JPS59137410A - Preparation of stable powdery vitamin a - Google Patents

Abstract

PURPOSE:To provide the titled easily handleable powder having high stability and water dispersibility, by heating a solution containing a sugar composition of maltose and an oligosaccharide at a specific concentration to effect the complete dissolution, cooling the solution, adding and emulsifying lecithin and vitamin A in the solution, and pulverizing the emulsion. CONSTITUTION:A sugar composition of (A) 5-50wt% of maltose or a saccharide composed mainly of maltose and (B) 50-95wt% of an oligosaccharide (e.g. sucrose, lactose, etc.) and/or hydrolyzed starch (e.g. dextrin, starch syrup, etc.) is added with water to adjust the solid sugar concentration of 30-85wt%. The mixture is heated at 90-150 deg.C to effect the complete dissolution of the saccharides, and the resultant sugar solution is cooled to 20-80 deg.C. Lecithin and vitamin A are added to the product, emulsified, and rapidly and efficiently dried to a water-content of <=5%. The obtained dried product containing vitamin A is pulverized to obtain the objective powder. The amount of lecithin is selected to give total phospholipid content of <=20%, especially 1-10% in the powdery vitamin A.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a "JA manufacturing method" for producing powdered vitamins that are stable and have excellent water dispersibility.

More specifically, a sugar composition consisting of 5 to 50% by weight of a saccharide whose main component is malus or malus and 50 to 95% by weight of an oligosaccharide or /' and a starch hydrolyzate. Add water to adjust the sugar solid concentration to 30-85% by weight, heat to 90-150°C, then add lecithin and vitamin A to the sugar aqueous solution cooled to 20-80°C, emulsify and mix. , relates to producing powdered vitamin A that is stable and has excellent water dispersibility by powdering.

Vitamin A has the function of maintaining normal vision, bones, and mucous membranes in humans and animals, and its deficiency can cause night blindness, corneal xerosis,
It causes growth inhibition and is an essential substance for health.

Vitamin A usually comes as a fatty acid ester, such as acetic acid or palmitic acid, and is an oily or crystalline substance that is insoluble in water.

However, vitamin A is extremely unstable to oxidation, and if dissolved in vegetable oil or animal oil, and left in an open state, most of the vitamin A will be decomposed within a day of soaking the seedlings.

Antioxidants are commonly used to stabilize vitamin A, including tocopherols, rosemary extract, gallic acid,
Since natural antioxidants such as γ-oryzanol have little effect, dibutylhydroxytoluene (BHT), butylhydroxyanisole (to B I-1), nordihydroguar acid (BHT), which have strong antioxidant ability, N
DGA), propyl gallate (PG) or NN'-
Synthetic antioxidants such as diphenylvarophenyl diamine (DPPD) have been used.

A powder containing vitamin A that is stable and has excellent water dispersibility.
Several attempts have been made to improve storage stability and ease of handling.

First, there is a method in which vitamin A is stabilized by coating it with gelatin, h-zein, dextrin, etc. in the form of granules or powder and cutting off contact with air.

However, because these granular or powdered vitamin A do not have sufficient coating effect with the base material, the stability of vitamin △ is poor, and in fact, the synthetic antioxidant mentioned above is added to improve stability. is the current situation.

Especially for food applications (under extremely complex conditions).
Since the use of synthetic antioxidants is undesirable as they must exhibit high stability and have strict safety requirements, there are no granular or powdered vitamins in practical use. be.

The present inventors have developed a water-dispersible powdered form of vitamin A that is easy to handle and has good stability, using a base material that has no safety issues.
The present invention was completed as a result of intensive studies aimed at manufacturing and providing the product to the food, medicine, or feed fields.

The first step of the present invention is to add water to a sugar composition consisting of 5-50% by weight of maltose or mal (hose) as a main component and 50-95% by weight of oligosaccharides or/and starch hydrolyzate. In addition, it is a step of adjusting the sugar solid content to 30-85% by weight and heating it to 90-150°C.Heating is a necessary step for complete dissolution of sugar molecules, and heating is insufficient. In this case, the aggregate of sugar molecules is only swollen by water, but is not sufficiently dissolved, and the sugar crystallizes due to hydrogen bonds between sugar molecules, resulting in insufficient sequestration of vitamin A.

Heating time is not particularly limited, but is usually 5 minutes or more.
40 minutes is sufficient. If the heating temperature is 90°C or lower, it is difficult to completely dissolve the saccharide composition, and if the heating temperature is 150°C or higher, the saccharide is likely to be decomposed, which is not preferable.

In the present invention, a sugar composition consisting of 5 to 50 ffl ff1% of maltose or maltose-based saccharide and 50 to 95% by weight of oligosaccharide or /' and starch hydrolyzate is used. This is because it prevents sugar crystallization in aqueous solutions containing these. In a sugar composition, several sugar molecules are dispersed as aggregates due to hydrogen bonds in an aqueous solution, so when heated to a sufficient temperature, each sugar molecule comes into contact with other types of sugar molecules, and It is thought that it completely dissolves without crystallizing easily.

The object of the first step of the present invention has been achieved by finding a sugar composition in which such crystallization is difficult to occur.

If the sugar composition of the present invention contains maltose or saccharides whose main components are 50% by weight or more, the composition becomes extremely deliquescent during the powdering process, making it difficult to powderize it. Moreover, if it is less than 5% by weight, it will be difficult to completely suppress crystallization of the sugar composition in a solution.

If the sugar solid content concentration in the sugar aqueous solution of the sugar composition of the present invention is 85% by weight or more, complete dissolution of the sugar becomes difficult;
This is not preferable because the viscosity of the sugar solution becomes extremely high and emulsification and mixing with vitamin A cannot be carried out sufficiently. Furthermore, if the sugar solid content concentration is 30% by weight or less, the amount of water evaporated during the drying process is large, which is uneconomical.

Oligosaccharides as used in the present invention are trisaccharides to hexasaccharides such as sucrose, lactose, cellbiose, 1-levalose, gentiobiose, melibiose, isomaltose, raffinose,
Stachyose, menzitose, panose, etc.
One or more of these can be used.

The starch hydrolyzate includes dextrin, starch syrup, powdered starch syrup, liquid sugar, etc., and one or more of these can be used.

In the second step of the present invention, the saccharide solution obtained in the first step is
This is a step of cooling to ~80°C, then adding lecithin and vitamin A, and emulsifying and mixing.

The present inventors added pitamine A to the amorphous sugar solution obtained in the first step.
We mixed and emulsified the mixture with emulsifiers such as glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, polyglycerin fatty acid ester, and lecithin, and then dried it to produce a prototype vitamin A powder. The results showed that it is stable under humid conditions, but is unstable under humidified conditions except when lecithin is used. That is, the reason why specific stability is obtained when lecithin is used is that lecithin effectively suppresses the movement of oxygen related to the oxidation of vitamin A in the amorphous sugar solution. This is because the phospholipid in lecithin is composed of three parts: a hydrophobic part, a polar part, and a hydrogen bond band sandwiched between these two parts, which is a feature not found in other emulsifiers, which protects lecithin. Film-forming ability is vitamin A
The present invention has been completed based on the discovery that this is extremely effective in improving the stability of

In the present invention, the sugar solution is cooled to 20 to 80°C to prevent decomposition into vitamins, and lecithin is used in combination to promote emulsification and dispersion of vitamin A and improve the water dispersibility of the resulting powdered vitamin A. In addition, this is because it is effective in stabilizing vitamin A based on the protective film-forming ability of lecithin as described above.

The vitamin A referred to in the present invention includes vitamin A1 vitamin 8 oil, vitamin A fatty acid Nisder, vitamin AiI, and the like.

In addition, lecithin in the present invention refers to soybean phospholipids, egg yolk lecithin, etc., and it is preferable to add the total phospholipids in the obtained powdered vitamin A in an amount of 20% by weight or less, preferably in the range of 1 to 10% by weight. . When the proportion exceeds 20% by weight, the obtained powdered vitamin A becomes highly hygroscopic, which causes unfavorable phenomena in powder products such as blocking.

The emulsification mixing of the present invention can be carried out using a high-speed stirrer type emulsifier, a piston homogenizer, an ultrasonic emulsifier, or the like.

In addition to the amorphous sugar solution of the present invention, vitamin A and lecithin, if necessary, animal and vegetable oils, propylene glycol,
A diluent such as ethanol and an emulsifier such as glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid nystère, polyglycerin fatty acid nisdelle can be used in combination.

The third step of the present invention is a powdering step. In the emulsified mixture containing the amorphous sugar solution, vitamins, and lecithin obtained in the second step, if the water content is high, vitamin A is easily oxidized, so it is quickly and efficiently dried to reduce the water content. It needs to be lowered to below 5%.

As for the drying method, any method is suitable as long as the oxidation of vitamin A during drying can be minimized, but drying can be done by freeze drying, vacuum drying, spray drying, etc. Further, if necessary, ventilation drying, fluidized bed drying, etc. may be combined with the above-mentioned method in order to further reduce the water content. Then, if necessary, the obtained vitamin A-containing dry product is pulverized using a roll pulverizer, an impact pulverizer, a centrifugal pulverizer, a ball mill, or the like.

In this way, powdered vitamin 8 which is stable and has excellent water dispersibility can be obtained.

Although the present invention aims at stabilizing vitamin A, it is thought that it can also be applied to stabilizing fat-soluble vitamins such as vitamin D, vitamin F, vitamin 1-ubiquinone, and prostaglasin, which are susceptible to oxidation.

The present invention will be explained below with reference to Examples and Test Examples, but the present invention is not limited to these Examples.

In addition, all percentages expressed in the examples are percentages by weight.

Example 1 Maltose starch syrup (solid content 75%, maltose 7 in solid content)
5%> 104L! ：Text t” 'J n(D E
7) Add 300g of 307+1 water to make the sugar solids concentration 54.1%, then heat to O-1 in a crepe at 130°C.
The mucilage obtained by heating for 10 minutes was cooled to 60°C and added with vitamin A acetate <2.8 million IU/(1)
Toog, 10 g of soybean lecithin, and sucrose fatty acid ester (+-ILB7) 5111 were mixed and dissolved in advance at 60° C., and the mixture was emulsified and mixed using a high-speed rotating stirring emulsifier. The resulting emulsion was then spray-dried at a working temperature of 160°C to obtain a stable and water-resistant powdered vitamin VIII of 54,60,000 IU/' (I).

Example 2 20g of full 1~-su and reduced powdered starch syrup (D F 17)
Add 170g of water to 380 (1) to bring the sugar solid concentration to 70.
After reducing the concentration to 2%, the resulting sugar solution was heated at 10/I°C for 30 minutes, cooled to 70°C (71 tl), water was added to adjust the sugar solid content concentration to 70%, and vitamin A acetate was added to this. (
2.8 million IU, ``!I) GIDI, person 0 lecithin 12
Mix and dissolve g in advance at 60°C, and emulsify and mix in a high-speed rotation stirring emulsifier. Next, the obtained emulsion was vacuum-dried at 70°C, and after drying, it was pulverized to give 370,000 IU/
(Powdered vitamin Δ which is stable as I and has excellent water dispersibility was obtained. 5g of the obtained powdered vitamin A was obtained, and
The water dispersion state did not change even after stirring for 1 minute and leaving it for 1 hour, and the water dispersibility was good.

Example 3 Maltose 50 liters and starch syrup (solid content 75%, DE30) 1
00 g, dextrin (D E 3 ) 350 (+) was added with 300 g of water to make the sugar solid content 59.4%, and then heated in a 1-t-clave at 140°C for 30 minutes. The liquid was cooled to 50°C and added with vitamin A acetate (2.8 million IU/g > 40g, soybean lecithin 30g, sorbitan fatty acid ester (HL B4.7).
) 5 g and 40 g of soybean oil were mixed and dissolved in advance at 60°C, and W was added thereto, and emulsified and mixed using a high-speed rotating stirring emulsifier. Next, the obtained emulsion was freeze-dried, and after drying, the emulsion was pulverized.18.
Powdered vitamin A was obtained which was stable at 50,000 IU/g and had excellent water dispersibility.

The obtained powdered vitamin Δ was subjected to the same water dispersibility test as in Example 2, and as a result, the water dispersibility was good.

Example 4 Maltose starch syrup (solid content 75%, malt-7 in solid content,
75%) 54g, = text') > (D E
12) Add 360g of water to 360g of water to make the panicle solids concentration 51.7%, then heat to O 1 in a crepe at 125°C.
, the sugar solution obtained by heating for 10 minutes was cooled to 70°C, and added with vitamin Valmite-1 (7.7 million I (J/q)
) 40! I+, H'jJll) 12g of unlecithin,
60 2q of sucrose fatty acid ester (HlB3.7) in advance
Add the mixture mixed and dissolved in 'C' and emulsify and mix with a bis 1~mbomogenizer. Next, the obtained emulsion was spray-dried at an air blowing temperature of 140° C. to obtain a stable powdered vitamin Δ of 148,000 IU/(+) and excellent water dispersibility.

The obtained powdered vitamin A was subjected to the same water dispersibility test as in Example 2, and as a result, the water dispersibility was good.

Test Example 1, Invention: Powder obtained in Example 1 Comparative Example 1: Powder obtained without using the soybean lecithin of Example 1 Comparative Example 2: The sugar solution of Example 1 was heated at 70°C without heat treatment. Comparative Example 3: Powder obtained by dissolving the sugar solution of Example 1 at 70°C without heat treatment and without using soybean lecithin. 13.7%) and 100g
The mixture was mixed uniformly so that the amount of vitamin A per serving was 160,001 tJ, sealed in a plastic bag, and placed in a thermostat at 35°C. The residual rate of vitamin A was measured orally. The results are shown in Table 1.

Table 1 Stability test results Test Example 2 Invention: Powder obtained in Example 2 Comparative Example 4: Powder obtained by using 4 g of sorbitan fatty acid ester (HlB 6.7) in place of soybean lecithin in Example 2 Comparative Example 5: The $li solution of Example 2 was heated to 70% without heat treatment.
Results of orally measuring the residual rate of vitamin A by placing 5 g of each powder sample obtained by dissolving at °C into a citrine, covering it, and placing it in a constant temperature and humidity chamber at 40 °C and 10% humidity. are shown in Table 2.

Table 2 Stability test results Test Example 3 Invention: Powder obtained in Example 3 Invention: Powder obtained without using the sorbitan fatty ester of Example 3 Comparative Example 6: Soybean lecithin of Example 3 Powder Comparative Example 7 obtained without using Example 3: Powder Comparative Example 8 obtained by dissolving the sugar solution of Example 3 at 70°C without heat treatment: Example 3. 70℃ without heat treatment of sugar/liquid
Each powder sample obtained without using soybean lecithin was mixed uniformly with wheat flour (moisture 14.5%) so that vitamin 8 was 16,000 IIJ per 100g, sealed in a brown glass pin and left at room temperature. 1. Table 3 shows the results of orally measuring the residual rate of vitamin A.

Table 3 Stability test results Test Example 4 Present invention: Powder comparative example 9 obtained in Example 4: Powder comparative example 10 obtained without using the purified powder lecithin of Example 4 in the evening: Sugar solution of Example 4 Each powder sample obtained by melting at 80℃ without heat treatment was uniformly mixed with wheat flour (moisture 14.5%) so that the vitamin △ was +130001 U per 100g.
After sealing it in a plastic bag, put it in a 3.5 J thermostat, and put it in a vitamin Δ
Table 4 shows the results of orally measuring the residual rate of
.

From the above results, it can be seen that the powdered hitamine obtained by the method of the present invention is significantly superior even under conditions of poor stability, such as in a ladle, in wheat flour, and at high humidity, as can be seen from comparison with comparative examples.

In addition, good results were not obtained when lecithin was not used and when the sugar solution was not heated.

Claims (1)

[Claims] 5 to 50% by weight of saccharides whose main component is mal-su or full-sugar and 50 to 95% by weight of oligosaccharides or/
Add water to the sugar composition consisting of J3 and starch hydrolyzate to adjust the sugar solid content concentration to 30 to 85% by weight, and
Lecithin and vitamin A are added to the saccharide aqueous solution which has been heated to 50°C and then cooled to 20-80°C, and after emulsifying and mixing, it becomes powder, resulting in a stable and highly water-dispersible solution. Excellent method for producing powdered vitamin A.