JP2000007510A - Antimicrobial sol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare antimicrobial sol excellent in antibiotic activity and useful for surface treatment or the like by including an antimicrobial silicone-based ammonium salt in a sol medium. SOLUTION: This antimicrobial sol is prepared by including (B) an antimicrobial silicone-based ammonium salt, pref. a compound of the formula [R1 is an alkoxy, a halogen or the like; R2 is methyl or ethyl; (a) is 0, 1 or 2; R3 is a (substituted) alkylene having <=20C; R4-R6 are each a 1-20C alkyl, an aryl or the like; X is an anion] in (A) a sol medium, pref. aqueous sol medium or nonaqueous sol one. It is pref. that the component B and the component A are immobilized through condensation reaction and the component B is included in the component A in a quantity of >=1 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an antibacterial sol having excellent antibacterial activity.

[0002]

2. Description of the Related Art Conventionally, an antibacterial sol obtained by imparting antibacterial activity to various types of colloid particles has been used for surface treatment, adhesives, fibers, medical treatment,
It is applied to various fields such as paper and paint. For example, colloidal silver is a typical antibacterial sol, and it is also known to use it in combination with other colloids (Japanese Patent Laid-Open No.
-112253, JP-A-3-122162).

Further, silica sol or alumina sol carrying antibacterial metal ions (Japanese Patent Application Laid-Open Nos. 2-292201 and 1-258792), and silica sol to which a tetramethylammonium salt or the like is added (Japanese Patent Application Laid-Open No. JP-A-202269, JP-A-3-197575), an antibacterial quaternary ammonium salt having a silane coupling property supported on an organic or inorganic base powder (JP-A-2-91008), phosphonium in a sol Ones supporting a salt (Japanese Unexamined Patent Publication No. Hei 7-187927) have also been proposed.

[0004]

However, an antibacterial sol carrying an antibacterial metal ion such as silver ion,
Although exhibiting a high antibacterial effect, there is a drawback that the phenomenon of being oxidized by light or heat to lower the antibacterial power and causing discoloration is inevitable, and the use is significantly restricted.

On the other hand, as for an antibacterial sol containing a quaternary ammonium salt-based antibacterial agent, the proposed compound is a quaternary ammonium salt such as tetramethylammonium chloride, and the silicone-based sol of the present invention. There is no disclosure of antibacterial ammonium salts.

The present inventors have conducted intensive studies on the development of an antibacterial sol that solves the above-mentioned problems, and as a result, have confirmed that silicone-based ammonium salts exhibit excellent antibacterial properties. The present invention has been developed based on such knowledge, and an object of the present invention is to provide an antibacterial sol having excellent antibacterial activity.

[0007]

The antibacterial sol according to the present invention for achieving the above object has a structural feature that a sol medium contains a silicone-based ammonium salt having antibacterial properties.

The silicone-based ammonium salt is represented by the following general formula (1)

[0009]

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Wherein R ¹ is an alkoxy group, a halogen atom, an acyl group, a hydroxyl group or a hydrogen atom, R ² is a methyl group or an ethyl group, a is 0, 1 or 2, R ³ is a substituted or unsubstituted An alkylene group having 20 or less carbon atoms,
Or 20 carbon atoms containing oxygen and nitrogen atoms
Or less alkylene groups, R ⁴ , R ⁵ and R ⁶ each represent a linear or branched alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, and the alkyl group, aryl group or aralkyl group is It may be substituted with a hydroxyl group or an alkoxy group. X represents an anion. ) Is preferred.

It is preferable that the silicone-based ammonium salt and the sol medium are fixed by a condensation reaction. Preferably, the sol medium is an aqueous sol or a non-aqueous sol. It is preferable that the sol medium contains at least lppm or more of a silicone-based ammonium salt having antibacterial properties.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The antibacterial sol of the present invention is characterized in that a sol medium contains a silicone-based ammonium salt having antibacterial properties. In the present invention, the sol medium is not necessarily a so-called colloidally strict sol, but refers to a medium in which fine particles are uniformly dispersed in a dispersion medium, and includes an emulsion. The form of the sol medium is not limited to an aqueous sol, but may be a non-aqueous sol, and may be an inorganic sol or an organic sol.

As the inorganic sol, for example, silica sol,
Alumina sol, titania sol, zirconia sol, antimony oxide sol, tin oxide sol, zinc oxide sol, iron oxide sol, barium sulfate, clay slurry and the like can be mentioned. Examples of the organic sol include a plastic sol such as polyvinyl chloride, a sol such as methylcellulose, hydroxymethylcellulose, and glucose, and a xanthan gum, guar gum, dextrin, or rubber emulsion. Furthermore, those obtained by surface-modifying the above various sols can also be used, and examples thereof include sols which have been surface-modified with oxides such as Al, Zr, Ti, and Fe. Further, among the above sols, silica sol and alumina sol are particularly preferable.

The dispersion medium of the sol is usually water, but the dispersion medium of the non-aqueous sol includes alcohols such as methanol, ethanol, propanol and butanol, benzene, and the like.
Organic compounds such as aromatic hydrocarbons such as toluene, acetone, ethylene glycol, methyl glycol acetate, and ethyl ether are used.

The silicone-based ammonium salt contained in the sol medium includes, for example, ammonium salts represented by the following general formula (1), and they may be used alone or as a mixture of two or more.

[0016]

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In the general formula (1), R ¹ represents an alkoxy group such as a methoxy group or an ethoxy group, a halogen atom, an acyl group, a hydroxyl group or a hydrogen atom. R ² represents a methyl group or an ethyl group, and a is 0, 1 or 2.
R ³ represents a substituted or unsubstituted alkylene group having 20 or less, preferably 2 to 6 carbon atoms, or an alkylene group having an oxygen atom or a nitrogen atom and having 20 or less carbon atoms.

R ⁴ , R ⁵ and R ^{6 each} have 1 to 20 carbon atoms.
, Preferably 1 to 18 linear or branched alkyl groups, aryl groups such as phenyl groups, or aralkyl groups such as benzyl groups, wherein the alkyl groups, aryl groups or aralkyl groups are hydroxyl groups or alkoxy groups. May be substituted. As R ^{4 to} R ⁶ , two groups are preferably a methyl group, and the remaining one group is preferably a combination of an alkyl group having 6 to 18 carbon atoms.

X represents an anion. Examples of the anion include halogen ions such as fluorine, chlorine, bromine and iodine, carboxyl ions such as formic acid, acetic acid and oxalic acid, sulfate ions, phosphate ions, methyl or dimethyl phosphate ions, and ethyl or diethyl phosphate ions. , Antimony fluoride ion, phosphorus fluoride ion, arsenic fluoride ion, boron fluoride ion, perchlorate ion and the like, and among them, halogen ion is preferable.

The silicone-based ammonium salt preferably has a silane coupling ability, has an alkoxysilane group in the compound, and reacts with a hydroxyl group on the sol surface and the alkoxysilane to be fixed on the particle surface.

The ammonium salt represented by the general formula (1) is, for example, 3- (trimethoxysilyl) -propyldimethyloctadecyl ammonium chloride 3- (trimethoxysilyl) -propyldimethylhexadecyl ammonium chloride 3- (trimethoxysilyl) ) -Propyldimethyltetradecylammonium chloride 3- (trimethoxysilyl) -propyldimethyldodecylammonium chloride 3- (trimethoxysilyl) -propyldimethyloctadecylammonium bromide and the like.

The content of the above-mentioned silicone-based ammonium salt in the sol medium is not uniform depending on the type, physical properties and application of the sol medium and the silicone-based ammonium salt, but is at least 1 ppm, specifically 10 ppm.
More than ppm is required. As a preferable content,
0.001 to 20% by weight, more preferably 0.01 to
It is in the range of 5% by weight.

The silicone-based ammonium salt preferably reacts with the sol medium by a condensation reaction and is fixed to the sol medium, but may be contained as a solution in the sol medium.

The antibacterial sol of the present invention contains the above-mentioned silicone-based ammonium salt in a sol medium or, if necessary, contains other antibacterial agents, chelating agents, dispersants,
Thickeners, defoamers, stabilizers, colorants, surfactants, and the like can be added. Other antibacterial agents include quaternary ammonium salts such as alkyldimethylbenzylammonium chloride and di-n-decyldimethylammonium chloride, tetraalkylphosphonium salts, 3- (trimethoxysilyl) -propyl-n-octylphosphonium chloride and the like. And phosphonium salts.

The antibacterial sol according to the present invention can be used for preserving various products such as paper, wood, rubber, plastics, fibers, paints, etc. by conventional methods such as dipping, spraying, roller coating and flow coating. Antibacterial properties can be imparted. Further, a desired solvent or a carrier such as powder, an auxiliary agent such as a surfactant, a coloring material, a dispersing agent, and other organic or inorganic antibacterial agents may be blended depending on the use and purpose.

The antibacterial sol of the present invention is composed of a sol medium containing a silicone-based ammonium salt having antibacterial properties. It has an excellent antibacterial effect against positive bacteria, gram-negative bacteria, molds, algae, yeasts, and the like, and also has an excellent algal protection effect against algae.

[0027]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 Colloidal silica [average particle size: 14 nm, 30% by weight Si
O ₂ , manufactured by Nippon Chemical Industry Co., Ltd., “Silica Doll”] 1
A predetermined amount (ammonium salt content per total weight: 2.5% by weight) of an antibacterial ammonium salt solution of 3- (trimethoxysilyl) -propyldimethyloctadecyl ammonium chloride was added to 00 g to prepare an antibacterial silica sol. .

Example 2 Colloidal silica [average particle size: 14 nm, 30% by weight Si
O ₂ , manufactured by Nippon Chemical Industry Co., Ltd., “Silica Doll”] 1
A predetermined amount (ammonium salt content per total weight: 2.5% by weight) of an antibacterial ammonium salt solution of 3- (trimethoxysilyl) -propyldimethylhexadecyl ammonium chloride was added to 00g to prepare an antibacterial silica sol. did.

[0030] Example 3 basic alumina sol prepared from aluminum chloride aqueous solution (average particle diameter: about 30 nm, 20 wt% A1 ₂ 0 ₃₎ 1
A predetermined amount (ammonium salt content per total weight: 2.5% by weight) of an antibacterial ammonium salt solution of 3- (trimethoxysilyl) -propyldimethyloctadecyl ammonium chloride was added to 00 g to prepare an antibacterial alumina sol. .

Example 4 Spherical large-particle-diameter silica sol obtained by growing particles of silica sol having an average particle diameter of 30 nm as a nucleus [dispersion medium having an average particle diameter of 300 nm;
Water-ethylene glycol (SiO ₂ : 32 wt%)]
After adding 2 g of 3- (trimethoxysilyl) -propyldimethyloctadecyl ammonium chloride and an appropriate amount of a dispersant to 100 g, the mixture was heated and stirred to prepare an antibacterial silica sol.

Example 5 1 g of basic aluminum chloride (A1 ₂ (OH) ₅ Cl) powder was added to 1000 g of a 1 wt% cellulose fiber dispersion.
Was added to hydrolyze the aluminum salt, and the aluminum hydrate was adhered to the cellulose. After cooling, 1 g of 3- (trimethoxysilyl) -propyldimethyloctadecyl ammonium chloride was added to the dispersion, and the mixture was added at 40 ° C. for 2 hours.
The mixture was hydrolyzed for 4 hours to fix an antibacterial agent on the aluminum-supported cellulose, thereby preparing about 1000 g of colloidal cellulose.

Example 6 Colloidal silica [average particle diameter 14 nm, 30 wt% Si
O ₂ , 0.02 wt% Na ₂ O, 0.1% Al ₂ O ₃ ,
pH 3.5] 100 g of 4 wt% acetic acid was added to 100 g, and the mixture was mixed uniformly. Then, 2 g of 3- (trimethoxysilyl) -propyldimethyloctadecyl ammonium chloride was added, and the mixture was hydrolyzed for 16 hours to disperse the antibacterial agent on the silica particles. This was immobilized to produce 202 g of a colloidal liquid.

(Antimicrobial activity test) The various antimicrobial wipes obtained in Examples 1 to 6 were subjected to an antimicrobial activity test.
The antibacterial activity test showed that Staphylococcus aureu was a representative of Gram-positive bacteria.
s) Antibacterial sol was allowed to act on IFO 12732 at the ammonium salt equivalent concentration and action time shown in Table 1. The results of the antibacterial activity test on Staphylococcus aureus are also shown in Table 1.

The evaluation of the antibacterial activity was carried out using physiological saline 54
6 ml of 710 ⁷ bacteria per ml was ingested per ml, the sample was brought into contact with the solution, and then the number of bacteria was measured by a solution dilution method. The numerical values in the table represent the number of bacteria (cells / ml), and the more the decrease in the number of bacteria with respect to the contact time, the stronger the antibacterial activity.

[0036]

[Table 1]

[0037]

As described above, the antibacterial sol according to the present invention has excellent antibacterial activity, for example, exhibits excellent antibacterial activity against various fungi, and has a surface-treated filler of various substrates. It is extremely useful for imparting antibacterial properties to adhesives, paints, papers, rubber products and the like.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Toshio Iijima 9-11-1, Kameido, Koto-ku, Tokyo Nippon Kagaku Kogyo Co., Ltd. Research and Development Division F-term (reference) 4H011 AA02 BA01 BC08 BC18 BC19

Claims (5)

[Claims] 1. An antibacterial sol comprising a sol medium containing an antibacterial silicone-based ammonium salt. 2. The silicone-based ammonium salt is represented by the following general formula (1): (Wherein, R ¹ is an alkoxy group, a halogen atom, an acyl group, a hydroxyl group or a hydrogen atom, R ² is a methyl group or an ethyl group, a is 0, 1 or 2, R ³ is a substituted or unsubstituted carbon atom. Is an alkylene group having 20 or less, or an alkylene group having an oxygen atom or a nitrogen atom and having 20 or less carbon atoms, and R ⁴ , R ⁵ , and R ⁶ are linear or branched having 1 to 20 carbon atoms. Wherein the alkyl group, the aryl group or the aralkyl group may be substituted with a hydroxyl group or an alkoxy group, and X represents an anion. 2. The antibacterial sol according to 1. 3. The antibacterial sol according to claim 1, wherein the silicone ammonium salt and the sol medium are fixed by a condensation reaction. 4. The antibacterial sol according to claim 1, wherein the sol medium is an aqueous sol or a non-aqueous sol. 5. The antibacterial sol according to claim 1, wherein the sol medium contains at least lppm or more of an antimicrobial silicone-based ammonium salt.