CN101130549A - Antibacterial agents - Google Patents

Abstract

The object of the present invention is to solve the problem of discoloration of silver-based zeolite antibacterial agents and the problem of resin discoloration caused by silver ions, etc., to provide a kind of antibacterial agent that has no or little discoloration tendency caused by time, and is suitable for compounding in resin molded products and paint products, etc. of antibacterial agents. The antibacterial agent of the present invention is characterized by containing a benzotriazole silver compound represented by the right general formula (1). It is a powder with a particle diameter of 0.05 to 50 μm, and the water content is preferably adjusted to 5% by weight or less. It is preferable to further contain a copper-containing compound or/and a zinc-containing compound. In the formula, R ₁ and R ₂ represent the same or different alkyl groups, aryl groups, halogen atoms, hydroxyl groups, amino groups or carboxyl groups, and p1 and q1 represent the same or different 0-2 integers.

Description

Antibacterial agents

technical field

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

Background technique

Metal ions such as silver, copper, and zinc have long been known to have antibacterial properties. Conventionally, those obtained by carrying these antibacterial metal components on inorganic particles, especially those introduced into zeolite or zirconium phosphate by ion exchange, have been used as antibacterial agents. In addition, introduction into layered silicates or clay minerals by ion exchange has also been proposed.

Conventionally, for example, an antibacterial composition is known in which a metal component having antibacterial properties is supported on powders such as zeolite, silica gel, and titanium oxide (for example, refer to Patent Document 1). However, conventionally known powdery antibacterial compositions have a serious problem of discoloration. Several solutions have been proposed to address this problem.

Patent Document 2 below proposes an antibacterial composition obtained by ion-exchanging metal ions of an inorganic oxo acid salt with antibacterial metal ions. Patent Document 3 below proposes an antibacterial agent containing an antibacterial alumina gel in which a metal having an antibacterial effect or a compound thereof adheres to the surface of alumina in the alumina gel. In Patent Document 4 below, an antibacterial agent composed of silver colloidal particles having high antibacterial properties is proposed. In the following Patent Document 5 and the following Patent Document 6, an antibacterial agent comprising an antibacterial inorganic oxide colloidal solution is proposed. In the following Patent Document 7, an antibacterial agent composed of a silver compound having a phenyl group or a naphthyl group is proposed. Patent Document 8 below describes a method for producing an antimicrobial agent in which a silver thiosulfate complex salt is supported on a silica gel and then coated with silica via an organosilicon compound.

On the other hand, benzotriazoles are inhibitors of discoloration and coloration of resins caused by photodegradation caused by ultraviolet rays and the like, and are also effective in preventing discoloration and coloration of resins by silver ions. Silver-based antibacterial agents and There are many applications for benzotriazole-based compositions (for example, refer to Patent Documents 9, 10, and 11).

Patent Document 1: Japanese Patent Laid-Open No. 2-225402

Patent Document 2: Japanese Patent Laid-Open No. 3-275627

Patent Document 3: Japanese Patent Laid-Open No. 1-258792

Patent Document 4: Japanese Patent Laid-Open No. 4-321628

Patent Document 5: Japanese Patent Laid-Open No. 6-80527

Patent Document 6: Japanese Patent Laid-Open No. 7-33616

Patent Document 7: Japanese Patent Laid-Open No. 2001-192307

Patent Document 8: Japanese Patent Application Laid-Open No. 6-1706

Patent Document 9: Japanese Patent Laid-Open No. 7-207061

Patent Document 10: Japanese Patent Laid-Open No. 6-14979

Patent Document 11: Japanese Patent Laid-Open No. 11-209533

Contents of the invention

Among various antibacterial metal components, the silver component has excellent antibacterial action and safety to the human body. However, conventionally known powdery antibacterial compositions have the following problems. That is, the silver-introduced zeolite or phyllosilicate tends to turn brown due to gradual discoloration of the powder over time or by the action of light or water. As a result, antibacterial properties cannot be exhibited. In addition, the method of supporting silver on a carrier has a problem in the sustained release performance of silver. The slow-release performance in pure water mostly occurs in a completely different large amount of release in salt water. Thus, it is not necessarily satisfactory in terms of sustained release performance.

Patent Document 2 proposes an antibacterial composition obtained by exchanging metal ions of an inorganic oxo acid salt with antibacterial metal ions, but it is not necessarily satisfactory in solving the above-mentioned problems. The form of the antibacterial alumina gel of Patent Document 3 is a colloidal solution, and its application is limited to paints and coating materials. The silver colloidal particles in Patent Document 4 are grayish brown in color and lack transparency. In addition, since the silver component itself is a colloidal particle, it is easy to aggregate and lacks stability. The antibacterial inorganic oxide colloidal solutions of Patent Document 5 and Patent Document 6 solve the problems unique to powdery antibacterial compositions, but the form of the colloidal solution limits the use to paints and coating materials. The silver compound having a phenyl group or a naphthyl group disclosed in Patent Document 7 is a water-soluble complex, and is supported or coated on another solid, so there is a problem in the above-mentioned sustained release performance. After the silver thiosulfate complex salt of Patent Document 8 is supported on the silica gel, the production method of the antimicrobial agent coated with silica by the organosilicon compound, in order to impart sustained release performance, the silica gel Silica coating on a porous body such as gelatin is not an appropriate manufacturing method, and there is a problem in maintaining the sustained-release performance for a long time.

Compositions aimed at preventing discoloration and coloration of the resin caused by silver ions described in Patent Documents 9, 10, and 11 are not to prevent discoloration of the antibacterial agent powder, but to prevent discoloration of the resin as the main component, which is different from the gist of the present invention . Although adding an anti-tarnish agent to the resin is also effective in preventing discoloration of the antibacterial agent powder, it is known that if only the anti-tarnish treatment is carried out on the anti-discoloration agent powder, much less anti-tarnish agent is used. In addition, the known benzotriazole The anti-tarnish effect is realized by forming a chelation compound between silver ions and benzotriazole, which is different from the silver benzotriazole and the coordination compound used in the present invention.

Therefore, the object of the present invention is to solve the problem of discoloration of the above-mentioned silver-based zeolite antibacterial agent and the problem of resin discoloration caused by silver ions, etc., to provide a kind of discoloration tendency caused by time without or little, suitable for resin molded products or coatings. Antimicrobial agent compounded in products, etc.

The inventors of the present invention conducted experiments on the formation of complex salts of benzotriazole and silver in the study of water-soluble silver-based antibacterial agents, and recognized the possibility of complex salt formation in the presence of a large amount of excess benzotriazole . On the other hand, in the reaction of approximately equal molar amounts of benzotriazole and silver, the benzotriazole silver salt of the present invention, which is not a complex salt, is obtained. In addition, because it is water-insoluble, it was considered to have no antibacterial effect, However, it has been recognized that silver benzotriazole is slightly soluble in water and has sufficient performance as an antibacterial agent.

The inventors of the present invention have carried out in-depth research and found that, as an antibacterial component, benzotriazole silver represented by a specific general formula has excellent performance in the sustained release of silver. In addition, as an antibacterial component, silver with a specific The benzotriazole copper represented by the general formula of has excellent performance in the sustained release of copper and can maintain antibacterial performance for a long time, thereby completing the present invention.

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

(In the formula, _R1 and _R2 represent the same or different alkyl, aryl, halogen atom, hydroxyl, amino or carboxyl, p1 and q1 represent the same or different 0-2 integers.)

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

(In the formula, R ₁ , R ₂ , p1 and q1 have the same meaning as above.)

Furthermore, the present invention provides a cosmetic composition, a resin composition, a paint, or a fungicide for plants containing the above-mentioned antibacterial agent.

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

(In the formula, _R3 and _R4 represent the same or different alkyl, aryl, halogen atom, hydroxyl, amino or carboxyl, p2 and q2 represent the same or different 0-2 integers.)

The present invention also provides a method for producing a benzotriazole copper compound represented by the following general formula (3), characterized in that, in a mixed solvent of water and an organic solvent, the following general formula (4) is carried out The reaction of benzotriazole compounds and water-soluble copper compounds.

(In the formula, R ₃ , R ₄ , p2 and q2 have the same meaning as above.)

According to the present invention, it is possible to provide an antimicrobial agent which is excellent in light resistance and water resistance, has little or no discoloration tendency with time, and is suitable for compounding into resin molded products, painted products, and the like.

Description of drawings

Fig. 1 is the X-ray diffraction figure of the benzotriazole silver (I) obtained in embodiment 1.

Fig. 2 is the X-ray diffraction figure of the benzotriazole silver (I) obtained in embodiment 2.

FIG. 3 is an X-ray diffraction diagram of benzotriazole copper (II) obtained in Example 3. FIG.

4 is a scanning electron micrograph showing the particle shape of benzotriazole silver (I) obtained in Example 1. FIG.

5 is a scanning electron micrograph showing the particle shape of benzotriazole silver (I) obtained in Example 2. FIG.

6 is a scanning electron micrograph showing the particle shape of benzotriazole copper (II) obtained in Example 3. FIG.

Detailed ways

Hereinafter, the present invention will be described in detail based on its preferred embodiments. The benzotriazole silver compound used in the present invention is a compound represented by the above general formula (1). R ₁ and R ₂ in the general formula (1) represent an alkyl group, an aryl group, a halogen atom, a hydroxyl group, an amino group or a carboxyl group. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group. Aryl is preferably phenyl, tolyl, xylyl, naphthyl. Examples of the halogen atom include chlorine, bromine, and iodine. p1 and q1 in the formula represent the same or different integers of 0-2. In addition, R ₁ and R ₂ may be the same group or different groups.

Preferred specific compounds of the benzotriazole silver compound represented by the above general formula (1) include benzotriazole silver (I), 4-methylbenzotriazole silver (I), 5-methylbenzotriazole silver (I), Silver (I) Benzotriazole, Silver (I) 4-Ethylbenzotriazole, Silver (I) 5-Ethylbenzotriazole, Silver (I) 4,5-Dimethylbenzotriazole , 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 Triazole silver (I), 4-chlorobenzotriazole silver (I), 5-chlorobenzotriazole silver (I), etc., among them, benzotriazole silver represented by the following structural formula (1a) is particularly preferred (I).

The powder color of this benzotriazole silver (I) at the time of synthesis is white, and the time-dependent change due to light is also extremely small, and it is not black like the conventional silver-based antibacterial agent, but has a cream color. In addition, it is relatively stable to heat, and does not change even when it reaches 170°C.

The antibacterial agent of the present invention consists essentially only of the benzotriazole silver compound represented by the above general formula (1), or contains this compound and other components. In any case, the antibacterial agent of the present invention is a powder or granular body with a particle size of 0.05-50 μm, especially 0.1-10 μm. For various uses such as fungicides for plants, etc., it is preferable because it is uniformly dispersed. Particle size is determined by scanning electron microscopic observation of the particles.

In addition, the moisture content of the antibacterial agent is preferably adjusted to be 5% by weight or less, more preferably 3% by weight or less. The use of antibacterial agents with a moisture content in this range has the advantage of being able to prevent foaming caused by dehydration during high-temperature molding of resin products or coating film foaming in paints when kneading into resins or compounding in paints.

The benzotriazole silver compound represented by the above-mentioned general formula (1) used in the present invention can be carried out by carrying out the benzotriazole compound represented by the above-mentioned general formula (2) and Manufactured by the reaction of water-soluble silver compounds. Specifically, a solution (liquid A1) in which a water-soluble silver compound is dissolved in water and a solution (liquid B1) in which a benzotriazole compound represented by the above general formula (2) is dissolved in an organic solvent are prepared, and the It can be produced by adding B1 liquid to the liquid and reacting. In particular, it is more preferable to use a solution in which a benzotriazole compound is dissolved in a mixed solvent of water and alcohol as the B1 liquid because a highly crystalline reactant can be obtained.

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 above-mentioned general formula (2) are groups corresponding to R ₁ and R ₂ in the above-mentioned general formula (1), and in addition, p1 and q1 in the formula Represents an integer from 0 to 2. On the other hand, as a water-soluble silver compound, silver nitrate, silver acetate, silver chlorate, silver perchlorate, silver fluoride, silver hexafluorophosphate, etc. can be used, for example. In addition, these water-soluble silver compounds may be hydrous salts or anhydrous salts. Usable organic solvents include alcohols having 1 to 5 carbon atoms such as methanol, ethanol, propanol, butanol, and pentanol, acetone, and the like. Among them, the use of alcohols is particularly preferable because it can obtain a substance with 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. In addition, the A1 liquid may be prepared as a mixed solvent of water and an organic solvent within the range in which the water-soluble silver compound can be dissolved. At this time, the mixing ratio of water and the organic solvent varies depending on the type of the water-soluble silver compound and the type of the organic solvent to be used, but in many cases, the organic solvent is preferably 5 to 50 parts by weight relative to 100 parts by weight of water, especially Preferably it is 5-30 weight part.

The concentration of the benzotriazole represented by the general formula (2) in the B1 liquid is preferably 0.1 to 5 mol/L, particularly preferably 0.3 to 2 mol/L. In addition, liquid B1 may be prepared as a mixed solvent of water and an organic solvent within the range in which the benzotriazole represented by the above general formula (2) is soluble. At this time, the mixing ratio of water and organic solvent in liquid B1 varies depending on the type of benzotriazole compound and the type of organic solvent to be used, but in many cases, it is preferably 5 to 50 parts by weight relative to 100 parts by weight of water. Parts by weight are particularly preferably 5 to 30 parts by weight. If the amount of solvent in the reaction system is small, then when using, for example, silver nitrate as a water-soluble silver compound, the reaction product becomes water-soluble due to inclusion of a complex salt [bis(benzotriazole) silver nitrate] of silver nitrate, Then the benzotriazole silver compound represented by the above-mentioned general formula (1) as the object of the present invention cannot be obtained. On the other hand, if the amount of solvent in the reaction system is too much, it is uneconomical. Therefore, it is preferable to make the concentration of A1 liquid and B1 liquid for the above range.

Add liquid B1 to liquid A1, and the benzotriazole compound in liquid B1 is preferably 1.0 to 2.0 times mole as benzotriazole (C ₆ H ₅ N ₃ ) with respect to the water-soluble silver compound in liquid A1, especially Preferably it is 1.0 to 1.5 times mole. The reason is that if the amount of benzotriazole exceeds 2.0 times mole relative to the water-soluble silver compound, a water-soluble coordination compound of benzotriazole and silver will be generated, and the yield will decrease. On the other hand, if it is less than 1 times the mole , unreacted Ag remains in the reaction solution, which is uneconomical.

The reaction conditions are that the reaction temperature is preferably 0-50°C, more preferably 10-30°C, and the reaction time is preferably 1 hour or more, more preferably 3-10 hours. After the reaction is completed, solid-liquid separation is performed according to a conventional method to recover the target object, then dried, pulverized and classified if necessary, thereby obtaining silver benzotriazole represented by the above general formula (1) used in the present invention.

The antibacterial agent of the present invention can also be used in combination with a compound releasing an antibacterial metal ion of a zinc compound or/and a copper compound. Such combined use has the effects of (a) broadening the antimicrobial spectrum, (b) prolonging the duration of antibacterial properties, (c) improving weather resistance, and (d) improving chemical resistance.

The combination and compounding ratio of silver and zinc or/and copper can be selected arbitrarily according to the purpose, and moreover, various kinds can be compounded. In particular, the combination with zinc is preferable because it can whiten the antibacterial agent.

Examples of the copper-containing compound used together with the benzotriazole silver compound represented by the above general formula (1) of the present invention include conventionally used antibacterial agents such as zeolite and zirconium phosphate carrying copper by ion exchange. In addition, products introduced into layered silicates or clay minerals by ion exchange can also be used. In the present invention, copper bromide CuBr, copper carbonate Cu ₂ CO ₃ , copper oxalate CuC ₂ O ₄ 0.5H ₂ O and other compounds with low solubility are preferred, and furthermore, from the viewpoint of low solubility and excellent antibacterial performance, the above-mentioned compounds are most preferred. A benzotriazole copper compound represented by general formula (3).

The inventors of the present invention discovered for the first time that the benzotriazole copper compound represented by the above general formula (3) is slightly soluble in water and has sufficient properties as an antibacterial agent.

_R3 and _R4 in the benzotriazole copper compound formula represented by the above general formula (3) represent an alkyl group, an aryl group, a halogen atom, a hydroxyl group, an amino group or a carboxyl group. The alkyl group is preferably a group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group. Aryl is preferably phenyl, tolyl, xylyl, naphthyl. Examples of the halogen atom include chlorine, bromine, and iodine. p2 and q2 in the formula represent the same or different integers of 0-2. In addition, R ₃ and R ₄ may be the same group or different groups.

Preferable specific compounds of the benzotriazole copper compound represented by the above general formula (3) include dibenzotriazole copper (II), bis(4-methylbenzotriazole) copper (II) , 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-phenylbenzotriazole)copper(II), bis(4-chloro Benzotriazole) copper (II), bis(5-chlorobenzotriazole) copper (II), etc. Among them, dibenzotriazole copper (II) represented by the following structural formula (3a) is particularly preferable.

The benzotriazole copper compound represented by the above general formula (3) can be obtained by reacting the benzotriazole compound represented by the above general formula (4) and a water-soluble copper compound in a mixed solvent of water and an organic solvent. manufacture.

Specifically, a solution (A2 liquid) in which a water-soluble copper compound is dissolved in water and a solution (B2 liquid) in which a benzotriazole compound represented by the above-mentioned general formula (4) is dissolved in an organic solvent are prepared, and prepared into A2 liquid It can be produced by adding liquid B2 to it 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 B2 liquid, since a reactant with high crystallinity can be obtained, it is more preferable.

Hereinafter, the manufacturing method of the benzotriazole copper compound represented by the said general formula (3) is demonstrated. R in the formula of the benzotriazole compound represented by the above-mentioned general formula (4) ₃ and R ₄ are equivalent to R ₃ and R ₄ in the above-mentioned general formula (3) The base, in addition, p2 and q2 in the formula Represents an integer from 0 to 2. On the other hand, as a water-soluble copper compound, copper sulfate, copper perchlorate, copper chloride, copper tetrafluoroborate, copper formate, copper chlorate, copper nitrate, etc. can be used, for example. In addition, these water-soluble copper compounds may be hydrous salts or anhydrous salts. Usable organic solvents include alcohols having 1 to 5 carbon atoms such as methanol, ethanol, propanol, butanol, and pentanol, acetone, and the like. Among them, the use of alcohols can obtain a substance with good crystallinity, so it is particularly preferred. .

The concentration of the water-soluble copper compound in liquid A2 is preferably 0.1 to 1 mol/L, more preferably 0.3 to 0.8 mol/L. In addition, the A2 solution may be prepared as a mixed solvent of water and an organic solvent within the range where the water-soluble copper compound can be dissolved. At this time, the mixing ratio of water and the organic solvent varies depending on the type of the water-soluble copper compound and the type of the organic solvent, but in many cases, the organic solvent is preferably 5 to 50 parts by weight relative to 100 parts by weight of water. , particularly 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. In addition, the liquid B2 may be prepared as a mixed solvent of water and an organic solvent within the range in which the benzotriazole represented by the above general formula (4) is soluble. At this time, the mixing ratio of water and organic solvent in the B2 liquid varies according to the type of water-soluble silver compound and the type of organic solvent used, but in many cases, the organic solvent is preferably 5 parts by weight relative to water of 100 parts by weight. ~50 parts by weight, particularly preferably 10 to 30 parts by weight.

The B2 liquid is added to the A2 liquid, and the benzotriazole compound in the B2 liquid is preferably 2.0 to 2.5 times moles as benzotriazole (C ₆ H ₅ N ₃ ) relative to the water-soluble copper compound in the A2 liquid, Particularly preferably, it is 2.0 to 2.1 times moles. The reason is that if the amount of benzotriazole exceeds 2.5 times the mole relative to the water-soluble copper compound, a water-soluble coordination compound of benzotriazole and copper is generated, and the yield decreases. On the other hand, when the amount is less than 2 times the mole , Unreacted Cu remains in the reaction solution, which is uneconomical.

The reaction conditions are that the reaction temperature is preferably 0-50°C, more preferably 10-30°C, and the reaction time is preferably 1 hour or more, more preferably 3-10 hours. After the reaction is completed, solid-liquid separation is performed according to a conventional method to recover the target object, and then dried, pulverized and classified as needed, thereby obtaining copper benzotriazole represented by the above general formula (3) used in the present invention.

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

In the antibacterial agent of the present invention, in addition to the benzotriazole silver compound represented by the above-mentioned general formula (1), it is also possible to use in combination quinaldic acid, quinoline-8-carboxylic acid, and salicylaldoxime. Salt.

As described above, the antimicrobial agent of the present invention can be suitably used in cosmetic compositions, resin compositions, and resin molded articles formed from the compositions, paints, fungicides for plants, and the like.

The antibacterial agent of the present invention can be used in various ways in applications requiring antibacterial properties. The antibacterial agent can be surface-treated by known modifying agents, such as dispersants, surfactants, coupling agents, anti-tarnish agents, antioxidants, ultraviolet absorbers, etc., within the range of not impairing its effect performance.

The dispersant is not particularly limited, and for example, the following waxes and low-melting resins can be used.

(1) Fatty acids and their metal salts

Synthetic or natural fatty acids and alkali metal or alkaline earth metal salts, zinc salts, aluminum salts, etc. of these. For example, stearic acid, oleic acid, etc., and sodium salts and ammonium salts thereof, etc., may be cited.

(2) Amides and amines

For example, erucamide, oleyl palmitamide, stearoyl erucamide, 2-stearamidoethyl stearate, ethylene bis fatty acid amide, N,N'-oleoyl stearoyl Ethylenediamine, N,N'-bis(2-hydroxyethyl)alkyl (C12～C18)amide, N,N'-bis(hydroxyethyl)lauric amide, fatty acid diethanolamine, etc.

(3) Fatty acid esters, alcohol esters

For example, n-butyl stearate, hydrogenated rosin methyl ester, dibutyl sebacate (di-n-butyl sebacate), dioctyl sebacate (including di-2-ethylhexyl sebacate) , di-n-octyl sebacate), glycerin fatty acid ester, pentaerythritol tetrastearate, polyethylene glycol fatty acid ester, polyethylene glycol fatty acid diester, diethylene glycol fatty acid diester, propylene glycol fatty acid diester wait.

(4) Waxes

For example, spermaceti wax, montan wax, carnauba wax, beeswax, wood wax, lanolin, polyethylene wax, polypropylene wax, epoxy-modified polyethylene wax, petroleum-based wax, etc. can be mentioned.

(5) Low melting point resins

Various resins with a melting point or softening point of 40 to 200°C, especially 70 to 160°C, for example, epoxy resins, xylene-formaldehyde resins, styrene-based resins, chromane-indene resins, other petroleum Resin, alkyd resin, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, low melting point acrylic resin, polyvinyl butyral, low melting point copolyamide, low melting point copolyester, etc.

As surfactants, cationic surfactants such as (a) primary amine salts, tertiary amines, quaternary ammonium compounds, and pyridine derivatives can generally be used; (b) sulfated oils, soaps, sulfated ester oils, sulfated amide oils , Sulfates of olefins, fatty alcohol sulfates, alkyl sulfates, fatty acid ethylsulfonates, alkylnaphthalenesulfonates, alkylbenzenesulfonates, succinatesulfonates, phosphates Anionic surfactants such as salts; (propylene) polyol partial fatty acid esters, fatty alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, fatty amine or fatty acid amide ethylene oxide adducts, Alkylphenol ethylene oxide adducts, alkylnaphthol ethylene oxide adducts, polyol partial fatty acid ester ethylene oxide adducts, polyethylene glycol and other non-ionic surfactants; ( but) Amphoteric surfactants such as carboxylic acid derivatives and imidazoline derivatives.

As the coupling agent, for example, the following can be used.

(1) Silane series coupling agent:

γ-Aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β(aminoethyl) base) amino silanes such as γ-aminopropylmethyldimethoxysilane. Methacryloxy-based silanes such as γ-methacryloxypropyltrimethoxysilane.

Vinyl-based silanes such as vinyltris(βmethoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltrichlorosilane.

β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, etc. Epoxy silane. Mercaptopropyl-based silanes such as γ-mercaptopropyltrimethoxysilane.

(2) Titanate coupling agent:

Isopropyl triisostearyl titanate, isopropyl tri-dodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraoctyl bis(di - Tridecyl phosphate) titanate, tetrakis (2,2-diallyl hydroxymethyl-1-butyl) bis (di-tridecyl) phosphate titanate, bis (dioctyl Dioctyl pyrophosphate) hydroxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethylacryl isostearate Acyl titanate, isopropyl isostearyl diallyl titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl tricumenylphenyl titanate, isopropyl Tris(N-aminoethyl-aminoethyl) titanate, dicumenylphenyl hydroxyacetate titanate, diisostearyl ethylene titanate, polydiisopropyl titanate , Tetra-n-butyl titanate, polydi-n-butyl titanate.

Examples of inorganic anti-tarnish agents include hydrotalcites, zinc oxide, magnesium oxide, calcium oxide, aluminum-containing phyllosilicates, alkali-aluminum composite hydroxide carbonates, etc.

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 in which antibacterial metal ions are ion-exchanged or supported are exemplified.

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 hinoki alcohol; chitosans; parabens; organic acids such as benzoic acid and dehydroacetic acid; salts of these organic acids;

Specifically, hinokitiol, chitosan, benzoic acid, benzoates, isopropyl cresol, undecylenic acid monoethanolamide, cetylpyridinium chloride, alkyl chloride Aminoethylglycine, chlorhexidine hydrochloride, cresol, chloramine, chloroxylenol, chlorocresol, chlorobutanol, salicylic acid, salicylates, bromide, sorbic acid and salts , thymol, thiram, dehydroacetic acid and its salts, trichlorodiphenylurea, parabens, p-chlorophenol, chlorofluorophenylurea, phenol, hexachlorophene, lauryl sarcosine Sodium acid sodium, resorcinol, iodophor (polyvinylpyrrolidone-iodine coordination compound) and its cyclodextrin inclusion body, iodine-alkyl polyether alcohol coordination compound (GS.I.), polyethoxy Polypropoxypolyethoxyethanol-iodine complex (Iocline), nonylphenoxypolyethoxyethanol-iodine complex, polyoxyethylene added vegetable oil-iodine complex, polyoxyethylene added Fatty acid-iodine complexes, polyoxyethylene addition fatty alcohol-iodine complexes, fatty acid amides-iodine complexes, etc.

Because the antibacterial agent of the present invention has excellent dispersibility to various resins (polymers), and the discoloration tendency is also small, it can be mixed in various resins (polymers), and can be molded in resin compositions and resins with antibacterial properties. Products, such as fibers, films, sheets, pipes, plates, containers, building materials, structural materials and other fields. In addition, the antimicrobial agent of the present invention can be used in the field of antimicrobial coating films by blending it in paint or the like.

The above-mentioned resin is not particularly limited, and a wide range of resins can be used. For example, polyolefin resin represented by polyethylene and polypropylene, polyvinyl chloride resin, polyvinylidene chloride, chlorine-based resin such as chlorinated polyolefin, polyamide, ABS resin, polyester, polystyrene, Polyacetal, polyvinyl alcohol, polycarbonate, acrylic resin, fluororesin, polyurethane elastomer, polyester elastomer, phenolic resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, polyurethane resin, silicon Resin, rayon, copper amine, acetate, triacetate, vinylidene resin, thermoplastic resin such as natural and synthetic rubber or thermosetting resin, etc. In addition, these resins may be copolymers, graft polymers, or mixed resins of two or more types. Among the above-mentioned resins, polyolefin resins, polyvinyl chloride resins, and ABS resins are particularly preferable.

When blending the antibacterial agent of the present invention in the coating, as the material of the coating, for example, oily coatings such as clear oil, oily varnish, oily enamel, cellulose derivative coatings such as nitrocellulose paint, acrylic paint, and the above-mentioned resin material Thermosetting resins and elastomeric polymers described in , etc. are made into paint-type synthetic resin paints.

Materials used in combination with resins and paints can also use conventionally used materials. For example, fats and oils, mineral oils, plasticizers, solvents, inorganic fillers, pigments, extender pigments and the like can be mentioned. Examples of inorganic fillers include finely powdered silica, activated alumina, zinc phyllosilicate containing alumina and its siliceous composite, magnesium phyllosilicate, hydrotalcite, zinc-modified hydrotalcite, lithium-aluminum Compound hydroxide salt, talc, clay, bentonite, dawsonite, diatomaceous earth, silica sand, calcium carbonate, etc.

Resin molded articles and paints containing the antibacterial agent of the present invention can also be contained in articles of any shape. For example, cloth products such as anti-woven fabrics, non-woven fabrics, mesh cloths, and braids; sheet products such as paper and films; powder products such as spreading agents and sprays; Liquid or pasty products such as mixtures and sealants, shaped products such as plates, rods, boxes, and porous bodies.

Examples of resin molded articles and coatings containing the antibacterial agent of the present invention include cling film and sanitary materials, kitchen and bathroom products, cosmetics, cosmetics, water treatment products, medical equipment, building materials, fishing nets, and the like. In addition, it can be added to cement mortar or coated on a cement concrete molded body to produce an antibacterial cement concrete product. In addition, it can be applied to various products for the purpose of antibacterial.

In the resin composition compounded with the antibacterial agent of the present invention, the compounding amount of the antibacterial agent in the resin varies in many ways according to the physical properties of the antibacterial agent, especially the carrying amount of the antibacterial component, the type of synthetic resin and its use, etc. . In many cases, it is preferable that it is the range of 0.1-30 weight part with respect to 100 weight part of resins. More preferably, it is 0.5-10 weight part. However, as a resin composition composed of a masterbatch, it can be blended up to 30 parts by weight. When the compounding quantity of an antimicrobial agent is less than 0.1 weight part, the antibacterial effect of a resin composition cannot be acquired substantially. In addition, the upper limit of the amount of compounding is often limited for economical reasons, and is set to a practical range.

Example

Hereinafter, an Example is given and this invention is demonstrated concretely. Each measurement value in an Example was calculated|required by the following method, respectively.

(a) Composition analysis:

Antimicrobial metals were quantified by inductively coupled plasma emission spectrometer (ICP) (manufactured by Varian, LIBERTY II type). Benzotriazole was quantified by measuring the amount of carbon with a total organic carbon analyzer (manufactured by Shimadzu Corporation, TOC-5000A), and converting it into molecular weight.

(b) Particle shape:

Observation with a scanning electron microscope (SEM) (manufactured by Hitachi, Model S-4500).

(c) X-ray diffraction pattern (XRD):

An X-ray diffraction apparatus (model RINT2400 manufactured by Rigaku) was used.

[Example 1]

Dissolve 20.0 g of silver nitrate in 220 g of water-ethanol (weight ratio: 10:1) mixed solvent, as A1 liquid. Dissolving in 220g water-ethanol (weight ratio is 10: 1) mixed solvent is 14.0g benzotriazole (C ₆ H ₅ N ₃ , pure chemical production, reagent) that is 1 times equivalent relative to the molar number of silver nitrate, As B1 solution. Add B1 solution slowly to A1 solution, and react at 25 degreeC for 3 hours. The resulting precipitate was filtered, washed with water, and dried at 50° C. for 10 hours, thereby obtaining silver (I) benzotriazole. Elemental analysis of the obtained benzotriazole silver (I) revealed that its composition was Ag(C ₆ H ₅ N ₃ ) _1.10 . In addition, the moisture lost by drying at 110°C was 0.85%. Measurement results of X-ray diffraction are described in FIG. 1 and Table 1. FIG. In addition, its scanning electron micrograph is shown in FIG. 4 . In the scanning electron micrograph, the shape of the particles is a plate crystal, the thickness of the particle diameter is 0.1-0.2 μm, the plane is 0.5-5 μm, and the average is about 2 μm.

【Table 1】

2θ(°) Interplane spacing d( Ȧ) 6.57 13.4 13.18 6.71 19.53 4.54 24.65 3.61 26.85 3.32

[Example 2]

Dissolve 20.0 g of silver nitrate in 240 g of water-ethanol (weight ratio: 5:1) mixed solvent, as A1 liquid. Dissolving in 240g water-ethanol (weight ratio is 5: 1) mixed solvent is 28.1g benzotriazoles (C ₆ H ₅ N ₃ , pure genuine chemical production, reagent) that is 2 times equivalent relative to the molar number of silver nitrate, As B1 solution. The liquid B1 was slowly added to the liquid A1, and it was made to react at 20 degreeC for 6 hours. The resulting precipitate was filtered, washed with water, and dried at 50° C. for 24 hours, thereby obtaining silver (I) benzotriazole. Elemental analysis of the obtained benzotriazole silver (I) revealed that its composition was Ag(C ₆ H ₅ N ₃ ) _1.21 . In addition, the water lost by drying at 110°C was 2%. The X-ray diffraction measurement results are shown in FIG. 2 and Table 2. In addition, its scanning electron micrograph is shown in FIG. 5 . In the scanning electron micrograph, the shape of the particles is an indeterminate crystal of a cubic or rectangular parallelepiped that is close to a circle, and the particle diameter is 0.1 to 1.0 μm, with an average of about 0.3 μm.

【Table 2】

2θ(°) Interplane spacing d( Ȧ) 6.57 13.4 7.92 11.2 8.51 10.3 13.61 6.50 14.30 6.19 14.68 6.03 19.55 4.54 26.86 3.32

[Example 3]

20.0 g of copper sulfate (II) pentahydrate was dissolved in 125 g of water-ethanol (weight ratio: 4:1) mixed solvent to obtain liquid A2. Dissolving in 125g water-ethanol (weight ratio is 4: 1) mixed solvent is 19.1g benzotriazoles (C ₆ H ₅ N ₃ , pure genuine chemical production, reagent) that is 2 times equivalent relative to the molar number of cupric sulfate, As B2 liquid. Slowly add liquid B2 to liquid A2, and react at 25° C. for 3 hours. The resulting precipitate was filtered, washed with water, and dried at 50° C. for 24 hours to obtain copper dibenzotriazole. Elemental analysis of the obtained dibenzotriazole copper (II) revealed that its composition was Cu(C ₆ H ₅ N ₃ ) _2.00 . The X-ray diffraction measurement results are shown in FIG. 3 and Table 3. In addition, its scanning electron micrograph is shown in FIG. 6 . In the scanning electron micrograph, the particle shape is approximately spherical, but there is also a shape in which agglomeration occurs and connects to a rod shape. The particle diameter of the primary particles is 0.03 to 0.3 μm, with an average of about 0.1 μm.

【table 3】

2θ(°) Interplane spacing d( Ȧ) 7.59 11.6 20.3 4.37 31.7 2.82

[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 thrown into 45 g of pure water, and stirring was continued for 24 hours. Then, it was separated by filtration, the powder was removed, and water was recovered. The water was chemically analyzed and the silver concentration in the water was 5 ppm. The elution test was repeated 35 times, and the silver concentration in water was also measured for the 35th elution test solution. The silver concentration in the water of the 35th time was 0.16 ppm.

[Reference example 1]

Using a glass beaker, 23.8 parts by weight of benzotriazole (C ₆ H ₅ N ₃ , produced by Junzheng Chemical Co., Ltd., reagent) was added to 40 parts by weight of ethanol, and stirred for 10 minutes to dissolve. Then, 17 parts by weight of silver nitrate and 160 parts by weight of pure water were added. The dissolution of silver nitrate and the generation of white precipitate proceeded simultaneously. The silver nitrate was dissolved in 3 hours, and then stirred continuously for 16 hours. The white precipitate was filtered, washed with water, and dried at 50° C. for 24 hours. Thus, white crystals were obtained. This white crystal can not confirm benzotriazole and _AgNO with X-ray diffraction Existence, by compositional analysis and thermogravimetric-differential thermal analysis (TG/DTA) measure, confirm to be bis(benzotriazole) silver nitrate ([ Crystallization of Ag(C ₆ H ₅ N ₃ ) ₂ ⁺ NO ₃ ⁻ ]).

Then, it carried out similarly to Example 4, and performed the confirmation of the sustained-release property of an antibacterial component. 5 g of the obtained bis(benzotriazole) silver nitric acid powder was thrown into 45 g of pure water, and stirring was continued for 24 hours. Then filter and separate to remove powder and recover water. The water was chemically analyzed and the silver concentration in the water was 800 ppm. The elution test was repeated 35 times, and the silver concentration in water was also measured for the 35th elution test solution. The concentration of silver in the water at the 35th time was 0.1 ppm or less. It can be seen that there is almost no elution of silver, and the antibacterial component is no longer eluted.

[Example 5]

For the antibacterial agent (A) obtained in embodiment 1, the antibacterial agent (B) obtained in embodiment 2 and the antibacterial agent obtained by mixing the antibacterial agent obtained in embodiment 3 and the antibacterial agent of embodiment 1 in equal amounts Agent (C) was tested for antibacterial properties. 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 (Aspergillus niger)

(4) Penicillium citrinum IFO 6352 (Penicillium citrinum)

B) test medium

NA: Normal agar medium [Eiken Chemical Co., Ltd.]

NB: Plain broth 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 medium [Eiken Chemical Co., Ltd.]

C) Preparation of bacterial solution

a) Test bacteria (1) and (2)

Inoculate the test bacteria cultured in NA medium at 37±1°C for 24 to 48 hours in NB medium, and cultivate at 37±1°C for 22 to 26 hours. The NB culture medium was used to adjust the culture solution so that the number of bacteria per 1 ml was 10 ⁶ -10 ⁷ , and the bacteria solution was prepared.

b) Test bacteria (3) and (4)

Suspend the spores formed after culturing in PDA medium at 25±1°C for 7 days in physiological saline supplemented with 0.05% polysorbate 80, adjust the number of spores per 1ml to 10 ⁶ to 10 ⁷ , and prepare bacteria liquid.

D) Preparation of plate culture medium for test

Add and mix 10ml of test bacteria (1) and (2) in 150ml NA medium respectively, add and mix 10ml of test bacteria (3) and (4) in 150ml of SDA medium, respectively Pour 15ml of the above culture medium into the Petri dish and let it solidify. Leave the petri dish at room temperature for another 30 minutes to dry the surface of the culture medium, then punch a hole in a cylindrical glass (diameter 12mm) sterilized by dry heat (180°C, 30 minutes), and use it as a plate culture medium for the test .

E) Test operation

The test body is used as a sample. Fill all the wells in the center of the plate medium for the test with samples, incubate the test bacteria (1) and (2) at 37±1°C for 24 hours, and incubate the test bacteria (3) and (4) at 25±1°C After 7 days, judge with the naked eye whether there is a bacteriostatic zone (halo) around the sample. In addition, the test bacteria (1) and (2) were mixed by dilution and mixing plate culture using NA medium (37±1°C, cultured for 2 days), and the test bacteria (3) and (4) were mixed by dilution using SDA medium. Plate culture method (25±1°C, cultivated for 7 days), measure the number of viable bacteria in the bacterial liquid, and convert it into the bacterial concentration per 1ml of the test plate medium.

[Table 4] Whether the test bacteria of the sample form a bacteriostatic zone (growth arrest zone)

Test bacteria concentration (/ml) Antibacterial agents A B C (1) Escherichia coli 1.6×10 ⁶ + + + (2) Pseudomonas aeruginosa 9.4×10 ⁵ + + + (3) Aspergillus niger 5.1×10 ⁵ ± ± + (4) Penicillium 6.3×10 ⁵ + + +

+: Inhibition zone observed

±: Slightly observed zone of inhibition (width <1mm)

-: no zone of inhibition observed

W=(T-D)/2

W: the width of the inhibition zone

T: total length of sample and inhibition zone

D: the length of the sample

[Example 6 and Reference Example 2, Comparative Example 1, Comparative Example 2]

Sheets made of vinyl chloride were produced in the present examples and comparative examples. In Example 6, 2 parts by weight of benzotriazole silver (I) produced in Example 1 was blended as an antibacterial agent. In Reference Example 2, 2 parts by weight of the 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 silver ion-exchanged zeolite, which is a commercially available antibacterial agent, was blended.

The vinyl chloride sheet was produced by the following method. The formulation-related resin compositions shown in Table 5 below were mixed vigorously in a plastic bag. The obtained composition was melt-kneaded for 5 minutes with two rollers whose surface temperature was adjusted to 150° C., and then formed into a sheet to produce a 1 mm thick, 5 cm square vinyl chloride sheet test piece.

【table 5】

PVC (ZEON 103EP) 100 parts by weight Dioctyl phthalate (DOP) 50 parts by weight Epoxidized soybean oil 3 parts by weight Ba-Zn series liquid stabilizer 1.5 parts by weight Ba-Zn series powder stabilizer 0.5 parts by weight Zn-A type zeolite stabilizer (produced by Nippon Chemical Industries, ゼオスタ-ZA-100P) 1 part by weight Antibacterial agents 2 parts by weight

The above-mentioned 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 below a fluorescent lamp (60W x 2), and the degree of discoloration after exposure for 30 days was evaluated by the following score.

○: no color change

△: Slightly discolored

×: severe discoloration

[antibacterial test]

The evaluation was performed according to the method established by the antibacterial product evaluation test method (the antimicrobial product technical association).

Test method: film covering method

Evaluation strains: Escherichia coli, Staphylococcus aureus

Bacterial liquid inoculation time: 24 hours

Evaluation: A bacterial solution was inoculated into a molded resin product to which an antibacterial agent was added, covered with a film, and the number of bacteria after 24 hours was measured, and evaluated by the following criteria.

◯: The reduction rate after inoculation with the bacterial solution was 1/100 or more.

Δ: The reduction rate after inoculation with the bacterial solution was 1/10 or more and less than 1/100.

×: The reduction rate after inoculating the bacterial solution was less than 1/10.

【Table 6】

Pilot projects Example 6 Comparative example 1 Comparative example 2 Reference example 2 Discoloration resistance test ○ ○ △ x Antibacterial test ○ x ○ ○

Claims (14)

1. antiseptic-germicide is characterized in that:

Contain the benzotriazole silver compound shown in the following general formula (1),

In the formula, R ₁And R ₂Represent identical or different alkyl, aryl, halogen atom, hydroxyl, amino or carboxyl, p1 and q1 represent identical or different 0～2 integer.

2. antiseptic-germicide as claimed in claim 1 is characterized in that:

Benzotriazole silver compound is the material that generates by the reaction of carrying out benzotriazole cpd shown in the following general formula (2) and water-soluble silver compound in the mixed solvent of water and organic solvent,

In the formula, R ₁, R ₂, p1 and q1 and above-mentioned same meaning.

3. antiseptic-germicide as claimed in claim 1 is characterized in that:

Benzotriazole silver compound is benzotriazole silver.

4. antiseptic-germicide as claimed in claim 1 is characterized in that:

Described antiseptic-germicide is that particle diameter is the powder body of 0.05～50 μ m, and moisture is adjusted to below the 5 weight %.

5. antiseptic-germicide as claimed in claim 1 is characterized in that:

Also contain copper-containing compound or/and zinc compound.

6. antiseptic-germicide as claimed in claim 5 is characterized in that:

Copper-containing compound is with following general formula (3) expression,

In the formula, R ₃And R ₄Represent identical or different alkyl, aryl, halogen atom, hydroxyl, amino or carboxyl, p2 and q2 represent identical or different 0～2 integer.

7. the manufacture method of the germ resistance benzotriazole silver compound shown in the following general formula (1) is characterized in that:

In the mixed solvent of water and organic solvent, carry out the reaction of benzotriazole cpd shown in the following general formula (2) and water-soluble silver compound,

In the formula, R ₁, R ₂, p1 and q1 and above-mentioned same meaning.

8. the manufacture method of germ resistance benzotriazole silver compound as claimed in claim 7 is characterized in that:

Organic solvent is an alcohol.

9. germ resistance benzotriazole copper compound is characterized in that:

With following general formula (3) expression,

In the formula, R ₃And R ₄Represent identical or different alkyl, aryl, halogen atom, hydroxyl, amino or carboxyl, p2 and q2 represent identical or different 0～2 integer.

10. the manufacture method of the germ resistance benzotriazole copper compound shown in the following general formula (3) is characterized in that:

In the mixed solvent of water and organic solvent, carry out the benzotriazole cpd shown in the following general formula (4) and the reaction of water-soluble copper compound,

In the formula, R ₃, R ₄, p2 and q2 and above-mentioned same meaning.

11. a cosmetic composition is characterized in that:

Contain each described antiseptic-germicide in the claim 1～6.

12. a resin combination is characterized in that:

Contain each described antiseptic-germicide in the claim 1～6.

13. a coating is characterized in that:

Contain each described antiseptic-germicide in the claim 1～6.

14. a kind of plant sterilant is characterized in that:

Contain each described antiseptic-germicide in the claim 1～6.

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