JPH01227759A - Deodorizing sheet-like material - Google Patents

Abstract

PURPOSE:To improve the fixability to a base material and to prevent easy dislodgment of the sheet-like material in spite of contact with water by incorporating a compsn. consisting of a ferrous salt, carboxylic acid compd. and sulfate or sulfite and a water repelling agent and/or resin into said sheet. CONSTITUTION:The compsn. consisting of the ferrous salt, the carboxylic acid compd. having >=2 carboxyl groups within the molecule and the sulfate or sulfite as the 3rd component and the water repelling agent and/or the resin are incorporated into the above-mentioned sheet. Ferrous sulfate, ammonium ferrous sulfate, ferrous chloride, and ferrous nitrate are used for the ferrous salt. Tartaric acid, maleic acid and citric acid are used for the carboxylic acid compd. Ammonium sulfate, sodium sulfate, sodium hydrogensulfate, potassium sulfate, ammonium sulfite, and sodium sulfite are used as sulfate and sulfite.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a deodorizing sheet material with improved adhesion to a substrate.

[Prior Art] Activated carbon has been widely used as a means for removing bad odors. In addition, there are methods to mask malodorous components with fragrances to alleviate irritation, and to neutralize them with acids and alkalis.
Alternatively, there are methods to chemically decompose and remove it, and many products have been commercialized for household use. However, the current situation is that these methods have not achieved sufficient effects.

For example, the method of adsorption and removal using activated carbon is relatively effective for organic gases, but the adsorption capacity is limited.
Also, it is difficult to say whether it is effective against ammonia, which is a typical malodorous component. In addition, the method of masking with fragrances is not a matter of essential removal, but a sensory deodorization.
The method of neutralizing with alkali is only effective against the malodorous components that combine with acid and Airekari.
.

On the other hand, a deodorizing material containing [-ascorbic and ferrous compounds (¥f Kosho No. 61-43091) has been proposed, and although it has been found to be effective in improving oxidation, it may decompose or change color over time. , and also fell off due to water, and the condition is still not completely satisfactory.

In addition, the present inventors have previously proposed a deodorizing material that has excellent long-term stability and is mainly composed of an oxycarboxylic acid compound and a ferrous salt. However, the adhesion to the base material (adhesiveness) tended to be weak, and it also fell off due to water, which was insufficient to obtain a satisfactory effect.

``Problems to be Solved by the Invention'' The purpose of the present invention is to improve the shortcomings of the prior art described above (11S), improve the adhesion to the base material, and improve the resistance to contact with water. The present invention also provides an excellent deodorizing sheet-like material that does not fall off easily.

"Means for Solving the Problems" In order to achieve the above object, the present invention has the following configuration.

(1) A composition consisting of a ferrous salt, a carboxylic acid compound having two or more carboxyl groups in the molecule, and a sulfate or sulfite as a third component, and a water repellent or/and a resin are added to a sheet-like material. A deodorizing sheet-like material characterized by containing:

(2) The deodorizing sheet material according to claim (1), wherein the composition is coated with a water repellent and/or a resin.

(3) The deodorizing sheet material according to claims (1) and (2), which is a resin or a resin having a microporous structure.

(4) @Claims (1) ~ covered with fat or water repellent
(3) The deodorizing sheet-like article described.

The present invention will be explained in detail below.

The ferrous salt used in the present invention is a component that deodorizes by chemically reacting with malodorous components, and specific examples thereof include ferrous sulfate, ferrous ammonium sulfate, ferrous chloride, and nitric acid. Examples include first iron.

When used, these may be used alone or in a mixture. When the ferrous salt is used in a solution state, it is usually prepared as an aqueous solution of 0.01 to 1 mol/U.

In addition, the carboxylic acid compound having two or more carboxyl groups in the molecule as used in the present invention effectively suppresses the oxidation of iron ions and maintains the active state through a chemical reaction with ferrous ions, and also has an odor itself. It is also a component that deodorizes by reacting with other components.

Specific examples include tartaric acid, maleic acid, malic acid, citric acid, etc. Also, a part of the carboxyl group of the compound may be an alkali metal salt or an ammonium salt, and these may be mixed as appropriate. It can also be used as

The compound (A) has (A>/
(B) -0,003/1 to 2/1 (molar ratio), preferably 0.01/1 to 1.5/1 (molar ratio), more preferably 0.1/1 to 1/1 (molar ratio) It can be said that the ratio) is preferable from the viewpoint of long-term stabilization of ferrous ions and long-term sustainability of the deodorizing effect. If the compound is below this range, it is insufficient for long-term stabilization of ferrous ions, and on the other hand, even if it exceeds this range, it is excessive in terms of stabilizing ferrous ions, and the deodorizing ability is impaired. decreases.

Further, the third component of the present invention, sulfate and sulfite, is intended to improve the sustainability of the deodorizing effect and improve the whiteness maintenance of the deodorizing molded product.

Specific examples of sulfates and Wt salts are not particularly limited as long as they are water-soluble salts, but examples include ammonium sulfate, sodium sulfate, sodium hydrogen sulfate, potassium sulfate, ammonium sulfite, and sodium sulfite. . In particular, ammonium sulfate and ammonium sulfite are good in terms of whiteness. These may be used alone or as a mixed component. The ratio of sulfate or sulfite (C) to ferrous salt (B) is (C)/(B)-〇.

05/1 to 10/1 (1 mole), preferably 0.1
/1 to 5/1 (1 mole) is preferable.

The composition in the present invention may be in the form of a solution, a dispersed solution, or a granule. When used in the form of granules, the composition is more effective if the composition is made into a solution and then dried by evaporation or the like to form granules.

Usually, the composition is 0.0.
1-200% by weight, 0.05-20% by weight as iron component
is used. Also, if expressed in another unit, the iron component is 0.1 to 10! J/Trl" is used. If the base material requires white or light color, 0.1 to 1 g/1 T12 is preferable in terms of discoloration.

In addition, the water repellent in the present invention is usually an emulsion,
Applied in the form of a solvent solution.

Examples of silicone water repellents include dimethylpolysiloxane, hydrogenpolysiloxane, methylhydrogenpolysiloxane, those having phenyl groups or alkoxy groups in the side chain, or organopolysiloxanes that are cocondensates of these. However, highly reactive modified silicones such as dimethyl silicone, amino-modified silicone with an aminoalkyl group introduced, epoxy-modified silicone with an epoxy group introduced, and alkylene oxide-modified silicone with an alkylene oxide group introduced are particularly useful. selected. Among these, amino-modified organopolysiloxanes are particularly preferred because they provide highly durable coatings. In some cases, durability can be improved by using a triazine-based or melamine-based polymer in combination. Further, a catalyst may be used in combination, if necessary.

Next, examples of fluorine-based water repellents include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, and fluorinated terpolymers copolymerized with these, such as tetrafluoroethylene/ Examples include hexafluoropropene copolymer, tetrafluoroethylene/ethylene copolymer, and tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer.

Among these, those having reactivity such as an acrylic acid water repellent having a per-70-roalkyl group in a side chain are preferably selected.

Further, the resin in the present invention includes resins such as natural resins, thermoplastic resins, thermosetting resins, and elastomers that are made of aqueous or non-aqueous organic media, and coating agents, binders, etc. are usually used. Examples include polyurethane, polyacrylic, polyethylene, polyamide, polyvinyl acetate resin, and the like. Among these, resins made of polyurethane elastomer having a microporous structure are preferred. As non-aqueous organic compounds, perchlorene, tricrene, ethyl acetate, methyl ethyl ketone, toluene, xylene, etc. are used.

Further, when using a resin made of an aqueous medium, it is preferable that the resin is coated with a water repellent.

On the other hand, the sheet-like material referred to in the present invention includes papers, knitted fabrics, woven fabrics, non-woven fabrics, plastics, films, etc., and sheet-like objects of knitted fabrics and non-woven fabrics are particularly preferred.

As a method for attaching the composition, water repellent, and resin to the sheet-like material, impregnation, spraying, coating, and the like can be used as appropriate.

For example, as a specific example: (1) A method of impregnating and drying a sheet-like material with a treatment liquid consisting of a liquid composition and a water repellent.

(2) A method in which a sheet material is impregnated with a treatment solution consisting of a liquid composition and dried, and then coated with a water repellent agent and/or a resin.

(3) A method in which a granular composition and a water repellent or/and a resin are mixed and coated on a sheet-like material.

(4) For treatment liquid consisting of water repellent? -Impregnating the plate/
Method of coating particulate composition and resin after drying.

(5) Impregnating the sheet-like material with a treatment liquid consisting of a water repellent/
After drying, the granular composition and resin are coated, and then the method is again impregnated with a treatment liquid consisting of a water repellent and dried.

Examples include, but are not particularly limited to. Further, the composition may be applied to part or all of one or both sides of the sheet-like object.

As mentioned above, by containing the composition and a water repellent agent or/and a resin, the adhesion to the substrate is improved, and it does not easily fall off when it comes into contact with water. It is possible to obtain an excellent deodorizing sheet material. In particular, deodorizing sheet-like materials in which the composition is coated with a water repellent and/or a resin are preferred because this effect is remarkable.

Examples will be described below.

[Example Example 1 Ferrous sulfate 0.5 mol/D, Citric acid 0.35 mol/D
α, 0.5 mol/fl of ammonium sulfate, and 10 g/ff of the water repellent Asahi Guard AG710 (manufactured by Kaisei Chemical Co., Ltd.).
It was padded so as to be squeezed and dried at 100'C for 3 minutes. Thereafter, it was heat treated at 160'C for 30 seconds. The amount of this material deposited was 2.8% by weight as an iron component.

Comparative Example A Ferrous sulfate 0.5 mol 10, citric acid 0.35 mol/L
The same Tetron fabric as in Example 1 was immersed in an aqueous solution containing 0.5 mol/a of ammonium sulfate, padded to 100% reduction, and dried at 130'C for 3 minutes. The amount of this material deposited was 2.9% by weight as an iron component.

The deodorizing sheet thus obtained was examined for its deodorizing effect on ammonia, trimethylamine, and methyl mercaptan, and for its adhesion (adhesion) to the sheet. The evaluation was performed as follows.

Adjust reagents containing various malodorous components to 1%,
Its aqueous solution 0. ! M! was collected and placed in a 1000 d Erlenmeyer flask. After being left for 1 hour, the deodorizing sheet No. 201 was hung in the Erlenmeyer flask, and the concentration of residual marsh scum after 10 minutes was measured using a scum detector.

Regarding the adhesion to the sheet (adhesiveness), the deodorizing sheet was immersed in water for 10 seconds, and after dehydration and drying, the weight change and deodorizing effect of the composition were examined.

The results obtained are shown in Table 1.

As can be seen from Table 1, the composition of this example does not come off even when exposed to water, and exhibits an excellent deodorizing effect against all malodorous gases.

On the other hand, in the comparative example, the composition fell off upon contact with water,
The deodorizing effect can hardly be seen.

Table 1-13 Example 2 7 parts of T7iM - A 75Ω/Tr12 nylon nonwoven fabric made of polyamide is immersed in an aqueous solution containing 0.30 mol/Q of iron, 0.30 mol/Q of tartaric acid, and 0.50 mol/U of ammonium sulfate. Then, it was batted to a 150% reduction and dried at 100'C for 3 minutes. After that, it was immersed in a solvent solution consisting of 3 parts of the solvent-based water repellent Asahi Guard AG610 (manufactured by Kaisei Kagaku) and 97 parts of xylene, padded to 100% aperture, dried at 80°C for 2 minutes, and then ,
Treated at 160'C for 30 seconds. The amount of this material attached is
The iron content was 2.6% by weight.

Comparative Example B Ferrous sulfate 0.30 mol/Q, tartaric acid 0.30 mol/U
, the same nylon nonwoven fabric as in Example 2 was immersed in an aqueous solution consisting of 0.50 mol/α of ammonium sulfate, and 150%
It was padded so as to be squeezed and dried at 100'C for 3 minutes. The amount of this material deposited was 2.6% by weight as an iron component.

Comparative Example C Solvent-based water repellent Asaji Guard AG610 (manufactured by Kaisei Chemical Co., Ltd.) 3
The same nylon nonwoven fabric as in Example 2 was soaked in a solvent solution consisting of 97 parts of xylene, padded to 100% aperture, dried at 80°C for 2 minutes, and then soaked at 160°C.
Heat treatment was performed at ℃ for 30 seconds.

The deodorizing sheet thus obtained was evaluated in the same manner as in Example 1, and the results are shown in Table 2. As can be seen from this, the sample of this example showed excellent deodorizing effects against all malodorous gases. Furthermore, the composition showed excellent deodorizing effect against water without falling off. On the other hand, in Comparative Example B, an excellent deodorizing effect was observed immediately after treatment, but when the sample was immersed in water, the composition fell off and almost no deodorizing effect was observed. Comparative Example C had an excellent water repellent effect, but no deodorizing effect was observed.

Table 2 15 Example 3 Ferrous chloride 0.45 mol/a, maleic acid 0.45 mol/D, ammonium sulfite 0.55 mol/r1. The aqueous solution consisting of was evaporated to dryness to obtain a granular composition. The Tetron fabric used in Example 1 was coated with a viscous liquid consisting of 10 parts of this granular composition, 25 parts of polyurethane elastomer, and 65 parts of dimethylformamide. Thereafter, it was coagulated with water and dried at 120°C for 2 minutes. The amount of this material deposited was 3.5% by weight as an iron component.

Comparative example The Tetron fabric used in Example 1 was coated with a viscous liquid consisting of powdered activated carbon (manufactured by Kanto Kagaku > 20 parts, polyurethane elastomer 20 parts, and dimethyl formamide 60 parts). After that, it was coagulated with water and It was dried for 2 minutes at 0.degree. C. The amount of powdered activated carbon deposited was 4.5% by weight.

The deodorizing sheet material thus obtained was evaluated in the same manner as in Example 1. The results obtained are shown in Table 3. As can be seen from Table 3, the product of this example did not come off even when exposed to water, and showed an excellent deodorizing effect.The product of the comparative example did not come off when exposed to water. Although I didn't see it, I didn't see any deep jealousy towards ammonia, which has a strong pungent odor.

Table 3-19 Example 4 Ferrous nitrate 0.5 mol/U, apple 10.5 mol/fl
, an aqueous solution consisting of 0.75 mol/a of sodium sulfite was evaporated to dryness to obtain a granular composition. -Water repellent 1 to -Re Silicone 5H-8700 (made by Toshi Silicone) 2
The Tetron fabric used in Example 1 was immersed in an emulsion containing 0 g/Q, padded to 100% squeeze, and dried at 140'C for 2 minutes. Thereafter, this Tetoron fabric was treated with 15 parts of the above granular composition and Sunblen LQ-
It was coated with a viscous liquid consisting of 40 parts of X31A (manufactured by Sanyo Chemical Co., Ltd.) and 45 parts of dimethylformamide, and coagulated with water. After that, I applied G610 (
After soaking in a solvent solution consisting of 1.5 parts (manufactured by Kaisei Chemical Co., Ltd.) and 98.5 parts of toluene and vat, heat treatment was performed at 160'C for 30 seconds. The adhesion amount of this material is 5.
It was 3% by weight.

The thus obtained deodorizing sheet was evaluated in the same manner as in Example 1. As a result, the composition did not fall off even when exposed to water, and the deodorizing effect was observed against all malodorous gases. .

[Effects of the Invention] The deodorizing sheet of the present invention has good adhesion (adhesiveness) of the deodorizing composition to the substrate, and does not fall off even when exposed to water. In addition, it chemically reacts and eliminates many bad odors such as ammonia, trimethylamine, and methyl mercaptan, so it has excellent long-lasting effects and can be expected to be used in a wide range of applications.

Claims (4)

[Claims] (1) A composition consisting of a ferrous salt, a carboxylic acid compound having two or more carboxyl groups in the molecule, and a sulfate or sulfite as a third component, and a water repellent or/and a resin are added to a sheet-like material. A deodorizing sheet-like material characterized by containing: (2) The deodorizing sheet material according to claim (1), wherein the composition is coated with a water repellent and/or a resin. (3) Claim in which the resin is a resin having a microporous structure (
1), the deodorizing sheet-like article described in (2). (4) Claims (1) to 1, wherein the resin is coated with a water repellent agent.
(3) The deodorizing sheet-like article described.