JPH08113874A - Antibacterial textile product and its production - Google Patents

Abstract

PURPOSE: To impart a textile product with durable antibacterial property, moisture-retaining property, ultraviolet-shielding property, etc., without damaging the human body or organisms. CONSTITUTION: A textile product made of natural, regenerated or synthetic fibers is coated with a mixture or a composite material containing a water-soluble salt or oxide of a group Ib element (copper or silver), a group IIa element (magnesium or calcium), a group IIb element (zinc), a group IIIb element (aluminum) and/or a group IVb element (tin) of the periodic table, chitosan and a water-soluble (meth)acrylic acid-type polymer or its water-soluble salt as essential components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention imparts durable multi-functions such as antibacterial properties, moisture retention properties, and UV blocking properties to textile products without damaging the human body or living organisms.

[0002]

2. Description of the Related Art Textile products, especially those based on synthetic fibers such as polyester fibers, are safe for the human body,
Moreover, it is not easy to impart durable antibacterial properties, and even though antibacterial agents and antibacterial agents have been used as fiber treatment agents for a long time, no one has achieved satisfactory results. .

Particularly, with the recent emergence of resistant bacteria such as MRSA, antibiotics are not said to be all-antibacterial, and it is 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.

On the other hand, inorganic compounds such as zeolite silver, copper or zinc ion exchangers have been tried as antibacterial agents showing strong antibacterial properties against resistant bacteria and not producing carcinogens. However, it has the drawback of poor wash resistance.

Periodic Table Group Ib, Group IIa, Group IIb
A water-soluble salt of a Group IIIb metal or Group IVb metal,
Known as a germicide. For example, water-soluble salts of silver, copper, zinc and the like have long been known as bactericides with little damage to humans and animals, but when they are applied to textile products, they have a poor washing resistance.

On the other hand, chitosan organic acid salt is known as a treating agent for textile products and is also known to have some antibacterial properties, but it is not possible to obtain sufficient antibacterial properties by itself.

Further, in Japanese Patent Laid-Open No. 4-193275, chitosan is immobilized on an inorganic or organic powdery substance, and thereafter, 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.

In the above-mentioned prior art, the treatment means is similar to that of the present invention, but there is no suggestion of imparting durable bactericidal property.

On the other hand, recently, it has been demanded by consumers for clothes that come into contact with the skin, such as underwear, sleepwear, and bed sheets, to be hygienic and comfortable to wear, that is, to impart appropriate hygroscopicity and water absorption. However, the treatment with only chitosan and a metal element is not sufficient in terms of hygroscopicity and water absorption.

The present inventors have reached the present invention as a result of continuing their research to obtain a textile product which is bactericidal, hygienic, and has appropriate hygroscopicity and water absorption.

[0012]

That is, the present invention provides an antibacterial fiber product which is improved in the above-mentioned drawbacks of the conventional antibacterial fiber product and has excellent washing resistance and does not impair human bodies and living things. In addition to obtaining, it also obtains moisture retention and hygroscopicity for improving wearing comfort.

[0013]

DISCLOSURE OF THE INVENTION The present invention is a fiber product comprising natural, regenerated or synthetic fibers, wherein the periodic table includes groups Ib, IIa, IIb, IIIb and / or
Alternatively, a water-soluble salt of a Group IVb metal or an oxide, chitosan and a water-soluble acrylic acid-based polymer of the above-mentioned metal or a mixture or complex containing the water-soluble salt thereof as an essential component is contained in the fiber product in terms of metal content. As 0.0
2-3% by weight, a chitosan content of 0.01 to 7% by weight, a metal-equivalent content of a water-soluble metal salt or metal oxide of 0.02 to 3% by weight, a water-soluble salt of a water-soluble acrylic acid-based polymer The content is 0.01 to 5% by weight.

The term "composite" as used herein means that the constituent substances form a salt, a complex salt, or are physically bound.

Examples of the natural, regenerated or synthetic fibers used in the present invention include natural fibers such as cotton, hemp and wool, regenerated fibers such as rayon, synthetic fibers such as polyester, polyamide and polyacrylonitrile. The composite is used in the form of fibers, threads, woven fabrics, knitted fabrics, non-woven fabrics, papers, and the like.

Periodic Table Group Ib, Group I used in the present invention
Water soluble salts of Group Ia, Group IIb, Group IIIb or Group IVb metals include Group Ib copper, silver, Group IIa magnesium, calcium, Group IIb zinc, Group Ib.
Water-soluble salts of group IIb aluminum and group IVb tin are preferred.

It is preferable that these salts are neutral or close to neutral, have little oxidizing or reducing property, and have little coloring. The reason is that it is important for preventing coloring, 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.

As the acid which constitutes the salts satisfying these conditions, salts of organic acids are preferable. 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 water-soluble salts selected from metals such as copper, silver, zinc, calcium and acids such as acetic acid, oxalic acid and lactic acid.

The particulate metal oxide used in the present invention is
The average particle size is 5 μm or less, preferably 1.0 μm or less, and the smaller the particle size, the more stable the suspended state in water, and the more uniform and durable fiber processing can be performed.

As mentioned above, examples of metal oxides are as follows.
Oxides of Group Ib copper, silver, Group IIa magnesium, calcium, Group IIb zinc, Group IIIb aluminum, and Group IVb tin are preferred. Particularly preferable oxides include oxides of copper, silver and zinc. The amount of the water-soluble salt or oxide of the metal 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 or oxide is too large, not only there are many obstacles such as coloring, discoloration, and deterioration, but also many metal salts or oxides are lost.
The harmful effects of lost items also occur.

The 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 textiles 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 metal salt or oxide, chitosan and acrylic acid type polymer forms a complex to form a film having excellent wash resistance on the treated fiber,
Particularly, since chitosan salt has a strong affinity for fibers, antibacterial fibers having excellent washing resistance can be obtained.

The acrylic acid-based polymer used in the present invention is acrylic acid or methacrylic acid alone or mainly, and a small amount of (meth) acrylic acid ester, acrylonitrile, vinyl-based compounds such as vinyl acetate, ethylene, A water-soluble polymer obtained by copolymerizing an olefin compound such as propylene or the like, or a soda salt thereof,
It is a water-soluble salt such as an ammonium salt, and its amount is preferably 0.01 to 5% by weight based on the fiber.

The acrylic acid-based polymer or its water-soluble salt is a polymer-bonded product in which a part of the carboxylic acid group or carboxylate group of the acrylic acid-based polymer is bonded to chitosan in the surface layer of the fiber. It is considered that the carboxylic acid group or carboxylic acid salt group in the free state forms a composite and is firmly adhered to the fiber product, and imparts moisturizing ability and water absorbing ability.

As a means for applying the metal salt or metal oxide, chitosan salt, and polyacrylic acid-based polymer to the fiber product, an aqueous solution or aqueous dispersion of each of the above-mentioned chemicals is padded or dipped according to a conventional method. It may be applied using a means such as. However, at this time, the chitosan salt concentration is 2
It is preferably 0% 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 preferable that these composites are formed firmly and tightly on the fiber product from the viewpoint of durability.
For that purpose, it is preferable that the water-soluble salt or oxide of the metal, the chitosan organic acid salt, and the acrylic acid-based polymer are separately applied to the fiber product (in any order).

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, antibacterial properties, water absorption, moisturizing properties,
The test of the ultraviolet blocking property was carried out by the following method.

Antibacterial property: A suspension of test bacteria (Staphylococcus aureus) 1 to 2 × 10 ⁴ / ml was prepared by the shake flask method, and then the viable cell count 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.

UV blocking property: spectrophotometer 150-20
(Manufactured by Hitachi Ltd.) was used to measure the ultraviolet transmittance (%) at 310 μm and 365 μm.

Sterilization rate, moisture retention, and UV resistance: Washing resistance: After the washing was repeated 30 times according to the method of JIS L 0217-103, the sterilization rate, the moisture retention and the UV protection were shown.

Washing resistance of chitosan salt: 1:20 of a 1% by weight aqueous solution of an acidic 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 respectively scoured and hydrogen peroxide bleached according to a conventional method and then padded (squeezing ratio 100%) with the solution of the first bath described below, and 100 ° C. After drying for 2 minutes at 120 ° C. and heat treatment at 120 ° C. for 2 minutes, the treatment liquid in the second bath is padded (squeeze ratio 100%) and further 100
It was dried at 0 ° C for 2 minutes and heat-treated at 120 ° C for 2 minutes.

Test cloth (1) 30-count cotton thread using 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 1st bath Chitosan lactate * 0.5% by volume Water remaining amount * 1: 1 solution of lactic acid (48%) of 80% deacetylation chitosan 2nd bath Zinc acetate 0.5% by volume Polyacryl Acid soda (polymerization degree about 1000) 0.3% by volume Water remaining

As Comparative Example 1, a test cloth (2) was used,
The same treatment as in Example 1 was performed using only the first bath formulation containing 0.5 vol% chitosan lactate, the formulation containing only 0.5 vol% zinc acetate as Comparative Example 2 and the following formulation as Comparative Example 3. Chitosan lactate 0.5% by volume Zinc acetate 0.5% by volume Water remaining

The obtained treated cloth was measured for antibacterial property, washing resistance, moisturizing property, and ultraviolet blocking property. The results are shown in Tables 1 and 2.

[Table 1]

[Table 2]

The test cloths (1), (2) and (3) are p
The test cloth was immersed in each of the solutions of H, 4,5, 8 and 11 and taken out from the bath, and after 30 minutes, the pH of the test cloth was measured, and it was found that the pH balance was good at around 7.

Example 2 The following three kinds of test cloths were respectively scoured and hydrogen peroxide bleached according to a conventional method and then padded (squeezing ratio 100%) with the solution of the following first bath formulation, and 100 ° C. And dried at 120 ° C. for 2 minutes. Next, padding is performed again with the solution of the following second bath formulation (drawing ratio 100%).
Then, it was dried at 100 ° C. for 2 minutes and heat-treated at 120 ° C. for 2 minutes. Test cloth (1) 30th cotton thread using a knitted fabric with 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))

First bath formulation Chitosan acetate * 0.5% by volume Zinc oxide * 0.3% by volume * Chitosan acetic acid (48%) 1: 1 solution with 80% deacetylation degree * * Average particle size 0 1 to 0.9 μ, 30% slurry Second bath formulation Sodium polyacrylate (polymerization degree: about 1000) 1.3% by volume Polyacrylic ester emulsion (30% by weight) 1.5% by volume

As Comparative Example 4, the test cloth (2) was used, and a formulation containing only 0.5% by volume of chitosan acetate, Comparative Example 5
Was treated in the same manner as in Example 1 with a formulation of 0.3% by volume of zinc oxide and a formulation of only the first bath as Comparative Example 6.

The obtained treated cloth was measured for antibacterial property, washing resistance, moisturizing property and ultraviolet blocking property. The results are shown in Tables 3 and 4.

[Table 3]

[0047]

[Table 4]

The test cloths (1), (2) and (3) are p
The test cloth was immersed in each of the solutions of H, 4,5, 8 and 11 and taken out from the bath, and after 30 minutes, the pH of the test cloth was measured, and it was found that the pH balance was good at around 7.

Example 3 Using the test cloth (2) used in Example 1, padding (squeeze ratio 100%) was performed with the treatment liquid having the following first bath formulation, and 10
It was dried at 0 ° C. for 2 minutes and heat-treated at 120 ° C. for 2 minutes. Next, padding (drawing ratio 10
0%), dried at 100 ° C. for 2 minutes, and heat-treated at 120 ° C. for 2 minutes. Further, as Comparative Example 7, after treatment with the liquid of the first bath formulation, drying and heat treatment under the same conditions were performed with the liquid of the second bath containing only calcium acetate (not containing the acrylic acid / ethyl acrylate copolymer). The results of the same treatment, drying and heat treatment are also shown. 1st bath prescription Chitosan acetate * 0.5% by volume (solution) Water remaining amount * 1: 1 aqueous solution of chitosan with deacetylation degree of 50% (48%) 2nd bath prescription Calcium acetate 1.0% by volume ( Solution) Acrylic acid / ethyl acrylate (molar ratio 9: 1) Copolymer soda salt 0.3% by volume (solution) Water remaining amount

Table 5 and Table 6 show the results of measuring antibacterial properties, washing resistance and moisturizing properties of the obtained treated cloth.

[0051]

[Table 5]

[Table 6]

[0052]

As shown in the examples, the product of the present invention exhibits excellent anti-washing properties and antibacterial properties, and also has significantly excellent moisturizing properties, resulting in significantly improved comfort.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location D06M 11/44 // D06M 101: 00

Claims (4)

[Claims] 1. A fiber product comprising natural, regenerated or synthetic fibers, which is represented by Group Ib, Group IIa, Group IIb or Group II of the periodic table.
Water-soluble salts of Group Ib and / or Group IVb metals or particulate oxides of the above metals Chitosan Water-soluble acrylic acid-based polymers or water-soluble salts thereof, and mixtures or composites containing these as essential components are the fiber products. As a metal conversion content rate of 0.02
To 3% by weight, a chitosan content of 0.01 to 7% by weight, and a water-soluble acrylic acid polymer or its water-soluble salt content of 0.01 to 5% by weight. Product. 2. The antibacterial fiber product according to claim 1, wherein the chitosan is chitin having a deacetylation degree of 30% or more. 3. The antibacterial fiber product according to claim 1, wherein chitosan is an organic acid salt. 4. A fiber product comprising natural, regenerated or synthetic fibers, which is represented by Group Ib, Group IIa, Group IIb or Group II of the periodic table.
Water-soluble salts of Group Ib and / or Group IVb metals or particulate oxides of the above metals Chitosan Water-soluble acrylic acid-based polymers or water-soluble salts thereof, and mixtures or composites containing these as essential components are the fiber products. As a metal conversion content rate of 0.02
To 3% by weight, a chitosan content of 0.01 to 7% by weight, and a water-soluble acrylic acid polymer or its water-soluble salt content of 0.01 to 5% by weight. Product manufacturing method.