JPH09195171A - Antibacterial textile material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial textile material excellent in resistance to washing by imparting an aqueous solution of a complex comprising an organic phosphonic acid (salt) as a component, to natural or synthetic textile material. SOLUTION: The water dispersion containing 0.01-10.0% of complex consisting of at least one kind of organic phosphonic acid or its salt selected from the group consisting of condensation product of cyanoguanidine and polyalkylenepolyamine, polyhexamethylenebiguanidine hydrochloride and chlorohexidine gluconic acid is prepared. The antibacterial textile material is obtained by imparting the prescribed water dispersion in dipping method, exhaustion method or spray method, etc., on a natural or synthetic textile material such as wool serge, nylon or polyester jersey, etc., washing and drying.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial fiber material whose antibacterial property is sufficiently retained even after repeated washing.

[0002]

2. Description of the Related Art As a method of imparting a washing resistance and an antibacterial property to a fiber material, a method using an organic silicon quaternary ammonium salt reactive with cellulose is well known. Since this organosilicon-based quaternary ammonium salt can chemically bond to the primary hydroxyl group of cellulose, it is possible to impart antibacterial properties with washing resistance to the cellulose fiber material. However, it is extremely difficult to impart antibacterial properties with washing resistance to synthetic fibers having no hydroxyl group. In addition, the fiber material treated with the chemical generally has high water repellency,
Therefore, it has been pointed out that the ability to absorb water (water absorption) is lowered.

As other drugs, polyhexamethylene biguanidine hydrochloride, glohlhexidine gluconate and the like are known. Both polyhexamethylene biguanidine hydrochloride and chlorhexidine gluconate are derivatives of condensation reaction products of cyanoguanidine and hexamethylenediamine. However, when the fiber material is treated with these agents, it does not lower the water absorption of the object to be treated, but imparts antibacterial properties with washing resistance to the object to be treated, The method is difficult.

When a condensation reaction product of cyanoguanidine and polyalkylenepolyamine is used, the washing resistance is improved to a considerable extent, but the compound gradually drops off from the fibers as the number of washings increases, so that the antibacterial effect is increased. Since it tends to decrease gradually, it was found that the antibacterial effect disappears after 30 times of repeated washing.

[0005]

Under the circumstances, the present invention provides a natural fiber material and a synthetic fiber material.
It is intended to provide an antibacterial fiber material which does not reduce water absorption and retains sufficient antibacterial property even after repeated washing.

[0006]

The present invention is directed to a condensation reaction product of cyanoguanidine and polyalkylene polyamine, an aqueous solution containing polyhexamethylene biguanidine hydrochloride or chlorhexidine gluconate, and organic phosphonic acid or a salt thereof. The water-insoluble complex (complex) that occurs when an aqueous solution containing is mixed has a very large affinity for natural and synthetic fiber materials, is easily adsorbed and fixed on the fiber surface, and is also removed by washing. It was completed by finding that the antibacterial property is sufficiently retained.

The present invention has the following configuration. That is, a complex containing at least one selected from a condensation reaction product of cyanoguanidine and polyalkylene polyamine, polyhexamethylene biguanidine hydrochloride and chlorhexidine gluconate and an organic phosphonic acid or a salt thereof is adsorbed on the surface of the fiber material. It is an antibacterial fiber material that is made up of at least one.

The condensation reaction product in the present invention contains 5 to 20 parts of polyalkylene polyamine and, if necessary, 1 to 1 part of glycols per 10 parts of cyanoguanidine in a reaction vessel.
0 parts, 1 part to 5 parts of an inorganic salt or organic acid salt, urea, etc. are charged, heated at 120 to 200 ° C. for several hours to cause a condensation reaction, and then 5 to 30 parts of water is added to dilute the reaction product. It can be obtained by further adding an organic acid or an inorganic acid for neutralization.
Glycols are used as a solvent for the condensation reaction. Further, it is not clear how inorganic salts, organic acid salts, urea and the like participate in the condensation reaction.

The polyalkylene polyamine is selected from polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tri (1,2-propylene) tetramine and ethylenediamine.

Examples of the organic phosphonic acid include aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and 1-hydroxyethylidene-1,1-diphosphonic acid. To be

Examples of the fiber material to which the present invention is applied include natural fiber materials such as cellulose fibers and natural polyamide fibers, and synthetic fiber materials such as polyester fibers, synthetic polyamide fibers, acrylic fibers and polyolefin fibers.

As a method for producing the antibacterial fiber material,
It is manufactured by a conventional method such as a dipping method, an exhaust method, or a spray method. In the exhaust method, a much higher drug adsorption rate than that of conventional synthetic fiber materials can be obtained, so that excellent antibacterial fiber materials can be easily manufactured.

An example of the method for producing the antibacterial fiber material is shown below. (1) 0.01 to 10.0% of a complex containing the condensation reaction product and an organic phosphonic acid or a salt thereof as components
The fibrous material is treated by the dipping method, the exhaust method, the spray method, or the like using the aqueous dispersion liquid contained therein, and if necessary, washed with water and dried.

(2) A fiber material using an aqueous dispersion containing 0.01 to 10.0% of a complex containing polyhexamethylene biguanidine hydrochloride or chlorhexidine gluconate and an organic phosphonic acid or a salt thereof. Is treated by a dipping method, an exhaust method or a spray method,
If necessary, wash with water and dry.

(3) 0.05-10% of the above condensation reaction product
The fibrous material is treated with a dipping method, a spray method, or the like with an aqueous solution containing, and dried if necessary. Then, it is treated again with an aqueous solution containing 0.05 to 10% of organic phosphonic acid or a salt thereof by a dipping method, a spray method or the like and dried.
You may wash with water, heat-process, etc. as needed. Alternatively, the order of the treatments may be reversed, for example, the treatment with the organic phosphonic acid or its salt may be performed first.

(4) 0.05% by weight of polyhexamethylene biguanidine hydrochloride or chlorhexidine gluconate.
The fiber material is treated with an aqueous solution containing 10% by a dipping method, a spray method, or the like, and dried if necessary. Then, it is treated again with an aqueous solution containing 0.05 to 10% of organic phosphonic acid or a salt thereof by a dipping method, a spray method or the like and dried. Next, if necessary, washing with water, heat treatment, etc. may be performed. Alternatively, the order of the treatments may be reversed, such as the treatment with the organic phosphonic acid or its salt being first. Thus, an antibacterial fiber having good washing resistance can be manufactured.

When processing by the exhaust method, the temperature of the processing liquid is usually from room temperature to 130 ° C., and the processing time is usually from 5 minutes to 60.
One minute is enough. The pH of the treatment liquid is usually in the range of 3 to 10, but when the pH is low, it is difficult to form a complex. The drying temperature is usually 50
There is no particular limitation at ~ 150 ° C. You may heat-process after that as needed. The heat treatment temperature is usually 120 to 180 ° C.
The processing time is 30 seconds to 30 minutes.

The amount of the complex adsorbed is usually 0.05 to 10% with respect to the weight of the fiber, and the preferable amount is usually 0.1.
It is in the range of 1 to 5.0%. When the amount is less than this range, sufficient antibacterial effect is not exerted, and there is no benefit even if it is adsorbed excessively.

Since the dispersion liquid of the complex formed when a surfactant containing a sulfonate or a sulfate is used instead of using the organic phosphonic acid or a salt thereof, the stability is poor and immediately precipitates. It is difficult to adsorb to fibers. It is also possible to separately treat the surfactant containing the condensation reaction product or polyhexamethylene biguanidine hydrochloride or chlorhexidine gluconate and the sulfonate or sulfate to adsorb the complex to the fiber. , In this case, the desired effect cannot be achieved. That is, the above-mentioned complex does not sufficiently retain the antibacterial performance, and therefore the antibacterial performance of the fiber material adsorbing the complex is not satisfactory. Further, since the affinity for the fiber material is not so large, the complex adsorbed on the fiber material is likely to fall off by repeated washing.

[0020]

The present invention will be described in detail below with reference to examples and synthetic examples, but the present invention is not limited to these examples and synthetic examples.

Synthetic Example 1 700 parts of cyanoguanidine, 600 parts of diethylenetriamine, 400 parts of ethylene glycol and 100 parts of ammonium chloride were charged in a reaction vessel and heated to 140 ° C. and reacted for 4 hours. Ammonia is generated violently. When the generation of ammonia is stopped, heating is stopped, 600 parts of water is added, and 270 parts of hydrochloric acid is further added to neutralize the reaction product to obtain an aqueous solution of the desired condensation reaction product.

Synthesis Example 2 620 parts of cyanoguanidine, 760 parts of tetraethylenepentamine and 500 parts of diethylene glycol were charged into a reaction kettle and heated to 135 ° C. and reacted for 5 hours. Ammonia is generated violently. When the generation of ammonia has stopped, heating is stopped and 500 parts of water is added to dilute the reaction product. Further, 160 parts of sulfuric acid is added to neutralize the reaction product. Thus, an aqueous solution of the desired condensation reaction product is obtained.

Synthesis Example 3 A reactor was charged with 720 parts of cyanoguanidine, 650 parts of pentaethylenehexamine, 500 parts of ethylene glycol and 50 parts of ammonium chloride, and the mixture was heated to 145 ° C. and reacted for 4 hours. Ammonia is generated violently. When the generation of ammonia is stopped, the heating is stopped, 600 parts of water is added, and 250 parts of hydrochloric acid is further added to neutralize the reaction product. Thus, an aqueous solution of the desired condensation reaction product is obtained.

Synthesis Example 4 720 parts of cyanoguanidine, 750 parts of dipropylenetriamine and 700 parts of diethylene glycol were charged into a reaction vessel, and the mixture was heated to 160 ° C. and reacted for 3 hours. Ammonia is generated violently. When the generation of ammonia is stopped, the heating is stopped, 500 parts of water is added, and 300 parts of hydrochloric acid is added to neutralize the reaction product. Thus, an aqueous solution of the desired condensation reaction product is obtained.

Example 1 The aqueous solution of the condensation reaction product obtained in Synthesis Example 1 was diluted with water to give 1
It can be seen that when a 0.25-fold liquid was added and 0.25% of 7-soda salt of diethylenetriaminepenta (methylenephosphonic acid) was added and stirred, the liquid became cloudy and a complex was formed. Dip acrylic muslin and polyester jersey in this water dispersion and squeeze 1 at a squeezing rate of 100%.
It was dried at 20 ° C. for 3 minutes and heat-treated at 140 ° C. for 90 seconds to obtain an antibacterial fiber material. Each was used as a test cloth for an antibacterial test, and an antibacterial test was performed. The results are shown in Tables 1 and 2.

Example 2 A 0.5% aqueous solution of chlorhexidine gluconate is prepared. To this, 0.25% of 7-soda salt of diethylenetriaminepenta (methylenephosphonic acid) was added and stirred to form a complex, which made the liquid cloudy. Acrylic muslin and polyester jersey were dipped in this aqueous dispersion, squeezed at a squeezing ratio of 100%, dried at 120 ° C. for 3 minutes, and heat-treated at 140 ° C. for 90 seconds to obtain an antibacterial fiber material. Each was used as a test cloth for an antibacterial test, and an antibacterial test was performed. The results are shown in Tables 1 and 2.

As a comparative example, the same fibrous material was similarly treated with the following agents. (Comparative Example 1) 0.5% of the condensation reaction product obtained in Synthesis Example 1
Aqueous solution, (Comparative Example 2) Aqueous dispersion containing 0.5% each of the condensation reaction product obtained in Synthetic Example 1 and sodium laurylsulfate salt (Comparative Example 3) 0.5% of soda salt of chlorhexidine gluconate and naphthalenesulfonic acid formalin condensate.
% Aqueous solution (stirring well because complex is likely to settle due to poor liquid stability), (Comparative Example 4) 0.5% aqueous solution of 3- (methoxysilyl) propyloctadecyldimethylammonium chloride, The acrylic muslin and polyester jersey treated fabrics, which were respectively treated in the same manner, were used as test fabrics for the comparative test, and the comparative test was performed.

Washing Method Using a household washing machine, after washing for 5 minutes in water at about 40 ° C. containing 1.5 g / l of Monogen Uni (manufactured by Procter & Gamble) as a detergent, rinsing for 2 minutes, dehydration, dry. The same operation is repeated 10 times and 30 times by setting this as one time.

Antibacterial Test Method According to the evaluation test method of the Textile Products Hygiene Processing Council, the bacterial count measurement method was carried out. Staphylococcus aureus (IFO)
12732) was used. In the table of the results, "after 18 hours" means 18 hours after inoculation of the test bacteria, and "after 10 times of washing and 30 times of washing" means that the treated cloth is 1
This means that the test cloth was washed repeatedly 0 times and 30 times.

[0030]

[Table 1]

[0031]

[Table 2] From this result, the condensation reaction product in the present invention, or the fibrous material treated with an aqueous dispersion containing a complex of chlorhexidigin gluconate and an organic phosphonate to adsorb the complex, It can be seen that the fiber material obtained by treating each treatment liquid has antibacterial performance with significantly higher wash resistance.

Example 3 A 7-soda salt of diethylenetriaminepenta (methylenephosphonic acid) and the condensation reaction product obtained in Synthesis Example 2 were mixed in equal amounts to prepare an aqueous dispersion of a complex containing 0.025% of each drug. To do. Using 200 grams of this solution,
Exhaust each 10 grams of nylon jersey and polyester jersey at room temperature for 10 minutes. It is observed that the cloudiness of the liquid disappeared and the complex was completely adsorbed on the fiber material. After the treatment, it was washed with water and dried to obtain an antibacterial fiber material. Each was used as a test cloth for an antibacterial test and an antibacterial test was performed. The results are shown in Tables 3 and 4.

Example 4 7-soda salt of diethylenetriaminepenta (methylenephosphonic acid) and polyhexamethylenebiguanidine hydrochloride were mixed in equal amounts to prepare an aqueous dispersion of a complex containing 0.025% of each drug. Using 200 g of this solution, 10 g of each of nylon jersey and polyester jersey is exhausted at room temperature for 10 minutes. It is observed that the cloudiness of the liquid disappeared and the complex was completely adsorbed on the fiber material. After processing, rinse with water and dry,
An antibacterial fiber material was obtained. An antibacterial test was conducted using each of them. The results are shown in Tables 3 and 4.

As Comparative Example (Comparative Example 5) 0.02 of the condensation reaction product obtained in Synthesis Example 2
5% aqueous solution, (Comparative Example 6) 0.025% aqueous solution of polyhexamethylene biguanidine hydrochloride, (Comparative Example 7) 0.025% aqueous solution of 3- (methoxysilyl) propyloctadecyldimethylammonium chloride The treated nylon and polyester jersey treated cloths were used as the test cloths for the comparative test, and these were used for the comparative test. The results are shown in Tables 3 and 4.

[0035]

[Table 3]

[0036]

[Table 4] From these results, the fibrous material exhausted by the condensation reaction product obtained in Synthesis Example 2 or the complex containing polyhexamethylene biguanidine hydrochloride and organic phosphonate as components was the compound of Comparative Example. It can be seen that the antibacterial efficacy and washing resistance are extremely superior to those of the treated fiber material.

Examples 5 to 6 The soda salt of ethylenediaminetetra (methylenephosphonic acid) and the condensation reaction product obtained in Synthesis Example 3 or Synthesis Example 4 were mixed in equal amounts and each contained 0.025% of each drug. Prepare an aqueous dispersion of both complexes. This liquid 200
10 g of each of wool surge and acrylic muslin are shaken at room temperature for 10 minutes to be exhausted.
It is observed that the cloudiness of the liquid disappeared and the complex was completely adsorbed on the fiber material. After treatment, wash with water 1
An antibacterial fiber was obtained by drying at 20 ° C. Each was used as a test cloth for an antibacterial test and an antibacterial test was performed. The results are shown in Tables 5 and 6.

Example 7 An equal amount of pentasodium salt of ethylenediaminetetra (methylenephosphonic acid) and polyhexamethylenebiguanidine hydrochloride were mixed to prepare an aqueous dispersion of both complexes containing 0.025% of each drug. To do. Using 200g of this solution, 10 wool wool and 10 acrylic muslin
Gram is shaken at room temperature for 10 minutes for exhaustion treatment. It is observed that the cloudiness of the liquid disappeared and the complex was completely adsorbed on the fiber material. After processing, wash with water 120
It was dried at ℃ to obtain antibacterial fiber. Each was used as a test cloth for an antibacterial test and an antibacterial test was performed. The results are shown in Table 5 and Table 6.
Shown in

As Comparative Example (Comparative Example 8) 0.02 of the condensation reaction product obtained in Synthesis Example 3
5% aqueous solution, (Comparative Example 9) an aqueous dispersion containing the condensation reaction product obtained in Synthesis Example 4 and 0.025% of sodium dodecylbenzenesulfonate, (Comparative Example 10) polyhexamethylene biguanidine hydrochloride and Add 0.0% sodium polyoxyethylene lauryl sulfate
An aqueous dispersion containing 25% each, (Comparative Example 11) a wool surge and an acrylic muslin treated cloth which were similarly treated with a 0.025% aqueous solution of 3- (methoxysilyl) propyloctadecyldimethylammonium chloride, and a comparative test. A cloth was used and an antibacterial test was performed using these. The results are shown in Tables 5 and 6.

[0040]

[Table 5]

[0041]

[Table 6] From this result, when the wool or acrylic fiber material was treated by the exhaust method with the aqueous dispersion containing the complex in the present invention, the complex was completely adsorbed on the fiber material, and the antibacterial effect was obtained even after repeated washing. It can be seen that, while an excellent antibacterial fiber material retaining the above can be produced, the antibacterial performance of the materials obtained in Comparative Examples is remarkably inferior.

[0042]

INDUSTRIAL APPLICABILITY The complex-adsorbed natural and synthetic fiber materials of the present invention have an excellent antibacterial effect without a decrease in water absorption and retain a sufficient antibacterial effect even after 30 times of repeated washing. . The method for producing the antibacterial fiber material is simple and can be produced by a conventional dipping method, exhaustion method, spray method, or the like. Since the complex has a high affinity for the fiber material, it is possible to produce an antibacterial fiber material having an extremely excellent antibacterial effect as compared with the conventional method even by the exhaust method.

Claims (1)

[Claims] 1. On the surface of a fiber material, at least one selected from a condensation reaction product of cyanoguanidine and polyalkylene polyamine, polyhexamethylene biguanidine hydrochloride and chlorhexidine gluconate and an organic phosphonic acid or a salt thereof are contained. An antibacterial fiber material that absorbs the complex that absorbs.