JPS61111138A - Deodorant for refrigerator and for freezer in combination with it - Google Patents

Abstract

PURPOSE:To adsorb efficiently ammonia odor or the like by using independently the salts which are hydrolyzed under the presence of water a show acidity or mixing the above-mentioned salts which are not allowed to react with each other even if two or more kinds thereof are mixed and manufacturing a deodorand therefrom. CONSTITUTION:A deodorant for a refrigerator and for a freezer in combination therewith is manufactured by using independently the salts which are hydroscop ic, deliquescent or water-soluble and hydrolyzed under the presence of water and show acidity, or mixing and using the above-mentioned salts which are not allowed to react with each other even if two or more kinds thereof are mixed or combining these salts with each other. For the hydroscopic or deliques cent salts capable of use, calcium chloride, strontium chloride plus magnesium chloride are used as the chloride and cobalt nitrate plus ferric nitrate are used as the nitrate. When these salts are packed into a vessel having moisture permea bility and air permeability and used, the salts exhibit strongly hygroscopicity and absorb strongly the cold moisture dissolved with ammonia odor.

Description

[Detailed Description of the Invention] Industrial Field of Application The present invention is applicable to odors in refrigerated refrigerators and freezers, especially between fish and shellfish,
A fast-acting deodorizer for refrigerators and frozen ground that powerfully and quickly converts alkaline internal odors such as ammonia odor and lower amine odor (mainly trimethylamine odor) generated by other meats into adsorbent compounds and makes them odorless. Regarding.

BACKGROUND OF THE INVENTION Coconut shell activated carbon is widely used as a deodorizing agent for refrigerators and freezers.

Problems to be Solved by the Invention Known coconut shell activated carbon is rarely effective against small-particle bad odors such as ammonia odor and lower amine odor. Therefore, it is difficult to sufficiently remove bad odors in refrigerators and freezers using coconut shell activated carbon alone.

Means for Solving the Problems The present invention is based on the fact that salts that are hygroscopic and deliquescent or water-soluble and undergo hydrolysis in the presence of water have a strong hygroscopic property, and that the ammonia odor increases as the temperature decreases. It should dissolve well [for example, about 1300 (2
The inside of a refrigerator or freezer is relatively dry and low temperature, and the air is circulating, so although there is little humidity, a large amount of ammonia odor can be emitted. Adsorbed by the above salts in a dissolved state, the above salts gradually solidify due to moisture absorption,
In the end, it may or may not become an aqueous solution, but
The above salts undergo hydrolysis in the presence of water and become acidic, so they cause an acid-alkali reaction and a substitution reaction (ion exchange reaction) with the odor of ammonia, which is an alkaline substance, and produce an ammonia odor as an ammonium salt. The same thing can be said for the odor of lower amines (mainly trimethylamine odor) as in the case of ammonia odor, and that trimethylamine ((CH3'>3 N) has a higher solubility in water than ammonia odor. Although the smell is small, it is an alkaline substance that is stronger than the ammonia odor, and when the air inside the refrigerator is circulated, it causes alkaline reactions and substitution reactions (ion exchange reactions) in the presence of the salts and water, as in the case of the ammonia odor. Some salts initially form ammonium salts in the presence of ammonia odor, become neutral or weakly alkaline, and then undergo a substitution reaction (ion substitution reaction). Deodorizing carboxylic acids (for example, barium chloride and calcium chloride salts are finally deodorized with acetic acid, etc.).

Additionally, some salts create ammonia odor and ammonia ions, which can be dissolved and deodorized (for example, some salts create molecular compounds such as steel sulfate, silver nitrate, silver chloride, and calcium chloride salts, especially chloride). In the case of calcium salts, graphite, which has a similar specific gravity, is effective as an anti-caking agent)
It consists of using a mixture or a combination of salts that do not react even when the salts are used alone or when two or more of them are mixed.

Function The present invention is directed to salts that are hygroscopic, deliquescent, or water-soluble, and which undergo hydrolysis in the presence of water to become acidic, or a mixture of salts that do not react when two or more of these salts are mixed together. When used or used in combination, the above salts exhibit strong hygroscopic properties when used in a moisture-permeable and air-permeable container, and can be used in low-temperature and low-humidity conditions inside the refrigerator or freezer. However, at low temperatures, the odor of ammonia, which dissolves well in drainage water, is absorbed as much as possible by the cold moisture dissolved in the seedlings, and the above salts undergo hydrolysis in the presence of water and become acidic. Acid-alkali reaction with ammonia odor and trimethylamine odor, which are alkaline substances.

A W-reaction (ion exchange reaction) occurs, and the -valent group exhibits strong alkalinity like alkali metals, so it reacts with strong acids such as hydrochloric acids and nitric acids to create neutral substances, and There are few substances that are effective in reacting with acids and weak acids to create alkaline substances.

However, sodium nitrate, which is an alkali metal salt, is hygroscopic and can absorb water that has absorbed the odor of ammonia, but does not cause acid-alkali reactions or substitution reactions (ion exchange reactions).

In addition, some substances, such as silver nitrate, create ammonia ions, but in this case, they do not necessarily absorb one ammonia even if they have a negative valence because they form complex salts (including coordination bonds).

Divalent salts have 2 ammonia odors and 2 trimethylamine odors, trivalent salts have 3 ammonia odors and 3 trimethylamine odors, and polyvalent salts have ammonia odors and trimethylamine odors corresponding to the number of odors and acids. Alkaline reaction, substitution reaction (
(ion exchange reaction) and becomes ammonium salt, which deodorizes. By the way, there are substances that create molecular compounds such as calcium chloride, substances that deodorize carboxylic acids such as barium chloride, substances that create ammonia odor and butyric compounds such as copper and silver salts, ferrous iron, There are substances such as cobalt chloride that deodorizes by forming a coordination bond (a type of complex salt) with ammonia odor.

Examples Examples of the present invention will be described below, including types of salts that can be used, experimental examples, test examples, etc.

The possible hygroscopic, deliquescent salts used are chlorides,
Calcium chloride salt, strontium chloride salt, nickel chloride salt, magnesium chloride salt.

Manganese chloride, chromium chloride, cerium chloride, aluminum chloride, silver chloride, cobalt chloride, and others, and in order of acidity, nitrate M salts,
Cobalt nitrate salts, ferric nitrate salts, cupric nitrate salts, aluminum nitrate salts.

Examples include magnesium nitrate, manganese nitrate, silver nitrate, and others. Acetate salts include cobalt acetate and others, and phosphate salts include phosphorus pentoxide and others.
Examples of sulfates include copper sulfate and others. In addition, when using a mixture of two or more types of salts, for example, the salts of Gozo Doshi may be mixed with magnesium chloride salt, magnesium nitrate salt, and the like. Mainly hygroscopic, iI-decomposable salts (salts formed by reacting strong acids with weakly alkaline earth metals or other elements) undergo hydrolysis in the presence of water and become acidic. It is most effective for presenting

The above salts, with the exception of calcium chloride salts, do not form molecular compounds, so they undergo hydrolysis in the presence of water and become acidic, causing simple acid-alkali reactions and substitution reactions (ion exchange reactions), resulting in alkaline substances. It deodorizes ammonia odor and lower amine odor (mainly trimethylamine odor). For example, in general, substances with strong acids are more likely to react with acid-alkali reactions due to the absorption of alkaline ammonia odors and lower amine odors, than substances with weak acids.
Substances that have a strong substitution reaction (ion exchange reaction), and strong moisture absorption and deliquescent properties have a strong ability to remove ammonia odor (absorbed in a dissolved state in water).

In addition, salts that are only water-soluble absorb and react with ammonia and lower amine odors through air circulation inside the refrigerator.
Its effect is weak. In the case of divalent salts of alkaline earth metals, if magnesium chloride salt is used, it will produce two ammonia odors and two lower amine odors, acid-alkali reaction, and l-conversion.

In the case of a trivalent salt, if an aluminum chloride salt is used, it will produce three ammonia odors and three lower amine odors, acid-alkali reaction, and substitution reaction (ion exchange reaction). All of them produce ammonium salts to deodorize, but their staying power is greater than that of trivalent salts and divalent salts.
/2 times, and if it is a polyvalent salt, it will increase to /2 times the polyvalent salt of a divalent salt.

Water-soluble salts that can be used include aluminum sulfate (#2 (304)3), nickel sulfate (NLSOa 7HzO), magnesium sulfate (
hJS04・7H20), chlorides include nickel chloride, ammonium chloride, nitrates include zinc nitrate, acetates include manganese acetate, and others.

Therefore, the above-mentioned various salts are not only used alone as a suitable drug in chloride, acid, or water-soluble form, but also in an appropriate mixture of two or more of these drugs. . In the case of mixed use, those that do not react with each other to produce insoluble substances are preferred (for example, magnesium chloride salt and magnesium nitrate salt, aluminum chloride salt and magnesium nitrate salt, etc.). In addition, an aqueous solution of rare acids and the above salts may be mixed and used, but in this case as well, it is preferable not to react with the above salts to create insoluble substances (for example, magnesium chloride salt and dilute nitric acid aqueous solution, etc.) etc).

The above salts are not limited to being used alone or in combination, but two or more types can be used in combination as appropriate. For example, calcium chloride and magnesium chloride salts, aluminum chloride and calcium chloride salts, and others can be considered.

In addition, various combinations can be considered in the case of combined use, such as a combination of an aqueous solution of acids and the above salts, a combination of the above salts and an alkaline substance or coconut husk activated carbon.

When the above-mentioned salts are used alone, in a mixture, or in combination, a stable substance that does not react even when mixed with the salts can be mixed and used as an anti-caking agent or a porosity-retaining agent. As an anti-caking agent that can be used in combination, graphite (specific gravity 1
．． 8 to 2.2, have extremely high melting points, are stable against chemicals such as acids and alkalis, and are not attacked by anything other than fluorine, etc.), and by mixing them, the above-mentioned Salts (e.g. calcium chloride Js
Even if g) solidifies due to moisture absorption, it can be prevented from solidifying into lumps, and fine communicating voids are maintained with graphite or other materials, allowing cool moisture to circulate well within the voids. be able to. There are two possible types of void retaining agent: one with a deodorizing effect and one without, but in addition to the above-mentioned stability, the conditions are that it is a particle and that it is an acid-resistant organic or inorganic substance. Things that have a deodorizing effect include acid activated coconut shell activated carbon and bare ash.

Possible materials include silicon dioxide particles (silica gel particles), and examples without deodorizing properties include acid-resistant synthetic resin pellets, common salt, coke particles, ceramic membranes, and the like. The void retaining agent is
It is mixed for the same purpose as an anti-caking agent, but may also be used simply in combination. Other deodorizing agents that can be used in combination include, in addition to the ones mentioned above, uric acid aqueous solution (main components are carbolic acid, guaiacholic acid, etc.), alkali-stabilized chlorine dioxide aqueous solution, and antifreeze aqueous solution (for example, propylene glycol, ethylene glycol). Possible examples include agar gel containing a mixture of sulfonated coal or cation exchange resin, granules impregnated with an aqueous solution obtained by blending the above antifreeze solution with sulfonated coal or cation exchange resin, and a mixture of ferrous iron and ascorbic acid. It will be done.

When used in a refrigerator or freezer, use the above salts alone or in combination, or in combination with the above salts.

A mixture of an anti-caking agent or a porosity-retaining agent is made into a thermoplastic synthetic resin perforated film bag (e.g., polyolefin resin, vinyl chloride resin, nylon resin, Tetron resin, vinylidene chloride resin, Teflon resin, etc.) and ventilated. Non-woven bag making with good elasticity and moisture permeability (for example, polyolefin resin fibers, thermoplastic synthetic resin fibers mentioned above).

Acid-resistant metal fibers, glass fibers, carbon fibers, nonwoven fabrics made of other fibrous materials, etc.), woven bag making (for example, woven fabrics made of the same fibers as those used in the nonwoven bag making mentioned above).

human silk fabrics, cotton fabrics, raw silk fabrics, linen fabrics, other animal and plant fiber fabrics, acid-resistant metal fiber fabrics, glass fiber fabrics, etc.)
1 Breathable and moisture permeable, non-hydrophilic polyolefin porous sheet-like synthetic resin bags (for example, Tokuyama Soda Co., Ltd.'s product name NF Receipt, Sekisui Chemical Co., Ltd.'s product name Cellbore, etc.), etc. After being sealed in a container, it is placed in an air-permeable and moisture-permeable container (such as a box with an opening/closing lid).
to be accommodated. In addition, after sealing the salts alone or a mixture thereof, or the salts mixed with an anti-caking agent or a porosity retaining agent, and another deodorizing agent in separate air-permeable and moisture-permeable containers, They can be stored in one container, or the salts alone and the void retaining agent with deodorizing properties can be sealed in separate bags and used together by storing them in one container. can. Furthermore, a number of small chambers are defined inside the air-permeable and moisture-permeable container, and the small chambers are configured to allow air and moisture to pass through each other (for example, the salts, the porosity retaining agent, A large number of ventilation holes smaller than the particle size of anti-caking agents etc. are drilled in the partition wall, and every other small chamber is filled with the above salts alone or in combination, or the above salts are mixed with an anti-caking agent or a void retaining agent. It is possible to directly store the stored items without putting them in the container.

The air-permeable and moisture-permeable bag and container are characterized in that the salts include strong acids, moderate acids, weak acid salts, etc., and the salts include calcium chloride salts, etc. When it becomes an aqueous solution, hydrolysis occurs and the PH
Considering that there are some species that exhibit acidity of 6 or less,
Preferably, the material is acid-resistant and alkali-resistant.

The container has air permeability and moisture permeability, and in consideration of the fact that among the salts there are substances that may liquefy due to moisture absorption, such as calcium chloride, ventilation holes are provided at appropriate locations in the soil of the surrounding wall. At the same time, the lower part and the bottom of the peripheral wall are constructed without opening ventilation holes, and the inside of the container is constructed with a partition wall that allows ventilation and moisture permeability (for example, particles such as the above-mentioned salts, anti-caking agents, porosity-preserving agents, etc.). A horizontal wall with countless small ventilation holes (with a diameter of less than
The lower part is a water absorption chamber (coconut shell activated carbon, cotton, cotton valve as water absorption material).

Silicon dioxide particles, thick filter paper, zeolite, sponge.

(open-cell polyurethane foam or other absorbent material) to prevent water leakage in refrigerators and freezers. The air-permeable and moisture-permeable container is provided with an air-permeable and moisture-permeable opening/closing lid to prevent contents from leaking out and to enable replacement. In addition, instead of the above-mentioned container that has air permeability and moisture permeability, it is possible to use a deodorizer container for refrigerators that is already widely used, but since it does not have water absorption capacity, You need to be careful. In view of the above, it is convenient to make the entire or part of the container (the lower part of the peripheral wall and the bottom) transparent, which has air permeability and moisture permeability, so that the extent of the change in the salts can be confirmed by seeing through the container. As the material of the container, acid-resistant and alkali-resistant materials such as acrylic resin, acrylic styrene resin, polystyrene resin, A, BS resin, polypropylene resin, vinyl chloride resin, medium-low pressure polyethylene resin, and high impact styrene resin can be used. be.

The above-mentioned salts are highly hygroscopic (however,
In the case of water-soluble salts, it can absorb moisture in the refrigerator or freezer (including mixing or combination) and strongly remove bad odors, and when using hygroscopic and WA-decomposable salts in the freezer. Even if it is impossible to remove frost that has already formed, it can prevent new frost from forming due to its hygroscopic action.

Experimental Example 1 Hygroscopic, deliquescent salts (calcium chloride salts) 70% porosity retaining agent (from coal) 25% anti-caking agent (adding graphite particles or powder to calcium chloride salt) 5% of the above salts (
Since the specific gravity of the anti-caking agent (specific gravity 1.8 to 2.2, the finer the particles, the lighter the specific gravity) is about the same, the two cannot be separated. Even if the salts solidify due to moisture absorption, by attaching them to the surface of the salts, the anti-caking agent prevents caking, and the pore-maintaining agent maintains the fine communication gaps between the salts, so that the inside of the refrigerator is maintained. odor comes into contact with salts, and the deodorizing effect can be prevented from deteriorating over time.

Experimental example 2 Example of use of magnesium chloride salt (divalent salt) N H3+ H
20 → N H< OH (Cold humidity inside the refrigerator that dissolved ammonia odor) -C 2nd + 2
NH40H→ 2NHa CR+t'b (OH)2 Experimental example 3 Example of use of aluminum chloride salt (trivalent salt) NH3+H2
0-+HH40H (Cold humidity inside the refrigerator containing dissolved ammonia) MCj 3
+ 3NH' 40H→3NH,s C1+AI
(OH)3 In both of the above two examples, divalent salts and trivalent salts undergo hydrolysis in the presence of water and become acidic; the former produces two ammonia odors, and the latter produces three ammonia odors. An acid-alkali reaction and a substitution reaction (ion exchange reaction) occur, respectively, to generate ammonium chloride salt and deodorize it.

Experimental example 4 When deodorizing carboxylic acids with calcium chloride salts.

Possible in the presence of ammonia odor when using acetic acid) N Ha 1820-+HHa OH (cold humidity in the refrigerator with ammonia odor dissolved) C'H3C0
OH+NH40H- CH3GOONH4+H20 2CH3COON Ha + Ca C12→Ca (
CH3Coo)2 +2N84 C1 In this case, neutral or weakly alkaline ammonium acetate is first produced, and then a substitution reaction (ion exchange reaction) with acidic calcium chloride salt occurs to produce ammonium chloride salt for deodorization.

Test Example When the same items as shown in Experiment 1 above were placed at the top and bottom of a refrigerator, the results were lower than those placed at the top.
It was found that the one placed at the bottom had a better deodorizing effect. This excellent deodorizing effect is due to the fact that the fine communicating voids between the salts are secured by the void retaining agent, and the caking is prevented by the anti-caking agent, allowing the odor inside the refrigerator to enter the fine communicating voids. This is thought to be due to frequent contact with salts. In this case, it was found that the deodorizing effect was more pronounced and more sustainable when the salts were moistened to some extent.

Effects of the Invention Since the present invention has the above-mentioned structure, the hygroscopic action of salts and the odor of lower amines (mainly trimethylamine odor), etc., which could not be sufficiently deodorized with well-known deodorizers, such as ammonia odor (which is particularly easily absorbed by moisture), etc. Air circulation in the refrigerator or freezer allows salts to be adsorbed, and
Salts undergo hydrolysis in the presence of water and become acidic, giving off the odor of ammonia, which is a monoalkaline substance.

Causes acid-alkali reactions and substitution reactions (ion exchange reactions) with lower amine odors (mainly trimethylamine odors),
Since the adsorption and deodorizing reaction is added as an ammonium salt, the deodorizing effect is improved, and the fast-acting and
Demonstrates a long-lasting deodorizing effect. If hygroscopic and deliquescent salts are used in the freezer, their strong hygroscopic action will prevent the formation of frost on the bond, even if it is impossible to remove the frost that has already formed, and will also eliminate the odor in the refrigerator. Similar bad odors inside the refrigerator can be removed.

Patent applicant: Matsushita
Toshiko Procedural Amendment December 1980 / Date 1, Indication of the case 1982 Patent Application No. 234254 2, Name of the invention Deodorizer for refrigerators and freezers 3, Relationship with the person making the amendment Patent application Person name (name)
Toshiko Matsushita 4, Agent ゛ Showa Month/Date Amendment Book L All the descriptions of "alikari" on page 3, line 1 and page 7, lines 9-10 of the specification are amended to "alkali".

2. On page 7, line 9 of the same book, next to the description ``deliquescent j'', ``(
03, the statement "3/2 times" on page 8, line 17 of the same book is amended to the statement r-4-J.

& Same book, page 9, line 1 r (Adz (SO4)s)J
The description is corrected to r (Adz (8041) J).

6. “(NLSo<・7&O) J” on page 9, line 2 of the same book.
Correct the description to r(Ni S 04.7HxO)J 07, page 9 of the same book, line 3, r(MgSo<
-7H20) J is written as r (Mgso, ・7&O)
Correct the description to J.

8. The statement "ammonium chloride/salt" in the 4th line on page 9 of the same book is amended to the statement "antiheptane chloride salt". ”, and insert the description “rare” next to “Also,” in the same column. ”
Insert the following description.

11. On page 11, line 9 of the same book, insert the description ``Others'' next to the description ``Ceramic grains''.

12. On page 10 of the same book, lines 10-U, after the description ``Other fibrous non-woven fabric J,'' and next to the description ``glass fiber fabrics'' on lines 14-15 of the same page, ``Others.''
Insert the following description.

13. Insert the description "salt" next to the description "ammonium acetate" on page 18 of the same book, lines 9 to 10.

14. In the fourth line of page 18 of the same book, insert the statement "ni" next to the statement "void retaining agent".

Procedural amendment (November 1985) Lambda day 1, Indication of the case 1988 Patent Application No. 234254 2, Title of the invention: Deodorizing agent for refrigerators before freezing 3, Person making the amendment Relationship with the case Patent Applicant name: Toshiko Matsushita 4, agent address: 5-14-7 Hakusan, Bunkyo-ku, Tokyo, Hayakawa Pill, telephone number: Tokyo 946-0531 (representative) 6, subject of amendment Invention of Mei IB Book Detailed explanation column (2) Ibid. 11, lines 19-20 [Prevent water leakage in refrigerators and freezers. ] After the statement, insert the following statement.

In addition, water-absorbing seedlings are prepared using water-absorbing paper containing a water-absorbing polymer and alkaline solid chemicals (e.g., anhydrous sodium silicate,
etc.) and the hygroscopic, m-degradable salts (e.g. calcium salts) are processed into an aqueous solution? 1i Sei Chuo February 6, 1988 Amended Description 1, Name of the invention Deodorizing agent for refrigerated floors and freezers 2, Claims Hygroscopic, deliquescent or water soluble with the presence of water A deodorizing agent for refrigerated floors and freezers, which is made of a single salt that becomes acidic when hydrolyzed in water, or a mixture or combination of salts that do not react even when two or more of these salts are mixed.

3. Detailed Description of the Invention Industrial Field of Application The present invention is directed toward reducing odors in refrigerators and freezers, especially fish and shellfish meat.
A fast-acting deodorizer for refrigerated floors and freezers that strongly and quickly converts the alkaline Atsunai odor, such as ammonia odor and lower amine odor (mainly trimethylamine odor) produced by other meats, into an adsorbent compound and makes it odorless. Regarding.

BACKGROUND OF THE INVENTION Coconut shell activated carbon is widely used as a deodorizing agent for refrigerators and freezers.

Problems to be Solved by the Invention The well-known coconut shell activated carbon is hardly effective against bad odors with small particles such as ammonia odor and lower amine odor. Therefore, it is difficult to sufficiently remove bad odors in refrigerators and freezers using coconut shell activated carbon alone.

Means for Solving the Problems The present invention is based on the fact that salts that are hygroscopic and deliquescent or water-soluble and undergo hydrolysis in the presence of water have a strong hygroscopic property, and that the ammonia odor increases as the humidity decreases. It should dissolve well [for example, about 1300 (2
Inside the refrigerator or freezer, the temperature is relatively dry and low, and the air is circulating, so there is a small amount of ammonia odor (although it is humid). The above salts are adsorbed by the above salts in a state in which a large amount of the salts are dissolved in water. In the presence of ammonia, it undergoes hydrolysis and becomes acidic, so it causes an acid-alkali reaction and a substitution reaction (ion exchange reaction) with the odor of ammonia, which is an alkaline substance, and adsorbs the odor of ammonia as an ammonium salt, lower amines. The same thing can be said about the odor (mainly trimethylamine odor) as in the case of the ammonia odor, and the above trimethylamine ((CH3)3
N) is an alkaline substance that has a lower solubility in water than the ammonia odor, but is stronger than the ammonia odor, and as in the case of the ammonia odor mentioned above, it is an alkaline substance in the presence of the salts and water due to the circulation of the air in the refrigerator. It is adsorbed and deodorized through alkaline reactions and substitution reactions (ion exchange reactions), and some salts initially form ammonium salts in the presence of ammonia odor and exhibit neutral or weak alkalinity. Next, a substitution reaction (ion exchange reaction) occurs, and T-”
A', IC/acids') ni odor Zk<t:j ni
.

For example, barium chloride and calcium chloride salts are finally deodorized by forming salts with acetic acid, etc.).

Additionally, some salts produce ammonia odor and ammonia ions that escape by dissolution (for example, some salts form molecular compounds such as copper sulfate, silver nitrate, silver chloride, and calcium chloride salts, especially chloride salts). In the case of calcium salts, graphite, which has a similar specific gravity, is effective as an anti-caking agent)
By paying attention to the above-mentioned salts, the above-mentioned salts may be used alone or in combination with salts that do not react even if two or more of them are mixed.

Function The present invention is directed to salts that are hygroscopic, deliquescent, or water-soluble, and which undergo hydrolysis in the presence of water to become acidic, or a mixture of salts that do not react when two or more of these salts are mixed together. When used in a moisture-permeable and air-permeable container, the above-mentioned salts exhibit strong moisture-absorbing properties and keep the inside of the refrigerator door and freezer in a low-temperature and low-humidity state. Despite this, it absorbs as much cold moisture as possible with a large amount of ammonia odor dissolved in low temperature water, and the above salts undergo hydrolysis in the presence of water and become acidic. Therefore, the odor of ammonia, which is a substance that exhibits alkalinity, and the odor of trimethylamine cause an acid-alkali reaction.

A substitution reaction (ion exchange reaction) occurs, and the -valent group exhibits strong alkalinity like alkali metals, so it reacts with strong acids such as hydrochloric acid and nitric acid to create neutral substances, and also produces neutral substances. There are few substances that are effective in reacting with acids and weak acids to create alkaline substances.

However, sodium nitrate, which is an alkali metal salt, is hygroscopic and can absorb water that has absorbed the odor of ammonia, but does not cause acid-alkali reactions or substitution reactions (ion exchange reactions).

In addition, some substances, such as silver nitrate, create ammonia ions, but in this case, they do not necessarily absorb one ammonia even if they have a negative valence because they form complex salts (including coordination bonds).

Divalent salts have 2 ammonia odors and 2 trimethylamine odors, trivalent salts have 3 ammonia odors and 3 trimethylamine odors, and polyvalent salts have ammonia odors and trimethylamine odors corresponding to the number of odors and acids. Alkaline reaction, substitution reaction (
(ion exchange reaction) and becomes ammonium salt, which deodorizes. By the way, substances that create molecular compounds such as calcium chloride, substances that deodorize carboxylic acids such as barium chloride, substances that produce ammonia odor and butyric compounds such as copper salts and silver salts, ferrous iron, There are some substances, such as cobalt chloride (II), which form a coordination bond (a type of complex salt) with the odor of ammonia and remove the odor.

Examples Examples of the present invention will be described below, including types of salts that can be used, experimental examples, test sequences, etc.

Hygroscopic and deliquescent salts that can be used include, as chlorides, calcium chloride salts, strontium chloride salts, nickel chloride salts, and magnesium chloride salts.

Manganese chloride salt, chromium chloride salt, cerium chloride t
salts, aluminum chloride salts, silver chloride salts, cobalt chloride salts, and others. Among other acids, nitrates include cobalt nitrate salts, ferric nitrate salts, cupric nitrate salts, and aluminum nitrate salts. .

Examples include magnesium nitrate, manganese nitrate, silver nitrate, and others. Acetate salts include cobalt acetate and its loosened salts, and phosphate salts include phosphorus pentoxide and others.
Examples of sulfates include copper sulfate and others. When two or more types of salts are used in combination, for example, salts of strong acids may be mixed with magnesium chloride salt, magnesium nitrate salt, and the like. Mainly hygroscopic and deliquescent (including water-soluble) salts (salts formed by reacting strong acids with weak alkaline earth metals or other elements) are hydrated in the presence of water. It is most effective because it causes decomposition and becomes acidic.

The above salts, with the exception of calcium chloride salts, do not form molecular compounds, so they undergo hydrolysis in the presence of water and become acidic, causing simple acid-alkali reactions and substitution reactions (ion exchange reactions), resulting in alkaline substances. Deodorizes ammonia odor and lower amine odor (mainly trimethylamine odor). For example, substances with strong acids generally exhibit stronger acid-alkali reactions and substitution reactions (ion exchange reactions) due to the absorption of alkaline ammonia odor and lower amine odor, and substances with strong moisture absorption and deliquescent properties. Deodorization of ammonia odor (absorbed in water)
is powerful.

In addition, salts that are only water-soluble absorb and react with ammonia and lower amine odors through air circulation inside the refrigerator.
Its effect is weak. In the case of divalent salts of alkaline earth metals, if magnesium chloride salt is used, two ammonia odors and two lower amine odors cause acid-alkali reactions, substitution reactions (ion exchange reactions), and three In the case of valent salts, if aluminum chloride salt is used, 3f [! Ammonia odor of 1 and lower amine odor of 3 and acid-alkali reaction, substitution reaction (
All of them produce ammonium salts to deodorize, but trivalent salts are seven times more durable than divalent salts, and polyvalent salts are seven times more durable than divalent salts. I will continue to improve.

Water-soluble salts that can be used include, as sulfates, aluminum sulfate salt (#2 (304) 3), WIW Nitsu'7) Li salt (NiSO<e 7H20), magnesium sulfate salt (1'bsO4.7H20), As chlorides, nickel chloride salt, antimony chloride salt.

Nitrates include zinc nitrate, acetates include manganese acetate, and others.

Therefore, the above-mentioned various salts are not only used alone as a suitable drug in chloride, acid, or water-soluble form, but also in an appropriate mixture of two or more of these drugs. . In the case of mixed use, it is preferable to use substances that do not react with each other to produce insoluble substances. For example, magnesium chloride salt and magnesium nitrate salt, aluminum chloride salt and magnesium nitrate salt, calcium chloride salt dihydrate and calcium chloride salt. anhydrous salt, etc.).

In addition, an aqueous solution of rare acids and the above salts may be mixed and used, but in this case as well, it is preferable not to react with the above salts to create insoluble substances (for example, magnesium chloride salt and dilute nitric acid aqueous solution, etc.) etc).

The above salts are not limited to being used alone or in combination, but two or more types can be used in combination as appropriate. For example, dried calcium salt anhydrous salt and calcium chloride salt dihydrate,
Calcium chloride salts and magnesium chloride salts, aluminum chloride salts and calcium chloride salts, and others may be considered. Furthermore, various combinations can be considered in the case of combined use, such as a combination of an aqueous solution of rare acids and the above-mentioned salts, a combination of the above-mentioned salts and an alkaline substance or coconut husk activated carbon.

When the above-mentioned salts are used alone, in a mixture, or in combination, a stable substance that does not react even when mixed with the salts can be mixed and used as an anti-caking agent or a porosity-retaining agent. As an anti-caking agent that can be used in combination, graphite (specific gravity 1
．． ．． 8 to 2.2, it has an extremely high melting point, is stable against chemicals such as acids and alkalis, and is resistant to chemicals other than fluorine.
By mixing these, the salts (for example,
Even if calcium chloride salt (calcium chloride salt) may solidify due to moisture absorption, it can be prevented from solidifying into lumps, and by maintaining fine communicating voids with graphite or other materials, cool moisture can circulate well within the voids. It can be done. There are two possible types of void retaining agent: one with a deodorizing effect and one without, but in addition to the above-mentioned stability, the conditions are that it is a particle and that it is an acid-resistant organic or inorganic substance.

Examples of substances that have a deodorizing effect include activated carbon, raw ash, silicon dioxide particles (silica gel particles), and others; examples of substances that do not have a deodorizing effect include acid-resistant synthetic resin pellets, common salt, coke particles, ceramic particles, Others are possible. The void retaining agent is mixed for the same purpose as the anti-caking agent, but may simply be used in combination. In addition to the above-mentioned deodorizers, other deodorizing agents that can be used in combination include an aqueous wood acid solution (main components are lime acid, guaiacolic acid, etc.), an alkali-stabilized chlorine dioxide aqueous solution, and an antifreeze aqueous solution (for example, propylene glycol, Agar gel containing ethylene glycol, etc.)
Possible examples include granules impregnated with an aqueous solution obtained by blending sulfonated lime or a cation exchange resin with the above antifreeze aqueous solution, and a mixture of ferrous iron and ascorbic acid.

When using the salts in a refrigerator or freezer, use a thermoplastic synthetic resin perforated film chopstick bag (for example, polyolefin-based resins, vinyl chloride resins, nylon resins, Tetron resins, vinylidene chloride resins, Teflon resins, etc.), breathable and moisture permeable nonwoven fabric bags, polyolefin resin fibers, and the above-mentioned thermoplastic synthetic resin fibers.

Acid-resistant metal fibers, glass fibers, carbon fibers, non-woven fabrics made of other fibrous materials, etc.), R-product bag making (for example, fabrics made of the same fibers as those used in the above-mentioned non-woven bag making), silk fabrics, cotton fabrics, raw silk fabrics, Linen fabric.

Other animal and plant fiber fabrics, acid-resistant metal fiber fabrics, etc.

Glass fiber fabric, etc.) 1. Has breathability and moisture permeability,
After sealing it in a bag made of a non-hydrophilic polyolefin porous sheet-like synthetic resin bag (for example, NF sheet manufactured by Tokuyama Soda Co., Ltd., Cellboa manufactured by Sekisui Chemical Co., Ltd., etc.), Store in a container that is breathable and moisture permeable (such as a box with an opening/closing lid). In addition, after sealing the salts alone or a mixture thereof, or the salts mixed with an anti-caking agent or a porosity retaining agent, and another deodorizing agent in separate air-permeable and moisture-permeable containers, They can be stored in one container, or the salts alone and the void retaining agent with deodorizing properties can be sealed in separate bags and used together by storing them in one container. can. Furthermore, several small chambers are defined inside the container having air permeability and moisture permeability, and the small chambers are configured to allow air and moisture permeability to each other (for example, the salts, the porosity retaining agent, A large number of ventilation holes smaller than the particle size of anti-caking agents etc. are drilled in the partition wall), and in every other small chamber, the above salts alone or in combination, or the above salts are mixed with an anti-caking agent or a void retaining agent. It is possible to directly store the stored items without putting them in the container. The air-permeable and moisture-permeable bag and container are characterized in that the salts include strong acids, moderate acids, weak acids, etc., and the salts include calcium chloride salts, etc. Considering that there are some materials that undergo hydrolysis when turned into an aqueous solution and exhibit acidity with a pH of 6 or lower, it is preferable that the material be acid-resistant and alkali-resistant. The container, which is breathable and moisture permeable, has ventilation holes in the upper part of the surrounding wall, taking into account that among the salts, there are substances such as calcium chloride that may liquefy due to moisture absorption but do not squirt. At the same time, the lower part and the bottom of the peripheral wall are constructed without opening ventilation holes, and the inside of the container is made of a wall that allows ventilation and moisture permeability (for example, the above-mentioned salts, anti-caking agents, void retaining agents, etc.). It is divided into upper and lower parts by a horizontal wall with countless small ventilation holes (with diameters smaller than the particle size), with the upper part being a deodorizing room and the lower part being a deodorizing room.

l into a water absorption chamber (coconut shell activated carbon and cotton as water absorption materials).

Cotton pulp, silicon dioxide particles, thick filter paper, zeolite,
chambers containing sponges, open-cell polyurethane foam, or other absorbent materials) to prevent water leaks in refrigerators and freezers. In addition, the water absorption chamber contains water-absorbing paper containing a water-absorbing polymer and an alkaline solid drug (for example, anhydrous sodium silicate salt, etc.).
and the hygroscopic, A4-degradable salts (e.g.
It is also used to improve safety by solidifying neutral, insoluble silicic acid through acid-alkali reactions and substitution reactions (ion-exchange reactions) to reduce the danger of calcium salts becoming aqueous solutions. The air-permeable and moisture-permeable container is provided with an air-permeable and moisture-permeable opening/closing lid to prevent contents from leaking out and to enable replacement. Note that in place of the air-permeable and moisture-permeable container described above, a deodorizer container for refrigerators that is already widely used can be used, but since it is not equipped with a water absorption chamber, it is difficult to prevent liquefied salt from accumulating. You need to be careful. In view of the above, it is convenient to make the entire or part of the container (the lower part of the peripheral wall and the bottom) transparent, which has air permeability and moisture permeability, so that the extent of the change in the salts can be confirmed by seeing through the container.

Materials for the container include acrylic resin, acrylic styrene resin, polystyrene resin, ABS resin, polypropylene resin, and vinyl chloride resin.

Acid-resistant and alkali-resistant materials such as medium-low pressure polyethylene resin and high-impact styrene resin can be used.

Since the salts have extremely high hygroscopic properties (however, in the case of water-soluble salts, they can be used in combination or in combination), they can strongly remove bad odors while absorbing moisture in the refrigerator or freezer. When using salts that are biodegradable and i11 decomposable in a freezer, even if it is impossible to remove frost that has already formed, it is possible to prevent new frost from forming due to its hygroscopic action.

Example 1 Hygroscopic, deliquescent salts (calcium chloride salts) 70% porosity retaining agent (from coal) 25% anti-caking agent (graphite particles or powder added to calcium chloride salt) 5% of the above salts (temperature 15 ℃ specific gravity 2.152> and the above anti-caking agent (specific gravity 1
．． 8-2.2, the finer the particles, the lighter the specific gravity) means that the specific gravity is about the same, so it is unlikely that the two will separate, and by attaching it to the surface of the salt, even if the salt solidifies due to moisture absorption. The anti-caking agent prevents caking, and the void retaining agent maintains fine communication gaps between the salts, preventing the odor inside the warehouse from coming into close contact with the salts and preventing the deodorizing effect from deteriorating over time. It is possible.

Experimental example 2 Example of use of magnesium chloride salt (divalent salt) NH3+H20
→NH< OH (cold humidity inside the refrigerator with ammonia odor dissolved) rc12+2
NH40H→ 2NH4Cf+l' + (OH,) 2 Experimental example 3 Example of using aluminum chloride salt (trivalent salt) NH3+H20
→NH40H (Cold humidity inside the refrigerator containing dissolved ammonia) AJ (J 3
+ 3N H40H→3NH4(J+AI (OH
)3 In both of the above two examples, divalent salts and trivalent salts undergo hydrolysis in the presence of water and become acidic; the former produces two ammonia odors, and the latter produces three ammonia odors. Alkali reaction, substitution reaction, ion exchange reaction) occurs, producing ammonium chloride salt and deodorizing it.

Experimental example 4 When deodorizing carboxylic acids with calcium chloride salts.

When acetic acid is used (possible in the presence of ammonia odor) NH3 + H20- → NH40H (cold humidity in the refrigerator with ammonia odor dissolved) CH3C0O
H+NH40H CH3GOONH4+820 2CH3GOONH4+CafJ2 →Ca (CH3
Coo)2 +2N84 C1 In this case, first a neutral or weakly alkaline ammonium acetate salt is generated, and then a substitution reaction (ion exchange reaction) with an acidic calcium chloride salt occurs to generate an ammonium chloride salt and deodorize it. .

Experimental Example 4 As a hygroscopic and deliquescent salt, a tetrahydrate (wet but granular) obtained by adding water to a calcium chloride dihydrate (granular) was used, and the tetrahydrate was filled with voids. Activated carbon (granules with a diameter of about 21TIT11) was used as a retention agent at a volume ratio (not based on the molecular weight ratio) of 1:'l.

Mix 1:2 (activated carbon) and 1:3 (activated carbon).
As a result of testing the deodorizing power and solidification state by placing each type of mixture on the upper, middle, and lower shelves of a refrigerator or freezer, very favorable results were obtained.

When calcium chloride salt absorbs moisture (water) and becomes a tetrahydrate salt, it solidifies when used alone, but it also solidifies in a refrigerator (below 4°C) or in a freezer (below 0°C).

However, each of the above three types of mixtures remains moist in the refrigerator or freezer, but remains in its original granular form, does not solidify even after about a month, and is strongly deodorized from ammonia and trimethylamine odors. There is. In addition, since the void retaining agent is activated carbon that has deodorizing power, the calcium chloride salt absorbs moisture (moisture) that reduces the absorption of other odors, keeping the dry state and exerting its effect (deodorizing power). There is.

The activated carbon used in this example is not only used as a void retaining agent, but also as an anti-caking agent for calcium chloride salts, and as a mixture agent that itself has deodorizing power, it is the best mixture agent for calcium chloride salts. I think that the. The same seems to apply to coconut shell activated carbon, acid activated activated carbon, and alkali activated activated carbon.

When calcium chloride salt absorbs moisture, it is easier to form molecular compounds with a strong ammonia odor and trimethylamine odor unless solidified, and it is also susceptible to acid-alkali reactions.
Easily causes ion exchange reactions. This is thought to be because when activated carbon is dry, its unique deodorizing effect is greater because its porous pores are not blocked by moisture.

Test Example When the same items as shown in Experiment 1 above were placed at the top and bottom of a refrigerator, the results were lower than those placed at the top.
It was found that the one placed at the bottom had a better deodorizing effect. This excellent deodorizing effect is due to the fact that the fine communicating voids between the salts are secured by the void retaining agent, and the caking is prevented by the anti-caking agent, allowing the odor inside the refrigerator to enter the fine communicating voids. This is thought to be due to frequent contact with salts. In this case, it was found that the deodorizing effect was more pronounced and more sustainable if the salts were kept slightly moist.

I have written about various drugs so far, but as a result of experiments, I found that calcium chloride @ (anhydrous salt, dihydrate salt, and mixtures thereof) and coconut shell activated carbon or porous high-quality activated carbon (
Mixing or using them together (some are acid-activated and some are alkali-activated, and each absorbs different components) can absorb odors over a particularly wide range and eliminate the drawbacks of each other. , I came to the conclusion that it is superior. Calcium chloride salt (anhydrous salt,
dihydrate salt or a mixture thereof) forms a molecular compound (see parenthesis above) with ammonia odor, trimethylamine odor, lower alcohol, and can absorb a large amount of vapor with a small amount of calcium chloride salt.On the other hand, it absorbs moisture. Steam calcium chloride salt has the disadvantage of solidifying due to water vapor. Even if it becomes an aqueous salt, it does not become an aqueous solution below 29.5°C, so it is possible to use coconut shell activated carbon or the above-mentioned high quality activated carbon as a pore retaining agent. On the other hand, coconut shell activated carbon or the high quality activated carbon has a very high
It is a drug with high porosity and strong adsorption and retention ability, and its odor includes sulfur compounds such as methyl mercaptan and methyl sulfide, alcohols, fatty acids, helogenated hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons, and esters. strongly absorbs. The disadvantage is that the pores become filled with moisture, resulting in a significant loss of absorbency. By using or mixing with calcium chloride salt, the calcium chloride salt absorbs the lost moisture and returns to the original dry state. Therefore, the coconut shell activated carbon can be kept in a dry state and deodorized for a long period of time. When these two types are mixed or used in combination with calcium chloride salt, if the ratio of calcium chloride salt is high, the coconut shell activated carbon may be dried out and may have an ammonia odor.

Absorption of trimethylamine odor, lower flucols, etc. becomes strong, and when the ratio of coconut shell activated carbon is high,
It was concluded that since the absorption of the above odors is strong, a product of excellent quality can be obtained by using a mixture or a combination of the two.

In addition, when used together, other void retaining agents (e.g., synthetic resin pellets, coal shavings, etc.) and anti-caking agents (e.g., graphite, others, etc.) may be mixed with calcium chloride salt to prevent caking. Do it like this.

Effects of the Invention Since the present invention has the above-mentioned structure, the hygroscopic action of salts and the odor of lower amines (mainly trimethylamine odor), etc., which could not be sufficiently deodorized with well-known deodorizers, such as ammonia odor (which is particularly easily absorbed by moisture), etc. Air circulation in the refrigerator or freezer allows salts to be adsorbed, and
Salts undergo hydrolysis in the presence of water and become acidic,
Ammonia odor, which is an alkaline substance.

Causes acid-alkali reactions and substitution reactions (ion exchange reactions) with lower amine odors (mainly trimethylamine odors),
Since the reaction of adsorption and deodorization as an ammonium salt is added, the deodorizing effect is improved and a fast-acting and long-lasting deodorizing effect is exhibited. If hygroscopic and deliquescent salts are used in the freezer, their strong hygroscopic action will prevent the formation of subsequent frost, even if it is impossible to remove the frost that has already formed. It is possible to remove bad odors inside the refrigerator.

Claims (1)

[Claims] Consists of the use of a single salt that is hygroscopic, deliquescent, or water-soluble and becomes acidic through hydrolysis in the presence of water, or a mixture or combination of salts that do not react when two or more of these salts are mixed together. Deodorizer for refrigerator and freezer.