JPH02178204A - Anti-fungus treating agent and anti-fungus treating method - Google Patents

Abstract

PURPOSE:To obtain an anti-fungus treating agent having excellent anti-fungus effect and capable of preserving said effect for a long period of time by mixing a specific anti-fungus agent, aminofunctional polysiloxane and specific organic metal compound. CONSTITUTION:An anti-fungus agent of an organosilicon quaternary ammonium salt or organosilicon amphoteric surface active agent is mixed with an amino- functional polysiloxane expressed by formula I [D is expressed by formula II (R' is R or 1-6C monofunctional hydrocarbon group; R'' is 1-6C bifunctional hydrocarbon group; m is 0 or 1); R is 1-6C hydrocarbon group; X is OH or 1-6C alkoxy; a, b and c are: 0 (a, b and c <=3 and 0 <(a+b+c)<4; D-group and X-group respectively exist at least one in each molecule] and an organic metal compound selected from an organic titanic acid esters, organic zirconium acid esters and organic germanium acid esters to afford the aimed treating agent. Said treating agent is adsorbed by a material to be treated to impart anti-fungus properties.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an antibacterial treatment agent for imparting antibacterial properties to objects to be treated, and an antibacterial treatment for suitably applying this antibacterial treatment agent. Regarding the method.

[Technical background]

It is generally known that microorganisms pose various hazards to the clothing and living environment of human life. Particularly in recent years, the temperature and humidity environment created by the spread of air conditioning equipment in buildings and the use of closed rooms in buildings has become an ideal habitat for microorganisms. These microorganisms can be found on wall materials, furniture, kitchen furniture, bathroom walls and window frames, paper such as wallpaper,
Not only do they cause alteration, deterioration, and corrosion of various textile products such as clothing and bedding, but they also cause diseases such as allergies for the people living there. Due to these circumstances, there has recently been a growing demand for means that can effectively prevent harm caused by microorganisms (
It has become.

Conventionally, the use of chemical agents, that is, antibacterial and antifungal agents, has been known as an antibacterial and antifungal means for preventing harm caused by microorganisms. Specifically, various halides,
Alcohols, phenols, diphenyls, diphenyl diketones, diphenyl ethers, carboxylic acids,
Acid amides, heterocyclic compounds, amidines and guanidines, metal ions and organometallic compounds, surfactants, and the like are known as antibacterial and fungicidal agents. These are used by methods such as impregnation, coating, and spraying onto the object.

[Problem to be solved by the invention]

In the method of using such antibacterial and fungicidal agents, it is important that the antibacterial and fungicidal agents used have 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 fungicidal agents exhibit excellent antibacterial properties and safety, but have the disadvantage that their adhesiveness to objects is not necessarily durable. does not fully satisfy the requirements of

Under such technical background, it has been found that a relatively good durability of the antibacterial effect can be obtained by using an aqueous composition comprising a specific antibacterial agent and an amino-functional polysiloxane. However, in this technique, in order to obtain a composition in which the amino-functional polysiloxane is stably dispersed, it is necessary to emulsify the amino-functional polysiloxane in advance using an appropriate surfactant. However, due to the presence of this surfactant, the reaction between the antibacterial agent and the amino-functional polysiloxane or their adhesion to the object to be treated is not always achieved sufficiently, 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 treatments or friction.

[Purpose of the invention]

The present invention has a high durability of adhesion to the target object, and even if it is repeatedly washed or comes into continuous contact with water or other substances, the excellent antibacterial effect is maintained for a long time. The purpose is to provide an antibacterial treatment agent.

Another object of the present invention is to provide an antibacterial treatment in which, when applying the antibacterial treatment agent, the desired reaction or action of each component is sufficiently achieved, and as a result, excellent durability of antibacterial effects can be obtained. The purpose is to provide a method.

[Means to solve the problem]

The antibacterial treatment agent of the present invention comprises the following component (a) and component (b).
) and component (c), and component (a) is 0.05% as an active ingredient per unit weight of the object to be treated.
The above composition is characterized in that component (b) is added at a ratio of 0.1 to 10% and component (c) is added at a ratio of 0.0001 to 10%.

Component (a): Antibacterial agent selected from organosilicon quaternary ammonium salts and organosilicon amphoteric surfactants Component (b) (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, m is 0 or 1), R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X represents a hydroxyl group or represents an alkoxy group having 1 to 6 carbon atoms, a, b and C are respectively Q<a≦3.0≦b≦3 and Q<c≦3 and 0<(a+b+c)<4, and D group and at least one X group is present in each molecule.) An amino-functional polysiloxane component (c) represented by;
An organometallic compound selected from organic titanate esters, organic zirconate esters, and organic germanate esters The antibacterial treatment method of the present invention comprises adding the component (a) to the object to be treated per unit weight thereof. 0.05 as an active ingredient
% or more, and then under humid conditions, the component (b) and the component (c) are applied to the object to be treated as an active ingredient per unit weight.
b) is 0.1 to 10% and component (c) is 0,0001
It is characterized by adsorption at a rate of ~10%.

Or, the component (b) and the component (c) are used as active ingredients per unit weight of the material to be treated.
) is 0.1-10% and component (c) is 0.0001-10%
10%, and then, under humid conditions, 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 of the object. Features.

[Operation and effects of the invention]

The antibacterial treatment agent of the present invention can be applied to natural fibers such as cotton, silk, and wool, synthetic fibers such as polyesternopebolyamide and polyacrylonitrile, natural leather, synthetic leather,
Objects made of wood, paper, non-woven fabric, natural rubber, synthetic rubber, plastic, ceramics, metal, etc. are treated to adsorb or adhere to the surface of the object, and if necessary, heat-treated to treat the object. An excellent antibacterial effect can be imparted to the object to be treated, and the durability of the antibacterial effect is extremely excellent.

The present invention will be specifically explained below.

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

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

General formula (1) % Formula % In the formula, X' is a hydrolyzable group such as a halogen atom, an alkoxy group, or an acyl group, and Y is a halogen atom such as chlorine or bromine. R' has 1 to 22 carbon atoms
is a monovalent aliphatic hydrocarbon group, in particular, two of the three R1 are methyl groups and the other one has 8 to 22 carbon atoms.
is preferably an alkyl group. R2 is a divalent hydrocarbon group, particularly preferably an alkylene group having 2 to 4 carbon atoms or CH, CH2CH2NHCH2CH2-. R3 is a lower alkyl group such as a methyl group, a phenyl group or a CF s CR2C82 group.

k represents 0, ■ or 2, preferably O.

Among the organosilicon quaternary ammonium salts as described above, those represented by the following formula are particularly preferred.

CH.

R'N"(cH2)3Sl(OCH3)-・αCH
.

(In the formula, R4 represents an alkyl group having 8 to 22 carbon atoms.) The organosilicon quaternary ammonium salt as described above is
As is known, it has an excellent antibacterial effect against Durham-positive bacteria, Durham-negative bacteria, molds, algae, yeast, etc., that is, it has an antibacterial effect against bacteria, an antifungal effect, and an antialgal effect.

Furthermore, the organosilicon amphoteric surfactant is a silyl group-containing compound represented by the following general formula (n).

General formula (II) R5M'+QM'+,,GU In the formula, R5 represents a hydrophobic monovalent hydrocarbon group, Q represents an alkylene group or phenylene group having 1 to 7 carbon atoms, and Ml and M2 are the same or different formulas
Formula (ii) Formula (1ii) Formula (iv) Formula (v) Formula (vi) (R' is a hydrogen atom or R7 (R,' is an alkyl group having 4 or less carbon atoms or a phenyl group), A1 is -ZCOO
A group having H (Z is an alkylene group or substituted alkylene group), A2 is a group having -zcoo-, A3 is a group having -Y'5iR8r(OR')3-r (Y' has 1 to 1 carbon atoms) 8 divalent hydrocarbon group (-
R@ represents an alkyl group, R9 represents an alkyl group or an acyl group, and r is 0.1 or 2. ). ), G is a group selected from R6, A1, A2 and A3 (R'
, A', A'' and A3 are as defined above.)
, n is 0 or an integer of 1 to 4, and at least one group represented by A1 or A2 is present in the molecule, and at least one group represented by A3 is present in the molecule. Further, the nitrogen atom present in the molecule may form a salt with hydrogen halide. however,
The group represented by formula (v) always coexists with the group represented by formula (iii). ] This organosilicon amphoteric surfactant is basically an amine compound having a carboxyl group and has the characteristics of a so-called carboxylic acid type amphoteric surfactant, and therefore exhibits an excellent antibacterial effect, Since it is a compound that also contains a silyl group, the silyl group allows it to not only physically adhere to the object to be treated, but also chemically bond and adhere to it. Adhesive properties provide great durability and long-lasting antibacterial effects.

In the present invention, specific amino-functional polysiloxanes are used as component (b). This particular amino-functional polysiloxane is an amino group-containing organoporinoxane represented by the average formula below.

(Here, R' is a hydrogen atom or a carbon atom having 1 to 6 carbon atoms.
R'' represents a divalent hydrocarbon group having 1 to 6 carbon atoms, m is 0 or 1), and R represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. represents the group,
X represents a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, and a, b and C each represent Q<a≦3.0≦b≦
3 and Q<c≦3 and O<(a + b+ c)
< 4 and at least one D group and at least one X group each exist in one molecule. ) R' is preferably a hydrogen atom, but may also be an alkyl group such as methyl, ethyl, propinopeptyl or isobutyl, a cyclohexyl group, or a phenyl group. R” is an alkylene group or a phenylene group, CH2CH2
CH2- or CH=CH(cR3)CR2- is preferred. Examples of the alkoxy group for X include methoxy, ethoxy, propoxy, and butoxy groups.

The amino group-containing organopolysiloxane has the structural formula D
S i 0sy2, DR5iO,z2, D R2S
IOl/2, DRX S 10 l/2, DX-3I
OI/2, RX S 102/2, R2X5iO+zz
, R25iOz72, R55iO+z□, R51Os
It is composed of siloxane units selected from z-a, X5iOtz2, S10<yt, and at least one D group and at least one X group must exist in one molecule. This organopolysiloxane may be linear, branched, or cyclic.

Examples of preferred organopolysiloxanes include, for example, R2X5iO (RzSiO), (DXSiO)qSiX
R2DX2SiO (R2SiO), 5iX=DR2XS
iO(RzSiO) and 5iXRD, and particularly preferred examples of amino group-containing alkaline polysiloxanes include the following.

X(cH*)2SiO((cH:+)2SIO)--(
DXSiO)-3i(cH=)2X.

D(X)2SiO((cH,), 5iO), 5i(X)
2D.

D(X)(cH3)SiO((cH,)-3iO). −
3+(cR3) (X)D.

X(cH-)zSiORCHt)zSiO)--3r
(cHs) (X) DDSi[((cH,)-Sio). 5i(cHs
)2X]i In each of the above formulas, X is -OH or 10 CH
3, and D is -CH2CH, CH2NH, or -C
H, CH2CH2NHCH2CH, NR2 is shown.

Such amine-functional polysiloxanes can be prepared by reacting an amino-functional alkoxysilane with a hydroxy-terminated polydiorganosiloxane or by reacting an amino-functional alkoxysilane with a hydroxy-terminated polydiorganosiloxane and an alkyl alkoxysilane. However, since the reaction is well known, detailed explanation will be omitted.

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

Specific examples of emulsifiers used in such cases include:
Non-ionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, polyox dialkylene alkyl esters, sorbitan alkyl esters, polyoxyalkylene sorbitan alkyl esters, aliphatic amine salts, quaternary Examples include cationic surfactants such as ammonium salts. As for the emulsifier actually used, it is desirable to select one that is not easily adsorbed by the object to be treated.

In the present invention, as component (c), an organometallic compound selected from organic titanate esters, organic zirconate esters, and organic germanate esters is used. This organometallic compound is an essential component for effectively adsorbing component (b) dissolved or emulsified in water onto fibers and other objects 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 Acetylacetotitanate, titanium ethyl acetoacetate, titanium lactate, and partially hydrolyzed condensates thereof, and organic zirconate compounds or organic germanate compounds in which the titanium atom in the above organic titanate compound is replaced with a zirconium atom or germanium atom. Mention may be made of compounds and their partially hydrolyzed compounds. These organometallic compounds can be used not only one type but also two or more types in combination.

The amount of component (c) added is as described above.
0.1 to 100 parts by weight per 100 parts by weight,
In treatment method 1 in which component (a) is adsorbed before component (b) and component (c), the residual concentration of component (a) in the treatment liquid to which component (c) is added is taken into consideration. It is particularly preferred that the amount is 1.0 parts by weight or more per 100 parts by weight of component (b), while component (b) and component (c)
In treatment method 2, in which component (b) is adsorbed prior to component (a), there is no need to consider the residual concentration;
) It can also be used in a proportion of 50 parts by weight or less per 100 parts by weight.

In the present invention, in addition to component (a), component Q)), and component (c), organic silane compounds, organometallic compounds such as tin, zinc, lead, and cobalt known as catalysts for condensation reactions, and other organic compounds are used. Additives can be used in combination.

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

[Treatment method 1] Dissolve the required amount of component (a) in an amount of water sufficient to completely immerse the object to be treated, and use this solution as a bath to immerse the object to be treated. Substantially all of component (a) is adsorbed. The fact that substantially all of component (a) has been adsorbed means that the presence or absence of component (a) remaining in the treatment solution of the bath can be determined by, for example, a color reaction with bromophenol blue (rBP).
B reaction). The temperature of the bath in this adsorption treatment is 30-70°C, especially 40-60°C.
Preferably it is 0°C. Also, adjust the pH of the bath to 7 to 10.
It is also possible to promote adsorption by adjusting the temperature within this range, and to add salts such as magnesium sulfate to stabilize the adsorption state to the bath.

After component (a) has been adsorbed in this way, the required amount of component (b) and component (c) are added to this bath while the object to be treated remains immersed, and the bath is diluted with an organic acid such as acetic acid. pH
is adjusted to 3 to 7, preferably 4 to 6, so that substantially all of the component (b) and component (c) are adsorbed onto the object to be treated. In this treatment, due to the action of component (c), component (b) and component (c) are selectively adsorbed to the object to be treated compared to other components. It is possible to suppress the adsorption of the emulsifier used for the emulsification of the emulsifier to the object to be treated. It can be confirmed that substantially all of component (b) and component (c) have been adsorbed by utilizing the property that the treatment liquid in the bath changes from a milky turbid 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 the above-mentioned two adsorption treatments, the object to be treated is
It is possible to simply perform dehydration and drying treatment, but it is also possible to
Preferably, it is heated to 180°C.

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

When component (b) is in use, it is preferably in the range of 0.1 to 10% based on the weight of the object to be treated in terms of active ingredient, and component (c) is preferably in the range of 0.0001 to 10%.

[Treatment method 2] The required amount of component (b) and component (c) are suspended in a sufficient amount of water to completely immerse the object to be treated, and this suspension is used as a bath, and an organic acid such as acetic acid is added to the suspension. The pH of the bath is adjusted to 3 to 7, preferably 4 to 6, and the object to be treated is immersed in this bath so that substantially all of component (b) and component (c) are adsorbed onto the object. It can be confirmed that substantially all of component (b) and component (c) have been adsorbed by utilizing the property that the treatment liquid in the bath changes from a milky turbid state to a transparent state. The temperature of the bath in this adsorption treatment is 10-60℃.
℃, especially preferably 20 to 40℃.

After component (b) and component (c) have been adsorbed in this way, the required amount of component (a) is added to this bath while the object to be treated remains immersed, and the component (a) is added to the object to be treated. ) is adsorbed. Whether substantially all of component (a) has been adsorbed can be determined by the presence or absence of component (a) remaining in the treatment liquid of the bath, for example, by BPB reaction. The temperature of the bath in this adsorption treatment is 30 to 70°C, especially 40°C.
It is preferable that it is -60 degreeC.

In addition, adsorption can be promoted by adjusting the pH of the bath to a range of 7 to 10, and salts such as magnesium sulfate that stabilize the adsorption state can be added to the bath.

After the above-mentioned two adsorption treatments, the object to be treated is
It is possible to simply perform dehydration and drying treatment, but it is also possible to
Preferably, it is heated to 180°C.

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

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

The method of applying the antibacterial treatment agent of the present invention is not limited to the above-mentioned treatment method 1 or treatment method 2.
, component (b) i and component (c) are dissolved or dispersed in water in the proportions described above for the object to be treated to obtain an antibacterial treatment liquid, and this treatment liquid is applied by a dipping method, a spraying method, etc. It is also possible to apply the agent by applying it to the object to be treated, or by adhering it to the object by padding. However, in this case, as a result of component (a) and component (c) coexisting in the same aqueous treatment solution, the reaction between components (a) is promoted more than the adsorption of component (a). is,
The semi-processing solution becomes gelatinous at an early stage. Therefore, in this method, it is not necessarily advantageous to sufficiently adsorb component (a) because it increases the concentration of component (a) in the treatment liquid.

According to the antibacterial treatment agent of the present invention, excellent durability of antibacterial effect can be obtained, as is clear from the description of the examples. The reason for this is not fully understood, but 5iOH groups are formed in the molecules of the antibacterial agent of component (a) and the amine-functional polysiloxane of component (b), and the amino functional group is It has a catalytic effect, and as a result, the reaction between antibacterial agents or between antibacterial agents and amino-functional polysiloxane is promoted, and this reaction forms a strong bond, siloxane bond (Si-0-3i), It is thought that a strong antibacterial film is formed on the object to be treated.

Furthermore, the functional groups formed by the organosilicon quaternary ammonium salt or the organosilicon amphoteric surfactant and the functional groups formed by the amino-functional polysiloxane react with and bond with the functional groups present in the object to be treated, resulting in an excellent It is thought that a durable antibacterial epidermis is formed.

It is also believed that the adsorption of component (b) is promoted by the organometallic compound of component (c), and as a result, the above effects are achieved with high efficiency.

〔Example〕

Examples will be described below, but the present invention is not limited thereto. Note that "parts" indicate parts by weight.

Example 1 [Example of treatment method 1] 44 parts of a mechanical silane compound represented by the formula (cH30)ssi(c1-h)-tJ, 44 parts of octadecyldimethylamine, and 12 parts of methanol were mixed, and nitrogen gas was added. 3-(trimethoxysilyl)propyloctadecyldimethylammonium chloride was prepared by reacting at 120° C. for 18 hours in an atmosphere, and diluted with methanol to prepare a methanol solution with a concentration of 42%. This will be referred to as "antibacterial agent solution A."

On the other hand, 7.5 parts of a compound represented by the formula %) was mixed with 1000 parts of polydimethylsiloxane having silanol groups at both ends and having a viscosity of about 12.500 cst at 25°C, and this was mixed with nitrogen gas. An amine-functional polysiloxane, which is a transparent liquid copolymer represented by the following formula, was produced by heating and stirring at 150° C. for 2 hours under a stream of air.

H, NCH2CH2NH (cH2).

CH3-3i-0-((cH=>23io), HCH3(x
= 500) 30 parts of this amino-functional polysiloxane were mixed with 3.5 parts of emulsifier "Tergitol TMN6",
The mixture was emulsified and stirred with 0.068B of glacial acetic acid and 66.44 parts of water to obtain an aqueous emulsion. This is referred to as "aqueous emulsion A".

One part of the antibacterial agent treatment solution A was dissolved in 3,000 parts of water to prepare a bath. A sample made of 100% cotton knit cloth was used as the object to be treated, and 100g of it was placed in the bath at 40°C.
It was soaked for 20 minutes. After this treatment, a BPB reaction was performed on the treatment solution in the bath, but the coloration was not tolerable.

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

After sufficiently dehydrating the sample treated in this way, it was 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 [20 examples of treatment method] 3.0 parts of the above aqueous emulsion A and 04 parts of di-n-7'' lopyloxy (triethanolamine) titanate were added to 3.000 parts of water, and the pH was adjusted to 6 with acetic acid. A sample made of 100% cotton knitted cloth was used as the object to be treated, and 100g of it was placed in the bath at 40%
℃ for 20 minutes. The treatment liquid in the bath, which was initially opalescent, became clear after this treatment.

Next, 1 part of the above antibacterial agent treatment solution A was added to the bath while the sample was still immersed, and the sample was left at 40° C. for 20 minutes.

After this treatment, a BPB reaction was performed on the treatment liquid in the bath, but no coloration was observed.

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

Example 3 [Example of treatment method 1] 13 parts of the above antibacterial treatment solution AO was dissolved in 3.000 parts of water, and the solution was adjusted to pH 9 with 10% sodium carbonate to prepare a bath. A sample made of 100% nylon jersey cloth was used as the object to be treated, and 100g of it was placed in the bath for 60 minutes.
℃ for 40 minutes. After this treatment, a BPB reaction was performed on the treatment liquid in the bath, but no coloration was observed.

Next, while the sample was still immersed, 2.0 parts of the above aqueous emulsion A, 0.5 parts of di-n-propyloxy(triethanolamine) titanate, and 0.0 parts of zinc acetate were added to the bath.
．． 2 parts, adjusted to pH 6 with acetic acid, and heated at 40°C.
When the solution was left for 60 minutes, the treatment solution, which was initially milky and cloudy, became transparent.

The thus treated sample 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 parts of di-n-propyloxy(triethanolamine) titanate, and 0.2 parts of zinc acetate were mixed in 3.000 parts of water. The pH was adjusted to 6 with acetic acid to prepare a bath. and nylon 10
Using a sample made of 0% jersey cloth as the object to be treated,
100g thereof was immersed in the bath at 40°C for 40 minutes.

The treatment liquid in the bath, which was initially opalescent, became clear after this treatment.

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

The thus treated sample 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 terminals and having a viscosity of 3Qcst at 25°C, 1.2 parts of a compound represented by the formula %, and a compound represented by the formula (cH3)-3;NHCHaCH2NH2 By mixing 0.3 parts and 0.081 fE of potassium hydroxide and reacting at 130°C for 3 hours, 25
An aminofunctional polysiloxane was produced having a viscosity of 3.500 cst at °C. This amine-functional polysiloxane was emulsified in the same manner as the amino-functional polysiloxane in Example 1 to prepare an emulsion. This is referred to as "aqueous emulsion B".

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

Next, with the sample still immersed, 84.0 parts of the above aqueous emulsion, 0.51% of di-n-propyloxy(triethanolamine) titanate), and 0.2 part of zinc acetate were added to the bath. Added, adjusted to pH 6 with acetic acid, 40
When the solution was left for 60 minutes at .degree. C., the treatment solution, which was initially milky and cloudy, became transparent.

After sufficiently dehydrating the sample treated in this way, it was dried in an oven at 80°C for 20 minutes, and further heat-treated in an oven at 100°C for 20 minutes.

Example 6 Aqueous emulsion B4. Off'lS and G-n-
Propyloxy (triethanolamine) titanate 0
．． 5 parts and 0.2 parts of zinc acetate were added to 3.000 II of water, and the pH was adjusted to 6 with acetic acid to prepare a bath. A sample of polyester urethane synthetic leather was used as the object to be treated, and 100 g of the sample was immersed in the bath at 40° C. for 30 minutes. The treatment liquid in the bath, which was initially opalescent, became clear after this treatment.

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

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

Comparative examples 1 and 2 Hs (cH,), Si+0-3i+,.

CH.

CH.

+OS++-O5l(cH3)3 CH.

An aqueous emulsion was prepared by emulsifying 30 parts of the compound represented by H,C-CH-CH2NHCH2CH,NH2 in the same manner as the amino-functional polysiloxane for aqueous emulsion B in Example 1. This is referred to as "aqueous emulsion C".

Then, the same treatment as in Example 1 and Example 2 was performed 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. A sample made of 100% cotton knit cloth was used as the object to be treated, and 100g of it was placed in the bath at 40°C.
It was soaked for 20 minutes. After this treatment, a BPB reaction was performed on the treatment liquid in the bath, but no coloration was observed.

The thus treated sample 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 parts of di-n-propyloxy(triethanolamine) titanate were added to 3.000 parts of water, and the pH was adjusted to 6 with acetic acid to prepare a bath. A sample made of 100% cotton knit cloth was used as the object to be treated, and 100g of it was placed in the bath at 40%
℃ for 20 minutes. The treatment liquid in the bath, which was initially opalescent, became clear after this treatment.

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

The samples obtained in Examples 1 to 6 and Comparative Examples 1 to 4 above were washed as follows. In each washing process, [Nissan Nonion NS-210j] was used as a detergent.
(manufactured by NOF ■) at a ratio of 0.5g to 1β of water, washed in a household electric washing machine for 5 minutes at a water temperature of 40℃ and a bath ratio of 1:30, and then for 5 minutes while washing with overflow water. Washed with water.

The antibacterial properties of each treated fabric after washing were measured by the shake flask method.

The above shake flask method is used in the US AATCCTe5tl
This is an improved method of Jethod 100, in which the test cloth is forcibly brought into contact with bacteria to create a condition that approximates the actual situation between skin and bacteria, and the antibacterial effect is quantitatively measured. Specifically, the following operations (1) to (6) are executed.

(1) Make a 0.75 g strip of the test sample (antibacterial treated fiber or raw cloth, etc.) and use this as the test piece.

(2) Pour 70% of sterilized phosphate buffer into an Erlenmeyer flask with a capacity of 200ml, and add E. coli (5ml)
iacoli^TCC8739) 1.5X10'~3
XIO'/ml! Inoculate 5 ml of bacterial solution containing the following ratio.

(3) Collect 1 ml of bacterial solution from this Erlenmeyer flask,
- Transfer to a test tube containing sterile phosphate buffer and mix evenly. Add 1 rm of this mixture to 9 ml of sterile phosphate buffer.
i! Mix and dilute with. Take a portion of this re-diluted bacterial solution, place it in a sterilized petri dish, and add 16 to 20 mj of tryptone glucose extract agar medium! Add and solidify. This is cultured at a temperature of 37° C. for 18 to 24 hours.

(4) Place the test piece from step (1) into the Erlenmeyer flask from step (2), and place it in the wrist action shaker (W
Shake for 1 hour with a 5-haker shaker.

Then, as in step (3), add the bacterial solution from the Erlenmeyer flask.
Directly or once or twice mixed and diluted with sterilized sulfuric acid tji and an equilibrated solution, the mixture is transferred to a petri dish, and the medium is added to culture.

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

Sterilization rate (%) (Number of viable bacteria in control) (6) As a control, perform the same operation on the same fiber or raw cloth, except that it is not subjected to antibacterial treatment.

The above results are shown in Table 1.

Table 1

Claims (3)

[Claims] (1) Consists of the following components (a), component (b), and component (c), with component (a) being 0.05% or more as an active ingredient per unit weight of the material to be treated, and component (b) is 0.1-10% and component (c) is 0.0001-10%
An antibacterial treatment agent characterized in that it is applied at a rate of %. Component (a): Antibacterial agent selected from organosilicon quaternary ammonium salts and organosilicon amphoteric surfactants Component (b): Formula D_aR_bX_cSiO [_4_-_a_-b_-_
c] ＿/＿2 {In the formula, D is ▲ Numerical formula, chemical formula, table, etc. ▼ (R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, 6 divalent hydrocarbon group, m is 0 or 1), R is a carbon atom number 1
-6 monovalent hydrocarbon group, 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. Big 0
<(a+b+c)<4, and at least one D group and at least one X group are present in each molecule. } Aminofunctional polysiloxane component (c) represented by: an organometallic compound selected from organic titanate esters, organic zirconate esters, and organic germanate esters (2) Claim 1 per unit weight of the object to be treated
The component (a) described in Claim 1 is adsorbed in a proportion of 0.05% or more as an active ingredient, and then the component (b) and the component (c) described in Claim 1 are adsorbed on the object to be treated under humid conditions. However, per unit weight, the active ingredient (
b) is 0.1 to 10% and component (c) is 0.0001%
An antibacterial treatment method characterized by adsorption at a rate of ~10%. (3) Claim 1 per unit weight of the object to be treated
Ingredient (b) is 0.1 to 10% and component (c) is 0.0% as active ingredients.
0.001 to 10%, and then under humid conditions, the component (a) according to claim 1 is added to the object to be treated at a rate of 0.0% as an active ingredient per unit weight of the object.
An antibacterial treatment method characterized by adsorption at a rate of 5% or more.