TW200812984A - Antimicrobial agent - Google Patents

Abstract

The invention provides an antimicrobial agent with slight or no tendency of discoloration with time, suitable to compounding in resin molded products, coating products, etc., through aiming to solve such problems as the discoloration of silver-based zeolite antimicrobial agents and resin discoloration attributable to silver ion. The antimicrobial agent comprises a benzotriazole silver compound of the general formula(1) (wherein, R1 and R2 are same or different and each an alkyl, aryl, halogen atom, hydroxy, amino or carboxy; and p1 and q1 are each an integer of 0-2). It is preferable that this agent be in the form of powdery granules 0.05-50 μm in size and the moisture content of this agent be adjusted to not more than 5 wt.%. Furthermore, it is preferable that this agent also contains a copper-containing compound and/or zinc-containing compound.

Description

200812984 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to the anti-separation of the antibacterial component of the antibacterial component, and the antibacterial component has the right ii dimethylidene, which is excellent in water resistance and heat resistance. Long-term fruit antibacterial agent. Further, the present invention, #菌效 知5, relates to an antibacterial agent suitable for blending with a cosmetic, a bismuth shaped article or a coated product. , 月曰 [Prior Art] Metal ions such as silver, copper, and zinc have been known to have antibacterial properties since ancient times. It is used as an antibacterial agent by using inorganic particles to hold the antibacterial gold. The one said, #成刀者4 inch, by using the parent to change the Buddha stone or strontium phosphate. Further, there are cases in which a layered agglomerate or a clay mineral is introduced by exchanging lice. In the past, for example, an antibacterial composition having an antibacterial metal component such as a zeolite or a powder such as lycopene or oxidized chin (see, for example, Patent Document) is known. However, in the conventional powdery antibacterial composition, there is a problem that the color of the four colors is large. There are several proposals for such problems. In the following Patent Document 2, an antibacterial composition is proposed, in which a metal ion of an inorganic acid-containing salt is ion-exchanged with an antibacterial metal ion. In the following document 3, there is proposed an antibacterial agent which is contained on the surface of the oxidized oxidized sol and adheres to an alumina sol having an antibacterial metallization compound thereof. In Patent Document 4 below, η wood has an antibacterial agent containing silver colloid particles having high antibacterial properties. Patent Document 5 and Patent Document 6 below propose an antibacterial agent comprising an antibacterial inorganic oxide colloid solution. In the following Patent Document 7, mention is made of 〇82-900〇-PF; and Ahddub 5 200812984 has an anti-caries agent, which comprises: In the following Patent Document 8, a silver compound of the right-hand side is shown. There is an antibacterial agent in the case. The silver thiosulfate salt is coated with Shishijiao η dioxide. The use of a dicing compound to impart a discoloration or coloring inhibitor to the triazole-based resin caused by ultraviolet light or the like, and to prevent the resin from being colored by silver ions, many of which are silver-based. An antibacterial agent and an application for stupidity (see, for example, Patent Document 9, 〇, u). [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problems to be Solved by the Invention] Among various antibacterial metal components, the silver component is excellent in antibacterial action or safety to human body. However, in the previously known powdery anti- 7082-9 〇〇〇-PF; Ahddub 200812984 bacterial composition, there are the following problems. That is, the introduction of citrate may result in a tendency for the powder to become brown due to the passage of time, or the effect of light or water due to the light or water of the bamboo or stone layer. Reduced to hundreds: The degree of comparison, the results often have the ability to show the antibacterial performance of the knife 钣 钣 ti ^ X ' in the method of the body, the performance of gray silver has a problem. In the pure water discharge performance, there is a point that a large amount of release is completely different from that in the brine, and thus the point of the release performance is not satisfied. Patent Document 2 proposes an antibacterial composition in which a metal ion of an inorganic oxyacid salt is exchanged with a metal ion having an antibacterial action, but it is not necessarily satisfactory in solving the above problems. By. = It is an antibacterial oxidized sol of the type 3, which is a type of colloidal solution. The use of the solution is limited to coatings and coating materials. According to Patent Document 4, the colloidal particles are colored in grayish brown & therefore, the transparency is lacking, and the silver is itself a colloidal particle colloidal particle, which has a problem of easy aggregation and lack of stability. The antibacterial inorganic oxide colloidal solution of Patent Document 5 and Patent Document 6 solves the problems peculiar to the powdery antibacterial composition, but in the form of a colloidal solution, the use thereof is limited to the coating material and the coating material. The phenyl or silvery silver compound of Patent Document 7 is a water-soluble compound which needs to be supported or applied to other solids, and the above-mentioned properties are problematic. Patent Document 8 'A method for producing an antibacterial agent for applying a silver dioxide sulphate salt to a sulphur sulphate by applying an antibacterial agent for applying a cerium oxide coating to a cerium compound The porous body of the rubber is subjected to a method of discomfort of the coating of the oxidized stone, and has a problem in maintaining the long-term performance of the release property. In order to prevent the discoloration and coloring of the silver ion resin of the silver ion resin described in Patent Document 9, 〇, u, the combination of the purpose of discoloration and coloring, #u #7冬,和. The discoloration prevention of the powder of the sub-Asian antibacterial agent is prevented, and the discoloration of the resin which is the main component is prevented, and even if the discoloration preventing agent is added by the resin, the discoloration of the antibacterial powder is effective, and only the antibacterial powder is used. The discoloration prevention treatment obviously uses a smaller amount of the discoloration preventing agent, and the effect of the benzotri(4) color prevention is known to be a silver ion plate, and the bis-oxazole is chelated to form a complex. Occasionally, the benzotriene used in the present invention is different in the compound of the Japanese compound itself. Therefore, the present invention solves the problem of discoloration of m-type (10) ions by the antibacterial property of the silver-based zeolite by solving the σ μ &, +, the determination of the line, and the above-mentioned. The color tendency is suitable for blending with an antibacterial agent for forming a mouth of a resin or coating a product. Table [Means for Solving the Problem] I, in the case of the water-soluble silver - in the study of the benzobisazole I # , '" training, the four leaves - the main salt of the main silver The presence of benzotriazole # I ^ Into the test, the formation of the complex formation in the presence of a large sitting, in the vicinity of the Mo Mo see 4. Another day today you have triazole salts However, in the first step of the present invention, the reaction is not the salt of the triazole silver, and it is considered that there is no antibacterial effect, but the hair=, due to the insoluble nature of the water, you The salt on the one-degree salt has a sufficient degree of water as the antibacterial agent, and the inventors have the same vocal π ^ 7 7 『 匕 匕 匕 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有Brother as an antibacterial ingredient to specifically abundance of diazole silver in silver, and, as a #2, you have excellent sexual properties as an anti-caries component with a specific '艮 性 性 具有 具有 具有 具有 具有 具有 具有 具有The benzotriazole copper was maintained at σ, and maintained antibacterial properties up to 7082-90〇〇^PF; Ahddub 200812984 completed The present invention provides an antibacterial agent comprising: benzotriazole salt compound represented by the following formula (1):

In the formula, R! and R2 represent the same or different alkyl group, aryl group, dentate atomic hydroxyl group, amine group or carboxyl group, and pi and ql represent the same or different numbers of 〇~2. According to still another aspect of the invention, there is provided an antibacterial benzotriene represented by the following formula (1). The method for producing a silver compound is characterized by reacting a benzotristrile compound represented by the following formula (2) with a water-soluble silver compound in a mixed solvent of water and an organic solvent.

(Ri)pK, VA N ( 2 )

Still further, the present invention provides a cosmetic composition, a material or a fungicide for plants comprising the above antibacterial agent. Resin Composition, Coating Further, the present invention provides an antibacterial benzene which is represented by the following formula (3): a tri-Wow copper compound, which is specifically 7082-9000-PF; Ahddub 9 200812984

No base, amine or thiol, p2 and q2 represent the same or an integer. Furthermore, the present invention provides a method for producing a bisoxazoline compound represented by the following formula (3), characterized in that a mixed solvent t of the agent is a benzo water-soluble copper compound represented by the following formula (4) Carry out the reaction: £, halogen atom, different 0~2 of the antibacterial benzene in water and organic dissolved trisodium compound with (~)

N

Η

An antibacterial agent which tends to change color over time according to the present invention. It can provide light resistance and water resistance. It is suitable for blending with resin molded products. No or few paint products, etc. [Embodiment] 7082-9000-PF/Ahddub 10 200812984 /, 1 person, Gongbei (4)® is described in detail. The benzotriazole silver compound used in the present invention is represented by the above formula (1) and the formula (1), and R1 and R2 represent an alkyl group, an aryl group, a halogen atom, a 'group, an amine group or a slow group. . As a stimulating group, a methyl group, an ethyl group, a propyl group, and a butyl group have a specific carbon number of 1 to 5. Pen | ...... A stupid base, a tolyl group, a xylyl group, and a bis group can be exemplified by chlorine, bromine, and moth. In the formula and ql are the same or different integers of °~2. Also, m may be the same group or a different group. u βΊ is represented by the above formula (1) > 婪:, a compound of the triazole silver compound, which may be a benzodiazolium < soil with 5-methylbenzotriazole Silver (j), , ' (),

Further, 4 ethyl benzotriazole silver (I), 5-ethylidene triazole silver (I), 4,5-dimethyl 3 ethyl benzoquinone basic triazole silver (1), 4 and triazole Silver (I), 5, 6-dimethyl hydrazine, - methyl group, f-triazole silver (1), 4 and triterpenoid silver (1), 4,6-diethylbenzotrisin (1), Η-B Basic and three-salt silver (1), 4-phenylene benzotrisin (1) which: ethylbenzene (I), 4-chlorobenzotrisin (ί), 5_ basic and tri-salt silver 'especially the following The number of structural formulae (la) indicates that the bis-oxazolyl (I) is preferred. 1 a The benzotriazine silver (1) has little change over time in the synthesis of the powder. &gt; 邑 is white, because the light is yellowish. In addition, the heat is relatively black, and the anti-solid agent becomes black and changes. 708到1701 does not have 7082-9000-PF; Ahddub 11 200812984 The antibacterial agent of the present invention is generally composed only of benzotriazine silver represented by the above formula α), or contains the compound and contains other components. . In the case of the present invention, the antibacterial agent of the present invention has a particle diameter of 5 to 5. Mouth, special 疋〇. 1 1 ο V m narration, the antibacterial agent is used in a cosmetic composition, a combination of a raw material, a resin composition, a resin composition, a paint, a plant bactericide, etc. For various purposes, the dispersion will be better. The particle size is determined by SEM observation of the particles. Further, the antibacterial agent is preferably 5% by weight or less, and more preferably 3% by volume or less. When the moisture content of the range is used, it is possible to prevent the dehydration or foaming of the resin product at the time of high-temperature molding or the expansion of the coating film of the paint when it is kneaded in the resin:&apos; or blended with the paint. In the present invention, the benzotriazole silver compound represented by the above formula [1. 弋 (1) is prepared by the above formula (7) in a mixed solvent of water and an organic solvent: The water-soluble silver compound is reacted to produce a specific 5, and the aqueous solution m can be prepared by arranging, and the solution of the above formula (2) dissolved in water in an organic solvent (B1 solution), < It is produced by a combined reaction and is preferably used as a β1 liquid, especially when a solution of a benzotriazine compound is dissolved in a solution of a B1 liquid solution, and the mixed melting point of the diol is preferable. f, , σ crystal orientation The method for producing the surface of the above formula (1) will be described below with reference to the above formula (2): the Rp R2 system in the present formula is equivalent to the above formula The formula of the compound... and the tearing. The base of (8), and the water-soluble 7082~9000-PF as the other side; Ahddub 12 200812984 Silver compound can be used, for example,

艮S-day silver, silver chlorate, silver perchlorate, silver fluoride, silver hexafluorophosphate, and the like. A 'Dan Than' may be an aqueous salt or a water-soluble silver compound. Examples of the organic solvent that can be used include alcohols and ketones having 1 to 5 carbon atoms such as T alcohol, ethanol, propanol, butanol, and pentanol. Among them, alcohols can be obtained in a good manner. The point of sex is particularly good. The water-bathing silver compound in the A1 liquid has a degree of 0.1 to 1.0 mol/L, and is 0.3 to 0.8 mol/L. Further, it is also possible to estimate that the ruthenium 1 solution is a water and an organic solvent in the range in which the water-soluble silver compound can be dissolved, and the solvent of W. At this time, the blending ratio of water to the organic agent varies depending on the type of the water-based silver compound or the type of the organic solvent used in the use of the eve pa η, but in the case of multiple emperors and eves, the weight of water is 100. The organic &gt; granules are 5 to 50 weight parts, especially η: I will be better than 5 to 30 parts by weight. The concentration of benzotrisole represented by the above formula (2) in the β1 solution is . .... ear / L' is especially. · 3 ~ 2 Mo / L is better. Further, the B1 liquid is also a mixed solvent which can dissolve the above formula (8, octyl benzotriazole) and an organic solvent. ^ ^%%, the ratio of the water to the organic solvent in the B1 solution Although it is based on the use of — 丨 丨 , , , , , , , , , , , , , , , , 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷50 reset parts, especially 5 勹 小 xiao, 里 邛 邛 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 糸 糸 糸[Bis(benzotris)-silver-stone sulphate: the amount of solvent of the reaction system represented by the above formula (1) which is not capable of obtaining the object of the present invention = the triazole silver compound, and the other tenth aspect If too much is not economic, it will make A1 liquid blood b 1 ', state eve, and song also reach ^1, and the night's degree is better than the above range. Adding A1 liquid is the benzotriazole compound in B1 liquid for 7082 -90〇〇^pF;Ahddub i3 200812984 A water-soluble silver compound in A1 liquid is benzotriazine (10)i)} 』~倍莫耳,特Do not use 5 times Mo. The reason is that the amount of the benzotriazole to the water-soluble silver compound exceeds 2·〇 imo, which produces a water-soluble complex of benzotris and silver to reduce the yield, and on the other hand, the product is not full. ^ The unreacted cockroach remains in the reaction liquid and becomes uneconomical. In the reaction conditions, the reaction temperature is preferably 0 to 5, i 〜 3 (the rc is better, the reaction time is preferably more than i hours, more preferably 3 to im, more preferably. The solid-liquid separation method recovers the target product', and then, by drying, pulverization and classification as needed, the present invention can be obtained by using the above-mentioned formula (1) of the present invention. Further, a compound capable of releasing an antibacterial metal ion of a zinc compound or a copper compound may be used in combination, thereby increasing the antibacterial range, (8) extending the duration of the antibacterial property, (6) improving the weather resistance, and (D) improving the resistance. The effect of pharmaceuticals, etc. Silver, the combination of rhetoric or / and copper and the ratio of blending can be selected according to the purpose of the task, or the combination of multiples. Especially the disk &quot; whitening point is better. The combination of zinc can be The antibacterial agent month &amp; as a copper-containing compound used together with the benzotrisinated silver represented by the above formula (1) of the present invention can be used as an ion exchange-supporting copper=or dish acid Antibacterial agent. Also, it can be used for ion exchange introduction. a product of a layered sulphate or a clay stone. In the present invention, in particular, a compound having a small solubility such as olfactory copper (10), copper carbonate Cu2C 〇3, strontium oxalate, ruthenium ruthenium, etc., is further processed to solubility. Small and antibacterial: Preferably, the benzotrisyl compound represented by the above formula (7) is the best. 7082-9000-pf; Ahddub 14 200812984 The above formula (3) is only slightly soluble, f is stupid and The trisin compound has a compound having sufficient properties as an antibacterial agent for water, and is the first discovery by the present inventors. The benzotriazole of the formula (3) In the formula of the copper sulphate compound, it is a methyl group, a sulphate, a sulphate, an aryl group, a phenyl group, a toluene, a propyl group, a butyl group or the like. The number of 1 to 5 is better. $子 can be τ phenyl, naphthyl is preferred. As a glutininogen, 虱, bromine, iodine. 0~2 敕 。. ν Ρ 2 and q2 are the same or different , 正, ., , ' ^ and R4 may be the same group or a different group. The benzotrisine compound represented by the above formula (3) Preferred specific compounds are - poor one cow and one triazole copper (II), bis (4-methylbenzotriene = copper ((1), bis (5-methylbenzotrim) ((1) , double u-ethyl benzo:: copper one (11), bis (5-ethyl benzotriazole) copper (11), double (4,5-dioxin and a copper (1)), double (4,6-dimethylbenzotriazole) copper (II), bis 5,6-methyl 4 and tri-Wow) copper (1)), bis(4,5-diethylbenzotris) copper ( II), bis (4 6- - r its f--, _ ethyl benzo-triazole) copper (II), bis (5,6-diethyl present: - copper (1)), bis (4-phenyl Benzotriazole) copper (1)), bis(5-phenylbenzotriene). Copper (1)), bis (4~chlorobenzotris) copper (1)), bis (5-gas benzotriene, sitting) copper ((1), etc., among them, especially in the following structural formula (5) Copper dibenzotriazole (; [丨) is preferred.

3a) 7082-9000-pF; Ahddub 15 200812984 Organic = benzotris-copper compound represented by the general formula (3), which can be represented by the above formula (4) by a mixed solvent of water and an organic agent The trisal compound is produced by reacting with a water-soluble copper compound. Specifically, the liquid-soluble copper compound can be dissolved in water, and the stupid and three-salt represented by the above formula (4) can be combined with the solution of the organic solvent. Adding a β2 liquid into a: butyl reaction to produce. As the B2 liquid, it is used in combination with water and alcohol (4) bath solution. When the solution of the compound is taken, it is preferred to obtain a highly crystalline reactant. The following describes the production method of the benzotrisyl copper compound represented by the above formula (3). R3 and R4 in the formula of the benzotriazole compound represented by the above formula (4) correspond to the groups of the above formula (3) and the group of h, and further, 2 and Q2 are indicated. An integer of ~2. As the other water-soluble copper compound, for example, 'copper sulfate, copper perchlorate, copper fluoride, tetra-rat copper borate, copper formate, copper chlorate, copper nitrate or the like can be used. Further, the water-soluble copper compound may be an aqueous salt or an anhydrous silver. The organic solvent can be used, and examples thereof include alcohols and ketones of carbon number such as methanol, ethanol, propanol, butanol or pentanol. Among them, the 'alcohol is particularly excellent in crystallinity. The concentration of the water-soluble copper compound in the A2 solution is 〇ι~ι〇mol, and is 0.3 to 0.8 mol/L. Further, the A2 liquid may be a mixed solvent of water and an organic solvent in a range in which the water-soluble silver compound is soluble. In this case, the ratio of the water to the solvent is different depending on the type of the water-soluble silver compound used and the type of the organic solvent. In most cases, the organic solvent of the weight of the water is 5 to 50 parts by weight, especially It is better to use 1〇~3〇 weight. 7082-9000-PF; Ahddub 16 200812984 The concentration of benzotriazole represented by the above formula (4) in n彳S liquid is particularly preferably 0.3 to 2 mol/L. Further, the B2 liquid is soluble in the above formula (4): it may be a mixed solvent with an organic solvent. At this time, the water blending ratio of the range of the second and the second saliva varies depending on the type of the formula: the type of the broad-available/gluten-silver compound, but the ##, the secondary organic solution/the water 10° weight portion The organic solvent is 5, heavy summer, especially with &quot;. The weight is better. J is the addition of B2 liquid to A2 liquid, β2 △ r r, the bis-oxazolidine 舲 A2 liquid, the f-soluble copper compound is stupid and three-salt ((4) 〇 2 · RI # inch 疋 疋 2.0~2· 1 time Mo is preferred. The reason is that the amount of benzene on the water-soluble copper compound exceeds 2.5 times mole, which produces benzo: saliva: a water-soluble complex of copper to reduce the production - the upper side of the production , less than 2 times grass 5, unreacted Cu remains in the reaction liquid, and it becomes uneconomical. The reaction conditions make the reaction temperature better than 〇~50〇C, and the reaction time is 1〇~3〇 'It is better to work for more than one hour, and m〇 is better.- After the end, the object is recovered according to the conventional solid-liquid separation, and then dried, pulverized as needed, and classified, and can be used on the present invention. The benzotriazole silver represented by the above is the ion-exchanged compound which is used as the zinc-containing compound represented by the above formula (1) of the present invention. A previously used antibacterial agent such as zeolite or zirconium phosphate. Further, °, ', 1 is used to introduce a layered tantalate or clay ore by ion exchange. Products: Yu Numing, especially zinc carbonate ZnC〇3, zinc sulfite dihydrate ZnS〇3. Bing 2, Nitrogen Oxide 靡2, Orthogonal Zinc Oxide Zn Secret, Zinc Oxide-Zinc W ^ 082-9000-PF; Ahddub 17 200812984 and other compounds with low solubility are preferred. In the antibacterial agent of the present invention, the above-mentioned formula (1) is used in combination with the bis-oxazolyl compound, and the water-insoluble silver-missing salt. In the above, the antibacterial agent of the present invention can be suitably used in a resin composition, a resin composition, a resin composition which is formed by the group, and which is formed into a dough and which is formed into a mouth material. Mouth, and fungicides for plants. σMaterials The antibacterial agent of the present invention can be used in various forms in the form of & At (4)". The antibacterial agent can be used for modifying the left side discoloration without damaging the effect of the antibacterial agent, such as a dispersant, a surfactant, a coupling agent, a white mouth, an antioxidant, and an ultraviolet absorption. The surface treatment of the agent or the like is not particularly limited as the dispersant, and for example, a class or a low-melting point resin can be used. (1) Fatty acids and their metal salts · · Synthetic or natural fatty acids and these alkali metal or alkaline earth metal salts, zinc salts, and so on! Lu salt and so on. For example, stearic acid, oleic acid, etc., and the like, and the like. 1 (2) Indoleamines, amines: For example, erucic acid amine, (Ζ)-Ν-9-octadecyl-hexadecane, stearyl phthalate, 2-stearylamine Ethyl stearic acid, ethylene double fatty amide, ν, ν, oleic acid stearyl ethylene diamine, hydrazine, hydrazine, bis(2-hydroxyethyl)alkyl (C12~C18) Indoleamine, hydrazine, Ν' bis (ethyl) laurel, fatty acid diethanolamine, and the like. (3) Fatty acid esters and alcohol esters 7082-9000-PF; Ahddub 18 200812984, for example, n-butyl acid, methyl abietic acid, dibutyl sebacate (n-butyl ester), hydrazine Dioctyl diacid (2-ethylhexyl, n-octyl), 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, and the like.曰(4) wax: For example, whale wax, mineral wax, palm wax, honey wax, wood wax, sheep/fat, polyethylene wax, polypropylene wax, epoxy modified polyethylene wax, petroleum system (wax Etc.... C5) Low melting point resin: melting point or softening point is 40~200 °C, especially 70~16 (various trees of TC such as epoxy resin, diphenylbenzene-tantalum resin, styrene resin 1 Benzophene eucalyptus, other petroleum resins, alkyd resins, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, low melting point acrylic resins, polyvinyl butyral, low melting copolymerized decylamine, Low-melting point copolyester, etc. (As a surfactant, generally, a cationic one such as a pseudo-primary amine salt, a tertiary amine, a quaternary ammonium compound, or a pyridine derivative, (B) a sulfated oil, a soap, or a sulfuric acid can be used. Ester oil, sulfated guanamine oil, sulfate salt of olefin, fatty alcohol sulfate salt, alkyl sulfate salt, fatty acid ethyl sulfonate, k-nine acid salt, alkylbenzene sulfonate, An anionic group such as succinate sulfonate or phosphate ester, (c) a polyvalent alcohol a fatty acid ester, an ethylene oxide adduct of a fatty alcohol, an ethylene oxide adduct of a fatty acid, an ethylene oxide adduct of an aliphatic amine or a fatty acid decylamine, an ethylene oxide of an alkyl phenol Addition product, ethylene oxide adduct of alkyl naphthol, partial fat of the polyvalent alcohol 7082-9000-pf; Ahddub 19 200812984 Ethylene oxide adduct of acid ester, (D) ^ ♦ A non-ionic carboxylic acid derivative such as an alcohol or an imidazole compound such as an imidazoline derivative. As the coupling agent, for example, the following may be used: (1) Crucible crucible coupling agent: r-aminopropyltriethyl Oxygen, &quot;(aminoethyl)-aminopropyltrioxoxadecane, N-stupyl-"aminopropyltrimethoxyxanthine, &quot;(aminoethyl)gamma-aminopropyl Amino decane such as methyl dimethoxy decane, methacryl oxiran oxane such as fluorenyl propylene oxypropyl trimethoxy decane, vinyl dimethoxy ethoxy decane, vinyl triethyl Vinyl decane such as oxoxane, vinyltrimethoxy decane or vinyltrichlorodecane. /5 (3,4% oxy-J-hexyl)ethyltrimethoxide, epoxy propylene oxide Epoxy decane such as propyl trioxoxane or r-glycidoxypropylmethyldiethoxy decane; fluorenyl decane such as τ-mercaptopropyltrioxane. 7-Chloropropyl Chloropropyl decane such as trimethoxy decane. (2) Titanate coupling agent:

Isopropyl triisostearyl strontium titanate, propyl trilauryl benzoate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraoctyl bis (disc acid) -tridecyl ester) titanate, tetrakis(2,2-dipropenyloxydecyl-1-butyl)bis(di-tridecyl)phosphate titanate, bis(dioctyl pyrophosphate) Ester) oxyacetic acid titanate, bis(dioctyl pyrophosphate) ethylene titanate, isopropyl trioctadecyl titanate, isopropyl dimethyl propylene oxime isostearyl strontium titanate Propyl isostearyl phthalate titanate, isopropyl tris(dioctyl phosphate) titanium sulphate, isopropyl tricumyl phenyl titanate, isopropyl tris(N-amino group Ethyl-aminoethyl) titanate, diisopropylphenyl phenyl oxetane titanate _, diiso 7082-9000-PF; Ahddub 20 200812984 Stearic acid lanthanum titanate, polydipropylene Wupropyl titanate, tetra-n-butyl titanate, poly-n-butyl titanate. As an inorganic discoloration preventive agent, I 4 , π 1 ^ 蜊 准 例如 例如 例如 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水Composite hydroxide carbonate and the like. Benming's antibacterial agent can be used in combination with other inorganic antibacterial agents. For example, 'ion exchange or zeolite carrying an antibacterial metal ion, apatite, phosphoric acid, or diarrhea, bismuth acid, glass, and the like.

The antibacterial agent of the present invention and the preservative are used in combination. For example, it can be mixed with other organic antibacterial agents, bactericides, hydrazine thiol, etc.; quinone-based parabens; organic acids such as benzoic acid and dehydrated acetic acid; Acid salts; fourth-grade strontium salts. Specifically, it may be thiol, chitin, benzoic acid, benzoate, isopropyl 19, undecylenic acid monoethanolamine, cetylpyridinium chloride chlorinated decylamine Glycolglycine, gasified chlorhexidine, cresol, chloramine, chloroxylenol, chlorocresol, chlorobutanol, salicylic acid, salicylate, milufen, sorbic acid and salts, Thymol, Dean, dehydrated acetic acid and salts, aniline fc dichloro, p-oxybenzoic acid ester, p-phenol, halogenated aniline, dentate, /, chlorine, lauric acid Sodium, resorcinol, yoshidan (polyethylene σ ratio alkanone iodine complex) and its lake crystal cage, iodine alkyl polyether alcohol complex (GS I), polyethoxylate Polypropoxypolyethoxyethanol·iodine complex (I 〇c ill ne), nonylphenoxypolyethoxyethanol·iodine complex, polyoxygen, chlorinated vegetable oil·moth complex, Polyoxyethylene Addition Fatty Acids, Dishes, Oxygen Ethylene Ethylene, Fatty Alcohol, E. Complex, Fatty Acid, Indole, Moth 7082-9000-pF; Ahddub 21 200812984 Complex. ... the antibacterial agent, due to the dispersibility of various resins (good, and less discoloration tendency σ) ... can be adjusted to various resins (poly people) resin group with resistance to bismuth, |. For use in u L or resin molded articles, for example, reticle, tube, plate, container, wire, sister, fiber, film, and the antibacterial agent of the present invention are blended in 泠, cheng. In addition, it can also be used in the field of antibacterial coatings as the upper and the f's Tusho Temple. There are no special restrictions on the resin as follows. For example, polyethylene and poly-binders can be used. For example, the resin can be removed by agglomeration, and the polyethylene (A) resin can be exemplified; for example, polyvinyl chloride ABS resin, poly-, polyphenylene B: Polychlorinated resin for polysulfurization; polyamine, K-vinyl, polyacetal, polyvinyl alcohol, acrylic resin, fluororesin, _X-anti-曰, I wind-day elastomer, polyester elastomer , phenol shaker, urea resin, dense π (10) 曰 曰, unsaturated poly ruthenium resin, epoxy resin, cyanide resin, tannin, gong Gong, copper ammonium, acetate, triacetate, A thermoplastic resin or a thermosetting resin such as ethylene or a natural rubber or a synthetic rubber. Further, 'the resins' may be a copolymer or a graft polymer or two kinds of a resin (four). In particular, the above resin Among them, a polyolefin resin, a vinyl chloride resin, or an ABS resin is preferred. 7 When the antibacterial agent of the present invention is blended with a paint, the material of the paint may, for example, be oily such as cooked oil, oil varnish or oil enamel. Cellulose derivative coatings such as paint, nitrate, cut-off, quasi-redundant paint, acrylic paint, etc. A thermosetting resin or an elastomer polymer described in the above-mentioned resin material is used as a coating type synthetic resin coating material. For materials used for blending with a resin or a coating material, a previously used material may be used. Mineral oils, plasticizers, solvents, no 7〇82-90〇〇-pF; Ahddub 22 200812984 Stick fillers, pigments, micro-powders of sulphur dioxide, = as inorganic fillers, e, rolling Aluminum, aluminum-containing layered niobate and its two =, = body, layered magnesium, hydrotalcite, rheologically modified hydrotalcite, :" emulsion salt, talc, clay, bentonite, dawsonite, bath Soil, sand, calcium carbonate, etc. Shape 1 is a molded article of a resin which blends the antibacterial agent of the present invention, and includes any paper such as 'woven fabric, non-woven fabric, mesh fabric, knitted fabric, etc.; oblique,:,: sheet product; dispersing agent, spray agent Powder products; brush coating: two = paint, roller coating, adhesive, sealant and other liquid or paste clothing mouth, plate, rod, box, porous body, etc. have formed products. As a resin molded article or coating for blending the lipid antibacterial agent of the present invention, steam can be used for fresh film or sanitary material product, kitchen bathroom product, cosmetic I: sputum, water treatment product, medical device product, building material product, fishing net, and the like. 2: Cement concrete products made of cement plaster or molded body of cement concrete. In addition, clothing and various products. The purpose of the application of the antibacterial agent is to blend the resin composition of the antibacterial agent of the present invention, and the antibacterial amount is based on the physical properties of the antibacterial agent, particularly the antibacterial component. It varies depending on the type of resin or its use. More love π. Resin m weight part. · Bu 3. The range of weights is good. : The system is better at the weight. In particular, the resin composition composed of the master batch was combined to 30 parts by weight. When the blending amount of the antibacterial agent is less than the weight portion, the antibacterial effect of the resin composition cannot be obtained. Further, the amount of blending: the limit body is limited by economic reasons, and is set in a practical range. '7082~90〇〇-PF; Ahddub 23 200812984 [Examples] The following examples are specifically described to illustrate the present invention. Each of the measured values in the examples was obtained by the following method. (a) Composition analysis: The antibacterial metal system was quantified by ICP (LIBERTY π type manufactured by Varian). The benzotriazine is measured by the total organic carbon (manufactured by Shimadzu Corporation, T〇c-5〇〇〇α), and is quantified by conversion into molecular weight. (b) Shape of the particles: f. Observed by SEM (Hitachi Seisakusho S-4500). (c) X-ray diffraction pattern (xrD): An X-ray diffraction device (RINT24 type) was used. [Example 1] 1 0 : 1) Mixed solution

On average, about 0.70 g of silver nitrate was dissolved in water-ethanol (weight ratio of 2,200 g, as a solution of A1, benzotriazine (cn; pure chemical reagent) i4 alcohol (weight ratio 10: 1) 220 g of a mixed solvent, and the reaction mixture was added to the A1 solution as a liquid to carry out a reaction at 25 C for 3 hours. The filtration and washing with water were carried out by drying i 〇 small _ p (I) at 50 ° C. The obtained benzotriazole Silver (I) was subjected to elemental analysis of Ag(C6H5N3)i.iG. Further, by X〇. (3 Drying minus denier to TJs, the results of XRD measurement are shown in Fig. 1 and Table 1. The photograph is shown in Fig. 4. In the SEM photograph, the particle size of the particles is 0.1 to the thickness of the plane nc 708 708-9000-PF; Ahddub 24 200812984 [Table 1] 2θ 间隔 spacing d (A) 6.57 13.4 13. 18 6.71 19.53 4. 54 24. 65 3.61 26. 85 3.32 [Example 2] Silver nitrate 2〇.〇g was dissolved in 240 g of a water-ethanol (5:1 by weight) mixed solvent as an A1 solution. For the molar amount of silver nitrate, 2 times equivalent of benzene was used. And triazole pure chemical reagent) 28· 1 § dissolved in water-ethanol (weight ratio 5: 〇 mixed solvent 24 〇 g, as B1 liquid. B1 liquid is slowly added to A1 liquid at 20 ° C The reaction was carried out for 6 hours, and the precipitate produced by the cockroach-rich was filtered and washed with water, and benzotriazine silver (1) was obtained by scratch drying for 24 hours. The elemental analysis of the obtained benzotrivial silver (1) was carried out*, and the composition was

Ag(CeH5N3)i.2i. In addition, the moisture of each reduction is 2% by Π c°c. The measurement results of XRD are shown in Fig. 2 and Table 2. Again, the SEM photographs of these are not shown in Figure 5. In the SEM photograph, the shape of the particles d is a crystal having a rounded edge or even a rectangular parallelepiped, and the particle size is about 0.3/m. Sentence [Table 2] 2 (9 (°) face spacing d (lT 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 7082-9000-PF; Ahddub 25 200812984 [Example 3] 41 steel (1)) pentahydrate 2QQg was dissolved in 125 g of a water-ethanol (heavy denier 4:1) mixed solvent as an A2 solution. For sulphur two, 2 彳立岑旦 AA # , ~ Wu Dou number. The intrinsic triazole in the field (Cdl; the pure chemical test reagent dissolved in water-ethanol (4:1 by weight) mixed solvent is called as / / B2 liquid is slowly added to the A2 solution to the muscle The reaction is "hours." = The raw material of the living room is dried and washed with water, and dried by 2 rc to obtain f and di-sphat copper. The obtained benzotris-ethyl ((1) elemental analysis of the composition is (10) secret) The measurement results of XRD are shown in Fig. 3. Further, the SEM photographs of these are shown in Fig. 6. In the _ photograph, the shape is close to the ball, and the one is agglomerated into a rod. "Primary particles": 〇· 03~0·3^' is about 0.1/zm on average. [Table 3] 2θ〇7.59 20.3 31.7 septum d(A) ~06 4. 37 2.82 [Example 4] Benzene obtained in the present Example 1 And antibacterial It was confirmed that the azole silver powder was 5 g, and 45 g of pure water was added and stirring was continued for 24 hours. Thereafter, the powder was separated by filtration to recover water, and the concentration of silver in water as chemical was 5 qing. The dissolution test was repeated: For a long time, the silver concentration in the water was also measured for the 35th dissolution test solution. The concentration of silver in the water of 35 times was 〇16 ppm.

[Reference example 1J 7082-90〇〇-pF; Ahddub 26 200812984 Use a broken glass beaker, in acetic acid X and one in B% 40 weight! Add a 23-8 weight portion of the open azole (C6H5N3; pure chemical test 觫华觫甘 A A), stir for 10 minutes to dissolve. Then add 17 7 蚩 蚩 石 石 你 / / / / / / / / / / / / / / 8 夂 silver and 16 〇 〇 〇 〇 。 。 夂 夂 夂 夂 夂 夂 夂 夂 夂 夂 夂 夂 夂 夂 夂 夂 夂 夂 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解N〇r, ^ JO inch elbow white precipitate filtration, washed with water to dry for 24 hours. So obtained, ^ J曰 has been a day. The crystal in XRD did not endure the presence of benzene and three read Ag, from red The analysis and the measurement confirmed the riding (the crystallization of the benzotriene [^(cn) ship 1]. Then, in the same manner as in the example 4, the anti-g component was confirmed, and the obtained double (stupid and three saliva) was obtained. Silverstone Xiaoyan powder (4) Human pure water sputum continued to search for Xiaozhe Shou. After that, 'filter separation and removal of powder, 16 water recovery. The water was chemically analyzed, the silver concentration in water was 800 Ppm. Furthermore, the dissolution test was repeated. 35 times, regarding the 35th dissolution test solution, the silver concentration in the water is also measured. The concentration of silver in the water is 〇·1 ppffl. And almost no silver dissolution, has not seen the dissolution of the antibacterial ingredient.

[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 antibacterial agent obtained in Example 3 with the antibacterial agent of Example 1 (C), an antibacterial test was carried out. The test results are shown in Table 4 below. The test method is as follows. A) Test bacteria (1) Escherichia coli NBRC 330 1 (coliform) (2) Pseudom〇nas aeruginosa NBRC 1 3275 (P. aeruginosa) (3) Aspergillus niger IFO 6341 (B. meliloti) 7082-9000-PF; Ahddub 27 200812984 (4) Penicillium citrinum IFO 6352 (penicillium) B) Test medium ΝΑ medium: common eucalyptus medium [Essence Chemical Co., Ltd.] ΝΒ Medium: Add gravy 〇 2% of ordinary broth medium [Yongyan Chemical Co., Ltd.] PDA medium: 钤 钤 葡萄糖 葡萄糖 葡萄糖 [ 荣 荣 荣 荣 荣 S S S S S S S S S S S S S S S S S S S S S S S S S S S S S 荣 荣 荣 荣 荣 荣 荣 荣 荣The test bacteria cultured in the NA medium at 37t:±rc for 24 to 48 hours were inoculated into the NB medium, and cultured at 37 t ± lt for 22 to 26 hours. The culture medium of 4 was adjusted to 1 〇 6 〜 1 〇? by using NB medium to adjust the number of bacteria as sputum. b) Test bacteria (3) and (4) After culturing for 7 days with PDA medium at 25 C ± 1 C, the formed cells are suspended in physiological saline supplemented with G.G5% polysorbate, and the ω is adjusted. The number of cells is 1〇6~107, which is used as a bacterial solution. D) Preparation of test plate culture medium Test bacteria (1) and (2) with NA medium, test bacteria (3) and (4) with SDa medium ISOnd ' separately added, mixed bacteria 1 〇m b this split I5mi is cured in k-culture dish. Further, the culture dish was allowed to stand at room temperature for another minute. After the surface of the I medium was dried, it was opened by dry heat sterilization (i8 (rc, 3 〇 minutes) of round enamel glass (diameter: 12 mm), and this was used as a test plate medium. 7〇82-90〇〇-pF; Ahddub 28 200812984 E) Test operation The sample was used as a sample. The sample was filled in the center of the test medium, and the test bacteria (1) and (2) were cultured for 24 hours at 37t:±rc, and the test bacteria (3) and (4) were cultured at 25°C±1°c for 7 days. Visually observe whether there is a halo around the material. In addition, the number of bacteria in the bacterial liquid is tested in bacteria (1) and (7) by using a mixed medium culture method using NA medium (37. 〇±1, culture for 2 days): in the test (7) and (4) to use SDA medium. Mixed plate: method (25t: ± rc, cultured for 7 days), the concentration of bacteria per plate of test medium was calculated. [Table 4] Test bacteria concentration (/ml) A Antibacterial agent r\ (1) Coliform 1.6xl06 + U + C + (2) Green version 囷 x IXxx + + + (3) Black cockroach 5. lxl 〇 5 (4) Penicillium 6.3x105 +· can be confirmed to the amount of garden soil ----------- + ------ 1 ---- + + + + Shi - · can not confirm the halo WKT-D)/2

WTD halo width sample and halo length total sample length ϋ Example Waow silver (I) 2 [Example 6 and reference array 2, comparative example comparative example 2] In this example and comparative example A vinyl chloride sheet 6 was produced, and as an antibacterial agent, benzo 7〇82-90〇〇-PF/Ahddub 29 200812984, which was produced in the Example, was blended. In Reference Example 2, the bis(benzotriazole) silver nitrate 2 weight portion produced by the applicant/test was blended. In the comparative example, y r 0 _ A sub-adjusted antibacterial agent. In Comparative Example 2, the silver of the commercially available antibacterial agent was removed from the household and the weight of the zeolite was changed. The gas-electric sheet was produced in the following manner. The blended resin composition shown in Table 5 below was vigorously shaken and mixed in a plastic bag coat. The obtained composition was melt-kneaded by a double roll having a surface temperature of 150 t for 5 minutes, and then formed into a sheet shape to prepare a test piece of a gas sheet having a thickness of 1 mm and 5 (10). [Table 5] Polyvinyl chloride CZJiON 1U3EP) ~- iOO weight Shao - 50 weight D0P ~ ring gasification big tongue ^ one - Ba-Zn system: 3⁄43⁄43⁄43⁄4 agent '~~&quot; 3 weight rock 戸 1. 5 weight Ba Zn-based powdered stabilizer 〇. 5 parts by weight Zn-A type zeolite stabilizer (ZEOSTAR ZA-100P manufactured by Sakamoto Chemical Industry Co., Ltd.) 1 part by weight antibacterial agent --- _2 by weight of the above-mentioned ethylene-ethylene sheet, as follows Methods The discoloration resistance test and the antibacterial test were carried out. The results are shown in Table 6. [Discoloration resistance test] A test piece of a vinyl chloride sheet was placed in a position of lm under a fluorescent lamp (60 Wx2), and the degree of discoloration was evaluated by the following score after exposure for 30 days. (3) No discoloration X: Significant discoloration [Antibacterial test] The antibacterial product was evaluated according to the method established by the antibacterial evaluation test method (Antibacterial Products Technology Association 7082-9000-PF; Ahddub 30 200812984). : Membrane adhesion method to evaluate strains: coliform, dragon-, and wide-stretched Staphylococcus aureus sputum vaccination time: 2 4 small care evaluation: add antibacterial agent such as τ plus molded product inoculation liquid, to determine the old mold The number of bacteria after 24 hours, ... 禋囷 禋囷 • • • • • • • • • • • • 如下 如下 如下 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 减少 ' 减少 ' ' ' ' ' ' ' ' ' ' 1/10 or more, less than 1/100. X: The reduction rate of the inoculum was less than 1/1 〇. [Table 6] Test item Example 6 ^ Discoloration resistance test δ] Comparative Example 2 Reference Example 2 Antibacterial Sexual test 〇 Δ 〇 X 〇 [Simplified description of the drawings] Fig. 1 is an X-ray diffraction diagram of the di-n-, di-t-bis oxadiazole silver (I) obtained in Example 1. Figure 2 is a diagram of Example 2. Xi Jiguang, the X-ray diffraction pattern of the triazole silver (I). Figure 3 is the benzotrisine obtained in Example 3. (9) The X-ray diffraction pattern is shown in Fig. 4. Fig. 4 is a SEM photograph showing the particle shape of the benzotriazole silver (1) obtained in Example 1. Fig. 5 is a view showing the silver benzotriazole (J) obtained in the second embodiment. SEM photograph of particle shape. 7 082-9000-PF; Ahddub 31 200812984

Particle shape of copper benzotriazole (11) obtained in P Fig. 6 is a SEM photograph showing an example. [Main component symbol description] No 0 7082-9000-PF; Ahddub 32

Claims (1)

200812984 X. Patent application scope: 1. An antibacterial agent comprising: a benzotriazole salt compound represented by the following formula (1): Wherein 4 and 1^2 represent the same or different alkyl group, aryl group, halogen atom, thiol group, amine group, pl and ql system, and represent the same or different integers. 2. The antibacterial agent described in the first paragraph of the patent scope, wherein the benzotriazole silver compound + is dissolved in a mixed solvent of water and an organic solvent, and the benzotriazole compound represented by the following formula (2) is dissolved in water. The silver generator reacts with the producer: (Ri)P&gt;&lt;&quot;VA N Wherein Ri, R2, Pl, and ql are synonymous with the above. 3. The antibacterial agent according to claim 1, wherein the benzoxazole silver compound is silver benzotriazole. — 4· If you apply for a patent scope! The antibacterial agent according to the invention, wherein the particle diameter is 粉.〇5~, and the water content is adjusted to 5% by weight or less. 5. The antibacterial agent of claim 1, wherein the method comprises: a compound containing copper or/and a compound containing zinc. 6. The antibacterial agent according to claim 5, which comprises a compound of Na 7 08 2-9000-PF; Ahddub 33 200812984, which is represented by the following formula (3). In the formula, R3 and R4 represent the same or different alkyl group, aryl group, halogen atom, f-hydroxy group, amine group or carboxyl group, and P2 and q2 represent the same or different integers of 〇~2. 7. A method for producing an antibacterial benzotriazole silver compound, which comprises producing an antibacterial benzotriazole silver compound represented by the following formula (1), wherein: in a mixed solvent of water and an organic solvent, The benzotriazole compound represented by the following formula (2) is reacted with a water-soluble silver compound: 8 · A method for producing an anti-i-benzotriazole silver-plated δ substance as described in the patent application No. 7 of the patent, wherein the organic solvent is an alcohol. 9 · An antibacterial benzodiazepine handle, + , an open-on-copper compound characterized by the following four general formula (3): 34 7〇82-90〇〇-pF; Ahddub 200812984 Wherein 'R3 and R4 represent the same or different alkyl group, a halogen group, a halogen atom, a trans group, an amine group or a carboxyl group, and p2 and q2 represent the same or different integers of 0 to 2. In the method for producing an antibacterial benzotriazole copper compound, an antibacterial benzotriazole copper compound represented by the following formula (3) is produced, which is characterized in that it is a mixed solvent of water and an organic solvent. The benzotriwax compound represented by the following formula (4) is reacted with a water-soluble copper compound. In the formula P2, R3, R4, p2, and q2 are synonymous with the above. Item 1 to 6 1 to 6. 11. A cosmetic composition comprising the antibacterial agent according to any one of the claims. The invention relates to an antibacterial agent according to any one of claims. 7082-9000-PF; Ahddub 200812984 I, 1 3. A coating comprising the antibacterial agent of any one of claims 1 to 6. A bactericidal agent for a plant, which comprises the antibacterial agent according to any one of claims 1 to 6. 7082-9000-PF/Ahddub 36 200812984 , VII. Designated representative map: (1) The representative representative of the case is: (2). (2) A brief description of the symbol of the representative figure: None. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention. N 7082-9000-PF/Ahddub