JP2006129707A - Freshness preservative or deodorant composition, and method for using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a freshness preservative or deodorant composition environmentally friendly and having high safety. <P>SOLUTION: The freshness preservative or deodorant composition comprises a composition having at least one kind selected from the group of (a) an inorganic-organic hybrid compound comprising titanium and an organic acid and (b) an organic acid and their metal salts. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a freshness-keeping or deodorant composition that can be used as a freshness-keeping agent and a deodorant, and more specifically, a safe and effective freshness-holding or deodorant composition that does not adversely affect the environment or human body, And its usage.

  Fruits such as apples and peaches, vegetables such as broccoli, and flower buds such as carnations are ripe and aged due to ethylene gas released from inside the fruits during transportation and storage after harvest.

  Ethylene gas also affects other fruits and vegetables in the same package and promotes a reduction in the overall freshness. For this reason, it has been difficult to ship fully ripe away from the production area, and it has been difficult to deliver sufficient taste and quality to consumers.

  Conventionally, as a solution to these problems, a method of decomposing ethylene gas with potassium permanganate and a method of oxidizing ethylene with ozone have been proposed. However, potassium permanganate is harmful to the human body and should not coexist with fruits and vegetables. In addition, ozone treatment produces formic acid, acetic acid, and formaldehyde due to oxidation of ethylene, which has problems with odor and safety.

  Furthermore, although it has been proposed to maintain freshness by low-temperature storage and control of carbon dioxide concentration, it requires a considerable amount of equipment and at the same time increases the cost during storage.

  In the preservation of freshness of fruits and vegetables, if the oxidative decomposition of the released ethylene gas is attempted, formic acid, acetic acid and formaldehyde are considered to be produced in the process. In the case of ozone oxidation, it is necessary to further treat these compounds produced in the middle with a catalyst in order to finally decompose them into carbon dioxide gas and water (Japanese Patent Laid-Open No. 2002-65152). That is, as a freshness-preserving agent that is environmentally friendly and highly safe for the human body, not only the decomposition of released ethylene, but also neutralization, addition, oxidation-reduction or formic acid, acetic acid, formaldehyde, etc. that are secondaryly produced as a result. It must be able to be converted to a safer one by decomposition or the like. In other words, it is necessary to have both freshness maintaining performance and deodorizing performance, and such a freshness maintaining agent has not been developed yet, and development is desired.

  An object of the present invention is to provide a freshness-preserving agent such as fruits and vegetables that is environmentally friendly and highly safe for the human body.

As a result of intensive studies to achieve the above-mentioned object, the present inventor has surprisingly found that the freshness-preserving agent having a high ability to remove ethylene according to the present invention has a surprisingly excellent deodorizing effect particularly on formaldehyde. The present invention was completed. That is, the present invention
Freshness characterized by comprising as a main component at least one selected from the group consisting of (a) an inorganic-organic hybrid compound comprising titanium and an organic acid, and (b) an organic acid and metal salts thereof. It relates to a composition for holding or deodorizing.

  The composition of the present invention has not only a freshness maintaining function but also an excellent deodorizing function, and can be used alone or has a more excellent deodorizing function. It can also be used in combination with an agent. In recent years, the toxicity of formaldehyde diffused from building materials such as sick house syndrome has become a problem, but the deodorant of the present invention is useful as an aqueous composition that is highly safe for the environment and the human body. That is, in such a case, the composition of the present invention can be used alone as a deodorant for reducing the removal of formaldehyde regardless of the freshness maintaining function.

  The composition of the present invention has not only a freshness-retaining property but also a deodorizing property. Therefore, it can be used as a freshness-retaining agent and / or a deodorizing agent. And unlike the conventional composition, the composition of the present invention is environmentally friendly and highly safe. In addition, as shown in Examples (Tables 1 to 3) described later, both freshness retention and deodorizing properties are provided. It exhibits excellent effects and is extremely practical.

  The inorganic-organic hybrid compound consisting of titanium and organic acid of group (a) used in the present invention is obtained by hydrolyzing titanium tetrachloride or titanium tetraisopropoxide (Ti-iPrO) in an organic acid solution. Is obtained. In the present invention, these compounds are directly used as an aqueous dispersion or an aqueous solution without isolation. Titanium tetrachloride reacts fast, but emits white smoke at room temperature, and the reaction is intense. Therefore, using Ti-iPrO is milder and preferable.

  The organic acid used in the present invention is not particularly limited, and examples thereof include acetic acid, acrylic acid, malic acid, citric acid, lactic acid, ascorbic acid, tartaric acid, succinic acid, maleic acid, and ricinoleic acid. It is done. Furthermore, a polymer of an organic acid can be used, and examples thereof include polyacrylic acid, polylactic acid, and a styrene-maleic anhydride copolymer. Among these, acetic acid, tartaric acid, malic acid, citric acid, ascorbic acid, and polyacrylic acid (molecular weight is usually about 500 to 2000) are particularly preferably used in consideration of environment and safety to human body.

  Although the reaction molar ratio of titanium and organic acid can be selected within a wide range, it is usually 0.5 mole: 6 mole, but precipitation is likely to occur when the molar ratio of titanium is large, and acidic when the molar ratio of organic acid is high. Is too strong, the range of 1 mol: 4 mol is particularly good. Content of an inorganic-organic hybrid compound is not specifically limited, It is the range of 0.1%-75% (weight) in the whole composition, It is preferable to adjust within this range. However, if the content is less than 0.1%, the effect of maintaining freshness and deodorizing properties cannot be expected so much. If the content is more than 75%, the viscosity of the reaction solution becomes too high, stirring becomes difficult and precipitation is likely to occur. Therefore, the content is 0.3% to 40% (weight), more preferably 0.5% to 20% (weight).

The organic acid of the present invention (b) is not particularly limited, and for example, acetic acid,
Acrylic acid, malic acid, citric acid, lactic acid, ascorbic acid, tartaric acid, succinic acid,
Examples include maleic acid and ricinoleic acid. Furthermore, a polymer of an organic acid can also be used, and examples thereof include polyacrylic acid, polylactic acid, and a styrene-maleic anhydride copolymer. Of these, food additives such as acetic acid, malic acid, citric acid, tartaric acid, lactic acid, ascorbic acid, polyacrylic acid (molecular weight is usually 500 to About 2000) is preferred.

The kind of metal salt used as the organic acid metal salt of the present invention is not particularly limited as long as it generates a metal salt. For example, silver, copper, zinc, lead, iron, tin, magnesium, manganese, cobalt, aluminum and the like can be exemplified, but silver, zinc, iron, magnesium and the like are preferable as safer metal salts that do not accumulate in the human body. .

  As the organic acid metal salt, a metal salt of the above organic acid is used, and more specifically, for example, iron malate, zinc citrate, magnesium ascorbate, zinc ascorbate, magnesium tartrate and the like can be mentioned as preferable examples.

The content of the organic acid or organic acid metal salt as an active ingredient of the composition for keeping freshness or deodorizing of the present invention can be adjusted from 0.1% to 80% (weight). If the active ingredient is less than 0.1%, the effect of maintaining freshness and deodorization cannot be expected so much, and if it exceeds 80%, precipitation tends to occur and its handling is difficult. Therefore, a content of 0.3% to 40% (weight) is appropriate,
A more preferred range is 0.5% to 20% (weight).

  The active ingredient of the freshness-keeping or deodorizing composition according to the present invention is usually in the form of an aqueous dispersion or an aqueous solution, but within the range that does not hinder the effects of the present invention in order to maintain stability, solubility and the like. Thus, a co-solvent or a surfactant can be used as necessary. Co-solvents include lower alcohols, glycols, glycol esters, glycol ethers and polyglycols. Examples of the lower alcohol include ethanol, propyl alcohol, and isopropyl alcohol. Examples of the glycol include propylene glycol, propylene glycol monomethyl ether, and polyoxyethylene glycol monophenyl ether. The amount used is 1 to 50% (weight) based on the total amount of the composition.

  Further, as the surfactant, an anionic surfactant or a nonionic surfactant can be blended for preventing precipitation of the aqueous dispersion and improving the stability. Examples of the anionic surfactant include, but are not limited to, alkylbenzene sulfonate, polyoxyethylene alkyl sulfate, sulfosuccinate, and amino acid anionic surfactant. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, sorbitan fatty acid esters, alkyl polyglycosides, and fatty acid glycoside esters. The amount used is 0.1 to 15% (weight) with respect to the total amount of the composition.

  In the composition of the present invention, a binder can be appropriately blended in order to maintain the freshness maintaining effect and the deodorizing effect over a long period of time and to make the coating agent compatible with various coating methods. Further, a film to which a binder has been added can be dried to form a film. Usable binder resins include, but are not limited to, water-soluble resins such as polyvinyl alcohol, vinyl acetate resin emulsions, ethylene-vinyl acetate copolymer emulsions, acrylic resin emulsions, and styrene-acrylic copolymer emulsions. is not. The amount of the binder added can be determined as appropriate depending on the type of the active ingredient, the type of binder to be mixed, compatibility with the coating method, and the like, but the composition of the present invention has wide selectivity.

  The amount of binder added is in the range of 1: 0.01 to 1:30 in the ratio of active ingredient to binder in terms of the solid content of the active ingredient and the added binder. When the binder is less than 0.01, the effect of adding the binder cannot be exhibited, and when it exceeds 30, the effect of the active ingredient is buried and cannot be exhibited. Accordingly, the preferred range is 1: 0.1 to 1: 3.

  Furthermore, an arbitrary component can be mix | blended with the composition of this invention as needed in the range which does not prevent the effect of this invention. Examples of optional components include fragrances, essential oils, bactericides, preservatives, thickeners, gelling agents, coloring agents, pH adjusting agents, and the like.

  Next, a freshness maintaining method and a deodorizing method using the composition of the present invention will be described. In order to maintain the freshness of the fruits and flowers, it is necessary that these fruits and flowers coexist in the same atmosphere as the composition of the present invention. The same applies when the composition of the present invention is used only for the purpose of deodorization.

  Since the composition of the present invention is in the form of an aqueous dispersion or an aqueous solution, it can be sprayed as it is, and this is the simplest method of use. The mode of spraying is not particularly limited, and can be performed on a large scale and with high efficiency using an air compressor, can be performed manually with a specific spray container, or can be sprayed as an aerosol. For example, fruits and vegetables can be put in a plastic bag, and the composition of the present invention can be allowed to coexist by spraying inside the plastic bag and stored. Moreover, in order to remove and reduce indoor formalin and malodor, it is also a simple method of use to spray the composition of the present invention. Furthermore, the composition of the present invention can be sprayed as a measure for reducing ammonia and trimethylamine, which are the sources of garbage odor, rot odor and fish odor in the summer of a garbage incineration plant.

Further, in the freshness maintaining method and the deodorizing method using the composition of the present invention, a method by coating and coating is also effective. In this method, it is advantageous to mix the appropriate binder described above and apply and apply as a coating agent. As an application method, it can be applied on-site with a roller brush, a spray gun or the like, or can be applied in advance to the inner surface of the cardboard case with a printing machine. For example, freshness can be maintained by using a cardboard case coated with the composition of the present invention by gravure printing for transportation of fruits and vegetables. In addition, a coating agent prepared from the composition of the present invention can be applied to the ceiling or wall surface of a room with a roller brush or the like, and the deodorizing effect can be maintained over a long period of time.

  Furthermore, the composition of the present invention is impregnated or adsorbed with an absorbent carrier such as paper or nonwoven fabric, or a porous carrier such as silica gel or activated carbon, so as to coexist with the object to maintain freshness or deodorize. There is also a method.

Spraying, coating, and impregnation as a freshness maintaining method and a deodorizing method are basic methods, and are not limited to these single methods in practice, and may be performed in combination.

  Next, the present invention will be described in more detail with reference to the evaluation test method and examples of the composition for keeping freshness and / or deodorant of the present invention, but the present invention is not limited to the following examples. As evaluation methods of the examples, the evaluation test methods 1, 2, and 3 described below were used.

<Evaluation Test Method 1> In order to evaluate the properties of the freshness-keeping agent, the effect of reducing ethylene gas was examined.
A cube made of 200 mm on a side and a transparent acrylic plate chamber is prepared, and apples are placed in a filter paper having a diameter of 10 mm impregnated with 10 g of the sample solution and dried. A fan was attached to the top of the chamber so that the internal atmosphere could be stirred. As an object, two untreated filter papers and apples are put in a chamber. The ethylene gas concentration in the chamber is measured at regular intervals using a gas detector tube. The experiment was conducted for 10 days, and the removal reduction rate was calculated from the difference in concentration between the subject on the last day and the test specimen, and evaluated by that value. In addition, the fluctuation of ethylene gas concentration of both for 10 days was also referred.

<Evaluation Test Method 2> By examining the removal reduction rate of formaldehyde which is one of the causative substances of sick house syndrome, it was determined as an evaluation method for safety and deodorizing effect on the human body.
In the test method, a glass bottle with a volume of 1 L was suspended by impregnating and drying 5 g of a test piece on a filter paper having a diameter of 150 mm. Using a micropipette, 25 μl of formalin (37% (weight)) was added, and aluminum foil and paraffin were added. Seal with film. Apply ultrasonic for 5 minutes and leave at room temperature for 24 hours. As a control, one untreated filter paper and formalin are added to a 1 L glass bottle. After leaving at room temperature for 24 hours, the formaldehyde concentration of the control and the specimen is measured using a gas detector tube, and the reduction rate of formaldehyde removal is calculated from the difference.

<Evaluation Test Method 3> The removal reduction rate of trimethylamine, which is one of the causative substances of fish odor, was examined and used as an evaluation method for the deodorizing effect.
In the test method, a glass bottle with a volume of 1 L was suspended by immersing and drying 2.5 g of a test piece on 1/2 sheet of filter paper having a diameter of 150 mm, and using a micropipette, 50 μl of a 3% (weight) trimethylamine aqueous solution was added. Seal with foil and parafilm. As a control, ½ sheet of untreated filter paper is suspended in a 1 L glass bottle, and 50 μl of 3% trimethylamine aqueous solution is added and sealed. After leaving at room temperature for 1 hour, the trimethylamine concentration of both is measured using a gas detector tube, and the removal reduction rate of trimethylamine is calculated from the difference.

  L-ascorbic acid 3.5 g (0.02 mol) was dissolved in a mixed solvent of purified water 70 g and isopropyl alcohol 20 g. While stirring this solution, 2.8 g (0.01 mol) of titanium tetraisopropoxide was gradually added dropwise at room temperature.

  Stirring was continued for 1 hour after the completion of the dropwise addition to obtain a reddish brown aqueous dispersion. The pH was adjusted to 3 with sodium hydroxide and evaluated according to Evaluation Test Methods 1, 2, and 3. The results are as shown in Table 1, Table 2, and Table 3, respectively, and exhibit excellent effects in maintaining freshness and deodorizing.

  6.3 g (0.03 mol) of citric acid monohydrate was dissolved in a mixed solvent of 70 g of purified water and 20 g of isopropyl alcohol, and 5.7 g (0.02 mol) of titanium tetraisopropoxide was stirred under stirring. Mol) was added dropwise at room temperature. After completion of dropping, the mixture was further stirred for 1.5 hours to obtain a colorless transparent solution. The pH was adjusted to 3 with sodium hydroxide, and the test was conducted by the evaluation test methods 1, 2, and 3 as in Example 1. The results are as shown in Table 1, Table 2, and Table 3, respectively.

  5 g of polyacrylic acid (Nippon Pure Chemicals, Jurimer) was dissolved in a mixed solvent of 55 g of purified water and 40 g of ethanol. While stirring this solution, 3.8 g (0.02 mol) of titanium tetrachloride was gradually added dropwise at room temperature. After completion of the dropwise addition, the mixture was further stirred for 1.5 hours to obtain a white aqueous dispersion. By the evaluation test methods 1, 2, and 3, the ethylene reduction effect, the formaldehyde removal reduction effect, and the trimethylamine deodorization effect were examined, respectively. The results are as shown in Table 1, Table 2, and Table 3, and can be expected from the excellent ethylene reduction effect and deodorization effect.

Magnesium chloride hexahydrate (4.1 g, 0.02 mol) was dissolved in purified water (60 g), and L-ascorbic acid (3.5 g, 0.02 mol) was added and dissolved therein. Further, 40 g of purified water was added for dilution, and the pH was adjusted to 5 with sodium hydroxide. The obtained slightly yellow transparent solution was tested based on Evaluation Test Methods 1, 2, and 3.
The results are as shown in Table 1, Table 2, and Table 3, respectively, and exhibit an excellent ethylene reduction effect and deodorization effect.

  Zinc chloride (5.4 g, 0.04 mol) is dissolved in purified water (60 g), and DL-malic acid (5.4 g, 0.04 mol) is added with stirring. Further, 30 g of purified water was added to obtain a colorless transparent solution. The pH was adjusted to 5 and the tests were conducted by evaluation test methods 1, 2, and 3, and the results shown in Table 1, Table 2, and Table 3 were obtained.

3.5 g of L-ascorbic acid was dissolved in a mixed solvent of 20 g of purified water and 5 g of isopropyl alcohol, and 2.8 g of titanium tetraisopropoxide was added dropwise to this solution at room temperature with stirring. After completion of the dropwise addition, the mixture was further stirred for 1 hour to obtain a dark red solution.
50% by weight of this dark red solution, 26% by weight of a styrene-acrylic acid copolymer emulsion having a solid content of 50% by weight, 1% by weight of a sorbitan fatty acid ester nonionic surfactant and 3% by weight of citric acid were mixed and stirred, and purified water 20 A quick-drying coating agent was prepared by diluting with wt%. When this coating agent was subjected to evaluation tests 1, 2, and 3, it was found that it had both an excellent freshness maintaining effect and a deodorizing effect. The results are as shown in Tables 1, 2, and 3.

  6.2 g of magnesium chloride hexahydrate was dissolved in 30 g of purified water, and 4.5 g of L-tartaric acid was added and dissolved. A colorless transparent solution was obtained by adjusting the pH to 3 with sodium hydroxide. 15% by weight of a 3% by weight aqueous solution of methylcellulose as a thickener is mixed with 50% by weight of this solution, and further 15% by weight of an ethylene-vinyl acetate copolymer emulsion having a solid content of 50% by weight is added and mixed and stirred. A dry spray was used. Evaluation tests 1, 2, and 3 were conducted. The results are shown in Tables 1, 2, and 3, respectively.

  40 wt% of a 20 wt% aqueous solution of L-ascorbic acid is mixed and stirred with 40 wt% of a vinyl acetate resin emulsion having a disodium ethylenediaminetetraacetate content of 1 wt% and a solid content of 40 wt%. The pH was adjusted to 5 with sodium oxide. Suitable for quick-drying coating agent. About this thing, the evaluation tests 1, 2, and 3 were performed, and it turned out that it is especially excellent in the deodorizing effect. The results are as shown in Tables 1, 2, and 3.

評価試験法１に従い、実施例１〜８とそれぞれの対照のエチレンガス濃度を測定し、それらの差から低減率を算出した。

According to Evaluation Test Method 1, the ethylene gas concentrations of Examples 1 to 8 and the respective controls were measured, and the reduction rate was calculated from the difference therebetween.

評価試験法２に従い、実施例１〜８とそれぞれの対照のホルムアルデヒド
（ＦＡ）濃度を測定し、それらの差から除去低減率を算出した。

In accordance with Evaluation Test Method 2, the formaldehyde (FA) concentrations of Examples 1 to 8 and the respective controls were measured, and the removal reduction rate was calculated from the difference therebetween.

評価試験法３に従い、実施例１〜８とそれぞれの対照のトリメチルアミン
（ＴＭＡ）濃度を測定し、それらの差から除去低減率を算出した。

According to the evaluation test method 3, the trimethylamine (TMA) density | concentration of Examples 1-8 and each control was measured, and the removal reduction rate was computed from those differences.

Claims (3)

  Freshness characterized by comprising as a main component at least one or more selected from the group consisting of (a) an inorganic-organic hybrid compound comprising titanium and an organic acid, and (b) an organic acid and metal salts thereof. A composition for holding or deodorizing.   A freshness-keeping or deodorizing composition, wherein the organic acid according to claim 1 is L-ascorbic acid. A method for impregnating a freshness-keeping or deodorizing composition according to claim 1 or 2 in a spray, coating or adsorbent.