JPH09299466A - Formaldehyde remover - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a formaldehyde remover in which a dry distillation part with a specified b.p. range obtd. by dry distillation of tea is incorporated as an effective ingredient and with which only formaldehyde can be selectively adsorbed and eliminated without decreasing action of a fragrant agent and an insectifuge. SOLUTION: A formaldehyde remover in which a dry distillation part with a b.p. range of 180-200 deg.C at 20mmHg obtd. by dry distillation of tea is incorporated as an effective ingredient is provided. A fragrant agent set consisting of a combination of the dry distillation part and a fragrant agent, and an insectifuge set consisting of a combination of the dry distillation part and an insectifuge are provided. A chemical contg. a fragrant agent and/or an insectifuge and a dry distillation part with a b.p. range of 180-200 deg.C at 20mmHg obtd. by dry distillation of tea are arranged together in a room or a furniture. It is possible thereby to selectively adsorb and remove formaldehdye without decreasing action of the fragrant agent and the insectifuge in the room and the furniture.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a formaldehyde removing agent, and more particularly to a formaldehyde removing agent for selectively removing only formaldehyde without lowering the activity of the aromatic agent and the insect repellent, the removing agent and the aromatic agent. Further, the present invention relates to an aromatic agent set, an insect repellent set combined with an insect repellent, and a method for removing formaldehyde.

[0002]

2. Description of the Related Art Plywood, particle boards, fiber boards, etc. are used for furniture such as chests of drawers, cabinets, etc. These are made by solidifying wood veneers or pieces of wood with an adhesive. Urea resins and melamine urea co-condensation resins are generally used for adhesives, but since these adhesives are manufactured using formaldehyde as one of the raw materials, residual formaldehyde in the adhesive volatilizes, It caused a bad odor (irritating odor) peculiar to furniture. Also, indoors, plywood, particleboard, fiberboard, etc. are used for makeup plywood, furniture, etc., causing volatilization of formaldehyde, causing a bad odor in the room.

On the other hand, the fact that the dry-distilled product of tea leaves has a deodorizing action is disclosed in JP-B-61-8694 and JP-A-53-66.
Although it is a known fact as described in Japanese Patent No. 434, it does not describe the action of removing formaldehyde, and it is also described that only formaldehyde can be selectively removed without adsorbing insect repellents and aromatic agents. Not not.

[0004]

In order to remove the malodor of formaldehyde in such furniture, deodorants such as activated carbon have been conventionally used. However, furniture and the like generally use an insect repellent at the same time. In that case, although activated carbon adsorbs formaldehyde, it also adsorbs the insect repellent and reduces the insect repellent effect. In addition, deodorants such as activated carbon are still used to remove the malodor caused by formaldehyde in the room. However, there are cases where fragrances are used in the room, and in this case, the activated carbon also reduces the aroma action. There was a problem.

Therefore, an object of the present invention is to provide a formaldehyde removing agent which can selectively remove only formaldehyde without deteriorating the effects of aromatic agents and insect repellents. Another object of the present invention is to provide an fragrance set comprising a combination of an fragrance and a dry distillation fraction of tea. Still another object of the present invention is to provide an insect repellent set comprising a combination of an insect repellent and a dry fraction of tea. Yet another object of the present invention is to provide a method for removing formaldehyde in a room or furniture by co-locating a fragrance and / or insect repellent and a chemical containing a dry distillation fraction of tea in the room or furniture. It is in.

[0006]

[Means for Solving the Problems] As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that dry distillation fraction of tea can adsorb formaldehyde, and further, it is sealed in a room, a closet, a cabinet, etc. It was found that formaldehyde can be selectively adsorbed and removed while maintaining the insect repellent and aroma effects when used as a formaldehyde removing agent for furniture having a space. The present invention has been completed based on this finding.

That is, the gist of the present invention is (1) 180 when the boiling point range obtained by dry distillation of tea is 20 mmHg.
Formaldehyde remover containing dry fraction at ~ 200 ° C as an active ingredient, (2) Fragrance, and a combination of dry fraction at 180 ~ 200 ° C when the boiling point range obtained by dry distillation of tea is 20 mmHg. Fragrance set, (3) Fragrance is terpene compound, aliphatic alcohol, aliphatic ester, aromatic alcohol, aromatic ester, musk xylol, coumarin, muscone, civetone, cyclopentadecanone, cyclopentadecanolide The fragrance set according to (2) above, which is at least one non-aldehyde fragrance selected from the group consisting of, ethylene blush rate, cis-jasmone, and maltol, (4) the above (2) used for indoor use ) Or (3) the aromatic agent set, (5) insect repellent, when the boiling point range obtained by dry distillation of tea is 20 mmHg And an insect repellent set comprising a combination of dry fractions at 180 to 200 ° C., (6) The insect repellent according to (5) above, which is at least one selected from the group consisting of paradichlorobenzene, naphthalene, and camphor. Agent set, (7) insect repellent set according to the above (5) or (6), which is used for furniture,
(8) A fragrance and / or insect repellent in a room or furniture,
It relates to a method for removing formaldehyde in a room or furniture, characterized in that when a boiling point range obtained by dry distillation of tea is 20 mmHg, a chemical agent containing a dry distillation fraction at 180 to 200 ° C. is placed together.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The composition of the dry distillation fraction of tea in the present invention is considered to be composed of flavanol, flavonol and other organic compounds, but the details are unknown and the adsorption mechanism is also unknown. It is presumed that it has a reactive OH group, which reacts with the aldehyde group of formaldehyde to form a chemical bond and is adsorbed. The dry distillation fraction of tea is 180 to 20 in the case where the boiling point range is 20 mmHg, which is mainly from the leaves of tea.
It is at 0 ℃ and has an ultraviolet absorption spectrum of 276 ± 2 nm.
A propylene glycol solution having a maximum absorption wavelength in (1000 times aqueous solution) and having 20% by weight thereof has a refractive index: n ²⁰ _D = 1.418 ± 0.02 Optical rotation: a ²⁰ _D = + 0.007 ° ± 0 0.002 ° specific gravity: a component having d ²⁰ ₂₀ = 1.025 ± 0.02.

The dry distillation fraction of tea according to the present invention is represented by
It can be prepared by the method described in 8694. Specifically, it can be obtained as follows. Mainly leaves of tea are subjected to dry distillation under reduced pressure, and dry distillation fractions having a boiling point range of 180 to 200 ° C. are collected under reduced pressure of 20 mmHg. Also, mainly the leaf portion of tea is extracted with a suitable solvent to obtain a dark green to dark brown powder or solid content, which is subjected to dry distillation under reduced pressure to give 180 at 20 mmHg.
You may make it collect the distillate of -200 degreeC.

The acute toxicity value (LD ₅₀ value) of a 20 wt% propylene glycol solution of this dry distillate was 3 in male and female rats.
It is 0 ml / kg or more and has extremely low toxicity. This dry distillate is used as it is, or mixed with ethyl alcohol, propylene glycol, glycerin, etc., in various forms such as granules, tablets, aerosols, dried products impregnated into unglazed bodies, etc. as a drug containing the dry distillate. Can be used. Preparation to these forms of use can be carried out by a conventional method, for example, the method described in JP-B-61-8694.

The fragrance set of the present invention comprises a combination of fragrance and a dry distillation fraction of tea, and is particularly preferably used as an indoor fragrance set. The dry distillation fraction of tea according to the present invention selectively binds to formaldehyde and does not bind to fragrance. Although the reason is not clear, it is presumed that the dry distillation fraction has a reactive OH group, which reacts with the aldehyde group of formaldehyde to form a chemical bond and is adsorbed. Does not combine with. For this reason, only formaldehyde can be selectively removed and the effect of the fragrance is not deteriorated. Therefore, it is used in a place where formaldehyde odor needs to be removed, such as indoors. In particular, it is most suitable as a deodorant and air freshener in a room with a closed space. In the present specification, furniture means furniture having a closed space such as a closet, a cabinet, a drawer, etc., and an indoor space consisting of a wall material and a floor material using plywood, particle board, fiber board, and / or the like. The space where the furniture is placed.

The fragrance used herein is not particularly limited as long as it is a compound having no aldehyde group, and examples thereof include terpene compounds, aliphatic alcohols, aliphatic esters, aromatic alcohols and aromatic compounds. Ester, Musk xylol, Coumarin, Muscon, Civetone, Cyclopentadecanone, Cyclopentadecanolide,
At least one or more non-aldehyde type aromatic agents selected from ethylene brushlate, cis-jasmone and maltol are desirable. Since these are non-aldehyde type fragrances, they do not bind to the dry distillate and the effect of the fragrance is not lost.

Examples of the terpene compound include alcohols such as geraniol, citronellol, linanol and L-menthol, ketones such as menthone and L-carvone, and formic acid and acetic acid esters of the above terpene alcohols. As the aliphatic alcohol, C ₆ ,
C ₉ unsaturated alcohols are preferred. Generally, a cis compound has a strong scent, and, for example, cis-3-hexenol is an aromatic agent that gives a fresh green scent of the plant kingdom. Preferable examples of the aliphatic ester include pineapple and allyl caproate having a rum-like aroma.

Examples of aromatic alcohols include benzyl alcohol, β-phenylethyl alcohol (rose scent), cincinamic alcohol (hyacinth scent), methyl cinnamate (strawberry-like scent) and the like.
Examples of the aromatic ester include methyl benzoate (flower scent). Musk xylol is a musk
It has a odor. Coumarin has an aroma similar to that of cherry blossom leaves.

Muscon and civetone have a musk-like aroma. Furthermore, cyclopentadecanone, cyclopentadecanolide, and ethylene brushlate also have a musk-like aroma. Cis-jasmone is the main scent component of natural jasmine oil, and maltitol is the scent of strawberries.

The method for combining the fragrance and the dry fraction is not particularly limited as long as the form of the dry fraction can selectively adsorb formaldehyde while maintaining the activity of the fragrance. For example, fragrance and dry distillate are tableted and put in separate containers, or the tablets are mixed and put in one container, fragrance and dry distillate are dissolved in a solvent and separated. It may be stored in a container, or may be dissolved in a solvent and aerosolized. The amounts of the aromatic compound and the dry distillation fraction of tea in the aromatic compound set of the present invention are not particularly limited and may be appropriately selected.

The insect repellent set of the present invention comprises a combination of an insect repellent and a dry distillation fraction of tea, and is particularly preferably used as an insect repellent set for furniture. The dry distillation fraction of tea according to the present invention selectively binds to formaldehyde and does not bind to insect repellents, as in the case of the above-mentioned aromatic agent set. That is,
The dry fraction has a reactive OH group, which reacts with the aldehyde group of formaldehyde to form a chemical bond,
It is presumed that it will be adsorbed, but it is considered that it does not bind to such an insect repellent having no aldehyde group. For this reason,
It is suitable as a deodorant and insect repellent for furniture that has a closed space such as a closet because it can selectively remove only formaldehyde without reducing the effect of the insect repellent.

The insect repellent used here is not particularly limited as long as it is a compound having no aldehyde group, and for example, at least one selected from paradichlorobenzene, naphthalene and camphor is desirable. These insect repellents are the most widely used insect repellents, and since they do not have an aldehyde group and do not chemically bond with the dry distillation fraction of tea according to the present invention, the action of the insect repellent does not decrease.

The combination method of the insect repellent and the dry fraction is not particularly limited as long as the form of the dry fraction can selectively adsorb formaldehyde while maintaining the activity of the repellent. For example, a method of tableting the insect repellent and the dry distillate and putting them in separate containers, or a method of mixing the tableted products into one container, dissolving the insect repellent and the dry distillate in a solvent, and separately It may be stored in a container, or may be dissolved in a solvent and aerosolized. The amounts of the insect repellent and the dry distillation fraction of tea in the insect repellent set of the present invention are not particularly limited and may be appropriately selected.

As described above, in the present invention, the fragrance and / or insect repellent and the chemical agent containing the dry distillation fraction of tea are placed together in the room or in the furniture to prevent the aroma and insect repellent effect from being lowered. , Formaldehyde alone can be selectively removed. In such a method for removing formaldehyde of the present invention, as a method for arranging a fragrance, an insect repellent, and a chemical containing a dry distillation fraction of tea, these tablets,
For example, in the case of furniture, a container containing a solvent in which these are dissolved is attached to the inner wall of the indoor furniture having a closed structure. It is also possible to provide a forced ventilation device in the interior furniture to generate an air flow and accelerate the removal of formaldehyde.

Further, a solvent in which a fragrance, an insect repellent, and a chemical containing a dry distillation fraction of tea are dissolved is contained in a porous container (such as unglazed) and dried to increase the surface area. It is desirable because it can For example, a porous sintered body of alumina, hydroxyapatite, SiC, zirconia or the like is impregnated with a solvent in which a chemical agent containing a dry distillation fraction of tea is dissolved and dried to leave a hollow inside of the porous sintered body. ,
By adding an aromatic agent or an insect repellent to this, the aromatic agent or the insect repellent can be gradually released. Further, since it is a porous body, it can have a large surface area and can increase the adsorption amount of formaldehyde.

Furthermore, it is also possible to put these tablets, paper impregnated with the solution, etc. in a storage case for storing clothes and the like in furniture. Alternatively, it can be used as an aerosol product, for example a fragrance, insect repellent,
It is also possible to spray and use a chemical solution containing a dry distilled fraction of tea. In this way, in furniture that has a closed space such as a closet, formaldehyde volatilizes from plywood, particle board, fiberboard, adhesives, paints, etc., causing an offensive odor. Depending on the minutes, formaldehyde is adsorbed to remove the formaldehyde and deodorize.

[0023]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

Example 1 (insect repellent + dry distillation fraction) (A) Production of dry distillation fraction of tea 250 g of dry leaf powder of tea (Thea Sisensis L) and 600 mg of isopropanol were charged in a Soxhlet extractor, 2
Dry distillation was carried out for 0 hours. Approximately 80 g of a dark green solid substance is obtained by filtering off the residue of the raw material from the extract and drying the filtrate under reduced pressure.
I got The composition was dry distilled under reduced pressure to 20 mmHg,
The dry fraction at 180 to 200 ° C was distilled into propylene glycol. The distillate was 1 g. This dry fraction is 1
As a 000-fold aqueous solution, it has an ultraviolet absorption spectrum of 27
The maximum absorption at 6 ± 2 nm, and the refractive index, optical rotation, and specific gravity of a solution prepared by dissolving 20% by weight of a dry fraction in propylene glycol are as follows. Refractive index: n ²⁰ _D = 1.418 ± 0.02 Optical rotation: a ²⁰ _D = + 0.007 ° ± 0.002 ° Specific gravity: d ²⁰ ₂₀ = 1.025 ± 0.02 _{20 of the} obtained dry fraction A weight% propylene glycol solution was impregnated into an unglazed body made of egg-shaped alumina and dried (containing about 4 g as a dry fraction).

(B) Insect repellent adsorption test for dry distillation of tea In a glass container having a volume of 2 liters, 5 g of repellents (p-dichlorobenzene, naphthalene, camphor) were placed,
After standing at 25 ° C. for 24 hours, the headspace gas was analyzed by gas chromatography. The conditions for gas chromatography analysis are as follows. Column: Silicon SE-30 (10%) φ3 mm x 2
m Injection temperature: 280 ° C. Column temperature: 150 ° C. Carrier gas: Nitrogen (50 ml / min) In addition, a control experiment was performed without impregnating the dry distillation fraction of tea prepared in (A) and placing the unglazed body. . The abundance of the insect repellent after 24 hours from the control experiment was determined as the peak area of gas chromatography, and the amount of adsorption of the dry distillation fraction of tea was similarly determined as the peak area of gas chromatography. Seeking
The adsorption removal rate of the insect repellent was calculated. The results are shown in Table 1.

[0026]

[Table 1]

(C) Formaldehyde adsorption test of dry fraction of tea: A glass container having a volume of 2 liters was charged with the unglazed body impregnated with the dry fraction of tea prepared in (A) and dried. % Formalin water (0.1m
l, 0.3mml, 0.5ml, 1.0ml, 2.0m
l) Put and seal. After left at room temperature for 1 hour, 10 or 5 ml of headspace gas was sampled, bubbled with 5 ml of water, collected, colored by AHMT method, and the absorbance at 550 nm was measured. In addition, a control experiment was conducted in which a unglazed body impregnated with a dry distilled fraction of tea was not placed. The amount of formaldehyde present after 1 hour from the control experiment was determined from the absorbance, and the amount of formaldehyde adsorbed by the presence of the dry distillation fraction of tea was determined to calculate the adsorption removal rate of formaldehyde. Table 2 shows the results.

[0028]

[Table 2]

From the experimental results of (B) and (C), it is understood that the dry distillation fraction of tea in the present invention does not adsorb the insect repellent at all, and is excellent in the selective adsorption effect of formaldehyde.

(D) Experiment of coexistence of dry distilled fraction of tea and insect repellent (1) A glass container having a volume of 500 ml was impregnated with 5 g of p-dichlorobenzene and the dry distilled fraction of tea prepared in (A) and dried, Add 0.1 ml of 37% by weight formalin water, and add 10 Drosophila, seal, leave at room temperature for 24 hours, then headspace gas 10 or 5
ml was sampled, bubbled in 5 ml of water, collected and collected by the AHMT method [4-amino-3-hydrazino-5-
Mercapto-1,2,4-triazole method (Supervised by Research Coordination Division, Planning and Coordination Bureau, Environment Agency, edited by Environmental Measurement and Analysis Method, “Environmental Measurement and Analysis Method Note, Volume 2, Measurement and Analysis Method for Air Pollutants” 1984 , Japan Environmental Measurement and Analysis Association (publisher Maruzen, page 265-269)].
The absorbance value at 0 nm was measured. In addition, the number of living Drosophila individuals after 24 hours was counted. As a result, all Drosophila were dead, and the removal rate of formaldehyde was 98%.

(E) Coexistence experiment of dry distilled fraction of tea and insect repellent (2) Ten clothes and scabbages were placed in a wardrobe lined with a cosmetic particle board, and 5 g of p-dichlorobenzene was added in the The unglazed body impregnated with the dry distilled fraction of tea prepared in A) and dried was put and left for 3 months. As a result, all the scrubs were dead, and the clothes were not damaged.

Comparative Example 1 (b) Insect repellent adsorption test of activated carbon Basically the same as in (B) of Example 1, except that instead of the unglazed body impregnated with the dry fraction of tea and dried, activated carbon 5 g
It was used. The results are shown in Table 3, which shows that activated carbon adsorbs the insect repellent.

[0033]

[Table 3]

(B) Formaldehyde adsorption test of activated carbon Basically the same as (C) of Example 1, except that 5 g of activated carbon was used instead of the unglazed body impregnated with the dry distillation fraction of tea and dried.
It was used. The results are shown in Table 4.

[0035]

[Table 4]

As can be seen from the comparison of Tables 1 to 4, the activated carbon is
Not only formaldehyde but also insect repellents are adsorbed and there is no selectivity. On the other hand, it is understood that the dry distillation fraction of tea selectively adsorbs only formaldehyde and not the insect repellent. Also, from the comparison of Tables 2 and 4, it is understood that activated carbon adsorbs formaldehyde, but deactivates when adsorbing high-concentration formaldehyde. On the other hand, it can be seen that the dry distillation fraction of tea can maintain its adsorption ability even when the formaldehyde concentration is high, and has a long life as a formaldehyde remover. The relationship between the formaldehyde concentration and the formaldehyde removal rate of the dry distillation fractions of activated carbon and tea is shown in the graph of FIG.

(C) Coexistence experiment of activated carbon and insect repellent (1) The same as in Example 1 (D), but 5 g of activated carbon was used instead of the dry distillation of tea. As a result, 8 out of 10 Drosophila were alive, and the removal rate of formaldehyde was 88%.

(D) Coexistence experiment of activated carbon and insect repellent (2) The same as in Example 1 (E), but 5 g of activated carbon was used instead of the dry distillation fraction of tea. As a result, it was observed that stag beetles were breeding and holes were broken through the clothes.

Example 2 (Fragrance + Dry Distillate) A 20 wt% propylene glycol solution of the dry distillate obtained in (A) of Example 1 was hollow and had an egg-shaped alumina sintered body (porosity 70 %) And dried (contains about 4 g as a dry fraction). This alumina sintered body has a porosity of 70% and has continuous pores. It is considered that the dry distillation fraction adheres to the pore wall surface. It is presumed that formaldehyde is chemically bound and adsorbed to this dry fraction. Further, the alumina sintered body has a hole in the upper portion so that the aromatic agent in the cavity is volatilized.

Inside the cavity, L-menthol, cis-3-hexenol, allyl caproate,
Gels containing β-phenylethyl alcohol, muskoxylol, coumarin, cis-jasmon, and maltol were respectively injected. The fragrance set consisting of this dry distillate and fragrance was placed in a room lined with decorative plywood and left for 1 week. After one week, a person who did not teach the name of the air freshener was asked to confirm the indoor odor. As shown in Table 5, only the odors of ~ were found, and no odor stimulating formaldehyde was found. .

[0041]

[Table 5]

Comparative Example 2 A fragrance set consisting of 5 g of activated carbon and the fragrances of Examples 1 to 2 was placed in a wardrobe lined with decorative particle board, and allowed to stand for 24 hours and for 1 week.
When the odor in the chest of drawers was confirmed, almost no odor was confirmed when left standing for 24 hours. When left for one week, an irritating odor of formaldehyde and an aroma of an aromatic agent were mixed, and an unpleasant odor that was unclear was confirmed. This is probably because the activated carbon was deactivated by the adsorption of formaldehyde, and the odors of formaldehyde and fragrance were mixed.

Comparative Example 3 Only the fragrances of Example 2 to 4 were placed in a room lined with decorative plywood and left for 24 hours. The irritating odor of formaldehyde and the fragrance of the fragrance mixed with each other. An unpleasant unpleasant odor was confirmed.

[0044]

Industrial Applicability According to the present invention, there is provided a formaldehyde removing agent comprising a dry fraction of tea, which can selectively remove only formaldehyde by adsorbing and removing it without deteriorating the action of an aromatic agent or an insect repellent.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the formaldehyde concentration (formalin injection amount) and the formaldehyde removal rate. The solid line shows the case of using the dry distillation fraction of tea, and the broken line shows the case of using the activated carbon.

Claims (8)

[Claims] 1. The boiling point range obtained by dry distillation of tea is 20 m.
In the case of mHg, a formaldehyde removing agent containing a dry distillation component at 180 to 200 ° C. as an active ingredient. 2. A fragrance set comprising a combination of a fragrance and a dry distillation fraction at 180 to 200 ° C. when the boiling point range obtained by dry distillation of tea is 20 mmHg. 3. The aromatic agent is a terpene compound, an aliphatic alcohol, an aliphatic ester, an aromatic alcohol, an aromatic ester, muskoxylol, coumarin, muscone, civetone, cyclopentadecanone, cyclopentadecanolide, ethylene. The fragrance set according to claim 2, which is at least one non-aldehyde type fragrance selected from the group consisting of brushlate, cis-jasmone, and maltol. 4. The use according to claim 2 or 3 for indoor use.
The described fragrance set. 5. An insect repellent set comprising a combination of an insect repellent and a dry distillation fraction at 180 to 200 ° C. when the boiling point range obtained by dry distillation of tea is 20 mmHg. 6. The insect repellent set according to claim 5, wherein the insect repellent is at least one selected from the group consisting of paradichlorobenzene, naphthalene, and camphor. 7. The method according to claim 5, which is used for furniture.
Insect repellent set described. 8. Arrangement of a fragrance and / or insect repellent in a room or furniture together with a chemical containing a dry fraction at 180 to 200 ° C. when the boiling range obtained by dry distillation of tea is 20 mmHg. A method for removing formaldehyde in a room or furniture, characterized by: