JPH08337966A - Metal ion-containing organic fiber improved in durability and its production - Google Patents

Abstract

PURPOSE: To obtain a fiber having deodorizing and antibacterial potencies and adequate washing durability by adding a metal ion elimination-preventing agent to an organic fiber having metal-containing carboxyl groups. CONSTITUTION: This production of a metal ion-containing organic fiber improved in durability is to graft polymerize methacrylic acid on an organic fiber such as a natural fiber e.g. cotton or wool, a synthetic fiber e.g. nylon or polyester, etc., for example, cotton yarns, treat the product with sodium hydroxide to change COOH into COONa, substitute Na with a metal ion such as copper, zinc, iron, nickel, cobalt or silver to obtain the cotton yarns having metal- containing carboxyl groups, then add a metal ion elimination-preventing agent comprising at least one compound selected from a group consisting of benzotriazole-based compounds, imine ring-containing compounds, triazine thiol compounds or silane coupling agents containing amino groups, mercapto groups or tertiary ammonium salts, e.g. 2,2-bishydroxymethylbutanol tris2[3(1- aziridinyl)]propionate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal ion-containing organic fiber which prevents metal ions from falling off and has improved durability, and a method for producing the same.

[0002]

2. Description of the Related Art It is known that an organic fiber is introduced with a metal-containing carboxyl group represented by --COOM (wherein M represents a metal ion). Such a fiber can be used as a deodorant fiber because it captures a bad odor of ammonia, trimethylamine, methyl mercaptan, hydrogen sulfide and the like due to the action of the metal-containing carboxyl group. Further, the fiber can be used as an antibacterial fiber due to the action of the metal-containing carboxyl group. However, in the fiber containing a metal-containing carboxyl group as described above, the binding force of the metal ion to the carboxyl group is not so strong that the metal ion is removed from the fiber when subjected to washing treatment such as washing. It has the drawback of being easy to do.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a metal ion-containing organic fiber having improved durability in which metal ions do not drop off and a method for producing the same.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by binding a specific compound to the surface of the metal ion-containing organic fiber, the metal ion The present inventors have found that falling off can be effectively prevented, and have completed the present invention. That is, according to the present invention, (i) a benzotriazole-based compound and (ii) an imine ring are added to an organic fiber containing a metal-containing carboxyl group represented by the general formula —COOM (wherein M represents a metal ion). A metal having excellent durability, which is obtained by binding at least one compound selected from the group consisting of compound-containing compounds, (iii) triazine thiol compound and (iv) amino group, mercapto group or quaternary ammonium salt group-containing silane coupling agent. Ion-containing organic fibers are provided. Further, according to the present invention, an organic fiber containing a metal-containing carboxyl group represented by the general formula —COOM (wherein M represents a metal ion) is prepared by using (i) a benzotriazole compound and (ii) an imine ring. It is characterized in that it is contacted with a solution containing a compound containing (iii) a triazine thiol compound and (iv) a silane coupling agent containing an amino group, a mercapto group or a quaternary ammonium salt group. Provided is a method for producing a metal ion-containing organic fiber having excellent durability.

The organic fiber used as a raw material to be treated in the present invention contains a metal ion-containing carboxyl group represented by -COOM. Such fibers are
The carboxyl group-containing fiber is produced by various methods such as graft-polymerizing a monomer having a carboxyl group onto the fiber, or synthesizing the fiber by using a polymer or a copolymer having a carboxyl group. It can be obtained by binding a metal ion to.

As the organic fibers, various conventionally known ones, for example, natural fibers such as silk, wool and cotton, synthetic fibers such as polyester, nylon, vinylon and acrylic, rayon, cupra, acetate, promix and the like can be used. Semi-synthetic fibers and the like can be mentioned. The forms of organic fibers include threads, fabrics,
It can be in various forms such as a fiber mat, a non-woven fabric and a knitted fabric. As the metal ion M, an ion of a transition metal such as copper, zinc, iron, nickel, cobalt or silver is generally used.

Carboxyl groups (--CO contained in fibers
The equivalent number of (OH) is 0.0001-0.
The ratio is 005 equivalents, preferably 0.0005 to 0.003 equivalents. In addition, 20% of the carboxyl groups
As described above, it is preferable that 30 to 100% is converted to -COOM.

In order to produce a metal ion-containing organic fiber according to the present invention, a metal ion drop-preventing agent is bonded (attached) to the above-mentioned metal ion-containing organic fiber. The metal ion loss preventive agent is capable of preventing the loss of metal ions from the carboxyl group, and as such, the following ones are used. (Benzotriazole-based compound) 1,2,3-benzotriazole, bisethanolaminomethylbenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole and the like. (Imine ring-containing compound) ethyleneimine, 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl)] propionate, N-stearyl-
N ′, N′-ethyleneurea, diphenylmethane-bis-4,4′-N, N′-diethyleneurea and the like. (Triazine thiol compound) 2,4,6-trimercapto-S-triazine, 2-dibutylamino-4,6-
Dimercapto-S-triazine and the like. (Amino group-containing silane coupling agent) γ-aminopropyltriethoxysilane, N-β- (aminoethyl)-
γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and the like. (Mercapto group-containing silane coupling agent) 3-mercaptopropyltrimethoxysilane, etc. (Quaternary ammonium base-containing silane coupling agent)
Dimethyl octadecyl ammonium chloride propyl trimethoxy silane, diethyl octadecyl ammonium chloride propyl trimethoxy silane, etc.

In order to bond the above-mentioned metal ion drop preventing agent to the metal ion containing fiber, the metal ion containing organic fiber may be brought into contact with a solution containing the metal ion drop preventing agent. Examples of the contact method include a dipping method and a spray method. As the solution, an aqueous solution, an organic solvent solution,
A water / organic solvent mixed solution and the like can be mentioned, which is appropriately selected according to the kind of the metal ion shed prevention agent. The concentration of the metal ion shed inhibitor in the solution is not particularly limited, but is usually 0.
It is at least 01% by weight, preferably 0.02 to 0.5% by weight. The contact temperature is 15 to 120 ° C., preferably 2
The contact time is usually 5 minutes or longer, preferably 10 to 60 minutes. The binding amount (adhesion amount) of the metal ion loss preventive agent to the metal ion-containing organic fiber is
0.1 to 10% by weight, preferably 0.2
~ 5% by weight.

[0010]

Next, the present invention will be described in more detail with reference to examples. In addition,% shown below is weight%.

Example 1 Methacrylic acid: 1.8%, a sequestering agent (Crest NT
B, manufactured by Kirest Chemical Co., Ltd .: 0.03%, sulfuric acid (50 ° B)
e '): 0.07%, hydrogen peroxide (concentration 30%): 0.
The scoured cotton yarn was immersed in an aqueous solution containing 4% and ferrous sulfate: 0.02% and treated at 85 ° C. for 2 hours to obtain a cotton yarn with a grafting ratio of 11.6%. Then, in an aqueous solution containing 1% caustic soda, treatment is performed at 60 ° C.
Was changed to -COONa, then copper sulfate (CuSO ₄ ) 1%
Was treated in an aqueous solution containing 80 ° C. for 20 minutes to obtain a Cu-containing cotton yarn. The Cu content in this cotton yarn was 1.53% based on the weight of the fiber. Next, this Cu-containing cotton thread was used as a metal ion shedding inhibitor in an aqueous solution containing 0.3% of 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl)] propionate.
A product was obtained by treating at 20 ° C. for 20 minutes. The amount of the metal ion loss preventing agent attached was 3.2% with respect to the fiber.

Comparative Example 1 A product obtained in Example 1 by omitting the metal ion loss preventive agent adhesion treatment.

The products of Example 1 and Comparative Example 1 were evaluated for wash resistance. Washing resistance in this case is JIS L-0.
It was carried out by 20 repeated washing tests according to the 217 103 method. Table 1 shows the results.

[0014]

[Table 1]

Application Example 1 The product of Example 1 was tested for its deodorizing performance as follows. The results are shown in Table 2. (Deodorant performance test) (1) The odor of the gas concentration shown in Table 2 and 0.3 g of the sample for deodorization were enclosed in a 550 ml bottle, and after leaving it for the time shown in Table 2, the odor gas in the bottle The concentration was measured. The results are shown in Table 2. The deodorizing rate shown in Table 2 is obtained by the following formula. Deodorization rate (%) = (A−B) / A × 100 A: initial concentration of odorous gas B: odorous gas concentration after standing for a predetermined time Further, both the samples A and A ′ shown in Table 2 are 20
The product before the repeated washing test is shown, and B and B'show the products after the washing test.

[0016]

[Table 2]

Example 2 A knitted fabric was prepared by using 20% of the copper-containing cotton yarn treated with the metal ion shedding inhibitor shown in Example 1 and 80% of the scoured cotton yarn.

Comparative Example 2 A knitted fabric was prepared by using 20% of the copper-containing cotton yarn not treated with the metal ion shedding prevention agent shown in Comparative Example 1 and 80% of the scoured cotton yarn.

Next, the knitted fabrics obtained in Example 2 and Comparative Example 2 were tested for their antibacterial performance as follows.
Table 3 shows the results. (Antibacterial Performance Test) Test Method: Shake Flask Method Test Bacteria: Klebsiella peu
moniac, ATCC 4352) Shaking conditions: wrist action, 330 rpm x 1 hour Specimen weight: 0.75 g Further, A and A'shown in Table 3 are products before washing test, and B and B'are The product after 10 repeated washing tests by JIS L0217 103 method (however, neutral detergent Monogen Uni is used as the detergent) is shown.

[0020]

[Table 3]

Example 3 A product was obtained in the same manner as in Example 1, except that the metal ion shedding inhibitor shown in Table 4 was used. next,
The product thus obtained was subjected to 20 repeated washing tests, and then the copper content in the product was measured.
Shown in

[0022]

[Table 4]

Example 4 The copper-containing cotton yarn obtained in Example 1 was used at 40 ° C. at 100 ° C. in an aqueous solution containing 0.3% of the silane coupling agent shown in Table 5.
The product was obtained by processing for minutes. Next, this product was repeatedly subjected to a washing test 20 times, and then the copper content in the product was measured. The results are shown in Table 5.

[0024]

[Table 5]

Example 5 In the same manner as in Example 1, rayon cotton (2.5D × 51 m)
1.65% of copper was contained in m). This copper-containing rayon cotton was treated in an aqueous solution containing a metal ion shedding inhibitor shown in Table 6 to obtain a product. Next, this product was subjected to 20 repeated washing tests, and then the copper content in the product was measured. Table 6 shows the results. The contents of the symbols shown in the table are as follows. BNTA: 1,2,3-benzotriazole BHTAP: 2,2-bishydroxymethyl-tris [3- (1-aziridinyl)] propionate MEPMS: 3-mercaptopyropyrmethoxysilane

[0026]

[Table 6]

Example 6 In the same manner as in Example 1, bonnel cotton (acrylic fiber,
2.52 × 51 mm, manufactured by Mitsubishi Rayon Co., Ltd.) contained 1.62% of copper (II). This copper-containing Bonnell cotton was treated in an aqueous solution containing a metal ion shedding inhibitor shown in Table 7 to obtain a product. Next, this product was subjected to 20 repeated washing tests, and then the copper content in the product was measured. The results are shown in Table 7.

[0028]

[Table 7]

Example 7 Grain-polymerized rayon cotton (2.5D × 51 mm) was treated in an aqueous solution containing 1% of NaOH at 60 ° C. for 20 minutes in the same manner as in Example 1, and then zinc sulfate 1 % Rayon cotton was treated in an aqueous solution containing 80% of water for 20 minutes to give rayon cotton having a zinc content of 1.46%. The zinc-containing rayon cotton was treated in an aqueous solution containing 0.3% of the metal ion shedding inhibitor shown in Table 8 to obtain a product. Next, this product
The zinc content in the product was measured after being subjected to a repeated washing test of 0 times. Table 8 shows the results.

[0030]

[Table 8]

Example 8 Methacrylic acid: 1.5%, CHIREST NTB: 0.03
%, Sulfuric acid (50 ° Be ′): 0.5%, hydrogen peroxide (concentration 30%): 0.3%, reducing agent (Superlite C, manufactured by Mitsubishi Gas Chemical Company): 0.08% Wool top (refined) was treated therein at 50 ° C. for 60 minutes to obtain a wool top having a grafting rate of 12.5%. Next, this wool top is placed in an aqueous solution containing 0.1% of sodium carbonate,
After treated at 0 ° C. for 20 minutes, treated at 80 ° C. for 20 minutes in an aqueous solution containing 0.1% of copper sulfate to obtain a wool top having a copper content of 1.40%. Next, the wool top thus obtained was treated in an aqueous solution containing 0.3% of the metal ion shedding inhibitor shown in Table 9 to obtain a product. Next, this product 2
The copper content in the product was measured after being subjected to 0 repeated washing tests. The results are shown in Table 9.

[0032]

[Table 9]

Example 9 Cupra fibers (Bemberg, 2D × 51 mm, manufactured by Asahi Kasei Kogyo Co., Ltd.) were graft-polymerized in the same manner as in Example 1, and then 20 at 80 ° C. in an aqueous solution containing 0.1% of sodium carbonate.
After being treated for a minute, it was treated in an aqueous solution containing 1% of copper sulfate at 80 ° C. for 20 minutes to obtain Bemberg cotton having a copper content of 1.57%. Next, this Bemberg cotton was treated in an aqueous solution containing 0.3% of the metal ion shedding inhibitor shown in Table 10 to obtain a product. The product was then subjected to 20 repeated washing tests before measuring the copper content. The results are shown in Table 10.

[0034]

[Table 10]

Example 10 A silver content of 1.2 was obtained in the same manner as in Example 9 except that 0.08% of silver nitrate was used instead of 1% of copper sulfate.
% Bemberg cotton was obtained. Next, this Bemberg cotton was treated in an aqueous solution containing 0.3% of the metal ion loss preventing agent shown in Table 11 to obtain a product. Next, this product was subjected to 20 repeated washing tests and then the silver content was measured. The results are shown in Table 11.

[0036]

[Table 11]

Example 11 0.05 part by weight of benzoyl peroxide was dissolved in 0.4 part of a chlorobenzene type carrier (Carrier 30, manufactured by Nika Kagaku Kogyo Co., Ltd.) to obtain methacrylic acid of 2.2% and sodium carbonate of 0.03. % To 100 parts by weight of aqueous solution. Next, in this aqueous solution, scoured polyester cotton (6
D x 64 mm) and immerse it in a nitrogen gas atmosphere at 105 ° C
Sodium tripolyphosphate 0.05
%, Detergent (Neugen SS, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.2%
It was dipped in an aqueous solution containing it and subjected to a carrier removal treatment at 100 ° C. for 60 minutes to obtain a polyester fiber having a grafting rate of 10.6%. Next, this polyester cotton is treated in an aqueous solution containing 0.1% of sodium carbonate at 90 ° C. for 20 minutes to convert —COOH contained in the polyester cotton into —COONa.
After that, after thoroughly washing with water, ferrous chloride was reduced to 0.
It was treated at 90 ° C. for 20 minutes in an aqueous solution containing 1% to obtain polyester cotton having an iron content of 1.55%. Next, this polyester cotton is used as a metal ion loss preventive agent in 2,2-
120 in an aqueous solution containing 0.3% of bishydroxy-tris [3- (1-aziridinyl)] propionate.
The product was obtained by treating at 30 ° C. for 30 minutes. The bonding amount of the metal ion shedding inhibitor in this product was 2.8%. next,
After subjecting this product to repeated washing tests 20 times, the iron content was measured and found to be 1.45%. For comparison, the iron-containing polyester cotton which had not been treated with the metal ion shed inhibitor was subjected to 20 repeated washing tests and the iron content was measured to be 0.50%.

[0038]

EFFECTS OF THE INVENTION The metal ion-containing organic fiber of the present invention has a metal ion loss preventive agent bonded to its surface to improve durability, so that even if it is washed many times,
The metal ions are not easily released. The metal ion-containing organic fiber of the present invention has a deodorizing action and an antibacterial action due to the action of the metal-containing carboxyl group, and is advantageously used as various fiber products.

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[Procedure amendment]

[Submission date] July 13, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

Example 5 In the same manner as in Example 1, rayon cotton (2.5D × 51 m)
1.65% of copper was contained in m). This copper-containing rayon cotton was treated in an aqueous solution containing a metal ion shedding inhibitor shown in Table 6 to obtain a product. Next, this product was subjected to 20 repeated washing tests, and then the copper content in the product was measured. Table 6 shows the results. The contents of the symbols shown in the table are as follows. BNTA: 1,2,3- benzotriazole BHTAP: 2,2- bis-hydroxymethyl butanol - tris [3- (1-Ajirijiniiru)] propionate MEPMS: 3-mercapto pyromellitic pills silane

Claims (2)

[Claims] 1. An organic fiber containing a metal-containing carboxyl group represented by the general formula: —COOM (wherein M represents a metal ion), (i) a benzotriazole compound, (ii) an imine ring-containing compound, (Iii) Triazine thiol compound and (iv) Metal ion-containing organic material having excellent durability, which is formed by combining at least one compound selected from silane coupling agents containing amino group, mercapto group or quaternary ammonium salt group fiber. 2. An organic fiber containing a metal-containing carboxyl group represented by the general formula: —COOM (wherein M represents a metal ion), (i) a benzotriazole compound, (ii) an imine ring-containing compound, (Iii) Contact with a solution containing a triazine thiol compound and (iv) at least one compound selected from an amino group, a mercapto group or a quaternary ammonium salt group-containing silane coupling agent. An excellent method for producing an organic fiber containing metal ions.