KR20170050872A - Preparation Method of the Composit for use Preservation of Natural Food using Chitosan and Extract of Plant - Google Patents

Abstract

The present invention relates to a method for preparing a composition for preserving natural food by using chitosan with a low molecular weight and a plant extract. More specifically, provided is a method for preparing a composition for preserving natural food by forming micro-emulsion by emulsifying botanical essential oil and an antibacterial plant extract in a solution of low molecular weight chitosan and then using the same. The composition for preserving natural food, prepared in the present invention comprises the botanical essential oil and the antibacterial plant extract forms the micro-emulsion with the chitosan solution. Therefore, the composition for preserving natural food not only significantly increases antibacterial activity but also maintains antibacterial ability for a long period of time. The composition for preserving natural food prepared in the present invention can be effectively used to prevent deterioration and decay of various food materials and food, prevents deterioration of various beverages, fermented liquor, confectionery, fish, and processed meat products, and sea food, and can be used in a wide range such as drying fish, culturing fish, and stock feed.

Description

[0001] The present invention relates to a composition for preserving natural food using chitosan and a plant extract,

The present invention relates to a method for preparing a natural food preserving composition comprising chitosan and a plant extract as an active ingredient. More particularly, the present invention relates to a method for producing a microemulsion by emulsifying vegetable essential oil and plant extract into a low molecular weight chitosan solution, The present invention provides a method for preparing a composition for preserving natural food which is harmless and non-toxic to the human body.

The present invention relates to a composition for preserving natural food prepared by emulsifying low molecular weight chitosan, vegetable essential oil and plant extract. Chitosan is a natural food additive having various efficacy and stability among various natural antimicrobial agents known to date. Because of its different functionality, its applications are very diverse.

Chitosan is a biodegradable natural polysaccharide which is widely used in agricultural, food and cosmetic fields depending on its molecular weight. Cosmetics, food preservatives, detergents, moisturizers and the like using low molecular weight chitosan having relatively low molecular weight are widely used.

Japanese Patent Laid-Open Publication No. 63-120701 discloses a method for producing a polydisperse, low molecular weight chitosan having a molecular weight of 5,000 to 50,000 units by decomposing chitosan in sodium hypochlorite and aqueous hydrogen peroxide solution And Japanese Patent Application No. 2-214664 discloses a method for producing chitosan oligosaccharide by an enzymatic digestion method using Chitosanaze.

The low-molecular-weight chitosan and chitosan oligosaccharide prepared by the chitosan dissolution method used in the patented technology have a broad molecular weight distribution and a polydispersity, which is a disadvantage of relatively low antibacterial activity.

Meanwhile, in the method of decomposing chitosan by the photodissolution method provided by the present invention, the decomposition rate of the photocatalyst is accelerated by the irradiation time of the ultraviolet ray by accelerating the decomposition rate, and the molecular weight can be controlled by appropriately adjusting the irradiation time of ultraviolet ray. 100% low molecular weight chitosan is produced with high efficiency.

Can be obtained by extracting an antimicrobial plant extract containing a plant essential oil having antimicrobial activity from one or more selected sites such as flowers, leaves, stems, husks, roots, fruits and seeds of plants.

Canola, rose geranium, thyme, Thyme white are among the antimicrobial vegetable oils. Thyme red, clove bud, castor, nem oil and the like have been reported to have a relatively high antimicrobial activity, but are not limited thereto.

Among the plant extracts, there are grape seeds, cinnamon, mustard, pine, persimmon, apricot, grape seed, camellia seed, flaxseed, pine leaf, ginkgo leaf, persimmon leaf, green leaf, bamboo leaf, Etc., are known to have strong antibacterial and germicidal properties, but the present invention is not limited thereto.

Natural antimicrobial agents using water-soluble chitosan oligosaccharides prepared by enzymatic decomposition of chitosan with a relatively small molecular weight and natural food additives for food preservation are disclosed in JP-A-8-23891 and JP-A-11-28062 And many of the patented technologies have been developed since it is known about its food preservability.

Korean Patent No. 10-1428683 discloses a food preservative containing chitosan oligosaccharide as an active ingredient. Korean Patent No. 10-0799270 discloses a method for producing a natural antimicrobial composition comprising a sancho extract as an active ingredient and its antibacterial activity .

In the above-mentioned patent art, a food preserving composition comprising a simple mixture of chitosan oligosaccharide and a plant extract is disadvantageous in that the antimicrobial activity and the persistence of the food preservation effect are weak.

Recently, Korean Patent No. 10-1324309 discloses an antimicrobial active composition comprising an herbal medicine extract as an active ingredient and a method for preparing the same, a method for preparing a water-soluble licorice extract having food preservability in Korean Patent No. 10-178699, A natural antimicrobial agent derived from plants which improves the storage stability of the plant, and a production method thereof.

In the above patented technology, the plant extract is a simple mixture of two or more kinds of plant extracts, and the occurrence and proliferation inhibiting effects of various harmful bacteria, fungus and pathogenic bacteria are limited, and the limit of persistence in terms of food preservation effect can not be solved have.

When the antimicrobial activity of chitosan is applied as a food preservative food additive, about 100 ~ 1,000 ppm is added to the preservative effect. However, if the added amount is too high, the bitter taste and smell of chitosan can deteriorate the taste and odor of the food and adversely affect the taste of the food.

In order to solve the problems of the natural food preservative using chitosan, it is required to develop a special formulation technology capable of increasing the antibacterial power, the sterilizing power and sustaining for a long time.

In order to solve various problems of the conventional art concerning the above-mentioned natural food preservative, development of a new natural food preserving composition capable of not only improving antimicrobial activity but also maintaining antimicrobial activity for a long period of time is a technical problem to be urgently solved .

Recently, the school food service system has been expanding since the food poisoning has occurred frequently, and excessive consumption of synthetic food additives used in foods may harm health and seriously threaten life.

As a result, strict regulations on the use of synthetic food additives and restrictions on their use are becoming increasingly concerned about natural food additives.

In the present invention, a natural antimicrobial active microemulsion is prepared using antimicrobial plant extracts to prevent deterioration and corruption of foodstuffs and foodstuffs, and to improve quality, and a method for producing a harmless and nontoxic natural food preserving composition .

The present invention relates to a method for producing a natural food preserving composition capable of significantly improving antimicrobial activity and sustaining antimicrobial activity for a long time by emulsifying plant essential oils and plant extracts with a low molecular weight chitosan solution using a natural emulsifier to form a microemulsion .

The composition for preserving natural food prepared according to the present invention emulsifies vegetable essential oil and antimicrobial plant extract into a low molecular weight chitosan solution to form a microemulsion and disperses and stabilizes the extract in the plant extract to greatly improve the antimicrobial activity, .

The composition for preserving natural food prepared according to the present invention can be used for preventing the corruption and food poisoning of foodstuffs and foodstuffs, leading to the maintenance of foodstuffs, and prolonging the shelf life of foodstuffs.

In addition, there is a feature that it is possible to prevent deterioration of various beverages, fermented liquors, confectioneries, fish and meat products, and marine foods cooked with various vegetables, fruits, and the like, and to widely use such as fish drying, fish and livestock feeds.

1 shows the antimicrobial effect and antifungal effect of the composition for preserving natural food according to the present invention.
Fig. 2 is a flow chart of a process for producing a composition for preserving natural food according to the present invention.

The low molecular weight chitosan and the chitosan oligosaccharide produced by the conventional acid decomposition and enzymatic decomposition method are difficult to control the molecular weight, are multi-dispersible and difficult to be separated by molecular weight.

In order to solve the problems in the chitosan decomposition method, a low molecular weight chitosan can be prepared by a photolysis method, and the production method thereof is summarized as follows.

Production of low molecular weight chitosan with uniform molecular weight by photodissociation by ultraviolet irradiation using titanium dioxide (TIO2) as a photocatalyst in a 0.5 to 5 wt% chitosan solution in which 0.5 to 1 wt% of low molecular weight chitosan is dissolved in an organic acid solution can do.

In the production process of low molecular weight chitosan by the photolysis method, the decomposition rate of the photocatalyst is accelerated by the irradiation time of the ultraviolet ray, and thus the molecular weight is gradually lowered.

The present invention provides a method for producing a low molecular weight chitosan having a molecular weight ranging from 10,000 to 100,000 by decomposing a 1 to 5 wt% chitosan solution containing a high molecular weight chitosan in an organic acid solution by a photolysis method.

The present invention also provides a method for preparing a microemulsion by uniformly emulsifying vegetable essential oils and plant extracts in a solution obtained by dissolving the low molecular weight chitosan prepared as described above in an organic acid using an emulsifying apparatus and stabilizing the emulsion by adding a dilute alginic acid solution have.

There is a problem of deterioration of taste and smell due to the conventional technology for food preservative using chitosan, and more particularly, the bitter taste inherent to chitosan when added to food alone.

It is an object of the present invention to solve the technical problem of increasing the antibacterial and disinfecting power of the natural food preserving composition prepared using the low molecular weight chitosan, the vegetable essential oil and the plant extract and keeping it for a long time.

In the present invention, one or more kinds of antimicrobial plant extracts such as cinnamon, mustard, sancho, and coriander are selected from plant essential oils such as rapeseed oil, peppermint oil, lemon oil, castor oil and camellia oil and mixed at a certain ratio. And the mixture is emulsified to prepare a primary microemulsion (W / O).

A secondary microemulsion (W / O / W) is prepared by adding a low molecular weight chitosan solution to the primary microemulsion (W / O) and emulsifying it by a multiple emulsification method

The pH of the microemulsion (W / O / W) is adjusted to 3.5 to 5.0 with a sodium phosphate buffer solution, and a small amount of an aqueous solution of sodium alginate is added to stabilize the emulsion.

To prepare the low molecular weight chitosan solution, organic acids such as acetic acid, citric acid, lactic acid, tartaric acid, ascorbic acid, and sorbic acid may be used. In general, edible acetic acid and citric acid are preferably used.

Examples of the environmentally friendly emulsifier include pelaronic acid, polyethylene sorbitan fatty acid ester, polyoxyethylene oleylamine, ethoxylated castor oil, oleyl alcohol, sorbitan monooleate, and the like, and oleyl alcohol, It is preferable to use sorbitan monooleate in an amount of 5 to 15 parts by weight based on 100 parts by weight of the mixed solution of plant essential oils and plant extracts.

When preparing the composition for preserving natural food for use as a food preparation, the above-mentioned secondary microemulsion (W / O / W) is mixed with brown rice, garlic, onion, ginger fermented vinegar or plum, grape, apricot, apple, peach, plum, , Omija, orchid, etc., are preferably dispersed and stabilized in fermented vinegar.

It is preferable that the secondary microemulsion (W / O / W) is dispersed and stabilized in plant extracts such as pine needle, ginkgo leaf, persimmon leaf, green tea leaf,

Plant extracts can be produced by a general plant extraction method, for example, a compression method, a leaching method, an adsorption method, and a solvent extraction method. When the extraction solvent is water, it may be subjected to hot water extraction, leaching if the extraction solvent is an organic acid, and solvent extraction when the extraction solvent is a volatile solvent.

Cinnamon, mustard, sancho, gilt and the like can be dried and pulverized in powder form and extracted with a water-soluble organic solvent such as water, methanol, ethanol, isopropyl alcohol, acetone, fermented vinegar, etc., It is preferable to use a solvent instead of the organic solvent.

20 g of a dry sample can be pulverized and extracted with a reflux extraction method at 50 to 70 ° C for 6 to 72 hours using 100 to 200 ml of a syrup, After the extract is filtered, the solvent is recovered by using a rotary evaporator to obtain a concentrate.

(100 g) of leaves and stalks cut from leaves and stalks of P. vannamei, P. vannamei, P. vannamei, and P. vannamei were immersed in 0.5 to 2 L of a mixed solution of alcohol and acetic acid (1: 1 v / v) for 3 months or more and extracted by leaching .

Ethanol, edible acetic acid, and edible citric acid may be used in place of the alcohol used as the extraction solvent. Extraction conditions may be variously applied depending on the solvent, temperature, and time, and are not limited to the ranges specified above.

The preservative for natural food using the antimicrobial active microemulsion provided in the present invention is characterized by preventing the deterioration of various foods, beverages, fermented liquors, confectioneries, meat processing products, and marine foods cooked with grains, vegetables, fruits and the like.

The preservative of natural food prepared by the above method can greatly enhance the antibacterial activity by dispersing and stabilizing the plant extract and the plant extract by emulsifying the plant essential oil and the antibacterial plant extract into the low molecular weight chitosan solution.

1 to 30 parts by weight of microemulsion may be dispersed with respect to 100 parts by weight of the plant extract, and it is preferable to appropriately control the mixing ratio according to the food ingredients and foods to be used.

The composition for preserving natural food of the present invention is characterized by being able to effectively utilize chitosan in the preservation and processing fields of various food materials and foods because it has a unique bitter taste and smell and eliminates the antimicrobial activity for a long time.

The amount of the composition for preserving natural food of the present invention may be selected from the range of 0.01 to 10% by weight based on the type of the food and the characteristics of the food. In general, the amount of the composition is 0.05 to 1% by weight It is suitable.

In the method of using the composition for preserving natural food of the present invention, a stock solution of food preservative is added to liquid food such as beverage, fermented liquor, etc. and shaken, and the diluted solution is uniformly sprayed to the solid food.

Solid food ingredients such as tofu, fish, and meat, vegetables, and fruits are dipped in a dilute solution, washed and rinsed in running water, and baked with baking water containing natural preservative composition.

Meat processing and aquatic products It is effective to prevent discoloration, deterioration and corruption by suppressing the growth of bacteria and fungi by spraying diluted solution and taking it out after putting meat and fish into a diluted solution before drying meat and fish in factory . Hereinafter, the present invention will be described in more detail with reference to examples.

Preparation of low molecular weight chitosan by photolysis

1 g of titanium dioxide (TiO2) was added to a 5% chitosan solution prepared by dissolving 1 kg of chitosan in 20 liters of a 0.5% acetic acid solution of 0.5%, irradiated with ultraviolet light having a wavelength of 340 nm for 72 hours while stirring, 10,000, deacetylation degree: 90 ~ 95%).

Preparation of plant extracts (1)

50 g of dried cinnamon was pulverized and placed in 500 ml of 70% ethanol. The mixture was heated and extracted with stirring at 40 to 65 ° C for 12 hours using a reflux condenser, and then filtered. The filtrate was filtered using a rotary evaporator And the concentrate was frozen and stored.

In the same manner as in Example 1, except that cinnamon was replaced with 50 g of corn glue, a ganoderma extract was prepared.

Production of plant extracts (2)

The dried pine needle was washed thoroughly with water, and 500 g of the dried sample was placed in 5 L of 10% acetic acid solution (1: 1 v / v) at room temperature and immersed for at least one month while being occasionally stirred at room temperature, followed by filtration to prepare pine leaf extract.

Preparation of composition for preserving natural food

Step 1: 10 parts by weight of the seed oil, 5 parts by weight of the cinnamon extract and 5 parts by weight of the uroglycolipid extract were added to 100 g of water, and 5 parts by weight of the polyethylene sorbitan fatty acid ester was added. Then, the emulsion was emulsified at a stirring speed of 5,000 rpm Microemulsion (W / O) was prepared.

Step 2: 50 parts by weight of a 2.5% low molecular weight chitosan solution (average molecular weight: 10,000, deacetylation degree: 90-95%) was added to 50 parts by weight of the primary microemulsion (W / O), 5 parts by weight of sorbitan monooleate (W / O / W) was prepared by emulsifying the mixture at a stirring speed of 5,000 rpm using an emulsification apparatus.

The microemulsion (W / O / W) was adjusted to pH 4.5 with a sodium phosphate buffer solution, and then a small amount of dilute sodium alginate aqueous solution was added to stabilize the emulsion.

Step 3: For food preparation, 10 parts by weight of the microemulsion was dispersed and stabilized in 90 parts by weight of mulch vinegar.

Step 4: 10 parts by weight of the microemulsion was dispersed and dispersed in 90 parts by weight of the pine needle extract in order to inhibit the growth of various bacteria and fungi and proliferation in business premises such as maintenance of food ingredients, prevention of resistant bacteria in fishes and livestock feed, .

Experimental Example 1: Measurement of molecular weight of chitosan

The molecular weight of the chitosan was determined by gel chromatography using a detector equipped with a TSK gel column (Viscotek Corp., U.S.A.). The analytical sample was injected with 100 microliters and eluted at a flow rate of 0.8 mm / min. The molecular weight of the chitosan was measured according to the decomposition time and the results are shown in FIG.

The analytical sample was dissolved in 0.3 M acetic acid solution to prepare a 0.3% solution. The sample solution was adjusted to pH 4.5 with sodium phosphate buffer solution, filtered through 0.45 microfilter, and the acetic acid solution adjusted to pH 4.5 was used as a control.

As shown in FIG. 1, the molecular weight of chitosan rapidly decreased until 12 hours of ultraviolet irradiation, and after that, the molecular weight reduction rate was gentle. When irradiated with ultraviolet rays for 72 hours, the molecular weight decreased to 10,000 units or less

The low molecular weight chitosan produced by the above-described photolysis method has a purity and a yield of 100%, a uniform molecular weight, and a molecular weight can be freely controlled according to ultraviolet irradiation time.

Experimental Example 2: Antibacterial Test

0.025% and 0.05% of a sample for preserving natural food prepared in the same manner as in Example 4 were added to LB liquid medium (tryptone 1%, yeast extract 0.5%, NaCl 1%), and Escherichia. coli (ATCC 25922), Staphylococcus. aureus bacteria, Bacillus Substilis such as (ATCC 5923) (KCTC 1021) , Pseudomonas (ATCC 15442) plant pathogens and Penicillium citrinium of aeruginosa such as (ATCC 10121) Chaetomium globosum (ATCC 6205) vegetable mold inoculum of light (the test bacteria: 104 ~ 105CFU / ml) was adjusted to pH 3.6 or pH 6, and the strain was inoculated and cultured with shaking at 30 ° C for 24 hours.

The culture broth was evenly spread on an LB agar plate medium and cultured at 37C for 48 hours. The number of colony counts (CFU) was counted and the minimum inhibitory concentration (MIC,%) Respectively.

Comparative Example 1

The antimicrobial activity of the natural food preservative composition prepared using the antibacterial active microemulsion in Example 3 was tested and compared with a solution of low molecular weight chitosan (average molecular weight: 10,000, deacetylation degree: 90 to 95%).

[Figure 1] Antimicrobial effect and antifungal effect of a composition for preserving natural food

As shown in FIG. 1, the minimum growth inhibitory concentrations of S. aureus were 0.02% and 0.025% at pH 3.6 and 6.0, respectively, and the E. coli 0.025% and 0.035%, respectively.

The antimicrobial activity of the acidic solution was stronger than that of the alkaline solution, and the minimal inhibitory concentration of E. coli was slightly higher than that of S. aureus .

On the other hand, the pathogenic bacteria S. aureus and E. coli showed 100% reduction rate, 100% for pathogenic fungi B. subtilis, P. aeruginosa , 85% for P. citrimium and C. globosum, And more than 90%.

Experimental Example 2: Food preservation effect sensory test

(Size: 5 x 7 cm, thickness: 2 cm) was prepared by cutting the commercial tofu with a knife, uniformly spraying the 0.05% and 0.1% solutions of the natural food preserving composition prepared in the present invention, Changes in appearance were observed while stored.

Table 1 shows the results of testing the food preservation effect by obtaining the effective preservation days from the average value of the days taken until the evaluation score of the 10 test specimens became 1 point.

0 point: There is no change at all.

1 point: discoloration, softening, mold spot

2 points: 2 discoloration, softening, mold spots

3 points: discoloration, softening, mold spots spread about 1/2

Comparative Example 2

Table 1 shows the results of examining the food preservation effect by the same method as the food preservation effect test of Test Example 2 without adding the composition for preserving natural food of the present invention to the tofu specimen.

As a result of testing the preservation effect on the tofu of the composition for preserving natural food of the present invention, when the 0.05% and 0.1% of the samples were sprayed, the preservation period of 6.3 days and 13.1 days was prolonged, respectively.

Claims (7)

(1) preparing a low molecular weight chitosan by a photolysis method;
(2) preparing an antimicrobial plant extract;
(3) dissolving the low molecular weight chitosan in an edible acetic acid or citric acid solution;
(4) emulsifying plant extract (1) in vegetable essential oil to form primary microemulsion (W / O);
(5) emulsifying the primary microemulsion (W / O) in a low molecular weight chitosan solution to form a secondary microemulsion (W / O / W);
(5) dispersing and stabilizing the secondary microemulsion (W / O / W) in the plant extract (2); By weight based on the total weight of the composition. The method according to claim 1,
Addition of titanium dioxide (TiO2) to 1-5% chitosan solution prepared by dissolving the chitosan in organic acid, and in the range of hundreds of thousands in only the molecular weight of chitosan according to the decomposing time in the decomposition step of irradiating ultraviolet rays having a wavelength of 340 nm can be adjusted at will , And a method for producing low molecular weight chitosan by a photolysis method having a purity and a yield of 100% The method according to claim 1,
One of the plant essential oils such as rapeseed oil, mint oil, cinnamon oil, camellia oil, grape seed oil and flaxseed oil is used as a microemulsion, and at least one plant extract such as cinnamon, W / O). The method of claim 3,
A 2.5% low molecular weight chitosan solution was added to the microemulsion (W / O) by dissolving the low molecular weight chitosan (average molecular weight: 5,000 to 100,000, acetylation degree: 85 to 95% (W / O / W) by multiple emulsification by secondary emulsification using an environmentally friendly emulsifier. The method of claim 4, wherein
In the microemulsion manufacturing process, 5 to 15 parts by weight of an environmentally friendly emulsifier such as oleyl alcohol and sorbitan monooleate are added to 100 parts by weight of the hydrophilic and lipophilic mixture and emulsified to prepare a microemulsion. Using a sodium phosphate buffer solution To adjust the pH to 3.5 to 5, and adding a small amount of dilute sodium alginate aqueous solution to stabilize the emulsion. The method of claim 1, wherein
The microemulsion (W / O / W) is dispersed and stabilized in fruit fermented vinegar such as brown rice, garlic, onion, ginger fermented vinegar or plum, grape, apricot, apple, peach, plum, cherry, A method for preparing a composition for preserving natural food for food. The method of claim 1, wherein
A composition for preserving natural food for preventing, preventing and preserving various kinds of foodstuffs that disperses and stabilizes the microemulsion (W / O / W) in one or more plant extracts from pine needles, gingko leaves, persimmon leaves, green tea leaves, ≪ / RTI >

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