JP2536892B2 - Antibacterial treatment composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an antibacterial treatment composition.

[Technical background]

It is generally known that there are various kinds of harmful effects of microorganisms on clothes and living environments in human life. In particular, in recent years, the temperature and humidity environment created by the spread of air conditioning equipment in buildings such as reinforced concrete and the closed room of buildings has become an excellent residence for microorganisms. And these microorganisms only change, deteriorate, and corrode various things such as wall materials, furniture, kitchen furniture, bathroom walls and window frames, paper such as wallpaper, and textile products such as clothes and furniture. Not
It is also a cause of diseases such as allergies to people who live there. Under these circumstances, recently, there has been an increasing demand for means capable of effectively preventing the damage caused by microorganisms.

Conventionally, as an antibacterial and antifungal means for preventing harm by microorganisms, means using a chemical agent, that is, an antibacterial and antifungal agent is known, and specifically various halides, alcohols, Phenols, diphenyls, diphenyl diketones, diphenyl ethers, carboxylic acids, acid amides, heterocyclic compounds, amidines and guanidines, metal salts and organometallic compounds, and surfactants are known as antifungal agents. ing. These are used by a method of impregnating, coating, spraying an object or the like.

[Problems to be Solved by the Invention]

In the method of using such an antibacterial and antifungal agent, the antibacterial and antifungal agent to be used has a high antibacterial effect, that the antibacterial effect is highly durable, and that it is highly safe for the human body and the environment. As an important condition,
Conventional antibacterial and antifungal agents, for example, exhibit excellent antibacterial properties and safety, but do not satisfy all the requirements, for example, they have the drawback that they do not always have sufficient durability against an object.

[Object of the Invention]

The present invention has an excellent antibacterial effect for a long time even when it has a large durability of adhesion to an object and is repeatedly washed or continuously contacted with water or the like. It is intended to provide an antibacterial treatment composition.

[Means for solving the problem]

The antibacterial treatment composition of the present invention comprises (A) an antibacterial agent selected from organosilicon quaternary ammonium salts and organosilicon amphoteric surfactants, (B) an aqueous polyurethane resin, and (C) the following formula: (D in the formula R'is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R "is a divalent hydrocarbon group having 1 to 6 carbon atoms, R
Represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, X represents a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, and m is 0.
Or 1 and a, b and c are each 0 <a ≦
3, 0 ≦ b ≦ 3 and 0 ≦ c ≦ 3 and 0 <(a + b +
c) ≦ 4. However, when (a + b + c) = 4, m
Is 1, and when (a + b + c) <4 and m = 0, there are at least two siloxane units containing R'-NH-R "in one molecule.) A silicon compound is included, and (A) the antibacterial agent is 0.05% or more and (B) the aqueous polyurethane resin is 0.1 to 1 per unit weight of the object to be treated.
0% and (C) the organosilicon compound are contained in the range of 0.05 to 3% in such a proportion that they are attached to the object to be treated.

[Action and effect]

The antibacterial treatment composition of the present invention can be obtained by using, for example, natural fibers such as cotton, wool and silk, synthetic fibers such as polyester, nylon and acrylic, genuine leather, synthetic leather, wood, paper, non-woven fabric, natural rubber and plastics. By subjecting the surface of an object made of ceramics, metal or the like to further heat treatment, an excellent antibacterial effect can be imparted to the object, and the antibacterial durability is extremely excellent.

 Hereinafter, the present invention will be specifically described.

The antibacterial treatment composition according to the present invention, a specific antibacterial agent,
It comprises an aqueous polyurethane resin and an amino-functional organosilicon compound.

In the present invention, an organosilicon quaternary ammonium salt or an organosilicon amphoteric surfactant is used as the antibacterial agent. The above-mentioned organosilicon quaternary ammonium salt is a known one represented by the following general formula (I) and is usually commercially available as an alcohol solution.

General formula _{^{(I) R 1 3 N +}} R 2 SiR 3 m X '3-m · Y - wherein X' is a halogen atom, an alkoxy group, a hydrolyzable group such as an acyl group, Y represents chlorine or It is bromine. R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms, particularly two of the three R ¹ are methyl groups and the other 1
It is preferred that one is an alkyl group having 8 to 22 carbon atoms. R ² is a divalent hydrocarbon group, particularly preferably an alkylene group having 2 to 4 carbon atoms or —CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ —. R ³ is a lower alkyl group such as a methyl group, a phenyl group or CF ₃ C
It is a H ₂ CH ₂ group. m represents 0, 1 or 2, and is preferably 0.

Among the above organosilicon quaternary ammonium salts, those represented by the following formulas are particularly preferable.

(In the formula, R ⁴ represents an alkyl group having 8 to 22 carbon atoms.) As described above, the organosilicon quaternary ammonium salt is a known gram-positive bacterium, gram-negative bacterium, mold, algae, yeast. It has an excellent antibacterial effect against bacteria, that is, an antibacterial effect against bacteria, an antifungal effect, and an algae controlling effect.

Further, the organosilicon amphoteric surfactant is represented by the following general formula (II).

In the general formula ^{(II) R 5 M 1 QM} 2 n G [ wherein, R ⁵ represents a monovalent hydrocarbon group of the hydrophobic, Q represents an alkylene group or a phenylene group having 1 to 7 carbon atoms, M ¹ and M ² are the same or different from each other, {R ⁶ is a hydrogen atom or R ⁷ (R ⁷ is an alkyl group having 4 or less carbon atoms or a phenyl group), A ¹ is a group having -ZCOOH (Z is an alkylene group or a substituted alkylene group), A ² is -ZCOO ^- group with, a ³ is -YSiR ⁸ _r (oR ⁹⁾ groups having _3-r (Y is a divalent hydrocarbon group (-COO- or -O- group or a cyclic structure having 1 to 8 carbon atoms R ⁸ represents an alkyl group, R ⁹ represents an alkyl group or an acyl group, r is 0,
1 or 2. ) Is represented. } Is a group selected from R, G is a group selected from R ⁵ , A ¹ , A ² and A ³ (R ⁶ , A ¹ , A ²
And A ³ are as defined above. ), N represents 0 or an integer of 1 to 4, and there is at least one group represented by A ¹ or A ² in the molecule, and at least one group represented by A ³ . The nitrogen atom present in the molecule may form a salt with hydrogen halide. However, the formula (v
The group represented by i) always coexists with the group represented by formula (iii). ] It is characterized by comprising a silyl group-containing compound represented by.

This organosilicon amphoteric surfactant is basically an amine compound having a carboxyl group and has characteristics as a so-called carboxylic acid type amphoteric surfactant, and therefore exhibits an excellent antibacterial effect and silyl group. Since it is a compound that also contains a group, the silyl group not only physically attaches to the substrate to which it is applied, but also chemically bonds and attaches it. As a result, great durability is obtained and the antibacterial effect is maintained for a long time.

The antibacterial treatment composition of the present invention comprises at least one of the above-mentioned organosilicon quaternary ammonium salt or organosilicon amphoteric surfactant, an aqueous polyurethane resin and an amino-functional organosilicon compound.

The aqueous polyurethane resin used in the present invention is
It may be dispersible or soluble in water by using an emulsifier, or may be dispersible or soluble in water by self-emulsification without using an emulsifier.

Specifically, the polyurethane resin has an isocyanate group (-
It can be obtained by reacting an isocyanate compound having NCO) with an active hydrogen-containing compound. Examples of the active hydrogen-containing compound here include a hydroxyl group-containing compound that forms a urethane bond, an amino compound or water that forms a urea bond, a carboxylic acid that forms an amide bond, a compound containing an -NHCOO- group that forms an allophanate bond, and a biuret bond. , A compound containing a -NHCONH- group, a compound containing a -NHCO- group forming an acylurea bond and the like.

Typical raw materials for polyurethane resins are polyisocyanates and polyols. Specific examples of the polyisocyanate include tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, aromatic diisocyanates such as 1,5-naphthylene diisocyanate and hexamethylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, Aliphatic diisocyanates such as 4,4'-dichlorohexylmethane diisocyanate and isophorone diisocyanate, and the like can be mentioned.

Specific examples of the polyol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene triol, polyether polyols such as polyoxytetramethylene glycol, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexylene adipate, Examples thereof include polyester-based polyols such as polyethylene-butylene adipate and polycaprolactone, acrylic polyols, castor oil, and the like.

And, as the chain extender or crosslinking agent in the polyurethane forming reaction, polyols, polyamines and water can be mentioned, and specific examples of the polyols include ethylene glycol, propylene glycol, butanediol, hexanediol, diethylene glycol,
Glycerin, trimethylolpropane and the like, and specific examples of polyamines include hydrazine, ethylenediamine, propylenediamine, diethylenetriamine, 4,
Examples thereof include 4'-diaminodiphenylmethane and 4,4'-diaminodicyclohexylmethane.

Aqueous polyurethane resin is commercially available and is produced by the following known method.

I. Method of using a water-soluble raw material A method of using a water-soluble oligomer such as polyoxyethylene glycol as a raw material polyol and forming a urethane resin by chain extension of this oligomer with a urethane bond.

II. Self-emulsifier By introducing a hydrophilic group (quaternary ammonium group, sulfonate, carboxylate) into the main chain or side chain of urethane,
This is a method of emulsifying a resin in water, and examples of the product include SOFTEX U-100 and UE-296A manufactured by Kao Corporation.

III. Method of performing elongation-reduction reaction in an emulsified state A method of performing elongation-reduction reaction of a urethane prepolymer with a polyamine such as hydrazine or ethylenediamine or water in an emulsifier aqueous solution.

IV. Method of using blocked isocyanates Isocyanate groups that react with water, oximes, lactams, phenols, active methylene compounds, amides, amines,
Block protection with alcohols, imides, sodium bisulfites, thiols, boric acid, etc. and dispersion with emulsifier in an aqueous emulsifier solution, or urethane prepolymer having blocked hydrophilic segment or hydrophilic group Can be dispersed or dissolved in water.
The product is Elastron A- from Daiichi Kogyo Seiyaku Co., Ltd.
42, Elastron W-11, Elastron MF-9; Nevahua Chemical Co., Ltd. Evaphanol N, Evaphanol NS, Evaphanol AS-1; Miyoshi Oil & Fat Co., Ltd. Muron FM-100
Are commercially available.

V. Method to forcibly emulsify urethane resin in an emulsifier aqueous solution As a product, Nevaka Chemical Co., Ltd. Evaphanol NS-
2, Evaphanol S-5 and the like.

The specific amino-functional organosilicon compound used in the present invention is an amino group-containing organosilane or amino group-containing organopolysiloxane represented by the following average formula.

(D in the formula R'is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R "is a divalent hydrocarbon group having 1 to 6 carbon atoms, R
Represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, X represents a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, and m is 0.
Or 1 and a, b and c are each 0 <a ≦
3, 0 ≦ b ≦ 3 and 0 ≦ c ≦ 3 and 0 <(a + b +
c) ≦ 4. However, when (a + b + c) = 4, m
Is 1 and when (a + b + c) <4 and m = 0, there are at least two siloxane units containing R'-NH-R "in one molecule.) R'is preferably a hydrogen atom. However, alkyl groups such as methyl, ethyl, propyl, butyl, and isobutyl,
It may be a cyclohexyl group or a phenyl group. R ″ is an alkylene group or a phenylene group, and is —CH ₂ CH ₂ CH ₂
- or _{-CH 2 CH (CH 3) CH} 2 - is preferably.
Examples of the alkoxy group of X include a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

When a + b + c = 4 in the above formula, it is an amino group-containing organosilane, Other examples include N-aminoethyl-3-aminopropyltrimethoxysilane and N-aminoethyl-3-aminopropylmethyldimethoxysilane.

When a + b + c <4 in the above formula, the amino group-containing organopolysiloxane has a structural formula of DSiO _3/2 , DRSiO _2/2 , DR ₂ SiO _1/2 , DRXSiO _1/2 , DX ₂
SiO _1/2 , RXSiO _2/2 , R ₂ XSiO _1/2 , R ₂ SiO _2/2 , R ₃ SiO _1/2 , R
At least one siloxane unit composed of a siloxane unit selected from SiO _3/2 , XSiO _3/2 , and SiO _2/2 and containing a D group in one molecule (when the D group is R′NHR ″ — The organopolysiloxane may be cyclic, linear or branched, for example R ₃ SiO (R ₂ SiO) _p (RDSiO) _q SiR ₃ , DX ₂ SiO (R ₂ SiO) _p SiX ₂ D.

As the object to which the antibacterial treatment composition of the present invention is applied, cotton, natural fibers such as wool, polyester, polyamide, acrylic, synthetic fibers such as polyvinyl alcohol,
Animal skins, synthetic leather, wood, paper, non-woven fabric, natural rubber,
Examples thereof include synthetic rubber, plastic, ceramic, metal and the like.

In order to apply the antibacterial treatment composition of the present invention to an object, an antibacterial agent comprising an organosilicon quaternary ammonium salt and / or an organosilicon amphoteric surfactant in an appropriate concentration is used as an aqueous polyurethane resin. A treatment liquid is obtained by dissolving it in a solvent such as water together with an amino-functional organosilicon compound, and an object to be treated in this treatment liquid is treated by an ordinary method such as dipping, padding, spraying or coating, and then dried. And heat treated. The temperature of this heat treatment is preferably 40 to 180 ° C., particularly 50 to 160 ° C., and the heat treatment time is preferably in the range of 30 seconds to 60 minutes. When the amino group-containing organopolysiloxane is used, it is preferable to add a surfactant such as a polysiloxane-polyglycol copolymer in order to accelerate the dispersion in the aqueous solution.

The amount of antibacterial agent attached to an object is related to the obtained antibacterial effect, and is 0 per unit weight of the object in terms of active ingredient.
It must be at least 05% by weight. It is not necessary to set the upper limit of the amount of antibacterial agent deposited, but in practice it is usually
A range of 10% or less is sufficient.

The amount of water-based polyurethane resin used, calculated as active ingredients,
It is within the range of 0.1 to 10% per unit weight of the object.
If the amount of the aqueous polyurethane resin used is large, the viscosity of the treatment liquid may be high and the treatment operation may be difficult.

The amount of the amino-functional organosilicon compound used is, in terms of active ingredient, in the range of 0.05 to 3% per unit weight of the object, and particularly preferably 0.05 to 2%. If the amount used exceeds 3%, the viscosity of the treatment liquid may increase, causing yellowing of the treated material.
If it is less than 05%, the object of the present invention cannot be sufficiently achieved.

Although the reason why the excellent effect is obtained by the antibacterial treatment composition of the present invention has not been clarified, the three-dimensional network structure of the antibacterial agent produced in the aqueous solution and by the heat treatment and the three-dimensional network structure of the aqueous polyurethane resin have both Amino-functional organosilicon compounds having two or more amino groups that have a catalytic effect on the reactive groups and that themselves form a three-dimensional network structure are intricately entangled, and SiOH groups and organosilicones formed by reactive silicones Functional group based on quaternary ammonium salt or organosilicon amphoteric surfactant,
It is considered that the isocyanate group of the water-based polyurethane resin reacts with the functional group existing in the object to be bonded, and as a result, an antibacterial surface having excellent durability can be obtained.

If necessary, various antioxidants and other additives can be added to the treatment liquid used in the present invention.

〔Example〕

Examples will be described below, but the present invention is not limited thereto.

Example 1 3-trimethoxysilyl-propyloctadecyl-di
42% methanol solution of methyl-ammonium chloride
1.0% by weight of the heat-reactive aqueous polyurethane resin "Eras"
TRON MF-9 "(active ingredient 30%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
7.0% by weight and N-β-aminoethyl-γ-aminop
Ropil-trimethoxysilane "Dow Corning Z602
0 "(manufactured by Dow Corning, USA) at a ratio of 1.0% by weight.
A treatment liquid consisting of the mixed aqueous solution was prepared.

After immersing the exposed fabric of a jersey (raw fabric for dyeing test) of 100% wire fiber in hot water after immersing in this treatment liquid, squeeze
The squeezing machine "Pneumatic Mangle VPM-
2A type ”(manufactured by Tsujii Dyeing Machinery Co., Ltd.), and the ratio of each active ingredient is 0.42% owf, 2.1% owf per unit weight of the object to be treated.
It processed so that it might be 1.0% owf. Apply this treated cloth at 80 ℃ for 15
After drying for 1 minute, heat treatment was performed at 160 ° C. for 2 minutes.

In addition, "% owf" is the weight percentage of the antibacterial treatment composition component per unit weight of the test cloth.

Example 2 3-trimethoxysilyl-propyloctadecyl-di
42% methanol solution of methyl-ammonium chloride
1.0% by weight, a heat-reactive aqueous polyurethane resin "Evafu
6.5% of "Anor N" (active ingredient 30%, Nichika Chemical Co., Ltd.)
% And N-β-aminoethyl-γ-aminopropyl
-Trimethoxysilane "Dow Corning Z6020 '' 1.0
Prepare a treatment liquid consisting of a mixed aqueous solution containing it in a weight percentage.
Made.

Using this treatment liquid, the same treatment as in Example 1 was performed,
The percentage of each active ingredient is 0.42% owf, 1.95% owf and 1.0% o
Processed to be wf. The treated cloth was dried at 80 ° C. for 15 minutes and then heat-treated at 160 ° C. for 2 minutes.

Example 3 3-trimethoxysilyl-propyloctadecyl-di
42% methanol solution of methyl-ammonium chloride
1.0% by weight, a heat-reactive aqueous polyurethane resin "Evafu
ANOL AS-1 "(active ingredient 30%, Nichika Chemical Co., Ltd.) 6.
5% by weight and N-β-aminoethyl-γ-aminopro
Pill-trimethoxysilane "Dow Corning Z6020 ''
Treatment with a mixed aqueous solution containing 1.0% by weight of
A liquid was prepared.

Using this treatment liquid, the same treatment as in Example 1 was performed,
The percentage of each active ingredient is 0.42% owf, 1.95% owf and 1.0% o
Processed to be wf. The treated cloth was dried at 80 ° C. for 15 minutes and then heat-treated at 160 ° C. for 2 minutes.

Example 4 3-trimethoxysilyl-propyloctadecyl-di
42% methanol solution of methyl-ammonium chloride
1.0% by weight of the heat-reactive aqueous polyurethane resin "MU
Ron FM-100 "(made by Miyoshi Yushi Co., Ltd.) 5.0% by weight and N
-Β-aminoethyl-γ-aminopropyl-trimethoxy
Sisilane "Dow Corning Z6020 "1.0% by weight
A treatment liquid comprising the mixed aqueous solution contained in 1. was prepared.

Using this treatment liquid, the same treatment as in Example 1 was performed,
The percentage of each active ingredient is 0.42% owf, 1.95% owf and 1.0 owf
It was processed so that The treated cloth was dried at 80 ° C. for 15 minutes and then heat-treated at 160 ° C. for 2 minutes.

Example 5 3-Trimethoxysilyl-propyloctadecyl-di
42% methanol solution of methyl-ammonium chloride
1.0% by weight of water-based polyurethane resin "SOFTEX U
−100 ”(89% active ingredient, manufactured by Kao) and 2.0% by weight
N-β-aminoethyl-γ-aminopropyl-trimetho
Xysilane "Dow Corning Z6020 ”is 1.0% by weight
A treatment liquid consisting of a mixed aqueous solution containing the above components was prepared.

Using this treatment liquid, the same treatment as in Example 1 was performed,
The ratio of each active ingredient is 0.42% owf, 1.79% owf and 1.0% o
Processed to be wf. The treated cloth was dried at 80 ° C. for 15 minutes and then heat-treated at 160 ° C. for 2 minutes.

Example 6 3-Trimethoxysilyl-propyloctadecyl-di
42% methanol solution of methyl-ammonium chloride
2.0% by weight, a heat-reactive aqueous polyurethane resin "Evafu
"ANOL AS-1" (active ingredient 30%, Nichika Chemical Co., Ltd.) 1
4.0% by weight and N-β-aminoethyl-γ-aminop
Ropil-trimethoxysilane "Dow Corning Z602
0 "at a ratio of 2.0 wt%
A solution was prepared.

To this treatment liquid, 100% polyester taffeta (raw cloth for dyeing test) was washed with hot water and then immersed, and the same treatment as in Example 1 was performed except that the squeezing ratio was 50%. Treatments were 0.42% owf, 2.0% owf and 1.0% owf. After drying this treated cloth at 80 ℃ for 15 minutes, 160 ℃
And heat treated for 2 minutes.

Example 7 The same process as in Example 6 was carried out except that 100% nylon taffeta (raw fabric for dyeing test) was used as the test fabric.

Example 8 3-Trimethoxysilyl-propyloctadecyl-di
42% methanol solution of methyl-ammonium chloride
1.0% by weight, a heat-reactive aqueous polyurethane resin "Evafu
6.5% of "Anor N" (active ingredient 30%, Nichika Chemical Co., Ltd.)
% And an amino group-containing organopolysiloxane of the following formula (CH₃)₃SiO [(CH₃)₂SiO]₉₆−And polysiloxane-polyglycol copolymer "Dowko"
Training 190 Surfactant "(Dow Corning, USA)
1.5% by weight of a mixture of and with a weight ratio of 1: 2
Prepare a treatment solution consisting of a mixed aqueous solution containing
Was.

Using this treatment liquid, the same treatment as in Example 1 was performed,
The percentage of each active ingredient is 0.42% owf, 1.95% owf and 0.5% o
Processed to be wf. The treated cloth was dried at 80 ° C. for 15 minutes and then heat-treated at 160 ° C. for 2 minutes.

Comparative Examples 1-5 N-β-aminoethyl in the treatment liquids of Examples 1-5
-Γ-aminopropyl-trimethoxysilane "Dowco
Training Z6020 ”instead of γ-aminopropyltriene
Methoxysilane “A-1100” (manufactured by Nippon Unicar) 1.0
Except for using the treatment liquid contained in a proportion of weight%
Processed as in Examples 1-5.

Comparative Examples 6 to 7 N-β-aminoethyl in the treatment liquids of Examples 6 to 7
-Γ-aminopropyl-trimethoxysilane "Dowco
Training Z6020 ”instead of γ-aminopropyltriene
Methoxysilane "A-1100" (manufactured by Nippon Unicar) 2.0
Except for using the treatment liquid contained in a proportion of weight%
Processed as in Examples 6-7.

Comparative Examples 8 to 14 N-β-aminoethyl in the treatment liquids of Examples 1 to 7
-Γ-aminopropyl-trimethoxysilane "Dowco
Training "Z6020" was removed and used as the processing liquid
Others were processed similarly to Examples 1-7.

Comparative Examples 15-17 Cotton 100 similar to that used in Examples 1, 6 and 7.
% Jersey, 100% polyester taffeta and nylon 1
00% taffeta was used as a test cloth, and 3-
Using only trimethoxysilyl-propyloctadecyl-dimethyl-ammonium chloride, treatment was carried out so that the ratio of the active ingredient was 0.42% owf, and otherwise, drying and heat treatment were carried out in the same manner as in Example 1.

For each of the test cloths treated according to the above-mentioned examples and comparative rows, the sterilization rate was calculated by the shake flask method without washing or after washing a predetermined number of times.

In each washing treatment, "Nissan Nonion NS-210" manufactured by NOF CORPORATION was used as a detergent against 1 water.
It was used at a rate of 0.5 g, washed with a household electric washing machine at a water temperature of 40 ° C. and a bath ratio of 1:30 for 5 minutes, and then washed with water for 5 minutes while overflowing.

The shake flask method is based on the US AATCC Test Method.
It is an improved method of 100, forcibly contacting the test cloth and bacteria, making a state close to the state of actual skin and bacteria,
This is a method for quantitatively measuring the antibacterial effect. In particular,
The following operations (1) to (6) are executed.

(1) 0 of the test sample (antibacterial treated fiber or raw cloth).
Make a strip of 75g and use this as a test piece.

(2) 70 ml of sterilized phosphate buffer was placed in an Erlenmeyer flask with a volume of 200 ml, and 1.5 × 10 ^{5 to} 3 of the bacteria Klebsiella pneumoniae ATCC4352 was added.
Inoculate 5 ml of the bacterial solution containing x10 ⁵ / ml.

(3) Collect 1 ml of the bacterial solution from this Erlenmeyer flask, transfer to a test tube containing 9 ml of sterile phosphate buffer, and mix evenly. 1 ml of this mixed solution is further mixed and diluted with 9 ml of sterile phosphate buffer solution. Take 1 ml of this re-diluted bacterial solution, put in a sterilized petri dish, and add 16 to 20 ml of tryptone glucose extract agar medium to solidify. This is cultured at a temperature of 37 ° C. for 18 to 24 hours.

(4) Operation (1) for Erlenmeyer flask in operation (2)
The test piece of the above is put, and this is shaken with a wrist action shaker (Wrist Action Shaker) for 1 hour. Then, in the same manner as in the operation (3), the bacterial solution from the Erlenmeyer flask is directly or once or twice mixed and diluted with a sterilized phosphate buffer solution, and then transferred to a Petri dish, and the medium is added and cultured.

(5) Count the number of bacteria after culturing obtained in the operation (3) and the operation (4), and calculate the sterilization rate according to the following formula.

(6) The same operation is performed on the same fiber or raw cloth except that it is not subjected to antibacterial treatment.

The above results are shown in Table 1. The contents of the symbols in Table 1 are as follows.

"MF-9" ... "Elastron MF-9""E-N" ... "Evaphanol N""AS-1" ... "Evaphanol AS-1""FM-100" ... "Muron FM-100""U-100""... Softex U-100""Z6020" ... N-β-aminoethyl-γ-aminopropyl-trimethoxysilane "Dow Corning Z6020""A-1100" ... γ-aminopropyltrimethoxysilane "A-1100""C" ... Cotton "P" ... Polyester "N" ... Nylon From the results shown in Table 1, the antibacterial treatment composition of the present invention has excellent antibacterial effect and excellent washing resistance. it is obvious.

Claims (1)

(57) [Claims] 1. An antibacterial agent selected from (A) an organosilicon quaternary ammonium salt and an organosilicon amphoteric surfactant, (B) an aqueous polyurethane resin, and (C) the following formula: (D in the formula Is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ″ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and R is a monovalent hydrocarbon group having 1 to 6 carbon atoms. , X represents a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, m is 0 or 1, and a, b and c are each 0 <a ≦ 3,
0 ≦ b ≦ 3 and 0 ≦ c ≦ 3 and 0 <(a + b + c)
≦ 4. However, when (a + b + c) = 4, m is 1
And when (a + b + c) <4 and m = 0,
There are at least two siloxane units containing R'-NH-R "in one molecule.) An amino-functional organosilicon compound represented by the formula: and an effective amount per unit weight of the object to be treated. As a component, (A) antibacterial agent is 0.05% or more, and (B) aqueous polyurethane resin is 0.1 to 10
%, And (C) an organosilicon compound in an amount of 0.05 to 3% in such a proportion that they are attached to the object to be treated.