JPH10237763A - Antimicrobial agent for treating fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial agent for treating fibers capable of retaining excellent antimicrobial activities for the fibers even after repetitive washing by including a specific copolymer as an essential component therein. SOLUTION: This antimicrobial agent for treating fibers is obtained by synthesizing a copolymer containing a monomer represented by formula I (R1 and R2 are each H or methyl; R3 and R4 are each a 1-5C alkyl; X<-> is an anionic residue such as a halide ion or nitrate ion) such as diallyldimethylammonium chloride and a monomer represented by formula II (R5 is H or methyl; M is H) such as (meth)acrylic acid as essential components. A fabric such as a polyester or a nylon is padded in an aqueous solution of the antimicrobial agent, squeezed and then heat-treated to insolubilize the copolymer. Thereby, antimicrobial finishing excellent in durability is carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial agent for treating fibers, which is characterized in that when treated to fibers, the antibacterial properties are sufficiently maintained even after repeated washing.

[0002]

2. Description of the Related Art In recent years, the tendency toward cleanliness has increased,
There is a strong tendency to seek a more hygienic and comfortable life. Under such circumstances, fibers are no exception, and there is an increasing demand for fibers that retain sufficient antibacterial properties even after repeated washing. As a method for repeatedly imparting antibacterial properties with washing properties to fibers, a method of using a reactive organic silicone quaternary ammonium salt for cellulose fibers is well known. Since this organic silicone-based quaternary ammonium salt can chemically bond to the primary hydroxyl group of cellulose, it is possible to repeatedly impart antibacterial properties to cellulose fibers with washing properties. However, it is extremely difficult to repeatedly impart antibacterial properties with washing properties to synthetic fibers and the like having no hydroxyl group. Other antibacterial agents include polyhexamethylene biguanidine hydrochloride, chlorhexidine gluconate, halogenated phenols, vinyl polymers having quaternary ammonium salts, and the like. It is difficult to impart a potent antibacterial property by an ordinary method.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide an antibacterial agent for treating fibers, which can easily treat almost all fibers and has a repetitive washing property. Is what you do.

[0004]

Under the circumstances described above, the present inventor has conducted intensive studies to solve the above-mentioned problems, and as a result, by using a combination of highly selected monomer components,
The present inventors have found that a copolymer synthesized under the selected polymerization conditions can achieve the above objects, and have completed the present invention. That is, the present invention provides a general formula 3

Embedded image (.X wherein, R ₁ and R ₂ may be different even in the same, .R ₃ and R ₄ represents a hydrogen atom or a methyl group represents an alkyl group having 1 to 5 carbon atoms ^- is Chloride ion,
It represents a halogen ion such as a bromide ion, or an anion residue such as a nitrate ion or a sulfate ion. ) And the general formula 4

Embedded image (Wherein, R ₅ represents a hydrogen atom or a methyl group; M represents a hydrogen atom.) A copolymer containing a monomer represented by the following formula as an essential component is synthesized. An antibacterial agent for fiber treatment, which is obtained by substituting a part or all of M with a monovalent alkali metal or ammonia, and which is insoluble in water by evaporating to dryness at a temperature of 70 ° C. or more. To provide.

In particular, diallyldimethylammonium chloride wherein R ₁ and R ₂ are hydrogen atoms, R ₃ and R ₄ are methyl groups, and X ⁻ is a chlorine ion, is used as the monomer represented by the above formula (3). Is preferred. on the other hand,
Examples of the monomer represented by Formula 4 include acrylic acid and methacrylic acid.

The molar ratio of the monomer represented by the above formula (3), which is an essential component of the copolymer in the antibacterial agent of the present invention, to the monomer represented by the above formula (4) is usually 50 to 90. / 50 to 10 are preferred.

Further, the copolymer is represented by the following formula (3):
It may be a copolymer comprising a monomer represented by the formula as an essential component and, if necessary, copolymerizing with another copolymerizable monomer within a range not to impair the object of the present invention. Other copolymerizable monomers include, for example, acrylamide, methacrylamide, and the like.

The weight average molecular weight of the copolymer is 5
It is preferably from 000 to 500,000.

In order to obtain the copolymer, the above formula (3)
It is preferable that the monomers represented by Chemical Formula 4 are uniformly copolymerized at a desired molar ratio, and it is important to control the polymerization conditions strictly. That is, when a large amount of the homopolymer of the monomer represented by the above formula (3) is produced during polymerization, even if the fiber is subjected to heat drying treatment, water insolubilization does not occur, and therefore, it is easily dropped off by washing. The object of the present invention cannot be achieved.
On the other hand, when the amount of the homopolymer of the monomer represented by the above formula (4) is increased, a water-insoluble polymer complex is formed during the polymerization and cannot be subjected to fiber treatment.

Next, a method for synthesizing the antibacterial agent of the present invention will be exemplified.
Monomers 20 to 10 represented by the above formula as constituents
0 parts by weight are dissolved in 20 to 300 parts by weight of a water-soluble solvent such as water, and 0.05 to 5 parts by weight of a radical polymerization initiator is added. Then, under stirring, the monomers 1 to 1 represented by the above formula 4
A solution obtained by dissolving 45 parts by weight of 1 to 135 parts by weight of a water-soluble solvent such as water is added dropwise to carry out polymerization. After completion of the reaction, the copolymer is obtained by adjusting the pH by adding an aqueous alkali solution. Examples of the radical polymerization initiator include ammonium persulfate, persulfates such as potassium persulfate,
Radical polymerization generally used such as azo compounds such as 2,2'-azobis (2-amidinopropane) dihydrochloride, peroxides such as di-t-butyl peroxide, cumene hydroperoxide and hydrogen peroxide. Any initiator can be used without any particular limitation. At the time of dropping the monomer represented by the formula (4), in order to make the reaction proceed immediately after the dropping, the dropping is continued in a state where heat is constantly generated, and care is taken not to lower the internal temperature. It is preferable that the polymerization temperature is usually 40 to 90 ° C. and the polymerization time is usually about 2 to 10 hours. The pH in the system during the reaction is preferably from 1 to 2. Outside this range,
Gelation may occur during the reaction and the final polymer may not become insoluble in water after heat treatment. After completion of the reaction, the pH is adjusted to 3 to 8, particularly preferably 4 to 6, by adding an alkaline solution. As the alkaline liquid,
Examples include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and ammonia, but are not particularly limited thereto.

Fibers to be subjected to antibacterial treatment include natural cellulosic fibers such as cotton and hemp, regenerated cellulosic fibers such as rayon, polynosic rayon and cupola, polyvinyl alcohol fibers such as vinylon, and diacetate and triacetate. Animal fiber such as acetate fiber, wool, alpaca, cashmere, mohair, silk, synthetic fiber such as polyester, nylon, acrylic, etc., and any combination of these fibers can be used without any problems. We do not choose any kind.
The form may be any of a thread, a rug, a woven fabric, a knitted fabric, a non-woven fabric, and a final fiber product such as clothes and bedding products.

As a method of treating the fiber with the antibacterial agent, a method of directly treating the surface of the fiber such as a pad method or a spray method can be used. At this time, it is important that the fiber is treated with an antibacterial agent and then immediately dried to make the antibacterial agent insoluble in water before the next treatment. The drying temperature is usually 70 to 130 ° C. If necessary, heat treatment may be further performed at 130 to 200 ° C. The treatment amount is not particularly limited, and the concentration may be specified in a situation where the fiber product is used.
It is preferably from 1 to 10% by weight, more preferably from 0.1 to 5% by weight.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to Synthesis Examples and Examples, but the present invention is not limited to these Synthesis Examples and Examples. The percentages in the examples are by weight unless otherwise specified.

Synthesis of diallyldimethylammonium chloride-acrylic acid copolymer

Synthesis Example 1 (65/35 molar ratio) In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 370 g (1.5 mol) of diallyldimethylammonium chloride (65%) and water were added. 150g
Was added to the mixture, and the mixture was stirred to be uniformly dissolved. Then, the internal temperature was raised to 70 ° C., and 6 g of ammonium persulfate (20%) was added as a polymerization initiator under stirring. After the start of heat generation, an aqueous solution in which 70 g (0.8 mol) of acrylic acid (80%) and 70 g of water were mixed was dropped from the dropping funnel to an internal temperature of 70 to 70 ° C.
The solution was added dropwise over about 3 hours while maintaining the temperature at 85 ° C. After the completion of the dropwise addition, an aging reaction was performed for about 2 hours. Thereafter, 80 g of water was added and the mixture was stirred, and then cooled to complete the reaction. This is N / 4
Colloid titration was performed with a 00-polyvinyl potassium sulfate solution, and the conversion of diallyldimethylammonium chloride was measured to be 100%. No acrylic acid was detected in the measurement of residual acrylic acid by gas chromatography. Thereafter, an aqueous sodium hydroxide solution (about 20%) was added to adjust the pH to about 4.8. A colorless to pale yellow liquid aqueous solution having a concentration of about 40% was obtained. The weight average molecular weight of the obtained polymer obtained by liquid chromatography was 300,000. This is dried at 105 ℃,
After drying for 3 hours, it was insoluble when put in water.

Synthesis Example 2 (50/50 molar ratio) In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 370 g (1.5 mol) of diallyldimethylammonium chloride (65%) and water were added. 150g
Was added to the mixture, and the mixture was stirred to be uniformly dissolved. Then, the internal temperature was raised to 70 ° C., and 6 g of ammonium persulfate (20%) was added as a polymerization initiator under stirring. After the start of heat generation, an aqueous solution obtained by mixing 135 g (1.5 mol) of acrylic acid (80%) and 135 g of water was dropped from the dropping funnel to an internal temperature of 7 g.
The solution was added dropwise over about 3 hours while maintaining the temperature at 0 to 85 ° C. After the completion of the dropwise addition, an aging reaction was performed for about 2 hours. Thereafter, 70 g of water was added and the mixture was stirred, and then cooled to complete the reaction. This is N
The polymerization rate of diallyldimethylammonium chloride was measured by colloidal titration with a / 400-polyvinyl potassium sulfate solution and found to be 100%. No acrylic acid was detected in the measurement of residual acrylic acid by gas chromatography. Thereafter, an aqueous sodium hydroxide solution (20%) was added to adjust the pH to 4.8. Concentration about 40
% Of a colorless to pale yellow liquid aqueous solution was obtained. The weight average molecular weight of the obtained polymer obtained by liquid chromatography was 2
It was 50,000. This was dried in a drier at 105 ° C. for 3 hours and then insoluble in water.

Synthesis Example 3 (50/50 molar ratio) In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 100 g (0.4 mol) of diallyldimethylammonium chloride (65%) and water were added. 330g
Was added, and the mixture was stirred to dissolve uniformly, then the internal temperature was raised to 70 ° C., and under stirring, 1.5 g of ammonium persulfate (20%) was added as a polymerization initiator. After the start of heat generation, an aqueous solution obtained by mixing 36 g (0.4 mol) of acrylic acid (80%) and 150 g of water was dropped from the dropping funnel to an internal temperature of 7 g.
The solution was added dropwise over about 3 hours while maintaining the temperature at 0 to 85 ° C. After the completion of the dropwise addition, an aging reaction was performed for about 2 hours. Thereafter, the reaction was terminated by cooling. This was subjected to colloid titration with an N / 400-polyvinyl potassium sulfate solution, and the conversion of diallyldimethylammonium chloride was measured to be 100%.
No acrylic acid was detected in the measurement of residual acrylic acid by gas chromatography. Thereafter, an aqueous solution of sodium hydroxide (20%) was added thereto to adjust the pH to 4.0.
Adjusted to 8. A colorless to pale yellow liquid aqueous solution having a concentration of about 15% was obtained. The weight average molecular weight of the obtained polymer determined by liquid chromatography was 20,000. This was dried in a dryer at 105 ° C. for 3 hours and then dissolved in water.

Synthesis Example 4 (98/2 molar ratio) In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 340 g (1.37 mol) of diallyldimethylammonium chloride (65%) and water were added. 140
g, stir the mixture to dissolve uniformly,
The internal temperature was raised to 70 ° C., and 6 g of ammonium persulfate (20%) was added as a polymerization initiator under stirring. After the start of heat generation, 2.5 g (0.03 mol) of acrylic acid (80%)
An aqueous solution obtained by mixing water and 70 g of water was dropped from the funnel to an internal temperature of 7
The solution was added dropwise over about 2 hours while maintaining the temperature at 0 to 85 ° C. After the completion of the dropwise addition, an aging reaction was performed for about 2 hours. Thereafter, the reaction was terminated by cooling. This was subjected to colloid titration with an N / 400-polyvinyl potassium sulfate solution, and the conversion of diallyldimethylammonium chloride was measured to be 100%.
No acrylic acid was detected in the measurement of residual acrylic acid by gas chromatography. Thereafter, an aqueous solution of sodium hydroxide (20%) was added thereto to adjust the pH to 4.0.
Adjusted to 8. A colorless to pale yellow liquid aqueous solution having a concentration of about 40% was obtained. The weight average molecular weight of the obtained polymer obtained by liquid chromatography was 200,000. This was dried in a dryer at 105 ° C. for 3 hours and then dissolved in water.

Next, the performance evaluation method in the embodiment will be described below. Cloth treatment method Polyester tropical cloth and nylon taffeta cloth were used as test cloths. A 0.5% aqueous solution (in terms of solid content) was adjusted with a treating agent, and this was used as a treating solution. After padding the test cloth with this treatment liquid, it was squeezed at a pickup ratio of 100%, dried at 110 ° C. for 2 minutes with a pin tenter, and then dried at 170 ° C.
C. for 2 minutes.

Washing method Using a domestic washing machine, a nonionic activator "Alcopearl N-100" (manufactured by Hoechst Japan) is used as a detergent (0.54 g / l), and the treated cloth is heated to a temperature of about 40 ° C. 20
After washing in a bath for 5 minutes, rinsing was carried out twice for 2 minutes in the same bath volume with fresh water at room temperature, dehydrated and air-dried. This operation was performed once, and the same operation was performed 10 times.

Antimicrobial Evaluation Method The test method used was a bacterial count measurement method in accordance with the evaluation test method of the Textile Sanitary Processing Council. Staphylococcus aureus (IFO 12732) was used as a test bacterium. The test bacterium was poured into the treated cloth, the number of viable cells was measured after culturing at 35 to 37 ° C. for 18 hours, and the number of cells relative to the number of cultured cells was measured. Bacterial increase / decrease value difference = log (B / A) −log (C / A) =
log (B / C) A: Number of bacteria collected and dispersed immediately after inoculation of untreated cloth B: Number of bacteria collected and dispersed 18 hours after untreated cloth C: Number of bacteria collected and collected 18 hours after treatment of cloth If (B / A)> 2, the measurement is valid; if log (B / A) ≦ 2, a retest is required. Furthermore, the antibacterial effect is log (B /
The larger the value of C), the higher the antibacterial property. When log (B / C)> 1.6, it is recognized as a standard having antibacterial properties, and in particular, it is certified as an antibacterial and deodorized product by the Textile Sanitary Processing Council.

Example 1 The copolymer of Synthesis Example 1 was pad-treated on a polyester tropical cloth and a nylon taffeta cloth, and then washed with the treated cloth to evaluate antibacterial properties. The results are shown in Tables 1 and 2.

Example 2 The procedure of Example 1 was repeated, except that the copolymer of Synthesis Example 1 was replaced with the copolymer of Synthesis Example 2. The results are shown in Tables 1 and 2.

Comparative Example 1 A copolymer was prepared in the same manner as in Example 1 except that the copolymer prepared in Synthesis Example 1 was adjusted to pH 1 with hydrochloric acid. Tables 1 and 2 show the results.
Shown in

COMPARATIVE EXAMPLE 2 The copolymer of Synthesis Example 1 was adjusted to pH 1 with an aqueous sodium hydroxide solution.
The treatment was performed in the same manner as in Example 1 using the product prepared to be 0. The results are shown in Tables 1 and 2.

Comparative Example 3 The procedure of Example 1 was repeated, except that the copolymer of Synthesis Example 1 was replaced with the copolymer of Synthesis Example 3. The results are shown in Tables 1 and 2.

Comparative Example 4 A treatment was performed in the same manner as in Example 1 except that the copolymer of Synthesis Example 1 was replaced with the copolymer of Synthesis Example 4. The results are shown in Tables 1 and 2.

Comparative Example 5 A copolymer of Synthesis Example 1 was used as a mixture of polydiallyldimethylammonium chloride and sodium polyacrylate (65/35 molar ratio, molecular weight 200,000, pH
Processing was performed in the same manner as in Example 1 except that 4.8) was used. The results are shown in Tables 1 and 2.

[0029]

As is clear from the above results, the antibacterial agent of the present invention becomes insoluble in water by heat drying, so that it can be easily treated on almost all fibers, and has antibacterial properties even after repeated washing. Is an antibacterial agent for fiber treatment that is sufficiently retained.

Claims (1)

[Claims] (1) General formula (1) (.X wherein, R ₁ and R ₂ may be different even in the same, .R ₃ and R ₄ represents a hydrogen atom or a methyl group represents an alkyl group having 1 to 5 carbon atoms ^- is Chloride ion,
It represents a halogen ion such as a bromide ion, or an anion residue such as a nitrate ion or a sulfate ion. ) And the general formula 2 (Wherein, R ₅ represents a hydrogen atom or a methyl group; M represents a hydrogen atom.) A copolymer containing a monomer represented by the following formula as an essential component is synthesized. (1) An antibacterial agent for fiber treatment, wherein M is partially or entirely substituted with a monovalent alkali metal or ammonia, and insoluble in water by evaporating to dryness at a temperature of 70 ° C or higher.