JPWO2007086389A1 - Water-soluble polysaccharide derived from rice bran, process for producing the same, and emulsifier using the same - Google Patents

Water-soluble polysaccharide derived from rice bran, process for producing the same, and emulsifier using the same Download PDF

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JPWO2007086389A1
JPWO2007086389A1 JP2007555956A JP2007555956A JPWO2007086389A1 JP WO2007086389 A1 JPWO2007086389 A1 JP WO2007086389A1 JP 2007555956 A JP2007555956 A JP 2007555956A JP 2007555956 A JP2007555956 A JP 2007555956A JP WO2007086389 A1 JPWO2007086389 A1 JP WO2007086389A1
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名苗 藤井
名苗 藤井
戸邉 順子
順子 戸邉
中村 彰宏
彰宏 中村
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Abstract

米糠を有効活用するべく、効率よく水溶性の多糖類を抽出することを課題とした。ダイエタリーファイバーとしての機能の他に食品の物性や機能を改良する機能性素材として利用できないか検討することを目的とした。米糠を高温条件下、酸性条件で抽出し、細胞壁構成成分である機能性多糖類を効率よく抽出できる知見を得るに到った。加えて本発明の水溶性多糖類はダイエタリーファイバーとしての機能の他に乳化剤として機能する知見を得るに到った。In order to make effective use of rice bran, an object was to efficiently extract water-soluble polysaccharides. In addition to its function as a dietary fiber, the purpose was to examine whether it could be used as a functional material to improve the physical properties and functions of food. Rice bran was extracted under acidic conditions under high temperature conditions, and the knowledge that functional polysaccharides that are cell wall constituents can be efficiently extracted was obtained. In addition, the present inventors have found that the water-soluble polysaccharide of the present invention functions as an emulsifier in addition to the function as a dietary fiber.

Description

本発明は、米糠由来の水溶性多糖類およびその製造法に関し、詳しくは米糠から高温条件下、酸性条件で抽出することによる、乳化及び乳化安定機能に優れた米糠水溶性多糖類およびその製造法及び使用法に関する。   The present invention relates to a water-soluble polysaccharide derived from rice bran and a method for producing the same. And usage.

現在日本では年間100万tの米糠が精米の過程で排出されている。米糠のうち約40%は搾油の原料として使用されているが、その過程で生じる脱脂米糠はこれまで有効活用されることなく産業廃棄物として処理されるか、焼却処分されていた。   Currently in Japan, 1 million tons of rice bran is discharged during the milling process. About 40% of rice bran is used as a raw material for oil extraction, but the defatted rice bran produced in the process has been treated as industrial waste or incinerated without being effectively utilized so far.

米糠から多糖類成分を抽出する方法として、水性溶媒で抽出する方法、および酵素処理により細胞壁を部分的に分解することによって抽出する方法が報告されている。水性溶媒で抽出する場合、常圧で抽出を行なうとpH条件にかかわらず抽出効率が3.5重量%から8重量%と低い(特許文献1,2)。また100MPa以上と高圧条件でも常温であると同様に収率が低い(特許文献3)。また130℃,2MPaといった高温加圧条件下でも、pH未調整では試料をエクストルーダー等によりせん断しなければ効率よく多糖類を得ることができなかった(特許文献4)。高温加圧条件でも中性下での抽出効率は悪く、酵素分解の併用が必要である(特許文献5)。これら従来の米糠多糖類は食物繊維強化(ダイエタリーファイバー)としての用途が多く、食品の物性や機能を改善する機能性は見出されていない。   As a method for extracting polysaccharide components from rice bran, a method of extracting with an aqueous solvent and a method of extracting by partially decomposing a cell wall by an enzyme treatment have been reported. In the case of extraction with an aqueous solvent, when extraction is performed at normal pressure, the extraction efficiency is as low as 3.5 to 8% by weight regardless of pH conditions (Patent Documents 1 and 2). In addition, the yield is low as well at room temperature even under high pressure conditions of 100 MPa or more (Patent Document 3). Even under high temperature and pressure conditions such as 130 ° C. and 2 MPa, polysaccharides could not be efficiently obtained unless the sample was sheared with an extruder or the like if the pH was not adjusted (Patent Document 4). Even under high temperature and pressure conditions, the extraction efficiency under neutrality is poor, and a combination of enzymatic decomposition is required (Patent Document 5). These conventional rice bran polysaccharides have many uses as dietary fiber reinforcement (dietary fiber), and the functionality which improves the physical property and function of food is not found.

特公平6-11764 公報Japanese Patent Publication No.6-11764 特開平5-112455 公報Japanese Patent Laid-Open No. 5-112455 特許第3098553 公報Japanese Patent No.3098553 特公平2-100644 公報Japanese Patent Publication No. 2-100644 特開平5-219976 公報Japanese Patent Laid-Open No. 5-219976

米糠を有効活用するべく、効率よく水溶性の多糖類を抽出し、更にダイエタリーファイバーとしての機能の他に、食品の物性や機能を改良する機能性素材として利用することを課題とした。   In order to make effective use of rice bran, water-soluble polysaccharides were efficiently extracted, and in addition to the function as a dietary fiber, the problem was to use it as a functional material that improves the physical properties and functions of food.

上記課題を解決すべく鋭意研究した結果、米糠を高温条件下、酸性条件で抽出し、細胞壁構成成分である機能性多糖類を効率よく抽出できる知見を得るに到った。加えて本発明の水溶性多糖類はダイエタリーファイバーとしての機能の他に、例えば酵素による更なる加水分解処理等を行なうことなく、乳化剤として機能する知見を得るに到った。本発明はかかる知見に基づいて完成されたものである。   As a result of diligent research to solve the above problems, rice bran was extracted under acidic conditions under high temperature conditions, and it was found that functional polysaccharides that are cell wall constituents can be efficiently extracted. In addition, in addition to the function as a dietary fiber, the water-soluble polysaccharide of the present invention has come to the knowledge that it functions as an emulsifier without performing further hydrolysis treatment with an enzyme, for example. The present invention has been completed based on such findings.

すなわち本発明は、
(1)pH2.5以上pH4以下、且つ95℃以上140℃以下の処理により、米糠から水溶性画分を抽出することを特徴とする、水溶性多糖類の製造法。
(2)処理後に脱塩精製を行なうことを特徴とする、(1)に記載の多糖類の製造法。
(3)pH2.5以上pH4以下、且つ95℃以上140℃以下の処理により、米糠から水溶性画分を抽出して得た水溶性多糖類。
(4)(3)に記載の水溶性多糖類を有効成分とする乳化剤。
である。
That is, the present invention
(1) A method for producing a water-soluble polysaccharide, wherein a water-soluble fraction is extracted from rice bran by treatment at pH 2.5 or more and pH 4 or less and 95 ° C. or more and 140 ° C. or less.
(2) The method for producing a polysaccharide according to (1), wherein desalting and purification are performed after the treatment.
(3) A water-soluble polysaccharide obtained by extracting a water-soluble fraction from rice bran by treatment at pH 2.5 to pH 4 and 95 ° C. to 140 ° C.
(4) An emulsifier comprising the water-soluble polysaccharide according to (3) as an active ingredient.
It is.

米糠から酸性条件で95℃以上の高温で抽出することにより、効率良く水溶性多糖類を得ることができ、得られた水溶性多糖類は、乳化安定剤として機能を有していた。また本発明の多糖類を用いることで、上記機能に優れた食品を得ることが出来た。   By extracting from rice bran under acidic conditions at a high temperature of 95 ° C. or higher, a water-soluble polysaccharide could be obtained efficiently, and the obtained water-soluble polysaccharide had a function as an emulsion stabilizer. Moreover, the food excellent in the said function was able to be obtained by using the polysaccharide of this invention.

本発明に用いる米糠とは、米を精米する際に副生する米糠全般を指し、また脱脂米糠等を含む。米糠は不飽和脂肪酸に富む油脂分を多く含み、過酸化物となり風味上問題が起きやすいので、予めヘキサン等で脂質を脱脂した脱脂米糠が原料として好ましい。   The rice bran used in the present invention refers to all rice bran produced as a by-product when rice is polished, and includes defatted rice bran and the like. Rice bran contains a large amount of fats and oils rich in unsaturated fatty acids, and becomes a peroxide and easily causes a problem in flavor. Therefore, defatted rice bran obtained by defatting lipids with hexane or the like in advance is preferred as a raw material.

米糠多糖類の製造法を具体的に説明すると以下のようである。米糠をそのままあるいは粉砕し、これに加水を行ない、pH2.5以上pH4以下で95℃以上の温度域で高温抽出をおこなう。より低pH域になると多糖類の加水分解が促進され、全糖中の還元糖の割合が非常に高くなり、高分子画分の収率が低下する。また、抽出温度は95℃を切ると収率が悪化し、得られた抽出物は灰分等の夾雑物が増加する。高温になるに従って収率は増加するが、多糖類の加水分解が進むため、95℃以上140℃以下、好ましくは105℃以上140℃以下、より好ましくは110℃以上130℃以下の温度域で抽出することが望ましい。100℃を超える加熱は、加圧容器等の加圧下で行なわれる。抽出時間は特に制限されるわけではないが、2分から2時間程度であることが好ましい。   The method for producing rice bran polysaccharide will be described in detail as follows. Rice bran is crushed as it is or pulverized, and water is added to the rice bran. When the pH is lower, hydrolysis of the polysaccharide is promoted, the ratio of reducing sugar in the total sugar becomes very high, and the yield of the polymer fraction decreases. In addition, when the extraction temperature is below 95 ° C., the yield deteriorates, and the obtained extract increases impurities such as ash. The yield increases as the temperature increases, but the hydrolysis of the polysaccharide proceeds, so extraction is performed at a temperature range of 95 ° C to 140 ° C, preferably 105 ° C to 140 ° C, more preferably 110 ° C to 130 ° C. It is desirable to do. Heating exceeding 100 ° C. is performed under pressure in a pressurized container or the like. The extraction time is not particularly limited, but is preferably about 2 minutes to 2 hours.

高温抽出時にpHを調整する際の酸には特に制限はなく、いずれのものも利用できるが、酸性条件にするために塩酸,硫酸,リン酸等の無機酸、あるいは酢酸,クエン酸,乳酸,シュウ酸等の有機酸を使用することが出来る。   There are no particular restrictions on the acid used to adjust the pH during high-temperature extraction, and any acid can be used. However, in order to achieve acidic conditions, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, or acetic acid, citric acid, lactic acid, Organic acids such as oxalic acid can be used.

得られた抽出液のpHを任意に調整し、水溶性画分を遠心分離等により分離する。このpH調整の際に水酸化ナトリウム,水酸化カリウム,水酸化カルシウム,アンモニア等のアルカリを用いることが出来る。こうして得られた多糖類はそのまま乾燥して利用することも出来るが、混在する夾雑物を除去するために更なる精製をする方が好ましい。   The pH of the obtained extract is arbitrarily adjusted, and the water-soluble fraction is separated by centrifugation or the like. In this pH adjustment, an alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia or the like can be used. The polysaccharide thus obtained can be dried and used as it is, but it is preferable to carry out further purification in order to remove mixed impurities.

脱塩精製処理の方法として、メタノール,エタノール,イソプロパノール,アセトン等の極性有機溶媒を用いた沈殿法、電気透析処理,イオン交換樹脂あるいは疎水性樹脂、UF膜を用いた膜分画等が例示できる。これらの一法又は二法以上を組み合わせて用いることが出来る。中でも極性有機溶媒による沈澱法が効率的で好ましく、特にエタノールの使用が好ましい。こうして精製された米糠多糖類溶液を凍結乾燥、スプレードライ等により乾燥させ、粉体の米糠多糖類が得られる。   Examples of the desalting and purification treatment include precipitation using a polar organic solvent such as methanol, ethanol, isopropanol, and acetone, electrodialysis, ion exchange resin or hydrophobic resin, and membrane fractionation using a UF membrane. . One of these methods or two or more methods can be used in combination. Of these, the precipitation method using a polar organic solvent is efficient and preferable, and ethanol is particularly preferable. The purified rice bran polysaccharide solution is dried by freeze drying, spray drying or the like to obtain a powdered rice bran polysaccharide.

本発明で得られた多糖類の溶液の粘度は、特に制限されるものではないが5重量%溶液で20℃において50cP・s、好ましくは20cP・s以下の低粘度である。米糠水溶性多糖類の構成糖は特開平11-049682に記載の方法で分析した結果、グルコースとアラビノースを構成糖とする。得られた多糖類はいずれもゲル濾過HPLC(TSKgel-G-5000 PWXL ; TOHSO)で分析した平均分子量が100万以下、好ましくは50万以下の分子量を示す。この多糖類の平均分子量は、標準物質プルラン(昭和電工(株))を標準物質として測定した値である。   The viscosity of the polysaccharide solution obtained in the present invention is not particularly limited, but it is a low-viscosity of 5 wt% solution at 50 ° C., preferably 20 cP · s or less at 20 ° C. As a result of analyzing the constituent sugars of the rice bran water-soluble polysaccharide by the method described in JP-A-11-049682, glucose and arabinose are used as constituent sugars. All the obtained polysaccharides have a molecular weight of 1 million or less, preferably 500,000 or less, as analyzed by gel filtration HPLC (TSKgel-G-5000 PWXL; TOHSO). The average molecular weight of this polysaccharide is a value measured using a standard substance pullulan (Showa Denko KK) as a standard substance.

本発明の水溶性多糖類は単独で乳化剤として利用することが出来る。また、他の品質改良剤や乳化剤も併用することが出来る。本乳化剤はいかなるpH域でも乳化物を作ることが可能であるが、pH4〜pH9で乳化物を作ることが好ましく、pH6〜pH8の中性pH域がより好ましい。添加量は特に限定されるものではないが、乳化物中への添加量が0.05重量%から25重量%、好ましくは0.1重量%から15重量%により、油分5重量%から50重量%の乳化物を作ることが出来る。本水溶性多糖類の添加時期についても特に制限されるものではないが、水相に予め溶解するか、油相に分散する事により乳化物を得ることが出来る。   The water-soluble polysaccharide of the present invention can be used alone as an emulsifier. Other quality improvers and emulsifiers can also be used in combination. Although this emulsifier can make an emulsion in any pH range, it is preferable to make an emulsion at pH 4 to pH 9, and a neutral pH range of pH 6 to pH 8 is more preferable. The addition amount is not particularly limited, but the addition amount in the emulsion is 0.05 to 25% by weight, preferably 0.1 to 15% by weight, and the emulsion has an oil content of 5 to 50% by weight. Can be made. The addition timing of the water-soluble polysaccharide is not particularly limited, but an emulsion can be obtained by dissolving in advance in the aqueous phase or dispersing in the oil phase.

以下実施例を例示して本発明を説明するが、これらは例示であって本発明の内容がこれらの例示によって制限されるものではない。なお例中の%は特にことわらない限り重量基準を意味するものである。   Hereinafter, the present invention will be described by way of examples, but these are examples and the contents of the present invention are not limited by these examples. In the examples, “%” means a weight basis unless otherwise specified.

市販の脱脂米糠150gを3kgに加水して塩酸を用いてpH2〜7に調整した。これらを110℃,90分加圧加熱して水溶性多糖類を抽出した。pHを7に調整後、得られたスラリーを遠心分離し(8000 G×30分、室温)、上清にエタノールを60%濃度となるように加えた。沈殿を遠心分離(8000 G×30分、室温)により回収し、凍結乾燥した。表1は、この実施例により得られた米糠多糖類の組成分析値を示す。これら多糖類の組成分析法として、全糖はフェノール硫酸法、澱粉はヨウ素澱粉法、還元糖はソモジ・ネルソン法、ウロン酸はBlumenkrantz法、粗蛋白質はケルダール法を用いて定量した。尚、水溶化率とは原料の固形分に対して加熱抽出後に水溶化した固形分の割合を、エタ沈収率とは原料の固形分に対してエタノール沈澱の固形分の割合を、それぞれ重量%で示した値である。   150 g of commercially available defatted rice bran was added to 3 kg and adjusted to pH 2-7 using hydrochloric acid. These were heated under pressure at 110 ° C. for 90 minutes to extract water-soluble polysaccharides. After adjusting the pH to 7, the obtained slurry was centrifuged (8000 G × 30 minutes, room temperature), and ethanol was added to the supernatant to a concentration of 60%. The precipitate was collected by centrifugation (8000 G × 30 minutes, room temperature) and lyophilized. Table 1 shows the compositional analysis values of the rice bran polysaccharides obtained by this example. As a composition analysis method for these polysaccharides, the total sugar was quantified using the phenol-sulfuric acid method, the starch was quantified by the iodine starch method, the reducing sugar was quantified by the Sommoji Nelson method, the uronic acid was quantified by the Blumenkrantz method, and the crude protein was quantified by the Kjeldahl method. The water-solubilization rate is the ratio of the solid content that has been water-solubilized after heat extraction to the solid content of the raw material, and the eta precipitation yield is the ratio of the solid content of ethanol precipitation to the solid content of the raw material It is a value expressed in%.

[表1]110℃抽出時の各pHにおける組成分析値

Figure 2007086389
[Table 1] Composition analysis values at each pH at 110 ° C extraction
Figure 2007086389

これより、pH5以上では水溶化率、エタ沈収率ともに低く、全糖すなわち多糖類純度も低い。また中性付近では蛋白質含量が増加することから、抽出に適した範囲はpH4以下であると判断された。pH2で抽出すると、水溶化率は高いが、得られた多糖類のエタ沈収率が8%と悪かった。また分子量分布をHPLCにより測定したところ、高分子画分が得られないことが明らかとなり、強酸条件により分解が進んでいると考えられた(図1)。よって抽出時のpHは2.5以上4以下が適当であると判断した。   Thus, at pH 5 or higher, both the water-solubilization rate and etaprecipitation yield are low, and the purity of all sugars, ie polysaccharides, is also low. In addition, since the protein content increased near neutrality, the range suitable for extraction was judged to be pH 4 or lower. When extracted at pH 2, the water solubilization rate was high, but the eta precipitation yield of the obtained polysaccharide was as bad as 8%. Further, when the molecular weight distribution was measured by HPLC, it became clear that a polymer fraction could not be obtained, and it was considered that the decomposition was progressing under strong acid conditions (FIG. 1). Therefore, it was judged that the pH during extraction was 2.5 or more and 4 or less.

市販の脱脂米糠5gを100gに加水して塩酸を用いてpH3に調整した。これらを、60〜150℃の条件下90分抽出した。100℃以下では湯浴上、110℃以上はオートクレーブを用いて加熱を行った。pHを7に調整後、得られたスラリーを遠心分離し(8000 G×30分)、上清にエタノールを60%濃度となるように加えた。沈殿を遠心分離(8000 G×30分)により回収し、凍結乾燥し粉体の米糠多糖類を得た。表2は、この実施例により得られた米糠多糖類の組成分析値を示す。   5 g of commercially available defatted rice bran was added to 100 g and adjusted to pH 3 with hydrochloric acid. These were extracted for 90 minutes under conditions of 60 to 150 ° C. Heating was performed in a hot water bath at 100 ° C. or lower, and using an autoclave at 110 ° C. or higher. After adjusting the pH to 7, the obtained slurry was centrifuged (8000 G × 30 minutes), and ethanol was added to the supernatant to a concentration of 60%. The precipitate was collected by centrifugation (8000 G × 30 minutes) and lyophilized to obtain a powdered rice bran polysaccharide. Table 2 shows the compositional analysis values of the rice bran polysaccharides obtained by this example.

[表2]pH3抽出時の各温度における組成分析値

Figure 2007086389
[Table 2] Composition analysis values at each temperature during pH3 extraction
Figure 2007086389

その結果、pH3の酸性条件で抽出した場合、60℃,80℃では水溶化率が低く、全糖すなわち多糖類純度が低く、灰分が多かった。110〜130℃ではエタ沈収率が高く好ましいが、135℃では加水分解による還元糖の増加、および灰分が増加する傾向が若干認められ、150℃では明らかに水溶化率の低下,全糖の減少,還元糖の増加等が認められた。
[製造例1]
As a result, when extracted under acidic conditions at pH 3, the water-solubilization rate was low at 60 ° C. and 80 ° C., the total sugar, that is, the polysaccharide purity was low, and the ash content was high. 110-130 ° C is preferable because of high etaprecipitation yield, but 135 ° C shows some tendency to increase reducing sugar and ash content due to hydrolysis. A decrease and an increase in reducing sugar were observed.
[Production Example 1]

市販の脱脂米糠5gを100gに加水して塩酸を用いてpH3に調整した。これらをオートクレーブを用いて、110℃の条件下90分抽出した。pHを7に調整後、得られたスラリーを遠心分離し(8000 G×30分)、上清にエタノールを60%濃度となるように加えた。沈殿を遠心分離(8000 G×30分)により回収し、凍結乾燥し粉体の米糠多糖類Aを得た。   5 g of commercially available defatted rice bran was added to 100 g and adjusted to pH 3 with hydrochloric acid. These were extracted for 90 minutes at 110 ° C. using an autoclave. After adjusting the pH to 7, the obtained slurry was centrifuged (8000 G × 30 minutes), and ethanol was added to the supernatant to a concentration of 60%. The precipitate was collected by centrifugation (8000 G × 30 minutes) and freeze-dried to obtain powdered rice bran polysaccharide A.

○乳化安定性の評価
表3の配合で水相に油相を添加した後超音波処理(5281型振動子;KAIJO DENKI)により乳化物を調製し、4℃で静置保存した。尚、表3中の%は容積%である。
Evaluation of emulsification stability After adding the oil phase to the aqueous phase with the composition shown in Table 3, an emulsion was prepared by ultrasonic treatment (5281 type vibrator; KAIJO DENKI) and stored at 4 ° C. In Table 3, “%” is volume%.

[表3]乳化物配合

Figure 2007086389
[Table 3] Formulation of emulsion
Figure 2007086389

これら乳化物の粒子径を、レーザー粒度分布計(SALD-2000;島津製作所)を用いて経時的に測定した。表4に0,1,7日後の平均乳化粒子径を示す。   The particle size of these emulsions was measured over time using a laser particle size distribution analyzer (SALD-2000; Shimadzu Corporation). Table 4 shows the average emulsified particle size after 0, 1, 7 days.

[表4]各乳化物の粒子径変化

Figure 2007086389
[Table 4] Particle size change of each emulsion
Figure 2007086389

以上の結果、乳化剤として米糠多糖類Aを使用した乳化物は、油分の分離等がなく一週間保存後も安定な乳化状態を維持していた。特に中性条件下で粒子径が小さく安定した乳化状態を維持しており、非常に強い乳化力を持っていた。   As a result of the above, the emulsion using rice bran polysaccharide A as an emulsifier did not separate oil and maintained a stable emulsified state even after storage for one week. In particular, it maintained a stable emulsified state with a small particle size under neutral conditions, and had a very strong emulsifying power.

本来産業廃棄物として処理されていた米糠もしくは脱脂米糠から効率よく水溶性多糖類を抽出可能となったことにより、環境への付加を軽減することが可能となる。また得られた多糖類を乳化安定剤として利用することにより、合成乳化剤を使用しない安全な食品を製造することが可能となった。   Addition to the environment can be reduced by efficiently extracting water-soluble polysaccharides from rice bran or defatted rice bran originally treated as industrial waste. Further, by using the obtained polysaccharide as an emulsion stabilizer, it has become possible to produce a safe food that does not use a synthetic emulsifier.

水溶性米糠多糖類の分子量分布のゲル濾過を示す。Fig. 2 shows gel filtration of molecular weight distribution of water-soluble rice bran polysaccharides.

Claims (4)

pH2.5以上pH4以下、且つ95℃以上140℃以下の処理により、米糠から水溶性画分を抽出することを特徴とする、水溶性多糖類の製造法。 A method for producing a water-soluble polysaccharide, characterized in that a water-soluble fraction is extracted from rice bran by treatment at pH 2.5 to pH 4 and from 95 ° C to 140 ° C. 処理後に脱塩精製を行なうことを特徴とする、請求項1に記載の多糖類の製造法。 The method for producing a polysaccharide according to claim 1, wherein desalting and purification are performed after the treatment. pH2.5以上pH4以下、且つ95℃以上140℃以下の処理により、米糠から水溶性画分を抽出して得た水溶性多糖類。 A water-soluble polysaccharide obtained by extracting a water-soluble fraction from rice bran by treatment at pH 2.5 to pH 4 and at 95 ° C. to 140 ° C. 請求項3に記載の水溶性多糖類を有効成分とする乳化剤。 The emulsifier which uses the water-soluble polysaccharide of Claim 3 as an active ingredient.
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