JP4262179B2 - Acid oil-in-water emulsified composition - Google Patents

Acid oil-in-water emulsified composition Download PDF

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JP4262179B2
JP4262179B2 JP2004273813A JP2004273813A JP4262179B2 JP 4262179 B2 JP4262179 B2 JP 4262179B2 JP 2004273813 A JP2004273813 A JP 2004273813A JP 2004273813 A JP2004273813 A JP 2004273813A JP 4262179 B2 JP4262179 B2 JP 4262179B2
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oil
fatty acid
pse
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acidic oil
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尚人 工藤
大介 椎葉
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Kao Corp
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Priority to DE602005003621T priority patent/DE602005003621T2/en
Priority to EP05020496A priority patent/EP1637040B1/en
Priority to US11/229,677 priority patent/US7550170B2/en
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本発明は、特にマヨネーズ類、ドレッシング類に好適に使用される酸性水中油型乳化組成物に関する。   The present invention relates to an acidic oil-in-water emulsified composition that is suitably used particularly for mayonnaises and dressings.

近年、ジグリセリドが肥満防止作用、体重増加抑制作用等を有することが明らかにされるに至り(特許文献1)、これを各種食品に配合する試みがなされている。そして、ジグリセリドを高濃度に含むグリセリド混合物を油相に用いれば、脂肪量を低減した場合においても豊かな脂肪感を有し、風味が良好な食用水中油型乳化組成物が得られることが報告されている(特許文献2)。   In recent years, it has been clarified that diglyceride has an obesity-preventing action, a weight gain-inhibiting action, and the like (Patent Document 1), and attempts have been made to blend this into various foods. And if a glyceride mixture containing diglyceride at a high concentration is used in the oil phase, it is reported that an edible oil-in-water emulsion composition having a rich fat feeling and good flavor can be obtained even when the amount of fat is reduced. (Patent Document 2).

また、酸性水中油型乳化組成物中の全リン脂質に対しその15%(リン量基準)以上をリゾリン脂質とすることにより、安定的な水中油型乳化組成物が得られることが報告されている(特許文献3)。しかし、酸性水中油型乳化組成物の油相としてジグリセリド高含有油を使用した場合、原料となる油脂を構成する脂肪酸の種類によっては、冷蔵庫内条件下(−5℃〜5℃)においてジグリセリドの一部が結晶化することにより乳化破壊を生じ、油水分離が発生する場合がある。そこで、低温耐性を向上させるために、特定範囲の乳化剤が結晶抑制剤として有効であることが報告されている(特許文献4)。   In addition, it has been reported that a stable oil-in-water emulsion composition can be obtained by using lysophospholipid at 15% (phosphorus level basis) or more of the total phospholipid in the acidic oil-in-water emulsion composition. (Patent Document 3). However, when a high diglyceride-containing oil is used as the oil phase of the acidic oil-in-water emulsion composition, depending on the type of fatty acid that constitutes the raw oil and fat, diglyceride under conditions in the refrigerator (-5 ° C to 5 ° C) A part of the crystallization may cause emulsion breakage and oil-water separation may occur. Therefore, it has been reported that a specific range of emulsifiers is effective as a crystallization inhibitor in order to improve low temperature resistance (Patent Document 4).

ここで、水中油型乳化組成物に植物ステロールを添加した技術があるが(特許文献5)、これは流通時の振動負荷などでの乳化破壊の防止に関するものである。一般に、植物ステロール、植物ステロールエステルを溶解させた場合、油脂中でそれらが結晶化し易くなることが知られており、植物ステロールの結晶化を抑制する手法が報告されている(特許文献6及び7)。また、植物ステロール類を含有する酸性水中油型乳化物の安定化方法として酵素処理卵黄を用い、ジグリセリドも含む酸性水中油型乳化物の技術があるが(特許文献8及び9)、これらのジグリセリド濃度はいずれも低い。   Here, there is a technique in which a plant sterol is added to an oil-in-water emulsion composition (Patent Document 5), which relates to prevention of emulsion breakage due to vibration load during distribution. In general, it is known that when plant sterols and plant sterol esters are dissolved, they are easily crystallized in fats and oils, and methods for suppressing the crystallization of plant sterols have been reported (Patent Documents 6 and 7). ). In addition, as a method for stabilizing acidic oil-in-water emulsions containing plant sterols, there is a technique of acidic oil-in-water emulsions using enzyme-treated egg yolk and also containing diglycerides (Patent Documents 8 and 9). All concentrations are low.

本発明者がジグリセリド含量の高い酸性水中油型乳化組成物の実用化に向けて、さまざまな使用場面を想定した試験を予め行ったところ、物性と風味の点で必ずしも十分ではない場合があった。即ち、マヨネーズ製品は開封後、腐敗防止の観点から冷蔵庫(−5〜5℃)に保管され、使用時には室温に戻され、使用後には再度冷蔵庫に戻されるという温度変化が幾度となく繰り返される。また、寒冷地において、夜間寒気にさらされたものが、昼間暖房により暖められるケースもある。このような温度変化に伴って、乳化状態が不安定化したり、風味が劣化する場合がある。また、これらの物性は、製造時の配管移送シェアや充填シェアの影響も受ける場合がある。   When the present inventor conducted tests assuming various use scenes in advance for practical application of an acidic oil-in-water emulsion composition having a high diglyceride content, there were cases where physical properties and flavor were not always sufficient. . That is, after opening, the mayonnaise product is stored in a refrigerator (-5 to 5 ° C.) from the viewpoint of preventing corruption, returned to room temperature when used, and then returned to the refrigerator again after use. Also, in cold districts, those exposed to cold at night can be warmed by daytime heating. With such temperature change, the emulsified state may become unstable or the flavor may deteriorate. In addition, these physical properties may be affected by a pipe transfer share and a filling share at the time of manufacture.

更に、樹脂製の一般的なマヨネーズ容器に充填したマヨネーズ等の酸性水中油型乳化組成物は、使用するたびに押し圧(ボトル加圧シェア)が加わるため、場合によっては乳化が不安定化し、更には乳化破壊、離水等の品質低下が引き起こされることもあった。   Furthermore, acidic oil-in-water emulsified compositions such as mayonnaise filled in resin-made general mayonnaise containers are subjected to pressing pressure (bottle pressurization share) every time they are used, and in some cases, emulsification becomes unstable. Furthermore, quality degradation such as emulsion breakage and water separation may be caused.

そのため、ジグリセリド含量の高い酸性水中油型乳化組成物には、使用時に繰り返し発生するボトル加圧シェアと温度変化に対し、物性と風味の点で高度な安定性を有することが求められる。しかし、上記乳化剤等の結晶抑制剤ではこれら全てを満たすことはできなかった。また、これらを多用したのでは、酸性水中油型乳化組成物の風味等に影響を与えるため好ましくない。
特開平4−300828号公報 特開平3−8431号公報 特開2001−138号公報 特開2002−176952号公報 国際公開第03/047359号パンフレット 特開2003−226890号公報 特開2003−160795号公報 特開2002−171931号公報 特開2002−206100号公報
Therefore, acidic oil-in-water emulsion compositions with a high diglyceride content are required to have high stability in terms of physical properties and flavor against bottle pressurization shear and temperature changes that occur repeatedly during use. However, the crystal inhibitors such as the above emulsifiers cannot satisfy all of them. Moreover, it is not preferable to use many of these because it affects the flavor and the like of the acidic oil-in-water emulsion composition.
Japanese Unexamined Patent Publication No. 4-300828 Japanese Patent Laid-Open No. 3-8431 JP 2001-138 A JP 2002-176852 A International Publication No. 03/047359 Pamphlet JP 2003-226890 A Japanese Patent Laid-Open No. 2003-160795 JP 2002-171931 A JP 2002-206100 A

本発明の目的は、保存時の低温耐性に加え、使用時に繰り返し発生するボトル加圧シェアと温度変化に対し、物性と風味の点で高度な安定性を有する、ジグリセリドを高濃度で含有する酸性水中油型乳化組成物を提供することにある。   The object of the present invention is to have high stability in terms of physical properties and flavor, with a high concentration of diglyceride against bottle pressure share and temperature changes that occur repeatedly during use, in addition to low temperature resistance during storage. The object is to provide an oil-in-water emulsion composition.

通常の油脂(即ちトリグリセリド)中に植物ステロール類を溶解させた場合、油脂中でそれらが結晶化し易くなることが知られており、植物ステロールの結晶化を抑制する手法が検討されていることは前述の通りである。ジグリセリドはトリグリセリドと異なり分子中にOH基を1つ多く有しているため、トリグリセリドより融点が高く、結晶化しやすいことが一般的に知られている。ここで、特定範囲のポリグリセリン脂肪酸エステルがジグリセリドの結晶化抑制効果を有することは前述の通りであるが、ジグリセリド高含有油に植物ステロール類を配合した場合に生ずる油脂全体の結晶化を防止することはできない。   It is known that when phytosterols are dissolved in ordinary fats and oils (that is, triglycerides), they are known to be easily crystallized in fats and oils, and methods for suppressing crystallization of plant sterols are being studied. As described above. Since diglyceride has one OH group in the molecule unlike triglyceride, it is generally known that it has a higher melting point than triglyceride and is easily crystallized. Here, as described above, the polyglycerin fatty acid ester in a specific range has an effect of suppressing crystallization of diglyceride, but prevents crystallization of the entire fat and oil that occurs when plant sterols are blended with a diglyceride-rich oil. It is not possible.

しかし本発明者は、本知見からは全く予想されない結果を得た。即ち、ジグリセリド高含有油脂と卵黄を用いた酸性水中油型乳化組成物において、ポリグリセリン脂肪酸エステルと特定組成の植物ステロール類を併用することにより、油脂全体の結晶化は防止できないにも関わらず、乳化物の低温耐性を向上させると同時に、加圧シェア耐性、温度変化耐性を有し、乳化物の物性が変化せず、更に乳化物自体の風味、特にコク味が向上することを見いだし、本発明を完成した。   However, the present inventor obtained a result that was not expected at all from this finding. That is, in an acidic oil-in-water emulsion composition using high fat and oil containing diglyceride and egg yolk, crystallization of the whole oil and fat cannot be prevented by using a polyglycerol fatty acid ester and a plant sterol having a specific composition in combination. It has been found that it improves the low temperature resistance of the emulsion, and at the same time has pressure shear resistance and temperature change resistance, and does not change the physical properties of the emulsion, and further improves the flavor of the emulsion itself, especially the richness. Completed the invention.

即ち、本発明は、次の(A)、(B)、(C)及び(D):
(A)ジグリセリド含量が30質量%以上である油脂、
(B)卵黄、
(C)植物ステロール(PS)と植物ステロール脂肪酸エステル(PSE)の質量比がPSE/(PS+PSE)>0.3を満たし、かつPSEを構成する脂肪酸の80質量%以上が不飽和脂肪酸であるPS及びPSE、
(D)ポリグリセリン脂肪酸エステル
を含有する酸性水中油型乳化組成物を提供するものである。
That is, the present invention provides the following (A), (B), (C) and (D):
(A) a fat or oil having a diglyceride content of 30% by mass or more,
(B) egg yolk,
(C) PS in which the mass ratio of plant sterol (PS) and plant sterol fatty acid ester (PSE) satisfies PSE / (PS + PSE)> 0.3, and 80% by mass or more of the fatty acids constituting PSE is unsaturated fatty acid. And PSE,
(D) An acidic oil-in-water emulsion composition containing a polyglycerol fatty acid ester is provided.

本発明によれば、ジグリセリドを高濃度で含有する酸性水中油型乳化組成物でありながら低温耐性を有し、使用時に繰り返し発生するボトル加圧シェアと温度変化に対し、物性低下と風味劣化を改善することができる。   According to the present invention, although it is an acidic oil-in-water emulsified composition containing diglyceride at a high concentration, it has low-temperature resistance, and with respect to bottle pressurization share and temperature change that occur repeatedly at the time of use, physical properties and flavor deterioration are reduced. Can be improved.

マヨネーズ類、ドレッシング類等の酸性水中油型乳化組成物は、冷蔵庫等の低温で保存された場合でも、結晶化、固化が起こらないように、低融点油脂を使用することが好ましい。本発明において用いるジグリセリドも、低融点であることが好ましい。具体的には、構成脂肪酸残基の炭素数が8〜24、特に16〜22であることが好ましい。また不飽和脂肪酸残基の量は、全脂肪酸残基の55質量%(以下単に%と記載する)以上が好ましく、更に70〜100%、特に90〜100%、殊更93〜98%であるのが好ましい。ジグリセリドは、植物油、動物油等とグリセリンとのエステル交換反応、又は上記油脂由来の脂肪酸とグリセリンとのエステル化反応等任意の方法により得られる。反応方法は、アルカリ触媒等を用いた化学反応法、リパーゼ等の油脂加水分解酵素を用いた生化学反応法のいずれでもよい。   The acidic oil-in-water emulsified compositions such as mayonnaises and dressings preferably use low-melting oils and fats so that crystallization and solidification do not occur even when stored at a low temperature such as a refrigerator. The diglyceride used in the present invention also preferably has a low melting point. Specifically, the carbon number of the constituent fatty acid residue is preferably 8 to 24, particularly 16 to 22. The amount of unsaturated fatty acid residues is preferably 55% by mass (hereinafter simply referred to as%) or more of the total fatty acid residues, more preferably 70 to 100%, particularly 90 to 100%, and particularly 93 to 98%. Is preferred. Diglyceride can be obtained by any method such as an ester exchange reaction between vegetable oil, animal oil or the like and glycerin, or an esterification reaction between fatty acid derived from the above fats and glycerin. The reaction method may be either a chemical reaction method using an alkali catalyst or the like, or a biochemical reaction method using an oil and fat hydrolase such as lipase.

本発明の酸性水中油型乳化組成物において、(A)油脂中のジグリセリド含量は、脂質代謝改善食品又は体脂肪蓄積抑制食品としての有効性、工業的生産性の観点から30%以上であり、好ましくは35〜100%、更に50〜99.9%、特に71〜95%であるのが望ましい。油脂には、ジグリセリド以外に、トリグリセリド、モノグリセリド、遊離脂肪酸等を含有させることができる。   In the acidic oil-in-water emulsion composition of the present invention, (A) the diglyceride content in the fat is 30% or more from the viewpoint of effectiveness as a lipid metabolism improving food or a body fat accumulation-inhibiting food, and industrial productivity. It is preferably 35 to 100%, more preferably 50 to 99.9%, particularly 71 to 95%. Oils and fats can contain triglycerides, monoglycerides, free fatty acids and the like in addition to diglycerides.

成分(A)油脂中のモノグリセリドの含量は、乳化性、風味、工業生産性の点から5%以下であるのが好ましく、更に0〜2%、特に0.1〜1.5%であるのが良い。モノグリセリドの構成脂肪酸は、工業的生産性の点でジグリセリドの構成脂肪酸と同じであるのが好ましい。   The content of the monoglyceride in the component (A) oil is preferably 5% or less, more preferably 0 to 2%, particularly 0.1 to 1.5% from the viewpoint of emulsifiability, flavor and industrial productivity. Is good. The constituent fatty acid of the monoglyceride is preferably the same as the constituent fatty acid of the diglyceride in terms of industrial productivity.

成分(A)油脂中の遊離脂肪酸(塩)の含量は、乳化性、風味、工業的生産性の点で1%以下であるのが好ましく、更に0〜0.5%、特に0.05〜0.2%であるのが良い。   The content of the free fatty acid (salt) in the component (A) fat is preferably 1% or less, more preferably from 0 to 0.5%, particularly from 0.05 to 5 in terms of emulsifiability, flavor and industrial productivity. It is good to be 0.2%.

成分(A)油脂中のトリグリセリドの含量は乳化性、風味、生理効果、工業的生産性の点で70%以下であるのが好ましく、更に0〜65%、特に0.1〜50%、殊更3.3%〜28.85%であるのが望ましい。   The content of triglyceride in the component (A) oil is preferably 70% or less, more preferably 0 to 65%, particularly 0.1 to 50%, especially in terms of emulsifying properties, flavor, physiological effects and industrial productivity. It is desirable that it is 3.3% to 28.85%.

本発明に用いる(B)卵黄は、生、凍結、粉末、加塩、加糖等任意の形態でよく、また卵白を含んだ全卵の形態で配合してもよい。組成物中の卵黄の含有量は、風味向上の観点から、液状卵黄換算で5〜20%であるのが好ましく、更に好ましくは7〜17%、特に好ましくは8〜15%、最も好ましくは10〜15%である。   The (B) egg yolk used in the present invention may be in any form such as raw, frozen, powdered, salted, and sweetened, or may be formulated in the form of whole egg containing egg white. The content of egg yolk in the composition is preferably 5 to 20% in terms of liquid egg yolk, more preferably 7 to 17%, particularly preferably 8 to 15%, and most preferably 10 from the viewpoint of improving the flavor. ~ 15%.

また、成分(B)卵黄は、一部又は全部が酵素処理されたものであることが、乳化安定性の点から好ましい。卵黄の酵素処理に用いる酵素としては、エステラーゼ、リパーゼ、ホスホリパーゼが好ましく、リパーゼ、ホスホリパーゼがより好ましく、ホスホリパーゼが特に好ましい。ホスホリパーゼの中でも、ホスホリパーゼA、すなわちホスホリパーゼA1及び/又はA2が最も好ましい。 In addition, the component (B) egg yolk is preferably partly or wholly enzyme-treated from the viewpoint of emulsion stability. As the enzyme used for the enzyme treatment of egg yolk, esterase, lipase and phospholipase are preferable, lipase and phospholipase are more preferable, and phospholipase is particularly preferable. Among the phospholipases, phospholipase A, that is, phospholipase A 1 and / or A 2 is most preferable.

酵素処理された卵黄のうち、卵黄の全リン脂質に対するリゾリン脂質の質量比率(以下、リゾ比率と記載する)がリン量基準で15%以上であることが好ましく、更に25〜75%、特に29〜65%とすることが、乳化安定性の点から好ましい。リゾリン脂質は、上述のように卵黄由来であることが好ましいが、大豆由来のものを用いることもでき、また卵黄由来のものと大豆由来のものを併用することもできる。なお、卵黄の一部を酵素処理されたものとする場合は、酵素処理していない卵黄と、別途酵素処理したものを混合した後に、配合することが好ましい。   Among the egg yolks treated with the enzyme, the mass ratio of lysophospholipid to the total phospholipid of egg yolk (hereinafter referred to as lyso ratio) is preferably 15% or more, more preferably 25 to 75%, especially 29. It is preferable to set it to -65% from the point of emulsion stability. The lysophospholipid is preferably derived from egg yolk as described above, but a soybean-derived one can also be used, and an egg yolk-derived one and a soybean-derived one can also be used in combination. In addition, when it is assumed that a part of the egg yolk is subjected to the enzyme treatment, it is preferable to mix after mixing the egg yolk not subjected to the enzyme treatment and the one subjected to the enzyme treatment separately.

酵素処理条件は、卵黄の全部に酵素処理卵黄を用いる場合、リゾ比率が15%以上となるような条件を適宜選択すればよい。具体的には、酵素添加量は、酵素活性が10000IU/mLの場合、卵黄に対して0.0001〜0.1%、特に0.001〜0.01が好ましい。反応温度は20〜60℃、特に30〜55℃が好ましい。反応時間は1時間〜30時間、特に5時間〜25時間が好ましい。また卵黄の一部に酵素処理卵黄を用いる場合、酵素未処理卵黄と酵素処理卵黄の合計のリゾ比率が上記範囲となるように酵素処理条件を選択すればよい。かかる酵素処理は、各原料を混合して乳化処理する以前の段階で行うことが好ましい。   The enzyme treatment conditions may be appropriately selected such that the lyso ratio is 15% or more when the enzyme-treated egg yolk is used for the whole egg yolk. Specifically, when the enzyme activity is 10,000 IU / mL, the enzyme addition amount is preferably 0.0001 to 0.1%, particularly preferably 0.001 to 0.01 with respect to the egg yolk. The reaction temperature is preferably 20 to 60 ° C, particularly preferably 30 to 55 ° C. The reaction time is preferably 1 hour to 30 hours, particularly 5 hours to 25 hours. When enzyme-treated egg yolk is used as part of the egg yolk, the enzyme treatment conditions may be selected so that the total lyso ratio of the enzyme-untreated egg yolk and the enzyme-treated egg yolk falls within the above range. Such an enzyme treatment is preferably performed before mixing and emulsifying each raw material.

本発明においては、血中コレステロール低下作用を有する(C)植物ステロール及び植物ステロール脂肪酸エステルを配合する。ジグリセリドと成分(C)との併用により、脂質代謝改善食品としての有用性を更に高めることができる。植物ステロール(PS)とは遊離体のことで、例えばα−シトステロール、β−シトステロール、ブラシカステロール、スチグマステロール、エルゴステロール、カンペステロール等が挙げられる。また、植物ステロール脂肪酸エステル(PSE)は、上記植物ステロールと脂肪酸とのエステル化反応、上記植物ステロールと油脂又は部分グリセライドとのエステル交換反応により得られたものを用いることができるが、天然油脂からの抽出濃縮生成物なども挙げられる。本発明においては、これらのフェルラ酸エステル、配糖体、混合物を一種又は2種以上用いることができる。   In the present invention, (C) a plant sterol and a plant sterol fatty acid ester having a blood cholesterol lowering action are blended. The combined use of diglyceride and component (C) can further enhance the usefulness as a lipid metabolism improving food. Plant sterols (PS) are free forms, and include, for example, α-sitosterol, β-sitosterol, brassicasterol, stigmasterol, ergosterol, campesterol and the like. Moreover, what was obtained by esterification reaction of the said plant sterol and a fatty acid and the transesterification reaction of the said plant sterol and fats and oils or a partial glyceride can be used for plant sterol fatty acid ester (PSE). And an extract-concentrated product. In the present invention, one or more of these ferulic acid esters, glycosides, and mixtures can be used.

上記PSEを構成する脂肪酸は、温度変化耐性、加圧シェア耐性、融点、扱いやすさ、価格などの点から、大豆油脂肪酸、ナタネ油脂肪酸、ひまわり油脂肪酸、コーン油脂肪酸、分別物、これらの混合物などの植物油を由来とする脂肪酸であるのが好ましい。PSEの脂肪酸組成において、不飽和脂肪酸の含量は80%以上、好ましくは85〜100%、更に88〜99%、特に90〜98%であるのが好ましい。また、PSEの構成脂肪酸中、オレイン酸の含量は15〜75%であるのが好ましく、更に20〜70%、特に25〜65%であるのが好ましい。リノール酸の含量は10〜60%であるのが好ましく、更に12〜45%、特に15〜30%であるのが好ましい。リノレン酸の含量は0〜15%以下であるのが好ましく、更に1〜12%、特に3〜9%であるのが好ましい。
本発明の酸性水中油型乳化組成物において、成分(C)の含有量は、成分(A)に対して、遊離の植物ステロールに換算して1〜10%、更に1.2〜10%、特に2〜5%であるのが好ましい。また、植物ステロール(PS)と植物ステロール脂肪酸エステル(PSE)に対するPSEの質量比(PSE/(PS+PSE))は、0.3より大であるのがよく、更に0.7〜1、特に0.8〜1、殊更0.9〜0.99であるのが、風味、温度変化耐性、加圧シェア耐性の点で好ましい。また、成分(C)のPSを、成分(A)に対して0.001〜0.3%、更に0.01〜0.2%、特に0.05〜0.15%とするのが、風味、温度変化耐性、加圧シェア耐性の点で好ましい。
The fatty acids constituting the PSE are soybean oil fatty acid, rapeseed oil fatty acid, sunflower oil fatty acid, corn oil fatty acid, fractions, and the like in terms of temperature change resistance, pressure shear resistance, melting point, ease of handling, price, etc. Fatty acids derived from vegetable oils such as mixtures are preferred. In the fatty acid composition of PSE, the content of unsaturated fatty acid is 80% or more, preferably 85 to 100%, more preferably 88 to 99%, and particularly preferably 90 to 98%. Further, the content of oleic acid in the constituent fatty acids of PSE is preferably 15 to 75%, more preferably 20 to 70%, and particularly preferably 25 to 65%. The content of linoleic acid is preferably 10 to 60%, more preferably 12 to 45%, particularly preferably 15 to 30%. The content of linolenic acid is preferably 0 to 15% or less, more preferably 1 to 12%, and particularly preferably 3 to 9%.
In the acidic oil-in-water emulsified composition of the present invention, the content of the component (C) is 1 to 10%, further 1.2 to 10% in terms of free plant sterol, with respect to the component (A). 2 to 5% is particularly preferable. Further, the mass ratio of PSE to plant sterol (PS) and plant sterol fatty acid ester (PSE) (PSE / (PS + PSE)) should be greater than 0.3, more preferably 0.7 to 1, and particularly preferably 0.8. 8 to 1, particularly 0.9 to 0.99 is preferable in terms of flavor, temperature change resistance, and pressure shear resistance. Further, PS of the component (C) is 0.001 to 0.3%, further 0.01 to 0.2%, particularly 0.05 to 0.15% with respect to the component (A). It is preferable in terms of flavor, temperature change resistance, and pressure shear resistance.

本発明における(D)ポリグリセリン脂肪酸エステルは、グリセリンの平均重合度が2〜12、構成脂肪酸の炭素数が12〜22、エステル化度70%以上、特に80%以上のものが好ましい。また、HLBが4.5未満、特に3.5未満であることが加圧シェア耐性、温度変化耐性の点から好ましい。本発明の酸性水中油型乳化組成物において、成分(D)の含有量は、成分(A)に対して、0.1〜5%であるのが好ましく、更に0.25〜3%、特に0.6〜2%、殊更0.7〜1.5%であるのが、風味、加圧シェア耐性、温度変化耐性の点で好ましい。   The (D) polyglycerol fatty acid ester in the present invention preferably has an average polymerization degree of glycerin of 2 to 12, a carbon number of constituent fatty acids of 12 to 22, an esterification degree of 70% or more, particularly 80% or more. Moreover, it is preferable from the point of pressurization shear tolerance and temperature change tolerance that HLB is less than 4.5, especially less than 3.5. In the acidic oil-in-water emulsion composition of the present invention, the content of the component (D) is preferably 0.1 to 5%, more preferably 0.25 to 3%, particularly with respect to the component (A). 0.6 to 2%, especially 0.7 to 1.5% is preferable in terms of flavor, pressure shear resistance, and temperature change resistance.

本発明の酸性水中油型乳化組成物の水相には、水、米酢、酒粕酢、リンゴ酢、ブドウ酢、穀物酢、合成酢等の食酢、食塩、グルタミン酸ソーダ等の調味料、砂糖、水飴等の糖類、酒、みりん等の呈味量、各種ビタミン、クエン酸等の有機酸及びその塩、香辛料、レモン果汁等の各種野菜又は果実の搾汁液、キサンタンガム、ジェランガム、グァーガム、タマリンドガム、カラギーナン、ペクチン、トラガントガム等の増粘多糖類、馬鈴薯澱粉等の澱粉類、それらの分解物及びそれらを化工処理した澱粉類、ショ糖脂肪酸エステル、ソルビタン脂肪酸エステル、ポリソルベート等の合成乳化剤、大豆タンパク質、乳タンパク質、小麦タンパク質等、あるいはこれらタンパク質の分離物や分解物等のタンパク質系乳化剤、レシチン又はその酵素分解物等の天然系乳化剤、牛乳等の乳製品、各種リン酸塩等を配合することができる。本発明においては、目的とする組成物の粘度、物性等に応じて、これらを適宜配合できる。   In the aqueous phase of the acidic oil-in-water emulsion composition of the present invention, water, rice vinegar, sake lees vinegar, apple vinegar, grape vinegar, grain vinegar, synthetic vinegar and other vinegar, salt, glutamic acid soda seasoning, sugar, Sugar, such as syrup, taste, such as liquor, mirin, various vitamins, organic acids such as citric acid and their salts, spices, juices of various vegetables such as lemon juice, xanthan gum, gellan gum, guar gum, tamarind gum, Carrageenan, pectin, thickened polysaccharides such as tragacanth gum, starches such as potato starch, degradation products thereof and starches modified by them, sucrose fatty acid ester, sorbitan fatty acid ester, synthetic emulsifier such as polysorbate, soy protein, Milk protein, wheat protein, etc., or protein-based emulsifiers such as isolates and degradation products of these proteins, lecithin or its enzyme content It can be blended natural emulsifiers such things, dairy milk, etc., various phosphates and the like. In the present invention, these can be appropriately blended according to the viscosity, physical properties and the like of the target composition.

かかる水相のpHは、風味と保存性の観点から酸性であるが、2〜6であるのが好ましく、特に3〜5であるのが好ましい。水相のpH調整には、上記した食酢、有機酸、有機酸の塩類、果汁類等の酸味料を使用できる。   The pH of the aqueous phase is acidic from the viewpoints of flavor and storage stability, but is preferably 2 to 6, particularly 3 to 5. To adjust the pH of the aqueous phase, acidulants such as vinegar, organic acids, salts of organic acids, fruit juices and the like can be used.

油相と水相の質量比は、10/90〜80/20であるのが好ましく、更に20/80〜75/25、特に35/65〜72/28、殊更60/40〜70/30であるのが望ましい。
本発明の酸性水中油型乳化組成物としては、例えば日本農林規格(JAS)で定義されるドレッシング、半固体状ドレッシング、乳化液状ドレッシング、マヨネーズ、サラダドレッシング、フレンチドレッシング等が挙げられるが、特にこれらに限定されるものではなく、広くマヨネーズ類、マヨネーズ様食品、ドレッシング類、ドレッシング様食品といわれるものが該当する。
The mass ratio of the oil phase to the water phase is preferably 10/90 to 80/20, more preferably 20/80 to 75/25, especially 35/65 to 72/28, especially 60/40 to 70/30. It is desirable.
Examples of the acidic oil-in-water emulsified composition of the present invention include dressings, semi-solid dressings, emulsified liquid dressings, mayonnaise, salad dressings, French dressings and the like defined by the Japanese Agricultural Standards (JAS). It is not limited to, but widely mayonnaises, mayonnaise-like foods, dressings and dressing-like foods.

本発明の酸性水中油型乳化組成物は、例えば以下の方法により製造することができる。まず(A)ジグリセリド含有油脂、(C)植物ステロール等、及び(D)ポリグリセリン脂肪酸エステルの油性成分を混合して油相を調製する。また、(B)卵黄、その他の水溶性原料を混合して水相を調製する。該水相に該油相を添加し、必要により予備乳化を行い、均質化することにより、酸性水中油型乳化組成物を得ることができる。均質機としては、例えばマウンテンゴウリン、マイクロフルイダイザー等の高圧ホモジナイザー、超音波式乳化機、コロイドミル、アジホモミキサー、マイルダー等が挙げられる。
このようにして製造された酸性水中油型乳化物は容器に充填され、容器入り乳化食品として、通常のマヨネーズ等と同様に使用することができる。例えば、タルタルソース等のソース、サンドイッチ、サラダの他、焼き物、炒め物、和え物といった調理に使用できる。
容器としては通常、マヨネーズ、ドレッシング等の酸性水中油型乳化食品に用いられるものであれば、いずれでも良い。特に、瓶に比べて使い勝手の良い可撓性容器、例えばプラスチック製のチューブ式容器が好ましい。プラスチック製容器の材質としては、ポリエチレン、ポリプロピレン、エチレン性酢酸ビニル、エチレン・ビニルアルコール共重合体、ポリエチレンテレフタレート等の熱可塑性プラスチックの一種又は二種以上を混合して中空成型したものや、これらの熱可塑性プラスチックからなる層を二層以上に積層して中空成形したもの等を用いることができる。
The acidic oil-in-water emulsion composition of the present invention can be produced, for example, by the following method. First, an oil phase is prepared by mixing oil components of (A) diglyceride-containing oil and fat, (C) plant sterol, and (D) polyglycerol fatty acid ester. Moreover, (B) egg yolk and other water-soluble raw materials are mixed to prepare an aqueous phase. An acidic oil-in-water emulsified composition can be obtained by adding the oil phase to the aqueous phase, pre-emulsifying if necessary, and homogenizing. Examples of the homogenizer include high-pressure homogenizers such as mountain gourin and microfluidizer, ultrasonic emulsifiers, colloid mills, azimuth homomixers, milders, and the like.
The acidic oil-in-water emulsion thus produced is filled in a container and can be used as an emulsified food in a container in the same manner as ordinary mayonnaise. For example, it can be used for cooking sauces such as tartar sauce, sandwiches, salads, grilled foods, fried foods, and seasonings.
Any container can be used as long as it is used for acidic oil-in-water emulsified foods such as mayonnaise and dressing. In particular, a flexible container that is easier to use than a bottle, such as a plastic tube container, is preferred. As the material of the plastic container, one or two or more thermoplastic plastics such as polyethylene, polypropylene, ethylenic vinyl acetate, ethylene / vinyl alcohol copolymer, polyethylene terephthalate, etc., which are hollow molded, or these A layer formed of two or more layers made of thermoplastic plastic and hollow-molded can be used.

〔卵黄液の調製〕
食塩濃度10%の卵黄液750g、水150g及び食塩15gを混合し、反応温度で十分予備加熱した。次いで、卵黄液に対して表1に示す量のホスホリパーゼA2を添加して反応を行い、酵素処理卵黄(卵黄1、2)を得た。反応時間、反応温度、リゾ比率を表1に示す。尚、リゾ比率は以下の方法により求めた。まず反応物をクロロホルム/メタノール(3:1)混合溶媒により繰り返し抽出を行い、反応物中の全脂質を得た。得られた脂質混合物を薄層クロマトグラフィーに供した。一次元=クロロホルム:メタノール:水(65:25:49)、二次元=ブタノール:酢酸:水(60:20:20)による二次元薄層クロマトグラフィーにより分画した。分画した各種のリン脂質を分取し、リン脂質中のリン量を市販の測定キット(過マンガン酸塩灰化法、リン脂質テストワコー、和光純薬工業株式会社製)を用いて測定した。リゾ比率(%)は(リゾリン脂質画分中のリン質量/全リン脂質中のリン質量)×100により求めた。
(Preparation of egg yolk liquid)
750 g of egg yolk solution having a salt concentration of 10%, 150 g of water and 15 g of sodium chloride were mixed and sufficiently preheated at the reaction temperature. Subsequently, phospholipase A 2 in an amount shown in Table 1 was added to the egg yolk liquid to carry out a reaction to obtain enzyme-treated egg yolks (egg yolks 1 and 2). Table 1 shows the reaction time, reaction temperature, and lyso ratio. The lyso ratio was determined by the following method. First, the reaction product was repeatedly extracted with a mixed solvent of chloroform / methanol (3: 1) to obtain total lipids in the reaction product. The resulting lipid mixture was subjected to thin layer chromatography. Fractionation was performed by two-dimensional thin layer chromatography with one dimension = chloroform: methanol: water (65:25:49) and two dimensions = butanol: acetic acid: water (60:20:20). Various fractionated phospholipids were collected, and the amount of phosphorus in the phospholipids was measured using a commercially available measurement kit (permanganate ashing method, phospholipid test Wako, manufactured by Wako Pure Chemical Industries, Ltd.). . The lyso ratio (%) was determined by (phosphorus mass in lysophospholipid fraction / phosphorus mass in total phospholipid) × 100.

Figure 0004262179
Figure 0004262179

参考例1〜5
ジグリセリド高含有油に対して表2に示した物質を配合し、次いで−5℃で1日間静置後の外観を観察した。その結果を表2に示す。尚、植物ステロール脂肪酸エステルは米国Archer Daniels Midland Company製CardioAid-Sを用い、植物ステロール(フリー体(遊離体))はタマ生化学社製、フィトステロールFを用いた。その植物ステロール組成、及び脂肪酸組成を表3に示す。ここで、植物ステロール脂肪酸エステルの添加量は、フリー体に換算した質量とし、エステル体質量/1.68=フリー体質量より算出した。
Reference Examples 1-5
The substances shown in Table 2 were added to the diglyceride-rich oil, and then the appearance after standing at -5 ° C for 1 day was observed. The results are shown in Table 2. As the plant sterol fatty acid ester, CardioAid-S manufactured by Archer Daniels Midland Company in the United States was used, and as the plant sterol (free body (free body)), phytosterol F manufactured by Tama Seikagaku Co., Ltd. was used. The plant sterol composition and fatty acid composition are shown in Table 3. Here, the addition amount of the plant sterol fatty acid ester was a mass converted to a free form, and was calculated from an ester form mass / 1.68 = a free form mass.

Figure 0004262179
Figure 0004262179

Figure 0004262179
Figure 0004262179

ジグリセリド高含有油、及びジグリセリド高含有油に対してポリグリセリン脂肪酸エステルと植物ステロール、及び/または植物ステロール脂肪酸エステルを加えたものは、いずれも−5℃において結晶化して凝固しており、ジグリセリド高含有油に対して結晶化抑制の効果は全く認められなかった。   High diglyceride content oil, and diglyceride high content oil added with polyglycerin fatty acid ester and plant sterol and / or plant sterol fatty acid ester are all crystallized and solidified at -5 ° C. No crystallization suppression effect was observed for the oil contained.

実施例1(本発明品1〜3、比較品1〜3)
表4に示す組成の油相及び水相を常法に従って調製した。次いで水相を撹拌しながら油相を予備乳化した後、コロイドミル(ストレートローター:PUC社製)を使用して3000r/min、クリアランス0.045mmで均質化し、体積平均乳化粒子径1.5〜2.8μmのマヨネーズを製造した。得られたマヨネーズについて各種評価を行った(試験例1〜5)。結果を表4に示す。
Example 1 (Invention products 1 to 3, Comparative products 1 to 3)
An oil phase and an aqueous phase having the composition shown in Table 4 were prepared according to a conventional method. Next, after pre-emulsifying the oil phase while stirring the aqueous phase, it was homogenized at 3000 r / min with a clearance of 0.045 mm using a colloid mill (straight rotor: manufactured by PUC). A 2.8 μm mayonnaise was produced. Various evaluation was performed about the obtained mayonnaise (Test Examples 1-5). The results are shown in Table 4.

試験例1(加圧シェア耐性物性評価)
製造したマヨネーズを加圧容器に詰め、圧力を負荷しながら(196kPa)内径4mm、長さ30cmの配管内を通して、加圧シェアを加えた。加圧シェア負荷前後の粘度を次法で測定した。次いでシェア負荷時の粘度低下率(%)を下式に従って求め、物性評価を行った。
粘度測定条件:20℃
BROOKFIELD社製DV−I型
No.6スピンドル、2r/min、30秒後測定。
粘度低下率=(シェア負荷後の粘度/シェア負荷前の粘度)×1000
Test Example 1 (Pressure shear resistance property evaluation)
The manufactured mayonnaise was packed in a pressure vessel, and a pressure share was applied through a pipe having an inner diameter of 4 mm and a length of 30 cm while applying pressure (196 kPa). The viscosity before and after the pressure shear load was measured by the following method. Subsequently, the viscosity reduction rate (%) at the time of shear load was determined according to the following formula, and physical properties were evaluated.
Viscosity measurement conditions: 20 ° C
BROOKFIELD DV-I type
No. 6 spindles, 2r / min, measured after 30 seconds.
Viscosity reduction rate = (viscosity after shear load / viscosity before shear load) × 1000

試験例2(ボトル加圧シェア耐性外観評価)
試験1で加圧シェアを負荷したマヨネーズを、プラスチック製チューブ式マヨネーズ容器(100mL)に約70体積%充填し、空気を排出し密閉した。この容器を繰り返し手で押し、500回押した後、チューブから搾り出した乳化物の外観を肉眼で観察し、下記基準に従って評価を行った。
評価基準
A:初期と変わらず、なめらかで光沢のある非常に良好な外観である。
B:僅かに肌が荒れるものの離水、離油は認められず、良好な外観である。
C:所々に離水、離油が認められ、不良な外観である。
Test Example 2 (Bottle pressurization shear resistance appearance evaluation)
About 70% by volume of the mayonnaise loaded with a pressure share in Test 1 was filled in a plastic tube-type mayonnaise container (100 mL), and the air was discharged and sealed. The container was repeatedly pressed by hand and pressed 500 times, and then the appearance of the emulsion squeezed out of the tube was observed with the naked eye and evaluated according to the following criteria.
Evaluation criteria A: The appearance is smooth and glossy and very good, unchanged from the initial stage.
B: Although the skin is slightly rough, water separation and oil separation are not recognized, and the appearance is good.
C: Water separation and oil separation were observed in some places, and the appearance was poor.

試験例3(低温耐性評価)
試験1で加圧シェアを負荷したマヨネーズをプラスチック製チューブ式マヨネーズ容器(100mL)に満量まで充填し、−8℃の恒温槽に保存した。1日後、2日後、3日後にそれぞれ室温に取り出し、次いで約6時間静置した後、チューブから搾り出した乳化物の外観を肉眼で観察し、試験例2と同様の基準に従って評価を行った。
Test example 3 (low temperature resistance evaluation)
The mayonnaise loaded with a pressure share in Test 1 was filled into a plastic tube-type mayonnaise container (100 mL) to a full capacity and stored in a thermostatic bath at -8 ° C. After 1 day, 2 days, and 3 days, each was taken out to room temperature and then allowed to stand for about 6 hours. Then, the appearance of the emulsion squeezed from the tube was observed with the naked eye, and evaluated according to the same criteria as in Test Example 2.

試験例4(温度サイクル耐性)
試験1で加圧シェアを負荷したマヨネーズをプラスチック製チューブ式マヨネーズ容器(100mL)に満量まで充填した。これを12時間毎に一定条件で温度が変化する恒温槽(25℃で2時間保持後、30分で0℃に低下、次いで0℃で9時間保持した後、30分で25℃に上昇)に30日間保存した。保存後、室温に約6時間静置し、次いでチューブから搾り出した乳化物の外観を肉眼で観察し、試験例2と同様の基準に従って評価を行った。
Test example 4 (temperature cycle resistance)
In test 1, the mayonnaise loaded with a pressure share was filled into a plastic tube mayonnaise container (100 mL) to the full capacity. This is a thermostatic chamber whose temperature changes at a constant condition every 12 hours (after holding at 25 ° C for 2 hours, it decreases to 0 ° C in 30 minutes, then holds at 0 ° C for 9 hours, then increases to 25 ° C in 30 minutes) Stored for 30 days. After storage, it was allowed to stand at room temperature for about 6 hours, and then the appearance of the emulsion squeezed out from the tube was observed with the naked eye and evaluated according to the same criteria as in Test Example 2.

試験例5(熟成後風味評価)
試験1で加圧シェアを負荷したマヨネーズを、プラスチック製チューブ式マヨネーズ容器(100mL)に満量まで充填し、容器上部空間部分を窒素にて置換した後、密栓し、20℃にて保存した。一ヵ月保存後、マヨネーズ自体の風味評価、及び野菜サラダの風味評価(レタス10g、プチトマト2切れ、スライスきゅうり3枚に対しマヨネーズ約8gをかけて食した)を43名のパネルで行った。風味評価の基準は、10点を最もおいしいとし、1点を最もおいしくないとした10段階とした。このようにして得られた点数から平均点を求め、各サンプルの評点とした。
その結果、本発明品はいずれも比較品に対し、風味が優れていた。特に、比較品においては、コク味が乏しく、野菜を咀嚼していくと水っぽくなり、青臭みやエグ味が感じられたのに対し、本発明品は、コク味が強く、野菜を咀嚼していっても、青臭みやエグ味が低減され、おいしく食することができた。
Test example 5 (flavor evaluation after aging)
The mayonnaise loaded with a pressure share in Test 1 was filled into a plastic tube-type mayonnaise container (100 mL) to the full capacity, the upper space of the container was replaced with nitrogen, sealed, and stored at 20 ° C. After storage for one month, the flavor evaluation of mayonnaise itself and the flavor evaluation of vegetable salad (lettuce 10g, 2 slices of cherry tomato, 3 pieces of sliced cucumber were eaten over about 8g of mayonnaise) were performed on 43 panels. The standard of flavor evaluation was made into 10 stages, with 10 points being the most delicious and 1 point being the least delicious. An average score was obtained from the scores thus obtained and used as a score for each sample.
As a result, the products of the present invention were superior in flavor to the comparative products. In particular, in the comparative product, the rich taste was poor, and when chewing the vegetables, it became watery, and a blue odor and a delicious taste were felt, whereas the inventive product had a strong taste and chewed the vegetables. However, the blue odor and taste were reduced and I was able to eat deliciously.

Figure 0004262179
Figure 0004262179

参考例で示された、低温耐性に対して全く向上効果がみられないジグリセリド高含有油脂組成物であっても、これを酸性水中油型乳化組成物とした本発明品は、配管移送シェア、充填シェアに相当する加圧シェア耐性、実際の使用時に相当する500回押し圧試験(ボトル加圧シェア耐性)、低温耐性、温度サイクル耐性のいずれの性能をも満たしており、さらに風味が優れていた。
一方、PS及び/またはPSEとポリグリセリン脂肪酸エステルの両者を含まない比較品はいずれも、加圧シェア負荷で粘度低下が著しかった。また、500回押し圧試験でも安定性が劣っており、温度サイクル耐性も劣っていた。さらにジグリセリド純度低下の影響としてジグリセリド高含有油の一部を大豆白絞油に置き換えた比較品では、乳化物の低温耐性が向上するものの、ボトル加圧シェア耐性、温度サイクル耐性の向上は見られず、また風味の向上もみられなかった。
Even in the case of a diglyceride-containing oil-and-fat composition that shows no improvement effect at all with respect to low-temperature resistance as shown in the reference example, the product of the present invention in which this is an acidic oil-in-water emulsion composition has a pipe transfer share, Satisfies both pressure share resistance equivalent to filling share, 500 times pressing test equivalent to actual use (bottle pressure share resistance), low temperature resistance, temperature cycle resistance, and excellent flavor It was.
On the other hand, any of the comparative products not containing both PS and / or PSE and polyglycerin fatty acid ester had a significant decrease in viscosity due to a pressure share load. Moreover, stability was inferior also in the 500 times pressing pressure test, and temperature cycle tolerance was also inferior. In addition, the comparative product in which part of the high diglyceride content oil was replaced with soybean white oil as an effect of diglyceride purity reduction improved the low temperature resistance of the emulsion, but improved bottle pressure share resistance and temperature cycle resistance were seen. In addition, the flavor was not improved.

Claims (5)

次の(A)、(B)、(C)及び(D):
(A)ジグリセリド含量が30質量%以上である油脂、
(B)卵黄、
(C)植物ステロール(PS)及び植物ステロール脂肪酸エステル(PSE)の質量比がPSE/(PS+PSE)>0.3を満たし、かつPSEを構成する脂肪酸の80質量%以上が不飽和脂肪酸であるPS及びPSEを成分(A)に対して、遊離の植物ステロールに換算して1〜10質量%
(D)ポリグリセリン脂肪酸エステル
を含有する酸性水中油型乳化組成物。
The following (A), (B), (C) and (D):
(A) a fat or oil having a diglyceride content of 30% by mass or more,
(B) egg yolk,
(C) PS in which the mass ratio of plant sterol (PS) and plant sterol fatty acid ester (PSE) satisfies PSE / (PS + PSE)> 0.3, and 80% by mass or more of the fatty acids constituting PSE is unsaturated fatty acid. And PSE with respect to component (A), in terms of free plant sterol, 1 to 10% by mass
(D) An acidic oil-in-water emulsion composition containing a polyglycerol fatty acid ester.
卵黄の一部又は全部が、酵素処理されたものである請求項1記載の酸性水中油型乳化組成物。   The acidic oil-in-water emulsified composition according to claim 1, wherein a part or all of egg yolk is subjected to an enzyme treatment. 酵素がホスホリパーゼである請求項2記載の酸性水中油型乳化組成物。   The acidic oil-in-water emulsion composition according to claim 2, wherein the enzyme is phospholipase. ホスホリパーゼにより処理された卵黄のうち、卵黄の全リン脂質に対するリゾリン脂質の比率がリン量基準で15質量%以上である請求項3記載の酸性水中油型乳化組成物。   The acidic oil-in-water emulsion composition according to claim 3, wherein the ratio of lysophospholipids to total phospholipids in egg yolks treated with phospholipase is 15% by mass or more based on the amount of phosphorus. 成分(C)のPSを、成分(A)に対して0.001〜0.3質量%含むものである請求項1〜のいずれか1項記載の酸性水中油型乳化組成物。 The acidic oil-in-water emulsion composition according to any one of claims 1 to 4 , wherein the component (C) PS is contained in an amount of 0.001 to 0.3% by mass relative to the component (A).
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