JP2000051337A - Deodorant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remove malodor gas mainly composed of formaldehyde by taking a specified formaldehyde scavenger compound as a principal component to cause an irreversible reacting with formaldehyde and take substantially odorless formaldehyde as the base. SOLUTION: A formaldehyde scavenger compound expressed by one of formulas I-III is used in various use forms as a formaldehyde deodorant. In the formulas, R1 and R2 are each hydrogen, alkyl group, or amino group, may form a ring, and at least one of them is an acyl group, or alkoxycarbonyl group. X is -CH- or -N-; R3 is an alkyl group, substituted alkyl group, and may form a bicylic compound with a phenyl ring; and (n) is an integer 2 or higher. R4-R6 may be the same or different, and is a hydrogen atom, alkyl group or acyl group, and R7 and R8 are each a hydrogen atom or alkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The indoor pollution caused by harmful substances (formaldehyde, etc.) originating from house building materials, furniture, etc.
Dizziness, headaches, nausea, imbalance,
It has become a social problem as "sick house syndrome" which causes various symptoms such as impressions of mucous membranes and skin. The most noticeable substance causing these symptoms is formaldehyde, which is generated from adhesives contained in plywood used for floors, walls, ceilings, furniture and the like of houses.
In addition, leather products tanned with formaldehyde and clothing using formaldehyde as a disinfecting and bleaching agent are widely used in daily life, and these cannot be overlooked. The present invention is a general-purpose deodorant, more specifically, a deodorant or a deodorant composition excellent in deodorizing performance of malodorous gas containing formaldehyde, which is a main cause substance of sick house syndrome, as a main component, in particular, building materials, furniture, house interior materials, The present invention relates to a deodorant suitable for use in decorative goods.

[0002]

2. Description of the Related Art For an odorous gas in the air, an adsorption method using an adsorbent such as activated carbon, a masking method using another fragrance, or a method of converting an odorous substance into another substance by a chemical reaction and removing it. And so on. However, in the adsorption method, there is a problem that the deodorizing performance of the adsorbent is deteriorated in a short time and the adsorbed harmful substances are released, and in the masking method using other fragrances, the fragrance used may give a new discomfort, Further, the method using a chemical reaction causes a problem that unnecessary chemical substances remain.

[0003] Even when the harmful substance is formaldehyde, various means for removing it have been proposed.
For example, a method of adsorbing and removing harmful substances such as formaldehyde by activated carbon, specifically, acetaldehyde using activated carbon carrying 0.1 to 20% by weight of a metal carboxylic acid formed into a honeycomb or fiber. JP-A-7-178152 describes oxidative removal of malodorous gases such as aliphatic aldehydes such as aldehydes and formaldehyde. It is said that this adsorbent is used as a deodorant in refrigerators or as an odor gas remover for indoor air purification.

[0004] Further, to a mixed aqueous solution containing a metal salt and hydrazine as an air purifying deodorant for removing acetaldehyde, formaldehyde, trimethylamine, NH _{3 and the} like, a chain magnesium fine powder having a particle size of 0.1 mm or less is added. A deodorant has been proposed in which the resulting suspension is applied to a carrier having air permeability and dried (Japanese Patent Application Laid-Open No. 6-178799).

[0005]

In particular, the conventionally proposed deodorizing agents and deodorizing methods for malodorous gas containing formaldehyde as a main component are mainly directed to the development of adsorbents. While it can remove harmful substances, it is in equilibrium with desorption, and has the disadvantage of releasing presumably adsorbed harmful substances. Therefore, in order to enhance the deodorizing effect, it is ideal to remove formaldehyde by converting and fixing it to another substance by a chemical reaction without a reverse reaction. Advanced.

Accordingly, the present invention provides a deodorizing agent for removing malodorous gas containing formaldehyde as a main component, which is mainly formed of a formaldehyde scavenger compound which causes an irreversible reaction with formaldehyde and is substantially odorless, and a deodorizing method using the same. The purpose is to provide.

[0007]

Means for Solving the Problems The present inventors have attained the above object by forming a formaldehyde scavenger compound represented by any of the following formulas (I) to (III) (hereinafter sometimes simply referred to as a scavenger compound or a scavenger). Have been found to be effectively achieved by using as a formaldehyde deodorant in various usage forms, and have reached the following inventions.

(1) General formula (I)

Embedded image (Where R ₁ and R ₂ represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, or an amino group, and R ₁ and R ₂ form a ring R ₁ , R
_At least one of ₂ is an acyl group, an alkoxycarbonyl group, a carbamoyl or an amino group. X is -CH
Represents-or -N-. )

Formula (II)

Embedded image (Here, R ₃ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and may form a bicyclic ring with a phenyl ring. N represents an integer of 2 or more.)

Formula (III)

Embedded image [Wherein R ₄ , R ₅ and R ₆ may be the same or different, and each represents a hydrogen atom, an alkyl group (eg, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, hydroxymethyl group, 2-hydroxyethyl group, methoxymethyl group, chloromethyl group, carboxymethyl group, cyanoethyl group, etc., alkenyl group (for example, allyl group, 2-butenyl group, 2-chloroallyl group, etc.) ), An aralkyl group (eg, benzyl group, phenethyl group, p-methoxybenzyl group, etc.), an aryl group (eg, phenyl group, p-tolyl group, p-methoxyphenyl group, o-chlorophenyl group, m-hydroxyphenyl group) Or an acyl group (eg, acetyl, propionyl, trifluoroacetyl, chloroacetyl, acryloyl, methacryloyl, etc.), and R ₇ and R ₈ are each a hydrogen atom or an alkyl group (for example, R ₄ to R ₆ ). (2) A formaldehyde scavenger compound is added to a fibrous base material selected from wood or plywood in an amount of 0.1 to 50 g / m ^2.
The deodorant according to the above (1), which is impregnated or applied at a ratio of (3) The deodorant according to the above (1), wherein a layer containing a formaldehyde scavenger compound is attached to the carrier sheet at a rate of 0.1 to 50 g / m ² . (4) A deodorizing method using the deodorizing agent according to any one of (1) to (3) for cleaning indoor air. (5) A board or square material in which the deodorant described in (1) is applied or impregnated to wood or plywood. (6) A fiber or sheet product in which the deodorant described in (1) is applied or impregnated to a fibrous base material or a single sheet. (7) A product in which the deodorant described in (1) is filled in a gas-permeable cartridge. (8) The deodorant described in the above (1) is applied to building materials such as wood and plywood, tatami mats, carpets, flooring materials for flooring, walls, ceiling cloths and boards at a ratio of 0.1 to 50 g / m ² . Impregnated or coated residential building materials, interior materials, and other materials necessary for constructing the house. (9) Furniture composed of a member obtained by impregnating or applying the deodorant described in (1) to wood or plywood and artificial wood in place of the deodorant at a rate of 0.1 to 50 g / m ² .

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred examples of the scavenger compounds represented by the above general formulas (I) and (II) [hereinafter sometimes referred to as scavenger compounds (I) and (II)] are [I-1]. ] To [I-7] and [II
-1] and [II-2]. However, a compound which can be changed into an enol form by tautomerism is also included.

[0012]

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[0013]

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[0014]

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Where R₉~ R₃₀Is hydrogen, alkyl,
Represents an substituted alkyl group, an aryl group, or a substituted aryl group;
₁₆, R₁₇, R₁₈And R₁₉Any one of R and R
_{twenty four}~ R₂₈Must be hydrogen.
R₉And R_Ten, R₁₁And R₁₂, R₂₉And R₃₀Forms a ring
Well, R₁₃~ R_Fifteen, R ₁₆~ R₁₉, R₂₀~ R_{twenty three}And R_{twenty four}
~ R₂₈Means that any two substituents in each group form a ring
It may be formed. m is an integer of 3 to 6, and l (ell) is 2 or more
Represents the above integer. General formulas [I-1] to [I-7],
Scavengers represented by [II-1] and [II-2]
Among them, particularly preferred are the following (S-1) to
(S-25), but is not limited to this.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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The compound (S-10) is an oligomer or a polymer having l (ell) repeating units. Scavengers (S-1) to (S-6) and (S-6)
-12) to (S-23) are commonly commercially available compounds, and (S-7) to (S-11) are "Bulletin of the
Chemical Society of Japan ", Vol. 39, 1559-156
7, 1734-1735 (1966), "Chemische
der Berichte "54B1802-1833, 244
1-2479 (1921), "Beilstein Handbuch de
r Organischer Chemie ", page 98 (1921), etc. (S-24) and (S-25) can be easily synthesized by" Beilstein Han
dbuch der Organischen Chemie "First Supplement, Volume 4, 35
It can be synthesized by the methods described on pages 4, 3 and 63 of the same book.

The compound represented by the general formula (III) (glycoluril compound) [hereinafter sometimes referred to as a scavenger compound (III)] is a polymer chain (for example, polyethylene chain) via a group of R ₄ to R _6. , Polypropylene chains, etc.). Further, in this case, a connecting group such as -CO-, -COO-,
H- and the like include those in which the group of R ₄ to R ₆ and the polymer chain are linked.

Preferred examples of the scavenger compound (III) are as follows. (S-26) to (S-56)

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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The scavenger compound (II) as described above
I) (S-26) to (S-56) are disclosed in British Patent No. 71.
No. 7287, U.S. Pat. Nos. 2,731,472 and 3,187.
No. 004, H. Pauly; Chem. Ber. 63B, 2063 (1
930), FBSlezak; J. Org. Chem. 272181 (1962), J. Ne.
matollahi; the following reaction route (A) or (B) from urea or a substituted urea and an α-diketo compound (glyoxal, methylglyoxal, diacetyl, etc.) according to the method described in J. Org. Chem. 282378 (1963). Are synthesized by

[0037]

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By subjecting glycoluril to alkylation, acylation, hydroxymethylation, alkoxymethylation, halomethylation, etc. by a conventional method, alkyl, acyl, hydroxymethyl, alkoxymethyl and halomethyl derivatives can be obtained. it can.

The following shows a synthesis example. Glycoluril (glycoluril), exemplified compound (S-2
Synthesis of 6) After adjusting 1451 g (10.0 mol) of a 40% aqueous glyoxal solution to pH 7.0, 721 g (12.0 mol) was prepared.
mol) of urea, and the mixture was stirred at room temperature for 5 hours. About 900
ml of water were distilled off under reduced pressure, and the precipitated crystals were filtered and dried to obtain 4,5-dihydroxy-2-imidazolidinon.
e was obtained in an amount of 768 g (65% yield). 4,5-Dihydroxy
-2-imidazolidinone 590 g (5 mol) and urea 300 g (5 mol) are dissolved in 1 liter of water and 30 ml
Was added and the mixture was stirred at 90 ° C. for 1 hour. After cooling, the precipitated crystals were filtered, washed with water, dried, and 526 g of Glycolur.
il was obtained (yield 74%). Melting point 300 ° C or higher.

Elemental analysis value (C ₄ H ₆ N ₄ O ₂ ) Theoretical value H; 4.26% C; 33.81% N; 39.42% Experimental value H; 4.17% C; 33.64% N; 39.45%

1-Methylgycoluril, an exemplary compound (S-
Synthesis of 27) 4,5-Dihydroxy-2-imidazolidinone 118g
(1 mol) and 74 g (1 mol) of methylurea,
Dissolve in 100 ml of water, add 5 ml of concentrated hydrochloric acid and add 90 ° C
For 1 hour. After distilling off about 50 ml of water, 300 ml of methanol was added and filtered. The crystals were washed with methanol and dried to obtain 100 g of 1-methylglycoluril (64% yield). 246-255 ° C (dec.)

Elemental analysis value (C ₅ H ₈ N ₄ O ₂ ) Theoretical value H; 5.16% C; 38.46% N; 35.88% Experimental value H; 4.95% C; 38.21% N; 35.95%

1,4-Dimethylglycoluril and 1,6-
Dimethylglycoluril, exemplified compounds (S-34) and (S
Synthesis of -35) 5 ml of concentrated hydrochloric acid was added to 145 g (1 mol) of a 40% glyoxal aqueous solution and 148 g (2 mol) of methylurea, and the mixture was reacted at 90 ° C. for 2 hours. After distilling off about 50 ml of water, 200 ml of methanol was added, and the mixture was cooled to room temperature and filtered. The crystals were washed with methanol and then dried.
100 g of a mixture of ylglycoluril and 1,6-dimethylglycoluril was obtained (yield 59%). 228-236 ° C
(Dec.)

Elemental analysis value (C ₆ H ₁₀ N ₄ O ₂ ) Theoretical value H; 5.92% C; 42.35% N; 32.92% Experimental value H; 5.80% C; 42.13% N; 32.94%

Scavenger (I) used in the present invention
To (III) may be used in combination of two or more,
It is also possible to use in combination with other known aldehyde scavengers. In order to use the scavenger compounds (I) to (III) of the present invention as a deodorant for malodorous gas containing formaldehyde as a main component, the scavenger compound may be used alone or as a solution or suspension in water or an appropriate solvent, if necessary. It is applied to building materials, furniture, etc. in any form together with other additives. Here, as the solvent, a solvent having a low boiling point and low harmfulness such as methanol, ethanol and acetone is preferable.

The scavenger compound (I) according to the present invention
Since the deodorant containing at least one of the compounds (III) to (III) has an extremely excellent formaldehyde collecting function, it can be used in any use form. For example, the present invention is applied to the treatment of formaldehyde-containing malodorous gas emitted from house interior goods, furniture, etc. by impregnating building materials, tatami, plywood, sheets, films, boards, cloths, and nonwoven fabrics constituting floors, walls, and ceilings. Specifically, a method of simply loading the scavenger compound into a hanger-type insect repellent container, a method of dissolving in water or an organic solvent and impregnating the material, a method of dispersing in water when insoluble in water, a method of using powder, After mixing with the composition raw material as it is, a method of molding, a method of kneading a compound compatible with the resin into the resin, etc. are conceivable, and it is present in any form of material to effectively reduce the concentration of formaldehyde in the air. Is possible.

For example, an aqueous solution of the above-mentioned scavenger compound is added to an appropriate concentration [for compounds (I) to (II), 1 to 3
0% by weight, and 1 to 15% by weight for the compound (III)], and the nonwoven fabric such as polypropylene or polyester is coated with a scavenger compound at 0.1 to 50 g / m ² , preferably 0.5 to 10 g / m ² . Impregnated so as to obtain the appropriate amount, or sprayed on a suitable base material such as a building material or plywood. Thus, the nonwoven fabric loaded with the scavenger compound of the present invention can be applied to carpets, building interior materials, decorative goods and the like. As the carpet material, for example, a polyolefin crimped fiber is used. The above scavenger compound is sprayed and applied in the form of a solution or a suspension, or kneaded into a material of the fiber and molded. When kneading into a fiber resin, it is usually preferable to mix in a range of 1 to 30% by weight.

Further, as a means for decorating the surface of architectural interior materials and decorative goods, there is a method of transferring a desired decorative layer using a transfer sheet. In many cases, a formaldehyde-emitting material is used. For example, an adhesive for forming a wood plywood, a particle board, a wood fiber board, or the like, a resin constituting the FRP, or a resin constituting the resin base material itself is a formaldehyde-emitting resin such as a urea resin. . When such a transfer object is used, formaldehyde is emitted from the transfer object itself into the room even when the decorative layer is transferred. Thus, in the present invention, a transfer sheet is provided by providing a layer containing the scavenger compound together with a decorative layer and an adhesive layer as a transfer layer on a carrier sheet. Here, as the carrier sheet, various papers, films and sheets of various resins such as polypropylene and nylon are used.

[0049]

The present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention. (Example 1) A regular hexahedron box assembled from six 30 cm square square acrylic plates was prepared and 0.2 ppm was prepared.
With formaldehyde gas. Table 1 below
Formaldehyde scavenger compound S-
5, S-27 was converted to an aqueous solution (S-5 concentration 10% by weight,
A nonwoven fabric of 20 cm square which was impregnated into a nonwoven fabric made of polyester and dried was placed in a constant temperature and humidity room at 30 ° C. The results of measuring the formaldehyde gas concentration after 24 hours are shown in Table 1.

[0050]

[Table 1]

Example 2 Scavenger Compound (S-
27) 5 g of scavenger compound in a newly built Western room 10 m ²
/ M ³ , which was installed in place of a chemical in a commercially available hanger-type insect repellent container instead of the chemical, and the formaldehyde odor was removed. The formaldehyde odor quickly disappeared.

Example 3 A compound shown in Table 2 was used as a scavenger, and a melt flow rate was 30 g / 1.
After blending 1% by weight of the compound in 0 minute polypropylene, it was melted and discharged at 180 ° C by an extruder, and the take-off speed was 60m.
/ Min to obtain a wound undrawn yarn. This undrawn yarn was drawn by a conventional method and subjected to hot air processing with a crimping device to obtain a crimped yarn. A formaldehyde absorption test was performed in the same manner as in Example 1 except that this crimped yarn was used instead of the nonwoven fabric of Example 1. Table 2 shows the obtained results.

[0053]

[Table 2]

The above crimped yarn can be used as a carpet material.

[0055]

According to the present invention, a formaldehyde deodorant containing a specific formaldehyde scavenger compound as a main component is removed by decomposing or fixing formaldehyde to another substance by a chemical reaction in which the scavenger compound has no reverse reaction. It shows very high deodorizing efficiency because it is possible.

Claims (9)

[Claims] 1. A deodorant for formaldehyde-containing malodorous gas comprising a formaldehyde scavenger compound represented by any of the following formulas (I) to (III) as a main component. General formula (I) (Where R ₁ and R ₂ represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, or an amino group, and R ₁ and R ₂ form a ring R ₁ , R
_At least one of ₂ is an acyl group, an alkoxycarbonyl group, a carbamoyl or an amino group. X is -CH
Represents-or -N-. ) General formula (II) (Here, R ₃ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and may form a bicyclic ring with a phenyl ring. N represents an integer of 2 or more.) General formula (III) Embedded image (Where R ₄ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group or an acyl group;
R ₇ and R ₈ each represent a hydrogen atom or an alkyl group. ) 2. The method of claim 1, wherein the formaldehyde scavenger compound is added to a fibrous substrate selected from wood or plywood in an amount of 0.1 to 50.
deodorant according to claim 1 formed by impregnating or coating at the rate of g / m ^2. 3. The deodorant according to claim 1, wherein a layer containing a formaldehyde scavenger compound is attached to the carrier sheet at a rate of 0.1 to 50 g / m ² . 4. A deodorizing method using the deodorizing agent according to claim 1 for purifying indoor air. 5. A plate or square material in which the deodorant according to claim 1 is applied or impregnated on wood or plywood. 6. A fiber or sheet product in which the deodorant according to claim 1 is applied or impregnated to a fibrous base material or a single sheet. 7. A product in which the deodorant according to claim 1 is filled in a breathable cartridge. 8. A deodorant according to claim 1, wherein the deodorant is a building material such as wood or plywood, a tatami mat, a carpet, a flooring for flooring,
0.1 ~ 50g / m for cloth and board for wall and ceiling interior
House building materials, interior materials, and other materials necessary for constructing a house impregnated or applied in the ratio of ² . 9. The method according to claim 1, wherein the deodorant is added to wood or plywood and artificial wood in place of the odor of 0.1 to 50 g / m ^2.
Furniture composed of members impregnated or coated at a rate of