JPS62218478A - Deodorizing antioxidant - Google Patents

Abstract

PURPOSE:To provide a deodorizing antioxidant which is harmless, has excellent shelf stability and can retain persistent effect, consisting of specified compds. CONSTITUTION:At least one compd. (A) selected from the group consisting of 0.01-80pts.wt. hydroxycarboxylic acids (e.g., citric acid) and alkali metal salts, ammonium salts and amine salts thereof and/or 0.02-70pts.wt. 12C or lower (un)saturated fatty acids (e.g., acetic acid) and alkali metal salts, ammonium salts and amine salts thereof, 0-50pts.wt. (per 100pts.wt. component A) synergist (B) such as glycine, natural fatty acid such as tall oil fatty acid, rosin fatty acid, etc., and a chlorophyllin compd. such as iron chlorophyllin sodium, etc. and optionally, 3-7pts.wt. emulsion stabilizer (C) such as glycerol fatty acid ester, sodium metaphosphate, etc., are dissolved or dispersed in 100pts.wt. water to obtain a deodorizing antioxidant.

Description

[Detailed Description of the Invention] [Industrial Application Field] There are surprisingly few substances that exhibit both deodorizing and antioxidant effects. There are many deodorants on the market, with different effects, and antioxidants are used to some extent, but as mentioned above, there are only a few that have both effects at the same time, and there are unresolved problems. In other words, if it satisfies the following conditions, it will be revolutionary, and its early appearance is eagerly awaited by the livestock industry, deodorant, meat, fish industry, building materials industry, plastic processing industry, etc. .

In other words, (1) long-lasting effect, (2) safety and hygiene, especially harmless as food, or non-toxic, (3) long shelf life as a product, and (4) coloring and other harmful effects during and after use. (5) The target of the effect is not limited and the effect is at least as good as possible in a short period of time; (6) Heat treatment is also possible if possible; (7) There is no peculiar odor caused by the treatment. (8) Preferably, it does not contain metals such as iron, etc., and the industrial fields of application will be wide-ranging.

In other words, in terms of deodorizing, it also takes into account the antioxidant effect, and is effective against industrial waste, sewage sludge, household waste such as swimming materials, livestock sheds, chemicals, etc.
It can be used to deodorize refrigerators, shoe racks, swimming tanks, etc. for livestock barns and households that contain fish and meat odors, animal odors, and animal frozen ground, and for oxidation prevention that also serves as deodorization, wrapping paper, paper containers such as cardboard, non-woven fabrics, etc.
Processed into bentonite, activated carbon, zeolite, plastic sheets, plastic bags, etc., such as fish, meat, etc.
It can be used to extend the freshness of vegetables, etc., or as a water-based deodorizing paint.It can also be used for both purposes, such as extending the freshness of cut flowers, promoting plant growth, cleaning the atmosphere, and potentially curing athlete's foot, etc. As a biotechnology, it has a wide range of uses and possibilities, such as the possibility of suppressing cancer cells and drinks.

However, this is only possible if the above-mentioned conditions are satisfied. This is exactly what each industry aspires to. Unfortunately, nothing that satisfies the above conditions has yet been found.

The product of the present invention satisfies all of these requirements and is expected to have great effects in the development of new uses in addition to the above.

[Prior Art] As mentioned above, there are very few commercially available or patented products that exhibit deodorizing and antioxidant effects at the same time. There is a method in which a divalent iron compound is treated with an oxycarboxylic acid and/or an alkyl lower fatty acid having 4 or less carbon atoms, as disclosed in Japanese Patent Application No. 60-241272 and Japanese Patent Application No. 60-255840.
It satisfies more than 80% of the above conditions, except for containing valent iron and having some problems with heat resistance. However, the product of the present invention is unique in that it has a special effect on deodorizing household waste. It is true that these substances are particularly effective in deodorizing household waste.

As a combination of divalent iron compound and L-ascorbic acid, which is already commercially available,
There are proposals such as those in Publication No. 6539, and there are some that contain anti-discoloration agents, and others that use activated carbon, zeolite, and bentonite as carriers, but the effect retention and product stability under each of the conditions mentioned above are important. Issues such as the duration of use, coloring and other issues, the issue of limiting the effect on targets (particularly certain chemicals, and the ability of heat treatment to be applied, etc., are not seen as expected), and the ability to perform heat treatment are all unsatisfied. .

In any case, among the conditions mentioned above, the holding and storage period is extremely short, and blackish brown discoloration or precipitation occurs.
Although it works for ammonia, other chemicals, especially swimming techniques, chicken manure, etc., do not have satisfactory effects, so it seems that it is far from satisfying the requirements.

What must also be clearly stated here is that the combination of divalent iron and oxycarboxylic acid and/or alkyl lower fatty acid having 4 or less carbon atoms, and the combination of divalent iron and L-ascorbic acid are both activated. The iron chain compound is the trump card for the effect, and since divalent iron is the main ingredient, the amount of iron compound used is the largest, and although the number of combinations is small, it is small, so depending on the concentration used, the deodorizing effect may be There is a concern that the odor may remain.

Also, there are many types of general deodorants, and most of them are physical, such as activated carbon, activated clay, etc., or because their deodorizing action is physical, it takes time for the effect to appear, and they are not particularly effective. is normal, and no further development can be expected. However, maintaining the freshness of animals, plants, and fish through the antioxidant effect is chemical, and if you consider this together with the deodorizing effect, it is largely due to both chemical and physical effects. The problem of discoloration and the possibility of thermal processing would be a revolutionary problem. Since heat treatment reduces activation, there is a limit to the use of divalent iron as a main component. There are no other deodorizing antioxidants that pose particular problems, and if something that satisfies each of the conditions listed above to the greatest extent possible appears, it would make a truly great contribution to each industry.

[Problems to be solved by the invention] As a result of the efforts of the present inventors to discover something that completely satisfies the above-mentioned conditions, the inventors have discovered the ability to be physically and chemically activated by themselves. Or, I have come to the conclusion that I can use what I potentially have. As a result, C0, which is easy to dissociate,
Alkali metal salts, ammonium salts, such as 0II group or the like,
It was concluded that the substance must have an amine salt and produce the following butyric compounds in water. That is, the present inventors have determined that the most desirable one is one that is estimated to produce the following butyric compounds. That is, the example is C
When taken as 0OH, R-GOOR+ H, O → [(H2o), (RCOO
),,]-(wherein R is an alkyl group or a substituted alkyl group, m.

n represents an integer of 5 or less).

As a result, the present inventors found that oxycarboxylic acids, alkali salts of oxycarboxylic acids, ammonium salts, amine salts, fatty acids having 12 or less carbon atoms, and alkali salts, ammonium salts, and amine salts of such fatty acids have this tendency. I came to discover. In other words, it has the strongest ability to generate butyric compounds, and [(
H2O) and (RCOO)n act as strong acid ions, and as oxycarboxylic acids, both citric acid and acetic acid among saturated and unsaturated fatty acids with 12 or less carbon atoms have the most satisfactory effects. It was successfully discovered.

[Means for Solving the Problems] and [Operation] As described above, the present invention is an antioxidant having deodorizing properties that satisfies the above-mentioned requirements, using one or more oxycarboxylic acids, Alkali metal salts of oxycarboxylic acids, ammonium salts of oxycarboxylic acids, amine salts of oxycarboxylic acids and/or saturated or unsaturated fatty acids having 12 or less carbon atoms, alkali metal salts of saturated or unsaturated fatty acids, ammonium salts of saturated or unsaturated fatty acids, saturated, It is a deodorizing antioxidant consisting of unsaturated fatty acid amine salts, among which oxycarboxylic acids include citric acid and saturated oxycarboxylic acids with 12 or less carbon atoms.

It has been discovered that acetic acid is the most suitable among unsaturated fatty acids. Oxycarboxylic acids are effective because they have strong acidity and metal-sequestering ability due to the OH group in their structure, and among these, citric acid, which has particularly strong metal-sequestering properties, is suitable for the purpose of the present invention. Other oxycarboxylic acids include lactic acid, dR-malic acid, tartaric acid, etc., and although they are all less effective than citric acid, they do not pose any problem in producing the effects of the present invention. In addition, in the case of saturated and unsaturated fatty acids having 12 or fewer carbon atoms, there are many types such as formic acid, acetic acid, propionic acid, acetic acid, etc., but the reason why acetic acid gave particularly favorable results is that even though it is a weak acid, the acid formation equilibrium constant At 25°C, for example, despite the ionic strength of divalent iron compounds being 0 in an aqueous solution, 1',
This is a fact that shows 40. This is presumed to be due to the fact that coordination butyric compounds are easily formed. Formic acid, propionic acid, acetic acid, and water-soluble unsaturated fatty acids also exhibit this tendency, but acetic acid is particularly superior among them. Therefore, citric acid and acetic acid unexpectedly belong to the category of food additives for which there are no standards for use, resulting in even more favorable results. That is,
It is judged that citric acid contributed to the purpose of the present invention because of its strong acidity and strong metal sequestering property, and because acetic acid had an excellent solute-forming ability despite being a weak acid. When using, the amount of alkali metal salts such as citric acid, sodium citrate, potassium citrate, ammonium citrate, and amine citrate is 10 parts water.
0.1 to 80 parts by weight, preferably 0.2 parts by weight
~20 parts by weight, 0.02 parts by weight for acetic acid per 100 parts by weight of water
The amount is 70 parts by weight, preferably 0.15 to 20 parts by weight, and when used in combination, 1 to 3 parts by weight of acetic acid is preferably used for 6 to 8 parts by weight of citric acid. As a synergist, natural fatty acids such as glycine, tall oil fatty iron, and rosin fatty acids, chlorophyll compounds such as sodium iron chlorophyllin and sodium copper chlorophyllin, various inorganic acids such as phosphoric acid, sulfuric acid, and hydrochloric acid, tuccinic acid, and succinic acid are used as synergists. Acid alkali metal salts, ammonium succinate, gallic acid, alkali metal gallic acid, oleic acid (as an emulsion in water of glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester), alkali metal oleate, ammonium oleate salt, oleic acid amine salt, tannic acid, alkali metal tannic acid salt, L-ascorbic acid,
Sodium L-ascorbate, potassium sorbate, thiamine hydrochloride, thiamine nitrate, erythorbic acid, sodium erythorbate, ethylenediaminetetracalcium acetate 2
1~lium, ethylenediaminetetraacetic acid disodium,
Ammonium alum, baked alum, ordinary alum, ferrous talconate, inorganic divalent iron compounds, ferrous malate, ferrous fumarate, ferrous gallate, ferrous iodide, There are ammonium chloride, ammonium sulfate, sodium chloride, potassium chloride, magnesium chloride, alcohols with 3 or less carbon atoms, but in addition to alcohols, there are oxycarboxylic acids and/or saturated and unsaturated fatty acids with 12 or less carbon atoms. The amount added is generally between 0 and 50 parts by weight, most preferably between 3 and 35 parts by weight. Among these, the alcohol having 3 or less carbon atoms is 1 to 3 parts by weight. For inorganic divalent iron compounds, the combined addition of L-ascorbic acid, sodium L-ascorbic acid, gallic acid, and tannic acid has not yielded very good results, so it is better not to use them in combination. Moreover, oleic acid is added in the form of emulsification, and the amount added is the same. In addition, glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, sodium metaphosphate, sodium birophosphate, and polyphosphoric acid are Syne.
It is also called an rgist auxiliary agent, and is mainly used for emulsification and stabilization, and is preferably used in an amount of 3 to 7 parts by weight per 100 parts by weight of the product of the present invention.
Parts by weight are preferred. Next, the product of the present invention is mixed with various polymeric compounds including various vinyl polymerization and copolymer resin aqueous emulsions, synthetic, natural rubber latex, wax-based aqueous emulsions, polyvinyl alcohol, and water-soluble cellulose derivatives, and the ratio thereof is determined according to the present invention. Product: Various emulsions and polymer compounds are 2/98 to 98/2. Of course, good compatibility is a prerequisite, or it is also possible to improve the compatibility by performing appropriate pretreatment. Therefore, it can be used as a deodorizing paint. By spraying, coating, or impregnating the product of the present invention, it can be effectively used on the surfaces of buildings, fibers, paper, paper cartons, nonwoven fabrics, wood, metal products, etc., and the objects and effects of the present invention can be exhibited. The aqueous solution of the present invention can be adsorbed onto activated carbon, bentonite, zeolite, or other harmless rock powder, and used as a powder or granular deodorizer, and the adsorption amount is about 0.02 to 40% by weight as the solid content of the present invention. is preferred. In addition, as for paper, it is generally preferable to use water-resistant paper with a basis weight of 30 to 60 g/m'', which is impregnated with the aqueous solution of the present invention in a size press or calender coating process, but with a solid content of 0.0
1 to 5 g/m2 is preferable, and drying is also carried out at 110°C, 1 to 2
Even if it is separated, the effect will not decrease in any way, and there is no risk of coloring. In this case, it is also preferable to use in combination the above-mentioned synthetic resin aqueous emulsion, wax-based aqueous emulsion, synthetic rubber latex, water-soluble polymer compound, etc., which have good compatibility.

In addition, the product of the present invention can be filled into metal containers or plastic containers and used as a deodorizing spray in homes and other places, making it ideal for deodorizing and cleaning hotels, hospitals, etc., and the concentration of the product of the present invention is 0.0.
It is preferably about 1 to 0.5%.

Furthermore, it is of course possible to make deodorizing sheets and bags by applying or rolling it onto plastic bags and sheets.

In addition to the above, there is no problem in adding anything that improves the effects of the present invention without hindering them, and all uses that can be obtained by quantitative adjustment fall within the scope of the present invention.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 The deodorizing effect is tested as follows.

Test solution preparation Each test solution was prepared according to the composition shown in Table 1.

Table 1 (g) Technique 5 When the above solution is diluted 5 times and 10 times with water, the content of uninvented products is as shown in Table 2 below.

Table 2 (g) Collect a predetermined amount of the following malodorous liquid into a 500cc beaker, and add the above 5x and 10x diluted solutions to 500cc oJ [atomizer (1
It was sprinkled with 0.7 cc of wipes. The results are shown in Table 3. In Table 3, those that were immediately deodorized within 4 wipes, those that were immediately deodorized within 0110 wipes, and those that had no O1 effect are marked with an x.

Table 3 Example 2 Antioxidant Effect Test A solution having the composition shown in Table 4 below was prepared and left in the air for a predetermined period of time.The solution, which was initially colored green, was oxidized and discolored by ferrous sulfate. The degree was observed. The results are also listed in Table 4.

Table 4 (g) From the above results, it can be seen that the deodorizing antioxidant of the present invention has a remarkable antioxidant effect.

Example 3 Deodorizing effect of the neutral product of the present invention Test solution preparation Each test solution was prepared according to the composition shown in Table 5.

Table 5 The deodorizing effect was confirmed by the method described in Example 1 using each of the above-mentioned adjustment solutions.

The results are shown in Table 6.

From the results in Table 6 and above, the effect of the present invention is found to be the most difficult to achieve in neutral to
It was confirmed that it is highly effective in weakly acidic conditions. Moreover, there were requests from various quarters to preserve the aroma, so the aroma became slightly easier when testing oranges and strawberries.
It was confirmed that enough water was left, and a large amount was added.

[Effects of the Invention] The advantages of the present invention are that it has a deodorizing effect and an antioxidant effect at the same time, and (1) has a long lasting effect, and (2) can be used as a food and is harmless.

(3) The product has a long storage period, (4) There is no coloration or other harmful effects before and after use, (5) The effect is not limited,
To demonstrate at least a commensurate effect in Ogaki time,
(6) It must be stable against heat, (7) It must not leave any special odors as a side effect from the processing agent, (8) It must not contain metals such as iron, (9) It must be free from bad odors if possible. Not only does it solve the absolute requirements of each industry, such as books that require removal of aromas and aromas, but the fact that it is highly effective even in neutral to weakly acidic conditions can be said to demonstrate its characteristics beyond the requirements.

As a result, the product of the present invention has both deodorizing and oxidizing effects, and can be used as a deodorizing agent for industrial waste, sewage sludge, household waste such as floor waste, etc.
It can be used in the form of mist or aqueous solution to deodorize deep animal beds in livestock barns, animal odors, deodorize and air purify hotels, hospitals, etc., deodorize hospital waste (used gauze, etc.), and the present invention. The product can be adsorbed in powdered or granular form, powdered activated carbon, zeolite, bentonite, etc., and used in household refrigerators, shoe cabinets, closets, etc. Next, the product of the present invention is made into an aqueous solution due to its antioxidant effect, and is added to thin paper, kraft paper, cardboard, nonwoven fabric, and textile products by impregnation, roll coating, or spraying, and is applied to paper, folding cartons, nonwoven fabric, etc. for contact packaging with deodorizing effect. It is highly effective in preserving the freshness of perishable products such as fish, meat, and vegetables.

Similar effects can be expected on buildings and building materials, and it can also be safely used as a drink. Also, pharmaceuticals (treatment of athlete's foot, etc.) are a future issue.

As a biotenology, it also has the possibility of suppressing cancer growth using ion. In any case, it is clear that a wide range of uses can be found by combining the components of the present invention in quantity, using a compensating agent, adjusting the concentration used, and the amount of adsorption or adsorption, and all of these are within the scope of the present invention. It is natural to enter. Therefore, the field is closely related to a wide range of fields including deodorant manufacturers, paper manufacturers, meat and fish transportation and storage companies, hotels, hospitals, households, paint manufacturers, pharmaceutical manufacturers, building materials manufacturers, plastic manufacturers, construction industries, energy saving manufacturers, and others. I am confident that it will become a reality.

Claims (1)

[Claims] 1) One or more oxycarboxylic acids, alkali metal salts of oxycarboxylic acids, ammonium salts of oxycarboxylic acids, amine salts of oxycarboxylic acids, and/or saturated or unsaturated fatty acids having 12 or less carbon atoms, saturated A deodorizing antioxidant consisting of , unsaturated fatty acid alkali metal salt, saturated and unsaturated fatty acid ammonium salt, and saturated and unsaturated fatty acid amine salt. 2) Natural fatty acids such as glycine, tall oil fatty acids, and rosin fatty acids, chlorophyll compounds such as sodium iron chlorophyllin and sodium copper chlorophyllin, as compensating agents;
Inorganic acids such as phosphoric acid, sulfuric acid, and hydrochloric acid, succinic acid, alkali metal succinate, ammonium succinate, gallic acid, oleic acid, alkali metal oleate, tannic acid, alkali metal tannic acid, L-ascorbic acid , L-sodium ascorbate, potassium sorbate, thiamine hydrochloride, thiamine nitrate, erythorbic acid, sodium erythorbate, disodium ethylenediaminetetraacetic acid calcium, disodium ethylenediaminetetraacetic acid, ammonium alum, baked alum, ordinary alum, Various inorganic divalent iron compounds such as ferrous gluconate, iron lactate, ammonium iron citrate, ferrous chloride, ferrous malate, ferrous fumarate, ferrous gallate, ferrous iodide ,Ammonium chloride,
The deodorizing antioxidant according to claim 1, in which one or more of ammonium sulfate, sodium chloride, potassium chloride, magnesium chloride, and alcohols having 3 or less carbon atoms are added together. 3) To improve the effect, if necessary, use glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester,
The deodorizing antioxidant according to claim 1, in which sodium metaphosphate, sodium pyrophosphate, sodium polyphosphate, etc. are added in combination. 4) Aqueous emulsions, synthetic rubber latexes, wax-based emulsions, and natural rubber latexes produced by polymerization or copolymerization of polymerizable monomers such as vinyl acetate, acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, styrene, and acrylonitrile with good compatibility. The deodorizing antioxidant according to claim 1, which is used in combination with a water-soluble polymer compound such as polyacrylic acid, polyvinyl alcohol, hydroxymethyl or ethyl cellulose, or methyl cellulose. 5) The deodorant antioxidant according to claim 1, which is adsorbed on activated carbon, zeolite, bentonite, or other harmless porous materials.