JPH0949170A - Antimicrobial textile product and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial textile product free from discoloration, resistant to washing, provided with balance between antimicrobial effect, humectancy and pH level, and not affecting human body and organisms. SOLUTION: This textile product comprising hydrophilic or hydrophobic fibers (if needed, oxidized layer is formed on fiber surface beforehand) contains a mixture or compound essentially containing chirosan and water-soluble salt(s) of at least one kind of metal selected from among calcium, zinc, magnesium and aluminum in such amounts, based on the fibers, as to be 0.01-7wt.% in chitosan content and 0.02-3wt.% in water-soluble metal salt content in terms of the metal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a durable, antibacterial, moisturizing and pH balance that does not damage the human body or organisms, has no coloring in textiles containing hydrophilic fibers or hydrophobic fibers. It imparts multiple functions such as sex.

[0002]

2. Description of the Related Art It is desirable to impart durable antibacterial properties to textiles in hospitals, nursing home curtains, sheets, furnishings such as sleepwear, household bedding, baby products, clothing, etc. However, imparting this antibacterial property is not easy. In particular, it is difficult to impart antibacterial properties to textile products containing hydrophobic fibers, and it has been possible to obtain satisfactory results even though bactericides and antibacterial agents have been used as fiber treatment agents for a long time. Not not.

Particularly recently, with the advent of resistant bacteria such as MRSA, antibiotics are no longer universal antibacterial,
It is also necessary to consider such resistant bacteria.

Further, it is necessary to consider the environment, such as the case where a carcinogen, dioxin, is produced when the processed fiber is incinerated like a diphenyl ether type antibacterial agent.

Inorganic compounds such as zeolite silver, copper or zinc ion exchangers have been attempted as antibacterial agents showing strong antibacterial properties against resistant bacteria and not producing carcinogens. The shortcoming is that it is poor.

Japanese Patent Publication No. 57-41950 discloses that a chitosan copper complex or a chitosan silver complex is supported as an active ingredient on a natural fiber in particular to produce a reusable bactericidal fiber sheet.

[0007] By carrying the chitosan copper complex or the chitosan silver complex on the above-mentioned fiber sheet, particularly a sheet made of natural fiber or leather, durable bactericidal property and antibacterial property can be imparted, but there are many problems. .

[0008] One of the problems is that the durability is still insufficient when applied to hydrophilic fiber products such as cotton and wool and hydrophobic fiber products such as synthetic fibers. Another problem is that it is difficult to obtain a fiber product having a desired color because the copper or silver complex is colored.

Further, in Japanese Patent Laid-Open No. 4-193275, chitosan is immobilized on an inorganic or organic powdery substance, and then atomic numbers 12 to 13, 20 to 30, 38 to 51, 57.
The technique for obtaining a powdery deodorant material by immobilizing one or more kinds of metal elements selected from the group consisting of metal elements of ~ 83 and 88-89 is described. However, in the above-mentioned prior art, although the treatment means is similar to that of the present invention, there is no suggestion of imparting bactericidal property.

[0010]

DISCLOSURE OF THE INVENTION The present invention has improved the above-mentioned drawbacks of conventional antibacterial textiles, has excellent washing resistance, is free from coloration, and has no antibacterial properties against human bodies, organisms, etc. The purpose of the present invention is to obtain a textile product, and also to impart durable moisture retention, water absorption, pH balance and the like.

[0011]

SUMMARY OF THE INVENTION The present invention is a fiber product containing hydrophilic or hydrophobic fibers, which is an aqueous solution of at least one metal selected from the group consisting of calcium, zinc, magnesium and aluminum. A mixture or complex containing essential salt and chitosan as essential components is contained in the fiber product at a chitosan content of 0.01 to 7% by weight and a metal salt content of 0.02 to 3% by weight. It is characterized by being Here, the complex means a salt, a complex salt formed or physically bound.

The textile product of the present invention is the above-mentioned Japanese Patent Publication Sho-57.
-41950 gazette, compared with the treatment with the chitosan complex of copper or silver, regardless of hydrophilic fiber or hydrophobic fiber, it is not colored and has excellent wash resistance, and particularly it has been wash resistant up to now. There is an excellent advantage that excellent washing resistance can be imparted to a fiber product containing hydrophobic fibers such as synthetic fibers, which have been difficult to impart antibacterial properties, and that coloring is not caused.

The present invention and the above-mentioned JP-A-4-193275
As can be seen from a comparison with No. 1, although there are chances that there is a common metal, the effects do not match, and the amounts of chitosan and metal salt contained in the object to be treated also differ.

For example, iron has an excellent ability to absorb malodorous gas, but has poor bactericidal property. Further, in the present invention, the content of chitosan contained in the textile product is 0.01 to 7% by weight, and the content of metal compound in terms of metal is 0.02 to 3% by weight. According to the examples, the chitosan content is 9.1 to 15.1% by weight, and the metal conversion content of the metal compound is 3.6 to 5.3% by weight. You can see that it is in a low place. Moreover, although it is known that chitosan organic acid salt shows antibacterial property, sufficient antibacterial property cannot be obtained by this alone. Particularly under alkaline conditions, there is a disadvantage that the acid is eliminated and the quaternized salt of the amino group serving as an antibacterial group disappears, and the antibacterial property is lost. However, when chitosan forms a complex with a metal to form a film on the surface layer of the object to be treated as in the present invention,
Antibacterial properties do not disappear even under alkaline conditions.

The hydrophobic fibers used in the present invention include semi-synthetic fibers such as cellulose acetate, polyamide,
Synthetic fibers such as polyacrylonitrile, etc. are mentioned, and the fiber products including hydrophobic fibers alone or composites with hydrophilic fibers such as cotton, wool, rayon, yarns, woven fabrics, knitted fabrics, non-woven fabrics, papers and the like include hydrophobic fibers. As.

Examples of hydrophilic fibers include natural fibers such as cotton, wool and hemp, regenerated fibers such as rayon and cupra, and synthetic fibers such as PVA fibers. Hydrophilic fibers alone or polyester, polyamide Fibers, yarns made of composites with hydrophobic fibers such as polyacrylonitrile,
Woven fabrics, knitted fabrics, non-woven fabrics, papers and the like are mentioned as fiber products containing hydrophilic fibers.

The fibers constituting the textile product to which the present invention is applied are extremely effective when the surface thereof is an oxidized layer. That is, the antibacterial washing resistance is dramatically improved by forming the oxide layer.

As a means for forming an oxide layer, sulfuric acid,
Chemically oxidize the fiber surface with chemicals such as caustic soda, or physical treatment such as plasma treatment, corona discharge treatment, ultraviolet irradiation treatment, high-energy ray irradiation treatment of X-rays, electron rays, γ rays, etc. There is a way.

The oxide layer is structurally different depending on the forming means, but an oxide layer formed by physical treatment is particularly effective, and an oxide layer formed by plasma treatment, corona discharge treatment or ultraviolet irradiation is particularly effective. Therefore, the antibacterial washing resistance is dramatically improved.

Ultraviolet irradiation treatment or corona discharge treatment,
Providing an oxide layer by plasma treatment is a means often taken in order to improve the adhesiveness of the fiber surface, printability, etc., and is an oily, that is, an adhesive using a medium mainly composed of a hydrophobic solvent, It is known that durable processing results can be obtained by applying ink or the like to a hydrophobic object, but it is durable when treated with a treatment agent using a hydrophilic solvent such as an aqueous solvent. No processing result is obtained.

In particular, when an oxidation layer is provided on the surface of a fiber product containing hydrophilic fibers or hydrophobic fibers, the processing effect of the treatment agent using an aqueous solvent is lower than that in the case where no oxidation layer is provided. For example, hydrophilic adhesives such as starch paste warp and decrease the adhesiveness, and hydrophilic dyes such as acid dyes warp and decrease the dyeability.

The same applies to the case where the polymer compound is applied to the surface of the fiber. For example, even if the aqueous solution of sodium polyacrylate is applied to the surface of the hydrophobic fiber product provided with the above-mentioned oxidation layer, it has washing resistance. No processing effect can be obtained.

However, only when an aqueous solution of chitosan salt is used, a stronger chitosan coating can be formed by providing an oxidation layer on the surface of the fiber regardless of hydrophilic fiber or hydrophobic fiber.

Corona discharge treatment is usually 10 to 25 kHz
Corrosion discharge is performed at a distance between electrodes of several millimeters at an oscillation frequency of, and an object to be processed is passed between them.

The UV treatment is preferably 150 to 300.
It is achieved by irradiating the textile with a relatively short wavelength of UV light of mm. The irradiation time depends on the type and intensity of the light source, but is about 10 to 60 seconds.

The water-soluble salt of calcium, zinc, magnesium or aluminum used in the present invention is preferably neutral or close to neutral, less oxidizing or reducing, and less colored. The reason is that it is important to prevent coloration, discoloration or deterioration of the textile product. Further, a metal salt that is easy to combine with chitosan to form a complex salt is preferable. This allows the metal salt to be firmly adhered to the textile product.

Salts satisfying these conditions are preferably salts of organic acids. Examples of organic acids include acetic acid, oxalic acid, lactic acid, tartaric acid, malic acid and the like. When it is unavoidable to use an inorganic acid salt, it is preferable to use a salt of a volatile acid, that is, a chloride. Particularly preferred water-soluble salts include acetate, oxalate and lactate.

The amount of the above-mentioned metal water-soluble salt attached to the fiber product is 0.02 to 3% by weight, preferably 0.1 to 2% by weight, in terms of metal content. If the amount of the metal salt is too large, not only there are many obstacles such as coloring, discoloration, deterioration, etc., but also many metal salts are dropped off, and the harmful effects of the dropped metal salts occur.

Chitosan used in the present invention has a free amino group obtained by deacetylating chitin obtained from crustaceans such as crabs and "mushrooms" with a high concentration of alkali. The degree of conversion is preferably 30% or more.

The above-mentioned chitosan is usually used as an organic acid salt, and as the organic acid, acetic acid, oxalic acid, lactic acid,
Examples include formic acid and malic acid. Particularly preferred acids are acetic acid, oxalic acid and lactic acid.

The amount of chitosan attached to the textile product is 0.0
It is 1 to 7% by weight, preferably 0.1 to 5% by weight.
If the amount of adhesion is too large, the fibers will turn yellow and the hand will be hardened. Therefore, the content of the mixture or composite of the metal salt and chitosan in the fiber is 0.03 to 8
It is preferably in the weight%.

At least a part of the above-mentioned metal salt and chitosan forms a complex to form a film having excellent washing resistance on the fiber to be treated. Especially, the chitosan salt has a strong affinity for the fiber. An antibacterial fiber having excellent wash resistance can be obtained.

As a means for applying the metal salt and chitosan salt to the fiber product, an aqueous solution or water dispersion of the both agents may be applied by a padding method, a dipping method or the like according to a conventional method. However, in this case, the chitosan salt concentration is preferably 20% or less and the pH is preferably in the range of 3 to 6. This is a condition under which the metal salt and chitosan salt form a complex and durability is exhibited.

Further, it is most preferable in terms of durability that the composite is formed on a fiber product, for which purpose the above metal salt and chitosan salt are separately applied to the fiber product (sequence). However, it is preferable to form a complex on the product.

Incidentally, dyes, fluorescent bleaching agents, antistatic agents, softening agents, texture adjusting agents and the like may be added appropriately along with this treatment.

Next, the present invention will be described in more detail with reference to Examples. In the examples, tests for antibacterial properties, water absorption properties, moisturizing properties, etc. were conducted by the following methods.

Antibacterial property: After a suspension of test bacteria (Staphylococcus aureus) of 1 to 2 × 10 ⁴ / ml was prepared by the shake flask method, the number of viable bacteria was measured. Next, after adding 0.75 g of the test piece and shaking at 320 rpm at 25 ° C. for 1 hour,
The viable cell count was measured again, and the sterilization rate was calculated by the following formula.

Moisture retention: Moisture content (1) after leaving the test piece in an atmosphere of 20 ° C. and 65% RH for 48 hours and 20 ° C.
It was shown by the water content (2) after standing for 60 minutes in an atmosphere of 95% RH.

Sterilization rate, moisture retention and washing resistance: JIS
The sterilization rate and the moisturizing property after the washing was repeated 30 times by the method of L 0217-103 were shown.

Washing resistance of chitosan salt: 1:20 of a 1% by weight aqueous solution of an acid dye (Kayanol Phloxine NK Hodogaya Chemical Co., Ltd.) which reacts with the amino group of chitosan salt on the acidic side.
It is dyed at 100 ° C. for 10 minutes in a dyeing bath having a bath ratio of, and judged by the color density. That is, the color density before washing is set to 5, and color comparison is performed by a gray scale 5-step method. The higher the density, the better the wash resistance.

Example 1 The following three kinds of test cloths were scoured and bleached with hydrogen peroxide according to a conventional method. Part of it is left as it is (hereinafter referred to as test cloth (B)), and ultraviolet light emitted from the low-voltage mercury lamp to other bleaching cloth (apparatus: Sen Special Light Source Co., Ltd., Photo Surface Processor, 185 mm to 315 mm wavelength) About 6
Irradiation treatment was performed for 0 seconds (hereinafter referred to as test cloth (A)).

The above-mentioned 3 kinds of test cloths (A) and 3 kinds of test cloths (B) were padded (squeeze ratio 100%) with a treatment liquid of the following formulation, dried at 100 ° C. for 2 minutes, and then 120 ° C.
And heat treated for 2 minutes.

Test cloth (1) 30-count cotton thread using a plain cloth knitted fabric (test cloth (1)) (2) polyester, cotton blended spinning (blending ratio 60:40) 3
Tenjiku-maru knitted fabric using No. 0 yarn (test cloth (2)) (3) 100% polyester Tenjiku-maru knitted fabric using No. 30 yarn (test cloth (3))

Prescription Chitosan Lactate ^* 0.5% by weight Zinc lactate 0.3% by weight * 1: 1 solution of chitosan lactic acid (48% aqueous solution) with a deacetylation degree of 80%

As Comparative Example 1, test cloth B (2) was used, and as Comparative Example 2, only 0.5% by weight of chitosan lactate was prepared, and as Comparative Example 2, 0.3% by weight of zinc lactate was prepared. The same process was performed.

With respect to the obtained treated cloth, antibacterial property, washing resistance, moisturizing property and pH balance property were measured. The result is
It is as shown in Table 1 and Table 2. Further, each test cloth was not colored.

[Table 1]

[0047]

[Table 2]

Further, the test cloth was dipped in each of the solutions having pHs of 4, 5, 8 and 11 and taken out from the bath.
When H was measured, it was found that the pH balance was good when the pH was around 7.

Example 2 The following three kinds of test cloths were scoured and bleached with hydrogen peroxide according to a conventional method. Next, a part of the cloth was left as it is (hereinafter referred to as test cloth (B)), and the other bleached cloth was subjected to high-frequency corona discharge treatment (generator: generation frequency 20 kHz, AC 100 V). The above 3 kinds of test cloths (A) and 3 kinds of test cloths (B)
Was subjected to a padding treatment (squeezing ratio: 100%) with a treatment liquid having the following formulation, dried at 100 ° C. for 2 minutes, and heat-treated at 120 ° C. for 2 minutes.

Test cloth (1) 30th count cotton thread using a plain cloth knitted fabric (test cloth (4)) (2) Polyester filament, cotton fiber composite thread using a plain cloth circular knit cloth (test cloth (5)) (3) Tenjiku circular knitted fabric with 100% polyester and 30th spun yarn (test cloth (6))

Prescription 1st pad bath Calcium lactate 1.0% by weight 2nd pad bath Chitosan lactate ^* 0.5% by weight * 1: 1 lactic acid (48% aqueous solution) solution of chitosan with 50% deacetylation degree

Further, the test cloth (5) was subjected to a one-bath padding treatment in a bath containing 1.0% by weight of calcium lactate and 0.5% by weight of chitosan lactate.

Tables 3 and 4 show the results obtained by measuring the antibacterial property, the washing resistance and the moisturizing property of the obtained treated cloth. In addition, each test cloth was not colored.

[0054]

[Table 3]

[0055]

[Table 4]

As is clear from the results of Tables 3 and 4, excellent durability was observed in all of antibacterial properties, moisturizing properties and ultraviolet blocking properties. In particular, it is understood that the test cloth A having the oxide layer formed by the corona discharge treatment has extremely excellent washing durability in each measurement item. Further, each test cloth was not colored.

Example 3 Using 3 kinds of test cloth A and 3 kinds of test cloth B used in Example 1, each was padded with a processing solution having the following formulation (squeezing ratio 100%) and dried at 100 ° C. for 2 minutes. Then 120
It heat-processed at 2 degreeC for 2 minutes. Prescription Chitosan acetate ^* 0.5% by weight Aluminum acetate 1.0% by weight * Acetate of chitosan with 48% deacetylation (48%)
1: 1 solution

Similar to Example 1, the test cloth (2) was used as Comparative Example 3 and the formulation of only chitosan acetate of 0.5% by weight and the formulation of Comparative Example 4 of 1.0% by weight of aluminum acetate were used. Was processed.

Antibacterial properties and washing resistance of the obtained treated cloth were measured. The results are shown in Table 5 below.
It can be seen that it exhibits excellent wash resistance. In particular, the test cloth which has been subjected to the ultraviolet irradiation treatment shows particularly excellent wash resistance.

[0060]

[Table 5]

Example 4 Using 3 kinds of test cloth A and 3 kinds of test cloth B used in Example 1, each was padded with a treatment liquid having the following formulation (squeeze ratio 100%) and dried at 100 ° C. for 2 minutes. Then 120
It heat-processed at 2 degreeC for 2 minutes. Prescription Chitosan acetate ^* 0.5% by weight Magnesium acetate 0.3% by weight * Acetate of chitosan (48%) with 50% deacetylation degree
1: 1 solution

As Comparative Example 5, the test cloth (8) was used, and the same procedure as in Example 1 was carried out except that only 0.5% by weight of chitosan acetate was used and Comparative Example 6 was 1.0% by weight of magnesium acetate. Was processed.

The antibacterial property and the washing resistance of the obtained treated cloth were measured. The results are shown in Table 6, and it can be seen that particularly those subjected to the ultraviolet irradiation treatment, as in the previous example, exhibit excellent wash resistance. Further, each test cloth was not colored.

[0064]

[Table 6]

[0065]

As shown in the examples, the textile products of the present invention are not colored and exhibit excellent anti-bacterial properties with excellent washing resistance. Particularly, the textile products provided with an oxidation layer have more excellent washing resistance. Antibacterial properties are obtained.

Claims (9)

[Claims] 1. A fiber product containing hydrophilic or hydrophobic fibers, wherein a chitosan and a water-soluble salt of at least one metal selected from the group consisting of calcium, zinc, magnesium, and aluminum are essential components. And a mixture or complex containing 0.01 to 7% by weight as a chitosan content and 0.02 to 3% by weight as a metal-equivalent content of a water-soluble metal salt in the fiber product. An antibacterial textile product characterized by 2. The antibacterial fiber product according to claim 1, wherein the surface of the fiber forming the fiber product containing the hydrophilic fiber or the hydrophobic fiber is an oxidized layer. 3. The antibacterial fiber product according to claim 1, wherein the fiber product contains a hydrophobic fiber. 4. The antibacterial fiber product according to claim 1, wherein the oxide layer is formed by physical treatment. 5. The oxide layer is formed by corona discharge treatment, plasma treatment or ultraviolet irradiation.
The described antibacterial textile product. 6. A water-soluble salt of at least one metal selected from the group consisting of calcium, zinc, magnesium and aluminum and chitosan are added to a fiber product containing hydrophilic fibers or hydrophobic fibers in an aqueous medium, The content of chitosan in the fiber product is 0.01% to 7% by weight, and the content of the water-soluble metal salt in terms of metal is 0.02% to 3% by weight.
A method for producing an antibacterial fiber product, which comprises adding to the above-mentioned fiber product so as to contain it in a weight percentage and forming a complex of the water-soluble metal salt and chitosan on the fiber. 7. The antibacterial property according to claim 6, wherein the fiber product is subjected to an oxidation treatment before the water-soluble metal salt and chitosan are applied to the fiber product containing hydrophilic fibers or hydrophobic fibers. Textile manufacturing method. 8. The method for producing an antibacterial fiber product according to claim 6, wherein the oxidation treatment is a physical treatment. 9. The method for producing an antibacterial fiber product according to claim 6, wherein the oxidation treatment is corona discharge treatment, plasma treatment or ultraviolet irradiation treatment.