JP3469523B2 - Process for producing deodorized products and deodorized products - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a deodorant processed product containing a deodorant excellent in removing aldehydes such as formaldehyde and other malodorous components, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, various proposals have been made to remove a bad odor caused by cigarette smoke or the like as a part of improving the living environment. Further, in a new house, a building material containing a chemical substance such as formaldehyde is frequently used, and a harmful effect caused by vaporization and dispersion of the chemical substance in a large amount, so-called sick house syndrome is a problem.

Therefore, as a means for solving these problems, it has been proposed to use a compound having an NN bond such as hydrazides, azoles and azines as a deodorant. These deodorants are used by being blended with wallpaper, resins, etc., or by treating wood materials such as plywood by spraying and treating them to remove malodorous components such as formaldehyde produced from plywood. Adsorb,
Since then, it has been used as a treatment agent for plywood without generation of formaldehyde.

[0004]

However, these deodorants have the effect of deodorizing aldehydes exclusively,
Not effective against malodorous substances other than aldehydes.

Therefore, the inventors of the present invention have studied using activated carbon, which is generally used as a physical adsorbent, and a compound having an NN bond in combination. However, in such a combination, the problem that the formaldehyde adsorption ability of the compound having an N—N bond is lowered has been clarified. In addition, when it is placed on a building material or the like to exhibit a deodorizing effect for a long period of time, an appropriate carrier for supporting the deodorant is required, but it is easy to handle and the deodorizing effect is maintained for a long period of time. At present, there is a demand for suitable carriers that can be used.

Therefore, the present invention aims to provide a deodorant processed product which contains a deodorant capable of adsorbing aldehydes such as formaldehyde and other malodorous substances and can maintain the deodorizing effect for a long period of time. And

[0007]

As a result of intensive studies to solve the above problems, the present inventor found an excellent means and completed the present invention. That is, the present invention, in the aqueous solvent,
(A) sebacic acid dihydrazide , (B) activated carbon,
(C) Prepare deodorant by mixing with water-based emulsion resin
And further after applying or impregnating the deodorant to the substrate,
Alternatively, after kneading the deodorant during the production of the base material,
The present invention relates to a manufacturing method for obtaining a deodorized product by heating at 185 ° C. The present invention also provides (A) seba in the presence of water.
Sinic acid dihydrazide, (B) activated carbon, and (C) aqueous system
Deodorant prepared by mixing with Maruzon resin is the base material.
It was written kneaded during preparation of the coating fabric or impregnated or substrates
After that, the present invention relates to a deodorized product that is heated at an ambient temperature of 185 ° C. In addition, the solubility in this specification is 1% of water at 30 ° C.
Saturated dissolution amount of solute with respect to 00 ml (g / 100 ml)
Say.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the deodorant of the present invention,
As (A) dihydrazides, sebacic acid dihydrazide is used as an active ingredient. General of dihydrazide compounds
As a specific example, for example, the general formula _{H 2 NHN-X-NHNH 2} (1) [X wherein represents a group -CO- or a group -CO-A-CO-. A represents an alkylene group or an arylene group. ] The dihydrazide compound represented by these can be mentioned.

In the above general formula (1), the alkylene group represented by A is, for example, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group or the like having 6 to 12 carbon atoms.
The straight chain alkylene group can be mentioned. Examples of the substituent of the alkylene group include a hydroxyl group and the like. As the arylene group, for example, a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group,
Examples thereof include a phenanthrylene group, and among these, a phenylene group and a naphthylene group are preferable. As the substituent of the arylene group, the same as the above-mentioned substituents of the aryl group can be mentioned.

Specific examples of the dihydrazide compound of the above general formula (1) include, for example, oxalic acid dihydrazide (0.45) (the number following the compound name indicates the solubility in water at 30 ° C., the same applies hereinafter). , Suberic acid dihydrazide (0.73), Azelaic acid dihydrazide (0.2
4), sebacic acid dihydrazide (0.1), dodecanediohydrazide (0.01), isophthalic acid dihydrazide (0.7), terephthalic acid dihydrazide (0.01),
Examples thereof include dibasic acid dihydrazides such as 2,6-naphthoic acid dihydrazide (0.01). Of these , the main
In the light, sebacic acid dihydrazide is used .

It is desirable to use those dihydrazides having a solubility in water of 1 (g / 100 ml) or less at 30 ° C. for the following reasons. That is, according to the research conducted by the present inventors, activated carbon and N--N are mixed when mixed in a wet manner.
The reason why the combination of compounds having a bond reduces both deodorant performance is that most of the compounds having an N—N bond are dissolved in a dispersion medium or a solvent and adsorbed on activated carbon, closing the pores of activated carbon. At the same time, it is considered that the ability of the adsorbed compound having an N—N bond to deodorize aldehydes is also reduced. For example, adipic acid dihydrazide, which is known as one of the compounds having the highest deodorizing ability for aldehydes, has a solubility in water at 30 ° C. of 12.5 g / 10.
It is as large as 0 ml, and when used in combination with activated carbon, the above-mentioned inconvenience occurs. Therefore, a specific dihydrazide having a small solubility in water, specifically, a solubility in water at 30 ° C. of 1 g /
By using 100 ml or less of dihydrazides, the above inconvenience can be solved.

As for the average particle size (median size) of dihydrazide, the lower limit is 1 μm or more, more preferably the lower limit is 2 μm or more, and the upper limit is 10 μm or less, more preferably 7 μm or less. If the particle size of dihydrazide is too large, the desired deodorizing effect is difficult to be expressed because the specific surface area is reduced.On the other hand, if the particle size is too small, the target deodorizing effect is not expressed by closing the pores of the activated carbon. is there. The above dihydrazide compounds may be used alone or in combination of two or more.

In the deodorant of the present invention, the compounding amount of the dihydrazides is not particularly limited and can be appropriately selected from a wide range, but it is usually relative to 100 parts by weight of the water-based emulsion resin (on a solid basis). The dihydrazides may be adjusted to 0.1 to 1000 parts by weight, preferably 1 to 100 parts by weight.

The activated carbon (B) usable in the present invention is not particularly limited and, for example, fibrous activated carbon, powdered activated carbon, granulated activated carbon, crushed activated carbon and the like can be used. Usually, specific surface area 300-3000m ² / g
Something is used. In the deodorant of the present invention, the blending amount of activated carbon is not particularly limited and may be appropriately selected from a wide range. Usually, 1 to 100 parts by weight of activated carbon is added to 100 parts by weight of the water-based emulsion resin (as solid).
It may be appropriately adjusted to be 500 parts by weight, preferably 5 to 200 parts by weight.

The above-mentioned (A) dihydrazides and (B) activated carbon are used by mixing with an aqueous solvent. As the water-based solvent, water as a dispersion medium for the water-based emulsion resin is preferable, but a mixture of water and a lower alcohol can also be used. Examples of the water-based emulsion resin (C) usable in the present invention include vinyl acetate polymer emulsion, ethylene-vinyl acetate copolymer emulsion, vinyl acetate-versatate copolymer emulsion, ethylene-vinyl acetate-vinyl chloride copolymer emulsion. , Ethylene-
Aqueous emulsions such as vinyl acetate-acrylic acid ester copolymer emulsion, acrylic acid ester polymer emulsion, acrylic acid ester-styrene copolymer emulsion, vinyl chloride polymer emulsion, silicone polymer emulsion, epoxy polymer emulsion and starch aqueous solution. Can be mentioned.

The deodorant of the present invention contains, if necessary, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a bactericide, a fungicide, an insect repellent, as long as its effect is not impaired. Ordinary additives such as pigments, colorants, and flavors may be blended.

The deodorant composition used in the present invention is composed of dihydrazides, which are poorly soluble in water, and is difficult to dissolve in an aqueous solvent such as an aqueous emulsion resin and dispersed therein. Since it does not block the pores of the activated carbon, it is possible to efficiently remove malodorous components, particularly aldehydes, and maintain the deodorizing effect for a long period of time.
Further, since the water-based solvent is used, it is possible to produce a deodorized product which is safe and has little harm to the living environment or the production environment, and which is simple and can maintain the deodorizing effect for a long period of time.

The above deodorized product can be obtained by fixing a deodorant obtained by mixing an aqueous solvent with dihydrazides and activated carbon onto a substrate by means such as coating or impregnation. As a specific example of such a deodorized product, for example, a deodorant sheet in which a deodorant is fixed to a sheet base material such as non-woven fabric, paper (paper, wallpaper, etc.), cloth, synthetic resin sheet,
For deodorant fibers with deodorant adhered to synthetic fiber and other wood base materials, and wood base materials such as wood (mainly plywood such as plywood, MDF plywood (medium fiber board), decorative boards, ceiling boards, etc.) Examples thereof include a deodorant building material having a deodorant adhered thereto, and a deodorant packaging material having a deodorant adhered to a film substrate such as a synthetic resin film.

As a method for producing these deodorized products , for example, the deodorant of the present invention may be prepared and then applied or impregnated on a substrate to produce the deodorant. In addition, while manufacturing the base material,
It is also possible to incorporate the deodorant of the present invention by kneading or the like. Further molding, known resin to deodorant composition described above (e.g., polyolefin resins, vinyl resins, and phenol resins, urea resin or the like) by mixing a deodorant resin composition, this by known means By doing so, various deodorized products (molded products) may be integrally manufactured. As a method for coating or impregnating, a known method can be adopted,
For example, a brush coating method, a spray coating method, a dipping method, or the like can be used. After coating and impregnating, for example, air drying,
Drying may be carried out according to a usual method such as drying using a dryer or the like, or drying in a dryer such as a thermostat.

[0020]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below. The term "part" means part by weight.

Examples 1 and 2 Sebacic acid dihydrazide (manufactured by Otsuka Chemical Co., Ltd., average particle size 5 μm, solubility: ion-exchanged water in the amounts shown in Table 1):
0.1 g / 100 ml-30 ° C. water), acrylic acid ester polymer emulsion, and commercially available coconut shell activated carbon powder were added, and the mixture was stirred and dispersed for 20 minutes to form a coating material. Thickness 0.1m
m aluminum plate (Japan Test Panel Osaka Co., Ltd. A105
P, 15 cm × 30 cm) was coated on one side with a thickness of 75 μm using an applicator (manufactured by Taiyu Equipment Co., Ltd.).
The coated plate was placed in a rotary heating furnace having an ambient temperature of 185 ° C. and heated for 1 minute to obtain a test piece.

[0022]

[Table 1]

Comparative Examples 1-2 Instead of using sebacic acid dihydrazide, adipic acid dihydrazide (manufactured by Otsuka Chemical Co., Ltd., average particle diameter 7 μm,
Solubility: 12.5 g / 100 ml-30 [deg.] C. water) The same as Example 1 except using. Comparative Example 3 The procedure of Example 1 was repeated except that sebacic acid dihydrazide was omitted.

Deodorant test method 3c was used for the test pieces obtained in Examples 1 and 2 and Comparative Examples 1 to 3.
It was cut into a size of m × 3 cm, placed in a Tedlar bag with a two-way cock having a volume of 1 L, and the opening was heat-sealed and hermetically sealed. A plurality of bags were prepared according to the measurement time. Formaldehyde gas diluted by nitrogen (Sumitomo Seika Chemicals Co., Ltd.) was introduced from a cock, and the formaldehyde concentration (ppm) in the bag was measured with a gas detector tube (Komei Rikagaku Co., Ltd. No. 171SB, ( Gastech Co., Ltd. No. 9
1 L). The test is conducted in a constant temperature room at 25 ° C,
The results are shown in Table 2.

[0025]

[Table 2]

As is clear from Table 2, Examples 1 and 2
It can be seen that the test piece of No. 1 adsorbs and removes a large amount of formaldehyde at an early stage. On the other hand, in the test pieces of Comparative Examples 1 to 3, the adsorption amount becomes dull over time, and it is assumed that the adsorption is almost saturated.

[0027]

EFFECTS OF THE INVENTION According to the method for producing a deodorized product according to the present invention, a deodorized product can be produced without lowering the ability of dihydrazides to adsorb aldehydes. Also,
The deodorized product according to the present invention is capable of adsorbing an aldehyde adsorption ability for a long period of time and also adsorbing other malodorous components. In particular, since the deodorant in which the dihydrazide and activated carbon are dispersed is used in the water-based emulsion resin ,
The manufacturing process of deodorized products is also simple.

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-8-280781 (JP, A) JP-A-9-273077 (JP, A) JP-A-2000-37447 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61L 9/01

Claims (2)

(57) [Claims] 1. An aqueous solvent containing (A) dihydric sebacate
A deodorant is prepared by mixing zido , (B) activated carbon, and (C) an aqueous emulsion resin, and the deodorant is used as a base material.
Deodorant after application or impregnation on the substrate or during manufacturing of the substrate
After kneading the agent, heating at ambient temperature 185 ℃
A method for producing a characteristic deodorized product. 2. (A) dihydric sebacate in the presence of water
Zido, (B) activated carbon, and (C) water-based emulsion resin
Deodorant prepared by mixing and is applied or impregnated on the substrate
Ambient temperature after being cured or kneaded during the manufacture of the substrate
Deodorizing process characterized by being heated at 185 ° C
Goods .