containing an antibacterial alumina sol in which a metal having an antibacterial action or a compound thereof is attached to the surface of aluminum oxide in the alumina sol. Patent Document 4 below proposes an antibacterial agent comprising silver colloid particles having high antibacterial properties. The following Patent Document 5 and Patent Document 6 propose an antibacterial agent comprising an antibacterial inorganic oxide colloid solution. Patent Document 7 below proposes an antibacterial agent made of a silver compound having a phenyl group or a naphthalene group. Patent Document 8 below describes a method for producing an antibacterial agent in which a thiosulfato silver complex salt is supported on silica gel and then silica coating is applied with an organosilicon compound.

  On the other hand, benzotriazoles are anti-coloring and coloring agents caused by photodegradation of resin due to ultraviolet rays, etc., and are also effective in preventing resin discoloration and coloring caused by silver ions. There are many combined composition applications (see, for example, Patent Documents 9, 10, and 11).

JP-A-2-225402 JP-A-3-275627 Japanese Patent Laid-Open No. 1-258792 Japanese Patent Laid-Open No. 4-321628 JP-A-6-80527 JP 7-33616 A JP 2001-192307 A JP-A-6-1706 JP 7-207061 A Japanese Patent Laid-Open No. 6-14979 JP-A-11-209533

  Among various antibacterial metal components, the silver component is excellent in antibacterial action and safety to the human body. However, conventionally known powdery antibacterial compositions have the following problems. In other words, zeolite and layered silicate into which silver has been introduced tend to discolor the powder gradually over time or due to the action of light or water, and to avoid this, the amount of silver supported is about several percent. However, the antibacterial performance may not be exhibited as a result. Further, the method of supporting silver on the carrier has a problem in the sustained release performance of silver. Sustained release performance in pure water often causes quite different mass releases in salt water. Thus, it was not satisfactory in terms of sustained release performance.

  Patent Document 2 proposes an antibacterial composition obtained by ion exchange of a metal ion of an inorganic oxoacid salt with a metal ion having antibacterial properties. However, in order to solve the above-mentioned problems, it is not always necessary. It was not satisfactory. The alumina sol having antibacterial properties of Patent Document 3 is in the form of a colloidal solution, and the usage is limited to paints and coating materials. The silver colloidal particles of Patent Document 4 are colored grey-brown and lack transparency, and the silver component itself is a colloidal particle, so that it has a problem that it easily aggregates and lacks stability. The antibacterial inorganic oxide colloidal solution of Patent Document 5 and Patent Document 6 solves the problems peculiar to the powdered antibacterial composition, but the use of the colloid solution is limited to paints and coating materials. Will be. The silver compound having a phenyl group or a naphthalene group in Patent Document 7 is a water-soluble complex, and is supported on or applied to another solid, and the above-mentioned sustained release performance becomes a problem. A method for producing an antibacterial agent in which a silver thiosulfate complex salt of Patent Document 8 is supported on silica gel and then silica-coated with an organosilicon compound is said to perform silica coating on a porous material such as silica gel in order to impart sustained release performance. It is a troublesome manufacturing method and there is a problem in maintaining its sustained release performance for a long period of time.

  The composition aimed at preventing discoloration and coloring of the resin by silver ions described in Patent Documents 9, 10 and 11 is not preventing discoloration of the antibacterial agent powder, but preventing discoloration of the main component resin. Are different. Even if the anti-discoloring agent is added to the resin to prevent discoloration of the antibacterial agent powder, it is possible to use a much smaller amount of the discoloration inhibiting agent if the antibacterial agent powder alone is treated. The effect of preventing discoloration of benzotriazole is known to occur when silver ions form a chelate with benzotriazole to form a complex, and benzotriazole silver used in the present invention, The compound itself is different from the complex.

  Accordingly, the present invention aims to solve the above-mentioned discoloration problems of silver-based zeolite antibacterial agents and resin discoloration problems due to silver ions, and has no or little tendency to discolor over time, such as resin molded products and paint products. It aims at providing the antibacterial agent suitable for the mixing | blending in.

  In the study of water-soluble silver antibacterial agents, the present inventors tested the formation of a complex salt of benzotriazole and silver, and obtained the knowledge of the possibility of complex formation in the presence of a large excess of benzotriazole. . On the other hand, in the reaction of benzotriazole and silver that are close to equimolar, the benzotriazole silver salt of the present invention is obtained instead of the complex salt, and it has been thought that there is no antibacterial action because it is insoluble in water. It has been found that it has a property of being slightly soluble in water and has sufficient performance as an antibacterial agent.

  As a result of intensive studies, the present inventors have found that benzotriazole silver represented by a specific general formula as an antibacterial component has excellent performance in the sustained release of silver, and benzotriazole represented by a specific general formula as an antibacterial component. It has been found that triazole copper has excellent performance in the sustained release of copper and can maintain antibacterial performance for a long period of time, thereby completing the present invention.

  The present invention provides an antibacterial agent containing a benzotriazole silver compound represented by the following general formula (1).

  Further, the present invention is represented by the following general formula (1), characterized in that a reaction of a benzotriazole compound represented by the following general formula (2) with a water-soluble silver compound is carried out in a mixed solvent of water and an organic solvent. And a method for producing an antibacterial benzotriazole silver compound.

  The present invention also provides a cosmetic composition, a resin composition, a paint or a plant fungicide containing the antibacterial agent.

  Furthermore, the present invention provides an antibacterial benzotriazole copper compound represented by the following general formula (3).

  Furthermore, the present invention is represented by the following general formula (3), characterized in that a reaction between a benzotriazole compound represented by the following general formula (4) and a water-soluble copper compound is performed in a mixed solvent of water and an organic solvent. A method for producing an antibacterial benzotriazole copper compound is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the antibacterial agent which is excellent in light resistance and water resistance, and there is little or no discoloration tendency with time, and is suitable for the compounding to a resin molded product, a paint product, etc. is provided.

Hereinafter, the present invention will be described in detail based on preferred embodiments thereof. The benzotriazole silver compound used in the present invention is represented by the general formula (1). R ₁ and R ₂ in the formula (1) represent an alkyl group, an aryl group, a halogen atom, a hydroxyl group, an amino group, or a carboxyl group. As an alkyl group, a C1-C5 thing, such as a methyl group, an ethyl group, a propyl group, a butyl group, is preferable. The aryl group is preferably a phenyl group, a tolyl group, a xylyl group, or a naphthyl group. Examples of the halogen atom include chlorine, bromine and iodine. P1 and q1 in a formula show the same or different integer of 0-2. R ₁ and R ₂ may be the same group or different groups.

  Preferred specific compounds of the benzotriazole silver compound represented by the general formula (1) include benzotriazole silver (I), 4-methylbenzotriazole silver (I), 5-methylbenzotriazole silver (I), 4 -Ethylbenzotriazole silver (I), 5-ethylbenzotriazole silver (I), 4,5-dimethylbenzotriazole silver (I), 4,6-dimethylbenzotriazole silver (I), 5,6-dimethylbenzotriazole Silver (I), 4,5-diethylbenzotriazole silver (I), 4,6-diethylbenzotriazole silver (I), 5,6-diethylbenzotriazole silver (I), 4-phenylbenzotriazole silver (I) 5-phenylbenzotriazole silver (I), 4-chlorobenzotriazole silver (I), 5-chlorobenzo Riazor silver (I) and the like, among these, benzotriazole silver (I) is particularly preferably represented by the following structural formula (1a).

  This benzotriazole silver (I) has a white powder color at the time of synthesis, a slight change with time due to light, does not become black like a conventional silver antibacterial agent, and is about a cream color. . Moreover, it is comparatively stable against heat and does not change up to 170 ° C.

  The antibacterial agent of the present invention consists essentially of the benzotriazole silver compound represented by the general formula (1) or contains the compound and contains other components. In any case, the antibacterial agent of the present invention has a particle size of 0.05 to 50 μm, particularly 0.1 to 10 μm. When applied to various uses such as a resin composition, a resin molded article, a paint, and a plant bactericidal agent, the dispersion is preferable. The particle size is measured by SEM observation of the particles.

  Further, the antibacterial agent is adjusted to have a water content of preferably 5% by weight or less, more preferably 3% by weight or less. Using a material with a moisture content in this range can prevent foaming due to dehydration during high-temperature molding of resin products and blistering of the coating film in the paint when it is kneaded into the resin or blended into the paint. There is an advantage that you can.

  The benzotriazole silver compound represented by the general formula (1) used in the present invention reacts with the benzotriazole compound represented by the general formula (2) and a water-soluble silver compound in a mixed solvent of water and an organic solvent. It can be manufactured by doing. Specifically, a solution (A1 solution) obtained by dissolving a water-soluble silver compound in water and a solution (B1 solution) obtained by dissolving the benzotriazole compound represented by the general formula (2) in an organic solvent are prepared, and A1 It can manufacture by adding B1 liquid to a liquid and reacting. In particular, when a solution in which a benzotriazole compound is dissolved in a mixed solvent of water and alcohol is used as the B1 liquid, a reaction product having high crystallinity is more preferable.

Hereinafter, the manufacturing method of the benzotriazole silver compound represented by the said General formula (1) is demonstrated. R ₁ and R _{2 in} the formula of the benzotriazole compound represented by the general formula (2) are groups corresponding to R ₁ and R ₂ in the formula of the general formula (1). p1 and q1 show the integer of 0-2. As one water-soluble silver compound, for example, silver nitrate, silver acetate, silver chlorate, silver perchlorate, silver fluoride, silver hexafluorophosphate and the like can be used. These water-soluble silver compounds may be hydrated salts or anhydrous salts. Examples of the organic solvent that can be used include alcohols having 1 to 5 carbon atoms such as methanol, ethanol, propanol, butanol, and pentanol, acetone, and the like. Among these, alcohol is particularly preferable in that it has good crystallinity. .

  The concentration of the water-soluble silver compound in the A1 liquid is preferably 0.1 to 1.0 mol / L, more preferably 0.3 to 0.8 mol / L. The A1 solution may be a mixed solvent of water and an organic solvent as long as the water-soluble silver compound can be dissolved. In this case, the mixing ratio of water and organic solvent varies depending on the type of water-soluble silver compound used and the type of organic solvent, but in many cases, the organic solvent is added in an amount of 5 to 50 parts by weight with respect to 100 parts by weight of water. In particular, the content is preferably 5 to 30 parts by weight.

  The concentration of the benzotriazole represented by the general formula (2) in the B1 solution is preferably 0.1 to 5 mol / L, particularly 0.3 to 2 mol / L. The B1 liquid may be a mixed solvent of water and an organic solvent as long as the benzotriazole represented by the general formula (2) can be dissolved. In this case, the mixing ratio of water and the organic solvent in the B1 liquid varies depending on the type of the benzotriazole compound used and the type of the organic solvent, but in many cases, the organic solvent is added in an amount of 5 to 50 parts per 100 parts by weight of water. It is preferable to use 5 parts by weight, particularly 5 to 30 parts by weight. When the amount of solvent in the reaction system is small, for example, when silver nitrate is used as a water-soluble silver compound, the reaction product becomes water-soluble with a complex salt [bis (benzotriazole) silver nitrate] incorporating silver nitrate. The benzotriazole silver compound represented by the general formula (1) cannot be obtained. On the other hand, too much solvent in the reaction system is uneconomical, so the concentrations of the A1 liquid and the B1 liquid are within the above range. It is preferable.

The addition of the B1 liquid to the A1 liquid is such that the benzotriazole compound in the B1 liquid is 1.0 to 2.0 times mol as the benzotriazole (C ₆ H ₅ N ₃ ) with respect to the water-soluble silver compound in the A1 liquid. It is preferable to make it become 1.0-1.5 times mole. The reason for this is that when the amount of benzotriazole exceeds 2.0-fold mol with respect to the water-soluble silver compound, a water-soluble complex compound of benzotriazole and silver is formed, resulting in a decrease in yield. This is because Ag of the reaction remains in the reaction solution and becomes uneconomical.

  The reaction conditions are preferably a reaction temperature of 0 to 50 ° C., more preferably 10 to 30 ° C., and a reaction time of preferably 1 hour or more, more preferably 3 to 10 hours. After completion of the reaction, the target product is recovered by solid-liquid separation according to a conventional method, and then dried, ground if necessary, and classified to obtain benzotriazole silver represented by the general formula (1) used in the present invention. be able to.

  The antibacterial agent of the present invention can be used in combination with a compound that releases an antibacterial metal ion of a zinc compound or / and a copper compound. This combination has effects such as (a) broadening the antibacterial spectrum, (b) extending the antibacterial duration, (c) improving the weather resistance, and (ii) improving the chemical resistance.

  The combination and blending ratio of silver and zinc or / and copper can be arbitrarily selected according to the purpose, and a plurality can be combined. In particular, the combination with zinc is preferable in that the antibacterial agent can be whitened.

Examples of the copper-containing compound used together with the benzotriazole silver compound represented by the general formula (1) of the present invention include conventionally used antibacterial agents such as zeolite supporting copper by ion exchange and zirconium phosphate. . In addition, products introduced by ion exchange into layered silicates and clay minerals can also be used. In the present invention, in particular, a compound having a low solubility such as copper bromide CuBr, copper carbonate Cu ₂ CO ₃ , copper oxalate CuC ₂ O ₄ .0.5H ₂ O, or a point having a low solubility and an excellent antibacterial performance. The benzotriazole copper compound represented by the general formula (3) is most preferable.

  The present inventors have found for the first time that the benzotriazole copper compound represented by the general formula (3) has a property of being slightly soluble in water and a property sufficient as an antibacterial agent. is there.

R ₃ and R _{4 in} the formula of the benzotriazole copper compound represented by the general formula (3) represent an alkyl group, an aryl group, a halogen atom, a hydroxyl group, an amino group, or a carboxyl group. As an alkyl group, a C1-C5 thing, such as a methyl group, an ethyl group, a propyl group, a butyl group, is preferable. The aryl group is preferably a phenyl group, a tolyl group, a xylyl group, or a naphthyl group. Examples of the halogen atom include chlorine, bromine and iodine. P2 and q2 in a formula show the same or different integer of 0-2. R ₃ and R ₄ may be the same group or different groups.

  Preferred specific compounds of the benzotriazole copper compound represented by the general formula (3) include dibenzotriazole copper (II), bis (4-methylbenzotriazole) copper (II), and bis (5-methylbenzotriazole). Copper (II), bis (4-ethylbenzotriazole) copper (II), bis (5-ethylbenzotriazole) copper (II), bis (4,5-dimethylbenzotriazole) copper (II), bis (4 6-dimethylbenzotriazole) copper (II), bis (5,6-dimethylbenzotriazole) copper (II), bis (4,5-diethylbenzotriazole) copper (II), bis (4,6-diethylbenzotriazole) ) Copper (II), bis (5,6-diethylbenzotriazole) copper (II), bis (4-phenylbenzotriazole) copper (II), bis (5-fur Nylbenzotriazole) copper (II), bis (4-chlorobenzotriazole) copper (II), bis (5-chlorobenzotriazole) copper (II) and the like, among these, in particular the following structural formula (3a) The dibenzotriazole copper (II) shown by these is preferable.

  The benzotriazole copper compound represented by the general formula (3) is produced by reacting the benzotriazole compound represented by the general formula (4) with a water-soluble copper compound in a mixed solvent of water and an organic solvent. be able to.

Specifically, a solution (A2 liquid) in which a water-soluble copper compound is dissolved in water and a solution (B2 liquid) in which the benzotriazole compound represented by the general formula (4) is dissolved in an organic solvent are prepared, and A2 It can manufacture by adding B2 liquid to a liquid and performing reaction. In particular, when a solution in which a benzotriazole compound is dissolved in a mixed solvent of water and alcohol is used as the B2 liquid, a reaction product having high crystallinity is more preferable.
Hereinafter, the manufacturing method of the benzotriazole copper compound represented by the said General formula (3) is demonstrated. R ₃ and R _{4 in} the formula of the benzotriazole compound represented by the general formula (4) are groups corresponding to R ₃ and R ₄ in the formula of the general formula (3). p2 and q2 show the integer of 0-2. As one water-soluble copper compound, for example, copper sulfate, copper perchlorate, copper chloride, copper tetrafluoroborate, copper formate, copper chlorate, copper nitrate and the like can be used. These water-soluble copper compounds may be hydrated salts or anhydrous salts. Examples of the organic solvent that can be used include alcohols having 1 to 5 carbon atoms such as methanol, ethanol, propanol, butanol, and pentanol, acetone, and the like. Among these, alcohol is particularly preferable in that it has good crystallinity. .

  The concentration of the water-soluble copper compound in the A2 liquid is preferably 0.1 to 1 mol / L, more preferably 0.3 to 0.8 mol / L. Further, the A2 liquid may be a mixed solvent of water and an organic solvent as long as the water-soluble copper compound can be dissolved. In this case, the mixing ratio of water and organic solvent varies depending on the type of water-soluble silver compound used and the type of organic solvent, but in many cases, the organic solvent is added in an amount of 5 to 50 parts by weight with respect to 100 parts by weight of water. In particular, the content is preferably 10 to 30 parts by weight.

  The concentration of the benzotriazole represented by the general formula (4) in the B2 liquid is preferably 0.1 to 5 mol / L, particularly preferably 0.3 to 2 mol / L. Moreover, B2 liquid is good also as a mixed solvent of water and an organic solvent in the range which can melt | dissolve the benzotriazole represented by the said General formula (4). In this case, the mixing ratio of water and the organic solvent in the B2 liquid varies depending on the type of the benzotriazole compound used and the type of the organic solvent, but in many cases, the organic solvent is added in an amount of 5 to 50 parts per 100 parts by weight of water. It is preferable to set it as a weight part, especially 10-30 weight part.

Addition of B2 liquid to A2 liquid is that the benzotriazole compound in B2 liquid is 2.0 to 2.5 times mol as benzotriazole (C ₆ H ₅ N ₃ ) with respect to the water-soluble copper compound in A2 liquid. It is preferable to be 2.0 to 2.1 times mol. The reason for this is that when the amount of benzotriazole exceeds 2.5 times moles of the water-soluble copper compound, a water-soluble complex compound of benzotriazole and copper is formed, resulting in a decrease in yield. This is because the reaction Cu remains in the reaction solution and becomes uneconomical.

  The reaction conditions are preferably a reaction temperature of 0 to 50 ° C., more preferably 10 to 30 ° C., and a reaction time of preferably 1 hour or more, more preferably 3 to 10 hours. After completion of the reaction, the target product is recovered by solid-liquid separation according to a conventional method, then dried, pulverized and classified if necessary, to obtain the benzotriazole copper represented by the general formula (3) used in the present invention. be able to.

Examples of the zinc-containing compound used together with the benzotriazole silver compound represented by the general formula (1) of the present invention include conventionally used antibacterial agents such as zeolite carrying zinc by ion exchange and zirconium phosphate. . In addition, products introduced into layered silicates and clay minerals by ion exchange can also be used. Particularly in the present invention, zinc carbonate ZnCO ₃ , zinc sulfite dihydrate ZnSO ₃ .2H ₂ O, zinc hydroxide Zn ( Compounds having low solubility such as OH) ₂ , zinc orthosilicate Zn ₂ SiO ₄ , zinc oxide ZnO, and zinc sulfide ZnS are preferred.

  In the antibacterial agent of the present invention, in addition to the benzotriazole silver compound represented by the general formula (1), a water-insoluble silver complex salt of quinaldic acid, quinoline-8-carboxylic acid, and salicimaldoxime can be used in combination.

  As described above, the antibacterial agent of the present invention can be suitably used for cosmetic compositions, resin compositions, resin molded products molded from the compositions, paints, and plant fungicides.

  The antibacterial agent of the present invention can be used in applications requiring antibacterial properties in various forms. This antibacterial agent should be surface-treated with a known modifying agent such as a dispersant, a surfactant, a coupling agent, a discoloration inhibitor, an antioxidant, an ultraviolet absorber, etc., as long as the effect performance is not impaired. Can do.

  Although it does not restrict | limit especially as a dispersing agent, For example, the following waxes and low melting-point resin are used.

(1) Fatty acids and their metal salts:
Synthetic or natural fatty acids and their alkali metal salts or alkaline earth metal salts, zinc salts, aluminum salts and the like. Examples thereof include stearic acid, oleic acid and the like, and sodium salts and ammonium salts thereof.

(2) Amides and amines:
For example, erucic acid amide, oleyl palmitoamide, stearyl erucamide, 2-stearomidoethyl stearate, ethylene bis fatty acid amide, N, N′-oleoyl stearyl ethylenediamine, N, N′-bis (2hydroxyethyl) Examples thereof include alkyl (C12 to C18) amide, N, N′-bis (hydroxyethyl) lauroamide, and fatty acid diethanolamine.

(3) Fatty acid esters and alcohol esters:
For example, n-butyl stearate, hydrogenated rosin methyl ester, dibutyl sebacate (n-butyl), dioctyl sebacate (both 2-ethylhexyl and n-octyl), glycerin fatty acid ester, pentaerythritol tetrastearate, polyethylene glycol fatty acid Examples include esters, polyethylene glycol fatty acid diesters, diethylene glycol fatty acid diesters, and propylene glycol fatty acid diesters.

(4) Waxes:
Examples thereof include spal acetyl wax, montan wax, carnauba wax, beeswax, wood wax, lanolin, polyethylene wax, polypropylene wax, epoxy-modified polyethylene wax, and petroleum wax.

(5) Low melting point resins:
Various resins having a melting point or softening point of 40 to 200 ° C., particularly 70 to 160 ° C., for example, epoxy resins, xylene-formaldehyde resins, styrene resins, chroman-indene resins, other petroleum resins, alkyd resins, ethylene-acetic acid Examples thereof include a vinyl copolymer, an ethylene-acrylic acid ester copolymer, a low melting point acrylic resin, polyvinyl butyral, a low melting point copolyamide, and a low melting point copolyester.

  Surfactants include (i) primary amine salts, tertiary amines, quaternary ammonium compounds, cationic compounds such as pyridine derivatives, (b) sulfated oils, soaps, sulfated ester oils, Sulfated amide oil, sulfates of olefins, fatty alcohol sulfates, alkyl sulfates, fatty acid ethyl sulfonates, alkyl naphthalene sulfonates, alkyl benzene sulfonates, succinate sulfonates, phosphate ester salts (C) partial fatty acid ester of polyhydric alcohol, ethylene oxide adduct of fatty alcohol, ethylene oxide adduct of fatty acid, ethylene oxide adduct of fatty amino acid or fatty acid amide, ethylene oxide addition of alkylphenol Product, alkyl naphthol ethylene Kisaido adducts, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, those of the non-ionic, such as polyethylene glycol, may be used (d) a carboxylic acid derivative, is generally that of amphoteric system such as imidazoline derivatives.

As the coupling agent, for example, the following can be used.
(1) Silane coupling agent:
γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, Amino-based silanes. Methacryloxy silane such as γ-methacryloxypropyltrimethoxysilane.
Vinyl-based silanes such as vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltrichlorosilane.
Epoxy silanes such as β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. Mercapto silanes such as γ-mercaptopropyltrimethoxysilane. Chloropropyl silanes such as γ-chloropropyltrimethoxysilane.

(2) Titanate coupling agent:
Isopropyltriisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylvirophosphate) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di) -Tridecyl) phosphite titanate, bis (dioctyl bisphosphate) oxyacetate titanate, bis (dioctyl bisphosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl) Phosphate) titanate, isopropyl tricumylphenyl titane DOO, isopropyl tri (N- aminoethyl - aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate, poly diisopropyl titanate, tetra-n-butyl titanate, polydiene normal butyl titanate.

  Examples of inorganic discoloration inhibitors include hydrotalcites, zinc oxide, magnesium oxide, calcium oxide, aluminum-containing phyllosilicates, alkali / aluminum composite hydroxide carbonates, and the like.

  The antibacterial agent of the present invention can be used in combination with other inorganic antibacterial agents. For example, zeolite, apatite, zirconium phosphate, silica gel, calcium silicate, glass and the like on which antibacterial metal ions are ion-exchanged or supported are listed.

  The antibacterial agent of the present invention can be used in combination with other organic antibacterial agents, bactericides, and preservatives. For example, tropolones such as hinokitiol; chitosans; paraoxybenzoic acid esters; organic acids such as benzoic acid and dehydroacetic acid; salts of these organic acids; quaternary phosphonium salts and the like.

  Specifically, hinokitiol, chitosan, benzoic acid, benzoates, isopropylmethylphenol, undecylenic acid monoethanolamide, cetylpyridinium chloride, alkylaminoethylglycine chloride, chlorhexidine chloride, cresol, chloramine, chloroxylenol, chlorocresol, chloro Butanol, salicylic acid, salicylates, domifene bromide, sorbic acid and salts, thymol, thiram, dehydroacetic acid and salts, trichlorocarbanilide, p-oxybenzoic acid ester, p-chlorophenol, halocarban, phenol, hexachlorophene, Lauroyl sarcosine sodium, resorcin, povidone iodine (polyvinylpyrrolidone / iodine complex) and its cyclodextrin inclusion, iodine / alkyl polyether Alcohol complex (GSI), polyethoxypolypropoxypolyethoxyethanol / iodine complex (Iocline), nonylphenoxypolyethoxyethanol / iodine complex, polyoxyethylene-added vegetable oil / iodine complex, polyoxyethylene-added fatty acid / iodine Examples include complexes, polyoxyethylene-added fatty alcohol / iodine complexes, fatty acid amide / iodine complexes, and the like.

  The antibacterial agent of the present invention is excellent in dispersibility in various resins (polymers) and has a low tendency to discolor. Therefore, it is blended in various resins (polymers) and has antibacterial resin compositions and resins. It can be used in the field of molded articles such as fibers, films, sheets, pipes, panels, containers, building materials, and structural materials. Further, the antibacterial agent of the present invention can be blended in paints and used in the field of antibacterial coatings.

  There is no restriction | limiting in particular as said resin, A wide range can be used. For example, polyolefin resin represented by polyethylene, polypropylene, polyvinyl chloride resin, polyvinylidene chloride, chlorinated resin such as chlorinated polyolefin, polyamide, ABS resin, polyester, polystyrene, polyacetal, polyvinyl alcohol, polycarbonate, acrylic resin, Thermoplastic resins such as fluororesin, polyurethane elastomer, polyester elastomer, phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, urethane resin, silicone, rayon, cupra, acetate, triacetate, vinylidene, natural and synthetic rubber Or a thermosetting resin etc. can be mentioned. These resins may be a copolymer or a graft polymer, or a mixed resin of two or more. In particular, among the above resins, polyolefin resin, polyvinyl chloride resin, and ABS resin are preferable.

  When blending the antibacterial agent of the present invention in a paint, examples of the paint material include oil paints such as boil oil, oil varnish, and oil enamel, fiber derivative paints such as nitrocellulose lacquer and acrylic lacquer, and the above resin materials And a synthetic resin paint made of the thermosetting resin or elastomer polymer described in 1).

  Conventionally used materials can also be used as materials used in blending with resins and paints. Examples thereof include fats and oils, mineral oils, plasticizers, solvents, inorganic fillers, pigments, extender pigments and the like. Examples of inorganic fillers include finely divided silica, activated alumina, aluminum-containing zinc phyllosilicate and its siliceous composite, magnesium phyllosilicate, hydrotalcite, zinc-modified hydrotalcite, lithium-aluminum composite hydroxide salt, talc, Examples include clay, bentonite, dosonite, diatomaceous earth, cinnabar sand, and calcium carbonate.

  The resin molded product or paint containing the antibacterial agent of the present invention includes any shape. For example, fabric products such as woven fabric, non-woven fabric, mesh fabric, knitted fabric, sheet products such as paper and film, powder products such as spraying agent, spray agent, brush paint, spray paint, roller paint, adhesive, sealant, etc. Ingredients such as liquid or pasty products, plates, bars, boxes, porous bodies, etc.

  Examples of resin molded products and paints containing the antibacterial agent of the present invention include freshness-preserving films, sanitary material products, kitchen bath products, toiletries, cosmetics, water treatment products, medical device products, building material products, fish nets, etc. Can do. In addition, it can be added to cement mortar or coated on a cement concrete compact to produce an antibacterial cement concrete product. In addition, it can be applied to various products for antibacterial purposes.

  In the resin composition in which the antibacterial agent of the present invention is blended, the blending amount of the antibacterial agent in the resin varies depending on the physical properties of the antibacterial agent, in particular, the amount of the antibacterial component supported, the type of synthetic resin, its use, and the like. In many cases, the amount is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the resin. More preferably, it is 0.5 to 10 parts by weight. However, in the resin composition constituted as a master batch, it can be blended up to 30 parts by weight. When the blending amount of the antibacterial agent is less than 0.1 parts by weight, the antibacterial action of the resin composition is not substantially obtained. In addition, the upper limit of the amount is often limited for economic reasons and set as a practical range.

The present invention will be specifically described below with reference to examples. Each measured value in the examples was determined by the following method.
(A) Composition analysis:
Antibacterial metals were quantified by ICP (Varian LIBERTY II type). Benzotriazole was quantified by measuring the carbon amount with a total organic carbon meter (manufactured by Shimadzu Corporation, TOC-5000A) and converting it to a molecular weight.
(B) Particle shape:
Observation was performed with an SEM (S-4500, manufactured by Hitachi, Ltd.).
(C) X-ray diffraction pattern (XRD):
An X-ray diffractometer (RINT 2400, manufactured by Rigaku) was used.

[Example 1]
20.0 g of silver nitrate was dissolved in 220 g of a mixed solvent of water-ethanol (weight ratio 10: 1) to obtain a solution A1. 14.0 equivalents of benzotriazole (C ₆ H ₅ N ₃ ; a reagent manufactured by Junsei Chemical Co., Ltd.) 1 equivalent to the number of moles of silver nitrate is dissolved in 220 g of a water-ethanol (weight ratio 10: 1) mixed solvent. did. The solution B1 was gradually added to the solution A1 and reacted at 25 ° C. for 3 hours. The generated precipitate was filtered and washed with water, and dried at 50 ° C. for 10 hours to obtain benzotriazole silver (I). The obtained benzotriazole silver (I) was subjected to elemental analysis and as a result, the composition was Ag (C ₆ H ₅ N ₃ ) _1.10 . Moreover, the water | moisture content by 110 degreeC drying loss was 0.85%. The XRD measurement results are shown in FIG. Moreover, the SEM photograph of this is shown in FIG. In the SEM photograph, the shape of the particles is a plate-like crystal, and the particle diameter is 0.1 to 0.2 μm in thickness, 0.5 to 5 μm on the plane, and about 2 μm on average.

[Example 2]
20.0 g of silver nitrate was dissolved in 240 g of a mixed solvent of water-ethanol (weight ratio 5: 1) to prepare a solution A1. 28.1 equivalents of benzotriazole (C ₆ H ₅ N ₃ ; manufactured by Junsei Chemical Co., Ltd.), 2 times equivalent to the number of moles of silver nitrate, are dissolved in 240 g of a water-ethanol (weight ratio 5: 1) mixed solvent. did. The solution B1 was gradually added to the solution A1 and reacted at 20 ° C. for 6 hours. The generated precipitate was filtered and washed with water, and dried at 50 ° C. for 24 hours to obtain benzotriazole silver (I). Elemental analysis was performed on the obtained benzotriazole silver (I), and as a result, the composition was Ag (C ₆ H ₅ N ₃ ) _1.21 . Moreover, the water | moisture content by 110 degreeC drying loss was 2%. The measurement results of XRD are shown in FIG. Moreover, the SEM photograph of this is shown in FIG. In the SEM photograph, the shape of the particles is an indefinite crystal having a rounded cube or rectangular shape, and the particle diameter is 0.1 to 1.0 μm, and the average is about 0.3 μm.

Example 3
20.0 g of copper (II) sulfate pentahydrate was dissolved in 125 g of a mixed solvent of water-ethanol (weight ratio 4: 1) to prepare an A2 solution. 19.1 g of benzotriazole (C ₆ H ₅ N ₃ ; manufactured by Junsei Chemical Co., Ltd.) equivalent to twice the number of moles of copper sulfate was dissolved in 125 g of a water-ethanol (4: 1 by weight) mixed solvent, and the solution B2 It was. The solution B2 was gradually added to the solution A2 and reacted at 25 ° C. for 3 hours. The generated precipitate was filtered and washed with water, and dried at 50 ° C. for 24 hours to obtain dibenzotriazole copper. As a result of conducting elemental analysis on the obtained dibenzotriazole copper (II), the composition was Cu (C ₆ H ₅ N ₃ ) _2.00 . The XRD measurement results are shown in FIG. 3 and Table 3. Moreover, the SEM photograph of this is shown in FIG. In the SEM photograph, the shape of the particles is close to a sphere but is agglomerated and some are connected in a rod shape. The particle diameter of the primary particles is 0.03 to 0.3 μm, and the average is about 0.1 μm.

Example 4
In this example, the sustained release property of the antibacterial component was confirmed. 5 g of the benzotriazole silver powder obtained in Example 1 was added to 45 g of pure water, and stirring was continued for 24 hours. Thereafter, the powder was removed by filtration and water was collected. When the water was chemically analyzed, the concentration of silver in the water was 5 ppm. Furthermore, the dissolution test was repeated 35 times, and the concentration of silver in water was also measured for the 35th dissolution test solution. The 35th silver concentration in water was 0.16 ppm.

[Reference Example 1]
Using a glass beaker, 23.8 parts by weight of benzotriazole (C ₆ H ₅ N ₃ ; a reagent manufactured by Junsei Kagaku) was added to 40 parts by weight of ethanol and dissolved by stirring for 10 minutes. Next, 17 parts by weight of silver nitrate and 160 parts by weight of pure water were added. The dissolution of silver nitrate and the formation of a white precipitate proceeded simultaneously, the silver nitrate dissolved in 3 hours, and then continued stirring for 16 hours. The white precipitate was filtered, washed with water and dried at 50 ° C. for 24 hours. White crystals were thus obtained. This crystal does not show the presence of benzotriazole and AgNO ₃ by XRD, and bis (benzotriazole) silver nitrate ([Ag (C ₆ H ₅ N ₃ ) ₂ ⁺ NO ₃ ⁻ ] is determined by composition analysis and TG / DTA measurement. The crystal was confirmed.

  Subsequently, the sustained release property of the antibacterial component was confirmed in the same manner as in Example 4. 5 g of the obtained bis (benzotriazole) silver nitrate powder was put into 45 g of pure water, and stirring was continued for 24 hours. Thereafter, the powder was removed by filtration and water was collected. Chemical analysis of the water revealed that the silver concentration in the water was 800 ppm. Furthermore, the dissolution test was repeated 35 times, and the concentration of silver in water was also measured for the 35th dissolution test solution. The 35th silver concentration in water at the 35th time is 0.1 ppm or less, and it can be seen that there is almost no elution of silver and the antibacterial component is no longer eluted.

Example 5
The antibacterial agent (A) obtained in Example 1, the antibacterial agent (B) obtained in Example 2, and the antibacterial agent obtained by mixing the same amount of the antibacterial agent obtained in Example 3 and the antibacterial agent of Example 1 About (C), the antibacterial property test was done. The test results are shown in Table 4 below. The test method is as follows.

A) Test bacteria (1) Escherichia coli NBRC 3301 (Escherichia coli)
(2) Pseudomonas aeruginosa NBRC 13275 (Pseudomonas aeruginosa)
(3) Aspergillus niger IFO 6341
(4) Penicillium citrinum IFO 6352 (blue mold)

B) Test medium NA medium: Ordinary agar medium [Eiken Chemical Co., Ltd.]
NB medium: Normal bouillon medium supplemented with 0.2% meat extract [Eiken Chemical Co., Ltd.]
PDA medium: Potato dextrose agar medium [Eiken Chemical Co., Ltd.]
SDA medium: Sabouraud Agar [Eiken Chemical Co., Ltd.]

C) Preparation of bacterial solution a) Test bacteria (1) and (2)
Test bacteria cultured in NA medium at 37 ° C. ± 1 ° C. for 24-48 hours were inoculated into NB medium and cultured at 37 ° C. ± 1 ° C. for 22-26 hours. This culture solution was adjusted using an NB medium so that the number of bacteria per ml was 10 ⁶ to 10 ^7, and used as a bacterial solution.
b) Test bacteria (3) and (4)
After culturing in PDA medium at 25 ° C. ± 1 ° C. for 7 days, the formed spores are suspended in 0.05% polysorbate 80-added physiological saline and adjusted so that the number of spores per ml is 10 ⁶ to 10 ^7. And used as a bacterial solution.

D) Preparation of test plate medium Test bacteria (1) and (2) were added to NA medium, test bacteria (3) and (4) were added to and mixed with 150 ml of SDA medium. It was dispensed and solidified. Furthermore, after allowing the petri dish to stand at room temperature for 30 minutes to dry the surface of the medium, a hole was made with a cylindrical glass (diameter: 12 mm) sterilized by dry heat (180 ° C., 30 minutes), and this was used as a test plate medium. .

E) Test procedure The specimen was used as a sample. Samples are filled in the whole hole in the center of the test plate medium. The test bacteria (1) and (2) are 37 ° C. ± 1 ° C. for 24 hours, the test bacteria (3) and (4) are 25 ° C. ± 1 ° C., 7 After culturing for a day, the presence or absence of halo around the sample was determined by visual observation. The number of viable bacteria in the bacterial solution is the test bacteria (1) and (2) is the pour plate culture method (37 ° C. ± 1 ° C., 2 days) using NA medium, the test bacteria (3) and (4) Was measured by the pour plate culture method using SDA medium (cultured at 25 ° C. ± 1 ° C. for 7 days) and converted to the bacterial concentration per 1 ml of the test plate medium.

[Example 6 and Reference Example 2, Comparative Example 1, Comparative Example 2]
In this example and comparative examples, vinyl chloride sheets were produced. In Example 6, 2 parts by weight of benzotriazole silver (I) prepared in Example 1 was blended as an antibacterial agent. In Reference Example 2, 2 parts by weight of bis (benzotriazole) silver nitric acid obtained in Reference Example 1 was blended. In Comparative Example 1, no antibacterial agent was blended. In Comparative Example 2, 2 parts by weight of a silver ion exchange zeolite which is a commercially available antibacterial agent was blended.

  The vinyl chloride sheet was produced by the following method. The resin composition according to the formulation shown in Table 5 below was vigorously shaken and mixed in a plastic bag. The obtained composition was melt-kneaded for 5 minutes with a two roll adjusted to a surface temperature of 150 ° C., and then molded into a sheet to produce a 5 cm square vinyl chloride sheet test piece having a thickness of 1 mm.

  The vinyl chloride sheet was subjected to a discoloration resistance test and an antibacterial test by the following methods. The results are shown in Table 6.

[Discoloration resistance test]
A test piece of a vinyl chloride sheet was placed at a position 1 m directly under a fluorescent lamp (60 W × 2), and the degree of discoloration after 30 days of exposure was evaluated according to the following score.
○: No discoloration.
Δ: Slightly discolored.
X: Vigorously discolored.

[Antimicrobial test]
Evaluation was performed in accordance with the method established by the Antibacterial Activity Evaluation Test Method for Antibacterial Products (Antimicrobial Product Technology Council).
Test method: Film adhesion method Evaluation bacterial species: Escherichia coli, Staphylococcus aureus Bacterial fluid inoculation time: 24 hours Evaluation: Inoculate bacterial solution into resin molded product with antibacterial agent, cover with film, and count the number of bacteria 24 hours later Measure and evaluate according to the following criteria.
○: Decrease rate from inoculum solution is 1/100 or more.
Δ: Decrease rate from inoculum solution is 1/10 or more and less than 1/100.
X: The rate of decrease from the inoculum is less than 1/10.

1 is an X-ray diffraction pattern of benzotriazole silver (I) obtained in Example 1. FIG. The X-ray-diffraction figure of the benzotriazole silver (I) obtained in Example 2. FIG. FIG. 3 is an X-ray diffraction pattern of dibenzotriazole copper (II) obtained in Example 3. 2 is an SEM photograph showing the particle shape of benzotriazole silver (I) obtained in Example 1. FIG. 4 is an SEM photograph showing the particle shape of benzotriazole silver (I) obtained in Example 2. FIG. The SEM photograph which shows the particle shape of the dibenzotriazole) copper (II) obtained in Example 3. FIG.

Claims (10)

An antibacterial agent containing a benzotriazole silver compound represented by the following general formula (1).
The benzotriazole silver compound is produced by reacting a benzotriazole compound represented by the following general formula (2) with a water-soluble silver compound in a mixed solvent of water and an organic solvent. Item 1. An antibacterial agent according to item 1.
  The antibacterial agent according to claim 1, wherein the benzotriazole silver compound is benzotriazole silver.   The antibacterial agent according to claim 1, wherein the antibacterial agent has a particle size of 0.05 to 50 µm and water content is adjusted to 5 wt% or less.   Furthermore, the antibacterial agent of Claim 1 containing a copper containing compound or / and a zinc containing compound. The antibacterial agent according to claim 5, wherein the copper-containing compound is represented by the following general formula (3).
  A cosmetic composition containing the antibacterial agent according to any one of claims 1 to 6.   A resin composition containing the antibacterial agent according to any one of claims 1 to 6.   A paint containing the antibacterial agent according to any one of claims 1 to 6. A plant fungicide containing the antibacterial agent according to any one of claims 1 to 6.