JPH03213562A - Deodorizing fiber and its production - Google Patents

Abstract

PURPOSE:To obtain the subject fiber effective in deodorizing the stench of ammonia, etc., and having excellent durability by coordinating a metal ion such as iron, copper, nickel or indium to an acrylic fiber containing amidoxime and carboxyl. CONSTITUTION:An acrylic fiber containing 0.05-1mmol/g of amidoxime group and 5-50mol% (based on the amidoxime) of carboxyl group is immersed in an aqueous solution containing ions of one or more kinds of metals selected from iron, copper, tin, silver, aluminum, chromium, zinc, nickel, lead, titanium, indium, zirconium, molybdenum and cobalt and heat-treated at 40-130 deg.C to obtain the objective fiber containing the metal ion coordinated to the amidoxime group and carboxyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a highly durable deodorizer #/IIM1 that deodorizes bad odors such as ammonia, and a method for producing the same.

<Prior art> Conventionally, deodorants have been known to utilize the physical adsorption properties of activated carbon, zeolite, etc., and those to utilize chemical reactivity such as ferrous sulfate. The ones that utilize the latter have poor effectiveness in adsorbing bad odors such as highly polar ammonia, and those that utilize the latter's chemical reactivity are used as an aqueous solution, which limits the way they can be used and lacks durability. Ta. As an improvement of this, the Journal of the Fiber Science Society 42゜P2O (198
6), ferrous sulfate/ascorbic acid type, or Journal of the Japan Textile Science Society 41. P267 (1985) suggests ferric phthalocyanine, but these also lack durability and stability in the absence of moisture, and even as an aqueous solution, they are exposed to air for long periods of time. If it is incorporated into fibers, its performance will tend to deteriorate due to the heat during spinning, and if it is incorporated into fibers in post-processing, it will have poor durability against washing, etc.

<Problems to be Solved by the Invention> The present invention solves the problems of conventional deodorants and provides a deodorant fiber with excellent durability and a method for producing the same.

[Countermeasures for Solving Problems] The present invention uses acrylic fibers with a thickness of 0.05 to 1 m m o L.
/t contains an amidoxime group and 5 to 50 moles of carboxyl group per amidoxime group, and these groups include iron, copper, tin, silver, aluminum, chromium, zinc, nickel, lead, titanium, A deodorizing fiber and L which are coordinated with at least one metal ion selected from the group of indium, zirconium, molybdenum and cobalt.
Acrylic fibers containing amide oxime groups of 5 to 1 mmoL/l and carboxyl groups of 5 to 50 molar ratios to the amide oxime groups are made of iron, copper, tin, silver, aluminum, chromium, zinc, nickel, lead, titanium, and indium. ,
A method for producing deodorizing fibers, which is characterized by heat treatment in an aqueous solution containing ions of at least one metal selected from the group of zirconium, molybdenum and cobalt.

In the present invention, metal ions, which are unstable in the metal ion state, are stabilized by being coordinated with amidoxime groups and hycarboxyl groups. (Due to its physical adsorption properties), it has a remarkable deodorizing effect not found in conventional deodorant fibers.

Furthermore, it can be used in any form and can be provided in a form depending on the purpose of use.

The basic fiber of the deodorizing fiber of the present invention is acryloni) I
These are acrylic fibers and modacrylic fibers made of polymers containing 10% by weight or more of 4% by weight.

The amount of amidoxime groups contained in the acrylic tram is (L O5
~1 mtnOL/t, and (LO5mmoL
If it is less than /, the amount of metal ions that will be coordinated to the group will be small and the deodorizing effect will be poor. When PIOt/9 is exceeded, there is little improvement in the deodorizing effect and it is disadvantageous in terms of cost.

The present invention has achieved the effect of accelerating the malodor chemisorption reaction of moisture absorption of carboxyl groups in addition to the durable metal bonding properties of the amidoxime groups contained in acrylic fibers and the chemical adsorption of bad odor of metal ions. The ratio of carboxyl groups to amidoxime groups is 5.
It is desirable that the number of carboxyl groups is 10 to 50 moles.If the number of carboxyl groups is less than 5 moles, the effect of promoting chemisorption of metal ions and bad odors due to moisture absorption will be poor, and if it exceeds 50 moles, the chemical adsorption will increase. Since metal ions coordinated with carboxyl groups inherently lack thermal stability, this has a large effect, and when deodorizing fibers are oxidized, they change color and their deodorizing properties decrease.

The introduction of amidoxime groups into the acrylic fibers of the substrate is achieved by copolymerizing an amidoxime group-containing vinyl monomer or by converting a nitrile group into an amidoxime with hydroxylamine. Introduction of carboxyl groups into acrylic fibers is achieved by copolymerization of carboxyl group-containing vinyl monomers such as acrylic acid or by hydrolysis of nitrile groups with alkali.

Metal ions to be coordinated to the amidoxime groups and carboxyls contained in the acrylic fiber include iron, copper, tin, silver, aluminum, chromium, zinc, nickel, lead, titanium, indium, zirconium, molybdenum, and cobalt. At least one selected metal ion is selected, and a metal ion is selected that is easily bonded in an ionic state to the three major malodors of ammonia, hydrogen sulfide, and methyl mercaptan, and is also easily bonded to an amidoxime group and a carboxyl group. These metal ions are believed to stably exist as ions within the acrylic fibers and chemically adsorb bad odors. It is desirable that the amount of metal ion is approximately equivalent to the content of amidoxime groups and carboxyl groups.

Coordination bonds of metal ions to amidoxime groups and carboxylic acid groups are copper sulfate, cupric chloride, ferric sulfate, stannous chloride,
Acrylic fibers containing amidoxime groups and carboxyl groups are immersed in an aqueous solution of tin chloride, silver nitrate, aluminum sulfate, dichromic sulfate, zinc sulfate, nickel sulfate, lead sulfate, titanium sulfate, zirconium sulfate, or indium sulfate and heat treated. It is done as follows. Heat treatment is 40-160℃
It will be held in Heat treatment and immersion in a metal ion-containing aqueous solution may be optionally performed in separate steps or in the same step. Heat treatment is not included and hot water resistance is inferior. Heat treatment is an essential step for stably coordinating metal ions to amidoxime groups and carboxyl groups.

<Example> The present invention will be explained below with reference to examples.

Note that in the examples, the weight is 14.4 owf and the weight is relative to the fiber. In addition, the content of amidoxime groups is calculated from the amount of saturated dyeing of orange (acidic dye), and the content of carboxyl groups is determined from the amount of saturated dyeing of methyl violet (basic dye). Atomic absorption spectrometry was used.

The moisture absorption rate was measured at 20"C and 654Rm based on J Engineering S.

Example 1 Acrylonitrile/methyl acrylate/sodium methacrylsulfonate = 91.247 & 04/(184
Acrylic fiber 3 (IX51m) was added with hydroxylamine sulfate and caustic soda as shown in Table 1, immersed in an aqueous solution with a bath ratio of 1:20, treated at boiling for 60 minutes, washed with water, and added with amidoxime groups and A carboxyl group-containing acrylic fiber was obtained.This fiber was further treated with 104 ovt of copper sulfate.
.

Treated for 30 minutes at boiling in an aqueous solution with a bath ratio of 1:20, and heated to 70°C.
The fibers were washed with hot water and dried at about 70°C to obtain hygroscopic fibers containing amidoxime groups, carboxylic acid groups, and copper as shown in Table 1. The deodorizing performance of this fiber was excellent as shown in Table 1. As an evaluation of these durability, 1
The performance after 00 cycles was also shown, and it was an extremely durable deodorizing fiber.

/ / / / / 1) 2) Carboxyl group ratio; molar ratio with amidoxime group, the amount of carboxyl groups divided by the amount of amidoxime groups, multiplied by 100 The remaining ammonia concentration 111 is the ammonia concentration of 9000 ppm Put it in a hexagonal flask 1
The residual concentration after a period of time was measured. The smaller the residual ammonia concentration, the better the deodorizing property.

Example 2 The amidoxime group- and carboxyl group-containing fibers obtained under the conditions of Example 1 Grave 6 before adsorption of copper were treated with aluminum sulfate, zinc sulfate, nickel sulfate, ferric sulfate, silver nitrate, zirconium sulfate, and cobalt sulfate at 10% each. Aluminum α1 is immersed in an aqueous solution with a pick-up rate of 87, then steamed at 98°C for 30 minutes and washed with hot water at 70°C. After drying, aluminum α1
1 mmol 1 g! , zinc α12 mmoL/f.

Nickel α14mmot/9, iron [110mmot/
f, silver α25 mmol/li, zirconium 0.15
mmot/ri and kobal) l 15 mmoL/f
Each contained nine fibers. The deodorizing performance of this fiber is 210,190,160°8 in terms of residual ammonia concentration.
It was a good deodorizing fiber with concentrations of 0.30, 130, and 180 ppm.

<Effects of the Invention> The deodorizing fiber of the present invention deodorizes ammonia and other odors extremely efficiently and is extremely durable.

Claims (1)

[Claims] 1. The acrylic fiber contains 0.05 to 1 mmol/g of amidoxime groups and 5 to 50 mol% of carboxyl groups based on the amidoxime groups, and these groups include iron, copper, A deodorant fiber in which at least one metal ion selected from the group of tin, silver, aluminum, chromium, zinc, nickel, lead, titanium, indium, zirconium, molybdenum and cobalt is coordinated. 2. Acrylic fibers containing 0.05 to 1 mmol/g of amidoxime groups and 5 to 50 moles of carboxyl groups per amidoxime group are mixed with iron, copper, tin, silver, aluminum, chromium, zinc, nickel, lead, 1. A method for producing deodorant fibers, which comprises heat-treating in an aqueous solution containing ions of at least one metal selected from the group of titanium, indium, zirconium, molybdenum, and cobalt.