JP2985548B2 - Fiber with antibacterial and antifungal properties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fiber having antibacterial and antifungal properties. More specifically, the present invention relates to a fiber having antibacterial and antifungal properties, which is treated with a compound having a guanidyl group.

[0002]

2. Description of the Related Art Many antibacterial fiber products have been developed. As important conditions for such a textile product, there are three points of being hygienic, durable and high in safety. A quaternary ammonium salt type silane compound is known as a treating agent satisfying this condition (see, for example, JP-A-2-6489). However, since the quaternary ammonium type compound is an ionic compound, it is easily affected by inorganic salts, saccharides, proteins, and the like, and has problems such as reduced bactericidal properties and discoloration. Further, since the alkyl group portion is larger than the polar group in the molecule, there is a disadvantage that the water absorption and the moisture absorption of the fiber are impaired. On the other hand, an antibacterial property-imparting compound comprising a silane compound having a guanidyl group has been known as a compound used in a cured rubber composition (see Japanese Patent Publication No. 61-18860). There was room.

[0003]

The present inventors have conducted various studies on antibacterial agents suitable for treating fibers, and have found that a group in which a cyano group or a guanidyl group is bonded to a guanidyl group (that is, a cyanoguanidyl group and a biguanide group). The fiber treated with the compound has excellent antibacterial and antifungal properties compared to conventional products, and its activity is permanently maintained,
Further, they have found that the compound has many characteristics and advantages, such as not impairing the water absorption and hygroscopicity of the fiber itself due to the high hydrophilicity of the fiber itself, and have completed the present invention.

[0004]

That is, the present invention relates to X ¹ X ² X ³ Si—Y
-NHC (= NH) NH-Z 1 ( wherein, among the X ¹ to X ^3, at least one is a hydrolyzable group, Y is an alkylene group of C1-C30, Z ¹ is -CN Or -C (= NH) NH-
Z ² (Z ² is hydrogen, alkyl or phenyl C1 to C20) to provide a fiber having an antibacterial antifungal which comprises treating a compound represented by a).

The compound used in the present invention comprises a substituted silane group, a guanidyl group, and an alkylene group connecting these two groups, as represented by the above formula. Of these,
The substituted silane group contains at least one hydrolysable group. The hydrolyzable groups are bonded to one to three Si atoms, and may be the same or different. Preferred hydrolyzable groups include alkoxy groups such as methoxy and ethoxy, and halogens such as chlorine. The remaining substituent is not particularly limited as long as it does not prevent the bond between the silane group and the surface and does not adversely affect the substrate (fiber). In practice, hydrogen or phenyl groups, or
A C1-C5 alkyl group such as a methyl group or an ethyl group is suitable.

As the guanidyl group, a cyanoguanidyl group (Z ¹ = -CN in the above formula) or a biguanide group (Z ¹ =-
C (= NH) NH-Z ² ) is used. Z ² is hydrogen, C 1
To a C20 alkyl group or a phenyl group, and the phenyl group may be substituted with a halogen such as fluorine, chlorine or bromine, or a trifluoromethyl group. From a synthetic point of view and antibacterial activity, a phenyl group substituted with halogen is preferred. Alkylene groups contain 1 to 30 carbon atoms. When the number of carbon atoms exceeds 30, hydrophilicity may be affected. From a synthetic point of view, a propylene group is preferred. These compounds may be used after being converted to a salt, if necessary. Typically used as the hydrochloride,
Any salt may be used as long as it does not adversely affect the substrate (fiber). Examples of such compounds include the following.

## STR2 ## (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NHC (= NH) NH—
CN <1>

Embedded image (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NHC (= NH) NHC
(= NH) NH-Z ² · HClZ ² = H <2> phenyl <3> p-chlorophenyl <4> p-trifluoromethylphenyl <5> n-hexyl <6>

The fibers used in the present invention include any of natural fibers, regenerated fibers, synthetic fibers, and semi-synthetic fibers. Natural fibers include, for example, cotton, hemp, wool, silk, etc., regenerated fibers include, for example, rayon and cupra, and semi-synthetic fibers include, for example, acetate and acetylated acetate (JP-A-59-223371). As the synthetic fiber, for example, a polyamide type, a polyester type, an acrylic type, a polyvinyl alcohol type, a polyvinyl chloride type or the like can be used. Natural fibers are particularly suitable as a substrate material from the aspect of drug binding. When producing fibers having antibacterial and antifungal properties, a solution prepared by dissolving the above antibacterial agent having a cyanoguanidyl group or a biguanide group in a suitable solvent can be used for treating a desired fiber by a dipping method or a spray method. It is. Examples of such a solvent include water, alcohols, esters, ketones, and hydrocarbons such as toluene.

The appropriate amount of the antibacterial agent applied to the fiber depends on the desired degree of the antibacterial activity and the like.
1 to 5 wt%. If the treatment amount is less than 0.01 wt%, a sufficient effect cannot be obtained, and if the treatment amount exceeds 20 wt%, the effect is saturated, and since the guanidyl group is contained in a large amount, it is exposed to heat or light for a long time. It is not preferable because it may be discolored when it is used. The treatment temperature varies depending on the fiber to be treated and the solvent used, but is usually 0 ° C to 1 ° C.
The temperature is 50 ° C, preferably about 5 to 100 ° C. In addition, the processing time, in the immersion method is a typical processing method,
The treatment may be performed for 0.01 minute to 5 hours, preferably for 0.1 minute to 2 hours. After the treatment, it is preferable to dry the fiber at 80 to 120 ° C in order to enhance the binding property of the drug to the fiber. Other treatment conditions and specific procedures are the same as the usual conditions or procedures for treating fibers with chemicals.

[0009]

The present invention will be described in more detail with reference to the following examples, which do not limit the present invention.
In addition, the compounds <1> to <exemplifying the production in Examples are described below.
6> is a compound described in the above “Composition of the invention” <
1> to <6>, and compound <7> is JP-B-61-1
Compounds of the following formula exemplified in JP 7860.

Embedded image (CH ₃ O) ₃ Si (CH ₂ ) ₃ N = C (N (CH ₃ ) ₂ ) ₂

[0010]

Example 1 Compound <1> was dissolved in 300 ml of water so as to have a concentration of 0.5 wt%, 30 g of cotton knitted fabric was immersed in this solution, and stirred slowly at 60 ° C. for 1 hour. The cotton knitted fabric was pulled out, squeezed to a squeezing ratio of 100%, and dried at 90 ° C. for 15 minutes. The resulting fiber is
Evaluation of antibacterial activity according to AATCC-100 (Test strain: Klebsi
ellapneumoniae) and water absorption according to JIS L-1018A method. Table 1 shows the results.

Example 2 A cotton knit fabric was treated in the same manner as in Example 1 except that the compound <2> was used in place of the compound <1>, and the antibacterial property and the water absorption were evaluated. Table 1 shows the results.

Example 3 A cotton knitted fabric was treated in the same manner as in Example 1 except that the compound <3> was used in place of the compound <1>, and the antibacterial property and the water absorption were evaluated. Table 1 shows the results.

Example 4 A cotton knit fabric was treated in the same manner as in Example 1 except that the compound <4> was used in place of the compound <1>, and the antibacterial properties and the water absorption were evaluated. Table 1 shows the results.

Example 5 A cotton knit fabric was treated in the same manner as in Example 1 except that the compound <5> was used in place of the compound <1>, and the antibacterial properties and the water absorption were evaluated. Table 1 shows the results.

Example 6 A cotton knitted fabric was treated in the same manner as in Example 1 except that the compound <6> was used in place of the compound <1>, and the antibacterial property and the water absorption were evaluated. Table 1 shows the results.

[0011]

Comparative Example 1 A cotton knitted fabric was treated in the same manner as in Example 1 except that the compound <7> was used in place of the compound <1>, and the antibacterial property and the water absorption were evaluated. Table 1 shows the results.

Comparative Example 2 A cotton knit fabric was treated in the same manner as in Example 1 except that trimethoxysilylpropyldimethyloctadecyl ammonium chloride (a quaternary ammonium salt type silane compound) was used in place of the compound <1>. The properties and the water absorption were evaluated. Table 1 shows the results.

Comparative Example 3 The same evaluation as in Example 1 was performed using a cotton knitted fabric not treated with an antibacterial compound. Table 1 shows the results.

[0012]

Table 1 Fiber antibacterial properties (sterilization rate%) water absorption (seconds) Example 1 92.5 1> Example 2 94.5 1> Example 3 98.8 1> Example 4 99.9 1> Example 5 99.9 1> Example 6 99.9 2 Comparative Example 1 80.1 1 Comparative Example 2 90.2 600 Comparative Example 3 0 1>

[0013]

Example 7 The fiber obtained in Example 4 was used in accordance with JIS 0217.
-After washing 10 times by the method according to the 103 method, AATCC-
An antibacterial test according to 100 and an antifungal test by the halo method were performed. Table 2 shows the results.

Example 8 After treating an acrylic fiber with the compound <4> in the same manner as in Example 1, washing was carried out in the same manner as in Example 7, and an antibacterial and antifungal test was carried out. Table 2 shows the results.

[0014]

Comparative Example 4 The fiber obtained in Comparative Example 2 was washed in the same manner as in Example 7 and then subjected to an antibacterial and antifungal test. Table 2 shows the results.

[Comparative Example 5] After washing a cotton knitted fabric in the same manner as in Example 7,
An antibacterial and antifungal test was performed. Table 2 shows the results.

[0015]

[Table 2] 1) The bacterial species used in the antifungal test and their evaluation are as follows: Species: Test A: Aspergillus niger Test B: Penicillium frequentans Test C: Rhizopus Evaluation: 1: Appeared in the inoculated part of the sample or test piece The area of the growing portion of the mycelium exceeds 1/3 of the total area. 2: The area of the hyphal growth part observed in the inoculated part of the sample or test piece does not exceed 1/3 of the total area. 3: No hyphal growth was observed in the inoculated portion of the sample or test piece. 2) Antibacterial activity was tested using Klebsiella pneumoneae.

As shown in the above results, the fiber having antibacterial and antifungal properties of the present invention has an antibacterial property higher than that of the fiber treated with the conventional quaternary ammonium salt type silane compound. Almost no loss of original water absorption.

[0017]

The guanidyl-containing silane-based antibacterial agent used in the present invention has the same binding property to the fiber as the silane coupling agent. The organic functional group containing the group is chemically immobilized on the fiber surface, and the antimicrobial active partial structure is not released or scattered from the fiber. Further, as a result of using a cyanoguanidyl group and a biguanide group as the guanidyl group, it is possible to impart excellent antibacterial properties to the fiber.
For this reason, the fiber of the present invention using the same has high antibacterial and antifungal properties with excellent durability and durability, is highly safe for the human body and the environment, and can be widely used in various applications. .

Claims (1)

(57) [Claims] (1) X ¹ X ² X ³ Si—Y—NHC (= NH) NH—Z ¹ (wherein at least one of X ^{1 to} X ³ is hydrolysable) a group, Y is an alkylene group of C1-C30, Z ¹ is
-CN or -C (= NH) NH-Z 2 (Z 2 is hydrogen, C1 to
A fiber having antibacterial and antifungal properties, which is treated with a compound represented by the formula (C20 alkyl group or phenyl group) or a salt thereof: