JPH0215011A - Composition for antimicrobial treatment - Google Patents

Abstract

PURPOSE:To obtain a composition for antimicrobial treatment having excellent durability of adhesion to target materials, maintaining excellent antimicrobial effects for a long period of time against repeated washing, etc., containing a specific antimicrobial agent and a specific amino functional polysiloxane in specific concentration, respectively. CONSTITUTION:(A) An antimicrobial agent selected from organosilicon quaternary ammonium salt and organosilicon ampholytic surfactant is blended with (B) a compound shown by formula I [D is H or 1-6C monofunctional hydrocarbon group; R'' is 1-6C bifunctional hydrocarbon group; m is 0 or 1); R is 1-6C monofunctional group; X is OH or 1-6C alkoxy; a-c are 0<a<=3, 0<=b<=3, 0<c<=3 and 0<(a+b+c)<4; one or more of D and X exist in one molecule, respectively] as active ingredients in such a way that >=0.05wt.% component A and 0.05-10wt.% component B based on a material to be treated are attached to the material to give a composition for antimicrobial treatment having the above- mentioned effects.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to compositions for antibacterial treatment.

[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. Under these circumstances, there has recently been an increasing demand for means that can effectively prevent harm caused by microorganisms.

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 an antibacterial and antifungal agent, it is necessary that the antibacterial and antifungal agent used has a high antibacterial effect, that the antibacterial effect has great durability, and that it is safe for human body and An important condition is high environmental safety. Conventional antibacterial and antifungal agents, for example, show excellent antibacterial properties and safety, but do not necessarily have sufficient durability of adhesion to objects. However, it does not fully satisfy all requirements, such as having some disadvantages.

[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 object of the present invention is to provide a composition for antibacterial treatment.

[Means to solve 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) the following formula % (R' is a hydrogen atom or a carbon R'' represents a divalent hydrocarbon group having 1 to 6 carbon atoms, m is 0 or 1), R is a monovalent hydrocarbon group having 1 to 6 carbon atoms, a monovalent hydrocarbon group, X represents a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, and a, b and C are respectively Q<a≦3.0≦b≦3 and Q<c≦3, and Q<(a+b+c)<4, and at least one D group and at least one X group each exist in one molecule. As an active ingredient (A) antibacterial agent is 0.
0.05% or more, and (B) amino-functional polysiloxane in a range of 0.05 to 10% in such a proportion that it is adhered to the object to be treated.

[Operation and effects of the invention]

The antibacterial treatment composition of the present invention can be made of, for example, natural fibers such as cotton, wool, and silk, synthetic fibers such as polyester, nylon, and acrylic, real leather, synthetic leather, wood, paper, nonwoven fabric,
By treating an object made of natural rubber, plastic, ceramic, metal, etc. to be treated so that it adheres to its surface and then heat-treating it, it is possible to impart an excellent antibacterial effect to the object. Extremely durable antibacterial properties.

The present invention will be specifically explained below.

The antimicrobial treatment composition according to the present invention contains a specific antimicrobial agent and a specific amine-functional polysiloxane.

In the present invention, an organosilicon quaternary ammonium salt or an organosilicon amphoteric surfactant is used as the antibacterial agent. The organosilicon quaternary ammonium salt described above is a known salt represented by the following general formula (1), and is usually commercially available as an alcohol solution.

General formula (1) R'+N''R25IR'i+X's-* 'Y-In the formula, R1 is a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms, and especially one of the three R1
Preferably, one is an alkyl group having 8 to 22 carbon atoms and the remaining is a methyl group. R2 is a divalent hydrocarbon group, especially an alkylene group having 2 to 4 carbon atoms or -C
H2CH2CH, NHCH, CH2- are preferred. R3 is a lower alkyl group such as a methyl group, a phenyl group or a CF s CH2CH2 group. k is 0.
It represents 1 or 2, preferably 0.

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

CH3 R'-N"(CH2)3Si(OCH3)3.CdoH3 (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.

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

General formula (II) R'M'+QM"+hG [wherein, R5 represents a hydrophobic monovalent hydrocarbon group, Q represents an alkylene group or phenylene group having 1 to 7 carbon atoms, and M' and M2 are the same or different from each other, and are expressed by the formula (1
) Formula (11) % Formula % Formula (iii) Formula (v) Formula (vi) (R6 is a hydrogen atom or R'(R' is an alkyl group or phenyl group having 4 or less carbon atoms), A1 is -ZCOOH
(Z is an alkylene group or substituted alkylene group), A2 is a group having -zcoo-, A3 is a group having -Y'SIR'r(OR')ir (Y' is a group having 1 carbon atom ~8 divalent hydrocarbon groups (-
R8 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 (R1
+, A1, A2 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 A'' is present in the molecule. The nitrogen atoms present may form a salt with hydrogen halide.However,
The group represented by formula (V) always coexists with the group represented by formula (iii). It is characterized by consisting of a compound having a silyl base represented by .

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. Because it is a compound that also contains a 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, and this excellent adhesion Due to its properties, it has great durability and maintains its antibacterial effect for a long time.

The antibacterial treatment composition of the present invention comprises at least one of the olkalisilicon quaternary ammonium salt or the organosilicon amphoteric surfactant, and an aminofunctional polysiloxane.

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

(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 aSb and C each represent Q<a≦3.0≦b≦
3 and Q<c≦3 and 0<(a+b+c)<4
and at least one D group and at least one X group are present in each molecule. ) R' is preferably a hydrogen atom, but may also be an alkyl group such as methyl, etynopebropyl, butynopeiisobutyl, a cyclohexyl group, or a phenyl group. R'' is an alkylene group or a phenylene group, -CH2CH,
CH,- or -CH2CH(CH3)CH,- is preferred. Examples of the alkoxy group for X include methoxy, ethoxy, propoxy, and butoxy groups.

The amine group-containing organopolysiloxane has the structural formula D
S! 03z□, DR3iO□7□, DR2S IOl
/2, D RX S +01/2, DXaSiO+z2
, RX S l02yz, RzXSi○172 , R2
5IOz/x, R35IO1/2, R31O, 7□,
It is constituted by siloxane units selected from X5i0,7□ and S10□72, and at least one D group and at least one X group must each be present in one molecule. This organopolysiloxane may be in the form of a chain, a branched steel, or a ring.

Examples of preferred organopolysiloxanes include, for example, R2X5iO(R,5iO), (DXSin), 5iX
R.

DX2SiO (R, 5iO), 5iX2DR2X S
There is IO(R2S r O) p S IX RD,
Particularly preferred examples of amine group-containing organopolysiloxanes include the following.

X(CH3)25+o((CHz)zsio).

(DXSiO), 5i(CH3)2X.

D(X)2510((C1-(,hsio), 5i(
X), D.

D(X)(CH,)SiO((CH,)2sio), -
3l(CH3)(X)D.

X(CH,)zs+o((CH3)asio), -3i
(CR3) (X) D DS! [((CH3)zS!0)-3l(CHs)aX
L In each of the above formulas, X is -OH or 10CH.

and D is -CH2CH2CH2N H2 or C
H2CH2CH2N HCH2CH2N Indicates H2.

The amino-functional polysiloxane of the present invention can be produced by reacting an amino-functional alkoxysilane with a polydiorganosiloxane containing a terminal hydroxyl group, or by reacting an amine-functional alkoxysilane with a polydiolkalisiloxane containing a terminal hydroxyl group and an alkylalkoxysilane. However, since the reaction is well known, detailed explanation will be omitted.

The composition for antibacterial treatment of the present invention comprising the above-mentioned components may be applied to the object to be treated as is, but it can also be applied as a solution diluted to an appropriate concentration with a co-solvent such as toluene. However, in order to perform this treatment reliably, the presence of water is required, and therefore it is preferable to use the antibacterial treatment composition in the form of an aqueous solution.

In order to make the antibacterial treatment composition into an aqueous solution,
A typical method is to form an oil-in-water emulsion from an amino-functional polysiloxane and to mix an antibacterial agent into the emulsion. Preferred alternative methods include (a) an antibacterial agent, (b) an amino-functional polysiloxane, (c) a solvent such as toluene, petroleum spirit, or water, (d) an aliphatic carboxylic acid or a derivative thereof, and, if necessary, There is a method of mixing it with (e) an emulsifier and diluting it with water before use. In this method, the emulsifier (e) is not necessarily essential since the antibacterial agent in the present invention itself has an emulsifying function. This latter method is preferable in terms of transportation and the like.

Various antioxidants and other additives can be added to the treatment liquid using the composition of the present invention, if necessary.

The objects to be treated to which the antibacterial treatment composition of the present invention is applied include natural fibers such as cotton and wool, synthetic fibers such as polyester, polyamide, acrylic, and polyvinyl alcohol;
Animal skin, synthetic leather, wood, paper, non-woven fabric, natural rubber,
Examples include synthetic rubber, plastic, ceramic, and metal.

In order to apply the antibacterial treatment composition of the present invention to an object to be treated, it must contain an antibacterial agent consisting of both or one of an organosilicon quaternary ammonium salt and an organosilicon amphoteric surfactant, and an aminofunctional polysiloxane. Treating the object to be treated with the treatment solution prepared as described above by a conventional method such as dipping, padding, spraying, coating, etc.
After that, it may be dried, and heat treatment may be performed if necessary. The temperature of this heat treatment is 40-180℃, especially 50-180℃
The temperature is preferably 60°C, and the heat treatment time is 30 seconds to 6
Preferably, the time is within the range of 0 minutes.

The amount of antibacterial agent adhered to the object to be treated is related to the antibacterial effect obtained, and in terms of active ingredient, it is 0.000000000000000000000 per weight of the object to be treated.
05 weight is required to be 1% or more. Although it is not necessary to specifically set the upper limit of the antibacterial agent adhesion 1, a range of 10% or less is usually sufficient for practical purposes.

The amount of amino-functional polysiloxane used is in the range of 0.05 to 10%, preferably 0.05 to 5%, based on the weight of the object to be treated, in terms of active ingredient. If the amount used exceeds 10%, there is a risk that the viscosity of the treatment liquid will increase and there is a risk that the object to be treated will turn yellow. Moreover, if it is less than 0.05%, the object of the present invention cannot be fully achieved.

The reason why the antibacterial treatment composition of the present invention provides excellent durability is not fully understood, but the reason is that 5iOH groups are formed in the molecules of the antibacterial agent and amino-functional polysiloxane in an aqueous solution. , the amine functional group has a catalytic effect on this 5iOH group, and as a result, the reaction between the antibacterial agents or between the antibacterial agent and the amino-functional polysiloxane is promoted, and this reaction forms a strong bond, the siloxane bond ( It is thought that Si-0-3i) is formed and 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 believed that a durable antimicrobial surface is formed.

〔Example〕

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

Examples 1-3 Formula (CHiO)ssi(CHz)3NHcHzcH2N
10 parts of a compound represented by H2, 70 parts of polydimethylsiloxane having silanol groups at both ends and having a viscosity of about 12.500 cst at 25°C, and 70 parts of polydimethylsiloxane having silanol groups at both ends and having a viscosity of about 4Qcst at 25°C. and 20 parts of polydimethylsiloxane having a viscosity of A 50% toluene solution consisting of a pale yellow transparent amino-functional polysiloxane having a viscosity at 25° C. of about 250 cst and represented by the following formula was obtained. This will be referred to as "siloxane solution A."

H, NCH2CH2NHCH2CH2CH, (CH30
).

5ho((CH3)zS+0)-3l(OCH3)2C
H2CH2CH2N HCH2CH2N H2 On the other hand, 44 parts of a compound represented by the formula (CHsO)3Si(CH,), (J, 44 parts of octadecyldimethylamine, and 12 parts of methanol were mixed, and 1
The reaction was carried out at 20°C for 18 hours, and 3-()! A methanol solution containing J methoxysilyl) propyl octadecyl dimethyl ammonium chloride at a concentration of 72% was prepared. This will be referred to as "antibacterial agent solution A."

Using the above siloxane solution A and antibacterial agent solution A, three types of aqueous compositions (1), (2) and (2) were prepared according to the following formulations.

Aqueous composition ■.

Siloxane solution A 80 parts Antibacterial solution A 6.6 parts Toluene
12.7 parts glacial acetic acid
0.7 parts Aqueous composition■ Siloxane solution A 80 parts Emulsifier A" 19 parts Glacial acetic acid
1.0 part Aqueous composition ■ Siloxane solution A 80 parts Emulsifier B" 16.4 parts Toluene
2.0 parts glacial acetic acid
1.6 Part Note 1) rNIKKOL BT-7
Polyoxyethylene secondary alcohol ether (manufactured by J Nikko Chemicals) 2) "Nymeen L-207J polyoxyethylene dodecyl methyl ammonium chloride manufactured by Nippon Oil & Fats ■ The aqueous composition obtained above and water into an antibacterial agent solution. An aqueous solution for antibacterial treatment was prepared according to the formulation shown in Table 1.

A cloth made of 100% cotton knit was used as the object to be treated, and after immersing it in each of the above antibacterial treatment aqueous solutions, it was squeezed with a mangle so that the absorption rate was 100%, and dried at 80°C for 15 minutes. , and then heat-treated at 160° C. for 2 minutes.

The resulting treated fabric was washed as follows. In each washing process, "Nirasan Nonion NS-2" was used as detergent.
10J (manufactured by NOF) was used at a ratio of 0.5g to 11 parts of water, washed in a household electric washing machine for 5 minutes at a water temperature of 40°C and a bath ratio of 1:30, and then allowed to overflow for 5 minutes. I washed it with water.

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

The shake flask method described above is based on the American Bl AATCCTes
This is an improved method of tMethod 1QQ, in which the test cloth and bacteria are forcibly brought into contact to create a condition that approximates the actual condition between skin and bacteria, and the antibacterial effect is quantitatively measured. Specifically, the following operations (1) to (6) are executed.

(1) 0 of the test sample (antibacterial treated fiber or raw cloth),
A 75 g strip is made and used as a test piece.

(2) 70mj of sterilized phosphate buffer in an Erlenmeyer flask with a capacity of 200rn1! and add Escherichia coli (Bscke) to this.
nichiacoli ATCC8739) to 1.5
Bacterial liquid 5 containing XIO'~3 XIO'/ml
- inoculate.

(3) Collect 1 ml of bacterial solution from this Erlenmeyer flask and
Transfer to a test tube containing sterile phosphate buffer and mix evenly. 1ml of this mixture! Add 9 m of sterile phosphate buffer
Mix and dilute with l. Take 1rnl of this re-diluted bacterial solution, place it in a sterilized petri dish, and add 16 to 20ml 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 a 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 after mixing and diluting once or twice with sterile phosphate buffer, transfer to a petri dish, add the medium, and 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 (%) (6) As a control, perform the same operation on the same fibers or cloth without antibacterial treatment.

These results are shown in Table 1.

Comparative Example 1 Aqueous composition (2) was prepared by mixing 40 parts of the compound represented by formula %, 6.6 parts of antibacterial agent solution A, 52.7 parts of toluene, and 0.7 parts of glacial acetic acid. Then, as shown in Table 1, an aqueous solution for antibacterial treatment was prepared in the same manner as in Example 1, except that this aqueous composition (■) was used instead of the aqueous composition (■) in Example 1. The samples were treated in the same manner as in Example 1, washed in the same manner, and their antibacterial properties were measured. The results are shown in Table 1.

Comparative Example 2 In Example 2, an aqueous solution for antibacterial treatment not containing the aqueous composition (1) was prepared and treated in the same manner as above, followed by washing and antibacterial properties. The results are shown in Table 1.

Examples 4 to 5 Using antibacterial agent solution A and the same aqueous composition (■) as in Example 1, an aqueous solution for antibacterial treatment was prepared according to the formulation shown in Table 2, and this was used to prepare the aqueous solution for antibacterial treatment in Example 1 described above. 100% polyester jersey and 100% nylon jersey were treated in the same manner as in Example 3. Furthermore, similar washing treatments and antibacterial properties measurements were performed. The results are shown in Table 2.

Example 6 7.5 parts of the compound represented by the formula % Formula % and 1000 parts of polydimethylsiloxane having silanol groups at both ends and having a viscosity of about 12.500 cst at 25°C were mixed and heated under a nitrogen stream. The reaction mixture was heated and stirred at 150° C. for 2 hours to produce a transparent liquid copolymer represented by the following formula.

CH3 H2NCH2CH2NH(CH2)3 Sl-〇-C
H3 ((CH3)isto), H(x2500) 35 parts of this copolymer and the emulsifier "Tergitol"
) 3.5 parts of 7MN6J, 0.06 part of glacial acetic acid,
61.44 parts of water was added and emulsified and stirred to obtain an aqueous emulsion.

Using this aqueous emulsion and antibacterial agent solution A, an aqueous solution for antibacterial treatment was prepared according to the formulation shown in Table 3, and treated in the same manner as in Example 4 using a 100% polyester jersey as the object to be treated. Washing treatment and antibacterial properties were measured. The results are shown in Table 3.

Comparative Example 5 A treatment liquid was prepared in the same manner as in Example 6, except that no aqueous emulsion was used, and the same treatment was performed using this. The results are shown in Table 3.

From the results shown in Tables 1, 2, and 3 of Table 3, it is clear that the antibacterial treatment composition of the present invention provides excellent antibacterial effects and excellent durability.

Claims (1)

[Claims] 1) (A) an antibacterial agent selected from organosilicon quaternary ammonium salts and organosilicon amphoteric surfactants, and (B) the following formula D_aR_bX_cSiO_(_4_-_a_-_b_
-_c/_2_) {In the formula, D is a ▲ mathematical formula, chemical formula, table, etc. ▼ (R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R'' is a 1 to 6 carbon atom number. 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. } An aminofunctional polysiloxane represented by:
05% or more, and (B) an amino-functional polysiloxane in a proportion in the range of 0.05 to 10% such that the composition adheres to the object to be treated.