JP5542460B2 - Antibacterial / antifungal aluminum silicate and method for producing the same - Google Patents

Description

  The present invention relates to an industrial antibacterial agent and a method for producing the same. More specifically, the antibacterial and antifungal properties are imparted by adding an organic antibacterial agent to amorphous aluminum silicate, and an organic compound having antibacterial and antifungal properties is slowly released. The present invention relates to an antibacterial and antifungal aluminum silicate that is eluted and has excellent weather resistance such as heat resistance and ultraviolet resistance, and can be applied to a wide variety of uses, and a method for producing the same.

  Conventionally, organic antibacterial compounds include quaternary ammonium salts such as benzalkonium chloride and cetylpyridinium chloride, alcohols such as ethanol and isopropanol, aldehydes such as formalin and glyoxal, carboxylic acids, cresol and xylenol. Many are known, such as phenols, carboxylic acids such as sorbic acid and benzoic acid, guanidines such as chlorhexidine and n-dodecylguanidine acetate, and others.

  However, the organic antibacterial compounds described above are effective antibacterial agents against bacteria and sputum, but have poor heat resistance, relatively high vapor pressure, and high solubility in water and other solvents. Due to its characteristics, it may not be available depending on the mode of use. For example, when heating such as kneading into fiber, paper, film, plastic, rubber, etc. is required, or high dispersibility in an organic solvent of an antibacterial agent such as blending into paints or sealants is required In the case where the antibacterial effect is to be maintained for a long time in an open space or running water, it is difficult to obtain a sufficient effect, which is inappropriate.

  On the other hand, as an inorganic antibacterial compound that is superior in heat resistance compared to organic ones, aluminosilicate, clay mineral belonging to phyllosilicate and zeolite belonging to tectosilicate, antibacterial silver, copper, An antibacterial agent in which metal ions such as zinc are supported by ion exchange has been proposed (see Patent Document 1, etc.). Moreover, in patent document 2, there exists a proposal about the phosphate type | system | group antibacterial agent which carry | supported silver as an antibacterial composition of an ABS type resin composition.

  However, antibacterial agents loaded with metal ions have problems with discoloration resistance, and the antibacterial properties of metal ions in a clean water environment are high, but their antibacterial properties are significantly reduced in systems with a large amount of contaminants such as organic matter. There is a problem of doing. Furthermore, although antibacterial activity against bacteria can be expected, it cannot be expected to suppress moths and algae.

  In order to solve such problems between conventional organic antibacterial compounds and inorganic antibacterial compounds, an inorganic-organic antibacterial complex in which an antibacterial compound is introduced between layers such as a crystalline layered inorganic salt is used. Technology has been developed. By this technique, we succeeded in overcoming the drawbacks of organic antibacterial compounds, increasing heat resistance, lowering vapor pressure and solubility, and as a result, fiber, paper, film, plastic, rubber as listed below Many antibacterial agents with high antibacterial effect, which can be kneaded into an organic solvent and have improved dispersibility in organic solvents, have been proposed.

  For example, Patent Document 3 discloses an inorganic-organic composite in which an aliphatic primary amine is inserted between layers of a crystalline layered phosphate to improve the thermal stability of the aliphatic primary amine and impart hydrophobicity. Among them, it mentions the use of aliphatic primary amines at high temperatures and the realization of high dispersibility in resins and the like based on their hydrophobicity. In Patent Documents 4 to 6, the intercalation compound has an antibacterial effect by supporting a quaternary ammonium salt or thiazole compound having an antibacterial action between layers of a layered phosphate such as aluminum tripolyphosphate. In addition to the above, it describes that there are advantages such as thermal stability and stability to a solvent. For example, in Patent Document 5, the thermal stability of a compound obtained by inserting benzalkonium chloride into aluminum tripolyphosphate is the difference / thermogravimetric change. It is described that it rose to.

  However, according to the study by the present inventors, there is a problem with organic antibacterial agents applied to sustained-release antibacterial agents in any of the above-described conventional techniques. That is, quaternary ammonium salts represented by benzalkonium chloride are excellent in antibacterial properties against bacteria, but are inferior in antibacterial properties against sputum. On the other hand, imidazole compounds such as 2- (4-thiazolyl) benzimidazole are excellent in antifungal properties but inferior in antibacterial properties against bacteria. Therefore, the application of the sustained-release antibacterial agent as described above has a problem that it is limited by the microbiota of the environment in which the antibacterial agent is used. In order to exert effective antibacterial properties against many microorganisms, It involves restrictions on the state of use, such as the use of a large amount of the above-mentioned compounds or the need to use compounds together.

  Furthermore, according to the study by the present inventors, there is a problem in that a layered phosphate is used as an inorganic carrier. That is, when the phosphate antibacterial agent having such a structure is burned, there is a risk of formation of irritating gas, toxic phosphorus oxide or organic phosphorus compound. For this reason, from the viewpoint of toxicity to the human body and the environment, it is desired to use a naturally occurring inorganic salt as a carrier.

  In contrast, by changing the inorganic carrier from phosphate to layered silicate and supporting the antibacterial organic compound, the dispersibility of the layered silicate compound is enhanced and the sustained release ability of the antibacterial organic compound is increased. There is also a proposal for a compound to which is given. For example, Patent Document 7 proposes an antifungal agent in which a triazole-type antifungal organic compound is supported between layered silicate layers, and Patent Document 8 discloses an antialgae and antifungal treated with an alkylammonium ion. An inertial layered silicate is disclosed. In Patent Document 9, an isothiazole-based compound and / or an imidazole-based compound having excellent antibacterial and antifungal properties, and excellent heat resistance, such as heat resistance and ultraviolet resistance, is used as an interlayer between layered silicates. Has proposed a compound supported on.

  As described above, various sustained-release antibacterial agents obtained by inserting an antibacterial organic compound into a layered silicate have been developed. According to the study by the present inventors, these patents are similar to those described above. In the literature, there is a problem with organic antibacterial agents applied to sustained-release antibacterial agents. That is, triazole compounds such as α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazol-1-yl-ethanol, and 2- Imidazole compounds such as (4-thiazolyl) benzimidazole have excellent antifungal properties but are inferior in antibacterial properties against bacteria. On the other hand, quaternary ammonium salts such as alkylammonium ions and isothiazolone compounds such as 4-methyl-5-chloroisothiazolin-3-one are excellent in antibacterial properties against bacteria but are inferior to sputum. Therefore, the application of the sustained-release antibacterial agent as described above has a problem that it is limited by the microbiota of the environment in which the antibacterial agent is used. In order to exert effective antibacterial properties against many microorganisms, It involves restrictions on the state of use, such as the use of a large amount of the above-mentioned compounds or the need to use compounds together.

  In order to solve such problems, Patent Document 9 discloses, as an antibacterial composition, a layered silicate using an isothiazole compound having a high effect on bacteria and an imidazole compound having a high effect on sputum. Used. However, the present inventors believe that the antibacterial spectrum and the antibacterial activity are still sufficiently improved and there is room for improvement.

（ただし、上記一般式において、Ｒ₁およびＲ₄は、炭素数１〜４の直鎖若しくは分岐の同一または異なるアルキレン基であり、Ｒ₂およびＲ₅は、水素原子、同一または異なるハロゲン原子、低級アルキル基または低級アルコキシ基であり、Ｒ₃は、炭素数２〜１２の直鎖若しくは分岐のアルキレン基であり、Ｒ₆は、炭素数１〜１８の直鎖若しくは分岐のアルキル基であり、Ｚは、塩素原子、臭素原子、ヨウ素原子若しくはＯＳＯ₂Ｒ₇基（Ｒ₇は、低級アルキル基若しくは置換或いは無置換のフェニル基である）である。） As an inorganic-organic antibacterial complex improved in this respect, a compound in which a compound of the following general formula is supported between layers of montmorillonite which is a layered silicate has been proposed (see Patent Document 10).

(In the above general formula, R ₁ and R ₄ are linear or branched identical or different alkylene groups having 1 to 4 carbon atoms, and R ₂ and R ₅ are hydrogen atoms, identical or different halogen atoms, A lower alkyl group or a lower alkoxy group, R ₃ is a linear or branched alkylene group having 2 to 12 carbon atoms, R ₆ is a linear or branched alkyl group having 1 to 18 carbon atoms, Z is a chlorine atom, a bromine atom, an iodine atom or an OSO ₂ R ₇ group (R ₇ is a lower alkyl group or a substituted or unsubstituted phenyl group).

  As mentioned in Patent Documents 11 to 14, the compound of the above general formula is excellent in antibacterial properties, antifungal properties, and antialgae properties, and has excellent activity against protozoa and protozoa. Yes. Therefore, the antibacterial agent of Patent Document 10 is considered to be an effective antibacterial agent without being influenced by the biota.

  However, the compound of the above general formula cannot be said to have a high function when paying attention to the sustained release property of the antibacterial agent, and there is a problem in that the antibacterial power is continuously and effectively exhibited only by the above compound. For the purpose of solving such problems, as in the prior art, when an antibacterial layered silicate carrying the above compound is used as an antibacterial composition, the mixing ratio of the above compound in the preparation must be increased. There is a problem of not becoming. In this case, there is a possibility of affecting the performance and quality of the product as in the prior art.

  In view of the above problems, focusing on improving the sustained release property, the pore size is large and widely distributed as in the amorphous and regular aluminosilicates described in Patent Document 1 or 2. It is considered that the inorganic substance used may be used as the carrier. For example, in Patent Document 1, an antibacterial agent comprising a combination of an aluminosilicate and an organic antibacterial compound in which hinokitiol is adsorbed and adsorbed on a regular amorphous tectosilicate is manufactured and its antibacterial property is evaluated. ing. However, the present inventors think that even in this inorganic-organic antibacterial complex, there are problems in the antibacterial power and antibacterial spectrum of the antibacterial agent to be adsorbed and adsorbed, its usefulness is low, and there is room for improvement ing.

  As described above, an inorganic-organic antibacterial complex in which an organic antibacterial agent having any of antibacterial, antifungal and antialgal properties is carried on an inorganic salt has so far been a layered phosphate-organic system. Developed with the combination of antibacterial agent, layered silicate-organic antibacterial agent, aluminosilicate-organic antibacterial agent, and they have weather resistance and discoloration resistance such as heat resistance and ultraviolet resistance, and organic system This is an improvement in the sustained release of the antibacterial component. However, until the development of a composite that satisfies all of its antibacterial, antifungal and antialgal properties, has heat resistance and weather resistance, and has sustained release properties, However, the present inventors have realized that it is necessary to reexamine the combination of an inorganic salt serving as a carrier and an organic antibacterial agent serving as an antibacterial component.

Japanese Patent Laid-Open No. 3-120204 JP-A-9-12836 JP-A-5-32406 Japanese Patent Laid-Open No. 5-124806 JP-A-5-186208 Japanese Patent Laid-Open No. 5-213609 JP-A-10-176124 JP 2003-342527 A JP 2004-155967 A JP 2006-45074 A JP 2006-1889 A JP 2006-22031 A JP 2006-21105 A JP 2006-22069 A

  The present invention has been made by paying attention to the above-mentioned problems in the prior art, has heat resistance and weather resistance, and exhibits a killing effect on many microorganisms such as bacteria, sputum, algae, protozoa, In addition, an object is to provide an extremely useful inorganic-organic antibacterial complex that has sustained release properties that enable it to exert its antibacterial activity continuously and contributes to the expansion of its use, and a method for producing the same. .

（ただし、上記一般式（１）において、Ｒ₁およびＲ₄は、何もないかまたは炭素数１〜４の直鎖若しくは分岐の同一または異なるアルキレン基であり、Ｒ₂およびＲ₅は、水素原子、または同一若しくは異なるハロゲン原子であり、Ｒ₃は、炭素数２〜１２の直鎖若しくは分岐のアルキレン基であり、Ｒ₆は、炭素数１〜１８の直鎖若しくは分岐のアルキル基であり、Ｚは、塩素原子、臭素原子、またはヨウ素原子である。） The above object is achieved by the present invention described below. That is, the present invention is the silicate aluminum, to provide antibacterial, antifungal aluminum silicate compound represented by the following general formula (1) is characterized Rukoto such are sorbed and adsorption.

(However, in the above general formula (1), R ₁ and R ₄ are nothing or a linear or branched alkylene group having 1 to 4 carbon atoms, or R ₂ and R ₅ are hydrogen. atom or a same or different halogen atom, R ₃ is a linear or branched alkylene group having 2 to 12 carbon atoms, R ₆ is a linear or branched alkyl group having 1 to 18 carbon atoms, There, Z is chlorine atom, bromine atom or iodine MotoHara child,.)

As a preferable form of the antibacterial / antifungal aluminum silicate, the aluminum silicate is a powder having a particle size distribution of 150 to 350 μm; the aluminum silicate has a chemical formula of Al ₂ O ₃ .9SiO _2. · xH ₂ O (x in the formula is an integer of 1 or more) it includes a compound represented by.

In addition, as a preferable form of the antibacterial / antifungal aluminum silicate, in the general formula (1), R ₁ and R ₄ are methylene groups bonded to the 3 or 4 position of the pyridine ring. , R ₂ and R ₅ are hydrogen atoms, R ₃ is a tetramethylene group, R ₆ is a group selected from an octyl group, a decyl group and a dodecyl group, and Z is a chlorine atom, a bromine atom or it is iodine MotoHara terminal; compound represented by the general formula (1) is the following compound (1) to be at least one of the compounds represented by (5); the general formula (1) It is mentioned that content of the compound represented by this is 5-45 mass parts per 100 mass parts of aluminum silicate.

Furthermore, another embodiment of the present invention, the water to a method for producing the antimicrobial-antifungal aluminum silicate, and the aluminum silicate, a compound represented by the front following general formula (1) Provided is a method for producing an antibacterial / antifungal aluminum silicate characterized by being contacted in a solvent, followed by solid-liquid separation and drying. Particularly preferred aspect, the production method of the water-containing solvent is water antibacterial, antifungal aluminum silicates and the like.

  According to the present invention, any of the antibacterial, antifungal and antialgal properties inherently possessed by the compound of the general formula (1) while being sorbed and adsorbed on aluminum silicate. It has excellent antibacterial and antifungal properties against a large number of microorganisms because it has an excellent activity against protozoa and protozoa. Since the compound can have a property of eluting, an antibacterial / antifungal aluminum silicate capable of exhibiting the above-described excellent performance over a long period of time is provided. Further, according to the present invention, since the compound of the above general formula (1) is sorbed and adsorbed on aluminum silicate, the thermal stability of the compound is remarkably improved. Antibacterial and anti-fouling aluminum silicates with excellent discoloration resistance are provided. For this reason, it becomes possible to mix | blend with fiber, paper, a film, a plastics, rubber | gum etc. which were difficult conventionally, and the expansion of the use can be anticipated. Further, the antibacterial / antifungal aluminum silicate of the present invention can be expected to be applied as an antibacterial composition for paints and sealants, and its utility value is great. Furthermore, according to the production method of the present invention, since the antibacterial / antifungal aluminum silicate having the above-described excellent performance can be produced in a large amount by a simple method, its industrial value can be further increased. it can.

The thermal analysis result (solid line: TG, wavy line: DTA) about the antibacterial / antifungal aluminum silicate. Thermal analysis results for compound (3) (solid line: TG, wavy line: DTA). Thermal analysis results for untreated aluminum silicate (solid line: TG, wavy line: DTA). Thermal analysis results for antibacterial and anti-fouling aluminum silicates. The thermal analysis result about a compound (3). Thermal analysis results for untreated aluminum silicate.

  The present invention will be described in detail with reference to preferred embodiments of the present invention. In order to achieve the above-described object of the present invention, the present inventors first basically have antibacterial and antibacterial properties as mentioned in Patent Documents 11 to 14 among organic antibacterial agents. Antibacterial and antifungal as represented by the above general formula, which is excellent in both fertility and anti-algae properties and has excellent activity against not only bacteria but also protozoa and protozoa The combination of antibacterial and antifungal compounds and inorganic salts that sorb and adsorb these compounds is considered to be useful as an organic antibacterial agent that sorbs and adsorbs organic compounds on inorganic salts We conducted an intensive study.

As a result, it was found that it is useful to use the compounds represented by the following general formula (1), particularly the compounds (1) to (5) shown below, as the antibacterial / antifungal compound. . Furthermore, as an inorganic salt for sorbing and adsorbing these compounds, an aluminosilicate is excellent, and more preferably, the chemical formula Al ₂ O ₃ .9SiO ₂ .xH ₂ O (wherein x is 1 or more) Is the most excellent support carrier for the compound of the general formula (1), which is an antibacterial / antifungal compound, and the antibacterial agent is an antibacterial agent when it is made into a composite having such a structure. It has been found that not only the sustained release property of the water- and anti-wetting compound is excellent, but also excellent in heat resistance, weather resistance and discoloration resistance. In addition, since aluminum silicate is a naturally occurring inorganic compound, it is considered to be a highly safe compound in handling during manufacture of the product and disposal by incineration after use. The configuration is very useful.

（ただし、上記一般式（１）において、Ｒ₁およびＲ₄は、何もないかまたは炭素数１〜４の直鎖若しくは分岐の同一または異なるアルキレン基であり、Ｒ₂およびＲ₅は、水素原子、同一または異なるハロゲン原子、低級アルキル基または低級アルコキシ基であり、Ｒ₃は、炭素数２〜１２の直鎖若しくは分岐のアルキレン基であり、Ｒ₆は、炭素数１〜１８の直鎖若しくは分岐のアルキル基であり、Ｚは、塩素原子、臭素原子、ヨウ素原子若しくはＯＳＯ₂Ｒ₇基（Ｒ₇は、低級アルキル基若しくは置換或いは無置換のフェニル基である）である。）

(However, in the above general formula (1), R ₁ and R ₄ are nothing or a linear or branched alkylene group having 1 to 4 carbon atoms, or R ₂ and R ₅ are hydrogen. An atom, the same or different halogen atom, a lower alkyl group or a lower alkoxy group, R ₃ is a linear or branched alkylene group having 2 to 12 carbon atoms, and R ₆ is a linear chain having 1 to 18 carbon atoms. Or, it is a branched alkyl group, and Z is a chlorine atom, bromine atom, iodine atom or OSO ₂ R ₇ group (R ₇ is a lower alkyl group or a substituted or unsubstituted phenyl group).

As described above, the technical feature of the present invention is that aluminum silicate, more preferably, the chemical formula Al ₂ O ₃ .9SiO ₂ .xH ₂ O (wherein x represents an integer of 1 or more) (hereinafter simply referred to as “aluminum silicate”) It can be achieved by the conventional technique by sorbing and adsorbing the compound of the general formula (1) on the aluminum silicate represented by Al ₂ O ₃ · 9SiO ₂ · xH ₂ O). The antibacterial and antifungal aluminum silicate that can exert the intended effect of the present invention is not found. As described above, the prior art does not disclose an inorganic-organic antibacterial complex having the structure of the present invention. In addition, as described above, the antibacterial / antifungal aluminum silicate having such a configuration has high thermal stability, weather resistance, and discoloration resistance, and is capable of killing many microorganisms such as bacteria, spider, algae, and protozoa. In addition, it has a destructive effect and has a sustained-release antibacterial ability that continuously exerts the antibacterial action, and is extremely useful that could not be achieved by conventional techniques.

The components constituting the antibacterial / antifungal aluminum silicate of the present invention will be described in more detail. The composition of the present invention is obtained by sorbing and adsorbing the compound of the general formula (1) in the structure of the inorganic aluminum silicate. The aluminum silicate used as the carrier has the chemical formula Al ₂ O. _An amorphous aluminum silicate having a solid acid represented by ₃ · 9SiO ₂ · xH ₂ O is particularly preferable. The average particle size of aluminum silicate is preferably a powder having a particle size of 350 μm or less, more preferably a powder having an average particle size of 0.02 to 200 μm, and a narrow particle size distribution and a uniform particle size. . By using a powder of such a size, the compound of the general formula (1) can be efficiently sorbed and adsorbed, and a sustained-release antibacterial effect can be obtained. Furthermore, considering the application as an antibacterial composition such as fiber, paper, film, plastic, rubber, paint, and sealing material, it is considered that the appearance and properties of the product are not affected, and such a size is preferable. . Further, the compound of the general formula (1) which is an antibacterial / antifungal compound can be obtained by the method described in JP-A-2006-45074 described above.

The method for producing the antibacterial / antifungal aluminum silicate of the present invention will be described. Production method of the present invention has the formula Al ₂ O ₃ · aluminum silicate represented by 9SiO ₂ · xH ₂ O, aqueous solvent and a compound represented by the general formula and a quaternary ammonium salt (1) It is characterized by solid-liquid separation after drying in contact and drying. According to the production method of the present invention, a desired antibacterial / antifungal aluminum silicate can be produced in a large amount while being a simple method.

In the production of the antibacterial / antifungal aluminum silicate of the present invention, an aqueous solution containing the compound of the above general formula (1) as a quaternary ammonium salt is added to the chemical formula Al ₂ O ₃ .9SiO ₂ .xH ₂ O. It is preferable to contact aluminum silicate represented by Since the aluminum silicate has a strong solid acid in its structure, the compound of the general formula (1), which is a quaternary ammonium salt, is easily sorbed on the aluminum silicate by ion exchange. it is conceivable that. However, sorption is not limited to sorption by ion exchange.

  As described above, the antibacterial / antifungal aluminum silicate of the present invention can be obtained by the production method as described above, and is excellent by utilizing ion exchange with a solid acid in the aluminum silicate structure. The compound of the general formula (1), which is an antibacterial compound, is sorbed in the aluminum silicate structure, and as a result, antibacterial and antifungal properties are imparted to the aluminum silicate in a good state.

  The antibacterial and antifungal aluminum silicate of the present invention that can be easily obtained by the method as described above is obtained by adding 5 of the compound of the general formula (1) to 100 parts by mass of the aluminum silicate as described above. It is preferable that the composition is sorbed and contained in an amount of about ~ 45 parts by mass. If the content is less than 5 parts by mass, the antibacterial and antifungal properties may not be sufficient or the effect may not be maintained over a long period of time. If so, a stable effect can be maintained over a long period, which is sufficient as a product.

  The contact between the aluminum silicate and the compound of the above general formula (1) as represented by the compounds (1) to (5) is carried out in a water-containing solvent by the aluminum silicate and the compound of the general formula (1). May be mixed and stirred. The organic solvent used for the hydrous solvent only needs to be arbitrarily mixed with water. Examples of the water-containing solvent that can be used in the present invention include mixed solvents of lower alcohols such as methanol, ethanol, isopropanol, n-butanol, and tert-butanol and water, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, and dipropylene. Glycol, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tripropylene Glycol solvent such as glycol monomethyl ether and water mixed solvent, dioxane, tetra Ether mixed solvent of solvent and water, such as Dorofuran, acetone, N, N- dimethylformamide, dimethylacetamide, dimethyl sulfoxide, a mixed solvent of polar solvent and water, such as acetonitrile and the like. However, water is most suitable for the most efficient aluminum silicate, for example, for sorption and adsorption of the above-mentioned compounds (1) to (5).

  The method for contacting the aluminum silicate with the compound of the above general formula (1) is not particularly limited, and the above general formula (1) in which the aluminum silicate and the quaternary ammonium salt are used in a water-containing solvent as described above. These compounds may be mixed using a stirring bar or an electric stirring bar. It is preferable to add aluminum silicate slowly and continuously in a water-containing solvent containing the compound of the general formula (1) under stirring conditions. For example, as described in Example 1 described later, when 5 g of aluminum silicate is added, it is preferably added over 10 minutes.

  The stirring temperature at this time is not particularly limited as long as it is not higher than the boiling point of the water-containing solvent, but is preferably from room temperature to 80 ° C.

  As described above, after the compound of the above general formula (1), which is a quaternary ammonium salt, is adsorbed and adsorbed on aluminum silicate, the solid phase is separated, washed, and the surplus general formula ( After removing the compound of 1), drying is performed to obtain aluminum silicate obtained by sorption and adsorption of the compound of the general formula (1) in the structure of aluminum silicate. The above method is extremely simple, and the antibacterial / antifungal aluminum silicate of the present invention can be efficiently and easily produced in large quantities by such a method.

  The antibacterial and antifungal aluminum silicate of the present invention obtained as described above is a structure in which the compound of the general formula (1) is adsorbed and adsorbed in the structure. It can be said that this is an important element that characterizes the present invention, and such a configuration can sufficiently exhibit the effects of the present invention. That is, such a composition exhibits antibacterial, antifungal and antialgal properties, and further, by stably eluting the compound of the general formula (1) in a sustained release manner, the antibacterial and antifungal properties can be obtained. It will have the durability of antiseptic and algal control effects. Further, by sorbing and adsorbing the compound of the general formula (1) on the aluminum silicate, the heat resistance, ultraviolet resistance and discoloration resistance of the compound of the general formula (1) are clearly improved.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples.

<Example 1>
[Production of antibacterial / antifungal aluminum silicate on which compound (3) is adsorbed / adsorbed (complex 1)]
2 g of compound (3) (trade name: manufactured by Hygenia Tama Chemical Co., Ltd.) was dissolved in 20 ml of distilled water, heated to 60 ° C. and stirred. To this solution, 5 g of sufficiently dried aluminum silicate [KYOWARD 700SEN, particle size distribution 150-350 μm (80.0%), manufactured by Kyowa Chemical Industry Co., Ltd.] was added in small portions over 10 minutes. After the addition, the mixture was further stirred at 60 ° C. for 30 minutes. Next, after cooling to room temperature, the stirred solution was filtered and washed with 10 ml of distilled water to obtain a synthesized product. This was sufficiently dried at 40 ° C. under vacuum. After drying, the mixture was pulverized in a mortar to obtain 6.16 g of the composite 1 that is antibacterial / antifungal aluminum silicate.

<Example 2>
[Production of antibacterial / antifungal aluminum silicate on which compound (3) is adsorbed / adsorbed (complex 2)]
2 g of compound (3) (trade name: manufactured by Hygenia Tama Chemical Co., Ltd.) was dissolved in 20 ml of distilled water, heated to 60 ° C. and stirred. To this solution, 5 g of sufficiently dried aluminum silicate (Kyoward 700PEL, particle size distribution 45 μm or less (95.9%), manufactured by Kyowa Chemical Industry Co., Ltd.) was added in small portions for 10 minutes. After the addition, the mixture was further stirred at 60 ° C. for 30 minutes. Next, after cooling to room temperature, the stirred solution was filtered and washed with 10 ml of distilled water to obtain a synthesized product. This was sufficiently dried at 40 ° C. under vacuum. After drying, the mixture was pulverized in a mortar to obtain 6.15 g of the composite 2 that is antibacterial / antifungal aluminum silicate.

<Example 3>
[Production of antibacterial / antifungal aluminum silicate on which compound (1) is adsorbed / adsorbed (complex 3)]
2 g of compound (1) was dissolved in 20 ml of distilled water, heated to 60 ° C. and stirred. To this solution, 5 g of sufficiently dried aluminum silicate (KYOWARD 700SEN) was added in small portions over 10 minutes. After the addition, the mixture was further stirred at 60 ° C. for 30 minutes. Next, after cooling to room temperature, the stirred solution was filtered and washed with 10 ml of distilled water to obtain a synthesized product. This was sufficiently dried at 40 ° C. under vacuum. After drying, the mixture was pulverized in a mortar to obtain 6.03 g of the composite 3 which is an antibacterial / antifungal aluminum silicate.

<Example 4>
[Production of antibacterial / antifungal aluminum silicate on which compound (2) is adsorbed / adsorbed (complex 4)]
2 g of the above compound (2) was dissolved in 20 ml of distilled water, heated to 60 ° C. and stirred. To this solution, 5 g of sufficiently dried aluminum silicate (KYOWARD 700SEN) was added in small portions over 10 minutes. After the addition, the mixture was further stirred at 60 ° C. for 30 minutes. Next, after cooling to room temperature, the stirred solution was filtered and washed with 10 ml of distilled water to obtain a synthesized product. This was sufficiently dried at 40 ° C. under vacuum. After drying, the mixture was pulverized in a mortar to obtain 6.15 g of the composite 4 that is antibacterial / antifungal aluminum silicate.

<Example 5>
[Production of antibacterial / antifungal aluminum silicate on which compound (4) is adsorbed / adsorbed (complex 5)]
2 g of the above compound (4) was dissolved in 20 ml of distilled water, heated to 60 ° C. and stirred. To this solution, 5 g of sufficiently dried aluminum silicate (KYOWARD 700SEN) was added in small portions over 10 minutes. After the addition, the mixture was further stirred at 60 ° C. for 30 minutes. Next, after cooling to room temperature, the stirred solution was filtered and washed with 10 ml of distilled water to obtain a synthesized product. This was sufficiently dried at 40 ° C. under vacuum. After drying, the mixture was pulverized in a mortar to obtain 6.33 g of the composite 5 that is antibacterial / antifungal aluminum silicate.

<Example 6>
[Production of antibacterial / antifungal aluminum silicate on which compound (5) is adsorbed / adsorbed (complex 6)]
2 g of compound (5) was dissolved in 20 ml of distilled water, heated to 60 ° C. and stirred. To this solution, 5 g of sufficiently dried aluminum silicate (KYOWARD 700SEN) was added in small portions over 10 minutes. After the addition, the mixture was further stirred at 60 ° C. for 30 minutes. Next, after cooling to room temperature, the stirred solution was filtered and washed with 10 ml of distilled water to obtain a synthesized product. This was sufficiently dried at 40 ° C. under vacuum. After drying, the mixture was pulverized in a mortar to obtain 6.33 g of the composite 6 that is antibacterial / antifungal aluminum silicate.

  Various tests were performed on the composites 1 to 6 obtained as described above. Hereinafter, the composites 1 and 2 will be described as representatives, but similar results were obtained for other composites.

<Test Example 1> Elemental Analysis To quantify the compounds (1) to (5) adsorbed and adsorbed on the antibacterial and antifungal aluminum silicates obtained in Examples 1 to 6, complexes 1 to 6 were used. Then, 10 mg each of the dried untreated aluminum silicate was used as a measurement sample, and elemental analysis (MT-5, manufactured by Yanagimoto) was performed to determine the amounts of carbon, hydrogen, and nitrogen. The results are shown in Table 1. Table 2 shows the elemental analysis results of the composite 2 having a different particle size distribution of the aluminum silicate used from the composite 1.

  From the amount of carbon in the elemental analysis results shown in Table 1, it was found that 1.25 g of the complex 1 was adsorbed and adsorbed as the compound (3) per 5 g of the composite 1. In addition, it was found that 1.28 g of the compound 3 was adsorbed and adsorbed as the compound (1) per 5 g of the complex 3. Moreover, in the composite 4, it turned out that 1.49g is adsorbed and adsorbed as the said compound (2) per 5g. Moreover, in the composite 5, it turned out that 1.21g is adsorbed and adsorbed as the said compound (4) per 5g. Furthermore, it was found that 1.37 g of the complex 6 was adsorbed and adsorbed as the compound (5) per 5 g of the complex 6.

  From the amount of carbon in the elemental analysis results shown in Table 2, it was found that 1.45 g of the complex 2 was adsorbed and adsorbed as the compound (3) per 5 g of the complex 2.

<Test Example 2> Differential thermogravimetric analysis and differential thermal analysis of antibacterial / antifungal aluminum silicate In order to confirm the thermal stability of the antibacterial / antifungal aluminum silicate (complex 1) of Example 1 Differential thermogravimetric analysis and differential thermal analysis (DTA-TG) were performed. Specifically, about 10 mg of the complex 1 as a measurement sample was weighed in a platinum pan, the control was α-alumina (aluminum oxide) about 10 mg, DTG-60 (Shimadzu Corporation) was used, and the heating rate was 5 The measurement was carried out at 40 ° C./500° C./min.

  FIG. 1 (a) shows the result of thermal analysis of the composite 1 which is the antibacterial / antifungal aluminum silicate of Example 1, and FIG. 1 (b) shows the compound used for the manufacture of the composite 1. The result of thermal analysis of (3) is shown, and the result of thermal analysis of untreated aluminum silicate is shown in FIG. The results are shown by DTA-TG curves (solid line: TG, wavy line: DTA), respectively. From the DTA-TG curve of Complex 1 shown in FIG. 1 (a), exothermic peaks at 331 ° C. and 380 ° C. accompanied by weight loss were observed, which were attributed to the detachment of crystal water from about 50 ° C. to about 170 ° C. A weight reduction of about 10% and a weight reduction of about 15% accompanying the combustion of the compound (3) from about 200 ° C. to about 400 ° C. were confirmed. On the other hand, endothermic peaks at 231 ° C. and 281 ° C. with weight reduction are observed from the DTA-TG curve of the compound (3) used for the production of the complex 1 shown in FIG. A 75% weight loss was observed over 320 ° C. From the DTA-TG curve of untreated aluminum silicate in FIG. 1 (c), water of crystallization was released up to about 400 ° C., and weight loss due to intramolecular dehydration was observed.

  From the above results, the endothermic / exothermic peak accompanying the weight reduction of the composite 1 of Example 1 increased from 231 ° C. to 331 ° C. When attention is paid to the weight decrease start temperature due to thermal decomposition of the compound (3) used at that time, the temperature of the compound (3) (FIG. 1 (b)) is increased by about 20 ° C. (from 180 ° C. to 200 ° C.). The end point of the weight loss due to the combustion increased by about 80 ° C. (increased from 320 ° C. to 400 ° C.). Therefore, the thermal stability of the compound (3) adsorbed and adsorbed on the composite 1 of Example 1 is improved, that is, the antibacterial / anti-fungal aluminum silicate of Example 1 (Composite 1) It was proved to be excellent in heat resistance. In addition, the gradual weight reduction between 200 ° C. and 400 ° C. of the composite 1 shown in FIG. 1 (a) indicates that the sorption / adsorption power of the compound (3) on aluminum silicate is not so strong. It can be said that it suggests. This is a result of expecting a desirable antibacterial property that the antibacterial and antifungal aluminum silicate of the present invention exhibits effective sustained-release antibacterial properties.

<Test Example 3> Differential Scanning Calorimetry of Antibacterial / Antidepressive Aluminum Silicate The thermal analysis of the composite 1 which is the antibacterial / antifungal aluminum silicate of Example 1 was conducted using a differential scanning calorimeter (DSC). Used and measured as follows. Specifically, 15.9 mg of the composite 1 of Example 1 as a measurement sample was weighed in an aluminum oxide dish, and the control was α-alumina (aluminum oxide). DSC6200 (manufactured by Seiko Denshi Kogyo Co., Ltd.) was used for the measurement, and the measurement was performed under atmospheric conditions between 30 ° C. and 510 ° C. at a heating rate of 10 ° C./min.

  FIG. 2 (a) shows the DSC curve of the complex 1 which is the antibacterial / antifungal aluminum silicate of Example 1, and FIG. 2 (b) shows the DSC curve of the compound (3) used in this case. FIG. 2 (c) shows the DSC curve of untreated aluminum silicate. From the DSC curve of the composite 1 in FIG. 2A, there was no noticeable change in calorie from 40 ° C. to 300 ° C., and a large calorie change at 350 ° C. was confirmed. Since this peak coincides with the exothermic peak accompanied by the weight reduction in FIG. 1A, it is considered that this peak represents oxidative thermal decomposition of the compound (3) adsorbed and adsorbed on the complex 1. It was.

  On the other hand, from the DSC curve of the compound (3) shown in FIG. 2 (b), melting of the compound at 43 ° C. and a change in calorie due to thermal decomposition between 240 ° C. and 280 ° C. were confirmed. Further, from the DSC curve of untreated aluminum silicate in FIG. 2 (c), a change in calorie due to dehydration of crystal water at 92 ° C. was observed. From the above results, it can be seen that the complex 1 of Example 1 does not show a change in calorie at the melting temperature and pyrolysis temperature inherent to the compound (3) and has high thermal stability. It was. This suggests that the composite 1 which is the antibacterial / anti-fungal aluminum silicate of the present invention can be kneaded into fibers, paper, films, plastics, rubbers, etc. The result was expected to be applied as an antibacterial composition of molecular products.

<Test Example 4> Slow release test and antibacterial test of antibacterial / antifungal aluminum silicate Slow release of composite 1 and composite 2 which are the antibacterial / antifungal aluminum silicates of Examples 1 and 2 Release and antibacterial performance were evaluated using ion-exchanged water as an elution solvent. Specifically, 5 ml of ion-exchanged water was added to 50 mg of each of Complex 1 and Complex 2, and the mixture was stirred at 25 ° C. for 1 hour. In this case, stirring contact was used to increase the elution rate. After 1 hour, the suspension was centrifuged (8900 G × 2 min) to obtain a supernatant (supernatant) and a precipitate of each complex treated with ion-exchanged water. The amount of elution of compound (3) from each complex was determined by measuring absorbance at the maximum absorption wavelength (265 nm) of compound (3) using the supernatant as a measurement sample. Furthermore, this operation was repeated 5 times, and the sustained release property was examined. The results are shown in Tables 3 and 4, respectively.

  From Tables 3 and 4, it was found that by washing Complex 1 and Complex 2 of Examples 1 and 2 with ion-exchanged water, compound (3) was eluted in the supernatant. Further, the elution occurred in a sustained release, and it was proved that the complex 1 and the complex 2 of Examples 1 and 2 have a sustained release function.

<Test Example 5> Antibacterial and antifungal aluminum silicate antibacterial test In Test Example 4, a diluted solution obtained by diluting the supernatant of 1 to 5 times obtained with each operation twice with sterile water; An equal amount of the bacterial solution prepared to 1 × 10 ⁶ cells / ml with sterile water was mixed and contacted with shaking at 30 ° C. for 30 minutes. After 30 minutes, 0.1 ml of the mixed solution was inoculated into 2 ml of a nutrient medium (Difco) dispensed into three test tubes. After culturing at 37 ° C. for 24 hours, the presence or absence of proliferation was visually determined, and the dilution factor (maximum dilution factor 256 times) showing bactericidal activity was determined. As the test bacteria, Staphylococcus aureus NBRC 12732 (S. aureus) and Escherichia coli NBRC 12713 (E. coli) were used. The results are shown in Tables 5 and 6.

  From Tables 5 and 6, it was found that the supernatants for the number of elution times 1 to 5 obtained in Test Example 4 have bactericidal properties at a dilution factor of 2 to 256 times. Therefore, complex 1 and complex 2 of Examples 1 and 2 elute compound (3), which is a bactericidal component, in a sustained release manner in ion-exchanged water, and the bactericidal component acts bactericidal against microorganisms. Proven.

  The antibacterial / antifungal aluminum silicate of the present invention has a feature of releasing antibacterial components gradually and exhibiting antibacterial properties over a long period of time as compared with conventional transient organic antibacterial agents . Further, heat resistance is improved by sorbing and adsorbing an antibacterial compound to aluminum silicate. Due to these characteristics, the antibacterial / antifungal aluminum silicate of the present invention is added to fibers, papers, films, plastics, rubbers, paints, sealants, and the like to impart antibacterial performance to these processed products and preparations. It becomes possible. Therefore, the antibacterial / antifungal aluminum silicate of the present invention can be expected to have a very wide application range as a material for antibacterial products for antibacterial, antifungal, antiseptic and antialgal effects. Further, since the production method is simple and capable of mass production, the industrial value of the antibacterial / antifungal aluminum silicate of the present invention is further increased, and the application range can be further expanded. I can expect.

Claims (8)

Silicate aluminum, antibacterial, antifungal aluminum silicate compound represented by the following general formula (1) is characterized Rukoto such are sorbed and adsorption.

(However, in the above general formula (1), R ₁ and R ₄ are nothing or a linear or branched alkylene group having 1 to 4 carbon atoms, or R ₂ and R ₅ are hydrogen. atom or a same or different halogen atom, R ₃ is a linear or branched alkylene group having 2 to 12 carbon atoms, R ₆ is a linear or branched alkyl group having 1 to 18 carbon atoms, There, Z is chlorine atom, bromine atom or iodine MotoHara child,.) The antibacterial / antifungal aluminum silicate according to claim 1, wherein the aluminum silicate is a powder having a particle size distribution of 150 to 350 μm. The aluminum silicate, antibacterial, anti according to claim 1 or 2 which is a compound represented by the chemical formula _{Al 2 O 3 · 9SiO 2 ·} xH 2 O ( where x in the formula represents an integer of 1 or more) Durable aluminum silicate. In the general formula (1), R ₁ and R ₄ are methylene groups bonded to the 3 or 4 position of the pyridine ring, R ₂ and R ₅ are hydrogen atoms, and R ₃ is tetramethylene. a group, R ₆ is a group selected from octyl, decyl and dodecyl groups, Z is a chlorine atom, according to a bromine atom or any one of claims 1 to 3 is iodine MotoHara element, Antibacterial and anti-fouling aluminum silicate. Compound represented by the general formula (1) is the following compound (1) to (5) an antimicrobial-anti according to any one of claims 1-4 is at least one compound represented by Durable aluminum silicate.

Content of the compound represented by the said General formula (1) is 5-45 mass parts per 100 mass parts of said aluminum silicates, Antibacterial property and antifungal property of any one of Claims 1-5 Aluminum silicate. A method for producing the antibacterial / antifungal aluminum silicate according to any one of claims 1 to 6,
Said aluminum silicate, after contacting the compound represented by the hydrous solvent Formula (1), solid-liquid separation, antimicrobial, antifungal aluminum silicate, characterized in that drying Manufacturing method . The method for producing an antibacterial / antifungal aluminum silicate according to claim 7 , wherein the water-containing solvent is water.

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