JPH057617A - Deodorizing blank material - Google Patents

Abstract

PURPOSE:To obtain the blank material which has a high deodorizing effect and excellent washing durability and can be regenerated by incorporating acidic groups substd. with at least one kind of the metal ions selected from a specific group into this material. CONSTITUTION:The acidic groups substd. with at least one kind of the metal ions selected from the group consisting of Zn<2+>, Cu<2+>, Ni<+>, Mn<2+>, Ag<+>, and Fe<2+> are incorporated at 1.16X10<-5> to 1.16X10<-2> gram equiv./gram polymer into the deodorizing blank material consisting of a polymer having the acidic groups. The acidic group refers to carboxylic acid and sulfonic acid groups. The removal of malodors is difficult if the amt. of the acidic groups is below the prescribed amts. The form of the deodorizing blank material is unstable if the amt. of the acidic groups exceeds the prescribed amt. The deodorizing blank material consists of the polymer having the acidic groups and the form thereof signifies structures consisting of fibers, namely staples, tow, top non- woven, fabrics, spun yarn, woven fabrics, knitting, etc., or film and plastic molded goods and is more preferably to be the fiber from having large specific surface areas.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorizing material that absorbs a bad odor and deodorizes it.

[0002]

2. Description of the Related Art Conventionally, the odor of socks and underwear has been regarded as a problem in the field of clothing, and from the viewpoint of antibacterial and antifungal properties, copper compounds (JP-A-61-231202) and quaternary ammonium salt compounds of organic silicones have been used. (JP-A-61-282474
No.) and various antibacterial agents (JP-A-61-258076) have been tried to deodorize.

Further, a mixture of ferrous sulfate and L-ascorbic acid (JP-A-61-29611) and a metal phthalocyanine compound (JP-A-62-6953, JP-A-62-6953).
No. 6978, JP-A No. 62-6986, etc.) has been attempted to eliminate a bad odor.

On the other hand, attempts have been made to deodorize with extracts from natural Camelliaaceae plants (Japanese Patent Publication No. Sho 61-22978) and substances extracted from natural conifers (Japanese Patent Laid-Open No. 59-225062). There is.

[0005]

However, these deodorizing and deodorizing techniques do not always provide a sufficient deodorizing effect.
It was poor in practicality.

The present invention provides a deodorizing material having a large deodorizing effect, excellent washing durability, and reproducible morphological stability.

[0007]

In order to achieve such an object, the present invention has the following constitution. That is, a deodorizing material composed of a polymer having an acidic group, Zn ²⁺ , Cu ²⁺ ,
1.16 × an acidic group substituted with at least one metal ion selected from the group consisting of Ni ⁺ , Mn ²⁺ , Ag ⁺ and Fe ²⁺
It is a deodorizing material characterized by containing 10 ^{−5 to} 1.16 × 10 ⁻² gram equivalent / gram polymer.

The contents of the present invention will be described in more detail below. In the present invention, the acidic group means a carboxylic acid or sulfonic acid group. In order to impart the deodorizing performance that is the object of the present invention, hydrogen ions of the acidic group are Zn ²⁺ , Cu ²⁺ , Ni ⁺ , Mn.
It is substituted with at least one metal ion selected from the group consisting of ²⁺ , Ag ⁺ , and Fe2 ⁺ .

In the present invention, the content of the acidic group thus substituted with a predetermined metal ion is 1.16 × 10 ^−5.
˜1.16 × 10 ⁻² gram equivalent / gram polymer.

When the amount of the acidic group substituted with a predetermined metal ion is less than 1.16 × 10 ⁻⁵ gram equivalent / gram polymer, the bad odor such as hydrogen sulfide odor which is the object of the present invention should be eliminated. If it exceeds 1.16 × 10 ^-2 gram equivalent / gram polymer, the form of the deodorizing material becomes unstable and the physical properties such as strength are remarkably deteriorated.

Further, in the present invention, in addition to the acidic group substituted with a predetermined metal ion, a free acidic group is 2.3 ×.
10 ^{-4 to} 1.14 × 10 ^-2 gram equivalent / gram Polymer is also included, and in addition to acidic malodor such as hydrogen sulfide, basic malodor such as ammonia and alkylamine can be deodorized at the same time. It is preferable because it is effective for deodorizing the bad odor which is the object of the present invention.

Further, in the present invention, in addition to an acidic group substituted with a predetermined metal ion and a free acidic group, an acidic group substituted with a quaternary ammonium ion is 5.81 × 10 ^−5.
〜3.49 × 10 ^-3 Gram equivalent / gram When polymer is also included, it can have antibacterial and deodorant properties as well as mite-proof properties when applied to clothing and bedding materials. Therefore, it is preferable.

The deodorizing material referred to in the present invention is made of a polymer having an acidic group, and its form is a structure made of fibers, specifically staple, tow, top non-woven fabric, Structures such as spun yarn, woven fabrics and knits,
Alternatively, it means a film, a plastic molded product or the like, but in order to effectively achieve the object of the present invention, a fiber form having a large specific surface area is preferable.

As the polymer material of the fiber at that time, synthetic fiber such as polyamide type, polyester type, polyacrylonitrile type, or semi-synthetic fiber such as rayon is used, and an acidic group is introduced. In this case, polyamide or polyester synthetic fibers are technically easier and preferable.

Next, as means for introducing an acidic group such as carboxylic acid or sulfonic acid into the inside of the deodorizing material, a method of copolymerizing a monomer having a carboxylic acid or sulfonic acid group with the deodorizing material polymer, carboxylic acid or sulfone is used. There is a method of blending a polymer having an acid group with a deodorant material polymer. Copolymerization includes random copolymerization, block copolymerization,
Although any of graft copolymerization can be applied, a method by graft copolymerization (hereinafter referred to as graft polymerization) is preferable because it is technically and economically easy.

Examples of the vinyl monomer having an acidic group referred to in the present invention include vinylcarboxylic acid compounds such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and butenetricarboxylic acid, allylsulfonic acid and styrenesulfonic acid. A vinyl sulfonic acid compound or the like is used.

As a method of graft-polymerizing these vinyl monomers having an acidic group onto a polyester-based molded article, for example, an organic peroxide such as benzoyl peroxide is preliminarily used with a swelling agent such as monochlorobenzene for polyester-based molding. A vinyl monomer having an acidic group such as acrylic acid or methacrylic acid alone or mixed and subjected to heat treatment in an aqueous solution to perform graft polymerization, or benzoyl peroxide. There is a method of performing a heat treatment in a liquid in which an organic peroxide catalyst, a swelling agent such as monochlorobenzene, and the above-mentioned vinyl monomer having an acidic group are present to perform graft polymerization.

As a method of graft-polymerizing the vinyl monomer having an acidic group on the polyamide polymer, a catalyst such as ammonium persulfate or potassium persulfate and the vinyl having an acidic group such as acrylic acid or methacrylic acid described above are used. There is a method in which a monomer is used alone or in combination and heat treatment is performed in a liquid to perform graft polymerization.

In order to provide the deodorant material of the present invention with higher durability and reproduction performance, it is preferable to introduce the above-mentioned acidic groups into the polymer of the deodorant material, but in some cases, the surface of the deodorant material may be introduced. The polymer layer having an acidic group may be discontinuously arranged to impart the durability performance and the reproduction performance, which are the objects of the present invention. In this case, it is preferable that the proportion of the surface of the polymer layer having an acidic group is large. In order to discontinuously dispose the polymer layer having an acidic group on the surface of the deodorizing material as described above, the polymer layer may be discontinuously attached to the surface by an ordinary resin processing method.

The deodorizing material of the present invention may be substituted with an quaternary ammonium ion for the acidic group, if necessary, in order to impart antibacterial properties in addition to the deodorizing performance.

As the quaternary ammonium ion source in that case, a saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group, or a hydrocarbon group constituting the nitrogen heterocycle of the nitrogen compound and these groups A quaternary nitrogen compound having a combination of hydrocarbon groups, which has antibacterial and antifungal properties, can be preferably applied.

Among them, the total number of carbon atoms in the above hydrocarbon group is 1.
A quaternary nitrogen compound having a value of 0 or more, preferably 15 or more has excellent performance.

A typical example of the quaternary nitrogen compound which can be used in the present invention is a quaternary ammonium salt represented by the following general formula.

[0024]

[Chemical 1]

Here, R _{1 to} R ₄ each represent a monovalent hydrocarbon group, but in place of any two or four of these hydrocarbon groups, a nitrogen-containing heterocycle may be formed. It may have a structure having one or two divalent hydrocarbon groups having a bond.

From the viewpoint of improving antibacterial properties, the total number of carbon atoms of all hydrocarbon groups is preferably 10 or more, particularly 15 or more.

Further, X ^- represents a halogen ion, typically chloride ion, bromine ion is used.

Specific examples of the compound represented by the general formula include lauryl dimethyl benzyl ammonium chloride, cetyl dimethyl benzyl ammonium bromide, stearyl trimethyl ammonium chloride, cetyl pyridinium chloride and the like.

These basic nitrogen compounds having antibacterial properties may be used alone or in combination of two or more.

In the deodorizing material of the present invention, in addition to the acidic group substituted with a predetermined metal ion, K ⁺ , Na ⁺ , Ca
^Even if some acidic groups substituted with other metal ions such as ²⁺ , Mg2 ⁺ and Al3 ⁺ are mixed, the object of the present invention is not impaired.

Further, even if the deodorizing material of the present invention contains various antibacterial substances, the object of the present invention is not impaired, and rather, antibacterial performance can be imparted at the same time, which is preferable.

The measuring method of the deodorizing performance in the present invention is as follows.

For deodorization of ammonia, 80 μl of 0.30% ammonia water was dropped into a 500 cc poly container, 3 g of the deodorant material was then placed in the polyethylene resin container, the container was sealed, and the residual ammonia concentration after 20 minutes was measured. . The measurement method uses a gas detector tube manufactured by Gastec Co., Ltd., and the amount of ammonia (ppm) in 100 cc of gas in the plastic container
To measure. In this method, the ammonia concentration at the start is about 150 ppm, and the value after 20 minutes is 10 p.
If it is pm or less, it can be said that it has a good ammonia deodorizing performance.

For deodorizing hydrogen sulfide, as in the case of ammonia, 300 mg of iron sulfide in a 500 cc container made of polyethylene resin,
100 μl of 0.6% sulfuric acid is dropped, and subsequently, 3 g of the deodorizing material is put in the poly container and sealed, and the residual hydrogen sulfide concentration after 20 minutes is measured. The measuring method used was a gas detector tube manufactured by Gastec Co., Ltd.
The hydrogen sulfide concentration (ppm) in 00 cc of gas is measured.
With this method, the hydrogen sulfide concentration at the start is about 20 ppm
If the value after 20 minutes is 5 ppm or less, it can be said that good hydrogen sulfide deodorizing performance is obtained. The present invention will be further described below with reference to examples.

[0035]

【Example】

(Examples 1 to 7 and Comparative Examples 1 to 15) 3 denier 51 mm staples made of 6 nylon were packed in an over-meier type package dyeing machine, scoured by a usual method, and then acrylic acid was applied to the object to be treated. A treatment bath containing 7% by weight, 21% by weight of methacrylic acid, 1% by weight of ammonium persulfate as a catalyst with respect to the object to be treated, and 3% by weight of a formalin condensate of sodium sulfite was prepared, and the treatment solution was changed from in to out. It was moved, the temperature was raised from 40 ° C. at a rate of 1 ° C./min, and heat treatment in liquid was performed at 70 ° C. for 60 minutes.

It was confirmed by neutralization titration that the carboxyl group of 2.12 × 10 ⁻³ gram equivalent / gram of the polymer was introduced into the inside of the fiber. Next, after washing this with water, the treatment bath is adjusted with an Overmeier type package dyeing machine in a similar manner so that sodium carbonate is 20% by weight with respect to the object to be treated, and heat treatment is performed at 80 ° C. for 30 minutes,
The hydrogen ion of the carboxyl group introduced into the fiber was replaced with sodium. It was confirmed by neutralization titration that the sodium substitution rate was 97.8%.

Next, this product was treated in the same manner with an over-meier type package dyeing machine, and various metal salts were applied to 1
The treatment bath was adjusted to 0% by weight, treated at 30 ° C for 10 minutes, heated to 80 ° C, continuously treated for 10 minutes, washed with water, and then washed with 2 cc / l acetic acid aqueous solution at 25 ° C.
For 5 minutes.

The product was measured by the above-mentioned deodorization measuring method, and as a result, as shown in Table 1, a good deodorizing performance was shown.

[0039]

[Table 1]

For comparison, ordinary 6-nylon staple without graft polymerization (Comparative Example 1), 6-nylon staple graft-polymerized with 7% by weight of free acrylic acid and 21% by weight of free methacrylic acid (Comparative Example 2) ),
And the sample prepared in Comparative Example 2 in which the hydrogen ion of the carboxyl group was replaced with Na ⁺ ion (Comparative Example 3)
Each of them was separately prepared and the deodorizing performance was measured, but good performance was not obtained as compared with the product of this example.

Further, Zn ²⁺ , Cu ²⁺ , Ni ⁺ , Mn ²⁺ , Ag ⁺ , Fe
Treatment with ions other than ²⁺ , that is, various metal ions such as Ca ²⁺ , Mg ²⁺ , and Al ³⁺ , did not give good deodorizing performance (Comparative Examples 4 to 6).

Further, the same treatments as those in the above-mentioned examples were carried out except that the substitution amount of predetermined metal ions was variously changed (Comparative Examples 7 to 12). Although the deodorizing performance of ammonia was good, the deodorizing performance of hydrogen sulfide was poor.

Separately, 50% by weight of acrylic acid and 150% of methacrylic acid were added to the object to be treated by the same method as in the above-mentioned embodiment.
Graft polymerization was performed in a weight percentage. The amount of free carboxyl groups grafted was 162.7 × 10 ⁻⁴ gram equivalent / gram polymer. For this sample, 50% by weight of sodium carbonate was used to replace the hydrogen ion of the carboxyl group with Na ⁺ ion, and then one of zinc sulfate, copper sulfate, silver nitrate, nickel chloride, manganese chloride, and ferrous chloride metal salt. 100% by weight of one type was used to prepare ones substituted with the amount of acidic groups and predetermined metal ions (Comparative Examples 13 to 18). Although these samples had good deodorizing performance, the fiber elongation was remarkably reduced, and spun yarns, non-woven fabrics, etc. could not be made in terms of physical properties.

The evaluation results of Comparative Examples 1 to 18 are shown in Table 1 together with the evaluation results of Examples 1 to 7.

(Examples 12 to 17) With respect to the deodorizing materials obtained in Examples 1 to 6, household detergent Zab [manufactured by Kao Corporation]
Using 2 g / l, a home-use washing machine manufactured by Toshiba Corp., with a bath ratio of 1:50, washing at 40 ° C. for 10 minutes, and after washing for 5 minutes, overflow water washing twice, and washing times once. After repeated washing 5 times, the deodorizing performance of ammonia and hydrogen sulfide was measured, and as shown in Table 2, good values were shown.

[0046]

[Table 2]

(Examples 18 to 23, Comparative Examples 24 to 29)
Ammonia 2,000 p was added to the deodorizing materials obtained in Examples 1 to 6.
After leaving it in a container of pm and hydrogen sulfide of 2,000 ppm for 1 hour to sufficiently absorb the odor, home washing was performed once by the same method as in Examples 12 to 17 to measure the deodorizing performance ( Examples 18-23).

For comparison, the deodorizing performance was also measured for those that were not washed after adsorbing the above-mentioned two kinds of gases (Comparative Examples 24 to 29). The results of these evaluations are also shown in Table 3. From Table 3, it can be seen that the deodorizing material of the present invention has extremely excellent washing durability and deodorizing performance with excellent reproduction performance.

[0049]

[Table 3]

Example 21 Alkyl phosphate surfactant (HLB: 11.3) prepared by adding a false twist textured woven fabric composed of ordinary polyethylene terephthalate 3 denier-48 filaments with 3 g / l of benzoyl peroxide and polyethylene glycol. ) 5 g / l, monochlorobenzene 10 g / l, acrylic acid 10% owf, methacrylic acid 3
In a liquid consisting of 0% owf, the temperature was gradually raised from a low temperature at a bath ratio of 1:20, and an in-liquid treatment was performed at 110 ° C. for 60 minutes.

Into this product, 2.91 × 10 ⁻³ gram equivalent / gram of carboxyl group was introduced.

Next, this product was added with sodium carbonate 8 g / l.
After treatment with the above solution at 60 ° C. for 30 minutes and washing with water, cupric chloride 10% owf and lauryldimethylbenzylammonium chloride 10% owf are added to the solution at 50 ° C. for 30 minutes.
The treatment was performed for a minute. Next, in an acetic acid solution of 1 cc / l, 25
After washing at C for 2 minutes, washing with water-deliquoring and drying were performed.

Of the carboxyl groups of the obtained deodorizing material, 1.20 × 10 ⁻³ gram equivalent / gram polymer was Cu.
Substituted with ²⁺ ions, 0.15 × 10 ^-3 gram equivalent / gram polymer is replaced with quaternary ammonium ion, and the rest 1.56 × 10 ^-3 gram equivalent / gram polymer is present in the form of free carboxyl group. Was.

The residual amount of ammonia in the deodorization measurement of this product was 1 ppm or less, and the residual amount of hydrogen sulfide was 1 ppm.
It was below ppm. In addition, the antibacterial performance was evaluated based on the method established by the Textile Products Sanitary and Processing Council (SEK). As a result, the difference in the increase / decrease value of the bacteria was 5.5 or more, and the antibacterial performance was extremely good.

Example 22 Acrylic fiber 3 denier-7 containing 75% by weight of acrylonitrile, 5% by weight of methyl acrylate and 20% by weight of sodium allyl sulfonate
A 6 mm staple was manufactured. This was gradually heated to 1% in a solution of copper sulfate 10% owf and a bath ratio of 1:30,
The treatment was performed at 00 ° C for 30 minutes. Next, sulfuric acid 0.5cc
A deodorizing material was obtained by performing a treatment for 2 minutes at 25 ° C. in a liquid of 1 / l.

Of the carboxyl groups of the obtained deodorizing material, 1.23 × 10 ⁻⁴ gram equivalent / gram polymer was Cu
It was replaced by ²⁺ ions.

The residual amount of ammonia in the deodorization measurement of this product was 4 ppm, and the residual amount of hydrogen sulfide was 2 pp.
It was m or less.

[0058]

EFFECTS OF THE INVENTION The present invention provides a molded article having excellent deodorizing effect of hydrogen sulfide and ammonia odor, which is excellent in durability and reproducibility, and can be used as bedding such as futon, sheets, blankets, mats and curtains. It can be widely used for deodorizing materials such as pets, fish and meat.

In particular, the zinc-substituted product is preferably used for products requiring coloring such as innerwear, socks and sportswear, since it is not colored by metal ions.

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Claims (2)

[Claims] 1. A deodorizing material composed of a polymer having an acidic group, which is at least one metal selected from the group consisting of Zn ²⁺ , Cu ²⁺ , Ni ⁺ , Mn ²⁺ , Ag ⁺ and Fe ^2+. A deodorizing material containing an ion-substituted acidic group in the range of 1.16 × 10 ⁻⁵ to 1.16 × 10 ⁻² gram equivalent / gram polymer. 2. The deodorizing material according to claim 1, wherein the deodorizing material has a fiber form.