JPS6352873B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention consists of two inventions, both of which relate to methods of preserving food products. In both cases, the synergistic effect of placing an oxygen absorber and a food preservation device (source of ethyl alcohol gas) in the closed container in which the food is stored prevents mold and bacteria from forming on the food. It has a remarkable effect of preventing the oxidation of fats and oils. In addition, in the present invention, the film used in the food preservation tool described above generally has good oxygen gas permeability when coexisting with food products, so as an embodiment of the present invention, an oxygen absorber is placed in the food preservation tool containing ethanol. , which can also be placed in a closed container with the food product. An object of the present invention is to provide a new method for preserving food products. Conventionally, various methods have been tried to prevent mold, corrosion, and oxidation of foodstuffs. In other words, to preserve bread, calcium propionate is mixed in during its production, potassium sorbate is mixed into processed fish products, or orthophenylphenol is applied to the surface of lemons. It has been done. However, mixing or coating chemicals in this way changes the taste and color of the food and reduces its flavor, and there are also problems with the use of certain preservatives under the Food Sanitation Act. Things that impede the preservation of food include the growth of mold and bacteria, and the oxidation of fats and oils in food. In order to prevent these problems, methods of using ethanol vapor and methods of using oxygen absorbers mainly composed of easily oxidizable substances have recently become popular. The former method includes, for example, the method disclosed in Japanese Patent Application Laid-Open No. 51-19146. However, in this proposal, the ethyl alcohol is placed in liquid form in the food storage container, so the alcohol comes into direct contact with the food and harms its flavor.Also, in this method, the alcohol evaporates all at once and gradually leaks out of the container. The major drawback is that it cannot replenish the amount that is lost. Currently, as a food preservation method using alcohol vapor, the method disclosed in Japanese Patent Publication No. 55-2273 filed by the present applicant is mainly practiced in the industry. This method uses an adsorbent in which ethyl alcohol is adsorbed onto an adsorbent, and has been evaluated as an excellent method. There are many methods of using oxygen absorbers mainly composed of easily oxidizable substances. For example, JP-A-52-
Transition metals (Se, Ti, V, Cr, Mn, Fe, Co,
At least one metal selected from Ni, Cu, Zn), Sn and Sb, water and activated carbon, diatomaceous earth, perlite, cellulose, zeolite, activated clay, activated alumina, silica gel, kaolin,
This method uses an oxygen absorbent made of a porous material that is poorly soluble in water, such as talc or asbestos. Furthermore, JP-A-51-119392 discloses an oxygen absorber which is characterized in that hydroquinone is mixed with anhydrous carbonated alkaline powder and activated carbon, and a small amount of water is added to the mixture immediately before packaging it in a breathable packaging material. A method of using the is disclosed. Furthermore, JP-A-51-117991 discloses a method of using an oxygen absorbent using pyrogalic acid or gallic acid instead of the above-mentioned hydroquinone. The method of using the alcohol adsorbent described in the above-mentioned Japanese Patent Publication No. 55-2773 is to enclose the ethyl alcohol adsorbent in a polyethylene film pouch with small holes, which is abbreviated as "pore poly" in practical terms, and store it together with food in a container. It is often used in . In this case, if excess ethyl alcohol is used as an adsorbent for ethyl alcohol, the excess ethyl alcohol will flow through the small pores and directly stain the food product or food container, and the liquid in the food will become "porous". This is considered a drawback when using an ethyl alcohol adsorbent in a perforated plastic bag. In addition, the adsorbent for ethanol is “pore poly”.
The disadvantages of storing food by putting it in a small bag and placing it in the storage body with the food are that the ``hole poly'' is not economically cheap and the operation of filling the ``hole poly'' bag with the adsorbent is fast. However, it is difficult to implement, and the cost ends up being high. The inventors of the present invention have conducted various studies to solve the above problem, and have found that at least one side of the film is made of a film with an ethyl alcohol gas permeability of 20 g/m ² / 24 hr / 50 RH / 40°C or higher. It is possible to achieve the above purpose without using ``porous polyester'' by using a food storage device in which ethyl alcohol is either directly contained in a food or by adsorbing it to an adsorbent material and sealed in place of an ethyl alcohol adsorbent. It became. It is preferable to use a polyethylene film pouch without holes as the above-mentioned "container". This invention has already been filed as Japanese Patent Application No. 54-47223 (Japanese Patent Publication No. 59-30072). In addition, the present inventors have invented a method of using gelatinized alcohol instead of liquid ethyl alcohol to prevent alcohol from leaking out and contaminating food items and their containers even if the sachet is damaged. . This invention was also patented in 1982.
43567 (Japanese Unexamined Patent Publication No. 142167/1983). Food storage methods that use oxygen absorbers to remove oxygen from food containers are effective in preventing the growth of aerobic bacteria and the oxidation of oil and fat components contained in foods, preventing discoloration and flavor deterioration. It is. However,
Food preservation methods using oxygen absorbers require the use of so-called oxygen-barrier packaging materials for food containers, and there is absolutely no leakage allowed in the packaging. Therefore, it has the disadvantage of increasing costs. Another disadvantage is that the container may be deformed depending on the material. The present inventors had previously conducted research on food preservation methods, and in order to further develop that research, they conducted various studies on the combination of the ethanol vapor method and the method of using an oxygen absorber, and as a result, they arrived at the present invention. . That is, the gist of the first invention is that "at least one surface has an ethyl alcohol gas permeability of 20
g/m ² /24hr/50RH/Ethyl alcohol 50% in a "container" made of film at 40℃ or higher
1. A method for preserving food products, which comprises coexisting with the food products in a closed container a food preservation tool and an oxygen absorber, which are sealed either as they are or by adsorbing a liquid containing % by volume or more with an adsorbent. ”. The gist of the second invention is that "At least one surface has an ethyl alcohol gas permeability of 20
g/m ² /24hr/50RH/Ethyl alcohol 50% in a "container" made of film at 40℃ or higher
1. A method for preserving food products, which comprises making a food preservation tool sealed with a gelled liquid containing % or more by volume and an oxygen absorber coexist with the food products in a closed container. ”. Ethyl alcohol gas permeability 20g/m ² /24hr/50RH/40 as described in the summary of the present invention above
℃ or higher refers to the ethyl alcohol gas permeability of the film used in the present invention, and is 40℃ or higher.
The weight of ethyl alcohol passing through 1 square meter of the film during 24 hours in an environment of 50% relative humidity is 20 g or more. Hereinafter, this will be abbreviated as "ethanol gas permeability" of 20 or more.
The measurement is carried out using 95° pharmacopeia ethyl alcohol in accordance with the method generally used for measuring water vapor permeability of resin films (JIS Z-0208). In addition, the concept of ``remono'' that is composed of a film with an ethanol gas permeability of 20 or more on one side includes, for example, a container made of metal, glass, or ceramic whose top surface is sealed with the above film. , or a bag made entirely of the above-mentioned film. The above concept of film also includes films supported by an air permeable porous mesh material such as Japanese paper. The oxygen absorbent of the present invention means an easily oxidizable substance itself or a composition in which an oxidation promoting substance is added to the easily oxidizable substance.
In general, an oxygen absorbent prepared by adding an oxidation promoter to an easily oxidizable substance is preferable because it has a stronger oxygen absorption ability. Known materials can be used as easily oxidizable substances and oxygen absorbers used in the present invention. Specifically, the details are as follows. Transition metals included in the fourth period of the periodic table, namely Se, Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
Zn and lower oxidation compounds of these metals and Sn,
Sb metal and its lower carbides, chlorides, sulfides,
Oxides are examples of easily oxidizable substances. Further, mixtures of hydrosulfite and alkali powder, mixtures of hydroquinone and alkali powder, and mixtures of pyrogalic acid or gallic acid and alkali powder are examples of oxygen absorbers. An easily oxidizable substance refers to a substance that is easily oxidized by oxygen in the air at room temperature. Therefore, in addition to the above-mentioned substances, unsaturated fatty acids, glycerides of unsaturated fatty acids, and vegetable oils and animal oils containing these compounds are also examples of easily oxidizable substances. Furthermore, butylhydroxyanisole and butylhydroxytoluene are also included in the concept of easily oxidizable substances. At least one side of the food preservation tool of the present invention is composed of a film with an "ethanol gas permeability" of 20 or more, and when we compared the actual values of the ethanol gas permeability of various films, we found the results shown in Table 1. be. From this table, the films that pass the above standards are 1, 2, 3, 4, 6, 7, 8, 9 in Table 1.
They are numbered 10 and 15. An "ethanol gas permeability" of less than 20 can be said to be a film that does not substantially permeate ethanol gas. The food preservation tool of the present invention contains ethyl alcohol.
A liquid containing 50% by volume or more may be sealed as is, or an adsorbent adsorbed to an adsorbent material may be sealed. As disclosed in Japanese Patent Publication No. 55-2273, starch, sugar, silicon dioxide, aluminum silicate, talc, absorbent cotton, microcrystalline cellulose, etc. are used as the adsorbent.

【table】

[Table] Represents calls.
Further, a gelled liquid containing 50% by volume or more of ethyl alcohol, which is a constituent feature of the second invention, can be obtained in the following manner. For example, the objective can be achieved by dissolving stearic acid in heated ethyl alcohol, neutralizing the stearic acid with potassium alcohol, and then cooling to room temperature. It is also possible to prepare gelled ethyl alcohol by dispersing a polymeric substance in ethyl alcohol containing 0 to 50% by volume of water. The closed container of the present invention may be a closed container made of metal, glass, ceramic, plastic, etc., as long as it is substantially impermeable to oxygen gas and ethyl alcohol gas. When choosing a plastic film as the material for the container, particular care must be taken to use a material that is substantially impermeable to oxygen and ethyl alcohol gases, such as polyethylene or nylon film coated with polyvinylidene chloride. The strong, thin material that is substantially impermeable to ethyl alcohol gas and described in Claim 3 of the present invention is the stretched polypropylene/PE film No. 5 in Table 1 and the chlorinated polypropylene film No. 11 in Table 1. Vinylidene coated nylon/PE film, No. 12 nylon/aluminum foil/PE film, No. 13 double-sided vinylidene chloride coated PVA film, and No. 14 vinylidene chloride coated polypropylene/PE film, etc., which can be expressed in general terms. Examples include stretched films (particularly biaxially stretched), films coated with vinylidene chloride and films coated with metal foil, or films with a combination of stretched, vinylidene chloride coated and metal foil coated treatments. If the above film is stacked with a film with an ethyl alcohol gas permeability of 20 g/m ² / 24 hr / 50 RH / 40°C or higher and sealed around the periphery to form a thin bag-like "container", it will be easier to mechanically process at high speed. It is a material suitable for mass production. That is, many films with an "ethanol gas permeability" of 20 or more are weak and difficult to mechanically process, but if they are combined with the above-mentioned strong film to form a thin bag-like film, they can be easily handled mechanically. Furthermore, if the inner surface of such a thin bag-like "container" is made of a heat-sealable film such as polyvinyl alcohol on both sides, if a thin layer of gelled ethyl alcohol is filled, the gel filling will be difficult. While this is done, the inner surface can be heat-sealed by applying a heated iron or the like from the outside. As a result, small-sized food preservation tools can be produced very easily from large-sized products, which is extremely advantageous industrially. EXAMPLES The present invention will be explained in more detail with reference to Examples below. Example 1 (including comparative example) Polyvinyl alcohol film No. 15 at the bottom of Table 1 (thickness 30μ, "ethanol gas permeability")
50) Prepare a 50mm x 50mm pouch and
0.5 ml of JP ethanol as an ethanol gas supply source, 2 g of ferrous chloride powder as an oxygen absorber, and 0.5 ml of JP ethanol and ferrous chloride.
A mixture of 2 g of iron is filled into each sachet and sealed. On the other hand, it is made of vinylidene chloride coated stretched nylon 20μ polyethylene 40μ film (film No. 11 in Table 1, "ethanol gas permeability" 7), which has substantially barrier properties (impermeability) to oxygen gas and ethanol gas. Pieces of bread (weighing 100 g) were placed in three bags each having an internal volume of 500 ml, and each of the three bags was filled and sealed as described above, and the openings were sealed. In addition, the same bread was put in a bag with an internal volume of 500 ml and the mouth was sealed, except that the bag was not stored, and this was used as a control.
The specimens were placed indoors at a temperature of 80% relative humidity and observed daily for mold growth. The results are shown in Table 2.

[Table] From the results in Table 2, mold growth was observed on the 6th day in the control plot, on the 15th day in the plot exposed to ethanol gas, and on the 8th day in the plot exposed to hypoxic conditions. On the other hand, in the plot according to the embodiment of the present invention in which ethanol gas and oxygen absorption were used together, no mold growth was observed even on the 40th day, showing a clear synergistic effect. Of the above sachets, ethanol and chloride No. 1
In a case where both iron and iron are mixed and filled, the ethanol serves as the ethanol gas supply source and also acts as an oxidation promoter for ferrous chloride, and immediately starts absorbing oxygen immediately after the two are mixed. The PVA film used as the above sachet does not have very high oxygen gas permeability and ethyl alcohol gas permeability under low humidity. Therefore, after filling the drug and sealing it, place it in a film bag that has barrier properties against oxygen and ethanol gas, and seal the opening of the bag to avoid contact with the outside air. Absorption capacity and ethanol gas supply capacity are hardly consumed. If this is stored in a closed container with food such as bread and used as a food preservative, the moisture contained in the food will increase the permeability of the PVA film to oxygen gas and ethanol gas, allowing it to perform its original function. do. Also, when ferrous chloride is oxidized to ferric chloride,
Due to its deliquescent property, it becomes liquid, but since the above-mentioned sachets are made of non-porous PVA film, the deliquescent liquid does not flow out of the sachets and contaminate the food, which is advantageous. However, if ferrous chloride is previously used in combination with a liquid solidifying agent such as silicon dioxide, liquefaction during deliquescence can be avoided. Example 2 (including comparative example) A, in which 50 mm x 50 mm pouches made of films No. 15, No. 14, No. 5, No. 11, and No. 10 in Table 1 were each filled with 0.5 ml of Japanese Pharmacopoeia ethanol and sealed; B, C, D
and E are prepared. Next, the thickness of No. 15 above is 30μ.
Chloride 1 in a 50mm x 50mm pouch made of PVA film.
Prepare 5 pieces F filled with 2g of iron powder and sealed. On the other hand, slices of bread (weighing 100 g) were placed in 5 bags each having an internal volume of 500 ml made of film No. 11, which has a substantial barrier property against oxygen gas and ethanol gas, and then the above A, B, C, One small bag each of D or E and one bag each of the above F were stored and the mouths were sealed. In addition, a test group was prepared as a control, in which only the same bread as above was sealed in a No. 11 film bag with an internal volume of 500 ml. Each of these test plots was placed indoors at 25°C and 80% relative humidity, and the status of mold growth was observed every day. The results are shown in Table 3. From this table 3, the film of food preservation equipment that supplies ethanol gas has "ethanol gas permeability"
It is clear that the effect of the present invention cannot be obtained when the value is less than 20, and the above-mentioned synergistic effect can be obtained when the value is 20 or more.

[Table] Example 3 (Comparative Example) 2.85g of stearic acid was mixed with ethyl alcohol (99.5g).
Volume %) Dissolve in 20ml by heating. Next, 5 ml of 2N-KOH ethyl alcohol solution was added while stirring at a warm temperature.
Make an ethyl alcohol solution of potassium stearate. On the other hand, one side is film number 14 (thickness
20μ/30μ, "ethanol gas permeability" 2), and the other side is film number 5, 11, 10, or 15 in the same table ("ethanol gas permeability" is 5, 7, 20, respectively)
Or 50, thickness is 20/20, 20/40, 15/60 respectively
Prepare four 200 mm x 300 mm bags made of polyethylene (or 30μ), and fill 5 ml of the above-mentioned ethyl alcohol solution into these plastic bags when warm. This solution is filled and cooled to form a soft gel, which is uniformly spread throughout the interior of the bag, the air removed, and the filled opening sealed to form a sheet as if it were a single film. Next, fold these four sheets with the No. 14 film on the outside (with the No. 5, 11, 10, or 15 film on the inside) and seal three sides to make each bag. This bag is called a storage bag, and each bag is designated A, B, C, and D in order of the ``ethanol gas permeability'' of the inner film, starting from the smallest. In addition, prepare a bag exactly the same as D using the same method as the bag described above, and call this bag E. Next, as an oxygen absorber, 1 g of iron powder, 0.1 g of salt, and 0.2 ml of water were added to a film made of EVA film (thickness 30μ, "ethanol gas permeability" 1000) shown in Table 1, No. 6.
It was filled into a mm x 20 mm pouch and sealed. A total of 5 of these oxygen-absorbing sachets were prepared, and 4 were used as ningyoyaki (sweets).
Put 400g in one bag each into A, B, C, and D above, seal the opening, and place these into A, B, and C, respectively.
and D test area. The above E bag contains 400 Ningyoyaki.
g was stored, the mouth was sealed, and this was designated as the E test group. Prepare two 200mm x 150mm bags made of the film No. 14 in Table 1 used for the outside of the above storage bag, store the remainder of the oxygen absorption sachet mentioned above together with 400g of Ningyoyaki in one bag, seal it, and store it. It was designated as test area F. Also above
Only 400 g of Ningyoyaki was stored in the remaining No. 14 film bag and sealed, and this was used as a control. 25 each test area
The specimens were placed indoors at a temperature of 80% relative humidity and observed daily for mold growth. The results are shown in Table 4.

[Table] From the results in Table 4, "Ethanol gas permeability"
It is clear that there is a synergistic effect between the above storage bag (a food storage device that supplies ethanol gas) composed of 20 or more films and the oxygen absorber. Example 4 (Comparative example including) 100 g of corn oil was weighed into a 200 ml beaker, and film No. 11 (thickness 20/20 mm) in Table 1 above, which has substantially ethanol gas and oxygen gas barrier properties, was weighed.
40μ, 200mm× made of “ethanol gas permeability” 7)
Store in a 300mm bag. Prepare 4 sets of this. On the other hand, a film made by pressing Japanese paper onto the EVA film No. 6 in Table 1 above ("Ethanol gas permeability")
(1) 1 ml of JP ethanol as an ethanol gas source (2) Dibutylhydroxytoluene (BHT) as an oxygen absorbent
1 mg (3) As a combined sample, fill each container with 1 ml of Japanese Pharmacopoeia ethanol containing 1 mg of BHT and seal. Next, (1) and (2) are added to each of the corn oil-filled plastic bags mentioned above.
Or, store either of the sealed sachets in (3) and seal the mouth. These are referred to in the order of (1) to (3) or as a test area. The remainder of the corn oil-filled plastic bag prepared above was used as a control test area in which ethanol and BHT were not involved.
Each test plot was left in a room at 40°C and relative humidity 80%, and its peroxide value (POV) was measured every 30 days.
Measurement of POV was performed by iodometric titration. Lard and head were also tested in exactly the same manner as the corn oil. The results are shown in Table 5.

[Table] The examples in this table are examples of the first invention, and the examples in this table are comparative examples.
Generally 100meq/Kg for vegetable oil, and 100meq/Kg for animal fat.
The rancidity point is 20mq/Kg. In the test of this example, 69.31meq/Kg was used in the control group using corn oil, 29.55meq/Kg in the ethanol gas supply group, and 53.42meq/Kg in the oxygen absorption group using BHT. Example) showed a remarkable antioxidant effect. This is considered to be due to the synergistic effect of ethanol gas supply and oxygen absorption. Similar trends were also observed for lard and head.

Claims (1)

[Claims] 1. A liquid containing 50% by volume or more of ethyl alcohol in a "container" whose at least one side is composed of a film with an ethyl alcohol gas permeability of 20g/m ² /24hr/50RH/40°C or more. A method for preserving foodstuffs, which comprises coexisting with the foodstuffs in a closed container a food preservation tool and an oxygen inhaler, which are sealed either as they are or by being adsorbed onto an adsorbent. 2 The periphery is closed and one side is made of a strong thin material that is virtually impermeable to ethyl alcohol gas, and the other side has an ethyl alcohol gas permeability of 20g/m ² /24hr/
The food preservation method according to claim 1, which uses a thin bag-shaped "container" made of a film with a temperature of 50RH/40°C or higher. 3 A gelled liquid containing 50% by volume or more of ethyl alcohol is sealed in a “container” whose at least one side is made of a film with an ethyl alcohol gas permeability of 20g/m ² /24hr/50RH/40°C or higher. 1. A method for preserving food products, which comprises making a food preservation tool and an oxygen absorbent coexist with the food products in a closed container. 4 The periphery is closed and one side is made of a strong thin material that practically does not allow ethyl alcohol gas to pass through, and the other side has an ethyl alcohol gas permeability of 20g/m ² /24hr/
The food preservation method according to claim 3, which uses a thin bag-like "container" made of a film with a temperature of 50RH/40°C or higher.