JPH0786082B2 - Antibacterial treatment agent and antibacterial treatment method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to an antibacterial treatment agent for imparting antibacterial properties to an object to be treated, and an antibacterial treatment for suitably applying the antibacterial treatment agent. Regarding the method.

[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 and the closed rooms of buildings has become a suitable home for microorganisms. And these microorganisms only change, deteriorate, and corrode various materials such as wall materials, furniture, kitchen furniture, bathroom walls and window frames, paper such as wallpaper, and textile products such as clothes and bedding. Not only that, but it also causes 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, diphenyldiketones, diphenylethers, carboxylic acids,
Acid amides, heterocyclic compounds, amidines and guanidines, metal ions and organometallic compounds, and surfactants are known as antibacterial and antifungal agents. 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 and antifungal agent has great durability, and that it is highly safe for humans and the environment. , Which is mentioned as an important condition, conventional antibacterial and antifungal agents, for example, show excellent antibacterial properties and safety, but have the drawback that the durability of adhesion to the object is not always sufficient, etc. Not all requirements are satisfied.

Under such a technical background, it has been found that an aqueous composition comprising a specific antibacterial agent and an amino-functional polysiloxane provides relatively good antibacterial effect durability. However, in this technique, in order to obtain a composition in which the amino-functional polysiloxane is stably dispersed, it is necessary to previously emulsify the amino-functional polysiloxane with an appropriate surfactant. However, due to the presence of this surfactant, the reaction between the antibacterial agent and the amino-functional polysiloxane or the adhesion to the article to be treated is not always sufficiently achieved, and as a result, There is a problem that the durability of the composition applied to the treated product is still insufficient and the antibacterial effect is gradually lost due to repeated washing treatment or friction.

[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. An object is to provide an antibacterial treatment agent.

Another object of the present invention is, when applying the antibacterial treatment agent, a desired reaction or action by each component thereof is sufficiently achieved, and as a result, an antibacterial treatment having excellent antibacterial effect durability is obtained. To provide a method.

[Means for Solving the Problems]

The antibacterial treatment agent of the present invention comprises the following component (a), component (b) and component (c), and the component (a) as an active ingredient is 0.05 per unit weight of the object to be treated. %
As described above, the component (b) is 0.1 to 10% and the component (c) is 0.000.
It is characterized by being added at a rate of 1 to 10%.

Component (a): Antibacterial agent selected from organosilicon quaternary ammonium salt Component (b): Formula {Where D is (R 'represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R "represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and m is 0 or 1.) R has 1 carbon atom
To 6 monovalent hydrocarbon groups, X represents a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, and a, b and c are 0 <a ≦ 3, 0 ≦ b ≦ 3 and 0 <c ≦ 3, respectively. And 0
<(A + b + c) <4, and at least one D group and one X group are present in each molecule. } Amino-functional polysiloxane represented by the following formula: Component (c): Organometallic compound selected from organic titanic acid esters The antibacterial treatment method of the present invention comprises: ) As an active ingredient in a proportion of 0.05% or more, and then, under wet conditions, the component (b) and the component (c) are added as an active ingredient per unit weight of the object to be treated. (B) is adsorbed at a ratio of 0.1 to 10% and the component (c) is adsorbed at a ratio of 0.0001 to 10%.

Alternatively, the component (b) is 0.1 to 10% and the component (c) is 0.0001 to 10% per unit weight of the material to be treated, with the components (b) and (c) as active ingredients. It is characterized in that the component (a) is adsorbed to the object to be treated at a rate of 0.05% or more as an active ingredient per unit weight under a wet condition.

[Operation and effect of the invention]

The antibacterial treatment agent of the present invention, for example, cotton, silk, natural fibers such as wool, polyester, polyamide, synthetic fibers such as polyacrylonitrile, natural leather, synthetic leather,
An object made of wood, paper, non-woven fabric, natural rubber, synthetic rubber, plastic, ceramics, metal, etc. is treated as an object to be treated so as to be adsorbed or adhered to its surface,
Further, by heat-treating as required, an excellent antibacterial effect can be imparted to the object to be treated, and the durability of the antibacterial effect is extremely excellent.

Hereinafter, the present invention will be specifically described.

The antibacterial treatment agent according to the present invention comprises a component (a) composed of a specific antibacterial agent, a component (b) composed of a specific amino-functional polysiloxane, and a component (c) composed of a specific organometallic compound. It consists of

In the present invention, an organosilicon quaternary ammonium salt is used as the component (a) 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 k X '3-k · Y - wherein X' is a halogen atom, an alkoxy group, a hydrolyzable group such as an acyl group, Y represents chlorine or It is a halogen atom such as bromine. R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms, and particularly 2 of 3 R ¹
It is preferred that one is a methyl group and the other is an alkyl group having 8 to 22 carbon atoms. R ² is a divalent hydrocarbon group, particularly an alkylene group having 2 to 4 carbon atoms or-
CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ − is preferable. R ³ is a lower alkyl group such as a methyl group, a phenyl group or CF ₃ CH ₂
It is a CH ₂ group. k represents 0, 1 or 2, and is preferably 0.

Among the above-mentioned 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.) The above-mentioned organosilicon quaternary ammonium salt is
As is known, it has an excellent antibacterial effect against Gram-positive bacteria, Gram-negative bacteria, molds, algae, yeasts, etc., that is, an antibacterial effect against bacteria, a fungicide-preventing effect and an algae-controlling effect.

In the present invention, a specific amino-functional polysiloxane is used as the component (b). This particular amino-functional polysiloxane is an amino group-containing organopolysiloxane represented by the following average formula.

{Where D is (Here, R ′ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ″ represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and m is 0 or 1. ), 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 a, b and c are 0 <a ≦ 3 and 0 ≦ b ≦, respectively.
3 and 0 <c ≦ 3 and 0 <(a + b + c) <4, and each of the D group and the X group is at least 1 in one molecule.
Exist. } R ′ is preferably a hydrogen atom, but methyl, ethyl,
It may be an alkyl group such as propyl, butyl or isobutyl, a cyclohexyl group or a phenyl group. R ″ is an alkylene group or a phenylene group, and is preferably —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH (CH ₃ ) CH ₂ —. The alkoxy group of X is a methoxy group, an ethoxy group or propoxy group. Examples thereof include a group and a butoxy group.

The amino group-containing organopolysiloxane has a structural formula DS
iO _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 , RSiO _3/2 ,
It is composed of a siloxane unit selected from XSiO _3/2 and SiO _4/2 , and at least one D group and at least one X group must be present in each molecule. This organopolysiloxane may be chain-like, branched-chain or cyclic. Examples of preferred organopolysiloxanes include, for example, R ₂ XSiO (R ₂ SiO) _p (DXSiO) _q SiXR ₂ DX ₂ SiO (R ₂ SiO) _p SiX ₂ DR ₂ XSiO (R ₂ SiO) _p SiXRD, Examples of particularly preferable amino group-containing organopolysiloxanes are as follows.

X (CH ₃ ) ₂ SiO {(CH ₃ ) ₂ SiO} _x- (DXSiO) _y Si (CH ₃ ) ₂ X, D (X) ₂ SiO {(CH ₃ ) ₂ SiO} _x Si (X) ₂ D , D (X) (CH ₃ ) SiO {(CH ₃ ) ₂ SiO} _x -Si (CH ₃ ) (X) D, X (CH ₃ ) ₂ SiO {(CH ₃ ) ₂ SiO} _x -Si (CH _{3) (X) D DSi [} {(CH 3) 2 SiO} x Si (CH 3) 2 X] 3 in the formulas above, X is -OH or -OCH _3, D is -CH
₂ CH ₂ CH ₂ NH ₂ or −CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ is shown.

Such an amino-functional polysiloxane is obtained by reacting an amino-functional alkoxysilane with a terminal hydroxyl group-containing polydiorganosiloxane or by reacting an amino-functional alkoxysilane with an terminal hydroxyl group-containing polydiorganosiloxane and an alkylalkoxysilane. Although it can be obtained by the method described above, the detailed description thereof is omitted because the reaction is known.

When the amino-functional polysiloxane used as the component (b) has a low solubility in water, it may be necessary to emulsify the amino-functional polysiloxane using an appropriate emulsifier before use. .

Specific examples of emulsifiers used in such cases include:
Nonionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, polyoxyalkylene alkyl esters, sorbitan alkyl esters, polyoxyalkylene sorbitan alkyl esters, aliphatic amine salts, quaternary ammonium Examples thereof include cationic surfactants such as salts. As an emulsifier to be actually used, it is desirable to select an emulsifier that is not easily adsorbed on the object to be treated.

In the present invention, an organometallic compound selected from organic titanic acid esters is used as the component (c). This organometallic compound is an essential component for effectively adsorbing the component (b) dissolved or emulsified in water to the fiber or other object to be treated.

Specific examples of this component (c) include di-n-propyloxy (triethanolamine) titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetrastearyl titanate, triethanolamine titanate, titanium. Mention may be made of acetylacetotitanate, titanium ethylacetoacetate, titanium lactate and their partial hydrolysis-condensation products. This organometallic compound may be used alone or in combination of two or more.

The addition amount of this component (c) is the same as that of the component (b) as described above.
It is 0.1 to 100 parts by weight with respect to 100 parts by weight, but in the processing method 1 in which the component (a) is adsorbed prior to the component (b) and the component (c), the component (c) is added. Considering the residual concentration of the component (a) in the treatment liquid, it is particularly preferable that the amount is 1.0 part by weight or more per 100 parts by weight of the component (b), while the components (b) and (c) are added to the component (b). In Treatment Method 2 in which adsorption is performed prior to a), it is not necessary to take the residual concentration into consideration, and therefore component (b) 100
It can also be used in a ratio of 50 parts by weight or less with respect to parts by weight.

In the present invention, in addition to the above-mentioned components (a), (b) and (c), organosilane compounds and organometallic compounds such as tin, zinc, lead and cobalt which are known as condensation reaction catalysts, and others Additives can be used together.

The above antibacterial treatment agent of the present invention is preferably applied to an object to be treated by the following treatment method 1 or treatment method 2.

[Treatment Method 1] A required amount of the component (a) is dissolved in a sufficient amount of water for completely immersing the object to be treated, and the solution is used as a bath to immerse the object to be treated in the object to be treated. Adsorb substantially all of component (a). The fact that substantially all of the component (a) is adsorbed means that the presence or absence of the component (a) remaining in the treatment liquid of the bath is determined by, for example, a color reaction with bromphenol blue (hereinafter referred to as “BP”).
"B reaction"). The temperature of the bath in this adsorption treatment is preferably 30 to 70 ° C, particularly 40 to 60 ° C. It is also possible to add to the bath a salt that promotes adsorption by adjusting the pH of the bath to a range of 7 to 10 and stabilizes the adsorption state such as magnesium sulfate.

After adsorbing the component (a) in this way, the required amount of the component (b) and the component (c) are added to the bath while the object to be treated is immersed, and the bath is treated with an organic acid such as acetic acid. The pH is adjusted to 3 to 7, preferably 4 to 6, so that substantially all of the components (b) and (c) are adsorbed on the object to be treated. In this process, the component (b) and the component (c) are selectively adsorbed to the object to be treated by the action of the component (c) as compared with the other components. It is possible to suppress the adsorption of the emulsifier used for emulsification of the above to the object to be treated. The fact that substantially all of the components (b) and (c) have been adsorbed can be confirmed by utilizing the property that the treatment liquid in the bath changes from an opalescent state to a transparent state. The temperature of the bath in this adsorption treatment is preferably 10 to 60 ° C, particularly 20 to 40 ° C.

The object to be treated that has undergone the above-described two adsorption processes is
It may be simply dehydrated and dried, but 100-180
It is preferred to heat to ° C.

The amount of the component (a) attached to the object to be treated is related to the magnitude of the antibacterial effect to be obtained, and needs to be 0.05% or more per unit weight of the object to be treated in terms of active ingredient.
The upper limit of the amount of the component (a) deposited is not particularly required to be specified, but a range of 2% by weight or less is usually sufficient for practical use.

The amount of component (b) used is in the range of 0.1 to 10% based on the weight of the treated material in terms of active ingredient, and the amount of component (c) is 0.000.
It is desirable to be 1 to 10%.

[Treatment Method 2] A required amount of the component (b) and the component (c) are suspended in a sufficient amount of water for completely immersing the object to be treated, and the suspension is used as a bath and an organic acid such as acetic acid. The pH of the bath is adjusted to 3 to 7, preferably 4 to 6, and the substance to be treated is immersed in the bath to adsorb substantially all of the components (b) and (c) to the substance to be treated. The fact that substantially all of the components (b) and (c) have been adsorbed can be confirmed by utilizing the property that the treatment liquid in the bath changes from an opalescent state to a transparent state. The temperature of the bath in this adsorption treatment is preferably 10 to 60 ° C, particularly 20 to 40 ° C.

After adsorbing the component (b) and the component (c) in this way, the required amount of the component (a) is added to the bath while the object to be treated is immersed, and the component (a) is added to the object to be treated. ) Is adsorbed substantially all. The fact that substantially all of the component (a) has been adsorbed can be determined by the presence of the component (a) remaining in the treatment liquid of the bath, for example, by the BPB reaction. The temperature of the bath in this adsorption treatment is preferably 30 to 70 ° C, particularly 40 to 60 ° C. It is also possible to add to the bath a salt that promotes adsorption by adjusting the pH of the bath to a range of 7 to 10 and stabilizes the adsorption state such as magnesium sulfate.

The object to be treated that has undergone the above-described two adsorption processes is
It may be simply dehydrated and dried, but 100-180
It is preferred to heat to ° C.

The amounts of the component (a) and the component (b) attached to the object to be treated are the same as those in the treatment method 1. However, this processing method 2
The amount of the component (c) to be used is preferably 0.0001 to 10% based on the weight of the object to be treated in terms of active ingredient.

According to the processing method 1 or the processing method 2 as described above, substantially all of the respective components (a), (b) and (c) are adsorbed on the object to be processed, so that the state of the treatment liquid in the bath is Alternatively, by appropriately adjusting or controlling the conditions, the antibacterial treatment agent of the present invention can be applied to the object to be treated with high efficiency, advantageously and economically.

The method of applying the antibacterial treatment agent of the present invention is not limited to the treatment method 1 or the treatment method 2 described above, and the component (a), the component (b) and the component (c) are added to the object to be treated. The antibacterial treatment liquid is dissolved or dispersed in water at the ratio described above, and the treatment liquid is applied to the treatment object by a method such as a dipping method or a spraying method, or attached to the treatment object by a padding method. It is also possible to apply.
However, in this case, the components (a) and (c)
As a result of coexisting in the same aqueous treatment liquid, the reaction between the components (a) is promoted more particularly than the adsorption of the component (a), and the treatment liquid becomes gelled earlier. Therefore, in this method, achieving sufficient adsorption of the component (a) results in increasing the concentration of the component (a) in the treatment liquid and is not necessarily advantageous.

According to the antibacterial treatment agent of the present invention, as is clear from the description of Examples, excellent antibacterial effect durability can be obtained. The reason has not been fully clarified, but SiOH groups are formed in the molecule of the antibacterial agent of component (a) and the amino-functional polysiloxane of component (b), and amino functional groups are attached to the SiOH groups. It has a catalytic effect, and as a result, the reaction between the antibacterial agents or the antibacterial agent and the amino-functional polysiloxane is promoted, and by this reaction, a strong siloxane bond (Si-O-Si) is formed, It is considered that a strong antibacterial film is formed on the object to be treated.

Furthermore, the functional groups of the organosilicon quaternary ammonium salt and the functional groups of the amino-functional polysiloxane react with the functional groups present in the object to be bonded, and as a result, the antibacterial epidermis has excellent durability. Are considered to be formed.

Further, it is considered that the adsorption of the component (b) is promoted by the organometallic compound of the component (c), and as a result, the above-mentioned action is achieved with high efficiency.

〔Example〕

Examples will be described below, but the present invention is not limited thereto. In addition, "part" shows a weight part.

Example 1 [Example of treatment method 1] 44 parts of an organic silane compound represented by the formula (CH ₃ O) ₃ Si (CH ₂ ) ₃ Cl, 44 parts of octadecyldimethylamine and 12 parts of methanol were mixed, and nitrogen was added. 3- (Trimethoxysilyl) propyloctadecyldimethylammonium chloride was prepared by reacting at 120 ° C. for 18 hours in a gas atmosphere, and this was diluted with methanol to prepare a 42% concentration methanol solution. This is designated as "antibacterial agent solution A".

On the other hand, the formula _{CH 3 (CH 3 O) 2} Si (CH 2) 3 - -NHCH compound 7.5 parts represented by ₂ CH ₂ NH _2, has a silanol group at both ends, a viscosity of about 12,500cst at 25 ° C. Is mixed with 1000 parts of polydimethylsiloxane having the formula (1), and the mixture is heated and stirred at 150 ° C. for 2 hours in a nitrogen gas stream to react with each other to give an amino-functional polysiloxane which is a transparent liquid copolymer represented by the following formula. Was manufactured.

30 parts of this amino-functional polysiloxane was emulsified and stirred with 3.5 parts of an emulsifier "Tergitol TMN6", 0.06 part of glacial acetic acid and 66.44 parts of water to obtain an aqueous emulsion. This is designated as "Aqueous Emulsion A".

A bath was prepared by dissolving 1 part of the antibacterial treatment liquid A in 3,000 parts of water. Then, a sample made of 100% cotton knit cloth was used as an object to be treated, and 100 g thereof was immersed in the bath at 40 ° C. for 20 minutes. After this treatment, a BPB reaction was performed on the treated liquid in the bath, but no coloration was observed.

Next, while the sample was still immersed, 3.0 parts of the above aqueous emulsion A and 0.5 part of di-n-propyloxy (triethanolamine) titanate were added to this bath, and the pH was adjusted to 6 with acetic acid. When left at 40 ° C for 40 minutes, the treatment liquid, which was initially in an opalescent state, became transparent.

The sample thus treated was thoroughly dehydrated, dried in an oven at 80 ° C. for 20 minutes, and then heat-treated in an oven at 120 ° C. for 10 minutes.

Example 2 [Example of treatment method 2] 3.0 parts of the above aqueous emulsion A and 0.4 part of di-n-propyloxy (triethanolamine) titanate were mixed with water.
The mixture was added to 3,000 parts and adjusted to pH 6 with acetic acid to prepare a bath. Then, a sample made of 100% cotton knit cloth was used as an object to be treated, and 100 g thereof was immersed in the bath at 40 ° C. for 20 minutes. The treatment liquid of the bath, which was initially in an opalescent state, became transparent after this treatment.

Next, 1 part of the above-mentioned antibacterial agent treatment liquid A was added to this bath while the sample was kept immersed, and the mixture was allowed to stand at 40 ° C. for 20 minutes. After this treatment, a BPB reaction was performed on the treatment liquid of the bath,
No coloration was observed.

The sample thus treated was dehydrated, dried and heat treated in the same manner as in Example 1.

Example 3 [Example of treatment method 1] 0.3 part of the above-mentioned antibacterial agent treatment liquid A was dissolved in 3,000 parts of water and adjusted to pH 9 with 10% sodium carbonate to prepare a bath. Then, a sample made of 100% nylon jersey cloth was used as an object to be treated, and 100 g thereof was immersed in the bath at 60 ° C. for 40 minutes.
After this treatment, a BPB reaction was performed on the treated liquid in the bath, but no coloration was observed.

Next, 2.0 parts of the above aqueous emulsion A, 0.5 parts of di-n-propyloxy (triethanolamine) titanate, and 0.2 parts of zinc acetate were added to the bath while the sample was immersed, and the pH was adjusted with acetic acid. When adjusted to 6 and left at 40 ° C. for 60 minutes, the treatment liquid, which was initially in an opalescent state, became transparent.

The sample thus treated was dehydrated, dried and heat treated in the same manner as in Example 1.

Example 4 [Example of treatment method 2] 2.0 parts of the above aqueous emulsion A, 0.4 part of di-n-propyloxy (triethanolamine) titanate and 0.2 part of zinc acetate were added to 3,000 parts of water, and the pH was adjusted with acetic acid. The bath was adjusted to 6. Then, a sample made of 100% nylon jersey cloth was used as an object to be treated, and 100 g thereof was immersed in the bath at 40 ° C. for 40 minutes. The treatment liquid of the bath, which was initially in an opalescent state, became transparent after this treatment.

Next, with the sample still immersed, 0.3 part of the antibacterial agent treatment liquid A was added to this bath, and the pH was adjusted to 9% with 10% sodium carbonate.
The temperature was adjusted to 60 ° C. and left at 60 ° C. for 40 minutes. After this treatment, a BPB reaction was performed on the treated liquid in the bath, but no coloration was observed.

The sample thus treated was dehydrated, dried and heat treated in the same manner as in Example 1.

Example 5 100 parts of dimethylpolysiloxane containing silanol groups at both ends having a viscosity of 80 cst at 25 ° C., 1.2 parts of a compound represented by the formula CH ₃ (CH ₃ O) ₂ SiNHCH ₂ CH ₂ NH ₂ , and ₃ ) ₃ SiNHCH ₂ CH ₂ NH ₂ compound (0.3 parts) and potassium hydroxide (0.08 parts) are mixed and reacted at 130 ° C for 3 hours to give a temperature of 25 ° C.
An amino-functional polysiloxane with a viscosity of 3,500 cst was prepared in. This amino-functional polysiloxane was emulsified in the same manner as the amino-functional polysiloxane in Example 1 to prepare an emulsion. This is designated as "aqueous emulsion B".

1 part of the antibacterial treatment liquid A was added to 3,000 parts of water and dissolved to prepare a bath. Then, a polyester urethane synthetic leather sample was used as the object to be treated, and 100 g of the sample was placed in the bath at 40 ° C.
Soaked for 40 minutes. After this treatment, a BPB reaction was performed on the treated liquid in the bath, but no coloration was observed.

Next, with the sample still immersed, 4.0 parts of the above aqueous emulsion B, 0.5 part of di-n-propyloxy (triethanolamine) titanate and 0.2 part of zinc acetate were added to this bath, and the pH was adjusted with acetic acid. When adjusted to 6 and left at 40 ° C. for 60 minutes, the treatment liquid, which was initially in an opalescent state, became transparent.

The sample thus treated was thoroughly dehydrated, dried in an oven at 80 ° C. for 20 minutes, and then heat-treated in an oven at 100 ° C. for 20 minutes.

Example 6 4.0 parts of the above aqueous emulsion B, 0.5 part of di-n-propyloxy (triethanolamine) titanate and 0.2 part of zinc acetate were added to 3,000 parts of water, and the pH was adjusted to 6 with acetic acid to form a bath. did. A sample of polyester-based urethane synthetic leather was used as an object to be treated, and 100 g of the sample was immersed in the bath at 40 ° C. for 30 minutes. The treatment liquid of the bath, which was initially in an opalescent state, became transparent after this treatment.

Next, with the sample still immersed, 1 part of the antibacterial agent treatment liquid A was added to this bath and left at 40 ° C. for 40 minutes. After this treatment, a BPB reaction was performed on the treated liquid in the bath, but no coloration was observed.

The sample thus treated was dehydrated, dried and heat treated in the same manner as in Example 5.

Comparative examples 1 and 2 An aqueous emulsion was prepared by emulsifying 30 parts of the compound represented by the formula (1) in the same manner as the amino-functional polysiloxane for the aqueous emulsion B in Example 1. This is designated as "Aqueous Emulsion C".

Then, the same treatments as in Example 1 and Example 2 were carried out, except that this aqueous emulsion C was used instead of the aqueous emulsion A in Example 1 and Example 2.

Comparative Example 3 1 part of the above antibacterial treatment liquid A was dissolved in 3,000 parts of water to prepare a bath. Then, a sample made of 100% cotton knit cloth was used as an object to be treated, and 100 g thereof was immersed in the bath at 40 ° C. for 20 minutes. After this treatment, a BPB reaction was performed on the treated liquid in the bath, but no coloration was observed.

The sample thus treated was dehydrated, dried and heat treated in the same manner as in Example 1.

Comparative Example 4 3.0 parts of the above aqueous emulsion A and 0.4 part of di-n-propyloxy (triethanolamine) titanate were mixed with water.
The mixture was added to 3,000 parts and adjusted to pH 6 with acetic acid to prepare a bath. Then, a sample made of 100% cotton knit cloth was used as an object to be treated, and 100 g thereof was immersed in the bath at 40 ° C. for 20 minutes. The treatment liquid of the bath, which was initially in an opalescent state, became transparent after this treatment.

The sample thus treated was dehydrated, dried and heat treated in the same manner as in Example 1.

The samples obtained in the above Examples 1 to 6 and Comparative Examples 1 to 4 were washed as follows. In each washing treatment, "Nissan Nonion NS-210" (manufactured by NOF CORPORATION) was used as a detergent at a ratio of 0.5 g per 1 water,
It was 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 for 5 minutes while allowing water to overflow. The antibacterial property of each of the treated cloths after washing was measured by the shake flask method.

The shake flask method is based on the US AATCC Test Method 10
It is an improved method of 0, 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) Test sample (such as antibacterial fiber or raw cloth)
Make a 0.75g strip and use this as the test piece.

(2) Sterilized phosphate buffer (70 ml) was placed in an Erlenmeyer flask with a capacity of 200 ml, and E. coli (Escherichia coli ATCC
Bacterial liquid 5m containing 8739) at a rate of ^{1.5 × 10 5 ~3 × 10 5} / ml
inoculate l.

(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) Insert the test piece of Erlenmeyer flask operation (1) in operation (2) and put it in the wrist action shaker (Wr
Shake for 1 hour with ist Action Shaker). 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) The number of bacteria after culturing obtained in the operation (3) and the operation (4) is counted, and the sterilization rate is calculated according to the following formula.

(6) As a control, the same operation is performed on the same fiber or raw cloth except that the antibacterial treatment is not applied.

The above results are shown in Table 1.

Claims (3)

[Claims] 1. A composition comprising the following component (a), component (b) and component (c), wherein the content of the component (a) as an active ingredient is 0.05% or more per unit weight of the object to be treated. An antibacterial treatment agent, characterized in that (b) is provided in a proportion of 0.1 to 10% and the component (c) is provided in a proportion of 0.0001 to 10%. Component (a): Antibacterial agent selected from organosilicon quaternary ammonium salt Component (b): Formula {Where D is (R 'represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R "represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and m is 0 or 1.) R has 1 carbon atom
To 6 monovalent hydrocarbon groups, X represents a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, and a, b and c are 0 <a ≦ 3, 0 ≦ b ≦ 3 and 0 <c ≦ 3, respectively. And 0
<(A + b + c) <4, and at least one D group and one X group are present in each molecule. } Amino-functional polysiloxane represented by the following: Component (c): Organometallic compound selected from organotitanates 2. The component (a) according to claim 1 is adsorbed to the object to be treated in an amount of 0.05% or more as an active ingredient per unit weight, and then, under wet conditions,
The component (b) and the component (c) according to claim 1 are used as an active ingredient in an amount of 0.1 to 10% of the component (b) and 0.0001 to 10% of the component (c) per unit weight of the object to be treated. The antibacterial treatment method is characterized in that it is adsorbed at a ratio of (3) 0.1 to 10% of the component (b) and the component (c) per unit weight of the object to be treated, wherein the component (b) and the component (c) according to claim 1 are used as active ingredients. 0.000
Adsorption at a ratio of 1 to 10%, and then, under wet conditions, the ratio of the component (a) according to claim 1 as an active ingredient per unit weight of the object to be treated is 0.05% or more. An antibacterial treatment method characterized by adsorbing with.