WO1989003694A1

WO1989003694A1 - Deodorant

Info

Publication number: WO1989003694A1
Application number: PCT/JP1988/001074
Authority: WO
Inventors: Yasuko Osawa; Yuji Narutomi; Keiko Kiuchi; Saburo Uchikuga
Original assignee: Sogo Pharmaceutical Company Limited
Priority date: 1987-10-23
Filing date: 1988-10-21
Publication date: 1989-05-05

Abstract

The invention relates to a deodorant which contains as the active ingredient a complex composed of polyamide or its derivative and a metal, and/or a cellulose derivative having acidic or basic groups or both of them bound to cellulose. Conventional deodorants have the defects that their deodorant effect is weak and lasts only a short time and that the effect immediately disappears by washing or the like. On the other hand, the novel deodorant of the present invention not only solves all of these problems but also can be prepared to have various forms adapted for various uses, so that it is particularly excellent in an industrial aspect.

Description

Specification

Title of invention

Deodorants

(Industrial applications)

The present invention relates to a deodorant comprising, as an active ingredient, a complex comprising a polyamine or a derivative thereof and a metal, or cellulose having an acidic group and a basic or basic group bonded thereto.

(Conventional technology)

In general, conventional methods for treating odors include adsorption methods using porous materials such as activated carbon and silicon gel, absorption methods using water and surfactants, oxidation-reduction methods using oxidizing agents and reducing agents, and the like. Various methods are known, such as a neutralization method using an acid or alcohol, a biochemical method using a microorganism or an enzyme preparation, and a combustion method 'a masking method, all of which have a low deodorizing effect and have a deodorizing effect. It has many shortcomings such as short time, secondary pollution, and high cost.

In recent years, the demand for textile products with deodorant functions has been increasing. Textile products have a wide variety of uses, from intermediate materials such as cotton and cloth to futons, interiors, sheets, masks, and disposable diapers. In addition, its role as a deodorant is becoming more important, especially in the comfort of indoor environments and the purification of living environments, as well as in geriatric medical facilities and welfare facilities. Textile products require not only direct contact with the body but also functional and deodorizing properties, as well as safety and washing resistance.

And in these conventional textile products, the deodorant function is It was applied by mechanical or physical post-processing and post-processing such as application, impregnation, coating and mixing.

(Problems to be solved by the invention)

An object of the present invention is to provide a deodorant which has a high deodorizing effect, has a long duration, does not cause secondary contamination, and can be industrially easily produced.

Textile products obtained by conventionally known treatments are limited to applications such as futons that cannot be washed and sheets that can withstand only a few washings. It has several drawbacks, such as loss of functionality in a short time and the potential for disposable products.

In addition, conventionally known treatments are mainly applied to the final textile products, not to the yarns that are the raw materials and the cellulose itself that is the basis of the yarns. It is also difficult to apply to paper and paper products, and the drawback that the scope of application is extremely limited is inevitable.

(Means for determining the problem)

The present inventors have previously found that a metal chelate compound of a sip base has a strong deodorizing effect. It was predicted that it also had the ability to deodorize.

Therefore, based on this finding, we screened many compounds and found that the metal complex of polyamine and its derivatives has a very strong deodorizing ability, and completed the present invention. The metal complex of polyamine or a derivative thereof, which is an active ingredient of the present invention, includes polyamine or a derivative thereof represented by the formula [I] and Co, Fe, NiJCu, Mn, Ti, V, Ce and Mo. And one or more metals selected.

H-CNR '

[I]

(Where £ is 2 or 3,

m is any integer from 0 to 200,

n represents any integer from 1 to 200,

R represents hydrogen or an alkyl group which may be bonded to a polymer,

RR〃 may be the same or different and is hydrogen or one [(0H ₂ ) _£ NH] _x — H (where X represents any integer from 0 to 100)

Conventionally, it has been known that polyvalent amides, such as ethylenediamine diethylenetriamine, form stable complexes with many metals, but these metal complexes have a deodorizing ability. There is no report that it has, and its use as a deodorant is a completely new finding.

Typical constituents of offensive odors are ammonia, hydrogen sulfide, meso-recaptans such as methyl mercaptan, and amines such as trimethylamine, and among them, hydrogen sulfide and mercaptans have extremely low odor thresholds. However, even a very small amount gives a strong odor, and is a source of odors that are difficult to remove with conventional deodorants.

The deodorant of the present invention is not suitable for these conventionally difficult to remove. It has a particularly effective deodorizing ability for odor sources. Although the deodorizing mechanism is unknown at present, it works very quickly against the smell of hydrogen sulfide and mercaptan, and its ability is exhibited effectively in both dry and wet conditions, thus limiting the operating environment.受け Can be provided for a wide range of applications.

The polyamine or a derivative thereof used in the present invention may be a low-molecular-weight polyamine such as ethylenedi'amine / diethylenetriamine or a derivative thereof, but may be a high-molecular-weight polyamine such as polyethyleneimine or a derivative thereof. Derivatives thereof are more preferable for formulation as a deodorant. For example, a complex is formed by reacting polyethylenimine with a metal salt that forms a complex in an aqueous solvent to form a complex, which is then impregnated into silica gel or activated carbon. 'The original deodorant powder can be easily obtained by holding it by an appropriate method such as coating.

It is also preferable to use a polyamine which is previously bound in the polymer. Examples of such polyamines include commercially available weakly basic ion-exchanged resins and chelating resins.For example, any polymer having a benzene ring can be chlormethylated and then dehydrochlorinated to remove any polyamine. It is also possible to obtain a polymer to which is bonded. When salicyl aldehyde or acetyl aceton is reacted with these polyamines, a polyamine Schiff base bound to the polymer can be obtained. In order to form a polymer or a derivative thereof bonded to a polymer into a complex with a metal, the polymer is converted to water or an organic solvent or What is necessary is just to disperse in these mixed solvents and to react with a metal salt in it. !

Metal to form a鍩体is Ri general der to use in the reaction in the form of a _{^{salt, "-, S 0 4 2}} -, N 0 3 -, CH 3 C 0 0 -, , etc. salts with the preferred New

It is also possible to add an alkali metal or a hydroxide of an alkaline earth metal as needed to remove the liberated acid radicals and adjust the pH of the reaction system.

As described above, a deodorant containing a polyamine complex as an active ingredient is a general deodorant that can be widely used for various purposes. A completely new type of deodorant, which has a structurally deodorizing function and is 'conventional', has also been developed by the present inventors.

That is, the other type of deodorant according to the present invention comprises a cellulose derivative obtained by binding an acidic group and / or a basic group to cellulose as an active ingredient.

As described above, in the textile product comprising the cellulose derivative according to the present invention, since the deodorant component is applied to the cellulose by covalent bonds between the deodorant component and the cellulose, the processing is not performed. Completely different from conventional deodorizing function imparting treatments such as application, impregnation, coating, mixing, etc. performed at the stage, and succeeded in imparting washing resistance, which was the first technical issue here It is. It was also confirmed that the textile product comprising the cellulose derivative according to the present invention did not lose its deodorant function even after washing many times. Ό was completed.

The form of the cellulose derivative used in the present invention is not particularly limited, and those generally used in the past, for example, fibers, yarns, cotton, paper, nonwoven fabrics, woven fabrics, and knitted fabrics Fabrics or other types of fabrics, such as pile fabrics, pillows, knitted fabrics, etc. can be used. In short acidic group, Or, if also has a hydroxyl group in cellulose capable of binding a basic group, an acidic group referred to in _c present invention which can be used Te to base What is Li phospho groups , A phosphite group, a polyphosphoric acid group, a carboxyl group and a sulfonic acid group.

In order to introduce these acidic groups, a conventional method may be used. For example, phosphating of phosphoric acid, S "phosphoric acid and polyphosphoric acid uses urea as a condensing agent and an ester between cellulose and cellulose. To form a bond, it is possible to introduce a phosphate group directly into cellulose by using oxychlorinated chloride, and to introduce a carbonyl group by using, for example, sodium chloroacetate. The sulfonic acid group can be easily introduced as a sulfopropyl group when the cellulose is treated with, for example, sultone. Is an amino group and 4-amino ammonium, and includes all primary, secondary and tertiary amino groups, and aliphatic and aromatic amino groups. Any of these salts Sex group can when particular good re introduced to process the alkylamine Mi emissions or the like having a suitable leaving group cellulose. If as a leaving sulfate groups, Nono androgenic, P- Torue And a sulfonyl group. For example, by reacting cellulose and monoethanolamine acidic sulfate in the presence of caustic soda, riaminoethylcellulose can be synthesized. DEA E-cellulose can be obtained by the same method. If cellulose is treated with P-toluenesulfonic acid chloride and tosylated, and then reacted with, for example, ammonia, an amino group can be directly introduced into cellulose.

Some of the cellulose derivatives thus obtained by various methods are shown below, but the scope of the present invention is not limited by them. Cellulose phosphate (P-cell mouth), cellulose phosphite, cellulose cellulose, carboxymethylcellulose (CM-cellulose), carboxy S, Smelechoetinoresenorelose (SE-cell mouth), Sulfopropircellulose, Amino cellulose, Amino ethyl cellulose (AE-cell mouth). GETILAMINO ETHYL CELLULOSE (DEA E CELLULOSE), TRIETYL AMINO ETHYL CELLULOSE (T EAE-CENOLELOSE), EC TE 0LA-CENOLE CELL, PE I-CELLULOSE Cyl (2-hydroxypropyl) amino ethylcellulose (QAE-cellulose), P-aminobenzinoresenorelose.

The details of the deodorizing mechanism of the cellulose derivative according to the present invention must be covered in future studies, but at present it is presumed to be due to a neutralization reaction with malodorous components. That is, a cellulose derivative to which an acidic group such as a phosphoric acid group is bound is basic. It causes a neutralization reaction with odorous substances such as ammonia and trimethylamine to quickly and efficiently deodorize these substances. Cellulose derivatives to which basic groups such as amino groups are bonded can cause a neutralization reaction with acidic malodorous substances, for example, hydrogen sulfide, methyl mercaptan, hydrochloric acid gas, sulfur dioxide gas, etc., and deodorize them. It has the effect of doing. Therefore, both the acidic group and the basic group are usually used in a free form. These deodorizing cellulose derivatives can be used not only in response to each offensive odors, but also to deal with all kinds of offensive odors. It can exhibit a deodorant function as an effective deodorant in a wide range of fields.

Next, the present invention will be described in more detail based on examples. Actual rotation example 1

12.6 g of styrene-dibininolebenzene copolymer beads were mixed with chloromethyl.methyl ether using anhydrous tin (IV) chloride as a catalyst. To this was added 65.1 g of a Schiff base obtained from salicylaldehyde and diethylenetriamine, and the Richsch base was bound to the beads via diamine derived from diethylenetriamine by dehydrochlorination. . This was treated in 6N hydrochloric acid at 60 ° C. for 24 hours to decompose the Schiff base to obtain beads bound only with ethylenediamine. ,

10 g of the obtained beads were dispersed in dimethylformamide, and 5.0 g of cobalt acetate tetrahydrate was added thereto and reacted to obtain 12.2 g of a complex-bound bead. . 0.5 g of these beads were put into a Tedlar bag, and 3 ppm of ethyl mercaptan of 240 ppm was enclosed. The degree of deodorization of the ethyl mercaptan was measured at predetermined time intervals using a gas detector tube, and the deodorization rate was determined. Table 1 shows the results.

Example 2

0.5 g of the bead to which the cobalt complex obtained in Example 1 was bound was put into a Tedlar bag, and 1800 ppm of hydrogen sulfide 2β was encapsulated. At regular intervals, the concentration of hydrogen sulfide was measured using a gas detector tube, and the deodorization rate was determined. A very strong deodorizing effect was observed. Table 2 shows the results.

Example 3

Disperse 10 g of a commercially available chelate resin (trade name: Diaion CR-20) in dimethylformamide, add 5.0 g of cobalt acetate tetrahydrate, and react to form 11.5 g of a complexed resin. Obtained. 0.5 g of this resin was put into a teddy bag, and 240 ppm of ethyl mercaptan 3β was encapsulated. At predetermined times and at intervals, the concentration of ethyl mercaptan was measured using a gas detector tube to determine the deodorization rate. As a result, a very strong deodorizing effect was observed. Table 1 shows the results.

Example 4

0.5 g of the chelate resin to which cobalt was obtained in Example 3 was put into a Tedlar bag, and 1800 ppm of sulfide and hydrogen 2β was encapsulated. A very strong deodorant was obtained by measuring the concentration of hydrogen sulfide using a gas detector tube at predetermined intervals and determining the deodorization rate. A lo effect was observed. Conclusion: ^ is shown in Table 2.

Example 5

10 g of the bead bound with diethylenetriamine obtained in Example 1 was dispersed in a mixed solvent of dimethylformamide and water, and S.Og of ferric chloride was added. An aqueous sodium hydroxide solution was added and the mixture was allowed to react under almost neutral conditions, thereby obtaining 10.6 g of solid-bound beads. 0.5 g of these beads was injected into a Tedlar bag, and 240 ppm of ethyl mercaptan 3 J¾ was encapsulated. At regular intervals, the concentration of ethyl mercaptan was measured using a gas detector tube to determine the deodorization rate. As a result, an extremely strong deodorizing ability was confirmed. Table 1 shows the results.

Example 6

2 * 3 g of polyethyleneimine having a molecular weight of 750 was dissolved in water and reacted with 1.7 g of cobalt acetate tetrahydrate. 10 g of silica gel powder was added to this aqueous solution, and the mixture was concentrated to dryness to obtain a silica gel powder holding a polyethyleneimine-cobalt complex. 0.5 g of this was put into a Tedlar knock, and 1800 ppm of hydrogen sulfide 2β was encapsulated. At regular intervals, the concentration of hydrogen sulfide was measured using a gas detector tube, and the deodorization rate was determined. Table 2 shows the results. Example 7

0.5 g of the beads to which the cobalt complex obtained in Example 1 was bound were dispersed in 50 mL of water and charged into an air bottle. 240 ppm of ethyl mercaptan 3β sealed in a teddy bag was circulated through the air-washing bottle by an air-pump. Inspection after 3 hours When the concentration of ethyl mercaptan was measured using a tube, it was not detected at all, and it was recognized that it had a very strong deodorizing ability even in water.

Example 8

Disperse 10 g of a commercially available weakly basic ion exchange resin containing primary amine (trade name: Diaion WA21) in methanol, and add 5.0 g of salicylaldehyde to form a Schiff base. After that, it was washed with methanol. This was dispersed in water to obtain a齚酸co Baltic tetrahydrate 5. Resin bound metal complex is reacted by adding 0 g 14. 2 _g. 0.5 _{g of} this resin was put into a Tedlar bag, and 240 ppm of ethyl mercaptan 3β was encapsulated. When the concentration of ethyl mercaptan was measured at predetermined intervals using a gas detector tube and the deodorization rate was determined, a very strong deodorizing effect was observed. Table 1 shows the results.

Table 1 Deodorizing effect on ethyl mercaptan

Deodorization rate (%)

30 minutes later 1 hour later 2 hours later 3 hours Results of Example 1 71 86 96 100

〃 3 "60 90 98 100

"5" 45 76 89 100 it 8 "68 89 98 100 z Table 2 Deodorizing effect on hydrogen sulfide

Example 9

10 g of the bleached broad cotton was washed with hot water and immersed in an aqueous solution containing 18 g of urea, 11.5 g of 85% orthophosphoric acid, and 20 g of water for 30 minutes. Then, squeeze the cloth, dry it with a drier at 60, heat it with a hot plate at 150 for 30 minutes, cool it down, wash it with hot water, and then dry it to make the cotton with cellulose bound to phosphoric acid. Obtained. The neutralization capacity of this cotton was 1.20 meq / g.

After the treatment with dilute hydrochloric acid, 0.5 g of the above-mentioned washed and dried broad cotton was put into a Tedlar bag filled with 7,000 ppm of ammonia 2 &. When the ammonia concentration was measured at predetermined intervals using a gas detector tube, the blown cotton showed a very strong basic odor eliminating effect in a short time. Table 3 shows the results.

Example 10

10 g of the bleached broad cotton was washed with hot water and immersed in an aqueous solution of 2 g of monoethanolamine acidic hydrophobic ester, 5 g of caustic soda, 0.4 mJ of cresol, and 13 g of water for 30 minutes. afterwards, The cloth was dried with a dryer at 60 ° C, heated with a 100-plate hot plate for 1 hour, allowed to cool, washed with water, washed with a dilute acetic acid solution, washed again with water, and dried. A blown cotton having a deodorizing function into which a mino group was introduced was obtained. The neutralization capacity of this cotton was 0.4 meq / g.

After the treatment with the dilute caustic soda solution, 0.5 g of the above-mentioned washed and dried cotton wool was put into a Tedlar bag filled with 250 ppm of sulfur dioxide gas 2 J2. When the concentration of sulfurous acid gas was measured at predetermined intervals using a gas detector tube, this broad cotton exerted the effect of deodorizing acidic malodorous substances. Table 3 shows the results. Example 11

10 g of commercially available carboxymethylcell α-snadium (CM-cell mouth-snadium) was suspended in 5% hydrochloric acid 50πιβ to form a free form. 200 ml of ethanol was added to the mixture, dispersed well, and filtered. It was further washed well with ethanol to remove hydrochloric acid and dried.

0.5 g of the CM-cellulose obtained in this way was injected into a teddy bag containing 7,000 ppm of odor gas containing ammonia 2 &. When the concentration of ammonia was measured at predetermined intervals using a gas detector tube, this CM-cellulose exhibited a very strong basic odor eliminating effect in a short time. Table 3 shows the results.

Example 12

0.5 g of commercially available PEI-cellulose (neutralization capacity: 1.50 nieq / g) was injected into a teddy bag containing 250 PPD1 of 2 & I entered. When the concentration of sulfurous acid gas was measured at predetermined times using a gas detector tube, the PEI-cellulose exhibited a very strong deodorizing effect on acidic malodorous substances in a short time. Table 3 shows the results.

Table 3

(The invention's effect) .

The deodorant according to the present invention is of a type having a metal complex of polyamine as an effective component, and a type having a cellulose derivative in which an acidic group and a basic or basic group are bonded to cellulose as an active component. All of them are new and have excellent deodorizing effects. '·

The delicate type deodorant is not only excellent in deodorizing properties, but this bulk powder can be mixed with other components according to the application. It can be formulated into dosage forms and used for a very wide range of applications. However, since the raw materials for the sesame ingredients can be used as they are, commercially available ordinary raw materials, the synthesis of active ingredients is carried out industrially and is excellent. The latter type of deodorant not only has an excellent deodorizing effect as in the former case, but also has a remarkable effect that it can deal with all types of malodors. At that time, there is no deterioration in shochu washability and deodorant function, and a new and outstanding effect that the deodorant effect is maintained for a long time is exhibited.

The present invention:-Since the most basic cellulose derivative itself is deodorized as described above, the deodorizing effect is fundamentally different from the conventional deodorizing treatment of a fiber product. Is high and lasts. Therefore, according to the present invention, the materials of textile products such as yarn, cloth, paper, etc. are also intermediate materials such as cotton cloth, cotton, cloth fabric, and final products such as futons, sheets, clothes, and disposable diapers. A deodorant function can be freely provided.

Moreover, the present invention can be freely applied not only to cotton products but also to deodorization of various paper products such as toy paper, disposable diapers, tissue paper and deodorant wrapping paper. Can be applied to a very good.

Claims

lb Claims

(1) A deodorant containing a polyamine or a derivative thereof and a metal composed of a metal as an impeachable component.

(2) The deodorant according to claim 1, wherein the polyamine is a compound represented by the formula [I].

R '

H- CNR '(CH ₂ ) _A ) _FFL -N- (CHJANR _{N N} -H (I)

(Where ώ is 2 or 3, m is any integer from 0 to 200,

II represents any integer from 1 to 200,

R represents hydrogen or an alkyl group which may be bonded to the polymer;

R 'and IT may be the same or different, hydrogen or

-C (CH ₂ ) j, NHD _x -H (where X represents any integer from 0 to 100).

(3) The deodorant according to claim 1, wherein the polyamine derivative is a Schiff base with salicylaldehyde or acetylaceton.

(4) The deodorant according to claim 1, wherein the metal is Fe. Ni, Cu, Mn, Ti, V, Ce, or Mo. .

(5) A deodorant comprising, as an active ingredient, a cellulose derivative having a deodorizing function obtained by bonding an acidic group and Z or a basic group to cellulose.

(6) The claim wherein the acidic group is a phosphoric acid group, a polyphosphoric acid group, a phosphorous acid group, a carboxyl group and Z or a sulfonic acid group The deodorant according to item 5.

(7) The deodorant according to claim 5, wherein the basic group is an amino group.

(8) A deodorant comprising, as an active ingredient, a complex comprising a polyamine or a derivative thereof and a metal, and a cellulose derivative having a deodorizing function obtained by binding an acidic group and a basic group to cellulose.