JPS62295665A - Deodorizing material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a material that eliminates bad odors, which are regarded as a sanitary problem in the clothing and non-clothing fields.

[Prior art]

Conventionally, activated carbon has been used as a deodorizing agent to eliminate bad odors in non-clothing fields, such as bad odors in refrigerators and odors emanating from industrial equipment.

In addition, some attempts have been made to treat clothing such as cotton with ferric sulfate and monoascorbic acid.

(Problems to be solved by the invention) However, in the clothing field, the use of activated carbon is difficult and the actual situation is that it has not been technically solved, and the latter technology has poor washing durability and is not worth the use. The problem was that it was small.

The present invention aims to provide a durable deodorizing material for use in the clothing and non-clothing fields.

[Means for solving problems]

In order to achieve the above-mentioned object, the present invention has the following configuration. .

(1) A molded article having 3.2×10 −4 (gram equivalent/gram) or more of acidic groups, at least a part of which has reacted with a metal complex, a deodorizing material.

(2) The deodorizing material according to claim 1, wherein the metal complex is an iron (III)-phthalocyanine derivative and/or a cobalt (n)-phthalocyanine derivative.

(3) The deodorizing material according to claim (1), wherein the metal complex is unevenly distributed in the surface layer of the molded article.

The acidic group in the present invention means a carboxylic acid group or a sulfonic acid group, and in materials such as synthetic fibers, carboxylic acid groups are preferred in order to stably maintain the form of clothing.

The content of these acidic groups needs to be 3.2X10-4 gram equivalent/gram or more, preferably 9,3X'IO' gram equivalent/gram or more in order to provide good deodorizing performance. .

This acidic group reacts with the iron(I[)-phthalocyanine derivative and/or the Kobal 1-(n)-phthalocyanine derivative to become an adsorption material made of a stable metal complex. Since the present invention is made of a material based on such chemical bonding, it has characteristics of stability and durability.

In the molded product of the present invention, it is preferable that the metal complex is unevenly distributed in the surface layer of the molded product, for example, in a core-sheath structure, since this has a greater deodorizing effect than if it is uniformly present throughout the interior.

As used in the present invention, iron (III)-phthalocyanine derivatives and/or cobalt (n)-phthalocyanine derivatives include, for example, iron (III)-phthalocyanine tetracarboxylic acid, iron (I[[)-phthalocyanine octacarboxylic acid, cobalt Examples include copolymers of (n)-phthalocyanine tetracarboxylic acid or these compounds with vinyl compounds such as polystyrene and polyvinylpyridine.

Ideally, the content of such a metal complex is equivalent to the mole of the acidic group, but substantially it is 3% or more, preferably 5% or more, based on the Durham equivalent of the acidic group. If it is, the effect will be achieved.

The metal complex of the present invention includes (a) a reaction involving hydrogen transfer by molecular oxygen, oxygen oxidation or autooxidation, (b) hydrogen peroxide oxidation, (c) r! It exhibits oxidation reaction behavior such as i-addition reaction, and this behavior is thought to be involved in the deodorizing effect.

The odor in the present invention refers to the odor generated from ammonia, hydrogen sulfide, mercaptans, amines, phenols, aldehydes, etc., but the present invention is particularly effective against ammonia, hydrogen sulfide, mercaptans, and amines. It is true.

Next, examples of materials constituting the molded product according to the present invention include synthetic fibers such as polyamide, polyester, polyacrylonyl, polyolefin, semi-synthetic fibers such as rayon and acetate, and natural fibers such as cotton and hemp. However, synthetic fibers such as polyamide and polyester are particularly selected from the viewpoint of the shape stability of the molded product and the durability of the deodorizing effect.

Molded products made of such materials include stable, tow, spun yarn, filament yarn, fiber molded products such as nonwoven fabrics, woven and knitted fabrics, plastic molded products such as films, and cut pile (cut short fiber). )
Examples include, but are not limited to, granular materials that have been transformed into powders, etc.

In addition, methods for containing acidic groups in such molded products include copolymerizing acidic vinyl monomers during the polymerization of fibers or plastics, and copolymerizing acidic vinyl monomers (with other monomers) in advance to form polymers. There are methods such as blending (including copolymers), or applying it to the inside or surface of the molded product by graft polymerization or adhesion processing based on affinity. From the standpoint of morphological stability, graft polymerization inside the molded product, polymerization onto the surface of the molded product in graph 1, adhesion processing based on affinity, etc. are preferred.

Of course, as for the macromorphology of the molded article, it is preferable that the molded article has many surface irregularities, cracks, or micropores, and has a large surface area.

The deodorizing effect as referred to in the present invention was measured by the following means.

Method A is an ammonia gas detection tube method in which a glass-lined column is filled with 3 g of deodorizing material, and ammonia gas with a concentration of 11,000 f)p is passed through it at an aeration rate of 3.3 cm/sec. Method B: Measuring the amount of breakthrough adsorption (northern type gas detection tube). Method B involves impregnating 0.25 ml of ammonia water (3 x 6 cm) with approximately 5% ammonia water, and then placing it in a 150 ml glass container. , at the same time 0 deodorizing materials
．． A method was adopted in which 5 g was poured into the bottle, the bottle was sealed tightly, and the change in odor was examined after the bottle was left for 4 hours.

There are other similar methods using hydrogen sulfide or mercaptan as an odor source, but in the present invention, one of the methods of the second party was adopted.

Hereinafter, a detailed explanation will be given using a specific example.

Example 1, Comparative Example 1.2 A stable made of nylon 6 Y-shaped cross-section fiber of 3 denier x y 6 mm was used as the 48th medium thread (spun yarn),
A smooth knitted fabric was knitted using this.

This knitted fabric was mixed with 10% owf of acrylic acid, 30% owf of methacrylic acid, 1% owf of ammonium persulfate, 3% owf of Superlite C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and a bath ratio of 1.
:7 at a rate of 1°C/min from room temperature under the conditions of 10.
The temperature was raised to 5°C, and graft polymerization was performed at 75°C for 60 minutes. When the degree of graft polymerization was measured by alkali-acid neutralization titration method, the carboxyl group was 2.8
It was confirmed that X10-3 grams per gram of fiber was contained.

Next, after washing this treated knitted fabric with water, 30% sodium carbonate was added.
owt aqueous solution at a bath ratio of 1:10 for 30 minutes at 60'CX. After roughly washing with water, in an aqueous solution of 20 g of iron (I[I)-phthalocyanine tetracarboxylic acid]
It was treated with 0'CX for 30 minutes, washed with water and dried to obtain a deodorized material (this example).

The reaction ratio of iron (III)-phthalocyanine tetracarboxylic acid in this deodorizing material to the equivalent of acidic groups contained in the fiber is 1
It was 0%.

Next, as a comparison, the nylon 6 knitted fabric of this example was subjected to graft polymerization under the same conditions as in this example.
It was treated with the above iron (Ill)-phthalocyanine tetracarboxylic acid aqueous solution (Comparative Example 1).

Further, in Comparative Example 2, Graph 1 was subjected to polymerization treatment and sodium carbonate treatment under the same conditions as in this example, but the treatment with the iron (■)-phthalocyanine tetracarboxylic acid aqueous solution was not performed.

The deodorizing properties of ammonia gas were measured for each of the above three levels, and the results are shown in the following table, confirming that the deodorizing material of the present invention is very effective.

Table 1 In the table, Method A: Breakthrough adsorption amount (!i!g, /g) Method B: Presence or absence of ammonia odor: With or without washing) η: Detergent (“Zabu” manufactured by Seisei Soap Co., Ltd. 2 g/Otsu, Washed at home at a bath ratio of 1:50 for 40'C x 5 minutes, washed with water, and dried.

Example 2 A 48 count spun yarn made of polyester fibers with a π-shaped cross section of 1.3 denier x 38 mm was knitted into a double jersey.

This knit was mixed with methacrylic acid 50g/O, benzoyl peroxynide 2g/O, and monochlorobenzene 10M.
B. Using a treatment solution consisting of 5 g/t of a 16 mol nonylphenolgide adduct, the temperature was gradually raised from room temperature to 105°C at a bath ratio of 1:50, and graft polymerization was carried out at that temperature for 60 minutes. did.

This jersey had 2.3 x 10-3 grams of fiber carboxyl groups introduced.

Next, 60℃×30 with 10g of sodium carbonate/Otsu water solution.
After treatment for 1 minute and washing with water, 6%
It was treated with 0'CX for 30 minutes, washed with water and dried, and the debromine side was removed by 1q (this example).

The reaction ratio of cobalt(II)-phthalocyanine octacarboxylic acid in this deodorizing material to the equivalent amount of acidic groups contained in the fibers was 7%.

When this deodorizing material was subjected to the same test as in Example 1, it exhibited excellent deodorizing effects as in Example 1. It was also found that the deodorizing performance did not change even after washing.

(Effects of the Invention) The present invention provides a molded product with excellent durability and deodorizing effect. Regardless of the form of the molded product, deodorizing performance can be easily imparted to the molded product. The material was provided for 1q.

Claims (3)

[Claims] (1) A deodorizing material having at least a part of the acidic groups reacted with a metal complex in a molded article having 3.2×10^-^4 (gram equivalent/gram) or more of acidic groups. (2) The deodorizing material according to claim (1), wherein the metal complex is an iron (III)-phthalocyanine derivative and/or a cobalt (II)-phthalocyanine derivative. (3) The deodorizing material according to claim (1), wherein the metal complex is unevenly distributed in the surface layer of the molded article.