JPS608041B2 - Method of producing flaxseed mucilage - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel flaxseed product having unique viscoelastic properties isolated from flaxseed.

The aqueous solution of flaxseed mucilage according to the present invention has a high viscosity and a low spinning ability. Alternatively, it provides significantly higher viscosity and elasticity than the viscosity when heated, exhibits intermediate physical properties between a fluid and a zeolite, and maintains these viscoelastic properties even in the presence of acids and salts.

Furthermore, the flaxseed viscous product according to the present invention can be prepared by heating the aqueous solution.
After the cooling treatment, the dried product is coagulated and separated using a hydrophilic organic solvent such as ethanol, methanol, inpropyl alcohol, or acetone, and the redissolved aqueous solution exhibits a higher viscosity than the aqueous solution that is not subjected to the heating-cooling treatment.

What is conventionally called linseed mucilage is extracted from flax seeds, which are raw materials for oil refining, or defatted linseed meal, which is produced in large quantities as a byproduct of oil refining, with water, dilute salt solution, dilute alcohol, etc., but this will be explained later. They obtained only a portion of the total mucilage contained in flax seeds as detailed in .

As a result, the conventional flaxseed lees material differed from the flaxseed mucilage material according to the present invention in that it had low viscosity, poor heat resistance, acid resistance, and salt resistance, and did not have heat history characteristics. That is, when flaxseed mucilage is separated from defatted flaxseed lees, 10 to 3 M of water is added to the weight of the defatted flaxseed lees, and the rope is extracted, but in this case, water-soluble proteins are also extracted, resulting in low-purity mucilage. Separated. Although there are methods of precipitating this water-soluble protein at the same point on the protein or removing the precipitate with a reagent such as phosphotungstic acid, a coprecipitation phenomenon with viscous substances is observed and a sufficient separation effect is not achieved.

In addition, when separating from flax seeds, soil and sand mixed in the raw material are removed.
Add 5 to 1 cup of water based on the weight of carefully selected seeds from which cross-breeding materials such as straw waste and sepals have been removed, and heat or leave for an appropriate amount of time without heating, or gently sprinkle on the surface of the seeds. After sufficiently swelling the existing mucilage, a clear frame is extracted. Regardless of which method is used, it is difficult to separate the so-called flaxseed mucilage in a good yield, and the viscosity of the flaxseed mucilage is higher than that of other polymeric glues, such as guar gum. , it is lower than locust bean gum, tragacanth gum, xanthan gum, etc., making it unsuitable for use as a thickener, etc., and its heat resistance, acid resistance, and salt resistance are inferior, so it cannot be used in foods, cosmetics, pharmaceuticals, etc. It was difficult. The flaxseed product having novel viscoelastic properties according to the present invention is different from the conventional so-called flaxseed product which has these drawbacks.The aqueous solution has a high viscosity and can be heated and cooled. It has significantly increased viscoelasticity, exhibits physical properties intermediate between a fluid and a jelly, and has excellent heat resistance, acid resistance, and salt resistance. As a result of research on perennial flaxseed mucilage, the present inventors found that the mucilage contained in flax seeds is not uniformly distributed on the seed surface, but is present in the outer layer of the seed (hereinafter referred to as the outer layer). We found that there is a significant difference mainly in viscoelastic properties between the mucilage present in the inner layer (hereinafter referred to as the inner mucilage) and the mucilage present in the inner layer (hereinafter referred to as the inner mucilage).

Flaxseed mucilage exists as the outermost layer of the epidermis of the seed, inside transparent and fragile cells.

Furthermore, it was found that the cells overlapped in more layers in the inner layer than in the outer layer, and that there was a significant difference in viscoelastic properties between the mucilage in the outer layer and the mucilage in the inner layer. This difference is presumed to be based on the molecular weight, constituent sugar, three-dimensional structure, etc. of the outer layer of the Sannohe Shibuyamono and the inner layer of mucilage, but there is no confirmation yet, and furthermore, the chemical formula of the outer layer of the mucilage is still unknown. Nothing is known about the three-dimensional structural formula, and the same applies to the inner layer mucilage of the present invention, which is a subject for future research. According to the research results of the present inventor, when separating flaxseed mucilage, it is possible to separate the outer layer mucilage and inner layer mucilage into several types by sequentially extracting and separating from the surface of the seed to the inside. found.

For this fractionation method, water is added to the selected seeds and concentrated to dissolve the viscous material, and the extraction is repeated. The obtained fractionated extract is centrifuged and/or filtered to remove fine dust, and then dried by a method such as fog drying, drum drying, or freeze drying, or by coagulating and precipitating the mucilage with a hydrophilic organic solvent. If the precipitate is dried and then crushed if necessary, a fractionated viscous product can be obtained in which the inner layer is sequentially fractionated from the outer layer. There are significant differences in the viscoelastic properties of the fractionated mucilages obtained in this way, especially the outer layer extract fraction, which is the outer layer mucilage near the seed surface, and the inner layer extract, which is the inner layer mucilage. Significant differences were observed between the fraction and the viscoelastic properties after the aqueous solution and heating-cooling treatment.

That is, it was found that the aqueous solution had a high viscosity and a viscous substance having thermal history characteristics due to heating and cooling treatment was present in the inner layer.
In order to obtain the inner mucilage of the present invention having such novel viscoelastic properties, it is necessary to separate the mucilage present in the inner layer of flax seeds as completely as possible.

The conventional so-called flaxseed mucilage is obtained by extracting and separating a part of the total mucilage contained in flax seeds, which contains substances corresponding to the above-mentioned outer layer extracted fraction. This is completely different from inner layer viscose products which have various viscoelastic properties, and generally has a low viscosity, little change in viscoelasticity due to heating-cooling treatment, and poor heat resistance, acid resistance, and salt resistance. The inner layer mucilage of the present invention is separated from the inner layer, which accounts for about 30 to 50% of the total mucilage contained in flax seeds, although there are some differences depending on the variety, production area, etc.

It was confirmed that the flaxseed whole-viscosity product containing the inner layer mucilage according to the present invention also has novel viscoelastic properties, unlike the conventional so-called flaxseed product.

Therefore, the aqueous solution has a high viscosity, and is given extremely high viscosity and elasticity by heating and cooling treatment, exhibits physical properties intermediate between a fluid and a jelly, and is excellent in heat resistance, acid resistance, salt resistance, etc.

The characteristic properties of the outer layer viscous product and the inner layer viscous product of the present invention will be explained in detail below.

{1} Viscosity of aqueous solution Both the outer layer and inner layer are completely dissolved in cold water, giving a viscous liquid, but the viscosity of the outer layer is low, but the viscosity of the inner layer is high and is used as a thickener. It can be used in a wide range of fields such as

Furthermore, the outer layer of mucilaginous material has a large spinning capacity, which has a negative effect on its use in food products, etc., whereas the inner layer of mucilaginous material has a small stringing ability. '2' Viscoelastic properties due to heating-cooling treatment of aqueous solution The viscosity of the outer layer of mucilage increases only slightly due to the heating-cooling treatment of the aqueous solution, but the viscosity of the inner layer of mucilage increases significantly in the low concentration range. Accepted, 0.2-0.5
When the concentration exceeds 50%, the viscosity increases and the viscoelasticity changes significantly, resulting in a so-called semi-jelly material exhibiting physical properties intermediate between a fluid and a jelly.

Normally, chicken egg whites are said to be composed of thick egg whites with high viscosity and watery egg whites with low viscosity, but the semi-jelly substance is similar to this thick egg white, and also resembles jellyfish and frog eggs. , can be lifted with chopsticks, forks, etc.

Furthermore, this semi-jelly-like substance is extremely difficult to dissolve in water, and is extremely unique in that it maintains its semi-jelly state even in water, similar to the above-mentioned semi-jelly-like substances such as concentrated egg white, jellyfish, and frog eggs. It has physical properties. '3} Heat resistance of aqueous solutions The viscosity of outer layer viscous products decreases when heated at high temperatures for long periods of time, but the viscosity of inner layer viscous products increases due to heating at high temperatures for long periods of time, as they have the characteristics of [2]. After cooling, it is observed that it exhibits semi-jelly-like physical properties.

[4] Acid resistance of aqueous solutions The viscosity of both the outer layer and the inner layer of the sticky material decreases with the addition of acid, but the inner layer of the sticky material has the characteristics of Viscosity increases by cooling treatment.

[51 Salt resistance of aqueous solution The viscosity of the outer layer mucilage and inner layer viscosity decreases to some extent by adding salt up to a salt concentration of about 1%, but the viscosity decreases further when more salt is added. Never.

Since the inner layer mucilage has the characteristic '2), its viscosity increases even in the presence of common salt by heating and cooling treatment.

'6} Preparation of high viscosity aqueous solution To obtain a high viscosity aqueous solution of the inner layer mucilage by heating and cooling, the aqueous solution after heating or heating and cooling is coagulated and precipitated by spray drying, drum drying, or a hydrophilic organic solvent. A highly viscous aqueous solution can be obtained by dissolving the dried product in cold water again.

Such a high viscosity aqueous solution cannot be obtained with the mucilage of the outer layer. As mentioned above, there is a significant difference mainly in viscoelastic properties between the outer layer mucilage material referred to herein and the inner layer mucilage material of the present invention, which is referred to as a so-called linseed mucilage material.

This property is enhanced by heating-cooling treatment, giving it excellent heat resistance, acid resistance, and salt resistance. In order to practically obtain the inner layer mucilage according to the present invention, the inner layer mucilage is separated after the outer layer mucilage referred to here, which is conventionally called linseed mucilage, is separated, or the outer layer mucilage is separated. It is sufficient to simultaneously separate all of the mucilage and the inner mucilage.

The outer layer mucilage can be separated using the conventional dissolution extraction method, but the inner layer mucilage is difficult to separate using the conventional solution extraction concept. Therefore, in order to completely separate the mucilage, a large amount of It has the disadvantage of requiring water and repeated extractions. In this way, the conventional so-called flaxseed products are based on the concept that seaweed polysaccharides such as alginic acid, carrageenan, facellan, and agar are separated by dissolution and extraction in acid or alkaline solutions, hot water, etc. The mucilage is separated, but the inventors of the present invention discovered and devised a method for breaking through this concept and peeling it off.

Peeling here refers to, for example, separating seeds from grape granules, by keeping the mucilage covering the surface of flax seeds in a swollen state with a small amount of water, and sequentially peeling off the seeds and mucilage.

In this case, the amount of water used is the amount necessary for the mucilage to swell, that is, 1.2 to 5. The needle sound is appropriate, and using a large amount of water will actually reduce the peeling effect.

The peeling method involves applying physical energy such as vibration, shock, or cutting to the swollen flax seeds to separate the seeds from the mucilage. Any method of physical energy such as vibration, impact, or scaling may be used as long as it is possible to separate the seeds from the mucilage, but it is necessary that the seeds are at least spared from being crushed. For example, a turbine-type high-speed rotating Takaazusa machine requires a high-speed rotation of 30 pm or more, and some models have a speed of 30 pm or more.
The following is also fine. There is no need to limit the upper limit, and any practically feasible range is appropriate. The present invention will be explained in detail below with reference to Examples.

Example 1 After adding 5.0 kg of water to 1.0 k9 of carefully selected flax seeds and allowing it to swell at room temperature, Chemistler (manufactured by Tokyo Rika Kikai, 3 B-100 type sailing wings, 5 skin rotation radius, below) After extracting the seeds for 91 rpm for 91 rpm using the same method, the mixture was separated into seeds and an extract while being suctioned using a Buchner funnel lined with a 20-mesh wire mesh to obtain a first extract IF. An additional 1.5 liters of water was added to the seed portion and extracted in the same manner to obtain a second extract 2F. Repeat this operation to obtain extracts 3F, 4F, 5F, and 6F.
,7F was obtained. *When obtaining extract 8F, in order to complete the extraction, the Nawa Azusa condition was set to 241 rpm, and then a 20-mesh wire mesh was attached to the basket part of a basket-type separator (manufactured by Domestic Centrifuge, H-110A model). 3,00 bipm
Centrifuge for 5 minutes and separate the seed part 1.42k9 and the extract 8F.
It was separated into

Each of the obtained extracts IF to 8F was filtered with a furnace cloth to remove fine dust, and then an equal weight of 9% ethanol was added.
The mucilage was coagulated and precipitated, and the precipitate was dried in a hot air dryer for 8 u for 30 minutes to obtain each fraction of mucilage IF to 8F. IF~8
The total yield of mucilage of F, that is, the total yield of mucilage was 64 min (calculated as anhydride). Table 1 shows the yield and proportion of each of IF to 8F in the total mucilage. Table 1 and Figure 1 show the viscosity of a 1% aqueous solution of IF to 8F and the viscosity after heating and cooling treatment.

The viscosity was measured using a B-type viscometer (manufactured by Tokyo Keiki, 3 ratio pm, 250○,
A 1% solution was used as the measurement sample (the same applies hereafter). The bad regions are respectively 970 qo, and the regions [B} are the cases where they are not heated.

As shown in FIG. 1, there is a significant difference between IF~4F and 5F~8F. That is, the viscosity of the aqueous solution is lower than that of IF - 4 days and 5F - 8 days, and even after the heating-cooling treatment, the viscosity increases only slightly. The viscosity of the aqueous solution of 5F to 8F is high, and the viscosity increases significantly upon heating and cooling treatment.

In this way, IF in the total mucilage contained in flax seeds
The viscosity of the aqueous solution of the outer layer mucilage of ~4F is low, and the viscosity increases only slightly even with heating-cooling treatment, but
The viscous substance in the inner layer of F has a high viscosity as an aqueous solution, and can be given a significantly high viscosity by heating and cooling treatment.

Example 2 1.0k9 of carefully selected flax seeds were added with 5.0ml of water, allowed to swell at room temperature, and then extracted with a chemister at a ratio of 15 pm for 15 minutes. Separate the seeds and extract liquid while suctioning with a funnel, and extract the outer layer part 3.
．． Got 12k9.

Add 2.0 liters of water to the seeds and mix with a Chemister stirrer.
After peeling for 1.5 pm, centrifugation was performed in a basket-type separator in the same manner as in Example 1 to obtain a seed part of 1.43 k9 and an inner layer part peeling liquid of 3.55 k9.

The seed part showed no stickiness and the mucilage was completely separated. The outer layer extract and the inner layer peeling solution were each treated in the same manner as in Example 1, and the outer layer viscous material was 38.0 ml (59.6% of the total viscous material) and the inner layer viscous material was 25.8 ml. Obtained aqueous solution (accounting for 40.4% of the total mucilage).

(All values are calculated as anhydrous) Example 3 Add 5.0 ml of water to 1.0 k9 of carefully selected flax seeds, immerse and swell at room temperature, and then peel off touzuka using a Chemister slurry at a ratio of 63 pm for 20 minutes. The mixture was centrifuged in a separator to obtain a seed portion of 1.42k9 and a stripping solution of 4.58k9.

The seed part showed no stickiness and the mucilage was completely separated.
The stripping solution was treated in the same manner as in Example 1 to remove all mucus 64.
5 ml (calculated as anhydrous) was obtained. The properties of the outer layer mucilage obtained in Example 2 and Example 3, the inner layer mucilage of the present invention, and the total mucilage of the present invention are as follows.

{1' General analysis value (anhydride equivalent) Table 2 As shown in Table 2, no difference is observed among ○, 1, and T in the general analysis.

(2) Threading ability of aqueous solution A plunger equipped with a glass bulb with a diameter of 5.0 ribs is immersed in a 1% aqueous solution (25o0) up to the center of the glass bulb, and pulled up at various speeds.

The aqueous solution exhibited threading ability, the distance the thread was pulled up until it broke was defined as the thread length, and the relationship between the thread speed and the thread length was measured. The results are shown in Fig. 2. The outer layer mucilage material 0 has a long string length, that is, the stringing ability is high, but the inner layer material 1 has a small stringing ability and the total stringiness material T is in the middle. Ta. {3-
Viscosity of aqueous solution and viscoelastic properties after heating-cooling treatment, Part 3
As shown in the figure and FIG. 4, the viscosity of the outer layer viscous material 0 is low and the viscosity increases only slightly even after the heating and cooling treatment shown by the dotted line in FIG. 3, but the viscosity of the inner layer 1 increases significantly. and forms a semi-jelly material when the aqueous solution concentration is high.

The solid line in FIG. 3 is the case without heating. It is insufficient to express the physical properties of this semi-jelly material by viscosity alone.

After the aqueous solution of each concentration was heated and cooled, it was placed in a vinyl chloride cylinder with a diameter of 4.4 arc and height of 5.0 cm with a wire mesh attached to the bottom and left for 30 minutes, allowing the contents to flow out and fall. It was determined whether or not.

For the wire mesh at the bottom, a Japanese Industrial Standard sieve was used as shown in Table 3. According to this method, substances exhibiting physical properties such as concentrated albumen, jellyfish-like, and frog egg-like do not pass through the mesh. As shown in Table 3, the mucilage in the outer layer does not have a semi-jelly-like appearance, so it flows out and falls regardless of the size of the mesh, but the mucilage in the inner layer and the whole mucilage have a semi-jelly-like appearance even at low concentrations. This prevents leakage from falling through the mesh. Furthermore, as described as a reference example, a 2% aqueous solution of guar gum and xantham gum, which are representative high-viscosity polysaccharides, did not exhibit any semi-jelly-like appearance as shown in the inner layer mucilage and the whole mucilage of the present invention, but flowed out from the mesh. fell down. Furthermore, even if the semi-jelly-like substance mentioned here was soaked in water and left to stand or slowly stirred, it did not dissolve again in water and remained semi-jelly-like, but quar gum and xanthan gum dispersed and dissolved in water and remained uniform. It became an aqueous solution. Third
Table note: × means that the water leaks out from the mesh of the wire mesh, and 〇 means 〃
〃 If it does not flow out and fall ○ Outer layer part viscous part 1 Inner layer 〃 T whole〃 In this way, the linseed mucilage, which was thought to have a low viscosity, has been given high viscosity and semi-jelly physical properties according to the present invention. The inner layer did not contain a mucilage material having novel viscoelastic properties.

■Heat resistance of aqueous solutions Figure 4 compares the relationship between heating temperature and viscosity for inner layer mucilage 1, outer layer mucilage ○, and total mucus T when heated for 30 minutes and cooled to 4000 to 12000. So, the fourth
As shown in the figure, the outer layer mucilage [1] is a commercially available phlegm. Like Santan Gum X and commercially available Guar Gum G, the viscosity decreases when heated at high temperatures, but the viscosity of Inner Layer Mucilage 1 increases significantly when heated and cooled.

It can be seen that the total viscous material T also exhibits almost the same viscosity behavior as the inner layer viscous material 1.

[5) Acid resistance of aqueous solution As shown in Figure 5, mucilage ○ in the outer layer and mucilage 1 in the inner layer
Both aqueous solutions exhibit a decrease in viscosity upon addition of acetic acid.

By the heating-cooling treatment, the viscosity of the outer layer viscous material ○ further decreases, but on the contrary, the viscosity of the inner layer viscous material 1 increases.

The dotted lines in the middle of FIG. 5 indicate the case where the samples were cooled after heating for 8000 min, respectively, and the solid lines indicate the case where they were not heated. '6} Salt Tolerance of Aqueous Solution As shown in Figure 6, the viscosity decreases when the amount of salt added is about 1%, but it does not decrease further even if more than that amount is added.

Although the outer layer mucilage 0 shows a slight increase in viscosity even after heating and cooling treatment after addition of salt, the inner layer mucilage 1 shows a significant increase in viscosity and exhibits a semi-jelly-like appearance. In FIG. 6, the dotted lines indicate the case where the 97003 female flanges were heated, and the solid lines indicate the case where they were not heated.

{7} Preparation of high viscosity aqueous solution The outer layer extract and inner layer peeling solution obtained by the same procedure as Example 2 were each divided into two,
One was heated as it was, and the other was heated to 9,000 for 30 minutes, then cooled to room temperature, and the viscous products were coagulated and precipitated with ethanol in the same manner as in Example 1. After drying, four types of viscous products were obtained as shown in Table 4. .

As shown in Table 4, if the inner layer mucilage stripping solution in Table 4 is heated and cooled, the redissolved aqueous solution after drying has a higher viscosity than the so-called unheated solution that is not heated and cooled. Ta.

{8} The viscoelastic properties of the flaxseed mucilage after the aqueous solution and heating-cooling treatment do not change even when frozen and thawed.

New applications can be expected by utilizing the properties described above (1' to '7).

For example, when used as a stabilizer (1), the viscosity is low when heated and the viscosity increases when cooled, resulting in excellent emulsifying properties and stability. ■ Low viscosity when unheated and when heated. Therefore, the workability is good, and the viscosity increases significantly after the heating-cooling treatment, resulting in an excellent thickening effect.

'3} Since it has both thickening and jelly-forming properties, it can be used for pastes that require extensibility, shape retention, and prevention of syneresis.

{Since it has tetravalent thermal resistance and acid resistance, it can be used in a wide range of applications.

Also {5) film-forming ability, etc. As described above, the flaxseed mucilage of the present invention has unique semi-elastic properties that are completely different from conventional flaxseed mucilages and commercially available polymer pastes, and it can be used as a food,
In addition to being used in various industries such as cosmetics and pharmaceuticals, it can also be used as a sizing agent for textile printing and paper, a spreading agent for paint, a thickener for toothpaste, an ice cream agent during freezing,
It can be used as a binder for compound feed, a dispersant for paint latex, a dispersant for printing ink, a stabilizer for ceramic clay, etc.

[Brief explanation of the drawing]

Figure 1 shows the viscosity of each fractionated mucilage solution obtained by fractional extraction with water from flax seeds, and Figure 2 shows the outer layer*occupied material ○, the inner layer mucilage 1, and the total mucilage T. Figure 3 shows the relationship between the string speed and string length for a 1% aqueous solution of A diagram showing the relationship between the concentration and viscosity of an aqueous solution. Figure 4 is a diagram showing the viscosity change due to heating of the inner layer mucilage, outer layer mucilage, total mucilage, commercially available guar gum, and commercially available xanthan gum. Figure 5 is the inner layer mucilage. Figure 6 shows the viscosity change due to the addition of acetic acid to the mucilage, outer layer mucilage, and total mucilage. Figure 6 is a diagram showing the relationship between the concentration of salt and viscosity due to the addition of salt to the inner layer, outer layer, and total mucilage. be. 1...Inner layer mucilage, T...Total mucus, 0
...Outer layer mucilage, G...Commercially available guar gum, X...Commercially available xanthan gum. Figure 2 Figure 1 Figure 4 Figure 3 Figure 5 Figure 6

Claims (1)

[Claims] 1. Extracting and removing the mucilage from the outer layer of the epidermis of flax seeds with water,
By extracting and separating the mucilage from the inner layer of the epidermis with water, or by extracting and separating the mucus from the outer layer of the epidermis and the mucus from the inner layer of the epidermis with water, a 1% aqueous solution of the same is prepared using a B-type viscometer at 30 rpm.
It has a viscosity of 100 to 1000 centipoise when measured at 25°C, becomes jelly-like after heating and cooling to at least 50°C, and has a viscosity of 500 to 20,000 centipoise when measured at 25°C at 30 rpm with a B-type viscometer. A method for producing a flaxseed mucilage having the following. 2. The flaxseed mucilage according to claim 1, which applies physical energy such as vibration, impact, shearing, etc. to the extraction and separation of the mucilage present in flax seeds with water, thereby peeling the mucilage from the flax seeds. How to manufacture.