KR20040008428A - Manufacturing method for rice which is coated alginic acid and chitosan - Google Patents

Abstract

PURPOSE: Provided is a method for producing alginic acid and chitosan-coated rice by coating the surface of rice with a mixture of ozone and water with irradiating an ultrasonic wave and drying. The rice has improved nutrition and palatability as well as preservability. CONSTITUTION: Ozone is aerated with water for 30min to 1hr to produce a mixture of ozone and water. Then, rice is washed with the mixture of ozone and water at about 10deg.C or less with irradiating an ultrasonic wave having a frequency between 10 to 40 MHz for 30sec to 15min and dried to a moisture content of 14 to 16% by weight. An alginic acid solution containing 200mg to 20g alginic acid and 100 to 200ml water and a chitosan solution containing 20 to 200mg chitosan and 100 to 200ml water are respectively coated on the surface of 1kg rice. The rice is then dried to a moisture content of about 14 to 16% by weight.

Description

Manufacturing method for rice which is coated alginic acid and chitosan}

The present invention relates to a functional rice manufacturing method, and more particularly to a rice manufacturing method of coating the alginic acid on the surface of the rice and then coated with chitonic acid on the top to enhance the palatability and functionality.

Alginic acid is known to be produced by some microorganisms ( Pseudomonas sp. And Azotobacter sp. ), But now most of them are extracted from brown algae, and uronic acid is the major component.

Alginic acid contained in the algal leaf cell wall of kelp, seaweed, gompi and moths in algae is produced for carbon assimilation of algae chlorophyll and contains about 20-30% of the algae.

Alginic acid varies in content depending on the type of brown algae, harvesting time, place of origin, and site, and especially kelp and seaweed are contained in brown seaweed.

Alginic acid is a type of seaweed polysaccharide. The physical and chemical properties of alginic acid are heteropolysaccharides composed of β-D-mannuronic acid and α-L-gluuronic acid with α-1,4 bonds or β-1,4 bonds. Is determined by the ratio of mannuronic acid / glaronic acid and the arrangement of molecular polymer segments. The ratio of uronic acid / glaronic acid varies depending on the type of algae, but in general, when the content of alginic acid is high, The ratio of glaronic acid also increases (Mizuno et al. , 1983; Nishide et al ., 1988; Hideki et al ., 1993).

Among the results of studies on the extraction method of alginic acid, molecular weight, the ratio of nuronic acid / glaronic acid and the physical properties by hydrolysis, Haug and Larsen (1963, 1964) reported that The composition of lonic acid was measured, and Haug (1967) determined the average degree of polymerization of uronic acid by measuring the mobility of alginic acid extracted from kelp by Ca ²⁺ and Na ⁺ electrophoresis, and Penman and Sanderson (1972) Alginic acid extracted from large kelp was fractionated into homopolymerized and double-polymerized fractions by pmr spectroscopy and peaks of mannuronic acid block (MM-block) and gluronic acid block (GG-block). The nuronic acid / glaronic acid ratio was measured by area.

Mackie et al. (1971) was elucidate the crystal structure of mannu acid and gluconic acid by X-ray diffraction analysis and infrared spectroscopic analysis, Grasdalen et al. (1979) is a ¹ H a bond structure characteristic of uronic acid residues in alginic acid The hydrogen bonding sites of mannuronic acid and gluronic acid were observed by -NMR, and Grasdalen et al . (1977, 1981) investigated the carbon binding sites by ¹³ C-NMR to determine the difference of uronic acid composition.

In addition, Gacesa et al . (1983) identified the composition of uronic acid of alginic acid by separately identifying manuronic acid and gluronic acid by ion exchange chromatography by HPLCdp.

Alginic acid easily undergoes low molecular weight due to acid or heat, and in the presence of alginic acid in combination with insoluble salts such as Ca ²⁺ and Mg ²⁺ , the alginic acid is changed to water solubility by substitution with sodium and potassium salts after alkali treatment.

Sodium and propylene glycol esters in alginic acid are soluble in water and have many properties such as viscosity, gelling, hydration, water retention, metal ion reactivity, binding, film formation, etc. It is used in ice cream, ice cream, syrup, snack, chocolate milk, bread, jelly, pudding, jam, fish meat products, and is widely used in cosmetics, toothpaste, medicine, textile, paper industry, paint, dental materials, rubber and welding rod. It is used.

There are many studies on the physiological effects of alginic acid, including the excretion of heavy metals, inhibition of blood pressure increase by ion exchange reaction, hypocholesterolemic action, hypoglycemic action, improvement of intestinal and constipation, protection of digestive tract mucosa, intestinal harmful microorganisms. It has various physiological functions such as proliferation inhibitory action, hemostatic action against upper digestive tract bleeding, immune enhancing action, erythrocyte and platelet aggregation action, promoting skin dermatitis formation, preventing reflux esophagitis, and promoting the release of harmful substances.

With respect to the heavy metal ex vivo excretion of alginic acid, alginic acid with free carboxyl groups is reactive with metal ions, and Harrison et al . (1996) promoted the excretion of radioactive calcium and strontium in rats. It depends on the ratio of gluconic acid and the more GG-block, the lower the mannuronic acid / gluronic acid ratio, the higher the metal ion-binding ability. Suppression of strontium absorption in humans showed a remarkable effect in alginic acid oligomers, which are mostly composed of gluronic acid.The lower the ratio of manuronic acid / gluronic acid was, the lower the ratio of heavy metal binding capacity of cadmium and calcium of alginic acid was measured by precipitation and dialysis. The larger the degree of polymerization, the higher the content of gluonic acid, the higher the binding capacity.

Alginic acid has the effect of inhibiting the increase in blood pressure by the ion exchange reaction, and investigated the binding ability between 36 kinds of dietary fiber and sodium, and in particular, it was confirmed that alginic acid easily binds by sodium and ion exchange reaction.

In animal experiments, ingesting potassium alginate in hypertensive naturally occurring rats suppressed an increase in blood pressure, increased potassium excretion in urine, and increased excretion of sodium in feces. Kimura et al . (1993) reported mannuronic acid / gluronic acid. Alginate with different ratios was prepared and the effect of the primary structure on the excretion of sodium into feces in rats and humans was investigated.The lower the manuronic acid / gluconic acid ratio, the higher the excretion of sodium due to feces. This facilitates the excretion of sodium, a blood pressure raising factor, and the absorption of potassium, calcium, and magnesium, blood pressure lowering factors. The mechanism is caused by the cation exchange reaction of carboxyl groups and other dietary fibers that do not cause other ion exchange reactions. External effects that inhibit the secretion of fermentation metabolites and insulin produced by microorganisms It has been reported that the increase in blood pressure is suppressed by (Armstrong et al . 1977; Brussaard et al . 1981: Schlamowitz et al ., 1987: Kosawa et al ., 1993; Kori et al ., 1993; Kimura et al ., 1993).

Many reports have been published on the blood cholesterol-lowering effects of alginic acid. Fahrenbach et al . (1966) reported that plasma cholesterol content was significantly reduced when high cholesterol diets containing alginic acid were fed to the white leghorn. Administration of alginic acid to rats induced by hypercholesterolemia inhibited the increase of serum and liver cholesterol and total lipids, alginic acid with higher viscosity than low viscosity, alginic acid with higher molecular weight than low molecular weight, and alginic acid with more insoluble than The effect is said to be elevated.

Alginic acid is said to inhibit cholesterol biosynthesis. Alginate propylene glycol esters have lower viscosity than the original alginic acid, but cholesterol lowering action is increased with increasing esterification degree. The elevation is suppressed (Watanabe et al ., 1992; Kobayashi et al ., 1997).

There are many studies on the hypoglycemic action of alginic acid (Reddy et al ., 1980: Lee, 1981; Fujihara and Nagumo, 1993; hajime et al ., 1994; Fujiki et al ., 1994). Alginic acid slows the rate of movement to the stomach or small intestine, inhibits the digestion of glucose into the gut, inhibits the rise of blood sugar and the rise of insulin in the blood (Trowell, 1973; McNeil, 1984).

The anti-cancer effect of alginic acid increases the immune activity as the content of MM-block is increased, that is, as the ratio of manuronic acid / glulon acid increases, which not only has a strong anti-cancer effect but also increases resistance to bacterial infection (Fujihara et al . , 1993; Fujiki et al ., 1994) Alginic acid increases the phagocytic acivity of macrophage, which means that the higher the content of MM-block and GG-block, the more the monosite (cytokine) is produced. monocytes) and are known to have anti-cancer activity by having normal macrophage activity (Chiharu et al ., 1991, 1992a, b; Fujihara et al ., 1993).

In addition, a study on the mechanism of anti-tumor and anti-tumor effects on various kinds of tumors such as Sarcoma-180 solid tumor of alginic acid (mannuronic acid / glulonic acid ratio; 2.84, molecular weight; 29,000) extracted from Sargassum fulvellum In the 50 mg / kg dose of Sarcoma-180 and Ehrlich's multiple tumors, ILS (increase in life span) showed significant anti-tumor effects of 141% and 222%, respectively. Alginate's anti-cultivation mechanism is due to host interposition due to macrophage activation and interferon induction.

Ingesting alginic acid slows the rate of weight gain (Hosoda et al. , 1989; 久 田et al ., 1992; Weaver et al ., 1992, 1996; Takahashi et al ., 1993, 1994a, b, c, 1995), (1992) significantly decreased the rate of body weight gain in 20% kelp powder, 10% alginic acid and 10% laminaran when rats were ingested with kelp powder, laminaran and alginic acid at different concentrations. Ikegami et al . (1990) showed that when rats ingested alginic acid and other types of indigestible polysaccharides, the weight gain rate was the slowest in alginic acid, and the decrease in sodium alginic acid was greater than that of alginic acid and calcium alginic acid. It depends on the type of fiber, viscosity, pH and water absorption. (Isaksson et al ., 1982; Ikegami et al ., 1983).

Alginate supplementation significantly reduced body weight gain and feed efficiency (Cho et al., 1986; Yang et al., 1996), and significantly increased body weight gain when rats and humans ingested partially hydrolyzed guar gum. (Takahashi et al ., 1993, 1994a, b, c, 1995). The decrease in weight gain caused by the intake of dietary fiber is not digested by the absorption and binding of viscous dietary fiber with moisture and nutrients in the body. It is rapidly excreted in vitro (久 田et al ., 1992; Takahashi et al ., 1993a, b, c 1995), and Ikegami et al . (1983) intestinal contents due to undigested components in the small intestine of rats fed alginic acid. It also increases the excretion of protein and fat into feces.

In addition, when alginic acid was ingested in rats, the decrease in feed intake, growth inhibition, and weight gain were observed, and fecal contents and intestinal weight and dry weight of feces increased. The weight of the contents was said to increase significantly. Harmuth-Hoene and Schwerdtfeger (1979) and Kang (1994) reported the effects of alginic acid and hydrolyzed alginic acid on the digestion and absorption of protein in rats. The availability was decreased, and the utilization efficiency of protein was significantly decreased, especially in hydrolyzed alginic acid.

Alginic acid has the effect of inhibiting the growth of intestinal harmful microorganisms (Duda et al ., 1992a, b, 1994). The intestinal microflora was remodeled by ingesting alginic acid. Eight healthy men were found to have increased fecal bifidus and decreased pH. Fermentation patterns vary according to the molecular weight, viscosity, content and pH of dietary fiber, and the intestinal pH is lowered by the production of dietary fiber metabolite, short-chain fatty acid (organic acid), and Bifidobacterium ( Bifidobacterium ) Lactobacillus ( Lactobacillus ) is maintained at the lowest pH of growth, inhibiting the growth of harmful microorganisms as a pot, promote the growth of beneficial bacteria to change the intestinal microflora and improve diarrhea and constipation to normal stool (Hosoda et al . , 1989; Takahashi et al ., 1993a, b, c).

Lactobacillus and Bifidobacterium produce large amounts of organic acids such as lactic acid and acetic acid to inhibit intestinal settlement of harmful microorganisms, thereby preventing intestinal diseases such as diarrhea and stimulating the immune system of the host to increase resistance to infection. (Russell, 1979; Mitsuka, 1982; Yazawa and Tamura, 1982).

The short-chain fatty acids produced by anaerobic fermentation of microorganisms, such as acetic acid, propionic acid and butyric acid, have different composition ratios of short-chain fatty acids due to differences in fermentation patterns depending on the type of sugar used as a substrate (Goodlad and Mathers, 1990; McIntyre et al ., 1991, 1993; Bianchine et al ., 1992), in general, dietary fiber has been reported to increase the content of butyric acid in short-chain fatty acids and relatively decrease in propionic and acetic acid contents. . (Adiotomere et al ., 1990; McIntyre et al ., 1991, 1993; Bianchini et al ., 1992; Takahashi et al ., 1993, 1994a; Kuda et al ., 1994).

The production of short-chain fatty acids promotes the absorption of sodium and water to improve the intestinal flora, and (Montgomery et al ., 1968; Vernia et al ., 1988), but in particular, butyric acid is used as an energy source for gastric mucosal cells. (Roedinger and Moore, 1981) affect the growth and differentiation of gastric mucosa (Kvietys and Granger, 1981: Van Soest, 1982; Sakata and Yajima, 1984). Butyric acid is a protein biosynthesis and hormone in tissue culture of colon cancer cells. It is known to be effective in suppressing abnormal cell division by secretion of morphogenetic cells, conversion of morphologically mutant cells, formation of normal protoplasm, and inhibition of cell growth in G1 of the cell cycle (Kruh, 1982).

The composition ratio of short-chain fatty acids in normal colon and carcinogenic colon showed that the content of butyric acid in normal colon was much higher than that of carcinogenic colon (C) (Weaver et al ., 1988; kashtan et al ., 1992). Even when fermented and fermented, the content of butyric acid was estimated to be correlated with the content of butyric acid and carcinogenesis rate because of its high content in normal colon (Clasussen et al ., 1991; Weaver et al ., 1996 ).

In addition, chitosan refers to a substance obtained by deacetylating chitin in crabs, crayfish, and shrimp shells. In 1811, French natural historian Bracono discovered an unknown ingredient, chitin, contained in mushrooms. . Later, in 1859, the chemist Rugue acetylated chitin to obtain a new material, which in 1894 was named chitosan. Gitosan's properties activate depleted cells, inhibiting aging, strengthening immunity and preventing disease. It also regulates biorhythms with the ability to activate the body's natural healing abilities. But the mechanism is not yet fully understood.

Efficacy of the disease is, firstly, the role of absorbing and excreting excess harmful cholesterol in the body, that is, acts as a decholesterol. Second, it has an anticancer effect of inhibiting the proliferation of cancer cells. Third, by inhibiting the absorption of chloride ions causing the increase in blood pressure in the intestine, and then discharged to the outside of the body to suppress blood pressure increase and to promote effective bacteria in the intestine and activate the cells. In addition, there are effects such as blood sugar control, liver function improvement, and the release of heavy metals and pollutants in the body.

On the other hand, as the competition between the mountains and farms intensifies, the 'Spring of the Spring National Period', in which only the finest rice that can satisfy consumers' preferences in the market distribution process in which the harsh economic principle works, is in full swing.

Rice was a prominent source of food and a symbol of wealth until the 1970s, when rice became a staple food on the Korean peninsula around 1,000 BC.However, as long as 30 years later, rice is no longer important. Interest is flowing qualitatively. In other words, which rice is delicious and which rice is good for you is the most important criteria for choosing rice. Brand rice, which appeared with the rice quality certification in 1992, is the first commercial use of this change.

As the old saying `` rice is a medicine '', functional high-quality rice, which is perfect for this horse, has been introduced to the market in recent years, attracting consumers' attention. Even if the demand for high-quality rice doubled nutrition and taste is increasing trend.

Healthy rice has recently been making its place in functional rice, which is a rice that has a special effect by applying special substances to special rice or by adding special substances. Can be.

The functional rice that is currently on the market, including natural ingredients such as gungjungjang, ginseng rice, mushroom rice, and green tea rice, is also showing rice with added nutrients such as chitosan, minerals, and calcium. Rice (washed rice) comes up, too. In addition, other bio-rice (bioactive rice), red mushroom rice, germanium rice, live rice (embryo) are on the market. These high-quality rice have the effect of preventing various diseases, and the taste is expected to be very popular in the future.

However, rice, which has been enhanced in functionality by alginic acid and chitosan, widely recognized by general consumers as a health food material, has not been put to practical use at present.

Therefore, the technical problem to be achieved by the present invention is to provide a manufacturing method that can be practical to use the rice coated on the surface of alginic acid and chitosan.

In order to achieve the above technical problem, the present invention

(a) generating ozone water by adding water to a predetermined container and aeration of ozone for 30 minutes to 1 hour to generate ozone water;

(b) a rice washing step of washing the surface of the rice by putting rice in a container while maintaining the temperature of the ozone water at about 10 ° C. or less and irradiating ultrasonic waves of 10 MHz to 40 MHz for about 30 seconds to 15 minutes;

(c) a rice re-washing step of removing ozone water from the vessel and washing the rice with water again;

(d) drying the rice to a water content of about 14 to 16 weight percent;

(e) an alginic acid coating step of coating alginic acid on the surface of the rice using a solution in which 200 mg to 20 g of alginic acid is dissolved in 100 to 200 ml of water based on 1 kg of rice;

(f) a chitosan coating step of coating chitosan on the surface of the rice by using a solution in which 20 mg to 200 mg of chitosan is dissolved in 100 to 200 ml of water based on 1 kg of rice; And

(g) it provides a method for producing alginic acid and chitosan coated rice comprising the re-drying step of drying the rice to a water content of about 14 to 16% by weight.

In the alginic acid and chitosan coated rice production method according to the invention, the alginic acid,

(A) warming the mixture of purified water and crushed brown algae to 90 to 100 ℃ and alkalinized by adding Na ₂ CO ₃ and maintained in a warmed state for 30 minutes to 10 hours;

(B) filtering the resultant of step (a) to 50 to 70 ° C. and then filtering to remove the brown algae; And

(C) Any of the filtrate removed and removed by the step (b) is heated again to 100 to 150 ℃ and selected from the group consisting of magnesium salt, calcium salt, iron salt, magnesium-EDTA, calcium-EDTA and iron-EDTA Mg ²⁺ , Ca ²⁺ or Fe ²⁺ prepared through the step of supersaturating magnesium, calcium or iron by adding one to maintain a warm state for 30 minutes to 10 hours is preferably alginic acid to which a high concentration is bound. Do.

In the alginic acid and chitosan coated rice production method according to the present invention, the chitosan preferably has a weight average molecular weight of about 600,000 and is water-soluble chitosan, such chitosan comprising: (1) washing chitosan with hydrogen peroxide solution; (2) adding the chitosan to a mixed aqueous solution of sodium chloride and ascorbic acid and applying ultrasonic waves of about 20 to 40 Hz for about 10 to 60 minutes; (3) removing the supernatant by centrifuging the resultant of step (2); And (4) it can be prepared through the step of washing and drying the product of step (3) with 95% or more of ethanol.

Hereinafter, the alginic acid and chitosan coated rice manufacturing method according to the present invention will be described in detail.

In order to prepare rice coated with alginic acid and chitosan, it is very important to prevent excessive absorption of identity into the rice during the washing process. This is because if the amount of water in the rice is too much, the rice becomes too soft, causing cracks in the rice during the coating process, and also causing cracks in the rice as the water comes out inside the rice during the drying process.

In order to solve this problem, the present invention used a method of washing the rice quickly using ultrasonic waves, and the inventors also found the optimal ultrasonic strength that does not cause cracks in the rice through various experiments alginic acid and chitosan It is to enable the practical use of this coated rice.

The first step of the alginic acid and chitosan coated rice production method according to the present invention is to generate ozonated water to remove bacteria and the like in the water for washing the rice.

The ozone water generation step is performed by placing water in a predetermined container and aeration of ozone for 30 minutes to 1 hour. Ozone aerated in water serves to ensure the safety of coated rice produced by sterilizing pathogenic bacteria, etc., which may be contained in water. It sterilizes bacteria that may be on the surface.

The amount of ozone released into the container does not matter much, and it is important to maintain the aeration time of ozone for 30 minutes to 1 hour in order to ensure sufficient sterilization and residual ozone.

The subsequent step is a rice washing step using ultrasonic waves, which will be described in detail below.

While keeping the temperature of the ozone water below 10 ℃, put the rice in a container containing ozone water to irradiate the ultrasonic wave of 10MHz to 40MHz for about 30 seconds to 15 minutes to wash the surface of the rice.

In the present invention, the ultrasonic wave is used for washing the rice, because when the washing time becomes longer, the water content increases in the rice, causing the rice to become soft, which causes cracks in the rice at a later stage of drying and coating. It is for quick cleaning that can be prevented.

In addition, the important thing in the rice washing step using the ultrasonic wave is the strength of the ultrasonic wave, if the ultrasonic strength is too weak, the cleaning time is long, if too strong, there is a problem that a crack occurs in the rice by the ultrasonic wave. To solve this problem, the inventors determined the most appropriate intensity of ultrasonic waves through various experiments, and the intensity is 10 MHz to 40 MHz. That is, if it is 10 MHz or less, it is not possible to quickly wash it in a short time, and if it exceeds 40 MHz, the amount of cracked rice becomes too large.

The reason why the temperature of the ozone water is maintained at 10 ° C. is because the rice becomes soft even when the washing time is short when the temperature is high.

In order to measure the relationship between the intensity of the ultrasonic wave and the crack generated in the rice, 5 kg of rice was put in 20 L of water at about 15 ° C., and after washing by varying the intensity of the ultrasonic wave for 60 seconds, It is shown in Table 1 below, it can be seen from the following Table 1 that the appropriate intensity of the ultrasound is 10MHz to 40MHz.

Ultrasonic intensity (MHz) Number of Cracks in Rice 0 One 10 23 20 32 30 60 40 207 50 409 60 442 70 444

Subsequently, after removing the ozone water from the vessel and passing the rice re-washing step to lightly steam the rice with water again, only the rice is separated from the vessel and dried.

The rice drying step is important to make the water content of the rice 14 to 16% by weight, it is to control the water content of the rice in advance so that cracks do not occur in the drying step of the finished coated rice, and also the alginic acid and This is because the degree of drying of rice, which gives the optimum flavor of chitosan coated rice, is about 14 to 16% by weight.

To dry the moisture content of the rice to about 14 to 16% by weight, put the rice in an infrared dryer, a hot air dryer, and keep the intensity or temperature of the infrared ray constant, and then sample it at regular intervals to measure the moisture content in the rice. It can be standardized by finding a time period of 14 to 16% by weight, and conversely, the amount and temperature of infrared rays of 14 to 16% by weight can be found and normalized within a predetermined time.

The following step is an alginic acid coating step, and this alginic acid coating step sprays a predetermined amount of a solution of 200 mg to 20 g of alginic acid in 100 to 200 ml of water based on 1 kg of rice at regular intervals, and at the same time, water using hot air. It can be made through the method of evaporating. The spraying alginic acid solution is most appropriately sprayed at an amount of about 5-20 ml per kg of rice at intervals of about 20 seconds.

Subsequently, the chitosan coating step is performed. The chitosan performing step is performed in the same manner as the alginic acid coating step, except that a solution in which 20 mg to 200 mg of chitosan is dissolved in 100 to 200 ml of water based on 1 kg of rice is used. do.

The reason for coating chitosan on alginic acid in the present invention is that alginic acid may be a food source of microorganisms, which may be a problem in the preservation of rice and rice made with this rice, but may be prevented when coating chitosan.

Finally, re-drying the alginic acid and chitosan-coated rice to a moisture content of about 14 to 16 wt% completes the preparation of the alginic acid and chitosan coated rice according to the present invention.

The alginic acid used in the present invention is not particularly limited. (A) After warming the mixture of purified water and crushed brown algae to 90 to 100 ° C., alkalizing by adding Na ₂ CO ₃ and warming for 30 minutes to 10 hours. Maintaining; (B) filtering the resultant of step (a) to 50 to 70 ° C. and then filtering to remove the brown algae; And (c) warming the filtrate remaining by the step (b) again to 100 to 150 ° C. and selecting from the group consisting of magnesium salt, calcium salt, iron salt, magnesium-EDTA, calcium-EDTA and iron-EDTA. Mg ²⁺ , Ca ²⁺ or Fe ²⁺ produced by the step of supersaturating magnesium, calcium or iron by adding any one and maintaining a warm state for 30 minutes to 10 hours is a high concentration of alginic acid desirable.

The method of preparing alginic acid in which Mg ²⁺ , Ca ²⁺ or Fe ²⁺ is bonded at a high concentration will be described in detail.

Extract alginic acid from brown algae, and in order to make the extracted alginic acid water-soluble sodium alginate, mix purified water and ground brown algae in a predetermined container, and then heat to a container containing this mixture and heat the mixture to 90 to 100 ° C. After warming, Na ₂ CO ₃ is added to alkalinize the liquid and remain warm for 30 minutes to 10 hours.

When mixing purified water with crushed brown algae, the mixing ratio thereof is not particularly limited, but in order to extract alginic acid, it is preferable to use purified water about 10 times the weight of brown algae. The larger the contact area with and the higher the extraction efficiency, the powder state of 20 mesh or less is good, but may have a particle size of about 20 to 80 mesh.

In addition, the addition of Na ₂ CO ₃ to alkalinize the liquid to extract alginic acid, and then to combine the extracted alginic acid with sodium ions to produce soluble sodium alginate, Na ₂ CO ₃ is a special limitation to the amount added It is preferable that the content of Na ₂ CO ₃ is 0.1 to 2% by weight based on the total mixture.

The reason for heating the mixture of crushed brown algae and purified water to 90 to 100 ° C. is to maximize the extraction efficiency of alginic acid, and to maintain 90 to 100 ° C. for about 30 minutes to 10 hours is sufficient to extract alginic acid. To do so.

In addition, in order to perform the preparation method according to the present invention can be used without any limitation if the kelp, seaweed, gompi, hatban and brown algae, but the maximum physiological activity of the extracted alginic acid is considered to be alginic acid extracted from kelp As widely known in the field of the present invention, it is preferable that the present invention is also kelp, particularly kelp collected from the east coast of Korea.

Next, a step of supersaturating magnesium, calcium or iron by adding any one selected from the group consisting of magnesium salt, calcium salt, iron salt, magnesium-EDTA, calcium-EDTA and iron-EDTA will be described.

First, before adding any one selected from the group consisting of magnesium salts, calcium salts, iron salts, magnesium-EDTA, calcium-EDTA, and iron-EDTA, in the present invention, the result of the sodium alginate production process is 50 to 50. After the temperature was reduced to 70 ° C., the crushed brown algae were removed by filtration.

Subsequently, the remaining filtrate removed in the filtration step is warmed back to 100 to 150 ° C. and magnesium is added by adding any one selected from the group consisting of magnesium salt, calcium salt, iron salt, magnesium-EDTA, calcium-EDTA and iron-EDTA. , Supersaturate calcium or iron.

Here, the temperature of the filtrate is warmed back to 100 to 150 ° C for supersaturating magnesium, calcium or iron, and the supersaturation state is not achieved when the temperature is less than 100 ° C as determined by many experiments by the present inventors. If the temperature exceeds 150 ° C., the magnesium salt, calcium salt, iron salt, magnesium-EDTA, calcium-EDTA and iron-EDTA do not dissolve and do not need to be heated to a temperature exceeding 150 ° C.

In addition, the magnesium salt and calcium salt can be used without particular limitation, in the present invention, the magnesium salt is preferably MgCO ₃ or MgCl ₂ , the calcium salt is CaCO ₃ or CaCl ₂ , in the case of iron iron salt It is preferable to use iron-EDTA rather than iron because iron is a bivalent cation in the form of a bivalent cation, which is an excellent material for absorption in the human body.

Finally, sodium alginate exchanges sodium ions with magnesium ions, calcium ions, or iron ions to bind Mg ²⁺ , Ca ^2+, or Fe ²⁺ in high concentrations, resulting in high ^mobilities of Mg ²⁺ , Ca ²⁺ or Fe ^2+. The process of preparing the combined alginic acid powder will be described.

The process is carried out through the step of maintaining the warmed state for 30 minutes to 10 hours at a temperature warmed in the supersaturation step and then drying the resultant and then grinding.

Here, the reason for maintaining for 30 minutes to 10 hours at 100 to 150 ℃ is to make the extracted alginic acid in the form of low molecular weight alginic acid oligosaccharide, to secure a time that can be sufficiently exchanged with sodium ions.

Alginic acid production method as described above may be referred to because it is filed in Patent Application No. 10-2001-0069372.

In addition, the chitosan to be used in the present invention is not particularly limited, but the weight average molecular weight is about 600,000 and preferably water-soluble chitosan, such chitosan is (1) washing the chitosan with hydrogen peroxide; (2) adding the chitosan to a mixed aqueous solution of sodium chloride and ascorbic acid and applying ultrasonic waves of about 20 to 40 Hz for about 10 to 60 minutes; (3) removing the supernatant by centrifuging the resultant of step (2); And (4) looking at the specifics that can be prepared through the step of washing and drying the resultant of step (3) with 95% or more of ethanol as follows.

First, the existing chitosan is added to a mixed aqueous solution of sodium chloride and ascorbic acid and then ultrasonicated to fractionate into high molecular weight and have water solubility.

Chitosan is a polymer having a chain structure. When ultrasonic molecules are vibrated by applying ultrasonic waves at the lowest energy state, the polymers are pulsated and can be receptive to a small amount of energy and fractionated into polymers. The ascorbic acid is a mechanism that helps the hydroxylation of chitosan, and sodium chloride is a substance that helps the relative energy wave of chitosan because of the high dispersant and external energy levels in the wave of energy.

In the sonication step, it is preferable to apply an ultrasonic wave of about 20 to 40 Hz for about 10 to 60 minutes.

In the mixed sodium chloride and ascorbic acid solution, the sodium chloride concentration is 0.05 to 0.15 molar concentration, and the ascorbic acid concentration is 0.05 to 0.015 molar concentration. It is advisable to add about 100 g of chitosan.

Subsequently, the supernatant is removed by centrifugation, and the supernatant is removed. The supernatant is submerged to wash 95% or more of ethanol and dried to obtain chitosan having a weight average molecular weight of about 600,000 and water soluble.

The reason for going through the centrifugation step and the ethanol washing step is to remove impurities, moisture, etc. on the surface of the chitosan in the sonication step.

It is possible to produce high molecular weight water-soluble chitosan through the process as described above, but in order to make the color of the chitosan produced white and to increase safety through sterilization, washing with excess hydrogen peroxide solution before the sonication step. It is preferable to go through.

In addition, the deacetylation degree of the high molecular weight water-soluble chitosan is 90% or more, so that the astringent taste can be removed, the resultant centrifuged in the above-described manufacturing method dissolved in water, filtered and lyophilized It is preferable.

The pore size of the filter at the time of filtration is preferably 25 to 50㎛, through the filtration step, ions, dust and the like contained in the aqueous solution may be removed to remove the astringent taste.

In addition, the freeze-drying step is carried out by rapid freezing at about -70 ℃ using a common lyophilizer, the water is almost completely removed through this freeze-drying step to increase the deacetylation degree to more than 90%.

For reference, the chitosan production method is a patent application in the Republic of Korea by the inventor No. 10-2001-19303.

Subsequently, a method for preparing rice coated with alginic acid and chitosan according to the present invention will be described in detail with reference to Examples.

(Alginic acid production example 1)

Mg ²⁺ Preparation of Alginic Acid with High Concentration

In this example, the native kelp native to the east coast was dried to less than 10% moisture and then pulverized to about 20mesh, and then purified water and ground kelp were mixed at a ratio of 1:10.

Subsequently, the mixture was heated up to 90 ° C. and Na ₂ CO ₃ was added in an amount of 0.2% based on the total weight of the mixture, followed by alkalizing, and then maintained for about 2 hours.

Next, after the temperature was reduced to 60 ° C. and filtered through 90mesh to remove kelp, MgCO ₃ was mixed to 8% with respect to the total weight and then heated to about 110 ° C., and maintained for about 2 hours.

After about 2 hours, the water-soluble chitosan having a weight average molecular weight of about 600,000 was mixed with 0.01% of the total weight, concentrated to 1/5 of the total weight, lyophilized and pulverized to obtain Mg ²⁺ according to the present invention. Preparation of alginic acid bound at high concentrations.

(Alginic acid production example 2)

Ca ²⁺ Alginate Manufactured at High Concentration

In this example, the native kelp native to the east coast was dried to less than 10% moisture and then pulverized to about 20mesh, and then purified water and ground kelp were mixed at a ratio of 1:10.

Subsequently, the mixture was heated up to 90 ° C. and Na ₂ CO ₃ was added in an amount of 0.2% based on the total weight of the mixture, followed by alkalizing, and then maintained for about 2 hours.

Next, after the temperature was reduced to 60 ° C. and filtered through 90mesh to remove kelp, CaCO ₃ was mixed to 8% with respect to the total weight and then heated to about 110 ° C. and maintained for about 2 hours.

After 2 hours, the water-soluble chitosan having a weight average molecular weight of about 600,000 was mixed with 0.01% of the total weight, concentrated to 1/5 of the total weight, lyophilized, and then pulverized to give Ca ²⁺ according to the present invention. Preparation of alginic acid bound at high concentrations.

(Alginic acid production example 3)

Fe ²⁺ Alginate Manufactured at High Concentration

In this example, the native kelp native to the east coast was dried to less than 10% moisture, and then pulverized to about 20mesh, and then, purified water and ground kelp were mixed at a ratio of 1:10.

Subsequently, the mixture was heated up to 90 ° C. and Na ₂ CO ₃ was added in an amount of 0.2% based on the total weight of the mixture, followed by alkalizing, and then maintained for about 2 hours.

Next, after the temperature was reduced to 60 ° C. and filtered through 90mesh to remove kelp, Fe-EDTA was mixed to 8% with respect to the total weight, and then heated to about 110 ° C., and maintained for about 2 hours.

After about 2 hours, the water-soluble chitosan having a weight average molecular weight of about 600,000 was mixed with 0.01% of the total weight, concentrated to 1/5 of the total weight, lyophilized, and then pulverized to obtain Fe ²⁺ according to the present invention. Preparation of alginic acid bound at high concentrations.

(Chitosan production example 1)

In this preparation example, chitosan was dissolved in acetic acid so that the concentration of chitosan was 1% by weight, and the chitosan having a viscosity of about 1200 cps was used as a starting material by measuring with a type B viscometer at 25 ° C.

2 liters of a mixed aqueous solution in which sodium chloride and ascorbic acid were dissolved in water so that their concentration was 0.1 mole each were placed in an ultrasonic extractor (Model Sox Wave 100, manufactured by Pro Lado, USA), followed by 200 g of the chitosan. It was added to the mixed aqueous solution and reacted by adding 20 Hz ultrasonic wave at 30 캜 for 20 minutes.

Subsequently, the reaction product was centrifuged at 7,000 rpm for 15 minutes through a centrifuge (Model VS-21SMTN manufactured by Vision Science), and then the supernatant was removed and then washed with excess 95% ethanol for 30 minutes.

Finally, the resultant washed naturally dried to prepare a high molecular weight water-soluble chitosan 180g (90% yield).

(Manufacture example 2 of chitosan)

In this preparation example, chitosan was dissolved in acetic acid so that the concentration of chitosan was 1% by weight, and the result was measured by a type B viscometer at 25 ° C., and the viscosity was about 1200 cps. Chitosan having a deacetylation degree of 80% or more was used as a starting material.

2 liters of a mixed aqueous solution in which sodium chloride and ascorbic acid were dissolved in water so that their concentration was 0.1 mole each were placed in an ultrasonic extractor (Model Sox Wave 100, manufactured by Pro Lado, USA), followed by 200 g of the chitosan. It was added to the mixed aqueous solution and reacted by adding 20 Hz ultrasonic wave at 30 캜 for 20 minutes.

Subsequently, the reaction product was centrifuged at 12,000 rpm for 30 minutes through a centrifuge (Model VS-21SMTN manufactured by Vision Science), and then the supernatant was removed.

Subsequently, the resultant obtained by centrifugation was dissolved in water to form an aqueous solution of about 2% by weight, and then filtered by a filter having a pore size of 30 μm using a vacuum pump.

Subsequently, the filtration residue was placed in a lyophilizer, frozen at −70 ° C., dried, and ground to prepare 120 g (yield 60%) of high molecular weight aqueous chitosan.

(Example of Alginic Acid and Chitosan Coated Rice)

20 liters of water is placed in a container, and ozone generated through an ozone sterilizer (product name: OKC1100, company name: Ozones Korea) is aerated in the water for 45 minutes to generate ozone water. After installing the internal ultrasonic generator (product name: Power sonic 520, company name: Hwashintec) of 5 kg of rice and washing the rice for about 1 minute while generating an ultrasonic wave up to about 20MHz.

Subsequently, discard the water in the container and pour rice again with about 20 liters of distilled water, then discard the water and put only the rice into an infrared dryer (product name: 9SDG2-120FG, company name: Daekyung Machinery) to dry the water content to 15% by weight. The rice was dried.

Subsequently, the dried rice was placed in a spray molding machine (product name: spray molding machine, company name: Youngjin machine) and the alginic acid was sprayed with 30 ml of the solution of 50 g of alginic acid prepared in Preparation Example 1 of Alginic acid in 600 ml of water at intervals of about 20 seconds. Was coated on the rice surface.

Next, chitosan was coated on the rice surface by spraying 10 ml of the solution in which the coating solution was dissolved in 600 ml of 500 mg of chitosan prepared in 1 for chitosan preparation, at about 20 second intervals.

Finally, an infrared dryer was used to dry the rice to 15% by weight of water, thereby preparing rice coated with alginic acid and chitosan.

(Preservation test)

General rice (indicated by F1), alginic acid-coated rice (indicated by F2) and alginic acid and chitosan-coated rice (indicated by F3) in the above preparation, cooked in an electric rice cooker, and then It is shown in Table 2 to measure the degree of occurrence of mold at time.

12 hours 24 hours 48 hours 72 hours 96 hours 120 hours F1 O O O X XX XXX F2 O O X XX XXX XXX F3 O O O O X X O: Mold does not bloom, does not smell hoarseness X: Husky smells XX: Mild fungus XXX: Very much fungus

In Table 2, the preservation of the alginate-coated rice was worse than that of the general rice, and the alginic acid and the chitosan-coated rice were found to have the best preservation.

According to the production method of the present invention as described above, it is possible to use the rice coated with alginic acid and chitosan having useful physiological activity can promote the consumption of rice, it is possible to promote the national health.

Claims (4)

(a) generating ozone water by adding water to a predetermined container and aeration of ozone for 30 minutes to 1 hour to generate ozone water; (b) a rice washing step of washing the surface of the rice by putting rice in a container while maintaining the temperature of the ozone water at about 10 ° C. or less and irradiating ultrasonic waves of 10 MHz to 40 MHz for about 30 seconds to 15 minutes; (c) a rice re-washing step of removing ozone water from the vessel and washing the rice with water again; (d) drying the rice to a water content of about 14 to 16 weight percent; (e) an alginic acid coating step of coating alginic acid on the surface of the rice using a solution in which 200 mg to 20 g of alginic acid is dissolved in 100 to 200 ml of water based on 1 kg of rice; (f) a chitosan coating step of coating chitosan on the surface of the rice by using a solution in which 20 mg to 200 mg of chitosan is dissolved in 100 to 200 ml of water based on 1 kg of rice; And (g) a method for producing alginic acid and chitosan coated rice, characterized in that it comprises a redrying step of drying the rice to a water content of about 14 to 16% by weight. The method of claim 1, The alginic acid (A) warming the mixture of purified water and crushed brown algae to 90 to 100 ℃ and alkalinized by adding Na ₂ CO ₃ and maintained in a warmed state for 30 minutes to 10 hours; (B) filtering the resultant of step (a) to 50 to 70 ° C. and then filtering to remove the brown algae; And (C) Any of the filtrate removed and removed by the step (b) is heated again to 100 to 150 ℃ and selected from the group consisting of magnesium salt, calcium salt, iron salt, magnesium-EDTA, calcium-EDTA and iron-EDTA Mg ²⁺ , Ca ²⁺ or Fe ²⁺ prepared through the step of supersaturating magnesium, calcium or iron by adding one to maintain a warm state for 30 minutes to 10 hours is a high concentration of alginic acid bound Alginic acid and chitosan coated rice production method. The method of claim 1, Alchinic acid and chitosan coated rice manufacturing method characterized in that the chitosan is a weight average molecular weight of about 600,000 and is water-soluble chitosan. The method of claim 3, The chitosan is (1) washing chitosan with hydrogen peroxide water; (2) adding the chitosan to a mixed aqueous solution of sodium chloride and ascorbic acid and applying ultrasonic waves of about 20 to 40 Hz for about 10 to 60 minutes; (3) removing the supernatant by centrifuging the resultant of step (2); And (4) Alginic acid and chitosan coated rice manufacturing method, characterized in that the chitosan produced through the step of washing and drying the resultant of step (3) with 95% or more of ethanol.