WO2004078334A1 - Emulsifier contianing polysaccharide-protein complex as the active ingredient, process for producing the same and emulsified composition - Google Patents

Emulsifier contianing polysaccharide-protein complex as the active ingredient, process for producing the same and emulsified composition Download PDF

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Publication number
WO2004078334A1
WO2004078334A1 PCT/JP2004/002669 JP2004002669W WO2004078334A1 WO 2004078334 A1 WO2004078334 A1 WO 2004078334A1 JP 2004002669 W JP2004002669 W JP 2004002669W WO 2004078334 A1 WO2004078334 A1 WO 2004078334A1
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emulsifier
protein
acidic
polysaccharide
saccharide
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PCT/JP2004/002669
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French (fr)
Japanese (ja)
Inventor
Akihiro Nakamura
Taro Takahashi
Junko Tobe
Ryuji Yoshida
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Fuji Oil Company, Limited
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Priority to JP2005503079A priority Critical patent/JPWO2004078334A1/en
Publication of WO2004078334A1 publication Critical patent/WO2004078334A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16Amines or polyamines
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/30Proteins; Protein hydrolysates

Definitions

  • Emulsifier comprising complex of polysaccharide and protein as active ingredient, method for producing the same, and emulsified composition
  • the present invention relates to an emulsifier. More specifically, an emulsifier having improved functions, which is obtained by heating a polysaccharide containing an acidic saccharide having a carboxylic acid group as a constituent saccharide and a protein or protein hydrolyzate under acidic conditions, and a method for producing the same, are provided.
  • the present invention also relates to an emulsified composition using the emulsifier.
  • emulsifiers can be broadly classified into monomolecular emulsifiers and polymer emulsifiers.
  • the monomolecular emulsifier is a so-called surfactant, and examples thereof include fatty acid stone / glycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like.
  • Polymeric emulsifiers include natural products such as gum arabic and casein, or synthetic products such as atalylate and polypinyl alcohol.
  • emulsifiers may be used alone depending on the application, or they may be used in an appropriate blend.However, monomolecular emulsifiers are generally vulnerable to changes in H, and are not sensitive to changes in concentration due to addition or dilution of salts. This leaves a problem that the emulsifiability is lost. In addition, the use of these synthetic monomolecular emulsifiers tends to be disliked, reflecting the recent health consciousness. On the other hand, there are also natural polymers with emulsifying power. But weak emulsifying power, high viscosity impairs the texture or physical properties of food
  • Proteins such as soybeans, wheat, milk, and hen's eggs have been widely used in food processing because of their functional properties of emulsification, foaming and water retention.
  • many proteins can be weakly acidic at pH 4 to 6, weakening the negative charge of the protein and reducing the repulsion between protein molecules, resulting in reduced solubility and consequently reduced functional properties.
  • milk proteins such as soy protein and casein, have a markedly reduced solubility under weakly acidic conditions and form precipitates, which lowers the emulsifying power.
  • Many foods are weakly acidic and do not efficiently utilize the functional properties of proteins.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 6-112192.
  • the water-soluble soybean polysaccharide extracted at a high temperature with a weakly acidic pH near the isoelectric point of soybean protein at pH 4.5 which is exemplified as a suitable condition here, does not always have sufficient emulsifying power.
  • the emulsifier could be emulsified only up to 4 times the weight of the emulsifier in terms of the weight ratio of the emulsifier, and the range of use was limited.
  • various studies have been made to impart new functions by complexing saccharides and proteins.
  • An object of the present invention is to provide an emulsifier having high safety and improved functional activity, a process for producing the same, and an emulsified composition using the emulsifier.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, reconfirmed that the dehydration condensation reaction of a compound having a lipoxyl group and a compound having an amino group also proceeds in an aqueous system. In addition, it was found that by adjusting this reaction system to a specific pH, the reactivity was dramatically improved, and the emulsifying ability of the complex obtained by the reaction was enhanced. Issued.
  • the present invention has been completed based on such findings. You. That is, the present invention provides an acid produced by heating a polysaccharide containing an acidic saccharide having a lipoxyl group as a constituent saccharide and a protein or protein hydrolyzate under an acidic condition of PH 2 to PH 5.
  • an emulsifier containing a polysaccharide-protein complex as an active ingredient provides an acidic polysaccharide comprising heating a polysaccharide containing an acidic saccharide having a hydroxyl group as a constituent saccharide and a protein or a proteolysate under an acidic condition of pH 2 to 5.
  • Examples of the acidic sugar having a hydroxyl group according to the present invention include carboxylic acids such as galacturonic acid, glucuronic acid and mannuronic acid, and carboxymethyl etherified glucose. And sulphonic acid etherified sugars.
  • Polysaccharides containing these as constituent sugars include, for example, natural polysaccharides such as vectin, alginic acid, and arabic gum; fermented polysaccharides such as dielan gum; lipoxymethyl cellulose; Examples thereof include synthetic polysaccharides such as alginic acid propylene glycol ester, and acidic oligosaccharides such as degraded products of alginate and alginic acid.
  • the hydroxyl group may be in a free or salt state, but is preferably present in a state in which alcohols such as methyl alcohol are ester-bonded. In addition, it is preferable that at least 50% of the hydroxyl group is esterified. If the degree of esterification is 50% or less, Depending on the pH and the presence of salts, gelation may occur and the reactivity may be reduced. There is no particular upper limit on the degree of esterification that is appropriate for use, but the degree of esterification of natural polysaccharides is usually up to about 80%. The higher the content of acidic sugars in the carbohydrate, the better, but preferably more than 10% by weight, more preferably more than 20% by weight, and more preferably more than 30% by weight. Is preferred, and there is no particular upper limit.
  • proteins include plant-derived proteins such as soybean protein, corn protein, wheat protein, endogenous bean protein, as well as casein, egg white albumin, and whey.
  • Animal proteins such as protein, gelatin, actin myosin, and silk protein may be used, and hydrolysates of proteins such as polypeptides, peptides, and amino acids. It is OK.
  • Polysaccharides and proteins containing acidic sugars having a lipoxyl group as constituent sugars can be used either in a water-soluble state or in an insoluble state.
  • the appropriate ratio for obtaining a complex of a protein and a polysaccharide containing an acidic saccharide having a carboxyl group ′ as a constituent saccharide is from 100: 1 to 1:20 for acidic polysaccharide: protein. It is preferably 50: 1 to 1:10, more preferably 10: 1 to 1: 2.
  • the complex is produced by mixing a polysaccharide containing an acidic saccharide having a lipoxyl group as a constituent saccharide and a protein in an aqueous system and then heating the mixture.
  • a polysaccharide containing an acidic saccharide having a lipoxyl group as a constituent saccharide and a protein in an aqueous system and then heating the mixture.
  • the raw material is suspended in an aqueous solution or water, and After adjusting the temperature, heat and separate the water-soluble fraction and dry it as it is.
  • aqueous solution or water For example, after neutralizing the heated solution, dialysis treatment, activated carbon treatment, resin adsorption treatment, or ethanol
  • inorganic precipitation hydrophobic substances or low-molecular substances by subjecting it to a Knoll precipitation treatment, etc., it is dried and then dried.
  • a polysaccharide-protein complex containing as a constituent sugar can be obtained.
  • Heating is performed at pH 2 to 5 and preferably at pH 3 to 4. If the pH is lower than 2, it is not preferable because decomposition, which is a side reaction during the complexation reaction, is promoted. When the pH exceeds 5, the reactivity is remarkably reduced.
  • the acid used at this time is not particularly limited, but when it is intended as an emulsifier for food use, it is used in the food industry, including hydrochloric acid, phosphoric acid, sulfuric acid, lactic acid, citric acid, oxalic acid, etc. Can be used.
  • the heating temperature during the reaction is preferably at least 80, preferably more than 100 ° C, at least 105, and more preferably at least 120. Generally, it is sufficient to heat under pressure while not dissolving or dispersing in water, or in a wet or pasted state.
  • the upper limit of the heating temperature is not particularly specified, but when the temperature is extremely high, a side reaction occurs and coloring becomes easy. Usually, it is performed at 180 ° C or lower, preferably at 150 ° C or lower.
  • the emulsifier according to the present invention containing a polysaccharide-protein complex containing an acidic saccharide having a lipoxyl group as a constituent saccharide as an active ingredient is a so-called emulsifier in comparison with individual acidic saccharide-containing saccharides and proteins before the reaction.
  • Functions of what is called Be improved or newly granted For example, levels of emulsifying power and emulsifying stabilizing ability not found in individual polysaccharides or proteins before the reaction, as well as improving physical properties of flour products, stabilizing dispersion, foaming, stabilizing foam, Functions such as water retention are expressed by the formation of the complex.
  • fragrances By utilizing these functional activities, emulsified fragrances, foods such as mayonnaise, dressing or creams, cosmetics such as hand creams, and coatings It can be widely used in the general living industry represented by medicines such as repellents and pesticides such as insecticides.
  • the method of evaluating the emulsifying ability used as an indicator of the functional activity of the emulsifier containing the polysaccharide-protein complex as an active ingredient in the present invention is as follows.
  • Soybean oil is added to 100 g of a 5% aqueous solution, and judgment is made based on the amount added until phase inversion. When the product of the present invention is used, the weight ratio of the oil / complex becomes 5 or more.
  • the emulsification conditions when adding soybean oil shall be homogenization with a homomixer ( ⁇ K homomixer; Tokushu Kika Kogyo Co., Ltd.) with vigorous stirring at 1000 rpm.
  • the product of the present invention can be used alone as an emulsifier, but by using it in combination with an existing emulsifier, the disadvantages of the existing emulsifier can be compensated.
  • Existing monomolecular emulsifiers include various anionic surfactants typified by fatty acid stones, cationic surfactants such as quaternary ammonium salts, glycerin fatty acid esters, and sucrose fatty acids.
  • Nonionic surfactants such as esters, polyoxyethylene sorbitan fatty acid esters, and both lecithin Surfactants and the like.
  • existing polymer emulsifiers include natural emulsifiers, for example, agar, carrageenan, phaceleran, tamarin seed polysaccharide, and water-soluble soy polysaccharide.
  • natural emulsifiers for example, agar, carrageenan, phaceleran, tamarin seed polysaccharide, and water-soluble soy polysaccharide.
  • albumin such as rubiagum, gelatin, whey, casein sodium, various starches, and the like.
  • Semi-synthetic pastes include carboxymethylcellulose (CMC), methylcellulose (MC), hydroxyxethylcellulose (HEC), propylene glycol 7-luginate, and the like.
  • Modified starch typified by luster and soluble starch can be exemplified, and examples of the synthetic paste include polyvinyl alcohol and sodium polyacrylate.
  • the effect of the emulsifier in the present invention may be further improved by using one or more of the above-mentioned various emulsifiers in combination, and the emulsifier can make up for the drawbacks of the various emulsifiers.
  • sugars such as sucrose and starch syrup
  • polyvalent alcohols such as glycerin, D-sorbitol, propylene glycol, and the like
  • Stability may be improved by adding an acidulant such as lactic acid, vinegar, citric acid, and phosphoric acid.
  • additives such as anti-fading agents and preservatives such as L-ascorbic acid, its derivatives, and aminocarbonyl reaction products can be added.
  • angiotensin II 0.5 mg is dissolved in 1501 lOOmM tartrate Na_HC1 buffer (pH 5.0) and heated at 120 ° C for 90 minutes. I did. The reaction product generated after the heating was separated by reverse-phase HPLC to recover the reaction compound. Subsequently, the structure was confirmed by mass spectral analysis of the recovered reaction compound. As shown in the results in Fig. 1, the results of mass spectral analysis indicate that tartaric acid contained in the buffer was amide-bound to the N-terminal of angiotensin II. Was confirmed.
  • angiotensin II was added to 1501 lOOmM tartaric acid-HC1 buffer (pH 2.0), lOOmmM tartaric acid Na-HC1 buffer (pH 3 PH 7.0), 100 mM Tartrate Na-NaOH buffer solution (pH 9.0, pHIO. 0), and dissolved at 120 ° C. Heating was performed for 90 minutes. The reaction product generated after the heating was separated by reversed-phase HPLC, and the reaction compound was quantified. As shown in the results in Fig. 2, the results of the quantitative analysis confirmed that the reaction products increased dramatically between pH 2 and pH 5, with pH 3.0 as the center. It was done.
  • TypeUSP-H Esterification degree 70.5; Sansho Co., Ltd. 200 g and soy protein (trade name“ Fujipro-E ”; Fuji Oil Co., Ltd.) 100 g with warm water 5
  • the pH was adjusted to 3.0 with hydrochloric acid, and the mixture was heated at 120 for 1.5 hours to produce a heated product of HM-vector and soybean protein.
  • the mixture was cooled to room temperature, centrifuged (100,000 G ⁇ 30 minutes), and the supernatant was dried to collect 25 g of a solid. This solid was converted to a 5% aqueous solution, and emulsified with a homomixer at 100,000 rpm while adding soybean oil. The phase was inverted when 250 g of soybean oil was added. The oil / composite weight ratio at this time was 50.
  • the pH was adjusted to 4.0 with hydrochloric acid, and the mixture was heated at 120 for 1.5 hours to produce a heated product of HM-vector and soybean protein.
  • the mixture was cooled to room temperature, centrifuged (100,000 GX for 30 minutes), and the supernatant was dried to collect 202.5 g of a solid. This solid was converted to a 5% aqueous solution, and soybean oil was added thereto using a homomixer.
  • the emulsification treatment was performed at 0.000 rpm, the phase was inverted when 12 Og of soybean oil was added to 100 g of an aqueous solution.
  • the oil / composite weight ratio at this time was 24.
  • the pH was adjusted to 2.0 with hydrochloric acid, and the mixture was heated at 120 for 1.5 hours to produce a heated product of HM-pectin and soybean protein. After heating, the mixture was cooled to room temperature, centrifuged (100,000 G ⁇ 30 minutes), and the supernatant was dried to recover 243 g of a solid.
  • the solid was converted to a 5% aqueous solution, and emulsified at 100 000 rpm with a homomixer while adding soybean oil to give 100 g of an aqueous solution.
  • the phase was inverted when 60 g of soybean oil was added.
  • the oil / composite weight ratio at this time was 12.
  • the pH was adjusted to 5.0 with caustic soda, and the mixture was heated at 120 ° C for 1.5 hours to produce a heated product of HM-pectin and soybean protein.
  • the mixture was cooled to room temperature, centrifuged (1000 GX 30 minutes), and the supernatant was dried. 184 g of a solid was recovered.
  • this solid was converted to a 5% aqueous solution and emulsified with a homomixer at lOOO rpm while adding soybean oil.
  • the phase was inverted when 45 g of soybean oil was added.
  • the oil / composite weight ratio at this time was 9.
  • the solid was converted to a 5% aqueous solution, and emulsified at 100 rpm with a homomixer while adding soybean oil to obtain a 100 g aqueous solution.
  • the phase was inverted when 5 g of soybean oil was added to the mixture.
  • the oil / composite weight ratio at this time was 1.
  • the solid was converted to a 5% aqueous solution, and emulsified with a homomixer at l OOOO rpm while adding soybean oil.
  • the phase was inverted when 15 g of soybean oil was added.
  • the oil / composite weight ratio at this time was 3.
  • soybean protein (trade name “Fujipro-E”; manufactured by Fuji Oil Co., Ltd.) was dissolved in 800 g of warm water, and the pH was adjusted to 3.0 with hydrochloric acid. The mixture was heated at 0 to 1.5 hours to obtain a thermally decomposed product of soybean protein. After heating, the mixture was cooled to room temperature, centrifuged (100,000 GX for 30 minutes), and the supernatant was dried to recover 11 g of a solid. Also, this solid When the mold was emulsified with a homomixer at 100,000 rpm while adding soybean oil to a 5% aqueous solution, 100 g of the aqueous solution was reconstituted. The phase was inverted when 22 g of soybean oil was added. The oil / composite weight ratio at this time was 4.4.
  • Comparative Example 3 and The decomposed product obtained in Comparative Example 4 was mixed at a weight ratio of 2: 1 to form a 5% aqueous solution, and the mixture was mixed with a homomixer while adding soybean oil.
  • the emulsification treatment was performed at 0.000 rpm, the phase inversion occurred when 12 g of soybean oil was added to 100 g of the aqueous solution.
  • the oil / composite weight ratio at this time was 2.4.
  • Warm water was added to the mixture so that the solid content concentration became 5%, and the mixture was heated at pH 4.0 and 105 for 180 minutes.
  • the product of the present invention 4 obtained by performing the same treatment as in Example 1 And 2 parts of sodium caseinate were dissolved in 69 parts of water, and 0.1 part of a commercially available Milk Flavor (“Milk FT-013”, manufactured by Takasago International Inc.) was added.
  • the meringue confectionery produced in this way shows a stable bubble state, there is little change over time during the squeezing operation, and the texture of each meringue confectionery is stable. Was. In addition, there was almost no structural destruction due to firing, and the texture after firing was fine and good.
  • LM-1 vector (trade name: LM-SN 325 J Esterification degree 24; Snow Brand Foods Co., Ltd.) 200 g and soy protein (trade name “Fujipro-E”; Fuji Oil Co., Ltd.) 1
  • the solution was gelled when the pH was adjusted to 3.0 with hydrochloric acid.
  • 900 g of hot water was further added to dilute and dissolve the gel, and the mixture was heated at 120 for 1.5 hours to produce a heated product of LM-pectin and soy protein.
  • the mixture was cooled to room temperature, centrifuged (100,000 G ⁇ 30 minutes), and the supernatant was dried to collect a solid.
  • this solid was prepared as a 5% 7) solution, and the soybean oil was added thereto, and the mixture was subjected to a milk mixing process at 100,000 rpm with a homomixer. The phase was inverted when 52 g of soybean oil was added to the aqueous solution of 1 g. The oil / composite weight ratio at this time was 10.4.
  • the complex obtained by the production method of the present invention in which a polysaccharide containing an acidic saccharide having a lipoxyl group as a constituent saccharide and a protein or protein hydrolyzate is heated under acidic conditions of pH 2 to 5 is different from a conventional conjugate as an emulsifier.
  • This is an emulsifier with significantly improved emulsifying activity, and is advantageously used in the production of emulsions containing a large amount of fats and oils relative to the amount of emulsifier.

Abstract

It is intended to provide a technique for obtaining an emulsifier having a high emulsifying capability, more specifically speaking, an emulsifier which is prepared by using a polysaccharide containing an acidic saccharide having carboxyl group as its constituting saccharide and a protein or a hydrolyzed protein as the starting materials and contains an acidic polysaccharide-protein complex as the active ingredient, a process for producing the same and an emulsified composition using the complex as an emulsifier. A polysaccharide containing an acidic saccharide having carboxyl group as its constituting saccharide and a protein or a hydrolyzed protein are heated under acidic conditions of pH 2 to 5 to thereby form an acidic polysaccharide-protein complex. An emulsifier containing this complex as the active ingredient shows a remarkably elevated emulsifying activity compared with those obtained by the existing methods.

Description

明 細 書 多糖と蛋白質との複合体を有効成分とする乳化剤およびその製 造方法ならびに乳化組成物 技術分野  Description Emulsifier comprising complex of polysaccharide and protein as active ingredient, method for producing the same, and emulsified composition
本発明は、 乳化剤に関するものである。 さらに言えば、 力ルポ キシル基を有する酸性糖を構成糖として含む多糖と蛋白質また は蛋白加水分解物とを酸性下で加熱することにより得られる、機 能が改良された乳化剤およびその製造方法であり、 また該乳化剤 を使用してなる乳化組成物に関するものである。 背景技術  The present invention relates to an emulsifier. More specifically, an emulsifier having improved functions, which is obtained by heating a polysaccharide containing an acidic saccharide having a carboxylic acid group as a constituent saccharide and a protein or protein hydrolyzate under acidic conditions, and a method for producing the same, are provided. The present invention also relates to an emulsified composition using the emulsifier. Background art
一般に、 乳化剤は、 単分子乳化剤と高分子乳化剤に大別するこ とができる。 単分子乳化剤とはいわゆる界面活性剤であり、 脂肪 酸石鹼ゃグリセリン脂肪酸エステル、 ショ糖脂肪酸エステル ポ リォキシエチレンソルビタン脂肪酸エステル等がある。高分子乳 化剤にはアラビアガムやカゼインのような天然物、或いはアタリ ル酸塩やポリ ピニルアルコールのような合成品がある。 これらの乳化剤は用途によって単独で使用されることもあり、 適当に配合して使用されることもあるが、単分子乳化剤は一般に Hの変化に弱かったり、 塩の添加や希釈による濃度の変化によ つて乳化性が失われるという問題を残している。 さらに、 近年の 健康志向を反映してこれら合成物である単分子乳化剤はその使 用が嫌われる傾向にある。 一方、 乳化力を持つ天然高分子物もあ るが乳化力が弱い、粘度が高く食品の食感もしくは物性を損ねるIn general, emulsifiers can be broadly classified into monomolecular emulsifiers and polymer emulsifiers. The monomolecular emulsifier is a so-called surfactant, and examples thereof include fatty acid stone / glycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like. Polymeric emulsifiers include natural products such as gum arabic and casein, or synthetic products such as atalylate and polypinyl alcohol. These emulsifiers may be used alone depending on the application, or they may be used in an appropriate blend.However, monomolecular emulsifiers are generally vulnerable to changes in H, and are not sensitive to changes in concentration due to addition or dilution of salts. This leaves a problem that the emulsifiability is lost. In addition, the use of these synthetic monomolecular emulsifiers tends to be disliked, reflecting the recent health consciousness. On the other hand, there are also natural polymers with emulsifying power. But weak emulsifying power, high viscosity impairs the texture or physical properties of food
PHの変化に弱い、 塩濃度の影響を受け易いなどの問題があり、 必ずしも満足できるものではなかった。 大豆、 小麦、 牛乳、 鶏卵等の蛋白質は、 それが保有する機能特 性である乳化力、起泡力や保水力が食品加工において広く利用さ れてきた。 しかしながら、 多くの蛋白質は、 pH 4から 6の弱酸 性下では、 蛋白質の負の電荷が弱くなり、 蛋白質分子間の反発力 が低下するため、 溶解性が下がり、 ひいては機能特性が低下する ことが知られている。 例えば、 大豆蛋白質やカゼイン等の乳蛋白 質は、 弱酸性下で著しく溶解性が低下し、 沈殿を形成するため、 乳化力が低下する。 多くの食品は弱酸性であり、 蛋白質の有する 機能特性を効率よく利用できていないのが現状である。 そこで、 蛋白質の電荷パランスを改変する方法として、 ァシル 化、 エステル化、 脱アミ ド化等の機能改善の研究が多く行われて きたが、 これらの化学修飾では多くの場合化学薬品を用いるため. 改質された蛋白質を食品用途で用いるには安全性の面からは忌 避されがちなものであった。 また、 特殊な改質にによって性能が アップされても、製造コス トがかかりすぎるという問題もあった, 一方、 アラビアガム、 キサン夕ンガム等の多糖類は、 溶解性で は pHの影響を受けない代わりに、 乳化力が弱い、 粘度が高く食 品.の食感もしくは物性を損ねるなどの問題があり、必ずしも満足 できるものではなかった。 そこで、 食品の物性に影響を与えない ようにべクチンを分解して低分子化する事により弱酸性下の乳 化力、 乳化安定化力を付与する方法 (特開平 1 0 - 489 4号公報) が 提案されているが、 当該方法によつて製造されたべクチン分解物 はアラビアガムよりは強い乳化力を示すものの、ぺクチン分解物 重量に対し重量比で 2倍量の油分の乳化物までしか良好に乳化 できず、 未だ満足のいく ものでは無かった。 さらに、ポリアクリル酸塩やポリビニルアルコールの様な合成 品もあるが、 乳化性に問題があったり、 使用用途が限られる場合 が多く、最近では安定供給可能な天然の高分子乳化剤が望まれて いた。 これらの課題を解決するべく、本出願人は以前に大豆由来の水 溶性多糖類を有効成分とする乳化剤に関する出願を行っているIt was not always satisfactory due to problems such as weakness in pH change and susceptibility to salt concentration. Proteins such as soybeans, wheat, milk, and hen's eggs have been widely used in food processing because of their functional properties of emulsification, foaming and water retention. However, many proteins can be weakly acidic at pH 4 to 6, weakening the negative charge of the protein and reducing the repulsion between protein molecules, resulting in reduced solubility and consequently reduced functional properties. Are known. For example, milk proteins, such as soy protein and casein, have a markedly reduced solubility under weakly acidic conditions and form precipitates, which lowers the emulsifying power. Many foods are weakly acidic and do not efficiently utilize the functional properties of proteins. Therefore, as a method of modifying the charge balance of proteins, many studies on functional improvement such as acylation, esterification, and deamidation have been conducted, but these chemical modifications often use chemicals. Use of the modified protein in food applications was often avoided from the viewpoint of safety. In addition, there was a problem that even if the performance was improved by special reforming, the production cost was too high.On the other hand, polysaccharides such as gum arabic and xansu gum were affected by pH in solubility. However, there were problems such as weak emulsifying power, high viscosity and impaired texture and physical properties of foods, which were not always satisfactory. Therefore, a method of imparting emulsifying power and emulsifying stabilizing power under weak acidity by decomposing pectin to a low molecular weight so as not to affect the physical properties of food (Japanese Patent Application Laid-Open No. H10-4894) ) Has been proposed, but the pectin degradation product produced by this method is Despite showing stronger emulsifying power than gum arabic, it could only be emulsified well up to twice the oil content of the weight of pectin hydrolyzate, which was not yet satisfactory. In addition, there are synthetic products such as polyacrylates and polyvinyl alcohols, but they have problems in emulsifying properties and their use is often limited.Recently, natural polymer emulsifiers that can be supplied stably have been desired. Was. In order to solve these problems, the present applicant has previously filed an application for an emulsifier containing a water-soluble polysaccharide derived from soybean as an active ingredient.
(特許文献 2 : 特開平 6- 1 2 1 92 2号公報) 。 しかし、 ここで好適 な条件として例示されている pH 4. 5 という大豆蛋白の等電点付 近の弱酸性 PHにて高温で抽出される水溶性大豆多糖類では、 乳 化力が必ずしも充分ではなく、乳化剤量に対し重量比で 4倍量の 油分の乳化物までしか良好に乳化できず使用範囲が限られ、適用 分野の拡大には更なる機能の向上が望まれていた。 一方で食品分野において糖質と蛋白質とを複合体化して新規 な機能を付与する検討が種々なされている。一般に利用されてい る化学反応としては、糖質中のカルポニル基と蛋白質中のアミノ 基とを結合させるァミノカルポニル反応が知られている。古くは 味噌、 醤油等食品の着色、 着香、 着味等に利用されており、 近年 ではいくつかの文献 (特開平 3 — 2 1 5 4 9 8号公報、 特開平 9 - 1 0 7 8 8 6号公報、 特開 2 0 0 0 — 3 2 5 0 4 7号公報) に 開示されているような糖質、蛋白質双方の欠点を補って乳化性を 付与した機能性新素材の開発に応用されている。 しかし、 これら従来のアミノカルポニル反応を利用して蛋白質 や糖質の改質を企図した糖質一蛋白質複合化組成物は、通常その 製造に非常に長時間を要し、着色もしくは不溶化などの不必要な 副反応が生じる等の問題があり、 さらに、 食味、 食感、 呈味性、 乳化性及び保水性などの各種機能についても満足のいく もので はなかった。 そこで、本出願人はァミノカルポニル反応に変わる糖質—蛋白 質の複合体化方法として、力ルポキシル基を有する酸性糖を構成 糖として含む糖質と蛋白質との加熱(特開平 1 0- 1 68097号公報)、 カルボン酸とアミノ酸の 105°C以上の加熱による脱水縮合反応(Patent Document 2: Japanese Patent Application Laid-Open No. 6-112192). However, the water-soluble soybean polysaccharide extracted at a high temperature with a weakly acidic pH near the isoelectric point of soybean protein at pH 4.5, which is exemplified as a suitable condition here, does not always have sufficient emulsifying power. However, the emulsifier could be emulsified only up to 4 times the weight of the emulsifier in terms of the weight ratio of the emulsifier, and the range of use was limited. On the other hand, in the food field, various studies have been made to impart new functions by complexing saccharides and proteins. As a commonly used chemical reaction, an aminocarbonyl reaction for bonding a carbonyl group in a saccharide to an amino group in a protein is known. In the past, it has been used for coloring, flavoring, flavoring, etc. of foods such as miso and soy sauce. In recent years, several documents have been used (Japanese Patent Application Laid-Open Nos. Heisei 3 (1995) -214498, Heisei 9-10778). No. 86, Japanese Patent Application Laid-Open No. 2000-3250747) to develop a functional new material that compensates for the defects of both carbohydrates and proteins and provides emulsifying properties. Applied. However, these carbohydrate-protein conjugate compositions intended to modify proteins and carbohydrates by utilizing these conventional aminocarbonyl reactions usually require a very long time to produce, and do not undergo coloration or insolubilization. There were problems such as the occurrence of necessary side reactions, and further, various functions such as taste, texture, taste, emulsification, and water retention were not satisfactory. Accordingly, the present applicant has proposed a method of forming a carbohydrate-protein complex in place of an aminocarbonyl reaction, by heating a carbohydrate containing an acidic sugar having a lipoxyl group as a constituent sugar and a protein (Japanese Patent Application Laid-Open No. H10-68097). Publication), Dehydration condensation reaction of carboxylic acid and amino acid by heating at 105 ° C or more
( W099/62935 ) を提案した。 しかし、 これらの反応条件では、 場 合によっては反応性が低く必ずしも満足のいく結果が得られる ものではなかった。 (W099 / 62935) was proposed. However, under these reaction conditions, the reactivity was low in some cases, and a satisfactory result was not always obtained.
発明の開示 Disclosure of the invention
本発明は、 安全性が高 く 、 機能活性が改質さ れた乳化 剤及びその製造法な ら びに該乳化剤を用 い る乳化組成 物を提供する事を 目 的とする も のであ る 。  An object of the present invention is to provide an emulsifier having high safety and improved functional activity, a process for producing the same, and an emulsified composition using the emulsifier.
本発明者 ら は、 前記課題 を解決すべ く 鋭意研究を進め た結果、 力ルポキシル基を有する化合物 と ア ミ ノ 基を有 する化合物の脱水縮合反応が水系 において も進行する こ と を改めて確認し、 さ ら に こ の反応系 を特定の p H に 調整する事によ り 反応性が飛躍的に改善さ れる事、 かつ 反応で得 ら れる複合体の乳化能が高ま る こ と を見出 し 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。 すなわち 、 本発明は、 力ルポキシル基を有する酸性 糖を構成糖と して含む多糖と 蛋白質 または蛋白加水分 解物 と を P H 2 か ら 5 の酸性下で加熱させる こ と によ り 生成する酸性多糖 -蛋白複合体を有効成分 とする乳化 剤であ る 。 ま た本発明は、 力 ルポキシル基を有する酸性 糖を構成糖 と して含む多糖 と蛋白質または蛋白分解物 と を P H 2 か ら 5 の酸性下で加熱させる こ と を特徴 とす る、 酸性多糖 -蛋白複合体を有効成分 とする乳化剤の製 造方法であ り 、 こ の乳化剤を用 い る乳化組成物であ る 。 発明 を実施する ための最良の形態 The present inventors have conducted intensive studies to solve the above problems, and as a result, reconfirmed that the dehydration condensation reaction of a compound having a lipoxyl group and a compound having an amino group also proceeds in an aqueous system. In addition, it was found that by adjusting this reaction system to a specific pH, the reactivity was dramatically improved, and the emulsifying ability of the complex obtained by the reaction was enhanced. Issued. The present invention has been completed based on such findings. You. That is, the present invention provides an acid produced by heating a polysaccharide containing an acidic saccharide having a lipoxyl group as a constituent saccharide and a protein or protein hydrolyzate under an acidic condition of PH 2 to PH 5. An emulsifier containing a polysaccharide-protein complex as an active ingredient. Further, the present invention provides an acidic polysaccharide comprising heating a polysaccharide containing an acidic saccharide having a hydroxyl group as a constituent saccharide and a protein or a proteolysate under an acidic condition of pH 2 to 5. -A method for producing an emulsifier containing a protein complex as an active ingredient, and an emulsified composition using this emulsifier. BEST MODE FOR CARRYING OUT THE INVENTION
以下本発明の好ま し い態様を詳述する。 本発明の、 力 ルポキ シル基を有する酸性糖 と しては、 ガ ラ ク ッ ロ ン酸 グルク ロ ン酸、 マ ンヌ ロ ン酸等の ゥ ロ ン酸類、 カルボキ シメ チルエーテル化グルコ ース等の力ルポ ン酸ェ一テ ル化糖等が挙げ ら れる。 これ ら を構成糖 と して含む多糖 と しては、 例えばべク チン、 アルギ ン酸、 ア ラ ビアガム 等の天然多糖類、 ジエ ラ ンガム等の発酵多糖類、 力ルポ キシメ チルセル ロ ース 、 アルギ ン酸プロ ピ レ ング リ コ 一 ルエステル等の合成多糖類、 ぺク チ ン分解物、 アルギ ン 酸分解物等の酸性オ リ ゴ糖類等が挙げられる。  Hereinafter, preferred embodiments of the present invention will be described in detail. Examples of the acidic sugar having a hydroxyl group according to the present invention include carboxylic acids such as galacturonic acid, glucuronic acid and mannuronic acid, and carboxymethyl etherified glucose. And sulphonic acid etherified sugars. Polysaccharides containing these as constituent sugars include, for example, natural polysaccharides such as vectin, alginic acid, and arabic gum; fermented polysaccharides such as dielan gum; lipoxymethyl cellulose; Examples thereof include synthetic polysaccharides such as alginic acid propylene glycol ester, and acidic oligosaccharides such as degraded products of alginate and alginic acid.
力ルポキシル基は遊離または塩の状態であ っ て も良 いが、 メ チルアルコ ール等のアルコ ール類がエステル結 合してい る状態で存在する も のが好ま し い。 さ ら に、 力 ルポキシル基は、 5 0 %以上がエステル化さ れてい る方が 好ま し い。 エステル化度が 5 0 %以下の場合には、 溶液の p H、 塩類の存在によ っ てはゲル化が起 こ り 、 反応性が低 下する こ とがあ る。エステル化度につ いて利用 の適正 と して上限は特にないが、 天然の多糖類では通常エステル 化度は 8 0 %程度までであ る 。糖質中の酸性糖含有量は 多い程良いが、 望ま し く は 1 0 重量%以上、 よ り 望ま し く は 2 0 重量% 、 さ ら に望ま し く は 3 0 重量%以 上含有する のが好ま し く 、 特に上限はない。 The hydroxyl group may be in a free or salt state, but is preferably present in a state in which alcohols such as methyl alcohol are ester-bonded. In addition, it is preferable that at least 50% of the hydroxyl group is esterified. If the degree of esterification is 50% or less, Depending on the pH and the presence of salts, gelation may occur and the reactivity may be reduced. There is no particular upper limit on the degree of esterification that is appropriate for use, but the degree of esterification of natural polysaccharides is usually up to about 80%. The higher the content of acidic sugars in the carbohydrate, the better, but preferably more than 10% by weight, more preferably more than 20% by weight, and more preferably more than 30% by weight. Is preferred, and there is no particular upper limit.
一方、 蛋白質 と しては、 大豆蛋白質、 ト ウモ ロ コ シ蛋 白質、 小麦蛋白質、 エン ド ゥ豆蛋白質等の植物由来の蛋 白質はも ち ろ ん、 カゼイ ン、 卵 白 アルブミ ン、 乳清蛋白 質、 ゼラ チン、 ァ ク チン ミ オシ ン、 絹蛋白質等の動物 性蛋白質で も 良 く 、 さ ら にポ リ ペプチ ド 、 ペプチ ド およ びア ミ ノ 酸等、 蛋白質の加水分解物であ っ て も よ い。  On the other hand, proteins include plant-derived proteins such as soybean protein, corn protein, wheat protein, endogenous bean protein, as well as casein, egg white albumin, and whey. Animal proteins such as protein, gelatin, actin myosin, and silk protein may be used, and hydrolysates of proteins such as polypeptides, peptides, and amino acids. It is OK.
力ルポキシル基を有する酸性糖を構成糖 と して含む 多糖な ら びに蛋白質は、 いずれも水に可溶な状態あ る い は不溶な状態の どち ら で も使用 が可能であ る。  Polysaccharides and proteins containing acidic sugars having a lipoxyl group as constituent sugars can be used either in a water-soluble state or in an insoluble state.
カルボキ シル基'を有する酸性糖を構成糖 と して含む 多糖 と蛋白質 と の複合体化を得る ため の両者の適当 な 比率は、酸性多糖:蛋白質が 1 0 0 : 1 〜 1 : 2 0 、 好ま し く は 5 0 : 1 〜 1 : 1 0 、 さ ら に好ま し く は 1 0 : 1 〜 1 : 2 であ る 。  The appropriate ratio for obtaining a complex of a protein and a polysaccharide containing an acidic saccharide having a carboxyl group ′ as a constituent saccharide is from 100: 1 to 1:20 for acidic polysaccharide: protein. It is preferably 50: 1 to 1:10, more preferably 10: 1 to 1: 2.
複合体は、前述の如 く 力ルポキシル基を有する酸性糖 を構成糖 と して含む多糖 と蛋白質 と を水系下に混合 し た後に加熱を行う こ と によ り 製造される が、製造条件の 一例を示す と以下の通 り であ る 。  As described above, the complex is produced by mixing a polysaccharide containing an acidic saccharide having a lipoxyl group as a constituent saccharide and a protein in an aqueous system and then heating the mixture. An example is as follows.
先ず、 原料を水溶液あ る い は水に懸濁状態に して、 P H を調整した後に加熱を行い、 水溶性画分を分取 し、 その ま ま乾燥するか、 例えばこ の加熱後の液を中和後、 透析 処理、 活性炭処理、 樹脂吸着処理あ る い はエタ ノ ール沈 澱処理等を行う こ と によ り 無機塩類、 疎水性物質あ る い は低分子物質を除去精製後に乾燥する こ と によ っ て、 目 的 とする力ルポキシル基 有する酸性糖を構成糖 と し て含む多糖一蛋白質複合体を得る こ とができ る 。 First, the raw material is suspended in an aqueous solution or water, and After adjusting the temperature, heat and separate the water-soluble fraction and dry it as it is.For example, after neutralizing the heated solution, dialysis treatment, activated carbon treatment, resin adsorption treatment, or ethanol By subjecting to inorganic precipitation, hydrophobic substances or low-molecular substances by subjecting it to a Knoll precipitation treatment, etc., it is dried and then dried. Thus, a polysaccharide-protein complex containing as a constituent sugar can be obtained.
加熱は p H 2 〜 5 、 好ま し く は p H 3 〜 4 で行 う p H 2未満では複合体化反応中 の副反応であ る分解が促 進さ れる為に好ま し く な く 、 また p H 5を超える と反 応性が著 し く 低下する。 こ の と き使用する酸は特に限定 されないが、 食品用途での乳化剤を意図する場合は、 塩 酸をは じめ、 燐酸、 硫酸、 乳酸、 ク ェ ン酸、 シユ ウ酸等 食品工業で使用 される酸が使用でき る。  Heating is performed at pH 2 to 5 and preferably at pH 3 to 4.If the pH is lower than 2, it is not preferable because decomposition, which is a side reaction during the complexation reaction, is promoted. When the pH exceeds 5, the reactivity is remarkably reduced. The acid used at this time is not particularly limited, but when it is intended as an emulsifier for food use, it is used in the food industry, including hydrochloric acid, phosphoric acid, sulfuric acid, lactic acid, citric acid, oxalic acid, etc. Can be used.
さ ら に反応時の加熱温度は、 8 0 以上、 好ま し く は 1 0 0 °C を超えて 1 0 5 以上、 さ ら には 1 2 0 以上の 温度にする こ と が好ま し い。一般的には水中 に溶解ない し分散状態で、 または湿潤状態、 あ る いはペース ト 状態 で加圧下に加熱すればよ い。 なお、 加熱温度の上限は特 に規定さ れないが、 極度に高温で行な う と、 副反応が起 きた り 着色 し易 く な る。 通常 1 8 0 °C以下、 好ま し く は 1 5 0 °C以下で行な う と 良い。  Further, the heating temperature during the reaction is preferably at least 80, preferably more than 100 ° C, at least 105, and more preferably at least 120. Generally, it is sufficient to heat under pressure while not dissolving or dispersing in water, or in a wet or pasted state. The upper limit of the heating temperature is not particularly specified, but when the temperature is extremely high, a side reaction occurs and coloring becomes easy. Usually, it is performed at 180 ° C or lower, preferably at 150 ° C or lower.
本発明 における力ルポキシル基を有する酸性糖を構 成糖 と して含む多糖一蛋白質複合体を有効成分 とする 乳化剤は、反応前の個々 の酸性糖含有糖質および蛋白質 に比べ、 いわゆ る乳化剤 と呼ばれる物の有する諸機能が 改良さ れる或いは新たに付与さ れる 。 例えば、 反応前の 個々 の多糖あ る いは蛋白質では認め られない レベルの 乳化力や乳化安定化能、 さ ら に小麦粉製品の物性改良能 分散安定化能、 起泡力、 気泡安定化能、 保水能等の機能 が、 複合体が形成さ れる こ と によ り 発現さ れる。 これ ら の機能活性を利用する事によ り 乳化香料やマ ヨ ネーズ、 ド レ ッ シ ングあ る い はク リ ーム類等の食品や、ハ ン ド ク リ ーム等の化粧品、 塗 り 薬等の医薬品、 殺虫剤等の農薬 等に代表さ れる 生活産業全般に広 く 利用でき る。 The emulsifier according to the present invention containing a polysaccharide-protein complex containing an acidic saccharide having a lipoxyl group as a constituent saccharide as an active ingredient is a so-called emulsifier in comparison with individual acidic saccharide-containing saccharides and proteins before the reaction. Functions of what is called Be improved or newly granted. For example, levels of emulsifying power and emulsifying stabilizing ability not found in individual polysaccharides or proteins before the reaction, as well as improving physical properties of flour products, stabilizing dispersion, foaming, stabilizing foam, Functions such as water retention are expressed by the formation of the complex. By utilizing these functional activities, emulsified fragrances, foods such as mayonnaise, dressing or creams, cosmetics such as hand creams, and coatings It can be widely used in the general living industry represented by medicines such as repellents and pesticides such as insecticides.
本発明における多糖一蛋白質複合体を有効成分 とす る乳化剤の機能活性の指標 と して用 いた乳化能の評価 方法は次の通 り であ る。  The method of evaluating the emulsifying ability used as an indicator of the functional activity of the emulsifier containing the polysaccharide-protein complex as an active ingredient in the present invention is as follows.
5 % の水溶液 1 0 0 g に対 して大豆油 を加えてい き、 転 相する までの添加量によ っ て判断する。本発明品を用 い れば こ の油分/複合体の重量比が 5 以上 となる。 なお、 大豆油を加え る 際の乳化条件はホモ ミ キサー( τ Kホモ ミ キサー ; 特殊機化工業株式会社) で 1 0 0 0 0 r p mの強撹拌 によ り 行 う も の とする。  Soybean oil is added to 100 g of a 5% aqueous solution, and judgment is made based on the amount added until phase inversion. When the product of the present invention is used, the weight ratio of the oil / complex becomes 5 or more. The emulsification conditions when adding soybean oil shall be homogenization with a homomixer (τK homomixer; Tokushu Kika Kogyo Co., Ltd.) with vigorous stirring at 1000 rpm.
本発明品は、 単独で乳化剤 と して使用する こ とができ るが、 既存の乳化剤 と併用する こ と によ り 、 既存の乳化 剤の欠点を補 う こ と もでき る 。  The product of the present invention can be used alone as an emulsifier, but by using it in combination with an existing emulsifier, the disadvantages of the existing emulsifier can be compensated.
既存の単分子乳化剤 と しては、脂肪酸石鹼に代表さ れ る各種ァニオ ン界面活性剤や 4 級ア ンモニゥム塩等の カチオン界面活性剤、 グ リ セ リ ン脂肪酸エス テル、 シ ョ 糖脂肪酸エステル、 ポ リ オキ シエチ レ ンソルビタ ン脂肪 酸エステル等の非イ オン界面活性剤、 レ シチンの様な両 性界面活性剤等が挙げ ら れる 。 Existing monomolecular emulsifiers include various anionic surfactants typified by fatty acid stones, cationic surfactants such as quaternary ammonium salts, glycerin fatty acid esters, and sucrose fatty acids. Nonionic surfactants such as esters, polyoxyethylene sorbitan fatty acid esters, and both lecithin Surfactants and the like.
一方、 既存の高分子乳化剤 と しては、 天然系乳化剤、 例え ば、 寒天、 カ ラ ギ一ナ ン、 フ ァ ーセ レ ラ ン、 タ マ リ ン ド種子多糖類、 水溶性大豆多糖類、 タ ラガム、 カ ラ ャ ガム、 ぺク チ ン、 キサンタ ンガム、 アルギ ン酸ナ ト リ ウ ム、 卜 ラガカ ン 卜 ガム、 ダワーガム、 口 一カス ト ビー ン ガム、 プルラ ン、 ジエ ラ ンガム、 ア ラ ビアガム、 ゼラチ ン、 ホェ一等のアルブミ ン、 カゼイ ンナ ト リ ウム、 各種 澱粉等が挙げ ら れる 。 また、 半合成糊剤 と しては、 カル ポキシメ チルセルロース ( C M C ) 、 メ チルセルロ ース ( M C ) 、 ヒ ド ロキシェチルセルロ ース ( H E C ) 、 7 ルギ ン酸プロ ピ レ ン ダリ コ 一ルエス テルおよび可溶性 澱粉に代表さ れる化工澱粉等が例示でき、合成糊剤 と し てはポ リ ビニルアルコールやポ リ ア ク リ ル酸ナ ト リ ウ ム等が例示でき る。  On the other hand, existing polymer emulsifiers include natural emulsifiers, for example, agar, carrageenan, phaceleran, tamarin seed polysaccharide, and water-soluble soy polysaccharide. , Tarragum, karaya gum, galactin, kissanthan gum, sodium alginate, tragacanth gum, dower gum, oral bean gum, pullulan, jelan gum, a Examples include albumin such as rubiagum, gelatin, whey, casein sodium, various starches, and the like. Semi-synthetic pastes include carboxymethylcellulose (CMC), methylcellulose (MC), hydroxyxethylcellulose (HEC), propylene glycol 7-luginate, and the like. Modified starch typified by luster and soluble starch can be exemplified, and examples of the synthetic paste include polyvinyl alcohol and sodium polyacrylate.
本発明にお ける乳化剤は、上記する各種乳化剤の一種 または二種以上 と併用する こ と によ り 一層効果が向上 する場合があ り 、各種乳化剤の欠点を補 う こ とができ る また、 水相 に蔗糖や水飴等のいわゆ る糖類や、 グ リ セ リ ン、 D — ソ ル ビ ト ール、 プロ ピ レ ン グ リ コ 一ルな どの 多価アルコ ール類や、 例えば、 乳酸、 食酢、 ク ェ ン酸、 り ん ご酸等の酸味料等を添加すれば、 安定性が向上する 場合があ る。 更に、 L — ァス コ ル ビ ン酸、 その誘導体、 ア ミ ノ カルポニル反応生成物な どの退色防止剤や防腐 剤等の添加物を入れる こ とができ る 。  The effect of the emulsifier in the present invention may be further improved by using one or more of the above-mentioned various emulsifiers in combination, and the emulsifier can make up for the drawbacks of the various emulsifiers. In the aqueous phase, so-called sugars such as sucrose and starch syrup, and polyvalent alcohols such as glycerin, D-sorbitol, propylene glycol, and the like, Stability may be improved by adding an acidulant such as lactic acid, vinegar, citric acid, and phosphoric acid. Further, additives such as anti-fading agents and preservatives such as L-ascorbic acid, its derivatives, and aminocarbonyl reaction products can be added.
実施例 以下、 実施例に よ り 本発明の実施態様を説明するが、 こ れは例示であ っ て本発明の精神がこれ ら の例示によ つ て制限さ れる も のではない。 なお、 例中、 部および% は何れも重量基準を意味する。 Example Hereinafter, embodiments of the present invention will be described with reference to examples. However, this is an exemplification, and the spirit of the present invention is not limited to these examples. In the examples, parts and% mean weight basis.
(実験 1 )  (Experiment 1)
0 . 5 m g の ア ンジォテンシ ン I I を 1 5 0 1 の l O O m M 酒石酸 N a _ H C 1 緩衝液 ( p H 5 . 0 ) に溶解 して 1 2 0 °Cで 9 0 分間加熱 を行 っ た。 加熱後に生 じた反応生成物を逆相 一 H P L C に よ り 分 離 して反応化合物を回収 した。 続いて、 回収 し た反応化 合物の マス ス ぺ ク ト ル分析を行 う こ と によ り 構造の確 認を行っ た。 図 1 の結果に示すよ う に、 マス ス ぺ ク 卜 ル分析の結果か ら 、 緩衝液中 に含まれていた酒石酸がァ ンジォテ ン シ ン I I の N 末端にア ミ ド結合 して いる こ とが確認さ れた。  0.5 mg of angiotensin II is dissolved in 1501 lOOmM tartrate Na_HC1 buffer (pH 5.0) and heated at 120 ° C for 90 minutes. I did. The reaction product generated after the heating was separated by reverse-phase HPLC to recover the reaction compound. Subsequently, the structure was confirmed by mass spectral analysis of the recovered reaction compound. As shown in the results in Fig. 1, the results of mass spectral analysis indicate that tartaric acid contained in the buffer was amide-bound to the N-terminal of angiotensin II. Was confirmed.
差替え用紙(規則 26) (実験 2 ) Replacement form (Rule 26) (Experiment 2)
0 . 5 m g のア ンジォテ ンシ ン I I を 1 5 0 1 の l O O m M 酒石酸 — H C 1 緩衝液( p H 2 . 0 ) , l O O m M 酒石酸 N a — H C 1 緩衝液 ( p H 3 . 0 力、 ら p H 7 . 0 ) 、 l O O m M 酒石酸 N a — N a O H緩衝液 ( p H 9 . 0 、 p H I O . 0 ) にそれぞ れ溶解して 1 2 0 °Cで 9 0 分間加熱を行っ た。加熱後 に生 じた反応生成物を逆相 — H P L C によ り 分離 して 反応化合物を定量した。 図 2 の結果に示すよ う に、 定量 分析の結果か ら 、 p H 3 . 0 を 中心と して p H 2 か ら 5 の間で反応生成物が飛躍的に多 く なる こ とが確認さ れ た。  0.5 mg of angiotensin II was added to 1501 lOOmM tartaric acid-HC1 buffer (pH 2.0), lOOmmM tartaric acid Na-HC1 buffer (pH 3 PH 7.0), 100 mM Tartrate Na-NaOH buffer solution (pH 9.0, pHIO. 0), and dissolved at 120 ° C. Heating was performed for 90 minutes. The reaction product generated after the heating was separated by reversed-phase HPLC, and the reaction compound was quantified. As shown in the results in Fig. 2, the results of the quantitative analysis confirmed that the reaction products increased dramatically between pH 2 and pH 5, with pH 3.0 as the center. It was done.
差替え用紙(規則 26) (実施例) Replacement form (Rule 26) (Example)
実施例 1  Example 1
HM ー ぺク チ ン (商品名 「ゲニューべク チン  HM-Pectin (Product name "Genuine Vectin"
typeUSP- H」 エステル化度 7 0 . 5 ; 三晶株式会社製) 2 0 0 g と大豆蛋白質 (商品名 「 フ ジプロ - E」 ; 不二 製油株式会社製) 1 0 0 g と を温水 5 7 0 0 g に溶 解後、 塩酸で P H を 3 . 0 に調整し、 1 2 0 で 1 . 5 時間加熱 して H M — べク チ ン と大豆蛋白質の 加熱物を生成させた。加熱後室温まで冷却 して遠心分離 し ( 1 0 0 0 0 G X 3 0 分) 、 上澄を乾燥 して固形物 2 2 5 g を回収 した。 また、 こ の固型物を 5 % の水溶 液と して、大豆油を加えなが ら ホモ ミ キサーにて 1 0 0 0 0 r p m で乳化処理を行つ た と こ ろ 、 100 g の水溶液 に対 して大豆油 を 250g加えた と こ ろ で転相 した。 こ の と き の油分 /複合体重量比は 50であ っ た。 TypeUSP-H ”Esterification degree 70.5; Sansho Co., Ltd.) 200 g and soy protein (trade name“ Fujipro-E ”; Fuji Oil Co., Ltd.) 100 g with warm water 5 After dissolving to 700 g, the pH was adjusted to 3.0 with hydrochloric acid, and the mixture was heated at 120 for 1.5 hours to produce a heated product of HM-vector and soybean protein. After heating, the mixture was cooled to room temperature, centrifuged (100,000 G × 30 minutes), and the supernatant was dried to collect 25 g of a solid. This solid was converted to a 5% aqueous solution, and emulsified with a homomixer at 100,000 rpm while adding soybean oil. The phase was inverted when 250 g of soybean oil was added. The oil / composite weight ratio at this time was 50.
実施例 2  Example 2
HM ー ぺク チン (商品名 「ゲニューべク チン  HM-Pectin (Product name "Genuvetin"
typeUSP-Hj エステル化度 7 0 . 5 ; 三晶株式会社製) 2 0 0 g と大豆蛋白質 (商品名 「 フ ジプロ - E」 ; 不二 製油株式会社製) 1 0 0 g と を温水 5 7 0 0 g に溶 解後、 塩酸で P H を 4 . 0 に調整 し、 1 2 0 で 1 . 5 時間加熱 して H M — べク チ ン と大豆蛋白質の 加熱物を生成さ せた。加熱後室温まで冷却 して遠心分離 し ( 1 0 0 0 0 G X 3 0 分) 、 上澄を乾燥して固形物 2 0 2 . 5 g を回収 した。 また、 こ の固型物を 5 % の 水溶液と して、大豆油を加えなが ら ホモ ミ キサー にて 1 0 0 0 0 r p m で乳化処理を行っ た と こ ろ 、 lOO g の水 溶液に対して大豆油 を 12 Og加えた と こ ろ で転相 した。 こ の と きの油分/複合体重量比は 24であ っ た。 TypeUSP-Hj Esterification degree 70.5; Sansho Co., Ltd.) 200 g and soybean protein (trade name "Fujipro-E"; Fuji Oil Co., Ltd.) 100 g with warm water 57 After dissolving to 100 g, the pH was adjusted to 4.0 with hydrochloric acid, and the mixture was heated at 120 for 1.5 hours to produce a heated product of HM-vector and soybean protein. After heating, the mixture was cooled to room temperature, centrifuged (100,000 GX for 30 minutes), and the supernatant was dried to collect 202.5 g of a solid. This solid was converted to a 5% aqueous solution, and soybean oil was added thereto using a homomixer. When the emulsification treatment was performed at 0.000 rpm, the phase was inverted when 12 Og of soybean oil was added to 100 g of an aqueous solution. The oil / composite weight ratio at this time was 24.
実施例 3  Example 3
HM ーぺク チ ン (商品名 「ゲニュ一ぺク チン  HM Parkin (Product name “Genuine Parkin”
typeUSP-Hj エステル化度 7 0 . 5 ; 三晶株式会社製) 2 0 0 g と大豆蛋白質 (商品名 「フ ジプロ - E」 ; 不二 製油株式会社製) l O O g と を温水 5 7 0 0 g に溶 解後、 塩酸で p H を 2 . 0 に調整 し、 1 2 0 で 1 . 5 時間加熱 して H M — ぺク チン と大豆蛋白質の 加熱物を生成させた。加熱後室温まで冷却 して遠心分離 し ( 1 0 0 0 0 G X 3 0 分) 、 上澄を乾燥して固形物 2 4 3 g を回収 した。 また、 こ の固型物を 5 % の水溶 液と して、大豆油を加えなが ら ホモ ミ キサーにて 1 0 0 O O r p m で乳化処理を行つ た と こ ろ 、 100 g の水溶液 に対して大豆油 を 60 g加えた と こ ろ で転相 した。 こ の と きの油分/複合体重量比は 12であ つ た。 TypeUSP-Hj Esterification degree 70.5; Sansho Co., Ltd.) 200 g and soybean protein (trade name "Fujipro-E"; Fuji Oil Co., Ltd.) lOO g After dissolution to 0 g, the pH was adjusted to 2.0 with hydrochloric acid, and the mixture was heated at 120 for 1.5 hours to produce a heated product of HM-pectin and soybean protein. After heating, the mixture was cooled to room temperature, centrifuged (100,000 G × 30 minutes), and the supernatant was dried to recover 243 g of a solid. The solid was converted to a 5% aqueous solution, and emulsified at 100 000 rpm with a homomixer while adding soybean oil to give 100 g of an aqueous solution. The phase was inverted when 60 g of soybean oil was added. The oil / composite weight ratio at this time was 12.
実施例 4  Example 4
II M —ぺク チ ン (商品名 「ゲニューべク チン  II M—Pectin (Product name “Genuvector”
typeUSP-Hj エス テル化度 7 0 . 5 ; 三晶株式会社製) 2 0 0 g と大豆蛋白質 (商品名 「フ ジプロ - E」 ; 不二 製油株式会社製) 1 0 0 g と を温水 5 7 0 0 g に溶 解後、 苛性ソーダで P H を 5 . 0 に調整し、 1 2 0 °Cで 1 . 5 時間加熱 して H M — ぺク チン と大豆蛋 白質の加熱物を生成させた。加熱後室温まで冷却 して遠 心分離 し ( 1 0 0 0 0 G X 3 0 分) 、 上澄を乾燥 して 固形物 1 8 4 g を回収 した。 また、 こ の 固型物を 5 % の水溶液と して、 大豆油を加えなが ら ホモ ミ キサーにて l O O O O r p m で乳化処理を行っ た と こ ろ 、 100 g の 水溶液に対 して大豆油を 45 g加えた と こ ろ で転相 した。 こ の と きの油分/複合体重量比は 9であ っ た。 typeUSP-Hj Esterification degree 70.5; Sansho Co., Ltd.) 200 g and soy protein (trade name “Fujipro-E”; Fuji Oil Co., Ltd.) 100 g and hot water 5 After dissolving to 700 g, the pH was adjusted to 5.0 with caustic soda, and the mixture was heated at 120 ° C for 1.5 hours to produce a heated product of HM-pectin and soybean protein. After heating, the mixture was cooled to room temperature, centrifuged (1000 GX 30 minutes), and the supernatant was dried. 184 g of a solid was recovered. Also, this solid was converted to a 5% aqueous solution and emulsified with a homomixer at lOOO rpm while adding soybean oil. The phase was inverted when 45 g of soybean oil was added. The oil / composite weight ratio at this time was 9.
比較例 1  Comparative Example 1
HM 一 べ 'ク チ ン (商品名 「ゲニューべク チン  HM one-button (trade name "Genuine vector"
typeUSP-Hj エステル化度 7 0 . 5 ; 三晶株式会社製) 2 0 0 g と大豆蛋白質 (商品名 「フ ジプロ - E」 ; 不二 製油株式会社製) 1 0 0 g と を温水 5 7 0 0 g に溶 解後、 塩酸で P H を 1 . 5 に調整し、 1 2 0 で 1 . 5 時間加熱 して H M ー ぺク チ ン と大豆蛋白質の 加熱物を生成させた。加熱後室温まで冷却 して遠心分離 し ( 1 0 0 0 0 G X 3 0 分) 、 上澄を乾燥して固形物 2 5 5 g を回収 した。 また、 こ の固型物 を 5 % の水溶 液と して、大豆油を加えなが ら ホモ ミ キサー にて 1 0 0 0 0 r p m で乳化処理を行つ た と こ ろ 、 100 g の水溶液 に対して大豆油を 5g加えた と こ ろで転相 した。 こ の と き の油分/複合体重量比は 1であ っ た。 TypeUSP-Hj Degree of esterification 70.5; Sansho Co., Ltd.) 200 g and soybean protein (trade name "Fujipro-E"; Fuji Oil Co., Ltd.) 100 g with warm water 5 7 After dissolving the solution to 100 g, the pH was adjusted to 1.5 with hydrochloric acid, and the mixture was heated at 120 for 1.5 hours to produce a heated product of HM-actin and soybean protein. After heating, the mixture was cooled to room temperature, centrifuged (100,000 G × 30 minutes), and the supernatant was dried to collect 255 g of a solid. The solid was converted to a 5% aqueous solution, and emulsified at 100 rpm with a homomixer while adding soybean oil to obtain a 100 g aqueous solution. The phase was inverted when 5 g of soybean oil was added to the mixture. The oil / composite weight ratio at this time was 1.
比較例 2  Comparative Example 2
HM —べク チン (商品名 「ゲニューべク チ ン  HM—Vectin (Product name “Genuine Vectin
typeUSP-Hj エステル化度 7 0 . 5 ; 三晶株式会社製) 2 0 0 g と大豆蛋白質 (商品名 「フ ジプロ -E」 ; 不二 製油株式会社製) 1 0 0 g と を温水 5 7 0 0 g に溶 解後、 苛性ソ ーダで p H を 7 . 0 に調整 し、 1 2 0 °Cで 1 . 5 時間加熱 して H M — べク チ ン と大豆蛋 白質の加熱物を生成させた。加熱後室温まで冷却 して遠 心分離 し ( 1 0 0 0 0 G X 3 0 分) 、 上澄を乾燥 して 固形物 2 3 0 g を回収 した。 ま た、 こ の固型物 を 5 % の水溶液 と して、大豆油を加えなが ら ホモ ミ キサー にて l O O O O r p m で乳化処理を行っ た と こ ろ 、 100 g の 水溶液に対して大豆油を 15 g加えた と こ ろで転相 した。 こ の と き の油分/複合体重量比は 3であ っ た。 TypeUSP-Hj Esterification degree 70.5; Sansho Co., Ltd.) 200 g and soybean protein (trade name "Fujipro-E"; Fuji Oil Co., Ltd.) 100 g were heated with hot water 57 After dissolving to 0 g, adjust the pH to 7.0 with caustic soda, heat at 120 ° C for 1.5 hours, and heat HM-vector and soybean protein. A white matter heated product was produced. After heating, the mixture was cooled to room temperature and centrifuged (1000 GX for 30 minutes), and the supernatant was dried to recover 230 g of a solid. The solid was converted to a 5% aqueous solution, and emulsified with a homomixer at l OOOO rpm while adding soybean oil. The phase was inverted when 15 g of soybean oil was added. The oil / composite weight ratio at this time was 3.
比較例 3  Comparative Example 3
HM — ぺク チ ン (商品名 「ゲニュ一ぺク チン  HM — Parkin (trade name “Genuine Parkin”
typeUSP- H」 エステル化度 7 0 . 5 ; 三晶株式会社製)typeUSP-H ”Esterification degree 70.5;
2 0 0 g を温水 3 8 0 0 g に溶解後 .. 塩酸で p H をAfter dissolving 200 g in 3800 g of warm water, adjust the pH with hydrochloric acid.
3 . 0 に調整し、 1 2 0 °Cで 1 . 5 時間加熱 して H M 一 べク チ ンの加熱分解物 を得た。 加熱後室温まで冷 却 して遠心分離し ( 1 0 0 0 0 G X 3 0 分) 、 上澄を 乾燥 して固形物 1 7 1 g を回収 した。 また、 こ の固型物 を 5 % の水溶液と して、 大豆油を加え なが ら ホモ ミ キ サ一 にて l O O O O r p m で乳化処理を行っ た と こ ろ 1 0 0 g の水溶液に対して大豆油を 7g加えた と こ ろ で 転相 した。 こ の と きの油分/複合体重量比は 1.2であ っ た 比較例 4 The temperature was adjusted to 3.0, and the mixture was heated at 120 ° C for 1.5 hours to obtain a thermally decomposed product of HM vector. After heating, the mixture was cooled to room temperature and centrifuged (1000 GX 30 minutes), and the supernatant was dried to collect 171 g of a solid. This solid was converted to a 5% aqueous solution, and emulsification was performed at lOOO rpm with a homomixer while adding soybean oil. The phase was inverted when 7 g of soybean oil was added. The oil / composite weight ratio at this time was 1.2 Comparative Example 4
大豆蛋白質 (商品名 「フ ジプロ - E」 ; 不二製油株式会 社製) 2 0 0 g と を温水 3 8 0 0 g に溶解後、 塩酸 で p H を 3 . 0 に調整し、 1 2 0 で 1 . 5 時間 加熱 して大豆蛋白質の加熱分解物を得た。加熱後室温ま で冷却 して遠心分離 し ( 1 0 0 0 0 G X 3 0 分) 、 上 澄を乾燥 して固形物 1 1 Ί g を 回収 した。 ま た、 こ の固 型物を 5 % の水溶液と して、 大豆油を加えなが ら ホモ ミ キサー にて 1 0 0 0 0 r p m で乳化処理を行っ た と こ ろ 、 1 0 0 g の水溶液に対 して大豆油を 22g加えた と こ ろ で転相 した。 こ の と きの油分 /複合体重量比は 4 . 4 であ っ た。 200 g of soybean protein (trade name “Fujipro-E”; manufactured by Fuji Oil Co., Ltd.) was dissolved in 800 g of warm water, and the pH was adjusted to 3.0 with hydrochloric acid. The mixture was heated at 0 to 1.5 hours to obtain a thermally decomposed product of soybean protein. After heating, the mixture was cooled to room temperature, centrifuged (100,000 GX for 30 minutes), and the supernatant was dried to recover 11 g of a solid. Also, this solid When the mold was emulsified with a homomixer at 100,000 rpm while adding soybean oil to a 5% aqueous solution, 100 g of the aqueous solution was reconstituted. The phase was inverted when 22 g of soybean oil was added. The oil / composite weight ratio at this time was 4.4.
比較例 5  Comparative Example 5
比較例 3 な ら びに.比較例 4 で得 ら れた分解物を重量 比で 2 : 1 の割合で混合 して 5 % の水溶液 と して、 大 豆油 を加えなが ら ホモミ キサー にて 1 0 0 0 0 r p m で乳化処理を行っ た と こ ろ 、 1 0 0 g の水溶液に対 して 大豆油を 1 2 g 加えた と こ ろ で転相 した。 こ の と きの油 分/複合体重量比は 2 . 4 であ っ た。  Comparative Example 3 and The decomposed product obtained in Comparative Example 4 was mixed at a weight ratio of 2: 1 to form a 5% aqueous solution, and the mixture was mixed with a homomixer while adding soybean oil. When the emulsification treatment was performed at 0.000 rpm, the phase inversion occurred when 12 g of soybean oil was added to 100 g of the aqueous solution. The oil / composite weight ratio at this time was 2.4.
実施例 5  Example 5
HM ー ぺク チン (商品名 「ゲニュ一ぺク チン  HM ぺ チ ン 商品 「(Product name“ Gen.
typeUSP-Hj エステル化度 7 0 . 5 ; 三晶株式会社製) と大豆蛋白質 (商品名 「フ ジプロ - E」 ; 不二製油株式会 社製) と を 2 : 1 の割合で混合 し これに固形分濃度が 5 % とな る よ う に温水を加え、 H3.0、 120 °C 、 1.5時間 の加熱 し 、 加熱後実施例 1 と 同様の処理を行い得 ら れた 本発明品 1 . 5部 と食塩 2.5部、 グルタ ミ ン酸ナ ト リ ウム 0.5部を水 13. 5部に溶解 して、 さ ら に食酢 12. 5部を加え ミ キサー に入れた。 こ の ミ キサー に精製キャ ノ ー ラ油 70 部を徐々 に加えて乳化 しマ ヨ ネーズ様 ド レ ッ シ ングを 得た。 こ のマ ヨ ネーズ様 ド レ ツ シングは油分が HMぺク チ ン -大豆蛋白複合体の 47倍量も使用 さ れてい る に もかか わ らず乳化粒子径は 4.3 mと細か く 、 良好な風味と物性 であ っ た。 typeUSP-Hj Esterification degree 70.5; Sansho Co., Ltd.) and soy protein (trade name "Fujipro-E"; Fuji Oil Co., Ltd.) are mixed at a ratio of 2: 1. Warm water was added so that the solid content concentration was 5%, and the mixture was heated at H3.0 at 120 ° C for 1.5 hours. After heating, the product of the present invention obtained by performing the same treatment as in Example 1 1. 5 parts, 2.5 parts of sodium chloride, and 0.5 parts of sodium glutamate were dissolved in 13.5 parts of water, and 12.5 parts of vinegar was added, and the mixture was added to a mixer. 70 parts of refined canola oil was gradually added to this mixer and emulsified to obtain mayonnaise-like dressing. This mayonnaise-like dressing has a fine emulsified particle size of 4.3 m, despite the fact that the oil content is 47 times that of the HM-pectin-soy protein complex. Good flavor and physical properties Met.
実施例 6  Example 6
LMぺク チ ン (商品名 「ゲニュ一ぺク チン typeASj ェ ステル化度 5 1 ; 三晶株式会社製) と乾燥卵 白 (キュ — ピー株式会社製) と を 5 : 1 の割合で混合 し これに固 形分濃度が 5 % と な る よ う に温水を加え、 pH 4 . 0、 105 180分の加熱 し、 加熱後実施例 1 と 同様の処理を行い得 ら れた本発明品 4 部 とカゼイ ンナ ト リ ウム 2 部を水 69 部に溶解 した。 これに、 市販の ミ ルク フ レーバ一 ( 「ミ ルク F T — 013 」 、 高砂香料 (株) 製) 0. 1 部を添加 した精製椰子油 25部を 70 °Cで加え、 ホモ ミ キサーにて予 備乳化をお こ な っ た。 次いで、 高圧ホモゲナイ ザー にて 乳化 (300 kgf/cm 2 ) して、 コ ー ヒー用ホワイ ト ナー を 得た。 こ のホ ワイ ト ナ一は油分が LMぺク チン -卵白蛋白 複合体の 6. 3倍量も使用 されてい る に もかかわ らず、 平 均粒径 1. 2 H m であ り 殺菌処理後に 1 ヶ月 冷蔵保存 して も安定であ っ た。また、砂糖 8 % を含むコ 一 ヒ一(炭 酸水素ナ ト リ ウムで pHを 6. 8 に調製) に加え、 121 で、 30分 レ ト ル ト殺菌 した後、 60 X で 3 ヶ月 保存 したが、 乳 化破壊な どは認め ら れなかっ た。  A mixture of LM pectin (trade name "Genuctin typeASj esterification degree 51; manufactured by Sanshin Co., Ltd.") and dried egg white (produced by K-P Co., Ltd.) in a ratio of 5: 1. Warm water was added to the mixture so that the solid content concentration became 5%, and the mixture was heated at pH 4.0 and 105 for 180 minutes. After heating, the product of the present invention 4 obtained by performing the same treatment as in Example 1 And 2 parts of sodium caseinate were dissolved in 69 parts of water, and 0.1 part of a commercially available Milk Flavor (“Milk FT-013”, manufactured by Takasago International Inc.) was added. 25 parts of refined coconut oil was added at 70 ° C, and preliminarily emulsified with a homomixer. Then, the mixture was emulsified (300 kgf / cm 2) with a high-pressure homogenizer to obtain a whitener for coffee. This whitener has an average particle size of 1.2 Hm, although the oil content is 6.3 times the amount of the LM pectin-egg protein complex, and is sterilized. It was stable even after being refrigerated for one month. In addition, add to sugar containing 8% sugar (pH adjusted to 6.8 with sodium hydrogen carbonate), sterilize by retlet at 121 for 30 minutes, and store at 60 X for 3 months However, no destruction of lactation was observed.
実施例 Ί  Example Ί
アルギ ン酸ナ ト リ ゥム(紀文フ一 ド ケ ミ フ ァ株式会社 製) と乳清蛋白 ( 日 本プロテイ ン株式会社製) と を 1 : 2 ;の割合で混合 し これに固形分濃度が 5 % となる よ う に温水を加え、 Ph5. 0、 120 、 120分の加熱 し、 加熱後 実施例 1 と 同様の処理を行い得 ら れた本発明品 4 部 と コ コ アパウダー 6 部、 小麦粉 15部、 砂糖 180部をよ く 混 合した後に卵 白 に加えて、 角が立つ までホイ ッ プする 。 ホイ ッ プ後に 1 g 前後に絞 り 出 し、 105でで 1時間焼成し た。 こ のよ う に して製造 したメ レ ンゲ菓子は、 安定な気 泡状態を示し、絞 り 出 し作業時の経時的な状態変化が少 な く 、個々 の メ レ ンゲ菓子のキメ が安定 していた。また、 焼成によ る組織の破壊も殆ど認め ら れず、 焼成後のキメ も細か く 良好な状態を示 していた A mixture of sodium alginate (manufactured by Kibun Food Chemical Co., Ltd.) and whey protein (manufactured by Nihon Protein Co., Ltd.) at a ratio of 1: 2 ; And heated to pH 5.0, 120, and 120 minutes. After heating, the same treatment as in Example 1 was performed, and 4 parts of the product of the present invention were obtained. Mix 6 parts of coco powder, 15 parts of flour and 180 parts of sugar, add to egg white, and whip until horns are formed. After whipping, it was squeezed out to about 1 g and baked at 105 for 1 hour. The meringue confectionery produced in this way shows a stable bubble state, there is little change over time during the squeezing operation, and the texture of each meringue confectionery is stable. Was. In addition, there was almost no structural destruction due to firing, and the texture after firing was fine and good.
参考例  Reference example
L M 一 べク チン (商品名 Γ LM-SN 325 J エステル化 度 24 ; 雪印食品株式会社製) 2 0 0 g と大豆蛋白質 (商品名 「フ ジプロ - E」 ; 不二製油株式会社製) 1 0 0 g と を温水 5 7 0 O g に溶解後、 塩酸で p H を 3 . 0 に調整した と こ ろ溶液のゲル化が起 こ っ た。そ こで、 更に温水 9 0 0 0 g を加えてゲルを希釈溶解さ せた後 に 1 2 0 で 1 . 5 時間加熱 して L M — ぺク チ ン と 大豆蛋白質の加熱物 を生成さ せた。加熱後室温まで冷却 して遠心分離 し ( 1 0 0 0 0 G X 3 0 分) 、 上澄を乾 燥 して固形物 を回収 した。 ま た、 こ の固型物を 5 % の 7] 溶液と して、大豆油を加えなが ら ホモ ミ キサー にて 1 0 0 0 0 r p m で乳ィ匕処理を行っ た と こ ろ 、 100 g の水 溶液に対して大豆油 を 52 g加えた と こ ろ で転相 した。 こ の と きの油分 /複合体重量比は 10.4であ っ た。  LM-1 vector (trade name: LM-SN 325 J Esterification degree 24; Snow Brand Foods Co., Ltd.) 200 g and soy protein (trade name “Fujipro-E”; Fuji Oil Co., Ltd.) 1 After dissolving the solution (0.0 g) in warm water (570 Og), the solution was gelled when the pH was adjusted to 3.0 with hydrochloric acid. Then, 900 g of hot water was further added to dilute and dissolve the gel, and the mixture was heated at 120 for 1.5 hours to produce a heated product of LM-pectin and soy protein. Was. After heating, the mixture was cooled to room temperature, centrifuged (100,000 G × 30 minutes), and the supernatant was dried to collect a solid. Also, this solid was prepared as a 5% 7) solution, and the soybean oil was added thereto, and the mixture was subjected to a milk mixing process at 100,000 rpm with a homomixer. The phase was inverted when 52 g of soybean oil was added to the aqueous solution of 1 g. The oil / composite weight ratio at this time was 10.4.
上記のよ う に、 エステル化度が 5 0 % よ り 低い酸性 多糖類を用 い る場合、本発明の複合体生成の p H範囲で は、 実施例 1 〜 4 の条件ではゲル化を起 こすため、 本参 考例のよ う に希釈する こ とが必要 と なる 。そのため複合 体化の効率も低 く な る。 こ のよ う に実用的には酸性多糖 のエステル化度は 5 0 %以上であ る こ とが望ま し い。 As described above, when an acidic polysaccharide having a degree of esterification of less than 50% is used, gelation occurs under the conditions of Examples 1 to 4 within the pH range for forming the complex of the present invention. To rub, ginseng It is necessary to dilute as in the example. As a result, the efficiency of complex formation is reduced. Thus, practically, it is desirable that the degree of esterification of the acidic polysaccharide is 50% or more.
産業上の利用可能性 Industrial applicability
本発明の力ルポキシル基を有する酸性糖を構成糖として含 む多糖と蛋白質または蛋白加水分解物とを PH 2から 5の酸性下 で加熱する製造方法により得られる複合体は乳化剤として従来 のものと比較して乳化活性が飛躍的に向上した乳化剤であり、乳 化剤量に対し多量の油脂を含む乳化物の製造に有利に利用され る  The complex obtained by the production method of the present invention in which a polysaccharide containing an acidic saccharide having a lipoxyl group as a constituent saccharide and a protein or protein hydrolyzate is heated under acidic conditions of pH 2 to 5 is different from a conventional conjugate as an emulsifier. This is an emulsifier with significantly improved emulsifying activity, and is advantageously used in the production of emulsions containing a large amount of fats and oils relative to the amount of emulsifier.

Claims

請 求 の 範 囲 The scope of the claims
1 . 力ルポキシル基を有する酸性糖を構成糖として含む多糖と蛋 白質または蛋白加水分解物とを pH 2から 5の酸性下で加熱す ることにより生成する酸性多糖-蛋白複合体を有効成分とする 乳化剤。 . 1. An acidic polysaccharide-protein complex formed by heating a polysaccharide containing an acidic sugar having a lipoxyl group as a constituent saccharide and a protein or protein hydrolyzate under acidic conditions of pH 2 to 5 is used as an active ingredient. Emulsifier. .
2 . カルボキシル基を有する酸性糖がゥロン酸である請求項 1記 載の乳化剤。  2. The emulsifier according to claim 1, wherein the acidic sugar having a carboxyl group is peronic acid.
3 ·酸性糖を含む多糖がぺクチンまたはべクチン分解物である請 求項 1記載の乳化剤。 3. The emulsifier according to claim 1, wherein the polysaccharide containing acidic sugar is a pectin or a pectin degradation product.
4 . 力ルポキシル基の 5 0 %以上がエステル化されている請求項  4. Claim that at least 50% of the lipoxyl groups are esterified.
1乃至 3に記載の乳化剤。  4. The emulsifier according to 1 to 3.
5 .乳化剤量に対し重量比で 5倍量以上の油分を乳化可能な乳化 能を有する請求項 1乃至 4に記載の乳化剤。  5. The emulsifier according to any one of claims 1 to 4, having an emulsifying ability capable of emulsifying an oil component in an amount of 5 times or more by weight relative to the amount of the emulsifier.
6 . 力ルポキシル基を有する酸性糖を構成糖として含む多糖と蛋 白質または蛋白分解物とを pH 2から 5の酸性下で加熱するこ とを特徴とする、 酸性多糖-蛋白複合体を有効成分とする乳化 剤の製造方法。  6. An acidic polysaccharide-protein complex as an active ingredient, wherein a polysaccharide containing an acidic saccharide having a lipoxyl group as a constituent saccharide and a protein or a proteolysate are heated under acidic conditions of pH 2 to 5. A method for producing an emulsifier.
7 . 加熱の pHが、 pH 2. 8 から 4. 2 である請求項 6に記載の乳 化剤の製造方法。 7. The method for producing an emulsifier according to claim 6, wherein the pH of the heating is from pH 2.8 to 4.2.
8 . 請求項 1乃至 5 に記載の乳化剤を使用してなる乳化組成物。 8. An emulsified composition using the emulsifier according to claim 1.
PCT/JP2004/002669 2003-03-04 2004-03-03 Emulsifier contianing polysaccharide-protein complex as the active ingredient, process for producing the same and emulsified composition WO2004078334A1 (en)

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