JP2020006158A - Deodorant structure - Google Patents

Abstract

To provide a deodorant structure that can quickly and persistently scavenge aldehydes.SOLUTION: Aldehydes are removed using a deodorant structure obtained by including in a base material one or more selected from O-substituted hydroxylamine derivatives represented by the general formula (1) in the figure and chemically acceptable salts thereof. (In the formula, R represents a hydrogen atom or C1-4 alkyl group; n represents an integer from 1 to 6; and multiple occurrences of R may be identical or different.)SELECTED DRAWING: None

Description

  The present invention relates to a deodorant structure effective for capturing aldehydes such as acetaldehyde and formaldehyde.

  Aldehydes such as acetaldehyde and formaldehyde are typical odor substances in a living environment, and cause an unpleasant odor even at a low concentration because the odor threshold is extremely low. It is known that these aldehydes are generated from synthetic resin, plywood, cigarette smoke and the like indoors and in automobiles, and cause sick house syndrome and sick car syndrome. These aldehydes are also suspected of being carcinogenic and pose a risk to health if humans are routinely exposed to them. Therefore, the Ministry of Health, Labor and Welfare specifies indoor concentration guideline values of 0.03 ppm for acetaldehyde and 0.08 ppm for formaldehyde. Accordingly, there is a need for a means for quickly and continuously removing aldehydes.

  Lower aldehydes such as acetaldehyde and formaldehyde have low boiling points, so that inorganic porous materials such as silica gel and activated carbon, which are widely used as deodorants, have low capture efficiency. Thus, a method of trapping aldehydes by chemically reacting an aldehyde with an aldehyde scavenger composed of a hydrazine derivative, an amine, an amino acid, or a urea derivative has been disclosed (for example, see Patent Documents 1 to 3).

  However, the methods described in these patent documents have problems such as insufficient capture efficiency, the capture agent itself becoming a source of odor, or the aldehydes being re-released over time even once the aldehydes are captured. there were. In addition, when the aldehyde scavenger described in these patent documents is used in a house or an automobile for the purpose of preventing sick house syndrome or sick car syndrome, these places become hot in summer and the like, so that performance is reduced. Was a problem.

JP-A-4-358536 JP-A-11-4879 JP 2012-120708 A

  In view of the background of the related art, an object of the present invention is to provide a deodorant structure that exhibits an excellent trapping effect upon contact with an aldehyde.

  Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that they contain at least one specific O-substituted hydroxylamine derivative or a chemically acceptable salt thereof. The present inventors have found that a sexual structure captures aldehydes promptly and continuously, and has completed the present invention.

That is, the present invention has the following gist.
[1]
A deodorant structure comprising at least one O-substituted hydroxylamine derivative represented by the following general formula (1) or a chemically acceptable salt thereof.

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. N represents an integer of 1 to 6. A plurality of Rs may be the same or different.)
[2]
In the O-substituted hydroxylamine derivative represented by the general formula (1), R is a hydrogen atom, and n is an integer of 1 to 4, or a chemically acceptable salt thereof. The deodorant structure according to [1], which contains one or more types.
[3]
The deodorant structure according to [1] or [2], wherein the substrate of the structure is a fibrous material, a sheet-like material, a sponge-like material, or a board-like material.
[4]
Fabrics, knits, non-woven fabrics, yarns, ropes, string-like fibrous materials whose base material of the structure is composed of synthetic fibers, semi-synthetic fibers, natural fibers, glass fibers, carbon fibers, ceramic fibers, and mixed fibers thereof; The deodorizing structure according to [1] or [2], which is a sheet or sponge made of natural rubber or synthetic rubber; or a board made of wood, plywood or gypsum.
[5]
The base material of the structure is a synthetic fiber such as a polyester fiber, a polyamide fiber, a polyacrylonitrile fiber, a polypropylene fiber, a polyethylene fiber, a polyvinyl chloride fiber, a fluorine fiber, an aramid fiber, a sulfone fiber, Semi-synthetic fibers such as rayon and acetate fibers, natural fibers such as cotton, wool, silk, and hemp, glass fibers, carbon fibers, ceramic fibers, and mixed fibers thereof. Fibrous materials: Sheets and sponges made of polyester resin, polyamide resin, polyethylene resin, polypropylene resin, fluorine resin, silicone resin, polyimide resin, polyvinyl chloride resin, natural rubber, and synthetic rubber [1] or a board-like material made of wood, plywood, gypsum, etc. Deodorant structure according to 2].
[6]
The method according to any of [1] to [5], wherein one or more O-substituted hydroxylamine derivatives represented by the general formula (1) or chemically acceptable salts thereof are supported on a substrate. A method for producing an odorous structure.
[7]
A method for removing aldehydes, comprising using the deodorant structure according to any one of [1] to [5].

  The deodorant structure of the present invention quickly and continuously captures aldehydes. As a result, aldehydes harmful to the human body can be reduced and the living environment of humans can be improved.

  The deodorant structure of the present invention is characterized by containing one or more kinds of specific O-substituted hydroxylamine derivatives or chemically acceptable salts thereof.

  In the O-substituted hydroxylamine derivative represented by the general formula (1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group includes a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. n represents an integer of 1 to 6. R is preferably a hydrogen atom, and n is preferably an integer of 1 to 4 from the viewpoint of high aldehyde scavenging ability.

  Part or all of the O-substituted hydroxylamine derivative (1) may be a chemically acceptable salt with an inorganic acid or an organic acid. The type of the salt is not particularly limited, but includes, for example, hydrochloride, hydrobromide, perchlorate, silicate, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate, phosphoric acid Inorganic salts such as salts, acetates, citrates, fumarates, maleates, trifluoromethanesulfonates, trifluoroacetates, benzoates, and organic acid salts such as p-toluenesulfonate. Inorganic acid salts are preferred because they are inexpensive, and hydrochlorides are more preferred.

  Since the O-substituted hydroxylamine derivative (1) has a carboxy group in the molecule, the carboxy group may form an inner salt with an alkoxyamino group in the molecule. Further, a part or all of the carboxy group may be a carboxylate. The type of the carboxylate is not particularly limited, and examples thereof include an alkali metal salt such as a lithium salt, a sodium salt, a potassium salt, and a cesium salt, and an ammonium salt.

  In the present invention, the O-substituted hydroxylamine derivative (1) or a chemically acceptable salt thereof, which is used as an aldehyde scavenger, is partially commercially available, but the method described in Patent Document (JP-A-5-86012) is used. Can be prepared.

  The base material of the deodorant structure of the present invention is not particularly limited. For example, polyester-based fibers, polyamide-based fibers, polyacrylonitrile-based fibers, polypropylene-based fibers, polyethylene-based fibers, polyvinyl chloride-based fibers, fluorine-based fibers Fibers, synthetic fibers such as aramid fibers and sulfone fibers, semi-synthetic fibers such as rayon and acetate, natural fibers such as cotton, wool, silk, hemp, glass fibers, carbon fibers, ceramic fibers, etc. Woven fabric, knitted fabric, non-woven fabric, fibrous material such as thread, rope, string, or polyester resin, polyamide resin, polyethylene resin, polypropylene resin, fluorine resin, silicone resin, polyimide resin, polyvinyl chloride Sheets or sponges made of resin, natural rubber, synthetic rubber, etc., or wood, plywood, plaster Board-like material or the like made of the like.

  The deodorant structure of the present invention can be used for any purpose depending on the purpose and use. Although the use is not particularly limited, for example, it can be used for curtains, carpets, wall coverings, automobile interior materials, furniture and the like.

  The method for producing the deodorant structure of the present invention is not particularly limited. For example, for example, an O-substituted hydroxylamine derivative represented by the general formula (1) or a chemically acceptable salt thereof (hereinafter, referred to as a salt) , "O-substituted hydroxylamines") on a substrate. The O-substituted hydroxylamines may be supported alone or as a mixture of two or more.

  The method for supporting the O-substituted hydroxylamines on the substrate is not particularly limited. For example, the O-substituted hydroxylamines are dissolved in a solvent such as water to form a solution, and then the solution is applied to the above-described substrate. A method of applying is exemplified.

Loading of O- substituted hydroxylamines to the substrate is freely adjustable according to the purpose, is not particularly limited, O- substituted hydroxylamines of 0.1 to 10 g / m ² The range is preferable, and the range of 0.5 to 5 g / m ² is more preferable.

  Hereinafter, the present invention will be specifically described, but the present invention should not be construed as being limited to these examples.

  The base material is a commercially available carpet (made of polyester / acrylic resin / manufactured by REC), a curtain (made of polyester / manufactured by Shinkol), a rubber sponge (made of natural rubber / manufactured by Tokyo Sound Protection Company), and a wallpaper (made of polyvinyl chloride resin / (Manufactured by Asahipen).

Examples 1 to 8
An aqueous solution of a capturing agent containing 5% by weight of (aminooxy) acetic acid was applied to a substrate (10 cm in length and 10 cm in width) at a rate of 20 g / m ² (amount applied as (aminooxy) acetic acid = 1 g / m 2). ² ) and dried at room temperature for 24 hours to obtain a deodorant structure. The deodorant structure was sealed in a Tedlar bag together with 5 L of nitrogen gas, and acetaldehyde gas was added. After standing at room temperature for 2 hours, the gas in the Tedlar bag was adsorbed on a cartridge (product name: Presep-C DNPH, manufactured by Wako Pure Chemical Industries) supporting 2,4-dinitrophenylhydrazine (DNPH). The DNPH-aldehyde condensate was eluted from this cartridge (eluent = acetonitrile), and the DNPH-aldehyde condensate in the eluate was quantified by liquid chromatography (device name: Agilent 1220 Infinity LC, manufactured by Agilent Technologies) and remained. The aldehyde concentration was calculated. Further, the aldehyde capture rate was calculated from the following equation.

  Aldehyde capture rate (%) = [(initial concentration of acetaldehyde−remaining acetaldehyde concentration) ÷ initial concentration of acetaldehyde] × 100.

Comparative Examples 1, 3, 5, 7
It carried out like Example 1-4 except not using (aminooxy) acetic acid.

Comparative Examples 2, 4, 6, 8
The procedure was performed in the same manner as in Examples 1 to 4, except that Chemcatch H-6000HS (hydrazide, manufactured by Otsuka Chemical Co.), which is an existing aldehyde scavenger, was used instead of (aminooxy) acetic acid.

  Table 1 shows the results of Examples 1 to 8 and Comparative Examples 1 to 8.

  As is clear from Table 1, the deodorant structure of the present invention shows higher acetaldehyde trapping performance as compared with the substrate alone or the substrate containing an existing aldehyde trapping agent, and also shows a higher ability to formaldehyde. It showed high capture performance.

Example 9
After the addition of acetaldehyde gas, the reaction was carried out in the same manner as in Example 1 except that the mixture was allowed to stand at room temperature for 24 hours. As a result, the acetaldehyde trapping rate was 99.9%, and the deodorant structure of the present invention passed for a long time. Thereafter, the high aldehyde trapping performance was maintained.

Example 10
The deodorizing structure after trapping acetaldehyde in Example 1 was sealed in a Tedlar bag together with 5 L of nitrogen gas, and allowed to stand at 65 ° C. for 2 hours. The acetaldehyde concentration was less than 0.01 ppm, and it was confirmed that the deodorant structure of the present invention did not release aldehyde again even at a high temperature.

  The deodorant structure of the present invention rapidly and continuously captures aldehydes. As a result, aldehydes harmful to the human body can be reduced and the living environment of humans can be improved.

Claims (7)

A deodorant structure comprising at least one O-substituted hydroxylamine derivative represented by the following general formula (1) or a chemically acceptable salt thereof.
(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. N represents an integer of 1 to 6. A plurality of Rs may be the same or different.)   In the O-substituted hydroxylamine derivative represented by the general formula (1), R is a hydrogen atom, and n is an integer of 1 to 4, or a chemically acceptable salt thereof. The deodorant structure according to claim 1, wherein the structure comprises one or more types.   The deodorizing structure according to claim 1 or 2, wherein the base material of the structure is a fibrous material, a sheet-like material, a sponge-like material, or a board-like material.   Fabrics, knits, non-woven fabrics, yarns, ropes, string-like fibrous materials in which the base material of the structure is composed of synthetic fibers, semi-synthetic fibers, natural fibers, glass fibers, carbon fibers, ceramic fibers, and mixed fibers thereof; 3. A sheet made of natural rubber or synthetic rubber; a sponge made of resin, natural rubber or synthetic rubber; or a board made of wood, plywood or gypsum. 2. The deodorant structure according to 1.   The base material of the structure is a synthetic fiber such as polyester fiber, polyamide fiber, polyacrylonitrile fiber, polypropylene fiber, polyethylene fiber, polyvinyl chloride fiber, fluorine fiber, aramid fiber, sulfone fiber, Semi-synthetic fibers such as rayon and acetate fibers, natural fibers such as cotton, wool, silk, and hemp, glass fibers, carbon fibers, ceramic fibers, and mixed fibers thereof. Fibrous material; polyester resin, polyamide resin, polyethylene resin, polypropylene resin, fluorine resin, silicone resin, polyimide resin, polyvinyl chloride resin, natural rubber, synthetic rubber; sheet material; polyester Resin, polyamide resin, polyethylene resin, polypropylene resin, fluorine A sponge-like material made of a resin, a silicon-based resin, a polyimide-based resin, a polyvinyl chloride-based resin, natural rubber, or synthetic rubber; or a board-like material made of wood, plywood, or gypsum. Item 3. The deodorant structure according to Item 2.   The deodorant according to any one of claims 1 to 5, wherein one or more O-substituted hydroxylamine derivatives represented by the general formula (1) or a chemically acceptable salt thereof are supported on a substrate. Method of manufacturing a structure.   A method for removing aldehyde, comprising using the deodorant structure according to claim 1.