JP2020012214A - Fiber composition having anti-bacterial, anti-virus and pollen disintegration properties, and fiber product containing the same - Google Patents

Abstract

To provide a fiber composition having anti-bacterial, anti-virus and pollen disintegration properties and also excellent in fiber permeability and the continuance of the effects.SOLUTION: A fiber composition contains amino acid silver, amino acid zinc, a carboxyvinyl polymer, and at least one of ethylenediamine-N,N,N',N'-tetraacetic acid copper(II) disodium salt tetrahydrate, glutamic acid copper, and amino acid copper.SELECTED DRAWING: None

Description

  The present invention relates to a fiber composition having antibacterial properties, antiviral properties, and pollen disintegration properties, and a textile product containing the same.

  BACKGROUND ART Antibacterial and antiviral compositions containing fine particles of metals such as silver and zinc have been conventionally known (for example, Patent Documents 1 to 6 and the like). Further, for example, compositions and textiles having antibacterial and antiviral properties have been proposed (Patent Documents 7-9).

JP-A-2004-2227 JP 2008-520570A JP 2010-70571 A JP-T-2004-528389 JP 2014-208606 A JP-T-2013-503124 JP 2010-30984 A JP 2009-57647 A Patent No. 5887090

  However, for example, when the antibacterial / antiviral compositions of Patent Documents 1 to 6 are applied to fibers, the antibacterial / antiviral components easily fall off the fibers, and the antibacterial / antiviral properties are maintained for a long period of time. Difficult to do. When the antibacterial / antiviral composition contains a metal such as silver, discoloration may occur.

  Also, in the case of the textile products of Patent Documents 7 and 8, there is a problem that the antibacterial and antiviral components easily fall off from the fibers, and the antibacterial and antiviral effects gradually decrease. Further, in the case of the textile products of Patent Documents 7 and 8, dyeing with dyes and pigments, softening, and the use of a processing solvent may inhibit the antibacterial and antiviral effects. There is also a problem in that important materials are greatly restricted.

  On the other hand, the composition of Patent Document 9 is capable of exhibiting an antibacterial / antiviral effect, although the antibacterial / antiviral component is suppressed to a certain degree from falling off and discoloration of the antibacterial / antiviral component from the fiber. Further improvement is desired. In addition, the composition of Patent Document 9 is in a liquid state, and it is considered that there is a point to be improved in the permeability to fibers and the durability of antibacterial and antiviral effects.

  Further, Patent Documents 1 to 9 discuss the antibacterial and antiviral effects of the composition, but do not discuss the pollen disintegrating effect. If a pollen disintegrating effect can be imparted to a composition having an antibacterial / antiviral effect, the use can be expanded and a product with higher added value can be provided.

  The present invention has been made in view of the above circumstances, has an antibacterial property, antiviral properties and pollen disintegration properties, permeability to fibers, and a fiber composition excellent in the persistence of the effect. It is an object of the present invention to provide a coated or impregnated fiber product.

In order to solve the above problems, the composition for fibers of the present invention is an antibacterial, antiviral and pollen disintegrating fiber composition,
Amino acid silver,
Amino acid zinc,
A carboxyvinyl polymer, and one or more of ethylenediamine-N, N, N ', N'-tetraacetic acid copper (II) disodium salt tetrahydrate, copper glutamate, amino acid copper,
It is characterized by including.

  In the fiber composition, the amino acids of the amino acid silver and the amino acid zinc are preferably L-pyrrolidone carboxylic acid.

  This composition for fibers preferably contains copper pyrrolidonecarboxylate.

  The composition for fibers preferably further contains glutamic acid.

  It is preferable that the composition for fibers further contains copper sulfate.

  The fiber product of the present invention is characterized in that the fiber is coated or impregnated with any one of the fiber compositions.

  The composition for fibers of the present invention has excellent antibacterial properties, antiviral properties and pollen disintegration properties, and has excellent permeability to fibers and long-lasting effects.

It is a microscope picture which shows the result of the pollen disintegration test by nitric acid. It is a microscope picture which shows the result of the pollen disintegration test by sulfuric acid. It is a microscope picture which shows the result of the pollen disintegration test by copper nitrate. It is a microscope picture which shows the result of the pollen disintegration test by silver nitrate. It is a microscope picture which shows the result of the pollen disintegration test by ethylenediamine-N, N, N ', N'-tetraacetic acid copper (II) disodium salt tetrahydrate. It is a microscope picture which shows the result of the pollen disintegration test by zinc L-pyrrolidonecarboxylate.

The fiber composition of the present invention has antibacterial properties, antiviral properties and pollen disintegration properties. And the composition for fibers of the present invention, in water as a solvent,
(A) amino acid silver,
(B) zinc amino acid,
(C) a carboxyvinyl polymer, and (D) one or two of ethylenediamine-N, N, N ', N'-tetraacetic acid copper (II) disodium salt tetrahydrate, copper glutamate, and amino acid copper that's all,
including.

  In the composition for fibers of the present invention, at least a part of the amino acid silver and the amino acid zinc is present in an ionized state.

  Examples of the amino acid in the amino acid silver and the amino acid zinc include glycine, alanine, valine, leucine, phenylalanine, tyrosine, threonine, tryptophan, methionine, aspartic acid, lysine, arginine, histidinepidolic acid, L-glutamic acid, and L-glutamic acid. , L-glutamic acid, L-glutamic acid lactam, L-glutiminic acid, L-pyrrolidone carboxylic acid, L-pyroglutamic acid, and oxoproline. Among these, L-pyrrolidone carboxylic acid is excellent in antibacterial and antiviral effects. Therefore, by blending silver pyrrolidone carboxylate and zinc pyrrolidone carboxylate with the composition for fibers of the present invention, antibacterial and antiviral The effect can be reliably increased.

  The amounts of the amino acid silver and the amino acid zinc can be appropriately designed. For example, it is preferable that the total amount of silver ion and zinc ion per 1000 ml of water is 2 mg / L or more. And the total of zinc ions is more preferably in the range of about 2 mg / L to 50 mg / L. When the amounts of the amino acid silver and the amino acid zinc are within the above ranges, the antimicrobial properties and antivirus are excellent, and the aggregation and discoloration of the fiber composition are suppressed, and the preferable gel state of the fiber composition is maintained.

  The carboxyvinyl polymer is also called a carbomer, and can appropriately gel the composition for fibers of the present invention. Specific examples include Carbopol (registered trademark) 980 Polymer manufactured by Lubrizol Advanced Materials. The compounding amount of the carboxyvinyl polymer is, for example, in the range of 0.001 to 10 g / L, preferably 1 g to 10 g / L, based on the whole composition.

  The composition for fibers of the present invention comprises one or more of ethylenediamine-N, N, N ', N'-tetraacetic acid copper (II) disodium salt tetrahydrate, copper glutamate, amino acid copper and the like. Including. By containing these copper compounds, it is possible to impart pollen disintegration to the composition. In particular, ethylenediamine-N, N, N ', N'-tetraacetic acid copper (II) disodium salt tetrahydrate is preferable because of its excellent pollen disintegration properties. The amount of ethylenediamine-N, N, N ', N'-tetraacetic acid copper (II) disodium salt tetrahydrate can be appropriately designed.

  Moreover, the composition for fibers of the present invention may contain other various copper compounds. Examples of other copper compounds include one or more of copper nitrate, copper chloride, copper sulfate, copper oxide, copper sulfate, copper iodide, copper carbonate, copper citrate, copper glutamate, amino acid copper, and the like. can do. Of these, the fiber composition preferably contains copper pyrrolidonecarboxylate. These copper compounds do not contribute to the pollen disintegration of the fiber composition, but can further enhance the antibacterial and antiviral effects. For example, when the fiber composition of the present invention contains copper sulfate, the amount of the compound is in the range of 0.1 g to 5 g / L, preferably 1.2 g to 2.4 g / L, based on the total amount of the composition. Can be exemplified.

  Further, the composition for fibers of the present invention can appropriately contain other metals such as nickel, magnesium, iron, and titanium.

  Furthermore, the composition for fibers of the present invention can contain potassium N-long complex acylamino acid as a surfactant. In potassium N-long complex acylamino acid, potassium ions easily bind to silver ions, zinc ions, and copper ions, and effectively bind to fibers. For this reason, potassium N-long complex acylamino acid has a role of retaining an antiviral component. In addition, potassium N-long complex acylamino acid can enhance the permeability of the fiber composition into the interior of the fiber as a surfactant and the cohesion due to pH. After the fiber composition penetrates into the fiber and agglomerates, the fiber composition is fixed to the fiber, so that the fiber composition is prevented from falling off and the antibacterial and antiviral properties can be maintained for a long period of time.

  In addition, the coagulability can be adjusted by blending various acids such as hydrochloric acid, nitric acid, phosphoric acid, acetic acid, sulfuric acid, and carboxylic acid into the composition for fibers of the present invention.

  Glutamic acid can be added to the composition for fibers of the present invention. Glutamic acid has excellent solubility in water and excellent correlation with carboxylic acid-based materials, and is also a raw material for pyrrolidone carboxylic acid, so that it can further enhance the permeability to fibers. The amount of glutamic acid can be set within a range that does not prevent gelation of the fiber composition, and for example, a range of 0.001 to 2 mg / L based on the whole fiber composition. .

  Further, citric acid can be added to the composition for fibers of the present invention. Citric acid is excellent in solubility and can further increase the permeability to fibers. The compounding amount when citric acid is compounded can be set within a range that does not prevent gelation of the fiber composition. For example, the range of 0.001 to 4 mg / L with respect to the entire fiber composition. Examples can be given.

  Furthermore, the composition for fibers of the present invention may be blended with various other additives in consideration of use, handling properties, storage stability and the like. For example, compounding agents usually used in pharmaceutical preparations, for example, surfactants, oils, alcohols, humectants, thickeners, preservatives, antioxidants, chelating agents, pH adjusters, fragrances, pigments, vitamins, crude drugs And a plant extract. Further, the pH can be adjusted using an acid such as zinc sulfate heptahydrate and copper sulfate pentahydrate, sodium hydroxide, or the like.

  In the textile product of the present invention, the textile composition as described above is applied or impregnated to the textile.

  The textile product contains at least a part of the fiber coated or impregnated with the antibacterial / antiviral composition, and can be made of a material formed into yarn, woven or knitted fabric, web, nonwoven fabric, paper, net, or the like. . Specifically, for example, as textile products, for example, clothing (including hats, gloves, handkerchiefs), bedding (including futons, pillows), curtains, wallpapers, carpets, mats, sheets, filters, masks, wipers, Examples include towels, protective clothing, protective nets, and the like, which can be used for daily life and inactivate bacteria and viruses flying and floating in living spaces.

  Further, the material of the fiber is not particularly limited. For example, cellulosic fibers (cotton, hemp, rayon, pulp, etc.), protein fibers (wool, silk, etc.), polyamide fibers, polyester fibers, polyacrylic fibers, polyvinyl Various natural fibers such as alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyolefin fibers, and polyurethane fibers, recycled fibers, semi-synthetic fibers, and synthetic fibers can be used.

  Furthermore, the method of applying or impregnating the fiber composition of the present invention to the fiber is not particularly limited. For example, a method of immersing a fiber or fiber product as a material in a solution containing an antibacterial / antiviral composition and drying the solution, or a solution containing an antibacterial / antiviral composition for the fiber or fiber product as a material. Examples of the method include spraying or coating and drying.

  The composition for fibers of the present invention comprises amino acid silver, amino acid zinc, carboxyvinyl polymer, and ethylenediamine-N, N, N ', N'-tetraacetic acid copper (II) disodium salt tetrahydrate, copper glutamate, amino acid Contains one or more of copper. Therefore, it exhibits excellent antibacterial properties, antiviral properties and pollen disintegration properties. In addition, since the fiber composition realizes a gel state, the composition has excellent permeability to the fibers, prevents components from falling off the fibers and discoloration, and also has excellent durability of the effects.

  In addition, the antibacterial property, antiviral property, and pollen disintegration properties of the fiber composition of the present invention applied to and impregnated into fibers are hardly inhibited by other materials such as dyes, pigments, softeners, and processing solvents. There are few restrictions. The fiber product coated or impregnated with the fiber composition of the present invention can inactivate bacteria, viruses, and pollen scattered and floating in a living space, and has excellent antibacterial / antiviral properties and pollen disintegration. Sex can be maintained.

  The textile composition and textile product of the present invention are not limited to the above embodiments.

  Hereinafter, the fiber composition of the present invention will be described with reference to examples, but the fiber composition of the present invention is not limited to the following examples.

<Example 1> Pollen disintegration test (1) Nitric acid Pollen was put into nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 1%, and the state of the pollen was observed with a microscope.

As shown in FIG. 1, no degradation of pollen was observed after 5 minutes to 120 minutes.
(2) Sulfuric acid Pollen was added to nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.1%, and the state of the pollen was observed with a microscope.

As shown in FIG. 2, no degradation of pollen was observed after 5 minutes to 120 minutes.
(3) Copper nitrate Pollen was added to copper nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 0.1%, and the state of the pollen was observed with a microscope.

As shown in FIG. 3, no degradation of pollen was observed after 5 minutes to 120 minutes.
(4) Others Similar tests were performed on copper sulfate pentahydrate and the like, but at a concentration of 1000 ppm, similarly, the disintegration of pollen could not be confirmed. Therefore, it was confirmed that it is difficult to promote the disintegration of the pollen by the organic acid.

<Example 2> Pollen disintegration test 2
(1) Silver nitrate Pollen was added to 1000 ppm of silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.), and the state of the pollen was observed with a microscope.

As a result, it was confirmed that less than 5% of the pollen collapsed after 5 minutes to 15 minutes, less than 10% of the pollen collapsed after 30 minutes, and less than 20% of the pollen collapsed after 60 minutes (FIG. 4). ).
(2) Ethylenediamine-N, N, N ', N'-tetraacetic acid copper (II) disodium salt tetrahydrate Ethylenediamine-N, N, N', N'-tetraacetic acid copper diluted to 0.1% (II) Pollen was added to disodium salt tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.), and the state of the pollen was observed with a microscope.

  As a result, less than 40% of the pollen collapses after 5 minutes, less than 50% of the pollen collapses after 10 minutes, 80% of the pollen collapses after 15 to 30 minutes, and less than 95% of the pollen collapses after 60 minutes. This was confirmed (FIG. 5).

  It was confirmed that ethylenediamine-N, N, N ', N'-tetraacetic acid copper (II) disodium salt tetrahydrate has particularly excellent pollen disintegration properties.

<Example 3> Pollen disintegration test 3
Pollen was put into a 0.1% aqueous solution of zinc L-pyrrolidonecarboxylate (manufactured by CSL), which is an amino acid metal, and the state of the pollen was observed with a microscope.

  As a result, less than 20% of the pollen disintegrates after 5 minutes to 10 minutes, less than 30% of the pollen disintegrates after 15 minutes, less than 40% disintegrates after 30 minutes, and less than 60% after 60 minutes. Collapse was confirmed (FIG. 6).

<Example 4> Preparation of composition for fiber Based on the results of Examples 1 to 3, amino acid-based metal ions having excellent antibacterial, antiviral, and deodorant properties, and ethylenediamine-N, N having particularly excellent pollen disintegration properties , N ′, N′-tetraacetate copper (II) disodium salt tetrahydrate was mixed to prepare a composition.

Specifically, a composition for fibers was prepared by the following procedure.
(1) Silver pyrrolidone carboxylate and zinc L-pyrrolidone carboxylate, ethylenediamine-N, N, N ', N'-tetraacetate disodium salt tetrahydrate in 1000 ml of pure water The composition was prepared by blending the Japanese products in the following proportions.
Formulation in 1000 ml of water: 2.5 g of silver pyrrolidonecarboxylate
・ 33 g of zinc L-pyrrolidonecarboxylate
・ Ethylenediamine-N, N, N ', N'-tetraacetic acid copper (II) disodium salt tetrahydrate 6.7 g
・ Carboxyvinyl polymer 5g
-Copper sulfate 1.2g-2.4g
It was confirmed that the composition did not cause discoloration even after a long time.

<Example 5> Deodorizing property of composition (1) The composition prepared in Example 4 was mixed with a cotton raw material at a ratio of 5/100, and the deodorizing property was tested under the following conditions.

Test method: (one company) SEK Mark Textile Product Certification Standard for Textile Evaluation Technology Council 21. Deodorization test (detection tube method, gas chromatograph method)
Initial gas concentration: 100 ppm ammonia, 30 ppm acetic acid, 38 ppm isovaleric acid
Test sample: detection tube method 100 cm ² , gas chromatography method 50 cm ²
Measurement time: 2 hours later (2) The results are shown in Table 1.

  As shown in Table 1, it was confirmed that the composition prepared in Example 4 had excellent deodorant properties.

<Example 6> Antibacterial property of composition (1) The composition prepared in Example 4 was kneaded into cotton, and the antibacterial property was tested under the following conditions.

  Test method: JSL1902: 2008 Quantitative test (bacterial solution absorption method). The washing method is based on the test method of JIS 0217 103. The viable cell count is measured by a pour plate culture method.

Test strain: Escherichia coli NBRC 3301
(2) Table 2 shows the results.

    As shown in Table 2, it was confirmed that the composition prepared in Example 4 had excellent antibacterial properties. The antimicrobial properties of this composition are superior to those of the composition proposed in Patent Document 9.

<Example 7> Antiviral properties of the composition (1) The composition prepared in Example 4 was subjected to ripping processing (weight ratio of 1/100, dried at 60 ° C) on sock fibers under the following conditions. The antiviral properties were tested.

  Test method: According to ISO18184 Textiles-Determination of antivirial activity of textile products.

Test virus: Influenza virus InfuenzaAvirus (H3N2): ATCC VR-1679
Table 3 shows the results.

  As shown in Table 3, it was confirmed that the composition prepared in Example 4 exhibited excellent antiviral properties. In addition, even when washing was performed 10 times, the composition hardly fell off, and it was confirmed that the antiviral property was maintained. In addition, it was confirmed that the antiviral property of this composition was superior to the composition proposed in Patent Document 9.

  As described above, the composition prepared in Example 4 contains silver amino acid, zinc amino acid, carboxyvinyl polymer, and ethylenediamine-N, N, N ', N'-tetraacetic acid copper (II) disodium salt tetrahydrate It has been confirmed that, in a gel state, the fiber has excellent permeability to fibers, and that remarkable antiviral properties, antibacterial properties, deodorant properties and pollen disintegration properties are maintained.

Claims (6)

An antibacterial, antiviral and pollen disintegrating fiber composition,
Amino acid silver,
Amino acid zinc,
A carboxyvinyl polymer, and one or more of ethylenediamine-N, N, N ', N'-tetraacetic acid copper (II) disodium salt tetrahydrate, copper glutamate, amino acid copper,
A composition for fibers, comprising:   The fiber composition according to claim 1, wherein the amino acid of the amino acid silver and the amino acid zinc is L-pyrrolidone carboxylic acid.   3. The fiber composition according to claim 1, further comprising copper pyrrolidonecarboxylate.   The fiber composition according to any one of claims 1 to 3, further comprising glutamic acid.   The fiber composition according to any one of claims 1 to 4, further comprising copper sulfate.   A fiber product, wherein the fiber is coated or impregnated with the fiber composition according to any one of claims 1 to 5.