JPH0769807A - Production of immobilized antifungal agent - Google Patents

Abstract

PURPOSE:To economically obtain a highly safe immobilized antifungal agent in high efficiency by simplifying complicated processes in the conventional technology therefor. CONSTITUTION:This immobilized antifungal agent can be obtained by coating a solid surface with a chlorine group-bearing silane coupling agent in a gaseous state followed by reaction of a tertiary amine in a gaseous state with the coupling agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method in which a silane coupling agent containing a chloro group is brought into contact with a solid surface in a gaseous state to coat the solid surface, and then a tertiary amine is reacted in a gaseous state. The present invention relates to a method for producing an immobilized antibacterial agent.

[0002]

Conventionally, antibacterial agents have been used in cosmetics, disinfectants, sanitizers, foods, animal feed, cooling water, metalwork water, hospital and medical applications, plastics, adhesives, tanned leather and leather, and slurry for paints. It is used. Although there are many conventionally known antibacterial agents, quaternary ammonium salt compounds are often used among them. This compound is known to have a strong antibacterial effect, but when used at high concentrations, it has problems such as transdermal absorption, irritation, and thermal stability, and solids were added. In this case, there is a problem that the quaternary ammonium salt compound is adsorbed on the surface of the solid to reduce the antibacterial activity. As described above, the quaternary ammonium salt compound was limited in its formulation. The immobilized antibacterial agent can be produced by using a silane coupling agent (APPL.ENVIRON.MICRO).
BIOL, Mar. 1984, 513-518), and a method of producing using a silicone polymer-coated solid (JP-A-5-70314). However, all of these methods are for immobilizing a quaternary ammonium salt compound by a solid-liquid reaction, and particularly when immobilizing on a powder surface, complicated steps such as filtration, washing, drying and pulverization are required. There is a need to do. Furthermore, the immobilized antibacterial agent produced by this method is
There was also a problem that the added amount was small and the antibacterial activity was weak.

[0003]

Therefore, the present invention simplifies the complicated steps of the above-mentioned prior art, and even if an antibacterial agent is immobilized, the antibacterial activity is not impaired, and the immobilized antibacterial agent is particularly excellent in safety. It aims at providing the manufacturing method of an agent.

[0004]

The inventors of the present invention firstly coat and modify the surface of an inorganic solid, which is particularly excellent in physical strength, with a silicone polymer, and further chemically modify the organic residue of the coating layer. And to impart stability to the silicone polymer and to provide the silicone polymer-coated inorganic solid with further functionality. Although some of these can be used as immobilized antibacterial agents, the present inventors have conducted extensive research to develop those having even better antibacterial activity, safety, stability, etc., and as a result, have undergone complicated steps. It was possible to modify the surface of the solid with a quaternary ammonium salt without using the gas-solid reaction. Then, they have found that this is excellent in antibacterial activity, heat stability and safety, and completed the present invention. That is, according to the present invention, a silane coupling agent containing a chloro group is brought into contact with a solid surface in a gas state to coat the solid surface, and then a tertiary amine is reacted in a gas state. A method for producing an immobilized antibacterial agent having a quaternary ammonium salt bound to a solid surface is provided. According to a preferred embodiment of the present invention, the chloro group derived from the silane coupling agent on the solid surface is acted by the amino group of the amine in a gas state to form a carbon-nitrogen covalent bond, thereby forming a quaternary group on the solid surface. An immobilized antibacterial agent having a quaternary ammonium salt bound thereto is obtained.

[0005]

[Detailed Description of Configuration] The method for producing the immobilized antibacterial agent of the present invention will be specifically described below. The solid substance used in the present invention may be any substance capable of adsorbing and binding a silane coupling agent in a gas state. When a hydroxyl group is present on the surface of the solid substance, the silane coupling agent bonds with this to obtain a more stable immobilized antibacterial agent. Incidentally, in consideration of convenience in using the immobilized antibacterial agent, antibacterial activity, etc., it is desirable that the solid substance be in a powder form,
Inorganic powders such as silica and titanium dioxide are preferable in terms of the adsorption ability of the silane coupling agent. The silane coupling agent containing a chloro group used in the present invention is represented by the formula (1). ClC _n H _2n SiX (1) (n is an integer of 3 or more, and X represents a hydrolyzable group such as halogen, alkoxy, amino, etc.) Examples of such a compound include ClC ₃ H ₆ Si ( OCH ₃ )
₃ , ClC ₃ H ₆ Si (OC ₂ H ₅ ) ₃ , ClC ₄ H _{8
Si (OCH 3) 3, ClC} 4 H 8 Si (OC 2 H 5)
₃ , ClC ₃ H ₆ SiCl _{3 and the} like can be exemplified.

Further, the term amine used in the present invention is used in a broad sense, and these include:
This is represented by the equation (2). R ¹ R ² NR ³ (2) (R ¹ , R ² and R ³ are each an alkyl group (preferably having a carbon number of 1 to 18) or a phenyl group, and have an OH at the terminal.
Examples of such a compound include (CH ₃ ) ₂ N (C ₆ H ₁₃ ), (CH ₃ ) ₂ N (C
₁₂ H ₂₉ ), (CH ₃ ) ₂ N (C ₁₄ H ₂₉ ), (CH ₃ ) ₂
N (C ₁₆ H ₃₃ ), (CH ₃ ) ₂ N (C ₁₈ H ₃₇ ), (C _{10
H 21) 2 N (CH 3} ) and the like can be exemplified.

According to the present invention, the solid surface is coated by bringing the silane coupling agent containing a chloro group into contact with the solid surface in a gas state. The treatment temperature is preferably in the temperature range from room temperature to the boiling point of the silane coupling agent. If necessary, the treatment may be performed under reduced pressure, the treatment may be performed in an inert gas atmosphere, or the treatment may be performed after impregnating water in advance.

Next, the immobilized antibacterial agent is obtained by covalently bonding a tertiary amine in a gas state onto the solid surface coated with the silane coupling agent containing a chloro group. The reaction conditions for the carbon-nitrogen covalent bond between the silane coupling agent and the tertiary amine can be appropriately selected depending on the type of the silane coupling agent and the amine used, but the treatment temperature ranges from room temperature to A temperature range up to the boiling point of the primary amine is preferred. If necessary, the treatment may be performed under reduced pressure, or the treatment may be performed after the steam treatment is performed in advance.

According to the present invention, as compared with the conventional solid-liquid reaction, the steps of filtration, washing, drying, crushing, etc. can be reduced, and the processing time can be greatly shortened. Furthermore, the economic merit of the present invention is extremely great, such as no loss caused by the filtration step.

The immobilized antibacterial agent obtained by the present invention can be used for external preparations for skin, oral products, cosmetics, paints, air conditioner-related filters, papers, fibers, sheets and the like.

[0011]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but it goes without saying that the scope of the present invention is not limited to these examples.

Example 1-1: Silane cup of fine particle silica
Particle size of 5 in a rotary double-cone type reaction vessel (stainless steel, with heat insulation jacket) with a coating capacity of 100 liters of pulling agent
4 kg of 0 nm fine particle silica was added. The temperature of the reaction tank and the processing liquid supply tank (stainless steel, with a heat insulation jacket) having a volume of 10 liters directly connected to the reaction tank, the heat medium heated to 80 ° C. is supplied to each heat insulation jacket from the heat medium heating layer by a circulation pump. By doing, 80 ℃
Held in. 2 kg of chloropropyltrimethoxysilane was added to the treatment liquid supply tank, nitrogen gas was supplied to the treatment liquid supply tank at 1.5 liter / min, and the treatment liquid was bubbled and introduced into the reaction layer in the gas phase. The reaction tank was rotated at intervals of 10 minutes for 1 minute in order to mix the fine particle silica. This operation was continued for 8 hours to obtain 3.9 kg of treated powder.

Example 1-2 In the same manner as in Example 1-1 except that the fine particle silica was replaced with fine particle titanium dioxide, fine particle titanium dioxide coated with a silane coupling agent was obtained.

Example 1-3 The same treatment was carried out by substituting the fine particle silica of Example 1-1 with sericite to obtain a silane coupling agent-coated sericite.

Example 2-1: N, N-dimethylalkyl
A particle size of 5 in a rotary double-cone type reaction vessel (stainless steel, with a heat insulation jacket) with an amine addition capacity of 100 liters.
3 kg of 0 nm silane coupling agent-coated fine particle silica was added. The temperature of the reaction tank and the processing liquid supply tank (stainless steel, with a heat insulation jacket) having a volume of 10 liters directly connected to the reaction tank, the heat medium heated to 80 ° C. is supplied to each heat insulation jacket from the heat medium heating layer by a circulation pump. The temperature was maintained at 80 ° C. 2 kg of N, N-dimethylhexylamine was added to the treatment liquid supply tank, and 1.5 liter / min of nitrogen gas was supplied to the treatment liquid supply tank.
The treatment liquid was bubbled, and N, N-dimethylhexylamine was introduced into the reaction layer. In addition, in order to mix the silane coupling agent-coated fine particle silica, the reaction tank was rotated at 10 minute intervals for 1 minute each. Continue this operation for 6 hours,
2.9 kg of an immobilized antibacterial agent in which the surface of fine particle silica was coated with a quaternary ammonium salt was obtained.

Example 2-2 The silane coupling agent-coated fine particle silica of Example 2-1 was replaced with the silane coupling agent-coated fine particle titanium dioxide, and the same treatment was carried out, and the fine particle titanium dioxide was converted to a quaternary ammonium salt. A coated immobilized antimicrobial agent was obtained.

Example 2-3 The silane coupling agent-coated fine particle silica of Example 2-1 was replaced with the silane coupling agent-coated sericite, and the same treatment was carried out to coat the sericite with a quaternary ammonium salt. A fixed antibacterial agent was obtained.

[0018]

EFFECT OF THE INVENTION An immobilized antibacterial agent having sufficient antibacterial activity and excellent safety can be produced by a simple process.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Michihiro Yamaguchi 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Shiseido Daiichi Research Center Co., Ltd.

Claims (2)

[Claims] 1. An immobilized antibacterial characterized in that a silane coupling agent containing a chloro group is brought into contact with a solid surface in a gaseous state to coat the solid surface, and then a tertiary amine is reacted in a gaseous state. Method of manufacturing agent. 2. The immobilized antibacterial agent according to claim 1, wherein the solid is a powder.