JPS6240273A - Preservation of packaged food and disoxidative preservation agent capable of removing acetaldehyde and used therefor - Google Patents

Abstract

PURPOSE:To obtain a packaged food having improved preservability, by packaging a food together with ethyl alcohol and disoxidation agent in combination with a substance capable of removing generated acetaldehyde. CONSTITUTION:A food is packaged with a disoxidation agent or disoxidation agent and ethyl alcohol. In the above food, a substance having amino group or its derivative, e.g., weakly basic anion exchange resin, amino acid, protein, etc., is placed in the package preventing the direct contact with the food, e.g., combining the disoxidation agent with the substance.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a method for preserving packaged foods and an oxygen scavenger having acetaldehyde removing ability used therein.

When oxygen absorbers are used in packaged foods such as rice cakes, rice cakes, Japanese and Western sweets, bean paste, bread, and smoked products, the inside of the packaging is kept anaerobic, which significantly inhibits the growth of aerobic microorganisms such as mold. Ru. Therefore, it appears that the shelf life has been significantly extended, and the use of oxygen absorbers in many packaged foods has become widespread.

However, many microorganisms grow vigorously even under anaerobic conditions.
It has been found that substantial preservability cannot often be ensured simply by using oxygen scavengers. Therefore, the present inventors have occasionally proposed a method of using ethyl alcohol, which has the property of enhancing antibacterial activity under anaerobic conditions.
Recently, combination methods are becoming popular.

``Problems to be solved by the invention'' As mentioned above, the combined use of ethyl alcohol and oxygen absorbers is extremely effective in improving the preservability of packaged foods. I found out that there is. That is, when ethyl alcohol vapor comes into contact with the oxygen scavenger,
Contrary to conventional chemical wisdom, we discovered that ethyl alcohol is oxidized and turns into acetaldehyde. To explain how this happened, we conducted a preservation test on packaged raw udon noodles using ethyl alcohol and oxygen absorbers in combination or alone.
Compared to the product for ethyl alcohol vehicles, the product used in combination with ethyl alcohol showed browning over time and the generation of a strange odor. When gas chromatography was performed on the headspace gas, a peak different from that of ethyl alcohol was observed only when used in combination.

Therefore, we conducted a model test using only ethyl alcohol and an oxygen scavenger, and confirmed that the newly generated peak showed a retention time above the chart for acetaldehyde G** quality, and also showed that the odor It was confirmed that the substance was also the same, and the substance was identified as acetaldehyde.

The mechanism by which acetaldehyde is produced from ethyl alcohol is estimated from the results of Experiment 1 as being that the oxygen scavenger acts as a catalyst and the oxygen gas in one package oxidizes ethyl alcohol.

[Experiment 1] A vinylidene chloride-coated polypropylene bag (hereinafter referred to as a KOP bag) had tissue vapor adsorbed with 5% ethyl alcohol 4d and a commercially available oxygen absorber (manufactured by Mitsubishi Gas Chemical Co., Ltd., commercially available oxygen absorber under the trade name Ageless F0). (When referred to as ``, it refers to the main rule)'' was contained and the sharp part was sealed. Next, an adhesive rubber plate (manufactured by Toray Engineering Co., Ltd.) was attached to the surface of the KOP bag.
Air or nitrogen gas was injected through the syringe in varying amounts so that the total gas amount was approximately 250 d. Oxygen gas concentration in these gases in the package is measured using Oxygen IT (Toshi Zirconia Oxygen Meter LC700T Model Sample Volume 5ILI2)
It was measured with After storage at 5° C. for about 1 day, nitrogen gas was added to replace the amount reduced by removing oxygen gas to bring the total gas amount to approximately 250 d, and acetaldehyde was measured using a gas chromatograph.

The conditions for measuring acetaldehyde in this experiment and the following experiments or examples are as follows.

As a result of Experiment 1, as shown in Table 1, the amount of acetaldehyde produced increased in proportion to the oxygen gas concentration in the packaging circle.

In addition, in this microscope, it was difficult to express the amount of acetaldehyde as a quantitative value, so the reagent acetaldehyde (
It is expressed as a relative value when the peak height of the heladspace gas of the reagent pin with the increased amount is set to 100.

Note that since the measurement limit is about 0.004, anything less than this value was indicated as "not detected".

The numerical values in Table 1 are also shown in this relative value.

Table 1 I couldn't come.

When the relative value is about 0.04 or more, a fairly strong odor of acetaldehyde is exhibited.

It has been found that the problem of acetaldehyde formation when using ethyl alcohol in combination with an oxygen scavenger occurs regardless of how ethyl alcohol is used in food products. for example,
If ethyl alcohol is effectively contained in food, such as denatured alcohol, alcoholic beverages, fermented seasonings, etc., by kneading it into food, spraying it, or including it in a carrier and allowing it to coexist in isolation with food, ethyl alcohol can be contained in the packaging. The vapor evaporates and comes into contact with the oxygen scavenger, producing acetaldehyde.

Furthermore, the present inventors have found that the production of acetaldehyde occurs not only due to the combined use of ethyl alcohol and an oxygen scavenger but also in the following cases.

In other words, the flavor of foods with high enzyme activity such as raw Japanese soba and dried noodles deteriorates during storage, and the main cause of this is the production of aldehydes, mainly acetaldehyde, based on the gas chroma of headspace gas. As a result of tograph analysis, I found out.

As is clear from the above, acetaldehyde is produced when ethyl alcohol is used in combination with an oxygen absorber, or when foods with high 1g2 activity such as raw Japanese soba are used. Not only is it a cause, but it is also toxic to the human body.

The present inventors have conducted extensive research into removing this acetaldehyde.

"Means for Solving the Problem" The present inventors conducted extensive searches for substances that remove acetaldehyde without substantially inhibiting the oxygen gas removal ability of oxygen scavengers. We have discovered that a substance that removes amino groups (hereinafter referred to as a ``substance that removes amino groups, etc.'') is extremely effective.

That is, the present invention provides a method for imparting preservability to packaged foods using an oxygen scavenger or an oxygen scavenger and ethyl alcohol. The second invention relates to an oxygen scavenging agent having acetaldehyde removal and retention ability, characterized in that a substance having an amino group or the like is arranged in an oxygen scavenging agent made of a composition.

In the present invention, substances having amino groups and the like refer to weakly basic anion exchange 81 fats, amino acids (lysine, arginine, glycine, glutamine, etc.), and proteins (egg white, casein, gluten, etc.).

Now that we've finished, we'll return to Saginai.Weakly basic anion exchange W fat is a polymer compound such as polystyrene with a large number of primary, secondary, or tertiary amines added to it. Examples of commercially available products include: RA-45, manufactured by Rohm and Haas Company (registered trademark, Amber Light)
J), manufactured by Uza Dakai Chemical Company (registered trademark,
DOWEX W (R, hereinafter referred to as "ion exchange NuB") is depleted.

Among the above-mentioned amino acids and proteins, the objects of the present invention may be achieved more effectively by using together an alkaline substance such as sodium carbonate, sodium hydroxide, or calcium hydroxide.

Next, Experiment 2 was conducted to clarify the appropriate usage amount of a substance having an amino group or the like.

"Experiment 2" The amount of the substance having amino groups etc. was changed and the substance was placed in a breathable bag (one side made of paper and the other side made of polypropylene) along with a real alkaline substance if necessary. This small bag, a commercially available oxygen absorber, and tissue paper impregnated with 4 d of 25% ethyl alcohol were placed in a KOP bag and sealed to remove air. Next, approximately 250 d of air was injected using the same method as in Experiment 1, and the mixture was stored at 25°C, and acetaldehyde in the headspace gas was measured after about 1 and 3 days. In addition, after one day of storage, in all experimental groups, a decrease in volume was observed due to the removal of oxygen gas, but replenishment with nitrogen gas was not performed (the same applies to the following examples).

Table 2 Table 2 (Continued) Table 2 (Continued) *From the results of the registered trademark Amberlite IRA-45 Experiment 2, when the combined air content in the package is 250 farts as the standard, L-
0.3g for lysine hydrochloride, 3g for powder (combined with alkaline substance), 0.2g for ion exchange Ni IIW A
It was found that 5 g of each was able to sufficiently remove acetaldehyde. A similar experiment was conducted with ion-exchange resin B, and it showed almost the same effect as ion-exchange resin A.

The amount of acetaldehyde produced can be considered to depend on the oxygen gas content in the packaged food, so if gas exchange packaging is performed using nitrogen gas or carbon dioxide gas during packaging, the amount of substances containing amino groups etc. will be reduced depending on the degree. Usage can be reduced. In this case, if the oxygen gas can be completely replaced to zero, there is no need to worry about acetaldehyde formation, and the important part to be solved by the present invention will also disappear. The use of oxygen agents also becomes meaningless. However, in reality, it is difficult to completely remove oxygen gas during packaging, and it is impossible to completely prevent oxygen gas from entering from the outside world with commonly used packaging materials.
is also difficult. In this regard, when alcohol coexists, the removal of acetaldehyde that is generated along with the function of the oxygen scavenger has become an urgent problem to be solved.The amount of acetaldehyde produced can be calculated as follows. That is, assuming that the air inside the package is 250d as a standard, this air contains approximately 2 mmol of oxygen gas. 2 mmol of oxygen gas has a maximum of 4 mmol J, or approximately 2001
g of ethyl alcohol is oxidized to produce approximately the same amount of acetaldehyde.

Usually, the air content in one packaged food is much less than 250 d, and the amount of ethyl alcohol used is much more than 200 mg (normally, more than 1 h% of ethyl alcohol is used in food. Case 10
Contains 1000 ml or more in 0 Jig of food. ), there is no need to worry about deterioration in storage stability due to loss of ethyl alcohol.

In the present invention, a general commercial product can be used as the oxygen absorber.
14, but it is necessary to use IM or 2[U''li of reducing substances such as iron powder, ascorbic acid, erythorubic acid and their salts, sagi dithionate, butylated hydroxytoluene, butylated hydroxya epinisole, etc. Depending on the conditions, a composition of these and an alkali metal or alkaline earth metal hydroxide, one part of activated carbon, one part of water, and other powdered or granular materials or porous materials may be appropriately prepared and used.

The above-mentioned oxygen scavenger and a substance having an amino group, etc.
In order to coexist without direct contact with food, each or a single product in a breathable bag or container can be placed in a small oxygen-permeable bag or container together with food containing or not using ethyl alcohol. By doing so, the first invention is achieved. When the substance containing amino groups or the like is water-soluble, the water bath solution may be adsorbed onto filter paper or the like and dried before use.

In the first invention, when an oxygen scavenger and a substance having an amino group, etc. are allowed to coexist in a packaged food, a portion of the acetal group dehyde generated upon contact with the oxygen scavenger may contain amino acids, etc. Since there is a risk that the oxygen scavenger and the substance containing an amino group or the like may not be removed by the oxygen absorber and may react with the food, the oxygen scavenger and the substance containing an amino group or the like should coexist as close as possible. This is desirable.

In this case, if the deoxidizing preservative having the ability to remove acetaldehyde obtained in the second invention is used, the above problem will not occur at all.

In the second invention, although there is not much difference in the preservative effect of amino groups and the like in the above-mentioned oxygen scavengers, homogeneous mixing is also rational for preparing the oxygen scavenging preservative. Among the substances that have amino groups etc. located in oxygen-reducing preservatives, amino acids, proteins, and white substances may reduce the oxygen removal ability slightly compared to the conditions or cause deterioration during long-term storage, so weak bases are recommended. Anion exchange resins are most preferred.

Hereinafter, this will be explained in detail using examples.

"Example 1 (first invention)" Fresh udon noodles (ethyl alcohol content 1.5%%) made using ethyl alcohol and other conventional methods 130
g was placed in a KOP bag and sealed with a commercially available oxygen absorber at an air content of approximately 200 d (control). In the invention area, in addition to the conditions of the control area, "L-lysine hydrochloride 0.3 g (No. 1)" and "Glycine 0.31
Mixture of 91 and 0.3 g of sodium carbonate (No. 2) J
, r A mixture of 3 g of egg white powder and 1 g of potassium carbonate (No.
3) J or “Ion exchange Frd fat AO 13g (No,
4) J wo1ffL% gender fa&, mff1 included,,
Ash coexisted.

Each of the above-mentioned packaged fresh udon noodles was stored at 18° C., and acetaldehyde in the headspace gas was measured over time. The results are shown in Table 3.

As clearly shown in Table 3, acetaldehyde production was observed in the control plot, whereas no acetaldehyde was observed in the invention plots (1 to 4).

Furthermore, after 7 days of storage, each packaged raw udon was evaluated for the degree of browning, odor, and general viable bacteria count measurement. The browning of the fruit was clear in the control plot, whereas l! In invention areas 11.1 to 4, almost the state immediately after manufacture was maintained. As for odor, a clear acetaldehyde odor was observed in the control plot, whereas N
It was not recognized at all in invention areas No. 1 to No. 4. −
Regarding the number of killing bacteria, the control area, the invention area (No. 1 to 4)
) both had extremely excellent results of 300/g or less.

"Example 2 (first invention)" Raw Chinese noodles (ethyl alcohol content: 12,000%) manufactured using ethyl alcohol and otherwise according to conventional methods,
12011 was housed in a KOP bag, a commercially available oxygen absorber was coexisted, and the air content was set to approximately 200 farts. In the invention area, in addition to the conditions of the control area, "a mixture of 014 g of L-arginine and 0.5 g of diatomaceous earth (No. 1
) J, or “Ion Exchange Grease Stealing B O, 3g (No, 2)
J injected into a breathable bag was allowed to coexist.

Each of the above-mentioned packaged raw Chinese noodles was stored at 5°C, and acetaldehyde in the headspace gas was measured over time. The results are shown in Table 4.

In the case of raw Chinese noodles in Table 4, unlike the case of raw udon noodles in Example 1, acetaldehyde detected in the control group after one day of storage decreased thereafter, and was not detected at all after seven days. This is thought to be because the acetaldehyde that was produced reacted with the ingredients in the raw Chinese noodles and was lost. This idea holds true in the control area\
This is supported by the fact that the reddish-brown change progresses orally.

In the invention plots (No. 1 to No. 2), neither the production of acetaldehyde nor the reddish-brown change was observed.

"Example 3 (first invention)" After uniformly spraying about 2 d of 95% ethyl alcohol onto a commercially available castella cutter (about 50 g), it was placed in a KOP bag, and a commercially available oxygen absorber was coexisted to remove air. The quantity was emphasized as almost a crime (control area). In the invention plot, in addition to the conditions of the control plot, 0.2 g of ion exchange resin B was placed in a breathable bag.

After storing the above packaged castella at 30"C for 2 days, acetaldehyde in the headspace gas was measured using a gas chromatograph. It was detected in the control group (relative value 0,
361), but it was not detected at all in the invention area.

"Example 4 (First Invention)" Approximately 120 g of one commercially available Western confectionery (product name: Sabalin (a fairly large amount of Western liquor is used)) was sealed in a polyethylene bag with many pinhole holes. was housed in a KOP bag, and a control oxygen absorber (A) prepared using Example ants (described later) was allowed to coexist between the inner bag and outer bag, and the air content was sealed at approximately 200 d (vs. 1M section). . In the invention area, the oxygen absorbing preservative (kl~No., '7) prepared in Example 11 was used instead of the oxygen absorber.

After storing each of the above packaged Sabalan at 10°C for 3 days, acetaldehyde in the headspace gas was measured, and it was detected in the control group (relative value 0.205), but it was not detected at all in the invention group. .

"Example 5 (first invention)" After uniformly spraying about 5 ml of 95% ethyl alcohol onto a commercially available cutter (about 500 g), it was housed in a laminated film of vinylidene chloride coated nylon and polyethylene, and was prepared as described below. Control oxygen scavenger (B) prepared in Example 11
were allowed to coexist and sealed with an air content of approximately 300 d (control area). In the invention area, the oxygen absorbing preservative prepared in Example 11 (No. 8 to No.
10) was used.

When the above packaging clips were stored at 25°C and acetaldehyde in the headspace gas was measured after 2 and 10 days, it was detected in the control group (relative value 0.413 after 2 days).
0,252) after 10 days, but it was not detected at all in the invention area.

In the above example, approximately % of the air content was replaced with nitrogen gas, and the experiment was conducted under the same conditions except for the same conditions, and results similar to those of the above example were obtained. However, the amount of acetaldehyde produced in the control group was slightly suppressed compared to the case of the above example.

"Example 6 (first invention)" Approximately 3 farts of fermented seasoning (containing ethyl alcohol at approximately 7%) was uniformly sprayed onto 3 commercially available inari sushi (approximately 230.9'), and the mixture was placed in a polyethylene bag. It was housed inside and sealed. This is further combined with a commercially available oxygen absorber. 25
゜、-5、Because □jl'EG! j! 150mj+aL
+, ：□：Mitshugegata (control area). In the invention area, 0.219% ion exchange resin A is added to the commercially available oxygen scavenger, and packaged inarizushi of □" or more is heated to 20'C.
After storing it for one day, I used it once it had cooled down.

When acetaldehyde was measured in Hibutospace gas, it was detected in the control group (relative value 0.150), but
It was not detected at all in the invention area.

"Example 7 (First invention)" 10 pieces of commercially available kamaboko (approximately 100 g) were placed side by side in a tray bag, and this was mixed with a commercially available ethyl alcohol carrier (Nippon Kayaku Co., Ltd. registered trademark Oitetsu 1 g) and an example described later. KOP along with the control oxygen scavenger (A) prepared in step 11.
It was placed in a bag and sealed with an air content of approximately 100 d (control). After storing the above packaged kamaboko at 10℃ for 3 days in the invention area, acetaldehyde in the headspace gas was measured, and it was detected in the control area (relative value 0.136).
), but it was not detected at all in the invention area.

"Example 8 (first invention)" 95% ethyl alcohol 2III2 in commercially available miso 1009
After kneading the mixture, it was placed in a polypropylene bag and sealed. This was placed in a KOP bag together with a control oxygen absorber (B) prepared in Example 11, which will be described later, and sealed with an air container volume of approximately 50 d (control). In the invention area, the oxygen absorbing preservative (No. 8) prepared in Example was used instead of the oxygen absorbing agent.

After storing the above packaged miso at 156C for 3 days, acetaldehyde in the headspace gas was measured, and it was detected in the control group (relative value 0.163), but not at all in the invention group.

"Example 9 (first invention)" 95% ethyl alcohol 1 part in 100 g of commercially available sweetened bean paste
．． When 5 elms were kneaded and the experiment was conducted in the same manner as in Example 8, acetaldehyde was detected in the control group (relative value 0.1).
22), but it was not detected at all in the invention area.

"Example 10 (first invention)" A commercially available oxygen absorber (control group) was added to 120 g of raw Japanese soba obtained by making noodles using a conventional method without using ethyl alcohol, or 0 ion exchange resin B was added to a commercially available oxygen absorber. It was placed in a KOP bag together with the one containing .2g (invention area) and sealed with an air content of approximately 50 g.

After storing each of the above-mentioned packaged fresh Japanese soba at 20°C for 3 days, the acetaldehyde in the headspace gas was measured, and the odor upon opening was also examined. As a result, acetaldehyde was detected (0,035) in the control plot and a strange odor was observed, but no acetaldehyde was detected in the invention plot.
Also, the occurrence of strange odors was significantly reduced.

"Example 11 (Second invention)" Oxygen scavenger A, B or C shown in 1 of Table 5 and substances having amino groups etc. shown in 2 of Table 5 (7 substances) The preservatives (No. 1 to No. 13) according to the present invention were obtained by distributing the combinations shown in Table 5, No. 3 (left column) and placing them in breathable bags. The distribution is
When both were powders, they were mixed uniformly, and when either or both were adsorbed on filter paper, they were layered alternately.

Deoxidizing preservatives according to the present invention obtained above, 1 to 1.

The acetaldehyde removal ability of No. 13 and control oxygen scavengers AC considered to belong to the known art was measured. That is, the deoxidizing preservative or deoxidizing agent is
It was placed in a KOP bag together with tissue vapor adsorbed with 4 d of ethyl alcohol, and the air content was set to approximately 250 d.

These KO% bags were stored at 25°C and acetaldehyde in headspace gas was measured orally. The results are shown in Table 5, 3.

1 in Table 5 2 in Table 5 2 in Table 5 (Continued) 3 in Table 5 3 in Table 5 (Continued) ne A-C are oxygen scavengers in 1 of Table 5, a-g are 2 of Table 5
Indicates a substance having an amino group, etc.

As shown in Table 5, 3, all of the deoxidizing preservatives (Magnetic 1 to Magnetic 13) according to the present invention had a strong ability to remove acetaldehyde.

In addition, the 13 types of oxygen-absorbing preservatives and the 3 control dishes (
The oxygen removing ability of the oxygen scavengers A-C) was investigated.

Each of these sachets, along with a small piece of water-soaked filter paper, was
After being stored in an OP bag and sealed with an air content of approximately 250 m, it was stored at 25°C for 1 day, and the oxygen gas concentration in the headspace gas was measured using an oxygen meter. As a result, the oxygen-removing preservative of the present invention showed the same oxygen removal ability as the control oxygen-removing agent (the oxygen gas concentration was o,
ooo-o, oot%).

"Example 12 (Second Invention)" Ion exchange resin A was placed in a commercially available oxygen scavenger at 0.1 to 0.5y to obtain an oxygen scavenging preservative according to the present invention.

When the above oxygen scavenging preservatives were examined for their acetaldehyde and oxygen scavenging abilities in the same manner as in Example 11, no difference was observed in their oxygen scavenging abilities and that of the commercially available control oxygen scavengers, and the acetaldehyde scavenging abilities were Replacement fat AO 12g or more (K
If the air content in the OP bag is ioo RI2, it is 0.1
(g or more) showed remarkable efficacy.

In addition, it was confirmed that the acetaldehyde removal ability did not decrease even if the ion exchange resin was previously subjected to acid, alkali, ammonium sulfate treatment, water washing treatment, or drying treatment.

Also, for reference, strongly basic anion exchange m fat, ``[+E
″′＃″″″″man゛!!-“′″″′；N′″″U
′″″″′″h d , t >'; e * llt
mooo”Nr7-t=t-.

When we investigated the aldehyde removal ability, it was found that it is very difficult to remove aldehyde.
Ah, 1ゎ. 14.64, Kae. care,. 1.
[I couldn't do it.]
``Effects of the Invention'' As stated above, according to the structure of the 8th aspect of the present invention, a method for imparting preservability to packaged foods using an oxygen absorber or an oxygen absorber and ethyl alcohol. , the acetaldehyde produced can be removed without any effect on its shelf life;

Claims (1)

[Claims] 1. A method for imparting preservability to packaged foods using an oxygen scavenger or an oxygen scavenger and ethyl alcohol, in which a substance having an amino group or a derivative thereof coexists with the food without direct contact with the food. A method for preserving packaged foods characterized by: 2. A deoxidizing preservative having an acetaldehyde removing ability, which comprises a deoxidizing agent made of a substance or composition having an oxygen removing ability, and a substance having an amino group or a derivative thereof disposed therein. 3. The deoxidizing preservative according to claim 2, wherein the substance having an amino group or a derivative thereof is a weakly basic anion exchange resin.