JP2785529B2 - Ethanol sustained release agent and food preservation composition using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sustained-release agent for ethanol and a composition for preserving food containing the same as an essential component.

[0002]

2. Description of the Related Art Sustained ethanol release agents have been frequently used to prevent spoilage and deterioration of various foods such as agricultural products before cooking, marine products, livestock products, and processed foods such as baked foods such as bread. Has been used.

[0003] It is also well known that oxygen absorbers are widely used to prevent deterioration in quality due to food being in contact with oxygen for a long period of time.

[0004] Therefore, both of the above are often used in combination for food preservation, but when they are used in combination, the released ethanol vapor is oxidized by the catalytic action of the oxygen scavenger to produce acetaldehyde, There is a drawback that this acetaldehyde causes a bad smell.

As a countermeasure against this disadvantage, for example, Japanese Patent Laid-Open No.
JP-A-2-220178 and JP-A-1-196284 describe a composition for preserving food that absorbs acetaldehyde generated using polyallylamine or polyvinylamine. These have excellent acetaldehyde absorption capacity because they use a polymer compound having a large number of moles of amino groups per unit mass, but the volume is bulky because the ethanol sustained release agent and acetaldehyde absorption agent are separate. Since the chemical reaction between the amino group and acetaldehyde via ethanol takes place in the gas phase, the reaction rate is low, which has the disadvantage of limiting the odor removing ability.

Further, conventional ethanol sustained-release agents such as silica, porous alumina, and polyacrylic acid gel still need to be improved in ethanol retention ability, and are characterized in that sustained sustained release action is maintained for a long period of time. Not satisfactory.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides an ethanol sustained-release agent having an excellent ethanol-retaining ability and a sustained-release action for a long period of time, and an ability to remove acetaldehyde, which is a cause of offensive odor. It is an object of the present invention to provide excellent substances and to provide an excellent food preservation composition obtained by using those substances.

[0008]

The inventors of the present invention have made intensive efforts to solve the above-mentioned problems, and as a result, allylamine-based and vinylamine-based polymer crosslinked products are excellent in both ethanol retention ability and acetaldehyde removal ability. That is, the present invention has been completed.

That is, the present invention relates to a crosslinked polymer of a polymer or copolymer obtained by using an allylamine-based or vinylamine-based monomer as at least one of polymerization components.
The gist of the present invention is a sustained-release agent for ethanol obtained by impregnating with ethanol and a composition for preserving food containing the ethanol as an essential component. Therefore, the sustained-release agent for ethanol of the present invention is obtained by supporting ethanol on a polymer crosslinked polymer or copolymer containing an allylamine-based or vinylamine-based monomer as at least one of the polymerization components. .

Hereinafter, the present invention will be described in detail. Examples of the polymer or copolymer of the allylamine monomer include monoallylamine homopolymer (hereinafter, referred to as polyallylamine), diallylamine homopolymer (hereinafter, referred to as polydiallylamine), and copolymer of monoallylamine and diallylamine. Coalescence and the like are used.

Examples of the polymer or copolymer of a vinylamine monomer include a vinylamine homopolymer (hereinafter, referred to as polyvinylamine), a copolymer of vinylamine and vinylformamide, and a copolymer of vinylamine and vinylacetamide. , Copolymer of vinylamine and vinyl alcohol, copolymer of vinylamine and styrene, copolymer of vinylamine and vinyl chloride, copolymer of vinylamine and acrylamide, copolymer of vinylamine with acrylic acid or methacrylic acid For example, a copolymer of vinylamine and an acrylate or methacrylate or a partially saponified product thereof, and a copolymer of vinylamine and acrylonitrile are used. Here, what is referred to as a vinylamine polymer or copolymer includes those obtained by decomposing or partially decomposing a side chain after a polymerization reaction of a vinylamine derivative. In these copolymers,
From the viewpoint of securing ethanol retention when the crosslinked product is used, the vinylamine content is desirably 50 mol% or more. When the amino group of the polymer is an acid salt, the polymer is neutralized with an alkali such as sodium hydroxide or potassium hydroxide so that the polymer can be used for adsorption and removal of acetaldehyde.

The molecular weight of the above-mentioned allylamine or vinylamine polymer or copolymer is not particularly limited, but is preferably about 1,000 to 1,000,000.
, Usually 1,000 to 300,000 are easy to handle.

The crosslinked polymer can be obtained as follows. For example, a polymer having a crosslinked structure itself, such as polydiallylamine, can be used as it is for carrying ethanol, but usually a polymer is reacted with a crosslinking agent to obtain a crosslinked polymer. As a crosslinking agent, a functional group that reacts with an amino group, for example, an epoxy group, an aldehyde group, a halogenated alkyl group, an isocyanate group, a carboxyl group,
An acid anhydride group, an acid halide group, an ester bond, etc.
Conventionally used compounds having 2 or more per molecule can be used. That is, examples of the compound include bisepoxy compounds, dihalides such as epichlorohydrin and dibromoethylene, dialdehyde compounds such as formalin and glyoxal, diglycidyl ethers of (poly) ethylene glycols, and diglycidyl ethers of (poly) propylene glycols And glycidyl ethers of dialcohols such as neopentyl alcohol and polyglycidyl ethers of glycerol, but are not limited thereto. The type of the cross-linking agent is selected in consideration of the ethanol absorption capacity, swelling property, mechanical properties, and the like of the cross-linked product.

The amount of the functional group is usually 20 units, regardless of the type of the crosslinking agent, with respect to the amine unit of the polymer.
Mole% or less is sufficient. However, when the degree of crosslinking is less than 1 mol%, the strength of the crosslinked product is low, and the drawback that the ethanol holding power cannot be maintained for a long time appears. On the other hand, the degree of crosslinking is 50
If it exceeds mol%, the ability to absorb and carry ethanol is reduced.

The obtained crosslinked polymer has generally good moldability and can be easily formed into various shapes such as spherical, flat, rod, and sheet in addition to dry powder. In addition to mechanically molding the crosslinked polymer, knitted fabric, nonwoven fabric, paper and the like are impregnated with an allylamine-based or vinylamine-based polymer and subjected to a crosslinking reaction,
It is also possible to obtain a crosslinked polymer sheet which can be subjected to secondary molding.

Ethanol is absorbed and carried by the crosslinked polymer to prepare an ethanol sustained release agent. After the crosslinked polymer is immersed in ethanol and the absorption of ethanol reaches equilibrium, a sustained-release agent for ethanol can be obtained by means such as filtration or centrifugation.

The resulting sustained-release ethanol solution has a very high ethanol content. For example, in the case of a crosslinked polymer composed of polyallylamine (molecular weight 10,000) and epichlorohydrin, the epoxy group and the methylene chloride group of epichlorohydrin were adjusted to be 10 mol% in total with respect to the amine unit of polyallylamine. It can carry ethanol about 4 times its own weight.

[0018] This ethanol sustained-release agent alone is effective for food preservation as a food preservation composition.
It can also be used in combination with other objects. Combination partners include dehumidifiers such as silica gel, activated carbon, organic acids, deodorants such as polycarboxylic acids or zeolites, oxygen absorbers containing metal powder as a main component, carbon dioxide generators, and flavoring agents. Can be If no inconvenience occurs in combination, three or more of the above components may be combined.

Among these combinations, a food preservation composition comprising a combination with a deoxidizer containing metal powder as a main component is particularly excellent. That is, the oxygen scavenger oxidizes ethanol slowly released by its catalytic action to generate acetaldehyde, which is a bad odor source, whereas the ethanol sustained release agent of the present invention has excellent acetaldehyde absorption and removal ability. Because it has. For this reason, this food preservation composition strongly prevents spoilage and deterioration of food from a long-term sustained release action of ethanol and a deoxygenation action, and does not sense any odor of acetaldehyde generated when ethanol is oxidized. .

The above various food preservation compositions are preferably used by filling them in a gas permeable storage container. In that case, the ethanol sustained-release agent and other components may be placed in the same storage container or in separate storage containers. Suitable storage containers include paper sachets and those laminated with effective polyethylene and the like.

The ethanol sustained-release agent and the food preservation composition of the present invention are used for preventing spoilage and deterioration of various foods including agricultural products, marine products, livestock products and processed foods thereof. It is preferably used for food, other pastries such as Japanese and Western confectionery, kamaboko and bamboo rings, processed meat such as ham and sausage, delicacies, and rice cakes.

[0022]

The gist of the present invention is an ethanol sustained-release agent obtained by adding ethanol to a polymer crosslinked product.
It is surprising that this is excellent in both absorption and support of ethanol, retention of absorbed ethanol for a long period of time, and adsorption and removal of acetaldehyde. Although the exact reason is unknown, the above-mentioned excellent properties exhibited by the sustained-release ethanol composition of the present invention are presumed to be based on the following reasons.

First, ethanol is well absorbed, and it can hold ethanol for a long period of time and release it slowly. This is because of the affinity between the amine unit of the crosslinked polymer and the hydroxyl group of ethanol. Seem. In addition, the sustained release ability is maintained for a long period of time because the crosslinked polymer is chemically stable, causing an undesired chemical reaction with ethanol or thermodynamic fatigue, resulting in cross-linking. This is probably because the formation does not change and deteriorate.

On the other hand, the reason that the ethanol sustained-release agent is extremely excellent in the ability to remove and adsorb acetaldehyde is that acetaldehyde in the outside air is efficiently dissolved in ethanol during the adsorption and removal, and thus, the amino group is removed in the ethanol liquid phase. This is probably because chemical bonding with acetaldehyde proceeds. It is obvious from the chemical reaction kinetics that the coupling reaction between an amino group and acetaldehyde via ethanol is much faster in the ethanol liquid phase than in the gas phase.

Further, the chemical stability of the crosslinked polymer can be determined by using the sustained release agent of the present invention as a food preservation composition in combination with various food preservation chemicals such as an oxygen scavenger. Making it possible.

[0026]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. It goes without saying that the present invention is not limited to only the examples described below.

Examples 1 to 5 illustrate the synthesis of a crosslinked polymer and the preparation of a sustained-release agent for ethanol. Example 6 Hereinafter, the efficacy of the composition for preserving food, comprising the ethanol sustained release agent exemplified in Examples 1 to 4 and the combination of the same and the oxygen scavenger will be described.

Example 1 50% polyallylamine hydrochloride (PAA-HCl-3)
L, molecular weight 10,000, manufactured by Nitto Boseki Co., Ltd.) Aqueous solution 1
44.5 g of a 48% aqueous sodium hydroxide solution was added to 00 g, followed by stirring and cooling. After that, 5 g of epichlorohydrin was added while maintaining the liquid temperature at 45 ° C to 55 ° C.
Stirring was continued at 50 ° C. for 3 hours to effect a crosslinking reaction.

The obtained crosslinked polymer (hereinafter, this crosslinked polymer is referred to as a) was washed in running water to sufficiently remove salts and residual monomers, and then dried under vacuum at 80 ° C. for 5 hours. The dried gel of a obtained by vacuum drying was prepared into fine powder having an average of 0.2 mm square or less using a crusher (manufactured by Torai Tekko Co., Ltd.), and was directly immersed in 500 ml of ethanol. The volume of the ethanol sustained-release agent obtained by absorbing ethanol for 20 hours was about 5.0 times that of the dried gel a.

Example 2 N-vinylformamide (10 g) and water (40 g) were mixed, and 2,2'-azobisamidinopropane dihydrochloride was added to the mixture.
1 g was added and polymerization was carried out at 60 ° C. for 5 hours. Further, 25 g of 35% hydrochloric acid was added, followed by saponification at 80 ° C. for 3 hours. The saponification reaction product was precipitated in methanol to obtain a sol-form partially neutralized polyvinylamine. The degree of saponification was 85%.

The obtained partially neutralized polyvinylamine was treated with 5N
After desalting with 10 ml of NaOH, the powder is dried with a hot air drier (manufactured by Yamato Scientific Co., Ltd.) to obtain a dry powder. 7 g of the dry powder was dissolved in 100 ml of water, 0.1 g of ethylene glycol diglycidyl ether was added, and the mixture was heated and stirred at 50 ° C. for 3 hours to obtain a crosslinked polymer (hereinafter, this crosslinked polymer is referred to as b). . After washing in running water, it is dried with a hot air drier (Yamato Kagaku Co., Ltd.), and prepared into a fine powder having an average of 1 mm square or less using a pulverizer (available from Torai Tekko Co., Ltd.). Dipped into 200 ml. 2
The volume of the ethanol sustained-release agent obtained by absorbing ethanol while stirring for 0 hour was about 5.5 times the dry fine powder of b.

Example 3 To a polymer obtained by adding 2.4 g of ammonium persulfate to 100 g of a 60% aqueous solution of diallylamine hydrochloride and polymerizing at 60 ° C. for 48 hours, 1 liter of 1N NaOH was added, stirred, filtered, and washed with water. The polymer gel was again filtered off. Subsequently, it was dried with a hot air dryer (Yamato Kagaku Co., Ltd.) and averaged using a crusher (Torai Tekko Co., Ltd.).
It is prepared into fine powder of less than
immersed in ml. The volume of the ethanol sustained-release agent obtained by absorbing ethanol while stirring for 15 hours was about 2.2 times the dry fine powder of the crosslinked polymer (hereinafter referred to as “c”).

Example 4 95% polyallylamine hydrochloride (PAA-HCl-3)
S, molecular weight 10,000, manufactured by Nitto Boseki Co., Ltd.) 200 g
Was dissolved in 160 g of a 25% aqueous sodium hydroxide solution.
Separately, 200 ml of chlorobenzene, 100 ml of o-dichlorobenzene and 2 g of sorbitan sesquiolate are mixed in a 1-liter round bottom flask to prepare a homogeneous solution.

1.58 g of epichlorohydrin was added to the above mixture of polyallylamine hydrochloride and sodium hydroxide, and the mixture was stirred for about 2 minutes. The mixture was poured into a mixture of organic solvents in a round-bottomed flask, and the stirrer was stirred at about 500 rpm. p. and further rotate and stir for 30 minutes. Next, the organic solvent mixture in which the polyallylamine is dispersed is heated and stirred at 50 ° C. for 3 hours,
A cross-linking reaction was performed to prepare fine particles of a cross-linked polymer (this cross-linked polymer is hereinafter referred to as d). The fine particles of d were washed by ethanol, water, 1N NaOH aqueous solution and water in this order after filtration. The washed microparticles were dried at 50 ° C. under reduced pressure (using a vacuum dryer manufactured by Yamato Scientific Co., Ltd.). The microparticles after drying had a particle size of 20 to 500 μm and a yield of about 16 g.

The microparticles were immersed in 300 ml of ethanol. The volume of the ethanol sustained-release agent obtained by absorbing ethanol while stirring for 15 hours was about 4.5 times that of the d microparticles.

Example 5 50% polyallylamine hydrochloride (PAA-HCl-3)
L, molecular weight 10,000, manufactured by Nitto Boseki Co., Ltd.) Aqueous solution 1
44.5 g of a 48% aqueous sodium hydroxide solution was added to 00 g, and 200 g of water was further added to dilute the whole.
A 6 cm × 33 cm cotton cloth was dipped, the impregnating solution was squeezed with a mangle, and air-dried at room temperature. The polyallylamine adhesion rate after drying was 19.5%. The polyallylamine-attached cotton cloth was placed in 500 g of a 1% aqueous solution of epichlorohydrin and heated at 55 to 60 ° C. for 5 hours to cause a crosslinking reaction.

After washing the above-mentioned cotton cloth having a crosslinked polymer surface in running water to sufficiently remove salts and residual monomers,
Vacuum dried at 60 ° C. for 5 hours. The dried gel obtained by vacuum drying was directly immersed in 5 liters of ethanol. The volume of the ethanol sustained-release agent obtained by absorbing ethanol for 20 hours was about 8.0 times that of the crosslinked polymer sheet.

Examples 6 to 10 Dry powders of the crosslinked polymer a to d synthesized in the above Examples 1 to 4 were each weighed in an amount of 20 g, and contained 20 g of ethanol for sustained release and deodorization. An ethanol sustained release agent was prepared for use in the test. Let them be A to D, respectively.

Next, the ethanol sustained-release agent alone or uniformly mixed with iron powder and sodium chloride having a deoxidizing effect was sealed in a small bag of rayon Japanese paper laminated with perforated polyethylene. . Using 50 g of Castella as a sample food, put it in a bag made of nylon / polyethylene laminated film with a capacity of 500 ml together with a small bag enclosing the food preservation composition, sealing it, observing the occurrence of mold and rot, and monitoring the acetaldehyde odor. The presence or absence was checked. The storage temperature of the sample was set at 25 ° C.

Table 1 shows the composition of the composition for preserving food, and Table 2 shows the measurement results. In Examples 6 to 9, a mixed composition of A to D, iron powder and sodium chloride was used.
Measurements were made using only

Comparative Examples 1 and 2 Ethanol (20 g) was absorbed by porous silicon dioxide (silica gel) powder (20 g), and this was used as a sustained release agent for ethanol.

Further, polyallylamine hydrochloride (PAA-
HCl-3L, molecular weight 10,000, manufactured by Nitto Boseki Co., Ltd.), and 15 parts each of a partially neutralized polyvinylamine obtained by saponifying an N-vinylformamide polymer by 85 mol% of a polyallylamine obtained by neutralizing with sodium hydroxide. weight%
An aqueous solution was prepared. 100 parts by weight of each of these aqueous solutions and 100 parts by weight of silica gel particles were mixed and dried under reduced pressure at 75 ° C. for 8 hours to prepare an acetaldehyde adsorbent in which polyallylamine or partially neutralized polyvinylamine coated the surface of the silica gel particles. Hereinafter, the one based on polyallylamine is referred to as E, and the one based on partially neutralized polyvinylamine is referred to as F.

The above silica gel ethanol sustained-release agent and silica gel aldehyde adsorbent were used in the same manner as in Examples 6 to 9 to prepare a mixed composition of iron powder and sodium chloride. Example 6-
10 Similarly, using 50 g of castella as a sample food, put it in a bag made of nylon / polyethylene laminated film with a capacity of 500 ml and sealing it with a small bag enclosing the food preserving composition, and observe the occurrence of mold and rot. The presence or absence of acetaldehyde odor was confirmed. The storage temperature of the sample is 25
Set to ° C.

Along with Examples 6 to 10, the composition of the food preserving composition is shown in Table 1, and the measurement results are shown in Table 2.

[0045]

[Table 1]

[0046]

[Table 2]

As shown in Table 2, the embodiment using the food preserving composition using the ethanol sustained-release agent of the present invention showed that silica gel was used as an ethanol sustained-release agent for both long-term preservation of food and removal of odor. It is superior to the comparative example used for (1). This means that the composition for preserving food using the sustained-release agent for ethanol of the present invention is extremely excellent in long-term retention of ethanol and ability to adsorb acetaldehyde gas in the air.

[0048]

As described in detail above, the sustained release agent for ethanol of the present invention and the composition for preserving food using the same have a sustained sustained ethanol release property for a long period of time, and are excellent in food preservation action. In addition, the ability to remove acetaldehyde is high, and unpleasant odors do not permeate foods.

In addition, since the ethanol sustained-release agent and the acetaldehyde removing agent are integrated, they are effective in a small amount as compared with the conventional combination type of both, and are economical because the number of manufacturing steps can be reduced. Since the material is a polymer, there is also an effect that molding is easy and the shape that can be molded is abundant.

Claims (5)

(57) [Claims] 1. An ethanol sustained-release agent obtained by impregnating a polymer cross-linked polymer or copolymer obtained by using an allylamine-based or vinylamine-based monomer as at least one of the polymerization components with ethanol. . 2. An ethanol sustained release agent comprising a polymer crosslinked polymer or copolymer containing at least one of an allylamine-based or vinylamine-based monomer as a polymerization component and ethanol supported thereon. 3. A food preserving composition comprising the ethanol sustained-release agent according to claim 1 or 2 as an essential component. 4. The ethanol according to claim 2, wherein the crosslinked polymer of a polymer or a copolymer obtained by using an allylamine-based or vinylamine-based monomer as at least one of the polymerization components absorbs and supports ethanol. A method for producing a sustained release agent. 5. A food preserving composition comprising the ethanol sustained-release agent according to claim 1 or 2 and an oxygen scavenger containing a metal powder as a main component.