TWI787186B - Tablet type freeze-dried cosmetic - Google Patents

Abstract

The present invention provides a tablet type cosmetic excellent in ease of handling.

The tablet type cosmetic composition of the present invention comprises (A) 30 to 91% by mass of trehalose, (B) 4.0 to 16% by mass of polyethylene glycol having a molecular weight of 11000 to 25000, and a bulk specific gravity of 0.1 to 0.5 g/ ml.

Description

Tablet freeze-dried cosmetics

The present invention relates to a lozenge-type freeze-dried cosmetic, in particular to improving its ease of handling as a lozenge.

Usually, high-performance skin care cosmetics formulated with active ingredients are mainly supplied in the form of liquids such as lotion and beauty essence, and their effects can be exerted through daily habitual use.

On the other hand, in recent years, opportunities to perform skin care in tourist destinations, business trip destinations, competition venues, etc. have increased, and therefore there are products that are less burdensome to carry. Furthermore, due to the improvement of beauty awareness in recent years, there is a demand for high-quality products that can provide the same or higher satisfaction as daily maintenance for skin care cosmetics used outside.

In addition, it is not limited to the above-mentioned skin care cosmetics for carrying, but also for daily use or depending on the state of the skin. It is also highly required that the product be in a form that is portable and can be used individually.

As one of the means to meet the above-mentioned requirements, it is conceivable to use a liquid composition such as lotion as a dry preparation, which is redissolved in water at the time of use.

As a technology related to the dry preparation of liquid compositions, for example, in Patent Document 1, it is described that L-ascorbic acid-2-phosphate, which is unstable in the presence of water, and sugar alcohol and low Hygroscopic oligosaccharides and water-soluble polymers are mixed to form an aqueous solution, and freeze-dried to maintain stability until use.

In addition, in Patent Document 2, it is described that a freeze-dried cosmetic obtained by freeze-drying an aqueous solution containing sodium hyaluronate, collagen, and an ascorbic acid derivative has no shrinkage and no shrinkage due to moisture absorption even after long-term storage. Cracks, deterioration caused by bacteria or oxidation, etc., and can be dissolved in a very short time when redissolved with water or lotion during use.

Also, Patent Document 3 describes obtaining a hyaluronic acid solid composition stable at room temperature by freeze-drying an aqueous solution containing sodium hyaluronate and sugars.

In addition, Patent Document 4 also describes the use of powder or granular cosmetics of freeze-dried products containing hyaluronic acid or sodium hyaluronate and an aqueous solution of magnesium-L-ascorbate phosphate, which can improve the solubility of the two components in water.

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2004-149468

[Patent Document 2] Japanese Patent Laid-Open No. 2006-182750

[Patent Document 3] Japanese Unexamined Patent Publication No. 2003-95955

[Patent Document 4] Japanese Patent Application Laid-Open No. 2-215707

However, the freeze-dried compositions taught in Patent Documents 1 to 4 are not suitable in terms of releasability from containers, etc., or redissolution properties, and the use feeling of redissolved liquids as freeze-dried products formed into tablet shapes. It is not sufficient, and it is difficult to manufacture a tablet-shaped cosmetic material that is highly portable and easy to use. In particular, since the hygroscopicity during storage is low, there is currently no known technique for imparting solubility to tablets that can be dissolved instantaneously when water is added.

In view of the above circumstances, the present invention aims to provide a tablet-type freeze-dried cosmetic that is excellent in ease of handling.

In order to solve the above problems, the inventors of the present invention conducted careful examination and found that a tablet-shaped composition is formed by freeze-drying in a manner that contains polyethylene glycol and trehalose of a specific molecular weight and has a specific volume specific gravity. , the tablet-shaped composition is low in hygroscopicity but dissolves instantaneously when water is added, has high release properties, and is excellent in ease of handling, and further completed the present invention.

That is, the tablet-type freeze-dried cosmetic of the present invention contains: (A) 30 to 91% by mass of trehalose, and (B) 4.0 to 16% by mass of polyethylene glycol with a molecular weight of 11,000 to 25,000, and has a volume specific gravity of 0.1 to 0.5g/mL.

Among the aforementioned cosmetics, it is preferable to contain (B) polyethylene glycol having a number average molecular weight of 15,000 to 20,000.

Among the aforementioned cosmetics, it is preferable to contain (C) hyaluronic acid and (D) a thickener.

In the aforementioned cosmetics, it is preferable that the blending amount of (C) hyaluronic acid is 0.01 to 2% by mass.

In the aforementioned cosmetics, it is preferable that the blending amount of the (D) thickener is 0.01 to 1.0% by mass.

In the aforementioned cosmetics, it is preferred that (D) the tackifier is selected from Sanxian gum, tamarind gum, sodium alginate (sodium alginate), gellan gum (gellan gum), agar, polyvinyl alcohol, carboxyethylene Polymers, quince seed.

According to the present invention, by formulating trehalose and polyethylene glycol with a specific number and average molecular weight, a tablet-shaped freeze-dried cosmetic that is suitable for skin and the like and can be instantly dissolved by adding a small amount of water can be obtained. In addition, the aforementioned tablet-shaped cosmetics have extremely low hygroscopicity, and can be provided as cosmetics having portability and portability.

Also, when hyaluronic acid and a thickener are added, a tablet-type freeze-dried cosmetic with excellent usability can be obtained.

[Mode of Carrying Out the Invention]

Hereinafter, the present invention will be described in detail.

The tablet-type freeze-dried cosmetic of the present invention contains trehalose and polyethylene glycol with a specific number average molecular weight, and is basically produced from a uniformly dissolved/dispersed liquid of the components by volatilizing the medium. First, the constituent components of the present invention will be described.

<Excipient>

The components formulated as excipients in the present invention are (A) trehalose and (B) polyethylene glycol.

(A) Trehalose

The (A) trehalose used in the present invention is a 2-saccharide in the form of two D-glucose bonds, and its bonding mode has three types: α, α-, α, β-, β, β-, generally It is observed that most of them exist in the α,α-bonding mode in nature.

Trehalose, which is a kind of sugar, has a strong water retention capacity. Compared with sugars such as erythritol, xylitol, and sorbitol, it has better stability, resolubility, and release properties as freeze-dried cosmetics. It is superior in point of view.

In cosmetics, the blending amount of trehalose is preferably 30 to 91% by mass. Moreover, when it is 65 to 91 mass %, it is more preferable at the point which is excellent in high-temperature stability. When it is less than 30% by mass, it is unfavorable in terms of high temperature stability and solubility in water at the time of redissolving may be insufficient. Also, when it exceeds 91% by mass, it is excellent in high temperature resistance, but it is not good in the point of being difficult to freeze and bumping, and in terms of usability.

As a commercial item of trehalose, Trehalose (for cosmetics) (manufactured by Hayashibara Co., Ltd.) etc. are mentioned, for example.

In addition to trehalose, other saccharides may be added within the range of not impairing the effect of the present invention.

Examples thereof include maltose, maltotetraose, maltosyl trehalose and the like.

(B) polyethylene glycol

Examples of (B) polyethylene glycol used in the present invention include those having a number average molecular weight of 11,000 to 20,000 from the point of view of lozenge excipient properties. Preferably, if it is 15,000 to 20,000, it is more preferable from the point of moldability and releasability.

When the number average molecular weight is less than 11,000, it is unfavorable from the point of view that the release property may deteriorate. Moreover, when the number average molecular weight exceeds 20,000, it is unfavorable from the viewpoint that resolubility may be poor and the usability may be poor.

In cosmetics, the blending amount of (B) polyethylene glycol is preferably from 4 to 16% by mass, more preferably from 12 to 16% by mass. When more than 16% by mass is blended, the release property and usability of the tablet may decrease.

In addition, the aforementioned polyethylene glycol may be synthesized by a known synthesis method, or a commercially available product may be used.

As a commercial item of polyethylene glycol, PEG-20000 (made by Sanyo Chemical Industry Co., Ltd.), etc. are mentioned, for example.

(C) Hyaluronic Acid

The (C) hyaluronic acid used in the present invention is a straight-chain macromolecule in which N-acetyl-D-glucosamine residues and D-glucuronic acid residues are interactively bonded, and it can be processed into powder Wait.

The aforementioned hyaluronic acid, for example, can be isolated and extracted from cockscombs or other animal tissues, or obtained by fermentation with microorganisms such as Streptococcus. In addition, in the present invention, for example, as hyaluronic acid derivatives, hyaluronic acid metal salts such as hyaluronic acid sodium salt and hyaluronic acid potassium salt can be used, or hyaluronic acid can be etherified, esterified, amidated, etc. Powder of hyaluronic acid derivatives obtained by acylation, acetalization, and ketalization.

In addition, commercially available hyaluronic acid can also be used. Examples of commercially available hyaluronic acid include hyaluronic acid HA-LQ (manufactured by QP Fine Chemicals), hyaluronic acid FCH (manufactured by Kikkoman Biochemifa Co., Ltd.), and the like.

Moreover, the molecular weight of (C) hyaluronic acid is not specifically limited, Preferably it is 100,000 or more, More preferably, it is about 500,000 to 3 million. When using hyaluronic acid with a low molecular weight of less than 100,000, the formability of tablets and the feeling of use after redissolving may not be sufficient. Moreover, when the molecular weight exceeds 3 million, it is unfavorable from the point that solubility and the usability after redissolving may be insufficient.

Among the above-mentioned excipients, especially (C) hyaluronic acid exhibits extremely high viscosity even in a low-concentration aqueous solution state, so its compounding amount has a high correlation with the properties of the freeze-dried tablet and its reconstitution solution .

In cosmetics, the blending amount of (C) hyaluronic acid is preferably 0.01 to 2% by mass, more preferably 0.05 to 0.2% by mass. When blending exceeds 2% by mass, it is not preferable because the solubility or release property of the tablet decreases.

(D) Tackifier

The (D) thickener used in the present invention is used to improve the moldability and release properties of tablet cosmetics.

As the (D) thickener, water-soluble polymers such as sanxian gum, tamarind gum, sodium alginate, gellan gum, agar, polyvinyl alcohol, carboxyvinyl polymer, and quince seeds can be used. Among them, it is preferable to use sanxian gum, tamarind seed gum, and quince seed in terms of stickiness and less stretchy feeling during drying when using lozenge cosmetics.

In cosmetics, the blending amount of the (D) thickener is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.1% by mass. When the compounding amount exceeds 1.0% by mass, the release property and the feeling of use of the tablet may decrease, and when the compounding amount is less than 0.01 mass%, the moldability and the release property may decrease.

Commercially available products of such thickeners include, for example, sanxian gum (Keltrol, manufactured by Kelco), tamarind gum (Glyloid 6C, manufactured by Dainippon Pharmaceutical Co., Ltd.), sodium alginate (Duck Algin NSPH, Kikkoman Biochemifa Co., Ltd.), gellan gum (Kelco Gel, DSP Gokyo Food & Chemical Co., Ltd.), agar (Ina Agar CS-110, Ina Food Industry Co., Ltd.), and the like.

In addition, the tablet-type freeze-dried cosmetic of the present invention may contain other components that are usually formulated in cosmetics or quasi-drugs in addition to the above-mentioned components within the range that does not impair the effects of the present invention. Also, in dry cosmetics, there is no problem even if it contains 1 to 5% by mass of water.

In the production of the present invention, it is preferable to use water-based components as other components, but it is also possible to prepare an oil-based component by solubilizing with a surfactant or the like.

As an aqueous component, a polyhydric alcohol, the water-soluble polymer other than (D)component, a chelating agent, a pH adjuster, a preservative, etc. are mentioned, for example.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butanediol, glycerin, polyethylene glycol and polyglycerin having molecular weights other than those described above.

Examples of water-soluble polymers include polymers other than those mentioned above. For example, examples of hydrophilic synthetic polymers include polyacrylic acid, polyethylene glycol, polyacrylamide, and polyalkylacrylamide/polyacrylamide copolymers. , carboxymethyl cellulose, cationized cellulose, Pluronic, macrogol, povidone, polyethylene methacrylate, polyethyleneimine, etc.; as hydrophilic Natural natural polymers, such as succinic acid, guar gum, locust bean gum, curdlan gum, alginic acid, carrageenan, and mannan , pectin, gum arabic, Sterculia urens gum, casein, alpha-cyclodextrin, dextrin, dextran, gelatin, collagen, pectin, starch, chitin and its derivatives Chitosan and its derivatives, elastin, heparin, heparan sulfate, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, etc. ; Examples of the hydrophilic clay minerals include laponite, bentonite, and bentonite.

Examples of the chelating agent include 1-hydroxyethyl-1,1-disulfonic acid, 1-hydroxyethyl-1,1-disulfonic acid tetrasodium salt, disodium edetate, ethylenediamine Trisodium Tetraacetate, Tetrasodium EDTA, Sodium Citrate, Sodium Polyphosphate, Sodium Metaphosphate, Gluconic Acid, Phosphoric Acid, Citric Acid, Ascorbic Acid, Succinic Acid, EDTA, Ethylenediamine Hydroxyethyl Trisodium triacetate, etc.

Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

Examples of preservatives include paraoxybenzoate, phenoxyethanol and the like.

Moreover, as an oily component, a fragrance|flavor, an oily drug (for example, vitamin A etc.) is mentioned, for example.

In addition, as ingredients that can be formulated, for example, humectants (for example, 2-methacryloyloxyethyl phosphorylcholine (2-Methacryloyloxyethyl phosphorylcholine, MPC) copolymer, PEG/PPG-14/7 dimethyl ether such as PEG/PPG dimethyl ether, water-soluble collagen, hydrogen peroxide-treated yeast hydrolyzate, sodium dl-pyrrolidone carboxylate, L-hydroxysupplementine, calcium chloride, magnesium chloride); various extracts (eg, Rose, Phellodendron, Cotton Lotus, Purple Root, Peony, Japanese Swertia (Swertia japonica), Birch, Sage (Salvia officinalis), Loquat, Carrot, Aloe Vera, Mallow (Malva sylvestris), Iris, Grapes, Barley , loofah, lily, saffron (Saffron), Chuanxiong, ginger, Hypericum erectum, Ononis spinose, garlic, pepper, tangerine peel, angelica, seaweed, etc.); other water-soluble agents (for example, Active ingredients such as tranexamic acid can impart desired effects to the cosmetic of the present invention by formulating such active ingredients.

In addition, the thickener and trehalose which are essential components can also impart a moisturizing effect to the present invention.

The tablet-type freeze-dried cosmetic of the present invention is obtained by dissolving or dispersing the above-mentioned compounded ingredients in volatile liquid media such as water and lower alcohols, preparing the solution before drying, freezing it, and sublimating it under reduced pressure to obtain a residual dry matter.

In the production of tablet-type freeze-dried cosmetics of the present invention, the above-mentioned excipient components dissolved in a medium such as water form a three-dimensional network structure in the medium. If only the medium is removed from such a state, the mesh structure shrinks due to drying, causing distortion or collapse, and it is generally difficult to maintain the structure. However, in the present invention, since the trehalose formulated together with the aforementioned excipient supports the network structure instead of the medium after volatilization of the medium, it is presumed that the structure formed by the excipient is almost maintained.

In addition, the dry product with the three-dimensional network structure of the excipient maintained is a porous state in which the medium part is removed from the structure, and when water is added for redissolution, water penetrates into the network structure from each hole to form a tablet. Dissolution of the entire preparation. In this case, the higher the density of the constituents containing the above-mentioned structure, the more difficult it is for water to permeate inside, and the dissolution of the preparation becomes difficult. On the other hand, when the density of the constituent components is too low, the preparation itself becomes fragile and easily collapses, and also absorbs moisture easily during storage.

Therefore, in order to make a preparation that has water that will permeate instantly to collapse the solubility of the preparation, and on the other hand, has extremely low hygroscopicity during storage, it is necessary to further set the volumetric specific gravity of the constituents within a certain range. .

Therefore, in the tablet-type cosmetic of the present invention, the above-mentioned constituents must be contained, and the volume specific gravity thereof is set to 0.1 to 0.5 g/mL, preferably 0.15 to 0.3 g/mL.

When the volumetric specific gravity is less than 0.1 g/mL, the hygroscopicity during storage tends to increase, and when it exceeds 0.5 g/mL, the solubility to water tends to decrease. On the other hand, if the volume specific gravity is within the above range, the pores of the pumping medium become moderate, and the network structure of the thickener is also fixed in a moderately diffused state, and when water is added for redissolution, there is very good dissolution. sex.

As a measuring method of volume specific gravity, it calculated from the weight (g) of the tablet after freeze-drying÷the volume (mL) of the freeze-drying mold.

The tablet-type cosmetic of the present invention is, for example, prepared by filling a tablet mold with a solution in which constituent components are dissolved or dispersed in a volatile liquid medium such as water or a lower alcohol, then freeze-drying it, and removing it from the The aforementioned mold is taken out and manufactured.

The present invention can be molded into any size and shape by setting the volume of the preparation and the amount of constituent components and media to satisfy the above-mentioned volume specific gravity.

However, an extremely thin shape or an overly complicated shape is not preferable because of problems such as formability.

In addition, the present invention has low hygroscopicity of the preparation, and high release property and is easy to be peeled off from the container, so it is not limited to the packaging form (for example, a blister pack) that is directly dispensed into the amount of each use in the state filled in the container. Blister pack) may be packaged in any form by simply peeling off the preparation from the container (mold).

The tablet-type cosmetic of the present invention can usually be used by adding an appropriate amount of water to redissolve the preparation, and applying the solution to the skin or the like. The amount of water to be added can be adjusted to a viscosity that is easy to apply based on the degree at which the preparation will completely dissolve as the lower limit. However, if it is too large, the concentration of the ingredients will be too low and sufficient effects may not be obtained. If it is too small, the coating will become sticky. Case. Therefore, although there is no particular limitation, it is preferable to adjust the addition amount to about 1 to 10 times the volume of the formulation.

In addition, the place where water is added to the preparation can be on the palm or on the application site, or in an appropriate container, etc. However, as the method of use of the present invention, it is preferable to put the dosage of the preparation at one time on the palm and add it to the preparation. After watering, apply the solution on the palm of the hand directly to the affected area.

In addition, if the formulation can be redissolved, lotion or the like may be used instead of water.

The ingot-shaped cosmetics of the present invention can be made into lotion, beauty lotion, facial mask, makeup remover, facial cleanser, hand cream, shampoo, conditioner, hair conditioner, sunscreen, etc. according to the formulated ingredients. In the form of products, it is especially suitable for use as lotion or beauty essence for moisturizing.

[Example]

Hereinafter, although an Example is given and this invention is described in detail, this invention is not limited to these. Unless otherwise specified, the compounded amount is expressed in mass % relative to the system in which the component is compounded.

First, the evaluation method and evaluation criteria used in the next surgery test will be described.

<Solubility>

The tablet-type freeze-dried cosmetic (about 100 mg) of each test example was placed on the palm of the hand, 500 μl of water was dripped, and the time required for mixing with fingers until the formulation was completely dissolved was evaluated according to the following criteria.

A: The preparation dissolves completely in an instant.

B: The preparation takes some time but dissolves completely.

C: The preparation is slightly insoluble and a part remains.

D: The formulation is poorly soluble and produces residue.

E: The formulation does not dissolve.

<usability>

Put the tablet-type freeze-dried cosmetic (about 100 mg) of each test example on the palm of your hand, add 500 μl of water to dissolve it, and evaluate the feeling of use (moisture, non-sticky feeling, smoothness of the skin) when applied to the skin. ), evaluated by a 10-member panel based on the following criteria.

A: More than 6 out of 10 responded that the product feels good in use.

B: 3 or more out of 10 and less than 6 answered that the feeling of use was good.

C: Less than 3 out of 10 responded that the feeling of use was good.

<Release>

After the drying step of the method for producing tablet-type freeze-dried cosmetics in each test example, the ease of detachment when the dried product was taken out of the container was evaluated according to the following criteria.

A: The preparation was very easily peeled off from the container.

B: The formulation was easily peeled from the container.

C: The preparation was slightly difficult to peel from the container.

D: The preparation was very difficult to peel from the container.

<formability>

The formability after the drying step of the manufacturing method of the tablet-type freeze-dried cosmetic of each test example was evaluated according to the following criteria.

A: The preparation is shaped from the container according to the forming die.

B: The formulation is shaped from the container approximately in accordance with the forming die.

C: The formulation produced small cracks from the container but could be molded.

D: The preparation was shrunk from the container, etc. and was not shaped according to the forming die.

E: The preparation has large cracks in the container or cracks due to fragility.

Compositions of test examples with formulations described in the following tables were prepared according to the following production methods.

<Manufacturing method>

Dissolve or disperse various formulated ingredients in volatile liquid media such as water or lower alcohols, inject them into forming molds, freeze, decompress and sublimate, and then remain as dry matter to obtain tablet-shaped freeze-dried cosmetics.

First, the present inventors examined the influence of sugar used as an excipient on the moldability of tablet cosmetics.

The formulations of the test examples shown in Table 1 below are as follows.

From this, it can be seen that trehalose is preferably used as the basic skeleton of the excipient among various sugars from the viewpoint of formability.

Therefore, the inventors of the present invention examined the preparation amount of trehalose relative to the solution before drying as follows. The compounded amounts in Table 2 are not in the freeze-dried cosmetics, but represent the compounded amounts of each component in the solution before drying.

From Test Examples 2-1 to 2-6, it can be seen that when the amount of trehalose formulated in the solution before drying exceeds 20% by mass, bumping occurs, which is unfavorable from the viewpoint of formability. Also, in terms of resolubility, when the prepared amount of trehalose exceeds 20% by mass relative to the solution before drying, insoluble residues are not preferable.

Then, the present inventors examined whether the moldability and release property of the tablet-shaped cosmetic after freeze-drying could be improved by adding (B) polyethylene glycol in solution as another component before drying. The compounded amounts in Table 3 are not freeze-dried cosmetics, but represent the compounded amounts of each component in the solution before drying.

(＊1)Trehalose; made by Hayashibara Co., Ltd.

From Test Examples 3-1 to 3-2, it can be seen that adding (B) polyethylene glycol to the solution before drying becomes an excipient with excellent formability and release property while maintaining resolubility.

The present inventors further examined usability as a lozenge cosmetic.

(＊3)BioHyalo 12; manufactured by Shiseido

(*4) Glyloid 6C; manufactured by Dainippon Pharmaceutical Co., Ltd.

(＊5) Lipdure-PMB (Ph10); made by NOF

It can be seen from Table 4 and Table 5 that in order to improve the usability of tablet cosmetics, by adding (B) polyethylene glycol and adding humectants and thickeners, the formability and release properties can be maintained. , Re-solubility, improve usability.

Secondly, the number average molecular weight of the formulated (B) polyethylene glycol was checked.

From Test Examples 6-1 to 6-7, it can be seen that the number average molecular weight of (B) polyethylene glycol is preferably 4,000 to 20,000 in terms of formability and usability.

Test Examples 7-1 to 7-6 are tablet cosmetics that are excellent in resolubility and usability, and also excellent in high temperature stability.

The formulation example of the tablet type freeze-dried cosmetic (cleaning agent) of the present invention is as follows.

The formulation example of the tablet type freeze-dried cosmetic (hair care treatment) of the present invention is as follows.

The formulation of the tablet-type freeze-dried cosmetic (shampoo) of the present invention is as follows.

Formulation examples 4 to 7 of the tablet-type freeze-dried cosmetic (cosmetic for skin application) of the present invention are as follows.

Claims (6)

A tablet-type freeze-dried cosmetic, which contains: (A) 30 to 91% by mass of trehalose, and (B) 4.0 to 16% by mass of polyethylene glycol with a molecular weight of 11,000 to 25,000, and has a volume specific gravity of 0.1 to 0.5 g/mL. The tablet-type freeze-dried cosmetic according to item 1 of the patent application, which contains (B) polyethylene glycol with a molecular weight of 15,000 to 25,000. The tablet-type freeze-dried cosmetic as described in item 1 or item 2 of the patent application, which contains (C) hyaluronic acid and (D) thickener. The tablet-type freeze-dried cosmetic as described in item 1 or item 2 of the patent application, wherein the compounding amount of (C) hyaluronic acid is 0.01 to 2% by mass. The tablet-type freeze-dried cosmetic as described in item 4 of the patent application, wherein the blending amount of (D) thickener is 0.01 to 1.0% by mass. The tablet-type freeze-dried cosmetic as described in item 4 of the scope of the patent application, wherein (D) the thickener is selected from Sanxian gum, tamarind gum, sodium alginate, gellan gum, agar, polyvinyl alcohol, carboxyl Ethylene polymer, quince seeds.