JP2874422B2 - Antibacterial compound having cyanoguanidyl group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound having a cyanoguanidyl group (> NC (NH) NHCN), which is useful as an antibacterial agent and a method for producing the same. Compounds of the present invention include, for example, fungicides, algicides, antibacterials, fungicides,
Useful as a deodorant and preservative, especially for fibers and fabrics,
It is useful as a treating agent for fibrous materials such as paper. Further, it can also be used as an additive to concrete, glass and other building materials, resins, paints, adhesives, shampoos, toothpastes, and the like, or as a treatment agent for these and inorganic substances such as metals.

[0002]

BACKGROUND OF THE INVENTION Organic silane compounds having a hydrolyzable functional group include glass, metals, ceramics,
Since it is chemically bonded to various materials such as wood, paper, fiber, and resin, it is used in a wide range of industrial fields as a silane coupling agent.

Attempts have been made to introduce a substituent having a bactericidal activity into a silane compound by making use of the chemical bonding of the silane compound to various surfaces to impart antibacterial properties to the material surface. Immobilization of the bactericidal part on the material surface improves durability and durability, increases safety, eliminates environmental pollution, makes resistant bacteria hard to appear, enables large-scale processing, continuous sterilization, etc. Numerous benefits arise.

A silane compound having a quaternary ammonium salt as such a bactericidal active site has been proposed (for example, JP-A-2-6489). However, since the quaternary ammonium salt type compound is an ionic compound, it is easily affected by coexisting substances such as inorganic salts, saccharides, proteins and the like, and has a problem that the bactericidal property is reduced and the surface is discolored. is there. In addition, since the polar portion, which is the active site, is smaller than the alkyl chain in the molecule, for example, when applied to the surface of a fiber, the fiber surface becomes water-repellent due to the introduction of a long-chain alkyl group, and the fiber is inherently Water absorption,
The hygroscopicity is remarkably impaired, and the woven fabric has a drawback that the permeability or permeability of water or water vapor is lost. For this reason, there has been a demand for a compound that imparts excellent bactericidal properties with excellent durability without impairing the inherent hydrophilicity of the fiber.

On the other hand, as antibacterial compounds, various compounds are known in addition to quaternary ammonium salt compounds. Biguanide-type compounds that have been known to have a biological activity such as antimalarial activity are one of them.

However, this kind of compound does not always exhibit excellent bactericidal properties due to the presence of the characteristic group. In general, it is known that the activity of an antibacterial compound changes remarkably depending on the type of a substituent (for example, a biguanide-type compound is described in J. Chem. Soc., 729 (194)
6)) Specifically, it is known that the type of the substituent greatly affects the bactericidal power and the bactericidal spectrum.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of conventional antimicrobial compounds, and to provide a compound which imparts continuous antimicrobial properties to a wide range of materials including fibers.

[0008]

The present inventors have produced a group of novel compounds in which a hydrolyzable silyl group is bonded to the molecular terminal of a cyanoguanidyl compound as an intermediate in the synthesis of a biguanide type compound. Some of these have very strong bactericidal properties and have been useful as antibacterial agents. In addition, since these compounds are also excellent in hydrophilicity and do not necessarily have an ionic site, they have obtained an unexpected finding that the above problems can be solved at once if used as an antibacterial property imparting compound. The present invention has been completed.

[0009]

That is, the present invention provides a compound represented by the general formula (I):
X ¹ X ² X ³ SiY (where X ¹ is halogen or C
1 to C5 alkyloxy groups, and X ² and X ³ are
1 to C5 alkyl group or alkoxy group or halogen, and Y is a monovalent group containing at least one cyanoguanidyl group).

X ¹ is a group generally used as a hydrolyzing group in a silane coupling agent, and specifically, is a halogen or a C1 to C5 alkoxy group. In terms of hydrolytic properties, chlorine is preferable as the halogen, and methoxy and ethoxy are particularly preferable as the alkoxy group. X ² and X ³ are the same as X ¹ ,
It may be a C5 alkoxy group or halogen, or a C1 to C5 alkyl group. Even when the number of carbon atoms exceeds 5, there is no change in the properties as a silane group, but rather adversely affects hydrophilicity. In the case of an alkyl group, a methyl group and an ethyl group are preferred. Y is a monovalent group containing at least one cyanoguanidyl group;
Alternatively, it is preferable that the compound contains two cyanoguanidyl groups. Cyanoguanidyl groups are acetic acid, citric acid,
It may be a salt of an organic acid such as gluconic acid or an inorganic acid such as hydrochloric acid or sulfuric acid.

By selecting a substituent that binds to the cyanoguanidyl group, the bactericidal property and the bactericidal spectrum can be changed. However, in order not to impair the hydrophilicity, the substituent may be hydrogen, C1 to C20. It is preferably an alkyl group or a phenyl group (which may be substituted with a group selected from a halogen, an alkyl group, a fluoroalkyl group and an alkoxy group).

The bonding portion between the silyl group and the cyanoguanidyl group may have the same structure as a general silane coupling agent. Specifically, from a synthetic point of view, a C1-C30 alkylene group (which may include a group selected from an oxy group, an azo group, a thio group, a hydroxymethylene group, an oxycarbonyl group, and a phenylene group). preferable.

The novel compounds having a cyanoguanidyl group of the present invention include the following compounds <A> and <B>.

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The present invention also relates to a process for producing the compound of the above formula (I), which comprises the following general formula (II): X ¹ X ² X ³ SiY ¹ (wherein Y ¹ has at least one amino group) And a silane compound represented by the formula:
A method characterized by reacting with (SCH ₃ ) NH ₂ or NaN (CN) ₂ .

Among the compounds of the formula (II), compounds such as X ¹ X ² X ³ Si (CH ₂ ) ₃ NH ₂ are commercially available as silane coupling agents and can be easily obtained.

In the reaction of the aminosilane compound of the formula (II) with the above nitrile, it is necessary to use a solvent which is stable against hydrolyzable silyl groups. The specific solvent can be selected according to the raw materials used in the reaction,
It is preferable to use alcohols, acetone, benzene, toluene and the like after sufficient dehydration.

The reaction temperature is 0 to 200 ° C., preferably 60
１５０150 ° C. The reaction conditions such as the reaction time are determined depending on the reactivity of the individual compounds, but are generally the same as the conditions for forming a cyanoguanidyl group using amines.

These compounds may be produced as a salt of an organic or inorganic acid, but the acid can be removed by treating with an alkali or the like. Conversely, if necessary, it may be converted into a salt by reacting with a salt of an organic or inorganic acid, or further converted into a salt of a desired acid.

The surface treatment of the material using the compound of the present invention having a cyanoguanidyl group can be performed in the same manner as the conventional surface treatment using a silane coupling agent. In addition, heat treatment may be performed after dissolving in an appropriate solvent depending on the application or applying the composition to the surface in order to enhance the bonding property with the surface.

The material of the surface to be applied may be any as long as it can bond with the silane coupling agent. However, in the field where the use of the organosilane-based antibacterial agent has been a major drawback, especially for fibrous materials. The application is valid. Specifically, it will have a particularly high practical value in sports clothing, socks, underwear, bedding, or towels and mats used around water in bathrooms, kitchens, toilets, and the like. Further, after the treatment with the compound, it may be treated with a dye or the like.
For example, dyeability with a hydrophilic dye is expected to be improved.

[0021]

The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention. Compounds A and B showing production examples in the following Examples are Compounds A and B described in the above description.

[0022]

Example 1 Production of Compound <A> γ-Aminopropyltriethoxysilane (KBE manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a 100 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introducing device. -9
03) in an amount of 10 g (45 mmol), NC-N = C (SC
5.2 g (45 mmol) of H ₃ ) NH ₂ and ethanol 5
0 ml was charged, and the mixture was heated and refluxed for 18 hours under a nitrogen atmosphere. The solvent was distilled off under reduced pressure to obtain 13.1 g of a pale yellow liquid. Water 3 so that the concentration of the compound is 0.5% by weight.
Then, 30 g of cotton knitted fabric was immersed in this solution, and the mixture was slowly stirred at 60 ° C. for 1 hour. After pulling up the cotton knitted fabric and squeezing it to 100%, 9
It was ring-dried at 0 ° C for 15 minutes. The resulting fiber is AATCC-
Evaluation of antibacterial activity according to 100 (test bacteria: Klebsiellapneumi
niae) and JIS L-1018A method. Table 1 shows the results.

[0023]

Example 2 Preparation of Compound <B> N-β was used instead of γ-aminopropyltriethoxysilane
10 g of (aminoethyl) γ-aminopropyltrimethoxysilane (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.)
The same operation as in Example 1 was performed except that 5 mmol) was used. 13.4 g of a pale yellow liquid were obtained. A woven fabric was treated using the obtained compound in the same manner as in Example 1 to evaluate antibacterial properties and water absorption. Table 1 shows the results.

[0024]

Comparative Example 1 A woven fabric was treated with γ-aminopropyltriethoxysilane in the same manner as in Example 1 to evaluate antibacterial properties and water absorption. Table 1 shows the results.

[0025]

Comparative Example 2 A woven fabric was treated with N-β (aminoethyl) γ-aminopropyltrimethoxysilane in the same manner as in Example 1 to evaluate antibacterial properties and water absorption. Table 1 shows the results.

[0026]

Comparative Example 3 A woven fabric was treated with trimethoxysilylpropyldimethyloctadecyl ammonium chloride (silicon quaternary ammonium salt compound) in the same manner as in Example 1 to evaluate antibacterial properties and water absorption. Table 1 shows the results
Shown in

[0027]

Comparative Example 4 The same evaluation as in the example was performed using a woven fabric not treated with an antibacterial compound. Table 1 shows the results.

[0028]

[Table 1]

As can be seen from the above results, the compound of the present invention has the same antibacterial property as the conventional quaternary ammonium salt organosilane compound, and almost impairs the original water absorption of the fiber. I do not.

[0030]

The antibacterial compound of the present invention can impart a sustained and excellent antibacterial property to a material. In addition, since the hydrophilicity as a molecule is large, even if the applied material originally has hydrophilicity such as water absorption, its characteristics are not impaired. Further, it is useful as an intermediate for producing a silane compound having a biguanide group.

──────────────────────────────────────────────────続 き Continued on the front page (56) References European Patent Application Publication 460385 (EP, A1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/18 CA (STN) REGISTRY (STN) ) WPI (DIALOG)

Claims (2)

(57) [Claims] 1. Formula (I): X ¹ X ² X ³ SiY
Wherein X ¹ is a halogen or a C1-C5 alkyloxy group, X ² and X ³ are a C1-C5 alkyl or alkoxy group or a halogen, and Y is a monovalent group containing at least one cyanoguanidyl group. An organosilane compound represented by the formula: 2. A process for the preparation of a compound of formula (I),
General formula (II): X ¹ X ² X ³ SiY ¹ (wherein X ¹ , X ² and X ³ are defined as in the formula (I), and Y ¹ is a monovalent compound containing at least one amino group. And a silane compound represented by NC-N = C (S
CH ₃₎ reacting with NH ₂ or NaN (CN) ₂ .