JPH04166073A - Freshness-retaining and deodorizing agent - Google Patents

Abstract

PURPOSE:To provide the subject agent efficiently adsorbing and removing ethyl ene, odorizing substances, etc., having excellent antibacterial, insecticidal and antifungal activities and useful for transporting, storing and preserving fresh materials. CONSTITUTION:A freshness-retaining and deodorizing agent contains as an active ingredient a condensed peracid obtained by reacting a metal element (e.g. titanium, tungsten, molybdenum vanadium, zirconium) and/or a compound thereof (e.g. vanadium titanate, tungsten trioxide, ammonium phosphomolybdenate, vanadium pentaoxide, zirconium nitrate) with hydroperoxide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a freshness-preserving agent and a deodorizing agent for preserving the freshness of flowers, fruits and vegetables, fresh foods, and the like.

(Prior art) In order to maintain the freshness of plants such as fruits, vegetables, and flowers, it is necessary to adsorb or decompose and remove ethylene gas, which promotes the maturation of these plants, or to activate the plants themselves. .

Examples of substances that have gas adsorption ability and are effective in preserving the freshness of flowers, fruits and vegetables, and other raw foods include activated carbon, zeolite, and Oya stone. Methods of using these to maintain freshness include packaging them together with fruits and vegetables, or kneading or coating them into resin films or sheets to use as packaging materials.

(Problem to be Solved by the Invention) However, many of the above-mentioned conventional y1 temperature retaining agents have low ethylene adsorption ability. Conventional adsorbents cannot sufficiently remove ethylene gas from fruits and vegetables that contain a large amount of ethylene, making it difficult to maintain their freshness for long periods of time.

In addition, freshness-preserving agents that use only ethylene adsorption are defenseless against phenomena such as rot, root rot, and water rot caused by the proliferation of bacteria.

Therefore, in order to maintain freshness for a long period of time, a freshness-preserving agent that also has antibacterial properties is desired.

It goes without saying that there are similar requirements regarding deodorizers.

The present invention aims to provide a freshness-preserving agent and a deodorizing agent that have high gas adsorption ability and antibacterial properties and can maintain the freshness of flowers, fruits and vegetables, and other raw foods for a long period of time.

[Structure of the Invention] (Means for Solving the Problems) The present inventor has conducted extensive research to obtain a material that has both gas adsorption ability and antibacterial properties, and as a result, has arrived at the present invention.

The present invention is a freshness-preserving and deodorizing agent containing as an active ingredient a peroxide condensed acid obtained from the reaction of a metal element and/or its compound with hydrogen peroxide.

Basically, any metal element in the periodic table can be used as the metal element. In particular, titanium, tungsten,
Typical examples include molybdenum, vanadium □, zirconium, etc., but they are not necessarily limited to these, and any material that reacts with hydrogen peroxide to give a peroxide condensed acid may be used. It may also be a metal compound. Metal compounds include salts, oxides, chlorides, hydroxides,
Examples include, but are not limited to, oxyacids, salts thereof, alkoxides, and the like.

For example, titanium and its compounds include titanium, titanium oxide, barium titanate, iron titanate, calcium titanate, magnesium titanate, aluminum titanate, lead titanate, titanium sulfate oxide, alkyl titanate, tetraalkoxy titanium, etc. Can be mentioned.

Tungsten and its compounds include tungsten, tungsten carbide, tungstic acid, tungsten trioxide, tungstic anhydride, tungstic acid, ammonium metavanadate, ammonium paratungstate, phosphotungstic acid, tungstic acid, bowtungstic acid, lithium tungstate. , sodium tungstate, potassium tungstate, sthorium metatungstate, sthorium paratungstate, ammonium penctungstate, ammonium heptatanchstate, sodium phosphotungstate, barium borotungstate, and the like.

Molybdenum and its compounds include molybdenum, molybdic acid, molybdic acid dioxide, ammonium phosphomolybdate, ammonium oxychloride molybdate, ammonium metamolybdate, ammonium paramolybdate 13, phosphomolybdic acid, silicomolybdic acid, paumolybdic acid, molybdenum Lithium acid, thorium molybdate, potassium molybdate, ammonium hebucmolybdate, lithium phosphomolybdate, phosphomolybdate, zinc molybdate, calcium molybdate,
Examples include magnesium molybdate, strondium molybdate, and barium molybdate.

Vanadium and its compounds include vanadium, vanadium pentoxide, lithium orthovanadate, mono-lithium orthovanadate, lithium metavanadate, potassium metavanadate, thorium metavanadate, ammonium metavanadate, sodium pyrovanadate, etc. , but are not necessarily limited to these.

Zirconium and its compounds include zirconium nitrate, zirconium sulfate, basic zirconium acetate, zirconium acetylacetone, ethylenediaminetetraacetate zirconium complex salt, nitrilotriacetate zirconium complex salt, zirconyl chloride, zirconyl nitrate, zirconyl acetate,
Zirconyl salts such as zirconyl sulfate and zirconyl ammonium carbonate can be used, but are not limited to these. Among these, zirconium acid chloride is the most commonly used because it is inexpensive and provides relatively high yield of zirconia.

These metal elements and/or compounds thereof may be used in combination, if necessary, under conditions such that a peroxide condensed acid can be obtained by reacting with hydrogen peroxide.

゛It is also possible to add phosphorus, silicon, boron, manganese, iron, cobalt, copper, etc. as a different element to the above metal element and use it as a heteropolyacid.

What is important here is that the peroxidized condensed acid obtained in the present invention is different from conventional oxyacids or oxyacid salts such as tungstic acid, molybdic acid 3, sodium tungstate, and sodium molybdate.

That is, many of these oxygen acids do not dissolve in neutral water or hydrophilic organic solvents. In addition, although oxyacid salts are not soluble in hydrophilic organic solvents, they are highly soluble in water, so they are mostly used in an aqueous form. on the other hand,
These oxyacids or oxyacid salts do not have film-forming properties. Due to these reasons, the current situation is that there are restrictions depending on the usage.

However, although the peroxidized condensed acid obtained by the present invention is considered to be a type of polyacid, the details are unknown. Polyacids are generally classified into two types. An acid that is produced by two or more metals is called a heteropolyacid, and is formed by coordinating one metal (or its equivalent) with a central atom and the polyacid group of another metal. It is often done. On the other hand, in contrast to heteropolyacids, acids produced by only one type of metal are called isopolyacids. Most of the peroxide condensed acids obtained by the present invention are obtained in the form of amorphous bodies, so their structures are not clear, but they contain peroxo groups (0-0), or ○
It is thought that a network structure is formed in which negative ions such as H are connected directly or via other molecules such as water. Therefore, the peroxidized condensed acid obtained by this method can be freely mixed with a hydrophilic organic solvent and can even completely replace the organic solvent, and furthermore, this peroxidized condensed acid has film-forming properties. Therefore, it is considered to be fundamentally different from conventional oxyacids or oxyacid salts.

The peroxide condensed acid in the present invention can be easily synthesized by reacting it with hydrogen peroxide at a temperature ranging from room temperature to 00°C, depending on the type of transition element. The hydrogen peroxide used here is a commercially available hydrogen peroxide of about 30 to 60%, which can be used as it is or diluted to an appropriate concentration. The amount of hydrogen peroxide used is approximately 1 gram mole or more per 1 gram atom of the transition metal. The reaction rate tends to increase as the hydrogen peroxide/transition metal (gram mole/gram atom) ratio increases. It is not very desirable from an economical and safety standpoint to leave a large excess of hydrogen peroxide behind after the reaction is complete. Therefore, the amount of hydrogen peroxide used is 1 transition element
Approximately I to 5, preferably 1, 2 to 3 gram moles per gram atom are suitable. The required amount of hydrogen peroxide may be added in its entirety at the start of the reaction, or may be added dropwise little by little as the reaction progresses. The same applies to the method of adding transition metals.

Next, the property of peroxycondensed acid to adsorb gases, organic substances, etc.
and the nature of its antibacterial action.

Peroxide condensed acid has a specific surface area of approximately 20 to 2000 m2
/g, the pore diameter is 2 to several nanometers, and it has porous properties. Therefore, it has excellent adsorption ability for various gases, organic substances, etc. Utilizing this effect, it adsorbs and removes ethylene, odorous substances, etc., and is used as a freshness-preserving agent and deodorizing agent. Although any specific surface area can basically be used, if it is less than 40 m2/g, the adsorption capacity will be low and it may not be preferable as a freshness-preserving agent or a deodorizing agent.

Since peroxide condensed acid is a type of peroxide, it has high antibacterial properties. Therefore, freshness-preserving agents and deodorizing agents containing peroxidized condensed acids have excellent antibacterial, insect repellent, and anti-mold properties, and also prevent flowers, fruits and vegetables, fresh foods, etc. from rotting, decreasing freshness due to disease, and deteriorating quality. There is a function to Furthermore, since it does not contain free peroxide, it does not have any harmful effects on the human body.

From the above, it is possible to obtain a freshness-preserving agent and a deodorizing agent for flowers, fruits and vegetables, and other raw foods by using a peroxide condensed acid. The peroxidized condensed acid may be used alone, or may be used in combination with a conventionally known freshness-preserving agent, deodorizing agent, or the like.

The freshness preserving agent and deodorizing agent obtained as described above can be used in various forms.

When used in the form of powder, granules, pellets, etc., it can be used, for example, by dispersing it in a solvent, or by kneading it into a resin or the like and forming it into a film or sheet for use as a packaging material. Moreover, the purpose of freshness preservation and deodorization can also be achieved by storing the product in a breathable pouch and packaging it together with fruits and vegetables. Other usage methods are not limited to these, and can be used in other ways depending on the purpose.

When used as a solution, it may be used by impregnating fibers, paper, etc., or it may be used by mixing with a resin etc.

To use it as a thin film, the peroxide condensed acid solution may be applied to some base material and dried. Examples of the base material include, but are not limited to, resin sheets, films, molded products, paper such as wrapping paper and cardboard, and inorganic base materials such as ceramics and plaster. , inorganic materials, metal materials,
Composite substrates can be used.

Further, the freshness preserving agent according to the present invention can also be used in combination with a resin face etc. In this case, it can be used as a paint, etc., and can also be made into a thick film, molded product, etc. Examples of the resin varnish include, but are not limited to, acrylic resin, vinyl resin, and polyester. Since the peroxidized condensed acid is stable in both water and organic solvents, various forms of the resin varnish can be used, such as solutions in water or organic solvents, or dispersions.

Next, the present invention will be explained in more detail with reference to Examples.
The following examples do not limit the scope of the present invention in any way. In addition, "part J" and "%" in the examples represent parts by weight and weight %, respectively.

〔Example〕

Production Example 1 10 parts of zirconium acid chloride and 20 parts of ion-exchanged water were put into a flask, the reaction temperature was adjusted to about 50°C, and 1
20 parts of 5% hydrogen peroxide were added dropwise over 30 minutes.

After 10 minutes of dropping, the mixture was further aged for 1 hour. Thereafter, 100 parts of isopropyl alcohol was added and concentrated using an evaporator. A clear peroxide condensed zirconium alcohol solution of approximately 50% solids was obtained. And 2
It was left at room temperature for 4 hours.

Production Example 2 5 parts of tetra-1so-propoxy titanium and 200 parts of isopropyl alcohol were placed in a beaker, and 100 parts of a 30% aqueous hydrogen peroxide solution was added thereto. After a vigorous reaction accompanied by bubbling, an acidic, pale yellow, transparent aqueous solution of peroxidized condensed acid was obtained.

Production Example 3 Put 8 parts of metallic tungsten powder into a beaker, and add 1 part to it.
70 parts of a 5% aqueous hydrogen peroxide solution was added. Through a vigorous reaction accompanied by foaming, the tungsten powder was dissolved in about 30 minutes, and a transparent aqueous solution of acidic, pale yellow peroxidized condensed tungstic acid was obtained. Thereafter, 30 parts of butyl cellosolve was added and the mixture was left at room temperature for 24 hours.

Thereafter, a platinum blackened platinum wire mesh was immersed in this to decompose unreacted hydrogen peroxide.

Production Example 4 Put 4 parts of ammonium tungstate, 4 parts of metal molybdenum powder, and 20 parts of ion-exchanged water into a beaker, and add 1 part to it.
50 parts of 5% aqueous hydrogen peroxide solution-a was added.

Through a vigorous reaction accompanied by bubbling, the metal molybdenum powder was dissolved in about 20 minutes, and a transparent aqueous solution of acidic, pale yellow peroxide condensed acid was obtained. Thereafter, 20 parts of butyl cellosolve was added and the mixture was left at room temperature for 24 hours. Thereafter, a platinum blackened platinum wire mesh was immersed in this to decompose unreacted hydrogen peroxide.

In addition, samples were also prepared by drying the peroxide condensed acid solutions of Production Examples 1 to 5 under reduced pressure at 80° C. to obtain peroxide condensed acid powder.

Test Example I Using a peroxide condensed acid powder dried under reduced pressure, the specific surface area and ethylene gas adsorption capacity were measured. The specific surface area was measured by the BET nitrogen adsorption method, and the ethylene adsorption capacity was measured using a BET surface area measuring device at a temperature of 24° C. and a pressure of 203 mmHg. Note that the dead volume was measured using helium gas. The measurement results are shown in Table 1. In addition, as a comparative example, the results of measurements on Oya stone are also shown.

Table 1 Measurement results of specific surface area and ethylene adsorption capacity Example 1 150 parts of the zirconium peroxide condensed acid powder obtained in Production Example 1 and 300 parts of low density polyethylene powder were blended,
A master hatch containing a freshness preserving agent was prepared using a Banbury mixer. Low-density polyethylene pellets (manufactured by Mitsui Petrochemical Industries, Ltd.) 96 parts per 40 parts of the master hatch
0 part was 1' live blended, screw diameter 50mmφ,
Inflation molding was carried out at a die diameter of 75 mmφ and a die temperature of 180° C. to obtain a film containing 2% freshness preserving agent, folded diameter 200 mm, and thickness 2° 5 μm. The film was laminated on the inner surface of a cardboard box to produce a packaging material.

Comparative Example 1 150 parts of Oya stone and 300 parts of low-density polyethylene powder were blended to prepare a masterbatch containing a freshness-preserving agent in a Banbury mixer. 960 parts of low-density polyethylene pellets I (manufactured by Mikata Petrochemical Industry Co., Ltd.) were triblended with 40 parts of the masterbatch, and Example 1 was prepared.
A film was obtained in the same way. The film was laminated on the inner surface of a cardboard box to produce a packaging material.

Example 2 10 parts of the zirconium peroxide peroxide condensed acid powder obtained in Production Example 1 was mixed with 75 parts of a water-based emulsion type paint resin varnish under the trade name Torcryl W-265 (manufactured by Toyo Ink Manufacturing Co., Ltd.). , dispersed, and prepared a paint. Apply the paint to corrugated paper at a concentration of 100 g/m2,
A packaging material was prepared by heating in a hot air oven at 80°C for 10 minutes to dry and harden.

In addition, a sample was prepared by applying the above paint to tissue paper for antibacterial testing.

Comparative Example 2 10 parts of Oya stone was mixed and dispersed in 75 parts of Torcryl W-265 (trade name, manufactured by Toyo Ink Manufacturing Co., Ltd.), which is a resin varnish for water-based emulsion quib paints, to prepare a paint. The coating material was applied to corrugated paper at a concentration of 100 g/m 2 and heated in a hot air oven at 80° C. for 10 minutes to dry and harden, thereby producing a packaging material.

In addition, a sample was prepared by applying the above paint to tissue paper for antibacterial testing.

Example 3 30 parts of acrylic acid, 50 parts of methyl methacrylate, and 20 parts of n-butyl acrylate were mixed with 150 parts of isopropyl alcohol.
A resin varnish with a solid content of 40% was synthesized by polymerization in a vacuum chamber.

A titanium peroxide condensed acid solution was prepared by adding 5 parts of tetra-1so-proboxydicine to 200 parts of isopropyl alcohol, and adding 50 parts of a 30% aqueous hydrogen peroxide solution thereto.

200 parts of the above resin, 20 parts of 28% ammonia water, and 400 parts of ion-exchanged water were added to the solution to prepare a titanium peroxide condensed acid-containing hydrosol. The thickness of the hydrosol is 20
A packaging material was prepared by coating a 15-μm high-density polyethylene film with a bar coater, drying it in a hot air oven at 80° C. for 5 minutes, and making a bag.

Comparative Example 3 A titanium oxide-containing hydrosol was prepared using ion-exchanged water instead of the hydrogen peroxide aqueous solution in Example 3. Thereafter, a packaging material was produced in the same manner as in Example 3.

Example 4 The peroxide condensed acid solution obtained in Production Example 4 was applied with a brush to the inner surface of a glass container with a volume of 21, and dried by heating in a hot air oven at 150° C. for 10 minutes to produce a freshness-preserving container.

For antibacterial testing, a sample was also prepared by applying the above peroxide condensed acid solution to Sly IJ glass for microscope use.

Example 5 50 g of the tungsten peroxide condensed acid powder obtained in Production Example 3 was placed in a Japanese paper pouch and the mouth was closed to prepare a pouch containing a freshness preserving agent.

Comparative Example 4 50 g of Oya stone was placed in a Japanese paper pouch and the mouth was closed to produce a pouch containing a freshness preserving agent.

Test Example 2 Antibacterial properties were evaluated using the antibacterial test samples obtained in Examples 1 to 4.

Pour 25 ml of Zabro glucose agar into a 90 mm diameter petri dish and let it solidify. After drying, add a spore suspension (approx.
Pour 0.1 ml of 0.6 parts of I) and spread it with a Conlage stick and place a 2 x 2 cm sample on the surface of the medium at 25°.
After culturing for C11 weeks and observing the growth state of the spores, similar crops were cultivated in the same manner, and the results shown in Table 2 were obtained. In addition,
In the table, "-" indicates that no spore growth was observed, and "2" indicates that spore growth was observed.

Table 2 Results of antibacterial test Test Example 3 Cadrea flowers immediately after harvest were placed in a cardboard box containing the packaging materials prepared in Examples 1 to 4 and the sachet containing the freshness preserving agent prepared in Example 5, and the flowers were heated at 20°C. A test was conducted in which the sample was stored at C for 7 days. The condition of the Cadrea flowers after storage for 7 days was observed and evaluated. The results are shown in Table 3.

Table 3 Hara flower storage test results Annotation ■）◎－－－－It maintains its original appearance.

○---Some wilting, fading, etc. have occurred.

△------Rotten and discolored.

×----One piece has some rot and discoloration.

[Effects of the Invention] The freshness-preserving agent and deodorizing agent obtained by the present invention have excellent adsorption ability for various gases, organic substances, and the like. Therefore, it can efficiently adsorb and remove ethylene, odor substances, various gases, organic substances, etc. that cause loss of freshness and quality deterioration of flowers, fruits and vegetables, raw fish, etc., and prolong the freshness of these foods. It is possible to hold it for a period of time.

In addition, the freshness preserving agent and deodorizing agent obtained by the present invention have high antibacterial properties, so they are excellent in antibacterial, insect repellent, and mold repellent properties, and are effective against rotting, disease, etc. of flowers, fruits and vegetables, and fresh foods. It also has the ability to prevent freshness and quality deterioration. Moreover, since it does not contain free peroxide, it does not have any adverse effects on the human body.

Furthermore, the freshness-preserving agent and deodorizing agent obtained by the present invention can be used in various forms such as powder, pellets, and solution, so they can be used together in packaging or used in packaging materials and containers. It also has the advantage of being usable.

Due to the above-mentioned features, the freshness preserving agent and deodorizing agent obtained by the present invention are effective at all stages of transporting, storing and preserving perishables: producer stage, distribution stage and consumer stage. Can be used for

The freshness-preserving agent and deodorizing agent obtained by the present invention are particularly suitable for transporting, storing, and preserving fresh fruits and vegetables, flowers, ornamental plants, etc.;

Claims (1)

[Claims] 1. A freshness-preserving and deodorizing agent containing as an active ingredient a peroxide condensed acid obtained from the reaction of a metal element and/or its compound with hydrogen peroxide.