JP5541161B2 - Method for producing phosphorylated water-soluble polysaccharide - Google Patents
Method for producing phosphorylated water-soluble polysaccharide Download PDFInfo
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Description
本発明は、蛋白質粒子の分散安定性を有するリン酸化水溶性多糖類、並びに当該多糖類を有効成分とする、蛋白質粒子の新規な分散安定剤に関する。 The present invention relates to a phosphorylated water-soluble polysaccharide having dispersion stability of protein particles, and a novel dispersion stabilizer for protein particles containing the polysaccharide as an active ingredient.
乳蛋白質を糖質と共に発酵させた、または有機酸の水溶液に分散させた、酸性乳飲料が知られているが、これにはハイメトキシペクチンやカルボキシメチルセルロース等が乳蛋白質粒子の分散安定剤として用いられてきた。特許文献1に開示されている、大豆から油脂及び蛋白質を分離除去したオカラを原料にして、酸性の条件下で高温加圧抽出して得られた水溶性大豆多糖類をこの分散安定剤として用いると、ペクチン等では達成できないpH4未満の酸性下で、非常に粘度の低い状態で乳蛋白質粒子を分散安定化できる。これにより、ペクチンを添加した糊状感のある重い飲み口の飲料とは異なる、それ以前にないすっきりとした軽い飲み口の酸性乳飲料を作製することが出来る(特許文献2)。 Acidic milk beverages are known in which milk proteins are fermented with sugars or dispersed in an aqueous solution of organic acids. For this purpose, high methoxy pectin and carboxymethyl cellulose are used as dispersion stabilizers for milk protein particles. Has been. As a dispersion stabilizer, water-soluble soybean polysaccharide obtained by high-temperature pressure extraction under acidic conditions using okara from which oil and fat and protein are separated and removed from soybean as disclosed in Patent Document 1 is used. In addition, milk protein particles can be dispersed and stabilized in an extremely low viscosity state under an acidity of less than pH 4 that cannot be achieved with pectin or the like. This makes it possible to produce a refreshing and light-taste acidic milk beverage that is different from a heavy-taste beverage with a pasty feeling to which pectin is added (Patent Document 2).
ところで、酸性乳飲料には、蛋白質を高配合したものや、発酵乳を用いて飲料を作製したものがある。これら飲料を水溶性大豆多糖類を用いてpH4未満の条件で調製すると、非常に酸味の強い飲料になってしまったり、低pHにより乳酸菌が生育できず、生菌タイプの乳酸菌飲料を作製することが出来ないといった問題がある。一方で、前述の水溶性大豆多糖類は、pH4.2を超えるpH域では、蛋白質粒子の充分な分散安定化能を示すことができず、あるいは添加量を増やすと、すっきりとした飲み口を阻害してしまう。そこで、pH4.2より高いpH環境で、且つ低粘度で、乳蛋白質粒子を分散安定できる水溶性多糖類が望まれている。 By the way, acidic milk drinks include those with high protein content and those made with fermented milk. If these beverages are prepared using water-soluble soy polysaccharides under a pH of less than 4, it will become a very sour beverage, or lactic acid bacteria cannot grow due to low pH, and a live type lactic acid bacteria beverage should be produced There is a problem that cannot be done. On the other hand, the above-mentioned water-soluble soybean polysaccharides cannot exhibit sufficient dispersion stabilizing ability of protein particles in the pH range exceeding pH 4.2, or if the amount added is increased, the refreshing mouth is not clean. It will interfere. Therefore, a water-soluble polysaccharide that can disperse and stabilize milk protein particles in a pH environment higher than pH 4.2 and low viscosity is desired.
乳蛋白質は、その等電点以下の酸性下で正電荷を帯びているが、酸性乳飲料中の乳蛋白質粒子を多糖類によって分散させるモデルについて、特にペクチンと水溶性大豆多糖類に関して研究が進められている(非特許文献1)。乳蛋白質粒子の分散安定性に寄与する多糖類は、自身の持つ負電荷によって蛋白質表面にイオン的、または疎水的に結合することで、電気的反発や立体障害によって蛋白質粒子の凝集沈殿が抑えられると考えられている。これまで多糖類の分散安定性を向上させるために、多糖類の持つ負電荷を増やす試みは数多く実施されてきた。例えばセルロースにカルボキシメチル基を導入して負電荷を増やしたカルボキシメチルセルロース(CMC)などである。しかし、CMCは必ずしも乳蛋白質粒子の高い分散安定化力を持つものではない上に、飲料の粘度が高くなり、すっきりとした飲み口の飲料を得ることは難しかった。 Milk proteins are positively charged under acidity below their isoelectric point, but research is progressing on models that disperse milk protein particles in acidic milk beverages with polysaccharides, especially pectin and water-soluble soybean polysaccharides. (Non-Patent Document 1). Polysaccharides that contribute to the dispersion stability of milk protein particles are ionically or hydrophobically bound to the protein surface by their own negative charges, thereby suppressing aggregation and precipitation of protein particles due to electrical repulsion and steric hindrance. It is believed that. To date, many attempts have been made to increase the negative charge of polysaccharides in order to improve the dispersion stability of the polysaccharides. For example, carboxymethyl cellulose (CMC) in which carboxymethyl groups are introduced into cellulose to increase the negative charge. However, CMC does not necessarily have a high dispersion stabilizing power of milk protein particles, and the viscosity of the beverage increases, making it difficult to obtain a refreshing beverage.
従来の水溶性大豆多糖類では安定力が低下する、蛋白質の等電点付近であるpH4.2を超えるpH域でも蛋白質粒子を分散安定化し、低粘度ですっきりした飲み口の酸性乳飲料を提供することを目的とする。 Disperse and stabilize protein particles even in the pH range above pH 4.2, which is near the isoelectric point of protein, where the stability of conventional water-soluble soybean polysaccharides is reduced. The purpose is to do.
本発明者らは、上記の課題に対して鋭意研究を重ねた結果、従来の水溶性大豆多糖類では安定化出来なかったpH4.2を超える等電点付近のpH域で乳蛋白質粒子を分散安定化することを見出し、本発明を完成させた。 As a result of intensive research on the above problems, the present inventors dispersed milk protein particles in the pH range near the isoelectric point exceeding pH 4.2, which could not be stabilized by conventional water-soluble soybean polysaccharides. The present invention has been completed by finding that it is stabilized.
即ち、本発明は、
(1)構成糖として酸性糖を有する水溶性多糖類に対し、二価金属イオンおよびリン酸類イオンで処理することを特徴とする、リン酸化水溶性多糖類の製造方法。
(2)構成糖として酸性糖を有する水溶性多糖類に対し、二価金属イオンで処理し、続けてリン酸類イオンで処理することを特徴とする、(1)に記載のリン酸化水溶性多糖類の製造方法。
(3)水溶性多糖類が大豆多糖類である、(1)に記載の製造方法。
(4)二価金属イオンがカルシウムまたはマグネシウムに由来するものである、(1)に記載の製造方法。
(5)リン酸類イオンがフィチン酸,メタリン酸,ポリリン酸から選ばれる1種以上に由来するものである、(1)に記載の製造方法。
(6)(1)乃至(5)に記載の方法で製造された、リン酸化水溶性多糖類。
(7)(6)に記載のリン酸化水溶性多糖類を有効成分とする蛋白質粒子の分散安定剤。
(8)(6)に記載のリン酸化水溶性多糖類を含んだ酸性蛋白食品。
(9)水溶性大豆多糖類に対し、二価金属イオン、およびリン酸類イオンで処理することを特徴とする、水溶性大豆多糖類の蛋白質粒子分散能増強方法。
(10)水溶性大豆多糖類に対し、二価金属イオンで処理し、続けてリン酸類イオンで処理することを特徴とする、水溶性大豆多糖類の蛋白質粒子分散能増強方法。
である。
That is, the present invention
(1) A method for producing a phosphorylated water-soluble polysaccharide, which comprises treating a water-soluble polysaccharide having an acidic sugar as a constituent sugar with a divalent metal ion and a phosphate ion.
(2) The phosphorylated water-soluble polysaccharide according to (1), wherein the water-soluble polysaccharide having an acidic sugar as a constituent sugar is treated with a divalent metal ion and subsequently treated with a phosphate ion. A method for producing sugars.
(3) The production method according to (1), wherein the water-soluble polysaccharide is a soybean polysaccharide.
(4) The production method according to (1), wherein the divalent metal ion is derived from calcium or magnesium.
(5) The production method according to (1), wherein the phosphate ions are derived from one or more selected from phytic acid, metaphosphoric acid, and polyphosphoric acid.
(6) A phosphorylated water-soluble polysaccharide produced by the method according to (1) to (5).
(7) A dispersion stabilizer for protein particles comprising the phosphorylated water-soluble polysaccharide according to (6) as an active ingredient.
(8) An acidic protein food containing the phosphorylated water-soluble polysaccharide according to (6).
(9) A method for enhancing the protein particle dispersibility of a water-soluble soybean polysaccharide, characterized by treating the water-soluble soybean polysaccharide with a divalent metal ion and a phosphate ion.
(10) A method for enhancing the ability to disperse protein particles of a water-soluble soybean polysaccharide, characterized in that the water-soluble soybean polysaccharide is treated with a divalent metal ion and subsequently treated with a phosphate ion.
It is.
本発明によれば、従来安定化力が低下した、乳蛋白質の等電点付近であるpH4.2を超えるpHで蛋白質を分散安定化し、低粘度ですっきりした飲み口の酸性乳飲料を提供することができる。また、乳酸菌が生育可能なpH域での酸性乳飲料の作製が可能となり、低粘度ですっきりした飲み口の生菌タイプの発酵乳入り酸性乳飲料ができる。 ADVANTAGE OF THE INVENTION According to this invention, the protein is disperse-stabilized by pH exceeding pH4.2 which is the isoelectric point vicinity of milk protein with which the stabilization power was reduced conventionally, and the acidic milk drink of a drinking mouth with low viscosity is provided. be able to. In addition, it is possible to produce an acidic milk beverage in a pH range where lactic acid bacteria can grow, and an acidic milk beverage containing fermented milk of a live mouth type with low viscosity and a clean drinking mouth can be obtained.
(水溶性多糖類)
以下、本発明を具体的に説明する。本発明における、構成糖として酸性糖を有する水溶性多糖類とは、カルボキシル基または硫酸基を有する酸性糖を、構成糖として有する水溶性多糖類である。その酸性糖がカルボキシル基を有する水溶性多糖類として、ビートやイモ類といった根菜類およびリンゴ,柑橘等の果実類から得られるペクチン、並びに大豆等から得られる水溶性大豆多糖類、アルギン酸等が挙げられる。また、その酸性糖が硫酸基を有する水溶性多糖類として、各種のカラギーナン等が挙げられる。本発明においては、酸性糖がカルボキシル基を有する水溶性多糖類が好ましく、特に水溶性大豆多糖類が、蛋白質粒子の分散能増強が著しいことから、好適である。(Water-soluble polysaccharide)
Hereinafter, the present invention will be specifically described. The water-soluble polysaccharide having an acidic sugar as a constituent sugar in the present invention is a water-soluble polysaccharide having an acidic sugar having a carboxyl group or a sulfate group as a constituent sugar. Examples of water-soluble polysaccharides whose acidic sugars have carboxyl groups include pectin obtained from root vegetables such as beets and potatoes, and fruits such as apples and citrus, and water-soluble soybean polysaccharides obtained from soybeans, alginic acid and the like. It is done. Moreover, various carrageenan etc. are mentioned as the water-soluble polysaccharide in which the acidic saccharide has a sulfate group. In the present invention, a water-soluble polysaccharide in which the acidic sugar has a carboxyl group is preferable, and a water-soluble soybean polysaccharide is particularly preferable because the dispersibility of protein particles is remarkably enhanced.
(水溶性大豆多糖類)
本願は種々の方法で得られる水溶性大豆多糖類を用いることができるが、例えば、特許文献1に記載された様な水溶性大豆多糖類を用いることができる。製造の一例を示せば、豆腐や豆乳、分離大豆蛋白質の製造時に副産物として得られオカラや、脱脂大豆粕(ミール)を原料として、これに加水を行い、抽出前のpHが3〜7となる条件下で、好ましくは100℃を超える温度域で抽出を行なう。抽出後、固液分離をおこない、上清を得る。得られた上清はガラクツロン酸のメチルエステルを、アルカリ処理等などの公知の方法により脱メトキシ処理することで、蛋白質粒子の分散能が増強され、好ましい。(Water-soluble soybean polysaccharide)
Although the present application can use water-soluble soybean polysaccharides obtained by various methods, for example, water-soluble soybean polysaccharides described in Patent Document 1 can be used. An example of the production is tofu, soy milk, and isolated soy protein produced as by-products in the production of okara and defatted soybean meal (meal) as raw materials, and the pH before extraction becomes 3-7 The extraction is carried out under conditions, preferably in the temperature range above 100 ° C. After extraction, solid-liquid separation is performed to obtain a supernatant. The obtained supernatant is preferably obtained by demethoxytreating methyl ester of galacturonic acid by a known method such as alkali treatment to enhance the dispersibility of protein particles.
(精製)
得られた水溶性大豆多糖類はそのままで用いることも可能であるが、より機能を発揮させるために蛋白質除去や脱塩等の精製を行うことが望ましい。
蛋白質の除去方法としては、pH調整し蛋白質を凝集させ、圧濾分離,遠心分離,ろ過や膜分離等の分離手段によって除去する方法、任意のプロテアーゼを用いて分解する方法、活性炭や樹脂を用いて不純物を吸着除去する精製方法等が挙げられる。脱塩処理の方法としては、塩類が分離除去出来るいずれの方法でも構わない。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,イオン交換樹脂等による吸着除去,UF膜を用いた膜分画等が例示出来る。これらの1法又は2法以上を組み合わせて用いることが好ましい。
これらの精製は、前述した脱メトキシ処理の前でも、後述する二価金属およびリン酸類イオン処理に続いても、行なうことができる。こうして精製された、または未精製の水溶性大豆多糖類溶液を、そのまま或いは殺菌処理や乾燥処理等を経た後、以降の処理を行なうことができる。(Purification)
The obtained water-soluble soybean polysaccharide can be used as it is, but it is desirable to carry out purification such as protein removal and desalting in order to exert more functions.
Protein removal methods include pH adjustment, protein aggregation, removal by pressure filtration, centrifugation, filtration, membrane separation, and other separation means, decomposition using any protease, activated carbon and resin. And a purification method for adsorbing and removing impurities. As a method for desalting, any method capable of separating and removing salts may be used. Examples thereof include precipitation using a polar organic solvent such as methanol, ethanol, isopropanol, and acetone, electrodialysis, adsorption removal using an ion exchange resin, and membrane fractionation using a UF membrane. It is preferable to use these one method or a combination of two or more methods.
These purifications can be performed either before the demethoxy treatment described above or following the divalent metal and phosphate ion treatment described below. The refined or unpurified water-soluble soybean polysaccharide solution can be subjected to the subsequent treatment as it is or after being sterilized or dried.
(二価金属イオンおよびリン酸類イオン処理)
水溶性大豆多糖類などのこれら酸性糖を有する水溶性多糖類に、二価金属イオンおよびリン酸類イオンによる処理を行なう。二価金属イオンは、第2属として分類される元素に由来するものであり、好ましくはカルシウムまたはマグネシウムに由来するもの、またはこの併用物であり、更に好ましくはカルシウムに由来するものである。この二価金属イオンを、種々の塩、好ましくは炭酸塩,塩化物塩、水酸化物塩の形態で用いることができる。リン酸類イオンとは、リン酸,フィチン酸,ポリリン酸,メタリン酸またはその塩等に由来するものが例示でき、好ましくはキレート能を有するリン酸類イオンに由来するものであり、更に好ましくはフィチン酸若しくはヘキサメタリン酸またはそれらの塩に由来するものであり、最も好ましくはフィチン酸塩に由来するものである。(Bivalent metal ion and phosphate ion treatment)
The water-soluble polysaccharide having these acidic sugars such as water-soluble soybean polysaccharide is treated with a divalent metal ion and phosphate ions. The divalent metal ion is derived from an element classified as the second genus, preferably derived from calcium or magnesium, or a combination thereof, and more preferably derived from calcium. This divalent metal ion can be used in the form of various salts, preferably carbonates, chloride salts and hydroxide salts. Examples of phosphate ions include those derived from phosphoric acid, phytic acid, polyphosphoric acid, metaphosphoric acid or salts thereof, preferably those derived from phosphate ions having chelating ability, and more preferably phytic acid. Alternatively, it is derived from hexametaphosphoric acid or a salt thereof, most preferably derived from phytate.
二価金属イオンおよびリン酸類イオン処理とは、これらの物質を前記水溶性多糖類の水溶液に直接添加するか、二価金属イオンおよび/またはリン酸類イオンを水溶液とし、その水溶液を水溶性多糖類の水溶液に添加することで行なわれる。二価金属イオンの添加量は、水溶性多糖類の酸性糖残基に対して好ましくは1〜300モル%、更に好ましくは5〜100モル%である。二価金属イオンが少ないと、後に述べる蛋白質粒子の分散安定効果が得られにくく、多いと風味劣化等の問題が生じる恐れがある。また、リン酸類イオンの添加量は、水溶性多糖類の酸性糖残基に対して好ましくは0.1〜300モル%、更に好ましくは1〜30モル%である。リン酸類イオンが少ないと、後に述べる蛋白質粒子の分散安定効果が得られにくく、多いと風味劣化等の問題が生じる恐れがある。 The divalent metal ion and phosphate ion treatment means that these substances are added directly to the aqueous solution of the water-soluble polysaccharide, or the divalent metal ion and / or phosphate ion is used as an aqueous solution, and the aqueous solution is used as the water-soluble polysaccharide. It is performed by adding to an aqueous solution. The addition amount of the divalent metal ion is preferably 1 to 300 mol%, more preferably 5 to 100 mol%, based on the acidic sugar residue of the water-soluble polysaccharide. If the amount of divalent metal ions is small, the effect of stabilizing the dispersion of protein particles, which will be described later, is difficult to obtain. The addition amount of phosphate ions is preferably 0.1 to 300 mol%, more preferably 1 to 30 mol%, based on the acidic sugar residue of the water-soluble polysaccharide. If there are few phosphate ions, it is difficult to obtain the effect of stabilizing the dispersion of protein particles, which will be described later.
(二段階処理)
前述した酸性糖を有する水溶性多糖類に対する、二価金属イオンおよびリン酸類イオンによる処理は、まず二価金属イオンによる処理を行ない、続けてリン酸類イオンによる処理を行なうと、本願効果は更に顕著に表われ、また金属イオンやリン酸類イオンの使用量を減らすことができる。更に、二価金属イオンによる処理の後、水溶性多糖類の水溶液について、上述した各種の脱塩方法による精製を行なうと、続けて行なうリン酸類イオンによる処理が一層効果的となる。この二段階処理を行う場合、二価金属イオンの添加量は、水溶性多糖類の酸性糖残基に対して好ましくは1〜100モル%、更に好ましくは1〜80モル%である。また、リン酸類イオンの添加量は、水溶性多糖類の酸性糖残基に対して好ましくは0.1〜30モル%、更に好ましくは0.1〜15モル%、最も好ましくは0.5〜5モル%である。(Two-stage processing)
The treatment with the divalent metal ions and phosphate ions for the water-soluble polysaccharide having an acidic sugar described above is performed first by treatment with divalent metal ions, followed by treatment with phosphate ions. In addition, the amount of metal ions and phosphate ions used can be reduced. Furthermore, if the aqueous solution of the water-soluble polysaccharide is purified by the various desalting methods described above after the treatment with the divalent metal ions, the subsequent treatment with the phosphate ions becomes more effective. When this two-stage treatment is performed, the amount of divalent metal ions added is preferably 1 to 100 mol%, more preferably 1 to 80 mol%, based on the acidic sugar residue of the water-soluble polysaccharide. The addition amount of phosphate ions is preferably 0.1 to 30 mol%, more preferably 0.1 to 15 mol%, and most preferably 0.5 to 5 mol% with respect to the acidic sugar residue of the water-soluble polysaccharide.
(精製)
同時処理または二段階処理により、二価金属イオンおよびリン酸類イオン処理を行なわれたリン酸化水溶性多糖類は、乾燥等を行ない種々の用途に用いることも可能であるが、より機能を発揮させるために、加えた過剰の二価金属イオンおよびリン酸類イオンを除去するために、上述した脱塩等の精製を行うことが望ましい。精製されたリン酸化水溶性多糖類溶液をプレート殺菌、或いは蒸気殺菌等の殺菌処理を経た後、凍結乾燥,スプレードライ,加熱乾燥後に粉砕する等の方法により、粉体のリン酸化水溶性多糖類が得られる。(Purification)
Phosphorylated water-soluble polysaccharides that have been treated with divalent metal ions and phosphates ions by simultaneous treatment or two-step treatment can be dried and used for various purposes, but they will exhibit more function. Therefore, it is desirable to perform the above-described purification such as desalting in order to remove excess divalent metal ions and phosphate ions added. The purified phosphorylated water-soluble polysaccharide solution is subjected to sterilization treatment such as plate sterilization or steam sterilization, followed by freeze drying, spray drying, heat drying, etc. Is obtained.
(分散安定剤)
本発明のリン酸化水溶性多糖類、特にリン酸化水溶性大豆多糖類は、蛋白質の粒子の凝集を防止し、分散安定状態を維持することができる、蛋白質の分散安定剤である。そのpH範囲はpH3付近よりpH4.2を超えるpH域までと広く、好ましくはpH3.4〜4.6、更に好ましくはpH3.6〜4.4の領域で効果的であり、酸性蛋白飲食品、特に酸性蛋白飲料に好適である。但し、pH4.2以下のpH領域での乳蛋白質の分散であれば、従来の水溶性大豆多糖類で達成出来るし、pH3.4未満のpH領域では、本発明でも達成が難しい場合がある。また、pH5.2を超えるpH域であれば、乳蛋白質は溶解を開始し、分散剤を用いる必要が少ない。本発明により製造されるリン酸化水溶性大豆多糖類から成る分散安定剤を用いることで、pH4.2を超えるpH域で酸性蛋白飲食品を調製することが出来る。(Dispersion stabilizer)
The phosphorylated water-soluble polysaccharide of the present invention, particularly phosphorylated water-soluble soybean polysaccharide, is a protein dispersion stabilizer that can prevent aggregation of protein particles and maintain a stable dispersion state. The pH range is wide from about pH 3 to a pH range exceeding pH 4.2, preferably effective in the range of pH 3.4 to 4.6, more preferably pH 3.6 to 4.4. Suitable for beverages. However, if the milk protein is dispersed in a pH range of pH 4.2 or lower, it can be achieved with a conventional water-soluble soybean polysaccharide, and it may be difficult to achieve in the present invention in a pH range of less than 3.4. In addition, in the pH range exceeding pH 5.2, the milk protein starts to dissolve, and there is little need to use a dispersant. By using a dispersion stabilizer composed of phosphorylated water-soluble soybean polysaccharide produced according to the present invention, an acidic protein food or drink can be prepared in a pH range exceeding pH 4.2.
本発明の分散安定剤は従来用いられているペクチン等と比較して、酸味が出やすく風味が良好であり、広い用途に使用できる。また、粘度が低い特徴もある。分散安定剤の物性を改良するために、必要に応じて、各種ガム質及び蛋白質及びその分解物を併用して使用することが出来る。これら併用物としては、例えば澱粉,加工デンプン,各種セルロース,寒天,カラギーナン,ファーセラン,グアーガム,ローカストビーンガム,タマリンド種子多糖類,タラガム,アラビアガム,トラガントガム,カラヤガム,ペクチン,キサンタンガム,プルラン,ジェランガム,などの多糖類の他、ゼラチン等の蛋白質を例示出来る。 Compared with conventionally used pectin and the like, the dispersion stabilizer of the present invention is easily sour and has a good flavor and can be used in a wide range of applications. There is also a feature of low viscosity. In order to improve the physical properties of the dispersion stabilizer, various gums and proteins and their degradation products can be used in combination as required. Examples of these combinations include starch, modified starch, various celluloses, agar, carrageenan, ferreran, guar gum, locust bean gum, tamarind seed polysaccharide, tara gum, gum arabic, tragacanth gum, karaya gum, pectin, xanthan gum, pullulan, gellan gum, etc. In addition to these polysaccharides, proteins such as gelatin can be exemplified.
(酸性蛋白飲食品)
本発明における酸性蛋白飲食品とは、動植物由来の蛋白質を含有する酸性飲食品であり、牛乳,豆乳等の動植物性蛋白質を使用した飲料、またはそれに果汁、若しくはクエン酸,乳酸などの有機酸若しくはリン酸を始めとする無機酸を添加してなる酸性蛋白飲料、アイスクリームなどの乳成分入りの冷菓に果汁等を加えた酸性アイスクリーム、フローズンヨーグルト等の酸性冷菓、プリン,ババロア等のゲル化食品に果汁等を加えた酸性デザート、並びにコーヒー飲料,酸性クリーム,ヨーグルト,乳酸菌飲料(殺菌タイプ、生菌タイプを含む),発酵乳,ケフィア等の酸性を帯びた蛋白飲食品を包含する。また、動植物性蛋白質とは、牛乳,山羊乳を始めとする獣乳,豆乳、さらにそれらを加工した脱脂乳,全脂粉乳,脱脂粉乳,ホエーパウダー,粉末豆乳,加糖乳,練乳,濃縮乳,カルシウム等のミネラルやビタミン等を強化した加工乳及び発酵乳を用いた飲食品を指す。本発明の酸性蛋白飲食品の典型的な例示として、乳蛋白質が分散した酸性乳飲料が挙げられる。(Acid protein food and drink)
The acidic protein food and drink in the present invention is an acidic food and drink containing protein derived from animals and plants, and beverages using animal and vegetable proteins such as milk and soy milk, or fruit juice, or organic acids such as citric acid and lactic acid, Gelatinization of acidic protein beverages made by adding inorganic acids such as phosphoric acid, acidic ice cream made by adding fruit juice to frozen desserts containing milk components such as ice cream, acidic frozen desserts such as frozen yogurt, pudding, bavalois, etc. It includes acidic desserts in which fruit juice is added to food, as well as protein foods and drinks with acidic properties such as coffee drinks, acidic creams, yogurt, lactic acid bacteria drinks (including bactericidal and live bacteria types), fermented milk, and kefir. Animal and vegetable proteins include cow milk, goat milk and other animal milk, soy milk, processed skim milk, whole milk powder, skim milk powder, whey powder, powdered soy milk, sweetened milk, condensed milk, concentrated milk, It refers to foods and drinks using processed milk and fermented milk that are enriched with minerals such as calcium and vitamins. A typical example of the acidic protein food and drink of the present invention is an acidic milk beverage in which milk protein is dispersed.
本発明により製造されるリン酸化水溶性大豆多糖類は、特に酸性蛋白飲料において、その蛋白質の分散安定化に対して機能を発揮する。従来の水溶性大豆多糖類では安定化出来ない、蛋白質の等電点付近のpH域でも蛋白質を分散安定化出来る。その際の蛋白質種は、乳蛋白質が酸性飲食品として最も汎用的であり、本発明の分散安定剤の効果が顕著に表われ、好ましい。その際の酸性蛋白飲料の粘度は、蛋白質や分散安定剤の濃度によっても異なるが、例えば後述する実施例1の配合では、本発明の分散安定剤を用いると10mPa・s以下の粘度の酸性蛋白飲料とすることが出来る。また、従来の水溶性大豆多糖類を用いたpH4.2以下の酸性乳飲料では乳酸菌が生存できなかったのに対し、本発明の安定剤を用いると、乳酸菌が生存できるpH域の飲食品が出来るため、乳酸菌醗酵乳を用いた、未加熱生菌タイプの乳酸菌飲料を作製することが出来る。 The phosphorylated water-soluble soybean polysaccharide produced by the present invention exerts a function for stabilizing the dispersion of the protein, particularly in acidic protein beverages. Proteins can be dispersed and stabilized even in the pH range near the isoelectric point of proteins, which cannot be stabilized by conventional water-soluble soybean polysaccharides. As the protein species at that time, milk protein is most widely used as an acidic food and drink, and the effect of the dispersion stabilizer of the present invention is remarkably exhibited, which is preferable. The viscosity of the acidic protein beverage at that time varies depending on the concentration of the protein and the dispersion stabilizer. For example, in the formulation of Example 1 described later, the acidic protein having a viscosity of 10 mPa · s or less is used when the dispersion stabilizer of the present invention is used. Can be a beverage. In addition, lactic acid bacteria could not survive in conventional acidic milk beverages using pH 4.2 or less using water-soluble soy polysaccharides, whereas when the stabilizer of the present invention was used, foods and drinks in the pH range where lactic acid bacteria can survive were obtained. Therefore, an unheated live bacteria type lactic acid bacteria beverage using lactic acid bacteria fermented milk can be produced.
本発明の蛋白質分散安定剤は、蛋白質濃度が10重量%以下の酸性飲食品において特に効果的であり、好ましくは酸性飲食品に対して0.05〜2.0重量%、より好ましくは0.1〜1.5重量%、更に好ましくは0.2〜1.0重量%添加することにより、蛋白質の等電点付近のpH域付近まで、蛋白質の良好な分散安定性を示す。例えば乳蛋白質では、pH3.4〜4.6程度の蛋白飲食品が調製出来、pH3.6〜4.4において特に効果的に凝集を抑制できる。分散安定剤が高濃度では、飲食品の風味に影響を与える場合があり、低濃度では分散安定能が発揮できない場合がある。
The protein dispersion stabilizer of the present invention is particularly effective in an acidic food or drink having a protein concentration of 10% by weight or less, preferably 0.05 to 2.0% by weight, more preferably 0.1 to 1.5% by weight, based on the acidic food or drink. More preferably, by adding 0.2 to 1.0% by weight, good dispersion stability of the protein is exhibited up to the pH range near the isoelectric point of the protein. For example, with milk proteins, protein foods and drinks having a pH of about 3.4 to 4.6 can be prepared, and aggregation can be particularly effectively suppressed at pH 3.6 to 4.4. When the dispersion stabilizer is at a high concentration, the flavor of the food or drink may be affected. At a low concentration, the dispersion stability may not be exhibited.
以下に実施例を記載する。尚、例中の%は特に断らない限り重量基準を意味するものとする。 Examples are described below. In the examples, “%” means a weight basis unless otherwise specified.
○製造例1(同時混合・ヘキサメタリン酸)
水溶性大豆多糖類(ソヤファイブS-DA300:不二製油(株)製)の10重量%水溶液100gに、ヘキサメタリン酸ナトリウム13.78gおよび塩化カルシウム3.3g(共にキシダ化学製・試薬特級)を添加し、pH5.0にて室温下1時間撹拌した。99重量%エタノールを100g添加し、遠心分離にて沈澱を回収した。得られた沈澱を更に、70重量%、90重量%、95重量%のエタノールで順次洗浄し、更に沈澱をホットプレート上にて乾燥し、リン酸化水溶性大豆多糖類Bを得た。同様に、ヘキサメタリン酸ナトリウム1.38g,塩化カルシウム0.33gを添加したものを、リン酸化水溶性大豆多糖類C、ヘキサメタリン酸ナトリウム0.14g,塩化カルシウム0.033gを添加したものを、リン酸化水溶性大豆多糖類Dとした。尚、水溶性大豆多糖類のみをエタノール精製したものを別途調製し、比較製造例である水溶性大豆多糖類Aとした。○ Production Example 1 (simultaneous mixing / hexametaphosphoric acid)
To 100 g of 10% aqueous solution of water-soluble soybean polysaccharide (Soya Five S-DA300: manufactured by Fuji Oil Co., Ltd.), add 13.78 g of sodium hexametaphosphate and 3.3 g of calcium chloride (both manufactured by Kishida Chemical Co., Ltd.) Stir at room temperature for 1 hour at pH 5.0. 100 g of 99 wt% ethanol was added, and the precipitate was recovered by centrifugation. The obtained precipitate was further washed sequentially with 70% by weight, 90% by weight and 95% by weight ethanol, and the precipitate was further dried on a hot plate to obtain phosphorylated water-soluble soybean polysaccharide B. Similarly, a solution containing 1.38 g of sodium hexametaphosphate and 0.33 g of calcium chloride was added to a solution of phosphorylated water-soluble soybean polysaccharide C, 0.14 g of sodium hexametaphosphate and 0.033 g of calcium chloride. Sugar D was designated. In addition, what refine | purified ethanol only about water-soluble soybean polysaccharide was prepared separately, and it was set as the water-soluble soybean polysaccharide A which is a comparative manufacture example.
○実施例1(酸性乳飲料の作製と安定性評価)
(発酵乳の調製)
脱脂粉乳(よつ葉乳業(株)社製)を21重量%含む水溶液を調製し、攪拌しながら95℃で加熱殺菌した。冷却後、市販のプレーンヨーグルトを接種し、40℃の恒温器中でpHが4.6になるまで発酵させた。発酵したヨーグルトをホモゲナイザー(150kgf)にてカードを砕いて均質化し、発酵乳とした。○ Example 1 (Production and stability evaluation of acidic milk beverage)
(Preparation of fermented milk)
An aqueous solution containing 21% by weight of skim milk powder (manufactured by Yotsuba Milk Industry Co., Ltd.) was prepared and sterilized by heating at 95 ° C. with stirring. After cooling, commercially available plain yogurt was inoculated and fermented in a 40 ° C. incubator until the pH reached 4.6. The fermented yogurt was crushed and homogenized with a homogenizer (150 kgf) to obtain fermented milk.
(酸性乳飲料の調製と評価)
発酵乳(均質化したヨーグルト)11.4gに、50%砂糖溶液を1.4g、上記各製造例で作製した水溶性大豆多糖類Aまたはリン酸化水溶性大豆多糖類B〜Dの0.8重量%各水溶液20gを加え総重量を40gとした(水溶性大豆多糖類の終濃度0.4重量%)。さらにクエン酸または水酸化ナトリウムの水溶液でpHを任意に調整した。超音波破砕機(カイジョー社製,5281型振動子)にで、30秒の処理を2回行なった。この1mlをエッペンドルフチューブに移し、80℃で30分間加熱した後に、10〜20℃まで冷却し、300rpmで20分間遠心分離を行ない、上澄を除いた沈澱重量を測定し、沈澱率を求めた。沈殿率は以下の式により算出した。
沈殿率(%)=(沈殿物重量)/(分取した酸性乳飲料重量)×100
沈澱率の評価は、沈殿率1%以下を◎、沈殿率1%を超え2%以下を○、沈殿率2%を超え4%以下を△、沈殿率4%を超えたものを×と表記した。(Preparation and evaluation of acidic milk beverages)
11.4 g of fermented milk (homogenized yogurt), 1.4 g of 50% sugar solution, 0.8% by weight of each aqueous solution of water-soluble soybean polysaccharide A or phosphorylated water-soluble soybean polysaccharides BD prepared in the above production examples 20 g was added to make the total weight 40 g (final concentration of water-soluble soybean polysaccharide 0.4% by weight). Further, the pH was arbitrarily adjusted with an aqueous solution of citric acid or sodium hydroxide. The treatment for 30 seconds was performed twice with an ultrasonic crusher (made by Kaijo Corp., 5281 type vibrator). This 1 ml was transferred to an Eppendorf tube, heated at 80 ° C. for 30 minutes, then cooled to 10-20 ° C., centrifuged at 300 rpm for 20 minutes, and the precipitation weight excluding the supernatant was measured to determine the precipitation rate. . The precipitation rate was calculated by the following formula.
Precipitation rate (%) = (precipitate weight) / (sorted acidic milk beverage weight) × 100
In the evaluation of the precipitation rate, ◎ indicates that the precipitation rate is 1% or less, ○ indicates that the precipitation rate exceeds 1% and 2% or less, △ indicates that the precipitation rate exceeds 2% and 4% or less, and X indicates that the precipitation rate exceeds 4%. did.
○表1.リン酸化水溶性大豆多糖類による酸性乳飲料の安定性(同時添加)
○ Table 1. Stability of acidic milk beverages with phosphorylated water-soluble soybean polysaccharide (simultaneous addition)
コントロールの大豆多糖類Aに比較して、塩化カルシウム及びヘキサメタリン酸ナトリウムを添加したリン酸化水溶性大豆多糖類B〜Dは、いずれも酸性乳飲料がpH4.4〜4.6の際の沈澱量が減少し、このpH域での乳蛋白質粒子の分散が安定化されていた。 Compared to the control soybean polysaccharide A, phosphorylated water-soluble soybean polysaccharides BD, to which calcium chloride and sodium hexametaphosphate were added, all had a reduced amount of precipitation when the acidic milk beverage was at pH 4.4 to 4.6. However, the dispersion of milk protein particles in this pH range was stabilized.
○製造例2(二段処理1・ヘキサメタリン酸)
水溶性大豆多糖類(ソヤファイブS-DA300)の5重量%水溶液1,000gに、塩化カルシウム3.68gを添加し、pH5.0にて室温下1時間撹拌した。99重量%エタノールを1,000g添加し、遠心分離にて沈澱を回収した。得られた沈澱を更に、70重量%、90重量%のエタノールで順次洗浄し、更に風乾して、Ca処理水溶性大豆多糖類を得た。
Ca処理水溶性大豆多糖類の5重量%水溶液100gに、ヘキサメタリン酸ナトリウムを0.4g,0.2g,0.025g添加し、pH5.0にて室温下1時間撹拌した。99重量%エタノールを100g添加し、遠心分離にて沈澱を回収した。得られた沈澱を更に、70重量%、90重量%のエタノールで順次洗浄し、更に風乾して、リン酸化水溶性大豆多糖類E〜Gを得た。○ Production Example 2 (Two-stage treatment 1, hexametaphosphoric acid)
To 1,000 g of a 5 wt% aqueous solution of water-soluble soybean polysaccharide (Soya Five S-DA300), 3.68 g of calcium chloride was added, and the mixture was stirred at room temperature for 1 hour at pH 5.0. 1,000 g of 99 wt% ethanol was added, and the precipitate was recovered by centrifugation. The resulting precipitate was further washed sequentially with 70 wt% and 90 wt% ethanol and further air dried to obtain a Ca-treated water-soluble soybean polysaccharide.
0.4 g, 0.2 g, and 0.025 g of sodium hexametaphosphate were added to 100 g of a 5 wt% aqueous solution of Ca-treated water-soluble soybean polysaccharide, and stirred at room temperature for 1 hour at pH 5.0. 100 g of 99 wt% ethanol was added, and the precipitate was recovered by centrifugation. The obtained precipitate was further washed successively with 70% by weight and 90% by weight ethanol and further air-dried to obtain phosphorylated water-soluble soybean polysaccharides E to G.
○製造例3(二段処理2・フィチン酸)
製造例2と同様にし、リン酸化水溶性大豆多糖類H〜Jを得た。但し、ヘキサメタリン酸ナトリウムの代りに、フィチン酸ナトリウム(sigma社製)を0.2g,0.1g,0.05g用いて調製を行なった。○ Production Example 3 (Two-stage treatment 2, phytic acid)
In the same manner as in Production Example 2, phosphorylated water-soluble soybean polysaccharides H to J were obtained. However, instead of sodium hexametaphosphate, preparation was performed using 0.2 g, 0.1 g, and 0.05 g of sodium phytate (manufactured by sigma).
○実施例2(酸性乳飲料の作製と安定性評価)
実施例1と同様にし、水溶性大豆多糖類A,およびリン酸化水溶性大豆多糖類E〜Jの評価を行なった。尚、各水溶性大豆多糖類は、酸性乳飲料に対する終濃度0.4重量%および0.8重量%の2種の系で評価した。○ Example 2 (Production and stability evaluation of acidic milk beverage)
In the same manner as in Example 1, water-soluble soybean polysaccharide A and phosphorylated water-soluble soybean polysaccharides E to J were evaluated. In addition, each water-soluble soybean polysaccharide was evaluated by two kinds of systems having a final concentration of 0.4% by weight and 0.8% by weight with respect to an acidic milk beverage.
○表2.リン酸化水溶性大豆多糖類による酸性乳飲料の安定性(二段添加)0.4%
○ Table 2. Stability of acidic milk drinks with phosphorylated water-soluble soybean polysaccharide (two-stage addition) 0.4%
○表3.リン酸化水溶性大豆多糖類による酸性乳飲料の安定性(二段添加)0.8%
○ Table 3. Stability of acidic milk beverages with phosphorylated water-soluble soybean polysaccharide (two-stage addition) 0.8%
終濃度0.4重量%の系(表2)では、本発明の処理を行なったリン酸化水溶性大豆多糖類は、全体的に沈澱率が低下し、乳蛋白質粒子の分散安定能が向上していた。特にリン酸化水溶性大豆多糖類F〜Jでは、pH4.4での沈澱率が著しく少なくなっており、乳蛋白質粒子の等電点付近における分散安定能が向上していることが判った。また、終濃度0.8重量%の系(表3)では、全体的な沈澱率は更に低下すると共に、特にフィチン酸ナトリウムを添加したリン酸化水溶性大豆多糖類H〜Jに於て、pH4.4での沈澱率が大きく改善されていた。 In the system having a final concentration of 0.4% by weight (Table 2), the phosphorylated water-soluble soybean polysaccharide subjected to the treatment of the present invention had an overall reduced precipitation rate and improved milk protein particle dispersion stability. . In particular, phosphorylated water-soluble soybean polysaccharides F to J have a significantly reduced precipitation rate at pH 4.4, and it has been found that the dispersion stability in the vicinity of the isoelectric point of milk protein particles is improved. Further, in the system having a final concentration of 0.8% by weight (Table 3), the overall precipitation rate is further reduced, and in particular, in the phosphorylated water-soluble soybean polysaccharides H to J to which sodium phytate is added, the pH is 4.4. The precipitation rate was greatly improved.
○製造例4(ペクチンへの応用)
HM-ペクチン(CP kelco社製、YM-150-LJ)の5重量%水溶液1,000gに、塩化カルシウム3.68gを添加し、pH5.0にて室温下1時間撹拌した。99重量%エタノールを1,000g添加し、遠心分離にて沈澱を回収した。得られた沈澱を更に、70重量%、90重量%のエタノールで順次洗浄し、更に風乾して、Ca処理ペクチンを得た。
Ca処理ペクチンの5重量%水溶液100gに、フィチン酸ナトリウムを0.1g添加し、pH5.0にて室温下1時間撹拌した。99重量%エタノールを100g添加し、遠心分離にて沈澱を回収した。得られた沈澱を更に、70重量%、90重量%のエタノールで順次洗浄し、更に風乾して、フィチン酸が結合したリン酸化ペクチンを得た。○ Production Example 4 (application to pectin)
To 1,000 g of a 5 wt% aqueous solution of HM-pectin (CP kelco, YM-150-LJ), 3.68 g of calcium chloride was added and stirred at pH 5.0 at room temperature for 1 hour. 1,000 g of 99 wt% ethanol was added, and the precipitate was recovered by centrifugation. The resulting precipitate was further washed sequentially with 70% by weight and 90% by weight ethanol and further air-dried to obtain a Ca-treated pectin.
0.1 g of sodium phytate was added to 100 g of a 5% by weight aqueous solution of Ca-treated pectin, and the mixture was stirred at room temperature for 1 hour at pH 5.0. 100 g of 99 wt% ethanol was added, and the precipitate was recovered by centrifugation. The obtained precipitate was further washed successively with 70% by weight and 90% by weight ethanol and further air-dried to obtain phosphorylated pectin to which phytic acid was bound.
○製造例5(カラギーナンへの応用)
ラムダカラギーナン(三栄源FFI社製、カラゲニンCSL-1)の5重量%水溶液1,000gに、塩化マグネシウム0.032gを添加し、pH5.0にて室温下1時間撹拌した。99重量%エタノールを1,000g添加し、遠心分離にて沈澱を回収した。得られた沈澱を更に、70重量%、90重量%のエタノールで順次洗浄し、更に風乾して、Mg処理カラギーナンを得た。
Mg処理カラギーナンの1重量%水溶液500gに、フィチン酸ナトリウムを0.1g添加し、pH5.0にて室温下1時間撹拌した。99重量%エタノールを500g添加し、遠心分離にて沈澱を回収した。得られた沈澱を更に、70重量%、90重量%のエタノールで順次洗浄し、更に風乾して、フィチン酸が結合したリン酸化カラギーナンを得た。○ Production Example 5 (Application to carrageenan)
To 1,000 g of a 5 wt% aqueous solution of lambda carrageenan (manufactured by Saneigen FFI, carrageenin CSL-1), 0.032 g of magnesium chloride was added and stirred at pH 5.0 for 1 hour at room temperature. 1,000 g of 99 wt% ethanol was added, and the precipitate was recovered by centrifugation. The resulting precipitate was further washed sequentially with 70% by weight and 90% by weight ethanol and further air-dried to obtain Mg-treated carrageenan.
0.1 g of sodium phytate was added to 500 g of a 1% by weight aqueous solution of Mg-treated carrageenan, and the mixture was stirred at room temperature for 1 hour at pH 5.0. 500 g of 99 wt% ethanol was added, and the precipitate was recovered by centrifugation. The obtained precipitate was further washed successively with 70% by weight and 90% by weight ethanol and further air-dried to obtain a phosphorylated carrageenan bound with phytic acid.
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JPH0759512A (en) * | 1993-08-20 | 1995-03-07 | Sanei Gen F F I Inc | Production of acidic milk drink |
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