JPS6131162A - Deodorant for refrigerator and freezer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Purpose of the Invention Industrial Field of Application The present invention is directed to the prevention of odors in refrigerators and freezers, especially fish and shellfish meat.
Ammonia odor, lower amine odor (mainly trimethylamine), and mercabutane odor emitted from other meats.
A deodorizer for refrigerators and freezers that strongly absorbs and deodorizes bad odors in the refrigerator, such as lower alcohols, and has fast-acting and long-lasting effects.The usage time can be adjusted freely depending on the amount of calcium chloride salt used. Regarding drugs.

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 Well-known coconut shell activated carbon has little effect on odor caused by 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.

The present invention is capable of powerfully removing odor in the refrigerator such as ammonia odor, lower amine odor, mercabutane odor, lower alcohol odor, etc., which are difficult to deodorize with coconut shell activated carbon alone, and the effect is fast-acting and long-lasting. The purpose is to provide an excellent quality deodorizer for refrigerators and freezers.

Means for Solving the Problems The present invention requires that calcium chloride salt has strong hygroscopic properties, that ammonia dissolves well in water at low temperatures, and that the inside of a refrigerator or freezer is relatively dry. Due to the low temperature and circulating air, a large amount of dissolved ammonia is absorbed into the calcium chloride salt, although there is little moisture.The calcium chloride salt gradually solidifies due to moisture absorption, and finally However, aqueous solutions of calcium chloride salts undergo hydrolysis in the presence of water and become acidic, so they undergo acid-alkali reactions and substitution reactions with ammonia, which is an alkaline substance. However, it also adsorbs ammonia odor by producing weakly acidic ammonium chloride salt and weakly alkaline calcium hydroxide salt, and at the same time creates molecular compounds, and also against lower amine odor (mainly trimethylamine). The same thing can be said as in the case of ammonia.The above trimethylamine ((CH3)3N) is an alkaline substance whose solubility in water is lower than that of ammonia, but is stronger than ammonia. In the same way, a molecular compound is created with calcium chloride salt, and in the presence of water, the calcium chloride salt that has absorbed moisture causes an acid-alkali reaction and a substitution reaction, and is adsorbed by the calcium chloride salt and deodorized.
Mercaptan is slightly soluble in water, heavier than air, and accumulates in low places, but as air circulates in refrigerators and freezers, it comes into contact with nocorsium chloride salt and forms a four-molecule compound (molecular compound). At the same time, generate Alcorado and 1
2.Alcolade is hydrolyzed and eventually transforms into a 4-molecule compound (molecular compound).Lower alcohols are very soluble in water, and together with calcium chloride salt, a 4-molecule compound (molecular compound). is created and adsorbed by calcium chloride salt as in the case of the lower amine odor,
Focusing on deodorization, we use calcium chloride salt alone or a mixture of calcium chloride salt and a void retaining agent that does not react with calcium chloride (including those with and without deodorizing properties). The calcium chloride salt and the above-mentioned pore-maintaining agent are used together, without being mixed, to maintain the fine communicating voids between the calcium chloride salts using a retaining agent.

Function The present invention consists of the use of calcium chloride alone or a mixture or combination of calcium chloride and a porosity retaining agent that does not react with calcium chloride. Calcium chloride salt exhibits strong hygroscopic properties, and despite the low temperature and low humidity inside the refrigerator or freezer, it absorbs cold moisture with a large amount of ammonia odor that dissolves well in water at low temperatures. At the same time, calcium chloride salts undergo hydrolysis in the presence of water and become acidic, causing acid-alkali reactions and substitution reactions with alkaline substances such as ammonia odor and trimethylamine odor. By making salt, calcium chloride salt exhibits the action of forming molecular compounds, making it possible to absorb moisture in refrigerators and freezers and powerfully remove bad odors. In this case, even if it is impossible to remove frost that has already formed, it is possible to prevent new frost from forming due to moisture absorption.

Examples Types of calcium chloride salts in which examples of the present invention can be used;
This will be explained below, including experimental examples and test examples.

Calcium chloride salts that can be used include anhydrous salts, -hydrate salts, dihydrate salts, tetrahydrate salts, hexahydrate salts, and acid-resistant, porous water-absorbing particles (including both inorganic and organic materials) that do not react with calcium chloride salts. ) have absorbed an aqueous solution of calcium chloride salt.

Furthermore, calcium chloride salts made by adding hydrochloric acid to elemental calcium, which is an alkaline earth metal, calcium chloride, calcium salt hydroxide, calcium carbonate, and other calcium salts.

Calcium chloride salt produced by chloride exchange reaction with strong or weak acids, ion exchange m1lFt.

It is also possible to use calcium chloride salts made from sulfonated coal, etc., and calcium chloride salts obtained by any other manufacturing method.

As a drug for the product of the present invention, is the trihydrate salt of calcium chloride available in granular form? It is the most suitable for use.

In order to prevent the calcium chloride salt particles from agglomerating due to moisture absorption, the porosity retaining agent is used when mixed with the calcium chloride salt, and when it is used without causing any problem even if the calcium chloride salt becomes agglomerated. 91 may be used. Therefore, the pore retaining agent may or may not have a deodorizing effect, but the above-mentioned conditions for mixed use and combination use include that it is a particle, and that it is a stable acid-resistant organic substance that does not react with calcium chloride salt or It must be inorganic. Specific examples of void retaining agents that can be used in combination include those with deodorizing properties (coconut shell activated carbon, raw ash, zeolite, silicon dioxide grains (silica gel grains))
etc.) and those without deodorizing effect (acid-resistant synthetic resin pellets, salt, coke grains, ceramic grains, etc.).In addition to the above-mentioned products that can be used in combination, there are also is carbolic acid.

guar V-colic acid, etc.), agar gel-like material containing an aqueous antifreeze solution (e.g., propylene glycol, ethylene glycol, etc.) in an alkali-stabilized chlorine dioxide aqueous solution (in this case, the inside of the refrigerator or freezer becomes dry). In order to determine the condition, agar gel-like material is obtained by blending the above antifreeze solution with sulfonated coal or cation exchange resin. There are also granules impregnated with an aqueous solution.

When using in a refrigerator or freezer, use calcium chloride salt alone or a mixture of porosity retaining agent in a thermoplastic synthetic resin perforated film bag (e.g., polyolefin resin, vinyl chloride resin, nylon resin, Tetoron resin, vinylidene chloride resin, Teflon resin, etc.), breathable and moisture permeable non-woven bags (e.g. polyolefin resin fibers, thermoplastic synthetic resins mentioned above, metal fibers, glass fibers, carbon fibers, other fibrous materials) (products, non-woven fabrics, etc.)
, woven bag-making (for example, two-layer silk fabric, cotton fabric, raw silk fabric, linen fabric, with the same mN as used for the non-woven bag-making above)
Other animals and plants NJII objects, metal II textiles, glass! l Miscellaneous fabrics, etc.) 9 Polyolefin porous sheet-like synthetic resin bags that are breathable and moisture permeable and non-hydrophilic (for example, Tokuyama Soda Co., Ltd. product name NF Receipt) Sekisui Chemical Co., Ltd. product After sealing the container in a bag such as Cellboa, etc., it is placed in an air-permeable and moisture-permeable container (such as a box with an opening/closing lid). In addition, calcium chloride salt alone or mixed with a porosity retaining agent and other deodorizing agents may be sealed in separate air-permeable and moisture-permeable containers, and then stored in one container. You can, and with calcium chloride salt alone.

The air gap retaining agent having deodorizing properties can be sealed in separate bags and housed in one container to be used together.

Furthermore, several small chambers are defined inside the air-permeable and moisture-permeable container, and the small chambers are configured to allow mutual ventilation and moisture permeability (for example, the small chambers are configured to have a diameter equal to or smaller than the particle size of the calcium chloride salt). A large number of ventilation holes are made in the picture wall), and calcium chloride or a mixture thereof with a porosity retaining agent can be directly stored in every small chamber without having to be placed in the container. The air-permeable and moisture-permeable container bag and container should be made of acid-resistant and alkali-resistant materials, considering that calcium chloride salt, when turned into an aqueous solution, undergoes hydrolysis and becomes acidic with a pH of around 5. is preferred. The container has air permeability and moisture permeability, and in consideration of the fact that calcium chloride salt liquefies due to moisture absorption, ventilation holes are bored in appropriate places in the soil of the surrounding wall, and no ventilation holes are made in the lower part of the surrounding wall. The inside of the container is divided into upper and lower parts by a wall that allows ventilation and moisture permeability (for example, a horizontal wall with countless small ventilation holes with a diameter smaller than the particle size of calcium chloride salt), and The deodorizing chamber, the lower part is the water absorption chamber (water absorption materials include coconut shell activated carbon, cotton, flocculent pulp, silicon dioxide particles, thick filter paper, zeolite 1 to 1.0 cm sponge, and open-cell polyurethane foam.

The room should be used as a chamber for storing other water-absorbing materials, and should be used to prevent water leakage inside the refrigerator or freezer. The inside of the refrigerator or freezer is relatively dry, so
If the door is not opened and closed very frequently, calcium chloride salt will absorb moisture and then solidify, but if the door is opened and closed very frequently when the temperature or humidity is high, the change from solidification to liquefaction may occur. Once it becomes an aqueous solution, it will not freeze even if stored in the freezer and is acidic, so care must be taken to prevent water leakage. The air-permeable and moisture-permeable container is equipped with an air-permeable and moisture-permeable opening/closing lid to prevent leakage of contents such as calcium chloride salt, porosity retaining agent, and other deodorizing agents, and to enable replacement. . Note that instead of the air-permeable and moisture-permeable container described above, it is possible to use a container for deodorizing agents for refrigerators that is already widely used, but in this case, since it does not have a water absorption chamber, calcium chloride It is necessary to pay attention to the accumulation of salt solution. In view of the above, it is convenient to make the entire or part (the lower part of the peripheral wall and the bottom) of the air-permeable and moisture-permeable container transparent, so that the degree of change in the calcium chloride salt can be confirmed by seeing through the container.

The materials used include acid-resistant and alkali-resistant materials such as acrylic resin, acrylic styrene resin (As resin), polystyrene resin, ABS resin, boria pyrene resin, vinyl chloride resin, medium-low pressure polyethylene resin, and high-impact styrene resin. It is possible.

Calcium chloride salts are suitable for use in the present invention because the anhydrous salt is a white, hygroscopic, deliquescent mass, and the dihydrate salt is a hygroscopic, particulate form. Calcium chloride salt has a very strong hygroscopic deliquescent property, and absorbs water and changes into anhydrous salt → -hydrate → dihydrate → tetrahydrate → hexahydrate → aqueous solution.

The tetrahydrate is solidified, and the hexahydrate is solidified and has a melting point of 29.5.
°C, and eventually becomes an aqueous solution. Calcium chloride salt is cold! Even though the interior of the refrigerator or freezer is relatively dry, it still absorbs moisture, depriving microorganisms and bacteria of the moisture they need to survive. Therefore, microorganisms and bacteria that decompose proteins and fats are inhibited from multiplying in the low parts of refrigerators and freezers without moisture, creating an atmosphere unsuitable for the survival of these microorganisms and bacteria. , food can be stored for a long time. Calcium chloride salts can be used in freezers to prevent new frost formation due to their strong hygroscopicity. The deodorizing principle of calcium chloride salt is
As shown in the experimental examples ■ and ■ below, it itself reacts chemically,
It deodorizes by creating molecular compounds (molecular compounds are molecules that have bonds between molecules with their respective atomic compositions unchanged), and have strong deodorizing power and long-lasting properties. .

Experimental Example ■ One molecule of calcium chloride salt reacts with eight molecules of ammonia odor to form a molecular compound called tlcp2.8N)+3, making it odorless.

Cl (! f2 + 8NH3 → Insect Leopard, ・8NH3 Ammonia is less soluble in water at lower temperatures, so at 0℃ it is 1300 times more soluble in water than in water, and at 20℃ it is 700 times more soluble in water than water) Since the calcium chloride salt is absorbed twice as much and becomes ammonia water, due to the excellent hygroscopicity of the calcium chloride salt, the ammonia odor is well absorbed at G1 temperature. Ammonia, which is not absorbed by water, comes into contact with calcium chloride salt through the air circulation inside the refrigerator, forms molecular compounds, and becomes odorless.

When the hygroscopicity of the calcium chloride salt progresses, in the presence of water, the ammonia odor becomes NH3+ 820-1N H40H, creating strongly alkaline aqueous ammonia. When this comes into contact with calcium chloride salt, -Cf2+ 2NH
401-1→ 2 N t1 4 C 4 and', a(Of-1)
2, which is a white compound that is slightly soluble in water, consisting of weakly acidic ammonium chloride salt and weakly alkaline calcium hydroxide salt.
At 25°C, 0.14 (I dissolved) per 100 g of water is produced and deodorized.

Here, the calcium hydroxide salt absorbs carbon dioxide gas and finally becomes a calcium carbonate salt.

koa(OH) 2 +go02→goa-COs+H
20 Therefore, if carbon dioxide gas exists in the refrigerator or freezer, it can be removed.

Also, in the presence of water, when ammonia gas comes into contact with calcium chloride salt, it becomes (LC12+2NH3'+282 0→ 2NH4(
? O+GotL(O)()2, and in the same way as above, a weakly acidic ammonium chloride salt and a weakly alkaline calcium hydroxide salt are generated and deodorized.

One molecule of calcium chloride salt creates a molecular compound with the odor of 8 molecules of trimethylamine among lower amines (mainly trimethylamine), making it odorless.

(icjz +8 (CH3) 3 N→Cωgo12
・8 (CH3) 3. N-lower amine odors are ammonia (NH3) substituted with an alkyl group (CH3-), and lower mi+J8 group amines have an odor (mainly trimethylamine) similar to the ammonia odor produced by decaying animals and plants. , is easily soluble in water and undergoes acid-alkali reactions and substitution reactions in the presence of water? Therefore, when calcium chloride absorbs moisture, it hydrolyzes in the presence of water and becomes acidic (PH5 pre-corrosion), so it has a strong alkaline trimethylamine odor and is deodorized in the presence of water. It reacts to produce a weakly acidic trimethylamine chloride salt for deodorization, and at the same time produces a weakly alkaline calcium hydroxide salt.

αC12+2 (CH3) 3 N + 2H
20→ 2 (CH3) 3 NHC'f
→ ecL (OH) 2 Experimental Examples ■ One molecule of calcium chloride salt reacts with four molecules of lower alcohol. For example, ethyl alcohol and (A, C
Creates a molecular compound called 12.4C2+5OH to make it odorless.

and αC12+ 4C2+5 OH → CLcf2 402 +5 OH Malodorous substances such as mercaptans (also called thioalcohols or dimols) produced by the decomposition of proteins are those in which the oxygen atom of the hydroxyl group of alcohol is replaced with a sulfur atom (
R-8H.

(R is an alkyl group), like alcohol, four molecules of mercaptan smell react with one molecule of calcium chloride salt to form a molecular compound and become odorless. Foods that emit a mercaptan odor are no longer edible, but the mercaptan has an unpleasant odor (salty odor) and produces a metal compound corresponding to alcoholade.

R-8M (Create mercaptide) ¥R;
Alkyl group, S: sulfur M: metal, (e.g. calcium, sodium, potassium, magnesium, etc.) Calcium salt alcoholade is hydrolyzed by water and returns to mercaptan, and finally becomes one molecule of calcium chloride salt. Four molecules of mercaptan odor are deodorized by forming a molecular compound, and a weakly alkaline calcium hydroxide salt (a slightly warm white compound in water, dissolves at 0.14 g per 100 ml of water at 25°C) is produced. Since calcium chloride is slightly alkaline, its acidity becomes weaker.

(R-8) 2 (1: Mountain + 2 days 20 → 2R-3 to 1 +., (O) () 21 As an example, if ethyl alcoholade calcium salt is hydrolyzed, (C2+5 S) 2 Dosaki+ 2820→ 2C2+
5. SH + Go (L (OH) 21-item test example ■ Calcium chloride salt dihydrate (150 l) was placed at the bottom of the refrigerator and the door was frequently opened and closed. Although the deodorizing power has been strengthened, the deodorizing power has been strengthened.
It seems that the deodorizing power of calcium chloride salt works better when the inside of the refrigerator is in a humid atmosphere. Usage period is 2
Although several months have passed, it continues to deodorize strongly.

Example of the same test ■ When I placed 150 fll of calcium chloride dihydrate on the top of the refrigerator and opened and closed the door occasionally, I found that the calcium chloride salt had solidified due to moisture absorption, but I could not touch it. When I rubbed it, it fell into small pieces. However, although it strongly deodorizes bad odors such as ammonia odor, trimethylamine odor, mercaptan odor, and lower alcohol, product test example (■) placed in the lower part of the refrigerator was even more powerful than this example. Then, in the summer, the calcium chloride salt in the refrigerator became lumpy, but the deodorizing power became even stronger. Although it has been in use for two months, it continues to deodorize strongly.

From the above test examples, moisture and odor (odor is particles)
seems to collect at the bottom of refrigerators and freezers.

Therefore, it seems that the deodorizing agent exerts a more pronounced deodorizing effect when placed in the lower part of the refrigerator. How to use refrigerators and freezers,
Although there are differences depending on the capacity etc., if you add some water to the calcium chloride salt dihydrate to moisten it from the beginning,
It is preferable as a product because it is fast-acting and there is no change in subsequent effects.

Test Example ■ 150g of dihydrate calcium chloride salt was placed in a plate-like layer in the upper and lower parts of a refrigerator and a freezer, and air permeability was observed.

Excellent deodorizing function was observed compared to Test Examples (1) and (2) in which the sample was simply filled in a moisture-permeable container.

When comparing the products placed at the top and bottom of each refrigerator, it was found that the deodorizing effect of the product placed at the bottom was 6 times greater than that of the product placed at the top. In this case as well, it is more preferable to add some water to the dihydrate salt of calcium chloride salt to moisten it and then pour it on, since it is quick-acting and there is no change in the subsequent effect.

Through this test, it was recognized that calcium chloride salt needs to be used in good contact with moisture and odors, and it was felt that it is necessary to ensure a large moisture absorption area and a large odor absorption area. Therefore, an air-permeable and moisture-permeable container alternately forms deodorizing chambers and empty chambers in which the calcium chloride salt can come into contact with moisture and odors, thereby ensuring air permeability and moisture-permeability of the chambers. It should be configured as follows.

Test Example■ When 70% dihydrate of calcium chloride salt was mixed with 30% coke grains as a pore retaining agent that did not react with the dihydrate and placed in the upper and lower parts of a refrigerator and freezer, respectively,
It was found that the deodorizing effect was better than that of Test Example (■). When comparing the products placed at the top and bottom of each refrigerator, it was found that the products placed at the bottom had a better deodorizing effect than those placed at the top. The excellent deodorizing effect exhibited in this test example is due to the fact that the fine communicating voids between the calcium chloride salts are secured by the void retaining agent, and the odor inside the refrigerator enters into the fine communicating voids between the calcium chloride salts. This is thought to be due to frequent contact. In this case as well, add some water to the dihydrate salt of calcium chloride from the beginning and moisten it! (If you keep it, it will have a quick effect,
Rb is preferable because there is no change in the subsequent effect.

Effects of the Invention The present invention consists of a pore retaining agent that does not react with calcium chloride salts or lucium chloride salts, and a mixture or combination of calcium chloride salts, so that known deodorizers cannot sufficiently deodorize. odors of ammonia (especially easily absorbed by moisture), trimethylamine odors, and mercaptan odors.

Terrible odor substances such as lower alcohols (odors emitted from fish and shellfish meat) are absorbed by calcium chloride salts due to the hygroscopic action of calcium chloride salts and air circulation in the refrigerator and freezer, and are chemically converted into molecular compounds. In addition, when calcium chloride salt is assimilated and turned into an aqueous solution by moisture absorption, it is hydrolyzed and becomes acidic quickly, so it undergoes an acid-alkali reaction and substitution with alkaline substances such as ammonia odor and lower amine odor (mainly trimethylamine odor). The addition of a reaction that creates salt increases the deodorizing effect and provides a fast-acting and long-lasting deodorizing effect. It also has the effect of removing moisture in the refrigerator or freezer and inhibiting the growth of microorganisms and bacteria. Furthermore, when used in the freezer, its strong moisture absorption action prevents the formation of subsequent frost, even if it is impossible to remove the frost that has already formed, and also eliminates the odor inside the refrigerator similar to the above-mentioned terrible odor. It is possible.

Therefore, in consideration of the fact that an aqueous solution of calcium chloride salt causes hydrolysis and accelerates acidity, consumers are advised to use pH indicators (for example, Lidmus test paper) that change color in an acidic aqueous solution of calcium chloride salt. , phenolphthalein, etc.) in a container, it is possible to provide a kind product that allows you to know the production of the aqueous solution with certainty.If a water-absorbing material is placed in the water-absorbing chamber at the bottom of the container, calcium chloride To provide a highly safe product that can absorb a salt aqueous solution and eliminates concerns about water leakage. In addition, if a white or transparent water-absorbing material (for example, silicon dioxide particles, thick filter paper, etc.) is impregnated with a PH indicator in advance, the discoloration caused by water absorption of the water-absorbing material can be used to detect the formation of a calcium chloride salt aqueous solution and to prevent water leakage. It is possible to achieve both prevention and prevention at once, and to provide even more kind and convenient products. What's more, if you decide on the amount of calcium chloride salt, pack it in a container, and affix a sticker to write the date of use on the surface of the container, you can determine how long it takes for the deodorizing chemical reaction to finish and when it needs to be replaced. We can provide a convenient product that allows you to know whether or not you want to do something.

Claims (1)

[Claims] A deodorizing agent for refrigerators and freezers, comprising a calcium chloride salt alone or a pore retaining agent that does not react with calcium chloride salt, and a mixture or combination of calcium chloride salt.