JP7022635B2 - Film and its manufacturing method - Google Patents

Description

The present invention relates to a film and a method for producing the same.

Conventionally, a galactose partial decomposition product of galactoxyloglucan (hereinafter referred to as "partial decomposition product") obtained by removing galactose constituting a part of the side chain of galactoxyloglucan as a polysaccharide by partially decomposing (partially decomposing) it. It may be simply referred to as "galactose partial decomposition product or partial decomposition product") (see Patent Document 1).

Even if the partially decomposed galactose is dissolved in water to form a gel-like composition and then dried to form a film, the obtained film is not sufficiently strong.

Therefore, a film having sufficient strength has been proposed using such a galactose partial decomposition product (see Patent Document 2).

On the other hand, a composition capable of exhibiting thickening and gelling action by containing a partially decomposed galactose of galactoxyloglucan and a polyphenol has been proposed (see Patent Document 3).

Japanese Unexamined Patent Publication No. 8-283305 Japanese Unexamined Patent Publication No. 2016-193892 Japanese Unexamined Patent Publication No. 2000-354460

However, it is desirable if the film containing the galactose partial decomposition product can be imparted with strength by a method other than the method of Patent Document 2.
On the other hand, Patent Document 3 discloses a gel composition of a galactose partial decomposition product by containing a polyphenol, but does not disclose its application to a film.

In view of the above circumstances, it is an object of the present invention to provide a film containing a partially decomposed galactose product but having excellent strength, and a method for producing the same.

As a result of diligent research to solve the above problems, the present inventors have found the following findings.
That is, the partially decomposed galactose is dissolved in water to form a gel composition, and the film obtained by drying this gel composition does not dissolve even when immersed in water. However, it swells to a high degree. Highly swollen films are significantly reduced in strength and very prone to disintegration. Therefore, it cannot be put into practical use.

However, surprisingly, it has been found that when the film thus formed is immersed in an aqueous solution of polyphenol, the strength of the film is improved in a short time. In addition, it has been found that it is convenient to manufacture by immersing in this way.
Moreover, it has been found that a similar film can be produced even if a film is once formed and then immersed in an aqueous solution of polyphenol, or a partially decomposed galactose product is previously dissolved in water together with polyphenol and then dried.
Furthermore, they have found that the strength of the film can be adjusted according to the concentration of the aqueous solution of polyphenol, and have completed the present invention.

That is, the film according to the present invention contains a galactose partial decomposition product of galactoxyloglucan and a polyphenol.
The strength is higher than that in the case where the polyphenol is not added.

According to such a structure, a film having excellent strength while containing a galactose partial decomposition product is obtained.

In the film having the above structure,
Further, it may contain glycerin.

According to such a configuration, the flexibility is enhanced by further containing glycerin.

In the film having the above structure,
The polyphenol may be a tea extract.

According to this configuration, since the polyphenol is a tea extract, the reactivity with the partially decomposed galactose is improved, so that the strength is further increased.

The method for producing a film according to the present invention is as follows.
A method for producing the film.
The present invention comprises a step of immersing a film-like composition obtained by dissolving a galactose partial decomposition product of galactoxyloglucan in water and drying a solution thereof in an immersion liquid containing polyphenol and water.

According to such a configuration, it is convenient because a film having higher strength than that before dipping and having excellent strength while containing a galactose partial decomposition product can be obtained only by immersing in the dipping solution.

In the method for producing a film having the above configuration,
The immersion liquid may further contain glycerin.

According to such a configuration, a more flexible film can be obtained.

In the method for producing a film having the above configuration,
The concentration of the polyphenol in the dipping solution may be 0.05 to 2.0% by mass.

According to such a configuration, a film having higher strength can be produced in a shorter time.

In the method for producing a film having the above configuration,
A tea extract may be used as the polyphenol.

According to this configuration, since the polyphenol is a tea extract, the reactivity with the partially decomposed galactose is improved, so that a film having higher strength can be obtained.

As described above, according to the present invention, there is provided a film containing a partially decomposed galactose product but having excellent strength, and a method for producing the same.

Graph showing the relationship between immersion time and breaking stress for each concentration of polyphenol (0% by mass to 2% by mass) A graph showing the relationship between the immersion time within 10 minutes and the breaking stress for each concentration of polyphenol (0% by mass to 2% by mass).

Hereinafter, embodiments of the film and the method for producing the film according to the present invention will be described.

The film of the present embodiment contains a galactose partial decomposition product of galactoxyloglucan and a polyphenol.
The strength is higher than that in the case where the polyphenol is not added.

The galactoxyloglucan is a nonionic high molecular weight polysaccharide that is a component of the cell wall (primary wall) of higher plants such as dicotyledons and monocotyledons, and is present as a storage polysaccharide of some plant seeds. be.
This galactoxyloglucan has glucose, xylose and galactose as constituent sugars, has glucose having β-1,4 bonds as a main chain, has xylose as a side chain, and further binds to the xylose. Has galactose.
The galactoxyloglucan may be any plant-derived galactoxyloglucan and can be obtained from the epidermis of grains such as tamarind, jatoba, nastatium seeds, soybeans, mung beans, bean, rice, barley or fruits such as apples. Considering that it is the most available and has a high content, galactoxyloglucan derived from the legume tamarind seed is preferable. As such a galactoxyloglucan, a commercially available product may be adopted. Examples of commercially available products include Glyroid (registered trademark, manufactured by DSP Gokyo Food & Chemicals Co., Ltd.).

The galactose partial decomposition product of galactoxyloglucan is a substance obtained by partially decomposing and removing the side chain galactose of galactoxyloglucan.
In the present embodiment, the galactoxyloglucan means a galactoxyloglucan (complete galactoxyloglucan) in which the side chain galactose is not removed by partial decomposition by an enzymatic treatment described later. Such a complete galactoxyloglucan may also be referred to as a native galactoxyloglucan.
Enzymes are used for the partial decomposition. Examples of the enzyme include β-galactosidase.

The β-galactosidase is an enzyme that hydrolyzes the bond between galactose and xylose contained in galactoxyloglucan to release galactose. The β-galactosidase may be derived from a plant or a microorganism, but an enzyme derived from the microorganism Aspergillus oryzae or Bacillus cyclans, or an enzyme in galactoxyloglucan-containing seeds is preferable. As such β-galactosidase, a commercially available one may be adopted.

In this enzymatic reaction with β-galactosidase, side chain galactose is partially removed as the reaction progresses, and when the removal rate reaches around 30%, the reaction solution rapidly thickens and gels. When the removal rate of galactose is in the range of 30 to 55%, it has a reversible thermal response gelling property that gels by heating and sol by cooling. If the galactose removal rate is less than 30%, the reactivity with polyphenols decreases, and if it exceeds 55%, the solubility of the galactose partial decomposition products in water decreases, making it difficult to prepare a uniform galactose partial decomposition product aqueous solution. Non-uniform film tends to be formed.

Considering this point, it is preferable to use the above-mentioned galactose partial decomposition product in which galactose is partially decomposed by 30 to 55%. When the galactose partial decomposition product is reacted with polyphenol by partially decomposing galactose by 30 to 55%, the film strength can be increased in a relatively short time. Therefore, a higher-strength film can be produced in a shorter time.

Galactoxyloglucan usually contains about 37% side chain xylose and about 17% side chain galactose (see Gidley et al., Carbohydrate Research, 214 (1991), pp. 219-314). Therefore, it is calculated that the partially decomposed galactose obtained by partially decomposing galactose contains 39 to 41% of side chain xylose and 8 to 12% of side chain galactose.
The partial decomposition rate of galactose (that is, the removal rate of galactose) is the amount of galactoxyloglucan oligosaccharide produced by the cellulase decomposition of the obtained partial decomposition product, which is referred to as high performance liquid chromatography (hereinafter referred to as HPLC). It can be calculated by measuring with (referred to as) (amino column).

Examples of the polyphenols include polyphenols which are chemically synthesized products and plant-derived polyphenols (plant polyphenols), and among these, plant polyphenols are preferable.
Plant polyphenols include green tea (matcha roasted tea, etc.), black tea, oolong tea, puer tea (black tea), tea leaves such as mate tea, white vegetables, citrus peels and seeds, grape peels and seeds (red wine, red grape juice, etc.). , Apples, persimmons, peaches, pears, onion skins, chestnuts, gobos, coffee beans, cocoa beans, etc., with warm water or the like (including solid and liquid extracts). This extract is rich in monomeric polyphenols and polymer polyphenols.

Examples of the monomer polyphenol include flavonoids, chlorogenic acid, gallic acid, ellagic acid and the like.
Examples of the flavonoids include catechins, quercetin, rutin, anthocyanins and the like.
Examples of the catechins include (+)-catechin, (+)-gallocatechin, (-)-epicatechin, (-)-epigallocatechin, and gallic acid esters thereof. Of these, as the catechins, (-)-epigallocatechin gallate of epigallocatechin (epigallocatechin gallate) is preferable.

Examples of the polymer polyphenol include condensed type and hydrolyzed type tannins.
Examples of the condensed type tannin include proanthocyanidins and the like, and examples of the proanthocyanidins include thearubigin and prodelphinidin.
Examples of the hydrolyzed tannin include tannic acid, gallotannin, and ellagitannin.

When the above-mentioned plant polyphenol is used, the above-mentioned extract itself may be used, or the extract obtained by concentrating (extracting) the active ingredient polyphenol may be used, or further. , The active ingredient polyphenol purified (separated) from the extract may be used. Of these extracts, a tea extract, which is an extract extracted from tea leaves, is preferable.
The plant polyphenol is not particularly limited to the above, and may be any as long as it is obtained from a plant containing polyphenol.
The polyphenol may be used as one kind or a mixture of a plurality of kinds.

The content of the galactose partial decomposition product in the film of the present embodiment may be appropriately set according to the desired strength of the film, and is not particularly limited.
For example, the content of the galactose partial decomposition product in the film is preferably 2 to 60% by mass, more preferably 5 to 50% by mass.
When the content of the galactose partial decomposition product in the film is 2% by mass or more, there is an advantage that the strength can be exhibited without containing excess water.
When the content of the galactose partial decomposition product in the film is 60% by mass or less, there is an advantage that the wettability and flexibility are excellent.

The content of polyphenol in the film of the present embodiment is appropriately set according to the degree to which the strength of the partially decomposed galactose film can be obtained and the degree of the thickness of the film, that is, according to the strength and thickness of the desired film. It suffices to be done, and is not particularly limited.

The thickness of the dried product (film-like composition) before immersion in the polyphenol solution in the present embodiment is preferably 0.005 to 0.2 mm, more preferably 0.05 to 0.1 mm.
When the thickness of the film-like composition is 0.005 mm or more, there is an advantage that it is not easily torn during processing such as production of a film by immersing it in a polyphenol solution.
When the thickness of the film-like composition is 0.2 mm or less, there is an advantage that it is easy to follow various shapes and it is easy to produce a film when the film is produced by immersion in polyphenol.

The thickness of the film of the present embodiment is preferably 0.05 to 0.5 mm, more preferably 0.1 to 0.3 mm.
When the thickness of the film is 0.05 mm or more, there is an advantage that it is difficult to tear and it becomes easy to produce a film having a certain strength.
When the thickness of the film is 0.5 mm or less, there is an advantage that it can easily follow various shapes.

The water content of the film of the present embodiment is preferably 40 to 98% by mass, more preferably 50 to 95% by mass.
When the water content of the film is 40% by mass or more, there is an advantage that the film has excellent wettability and flexibility.
When the water content of the film is 98% by mass or less, there is an advantage that the film can exhibit its strength without containing excessive water.
For the above water content, after removing excess water adhering to the surface of the film with a tissue or the like, the mass of the film (mass before drying) is measured, and the mass after heating and air drying at 50 ° C. for 30 minutes is measured. Then, the decrease in mass before and after drying is a value calculated as a percentage of the mass before drying.

The strength of the film of the present embodiment is preferably 0.005 MPa to 4 MPa, more preferably 0.01 MPa to 2.5 MPa.
When the strength of the film is 0.005 MPa or more, there is an advantage that it is hard to tear.
When the strength of the film is 4 MPa or less, there is an advantage that it has a better tactile sensation.

The film of the present embodiment may contain various additives usually added to cosmetics, medical products, and industrial products, if necessary. Examples of such additives include plasticizers, preservatives, water activity reducing agents, pH adjusting agents and the like. Examples of the plasticizer include glycerin, sorbitol, propylene glycol, polyethylene glycol and the like. In addition to the above, examples of the additive include excipients for coating films, and the excipients include, for example, various polysaccharides such as various starches (including modified starch, modified starch, starch, starch decomposition products, etc.). Can be mentioned.

The method for producing the film of the present embodiment is not particularly limited, but for example, the following production method can be adopted.

Next, a method for producing the film of the present embodiment will be described.

The film manufacturing method of this embodiment is
The method for producing the film of the present embodiment described above.
The present invention comprises a step (immersion step) of immersing a film-like composition obtained by dissolving a galactose partial decomposition product of galactoxyloglucan in water and drying a solution thereof in an immersion liquid containing polyphenol and water.

Specifically, the method for producing the film of the present embodiment is as follows.
A step of forming a film-like composition by dissolving a galactose partial decomposition product of galactoxyloglucan in water and drying the obtained solution (step of forming a film-like composition).
The film-like composition is provided with a step of immersing the formed film-like composition in a dipping solution containing polyphenol and water (immersion step).

(Step of forming a film-like composition)
The step of forming the film-like composition is, for example,
A dissolution step in which the partial decomposition product of galactose is dissolved in water while cooling to form an aqueous solution,
The present invention comprises a drying step (solution drying step) of obtaining a film-like composition by drying the obtained solution.
In the drying step, the aqueous solution of the galactose partial decomposition product may gel. In such a gelled state, drying may be temporarily stopped and then re-dried.

In the dissolution step, for example, the partial decomposition product of galactose can be dissolved in water while cooling so as to be 0.1 to 10% by mass.
In the dissolution, a conventionally known apparatus used for dissolution is appropriately used.
If the partially decomposed galactose can be dissolved in water, it does not need to be cooled.
In the dissolution step, in addition to the galactose partial decomposition product and water, the above-mentioned additives may be added.

In the step of drying the solution, for example, the obtained solution is dried so that the water content is 1 to 90% by mass to obtain a film-like composition. The water content is the difference between the mass of the film-like composition obtained by drying and the mass of the non-volatile component (non-volatile components other than water) contained in the solution before drying. Percentage to mass.
In drying, conventionally known devices used for drying are appropriately used.

The thickness of the film-like composition is not particularly limited and may be appropriately set so that the film formed in a later step has a desired thickness.
The thickness of the film-like composition of the present embodiment is, for example, preferably 0.005 to 0.2 mm, more preferably 0.05 to 0.1 mm, as described above.

(Immersion process)
In the dipping step, for example, the obtained film-like composition is dipped in the dipping solution contained in the container.
The concentration of the polyphenol aqueous solution in the dipping solution is not particularly limited, and can be appropriately set so that the strength of the film obtained in a later step becomes a desired strength.

For example, the higher the concentration of polyphenol, the higher the reactivity with the galactose partial decomposition product, and the higher the film strength tends to be. In addition, polyphenols tend to be more difficult to dissolve as the amount dissolved in a certain amount of water increases.
Therefore, for example, in consideration of such a viewpoint, the concentration of the polyphenol aqueous solution can be usually 0.05 to 2.0% by mass, preferably 0.1 to 1.5% by mass, and is 0. It is more preferably 1.1 to 1.0% by mass.
By setting the concentration of the polyphenol aqueous solution to 0.05 to 2.0% by mass, the polyphenol aqueous solution can be easily prepared, and the reactivity between the partially decomposed galactose product and the polyphenol can be improved, so that the film has higher strength. Can be manufactured in a shorter time.

The immersion can be performed, for example, at room temperature.
The soaking time is not particularly limited, but may be, for example, 2 to 10 minutes (as the minimum time).
In addition to polyphenols and water, the above-mentioned additives may be added to the dipping solution.

A film may be obtained by drying the soaked film-like composition so as to have a water content described later. In such drying, conventionally known devices used for drying are appropriately used.
The film may be obtained without such drying.

In the present embodiment, the water content of the film is not particularly limited, but is preferably 40 to 98%, more preferably 50 to 95%.
The water content is a value measured by the above-mentioned measuring method.

According to the film manufacturing method of the present embodiment, it is convenient because a film having higher strength than that before dipping can be obtained only by immersing in the dipping solution as described above.

As described above, the film of this embodiment is
Contains partial decomposition of galactose from galactoxyloglucan and polyphenols,
The strength is higher than that in the case where the polyphenol is not added.

According to the film of the present embodiment, the film has excellent strength while containing a galactose partial decomposition product.

In the film of this embodiment,
Further, it is preferable to contain glycerin.
Further, by containing glycerin, the flexibility is increased.

In the film of this embodiment,
The polyphenol is preferably a tea extract.
Since the polyphenol is a tea extract, the reactivity with the partial decomposition product of galactose is improved, so that the strength is higher.

The film manufacturing method of this embodiment is
A method for producing the film of the present embodiment.
The present invention comprises a step of immersing a film-like composition obtained by dissolving a galactose partial decomposition product of galactoxyloglucan in water and drying a solution thereof in an immersion liquid containing polyphenol and water.

According to the method for producing the film of the present embodiment, it is convenient because a film having higher strength than that before the immersion and having excellent strength while containing a partially decomposed product of galactose can be obtained simply by immersing the film in the above-mentioned dipping solution. be.
Further, by incorporating various components in the dipping solution, such components can be contained in the film, and therefore, a wide range of components are contained as compared with the film not immersed in the dipping solution (the film-like composition). Can be.

In the method for producing the film of the present embodiment,
It is preferable that the immersion liquid further contains glycerin.
This gives a more flexible film.

In the method for producing the film of the present embodiment,
The concentration of the polyphenol in the dipping solution is preferably 0.05 to 2.0% by mass.
When the polyphenol concentration is in the above range, a film having higher strength can be produced in a shorter time.

In the method for producing the film of the present embodiment,
It is preferable to use a tea extract as the polyphenol.
Since the polyphenol is a tea extract, the reactivity with the partial decomposition product of galactose is improved, so that a film having higher strength can be obtained.

As described above, according to the present embodiment, there is provided a film containing a partially decomposed galactose product but having excellent strength, and a method for producing the same.

Such a film of the present embodiment can be widely used in foods, pharmaceuticals, cosmetics, and industrial applications.

When the film of the present embodiment is stored in deionized water containing no polyphenol, the polyphenol tends to be removed and the strength tends to decrease.
Considering this point, the film may be formed by immersing it in a polyphenol aqueous solution and then stored in a state of being immersed in the polyphenol aqueous solution as it is.
In addition, after being taken out from the polyphenol aqueous solution, it may be stored in a packaging container or the like in a wet state as it is. If the wet state is maintained by the polyphenol aqueous solution in this way, the decrease in strength is suppressed. When using it, it can be used as it is by taking it out of the storage container.

Although the present embodiment has been described above, the present invention is not particularly limited to the above embodiment, and the design can be appropriately changed within the scope of the present invention.

For example, in the above embodiment, as a method for producing a film, a method of immersing a film-like composition in an immersion liquid is shown, but the film of the present invention can also be produced by another method.
For example, partial decomposition product of galactose, polyphenol, water, and any additive are dissolved while cooling to form an aqueous solution, and then heated to obtain a gel-like composition, and the obtained gel-like composition is dried. The film may be manufactured by.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Production Example 1) Production of partial decomposition product of galactose Add 1 g of galactoxyloglucan (manufactured by DSP Gokyo Food & Chemical Co., Ltd., Glyroid (registered trademark)) to 99 g of water, and stir at 75 ° C. for 15 minutes to prepare the substrate. A 1% by mass galactoxyloglucan aqueous solution containing 1% by mass was obtained. Using the purified enzyme β-galactosidase, a 1% by mass galactoxyloglucan aqueous solution was reacted at an enzyme concentration of 2.4 × ^10-5 % by mass at a pH of 5.6 and 50 ° C., and then heated at 100 ° C. for 20 minutes. , The reaction was stopped. The reaction solution gelled about 15 hours after the start of the reaction, whereby a gel-like composition was obtained. The galactose removal rate in the obtained gel-like composition was calculated by the following method.

Add 1 mL of cellulase Onozuka RS (Yakult Pharmaceutical Co., Ltd.) 0.15 mass% solution (50 mM acetate buffer, pH 4.0) to 7 g of the gel-like composition (1 mass% aqueous solution), and add 1 mL to 50 ° C. overnight. Reacted with. The 1% by mass galactoxyloglucan aqueous solution prepared above was also reacted in the same manner and used as a control. After the reaction, the enzyme was inactivated by heating the reaction solution at 98 ° C. for 30 minutes to obtain a sample. Then, the obtained sample was applied to a pretreatment cartridge (IC-SP manufactured by Toso Co., Ltd.) and a 0.45 μm cellulose acetate membrane filter, and 10 μL of the obtained filtrate was added to acetonitrile: water = 60: 40 (v /). Apply v) to an HPLC amino column running at 0.6 mL / min, and galactoxyloglucan oligosaccharides (7 sugars (0 galactose), 8 sugars (1 galactose), 9 sugars (2 galactose)). ) Was detected by a differential refractometer. Next, the amount of galactose per unit (7 sugars) was calculated by (area of 8 sugars + (area of 9 sugars × 2)) / (area of 7 sugars + area of 8 sugars + area of 9 sugars). The rate of decrease in the amount of galactose calculated for the gelled composition using the above formula from the amount of galactose calculated for the control galactoxyloglucan was further calculated as the galactose removal rate (%), and it was about 45%. there were.

Then, the gel-like composition obtained above was blown-dried, pulverized, and sieved to obtain a powdery galactose partial decomposition product.

(Test Example 1)
<Relationship between the presence or absence of polyphenols and the strength of the film>

(Preparation of aqueous solution of partially decomposed galactose)
Put 592.5 g of deionized water in a stainless beaker with a capacity of 1000 mL, add 7.5 g of the partially decomposed galactose obtained in Production Example 1, mix at room temperature, and stir in ice-warm water to 1 of the partially decomposed galactose. A .25 mass% aqueous solution was prepared.

(Preparation of aqueous polyphenol solution)
Put 600 mg of Sanphenone EGCg-OP (epigallocatechin gallate, manufactured by Taiyo Kagaku Co., Ltd.) as polyphenol in a polypropylene tube with a capacity of 50 mL, add deionized water and mix, and add 30 g of a 2% by mass aqueous solution of Sanphenon EGCg-OP. Prepared. The obtained 2% by mass aqueous solution of Sanphenone EGCg-OP was diluted with deionized water to prepare 0.1, 0.25, 0.50 and 1.00 mass% EGCg aqueous solutions.

(Preparation of a film in which a partial decomposition product of galactose and polyphenol are mixed in advance)
To a plastic dish having a diameter of 90 mm, 8 g of the galactose partial decomposition product aqueous solution and 0.1 mL of the 0.1 mass% EGCg aqueous solution were added (Example 1).
To a plastic dish having a diameter of 90 mm, 8 g of the galactose partial decomposition product aqueous solution, 0.1 mL of a 0.1 mass% EGC g aqueous solution, and 80 μL of a 50 mass% glycerin (glycerol) aqueous solution were added (Example 2).
Then, each mixture was allowed to stand in a dryer at 35 ° C. and dried overnight to prepare a film.
The film thus formed on the dish was used as a sample by cutting out a circular film having a diameter of about 24 mm using a commercially available belt punch.
The obtained sample was measured for strength and evaluated for flexibility by the following method. The results are shown in Table 1.

(Preparation of comparative film)
8 g of the above galactose partial decomposition product aqueous solution was added to a plastic dish having a diameter of 90 mm (Comparative Example 1).
To a plastic dish having a diameter of 90 mm, 8 g of the above galactose partial decomposition product aqueous solution and 80 μL of a 50 mass% glycerin aqueous solution were added (Comparative Example 2).
Then, it was allowed to stand in the dryer of 35 degreeC and dried overnight, and the galactose partial decomposition product film was prepared.
The film thus formed on the plastic dish was taken out from the plastic dish and cut into a circular film having a diameter of about 24 mm using a commercially available belt punch to use as a sample.
The obtained sample was measured for breaking strength and evaluated for flexibility by the following method. The results are shown in Table 1.

(Measuring method of breaking strength)
Two acrylic plates with holes with a diameter of 18 mm are stacked to form a set, and a silicone rubber with holes of the same shape and size is placed on the lower acrylic plate at the same position as the acrylic plate. Place the sample (circular film) so as to cover the hole, stack the upper acrylic plate on it, fix both ends of the two acrylic plates sandwiching the silicone rubber with double clips (one each on the left and right), and then fix them. The breaking stress of the fixed sample was measured using a creep meter (model: RE2-3305S, manufactured by Yamaden Co., Ltd.) (5 mm plunger, 1 mm / sec speed, unit: Pa). The results are shown in Table 1.
For the breaking stress in Table 1, the average value of the results of the two test tests is shown.

(Evaluation method of flexibility)
The sample (circular film) was grasped with both hands and bent while applying a force outward to the left and right, and the flexibility was examined depending on whether or not the sample cracked at this time, and evaluated according to the following evaluation criteria.
Sample does not crack: ○ (flexible)
Sample cracks: × (inflexible)

As shown in Table 1, the film containing EGCg had higher strength than the film containing no EGCg. Moreover, when glycerin was added, the strength of the film was smaller than that when glycerin was not added, but the flexibility was high.

(Test Example 2)
<Strength of film by immersing film-like composition in polyphenol aqueous solution>

(Preparation of film-like composition)
A film-like composition was prepared by adding 16 g of the above-mentioned 1.25 mass% galactose partial decomposition product aqueous solution to a plastic dish having a diameter of 90 mm, allowing it to stand in a dryer at 35 ° C., and drying it overnight. The water content of the film-like composition used was 3.7 ± 1.2% (mean ± standard deviation, n = 10).
The water content of the film-like composition is the difference between the mass of the galactose partially decomposed substance contained in the aqueous solution of the partially decomposed galactose added to the plastic dish and the mass of the film-like composition after drying. Calculated as a percentage of the mass of the composition ({(mass of the film-like composition after drying-mass of the partially decomposed galactose) / mass of the film-like composition after drying} × 100).

(Preparation of the film of the example)
The above-mentioned 2% by mass aqueous solution of EGCg-OP was diluted with deionized water to prepare 0.05, 0.1, 0.2, 0.5, 1 and 2% by mass EGCg aqueous solution.
After adding 5 mL each of 0.05, 0.1, 0.2, 0.5, 1 and 2% by mass of EGCg aqueous solution to the film-like composition on the plastic dish obtained in the preparation of the film-like composition. The film was prepared by closing the lid of the plastic dish, allowing it to stand at room temperature for a certain period of time (immersion time) shown in Table 2, and immersing it in a polyphenol solution.

(Preparation of comparative film)
A film was prepared by immersing the film-like composition only in deionized water without adding an EGCg aqueous solution (0% by mass) to the film-like composition on the plastic dish obtained by preparing the film-like composition. ..

The obtained film was taken out from a plastic dish and cut into a circular film having a diameter of about 24 mm using a commercially available belt punch to use as a sample.
Then, the thickness and the water content of the cut out sample were measured (n = 7). The results are shown in Table 2. The thickness was measured using a caliper.

The breaking stress of the obtained sample was measured by the above method. The results are shown in Tables 3 and 4. For the breaking stresses in Tables 3 and 4, the results of one test are shown respectively.

The resulting film was plotted with breaking stresses for the immersion time for each concentration of polyphenols shown in Tables 3 and 4. The results are shown in FIGS. 1 and 2.
FIG. 1 is a graph showing the relationship between immersion time and breaking stress for each polyphenol concentration (0% by mass to 2% by mass), and FIG. 2 is a graph showing the relationship between polyphenol concentration (0% by mass to 2% by mass). It is a graph showing the relationship between the immersion time within 10 minutes and the breaking stress.

(Evaluation of strength)
The film strength was examined by holding the obtained sample (circular film) with both hands and applying a force to the gel from side to side and outward, and evaluated according to the following evaluation criteria. The results are shown in Table 2.
Hard to tear: ○
Easy to tear: ×

As shown in Table 2, as the concentration of the aqueous polyphenol solution to be immersed increased, the thickness and water content of the film decreased. In particular, the film obtained by immersing in a 0.5% by mass to 2.0% by mass polyphenol aqueous solution is about 1/4 in thickness as compared with the film obtained by immersing in water (0% by mass). It decreased to a certain level, and the water content also decreased by about 10% to 40%.

As shown in Tables 3 and 4, even if the concentration of polyphenol in the aqueous polyphenol solution was 0.05% by mass, the strength of the film was increased by the addition. Further, as the polyphenol concentration increased, the strength increased several times to several hundred times.
As shown in FIG. 1, when the polyphenol concentration was 0.5% by mass or more, the increase in strength with the increase in concentration became small. This result is similar to the tendency of the thickness decrease shown in Table 2 described above.
As shown in FIG. 2, the improvement in strength due to the immersion of polyphenol was exhibited from a short time, but no significant increase in strength was observed even when measured for up to 2 days thereafter.
Therefore, the increase in intensity is considered to be extremely stable for at least a few days.
Therefore, it was found that by immersing the film-like composition in an aqueous polyphenol solution, a film having a stable and increased strength can be produced.
From the above results, in the film obtained by immersing in an aqueous solution of polyphenol, polyphenol penetrates into the intermolecules of the partially decomposed galactose in a relatively short time as compared with the film obtained by immersing in only water. It is presumed that this causes the elimination of some water molecules existing between the molecules and the accompanying cross-linking and aggregation by polyphenols, resulting in the development of strength.

(Test Example 3)
<Strength of a film when a film-like composition prepared by changing the concentration of a partially decomposed galactose aqueous solution is immersed in a polyphenol aqueous solution>

(Preparation of aqueous solution of partially decomposed galactose)
Put 298.5 g, 292.5 g, and 285 g of deionized water in a stainless beaker with a capacity of 500 mL, add 1.5 g, 7.5 g, and 15 g of the partially decomposed galactose obtained in Production Example 1, respectively, and mix at room temperature. , 0.5% by mass, 2.5% by mass, and 5% by mass aqueous solutions of the partially decomposed galactose were prepared by stirring in ice-warm water.

(Preparation of film-like composition)
To a plastic dish having a diameter of 90 mm, add 40 g of the above-mentioned aqueous solution of partially decomposed galactose in an amount of 40 g, 2.5% by mass of 8 g, and 5% by mass of 16 g, respectively, and allow the mixture to stand in a dryer at 35 ° C. and over. A film-like composition was prepared by drying with knight.

(Preparation of the film of the example)
After preparing a 0.1% by mass EGCg aqueous solution in the same manner as in Test Example 1 described above, 0.5% by mass and 2.5 with respect to each film-like composition on the plastic dish obtained by preparing the film-like composition. To the mass% film-like composition, 5 mL each of 0.1 mass% EGCg aqueous solution was added, while to the 5 mass% film-like composition, 20 mL of 0.1 mass% EGCg aqueous solution was added, and each plastic was added. A film was prepared by immersing the polyphenol solution by closing the lid of the dish and allowing it to stand at room temperature for 30 hours.
Similar to Test Example 1, the obtained film was taken out from a plastic dish and cut into a circular film having a diameter of about 24 mm using a commercially available belt punch to use as a sample.

The breaking stress of the obtained sample was measured in the same manner as in Test Example 1. The results are shown in Table 5. The breaking stress in Table 5 shows the results of one test.

As shown in Examples 49 and 50 of Table 5, even if the concentration of the galactose partial decomposition product aqueous solution is changed from 1.25% by mass (Test Example 1) to 0.5% by mass or 2.5% by mass, the film is formed. The state composition could be prepared. Further, a film having the same strength as when the film-like composition prepared from the 1.25 mass% galactose partial decomposition product aqueous solution was immersed in the 0.1 mass% polyphenol aqueous solution (corresponding to Examples 12 to 20) was prepared. We were able to.
Further, as shown in Example 51, even if the concentration of the galactose partial decomposition product aqueous solution was further increased to 5% by mass, a film having excellent strength could be produced.

Claims (5)

Contains partial decomposition of galactose from galactoxyloglucan and polyphenols,
The strength is higher than when the polyphenol is not added ,
A film in which the polyphenol is a tea extract . Contains partial decomposition of galactose from galactoxyloglucan, polyphenols and glycerin,
A film having higher strength than the case where the polyphenol was not added. The method for producing the film according to claim 1.
A method for producing a film, comprising a step of immersing a film-like composition obtained by dissolving a galactose partial decomposition product of galactoxyloglucan in water and drying a solution thereof in an immersion liquid containing polyphenol and water. .. The method for producing a film according to claim 3 , wherein the immersion liquid further contains glycerin. The method for producing a film according to claim 3 or 4 , wherein the concentration of the polyphenol in the dipping solution is 0.05 to 2.0% by mass.

Images