JP7490300B2 - Plastic fat composition - Google Patents
Plastic fat composition Download PDFInfo
- Publication number
- JP7490300B2 JP7490300B2 JP2019175381A JP2019175381A JP7490300B2 JP 7490300 B2 JP7490300 B2 JP 7490300B2 JP 2019175381 A JP2019175381 A JP 2019175381A JP 2019175381 A JP2019175381 A JP 2019175381A JP 7490300 B2 JP7490300 B2 JP 7490300B2
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- oil
- fat
- mass
- plastic
- composition
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- Edible Oils And Fats (AREA)
- Bakery Products And Manufacturing Methods Therefor (AREA)
Description
本発明は、可塑性油脂組成物に含まれる油脂が対称型トリアシルグリセロールを含有する、可塑性油脂組成物に関する。 The present invention relates to a plastic oil composition in which the oil contained in the plastic oil composition contains symmetric triacylglycerol.
可塑性油脂組成物は、ベーカリー生地への練り込みや折り込みに使用される。また、スプレッド、コーティングクリームおよびサンドクリームなどの用途に適している。可塑性油脂組成物は、典型的にはバターである。バターが使用されたベーカリー食品は、良好な風味と口どけを有する。しかしながら、バターは、高価であり、また、経時的に物性が変化するので、使い難い。そこで、安価で作業性がよい、バター（乳脂）以外の動植物性油脂を使用した、マーガリン、ファットスプレッド、ショートニングなどが開発されてきた。 The plastic fat composition is used for kneading and folding into bakery dough. It is also suitable for applications such as spreads, coating creams, and sandwich creams. The plastic fat composition is typically butter. Bakery foods that use butter have a good flavor and melt in the mouth. However, butter is expensive and its physical properties change over time, making it difficult to use. Therefore, margarine, fat spreads, shortenings, and the like that use animal and vegetable fats other than butter (milk fat), which are inexpensive and easy to work with, have been developed.
特にトランス脂肪酸の問題以降、可塑性油脂組成物には、パーム油、および、エステル交換および／または分別された油脂が使用されている。しかしながら、パーム油には、粗大結晶を生成し易い対称型トリアシルグリセロールが豊富に含まれる。また、エステル交換および／または分別により生成するトリアシルグリセロールは、ＳＳＳ、ＳＳＵ、ＳＵＳ、ＳＵＵ、ＵＳＵ、ＵＵＵ（Ｓ は飽和脂肪酸、Ｕはシス不飽和脂肪酸）に限られるため、可塑性油脂組成物を改質する選択肢は限られる。 In particular, since the issue of trans fatty acids, palm oil and oils and fats that have been transesterified and/or fractionated have been used in plastic oil compositions. However, palm oil is rich in symmetric triacylglycerols that tend to form coarse crystals. In addition, the triacylglycerols produced by transesterification and/or fractionation are limited to SSS, SSU, SUS, SUU, USU, and UUU (S is saturated fatty acid, U is cis-unsaturated fatty acid), so options for modifying plastic oil compositions are limited.
そのような状況下、例えば、特開２００２－０６９４８４号公報は、ＳＵＳとＵＳＵとからなるコンパウンド結晶を含有する油脂組成物を開示する。コンパウンド結晶は、安定な２鎖長のβ型結晶である。そのため、油脂組成物の経時的な物性の変化は、非常に少ないと考えられている。しかしながら、ＳＵＳとＵＳＵとがコンパウンド結晶を形成するためには、ＳＵＳとＵＳＵの存在比が１：１に近く、かつ、油脂組成物に含まれる油脂に占めるＳＵＳおよびＵＳＵの含有量が高い必要がある。ＳＵＳおよびＵＳＵの含有量が高い油脂を得るためには、高度な油脂加工技術が必要とされる。したがって、コンパウンド結晶の利用は、コストを非常に高くする。 Under such circumstances, for example, JP 2002-069484 A discloses an oil composition containing compound crystals consisting of SUS and USU. The compound crystals are stable β-type crystals with a chain length of two. Therefore, it is believed that the physical properties of the oil composition change very little over time. However, in order for SUS and USU to form compound crystals, the ratio of SUS to USU must be close to 1:1, and the content of SUS and USU in the oil composition must be high. In order to obtain oils with a high content of SUS and USU, advanced oil processing technology is required. Therefore, the use of compound crystals makes the cost very high.
したがって、パーム油等に由来する粗大結晶を生成し易い対称型トリアシルグリセロールを含有していても、良好な組織および良好な作業性を有する可塑性油脂組成物の開発が求められていた。 Therefore, there was a need to develop a plastic oil composition that has good structure and good workability even if it contains symmetric triacylglycerols derived from palm oil, etc., which tend to form coarse crystals.
本発明の目的は、粗大結晶を生成し易い対称型トリアシルグリセロールを含有していても、低いトランス脂肪酸含有量、良好な組織および作良好な業性を有する可塑性油脂組成物、および、その製造方法を提供することである。 The object of the present invention is to provide a plastic oil composition that has a low trans fatty acid content, good structure, and good workability even if it contains symmetric triacylglycerol that is prone to forming coarse crystals, and to provide a method for producing the same.
本発明者らは、上記課題について鋭意研究を行った。その結果、可塑性油脂組成物が、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を含むことにより、可塑性油脂組成物に含まれる油脂が対称型トリアシルグリセロールを含有していても、良好な組織および作良好な業性を有することを見出した。これにより、本発明は完成された。すなわち、本発明は、以下の態様を含み得る。 The present inventors have conducted extensive research into the above-mentioned problem. As a result, they have found that a plastic oil composition containing an oil powder having a melting point of 50°C or higher and double-chain length β-type crystals has good structure and good functionality even when the oil contained in the plastic oil composition contains symmetric triacylglycerol. This has led to the completion of the present invention. That is, the present invention can include the following aspects.
［１］粉末油脂組成物を含有する可塑性油脂組成物であって、前記粉末油脂組成物が、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を含み、前記可塑性油脂組成物に含まれる油脂に占めるＨＯＨの含有量が２０～６０質量％である、前記可塑性油脂組成物。
ただし、Ｈ、Ｏ、およびＨＯＨは、以下を意味する。
Ｈ：炭素数１６～２４の飽和脂肪酸
Ｏ：オレイン酸
ＨＯＨ：グリセロールの２位にオレイン酸（Ｏ）、１位および３位に炭素数１６～２４の飽和脂肪酸（Ｈ）がエステル結合したトリアシルグリセロール
［２］前記可塑性油脂組成物に含まれる油脂に占める前記油脂粉末の割合が、０．５～３０質量％である、［１］の可塑性油脂組成物。
［３］前記可塑性油脂組成物に含まれる油脂の、ＨＨＯ含有量とＯＨＯ含有量の合計量（ＨＨＯ＋ＯＨＯ）に対する、ＨＯＨ含有量の質量比（ＨＯＨ／（ＨＨＯ＋ＯＨＯ））が２．０を超える、［１］または［２］の可塑性油脂組成物。
ただし、ＨＨＯおよびＯＨＯは、以下を意味する。
ＨＨＯ：グリセロールの１位または３位にオレイン酸（Ｏ）、２位および３位、または、１位および２位に炭素数１６～２４の飽和脂肪酸（Ｈ）がエステル結合したトリアシルグリセロール
ＯＨＯ：グリセロールの１位および３位にオレイン酸（Ｏ）、２位に炭素数１６～２４の飽和脂肪酸（Ｈ）がエステル結合したトリアシルグリセロール
［４］前記可塑性油脂組成物に含まれる油脂に占めるＨＨＯ、ＯＨＯおよびＨＯＨの合計含有量が、２２～６４質量％である、［１］～［３］の何れか１つの可塑性油脂組成物。
［５］前記可塑性油脂組成物に含まれる油脂に占めるＨＵ２およびＵ３の合計含有量が、２０～７９．５質量％である、［１］～［４］の何れか１つの可塑性油脂組成物。
ただし、Ｕ、ＨＵ２およびＵ３は、以下を意味する。
Ｕ：炭素数１６～２４の不飽和脂肪酸
ＨＵ２：グリセロールに、１分子（１つ）のＨおよび２分子（２つ）のＵがエステル結合したトリアシルグリセロール
Ｕ３：グリセロールに、３分子（３つ）のＵがエステル結合したトリアシルグリセロール
［６］前記油脂粉末が５０μｍ以下の平均粒径を有する、［１］～［５］の何れか１つの可塑性油脂組成物。
［７］前記油脂粉末の粒子が２．５以上のアスペクト比（２）を有する板状形状である、［１］～［６］の何れか１つの可塑性油脂組成物。
［８］前記油脂粉末が、グリセリンの１位～３位に炭素数ｘの脂肪酸残基Ｘを有する１種以上のＸＸＸ型トリグリセリドを含み、前記炭素数ｘは１４～２２から選択される整数である、［１］～［７］の何れか１つの可塑性油脂組成物。
［９］前記粉末油脂組成物のゆるめ嵩密度が０．０５～０．６ｇ／ｃｍ３である、［１］～［８］の何れか１つの可塑性油脂組成物。
［１０］［１］～［９］の何れか１つの可塑性油脂組成物を含む食品。
［１１］５０℃未満の融液状態にある油脂組成物に、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を含む粉末油脂組成物を分散した後、冷却する、可塑性油脂組成物の製造方法。
［１２］５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を有効成分とする、可塑性油脂組成物の結晶化促進剤。
[1] A plastic oil composition comprising a powdered oil composition, the powdered oil composition comprising an oil powder having a melting point of 50°C or higher and a double-chain length β-type crystal, and the oil contained in the plastic oil composition has an HOH content of 20 to 60 mass%.
Here, H, O, and HOH have the following meanings:
H: saturated fatty acid having 16 to 24 carbon atoms; O: oleic acid; HOH: triacylglycerol in which oleic acid (O) is ester-bonded to the 2nd position of glycerol and saturated fatty acid (H) having 16 to 24 carbon atoms is ester-bonded to the 1st and 3rd positions of glycerol. [2] The plastic oil composition according to [1], wherein the proportion of the oil powder in the oil contained in the plastic oil composition is 0.5 to 30 mass%.
[3] A plastic oil composition according to [1] or [2], in which the mass ratio (HOH/(HHO+OHO)) of the HOH content to the total amount (HHO+OHO) of the HHO content and the OHO content in the oil composition contained in the plastic oil composition exceeds 2.0.
Here, HHO and OHO have the following meanings:
HHO: a triacylglycerol having oleic acid (O) at the 1st or 3rd position of glycerol and a saturated fatty acid (H) having 16 to 24 carbon atoms at the 2nd and 3rd positions or the 1st and 2nd positions of glycerol, which are ester-bonded. OHO: a triacylglycerol having oleic acid (O) at the 1st and 3rd positions of glycerol and a saturated fatty acid (H) having 16 to 24 carbon atoms at the 2nd position of glycerol, which are ester-bonded. [4] A plastic oil composition according to any one of [1] to [3], in which the total content of HHO, OHO and HOH in the oil contained in the plastic oil composition is 22 to 64 mass%.
[5] Any one of the plastic oil compositions of [1] to [4], wherein the total content of HU2 and U3 in the oil contained in the plastic oil composition is 20 to 79.5 mass%.
Here, U, HU2 and U3 have the following meanings:
U: an unsaturated fatty acid having 16 to 24 carbon atoms; HU2: a triacylglycerol in which one molecule (1) of H and two molecules (2) of U are ester-bonded to glycerol; U3: a triacylglycerol in which three molecules (3) of U are ester-bonded to glycerol; [6] Any one of the plastic oil compositions of [1] to [5], wherein the oil powder has an average particle size of 50 μm or less.
[7] Any one of the plastic oil and fat compositions of [1] to [6], wherein the oil and fat powder particles have a plate-like shape having an aspect ratio (2) of 2.5 or more.
[8] The plastic oil composition according to any one of [1] to [7], wherein the oil powder contains one or more XXX triglycerides having a fatty acid residue X with a carbon number x at positions 1 to 3 of glycerin, and the carbon number x is an integer selected from 14 to 22.
[9] Any one of the plastic oil compositions according to [1] to [8], wherein the powdered oil composition has a loose bulk density of 0.05 to 0.6 g/ cm3 .
[10] A food product comprising the plastic oil and fat composition according to any one of [1] to [9].
[11] A method for producing a plastic oil composition, comprising dispersing a powdered oil composition containing an oil powder having a melting point of 50°C or higher and double-chain length β-type crystals in an oil composition in a molten state below 50°C, and then cooling the mixture.
[12] A crystallization accelerator for a plastic oil composition, comprising as an active ingredient an oil powder having a melting point of 50°C or higher and double-chain length β-type crystals.
本発明は、対称型トリアシルグリセロールを含有し、低いトランス脂肪酸含有量、良好な組織および作良好な業性を有する可塑性油脂組成物を提供する。本発明は、また、粉末油脂組成物を使用した当該可塑性油脂組成物の製造方法を提供する。 The present invention provides a plastic oil composition that contains symmetric triacylglycerol and has a low trans fatty acid content, good structure, and good workability. The present invention also provides a method for producing the plastic oil composition using a powdered oil composition.
以下、本発明の可塑性油脂組成物について順を追って記述する。 The plastic oil composition of the present invention will be described in detail below.
＜粉末油脂組成物＞
本発明の可塑性油脂組成物は、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を含む粉末油脂組成物を含む。当該粉末油脂組成物は、常温（２０℃）で粉末状の固体である。また、当該５０℃以上の融点と２鎖長β型結晶を有する油脂粉末の原料となる油脂は、食用油脂である限り特に制限はない。例えば、５０℃以上の融点を有する、パームステアリン、極度硬化菜種油、極度硬化高エルシン酸菜種油、極度硬化ひまわり油、極度硬化紅花油、極度硬化パーム油などが挙げられる。これらの５０℃以上の融点を有する油脂は、１種または２種以上を組み合わせて使用してもよい。上記油脂粉末の原料となる油脂の融点は、好ましくは５５℃以上であり、より好ましくは５８℃以上であり、さらに好ましくは６１℃以上である。油脂粉末の原料となる油脂の融点が上記範囲内にあると、２鎖長β型の結晶シードとして効果的に機能する。なお、油脂粉末（の原料となる油脂）の融点は、基準油脂分析試験法（日本油化学会編-1996）2．2．4．2融点（上昇融点）に準じて測定できる。
<Powdered oil and fat composition>
The plastic fat composition of the present invention includes a powdered fat composition containing a fat powder having a melting point of 50°C or higher and double-chain length β-type crystals. The powdered fat composition is a powdery solid at room temperature (20°C). The fats and oils used as the raw material for the fat powder having a melting point of 50°C or higher and double-chain length β-type crystals are not particularly limited as long as they are edible fats and oils. For example, palm stearin, extremely hardened rapeseed oil, extremely hardened high erucic acid rapeseed oil, extremely hardened sunflower oil, extremely hardened safflower oil, extremely hardened palm oil, etc., each having a melting point of 50°C or higher, may be used alone or in combination of two or more of these fats and oils having a melting point of 50°C or higher. The melting point of the fats and oils used as the raw material for the fat powder is preferably 55°C or higher, more preferably 58°C or higher, and even more preferably 61°C or higher. When the melting point of the fats and oils used as the raw material for the fat powder is within the above range, it effectively functions as a double-chain length β-type crystal seed. The melting point of the oil powder (or the oils and fats that are the raw materials for the oil powder) can be measured in accordance with 2.2.4.2 Melting Point (Slip Melting Point) of the Standard Methods for Analysis of Fats, Oils and Related Materials (edited by Japan Oil Chemists' Society, 1996).
上記粉末油脂組成物に含まれる油脂粉末は、２鎖長β型結晶を含有する。ここで、油脂結晶が２鎖長とは、油脂結晶の長面間隔をＸ線回折測定することにより判定される。すなわち、油脂結晶の長面間隔を、２θが０～８度の範囲で測定する。このとき、４０～５０Åに相当する回折ピークを検出し、６０～６５Åに相当する回折ピークを検出しないか、検出してとしても４０～５０Åに相当する回折ピークの回折強度の１／５未満（好ましくは１／１０未満）の場合に、その油脂結晶は２鎖長構造であると判定される。また、ここで、β型とは、油脂の結晶多形の一つである。油脂の結晶には、同一組成でありながら、異なる副格子構造（結晶構造）を持つものがあり、結晶多形と呼ばれている。代表的には、六方晶型、斜方晶垂直型および三斜晶平行型があり、それぞれα型、β’型およびβ型と呼ばれている。ここで、油脂結晶の結晶形がβ型であるとは、上記油脂結晶が、２θが１７～２６度のＸ線回折測定において、４．５～４．７Å、好ましくは４．６Å付近に回析ピークを有し、特に、４．１～４．３Å、好ましくは４．２Å付近に回折ピークを有さない場合である。より具体的には、Ｘ線回折測定において、β型の特徴的ピークである２θ＝１９°（４．６Å）付近のピーク強度とα型（およびβ’型）の特徴的ピークである２θ＝２１°（４．２Å）付近のピーク強度の比率：１９°／（１９°+２１°）［４．６Å／（４．６Å+４．２Å）］を算出することでβ型結晶の存在量を表す指標とできる。本発明では、上記ピーク強度比が１であることが好ましい。しかし、ピーク強度比の下限値が、例えば０．４以上、好ましくは０．５以上、より好ましくは０．６以上、さらに好ましくは０．７以上、ことさらに好ましくは０．７５以上、最も好ましくは０．８以上であればよい。ピーク強度比が０．４以上であれば、油脂結晶の５０質量％超がβ型であるとみなすことができる。ピーク強度比の上限値は１であることが好ましいが、０．９９以下、０．９８以下、０．９５以下、０．９３以下、０．９０以下、０．８５以下、０．８０以下などであってもかまわない。ピーク強度比は、上記下限値および上限値のいずれか、もしくは、任意の組み合わせであり得る。油脂粉末の油脂結晶が２鎖長β型（ピーク強度比が上記範囲内）であると、２鎖長β型結晶シードとして効果的に機能する。 The oil powder contained in the powdered oil composition contains 2-chain-length β-type crystals. The term "2-chain length" is determined by X-ray diffraction measurement of the long-plane spacing of the oil crystals. That is, the long-plane spacing of the oil crystals is measured in the range of 2θ from 0 to 8 degrees. In this case, if a diffraction peak corresponding to 40 to 50 Å is detected and a diffraction peak corresponding to 60 to 65 Å is not detected, or if a diffraction peak is detected, the diffraction intensity is less than 1/5 (preferably less than 1/10) of the diffraction peak corresponding to 40 to 50 Å, the oil crystal is determined to have a 2-chain-length structure. In addition, the β-type is one of the crystal polymorphs of oils and fats. Some oil crystals have the same composition but different sublattice structures (crystal structures), and are called crystal polymorphs. Representative types include hexagonal, orthorhombic perpendicular, and triclinic parallel, which are called α-type, β'-type, and β-type, respectively. Here, the crystal form of the fat and oil crystals is β-type when the fat and oil crystals have a diffraction peak at 4.5 to 4.7 Å, preferably around 4.6 Å, in an X-ray diffraction measurement with 2θ of 17 to 26 degrees, and in particular, do not have a diffraction peak at 4.1 to 4.3 Å, preferably around 4.2 Å. More specifically, in the X-ray diffraction measurement, the ratio of the peak intensity at 2θ = 19 ° (4.6 Å), which is a characteristic peak of the β-type, to the peak intensity at 2θ = 21 ° (4.2 Å), which is a characteristic peak of the α-type (and β'-type), 19 ° / (19 ° + 21 °) [4.6 Å / (4.6 Å + 4.2 Å)] can be calculated as an index representing the amount of β-type crystals present. In the present invention, the peak intensity ratio is preferably 1. However, the lower limit of the peak intensity ratio may be, for example, 0.4 or more, preferably 0.5 or more, more preferably 0.6 or more, even more preferably 0.7 or more, particularly preferably 0.75 or more, and most preferably 0.8 or more. If the peak intensity ratio is 0.4 or more, more than 50% by mass of the fat crystals can be considered to be β type. The upper limit of the peak intensity ratio is preferably 1, but may be 0.99 or less, 0.98 or less, 0.95 or less, 0.93 or less, 0.90 or less, 0.85 or less, 0.80 or less, etc. The peak intensity ratio may be any of the above lower limit and upper limit values, or any combination. If the fat crystals of the fat powder are 2-chain length β type (peak intensity ratio is within the above range), they effectively function as 2-chain length β type crystal seeds.
上記の油脂の結晶多形を同定するＸ線回折法を補足説明する。回折の条件は下記のブラッグの式によって与えられる。
２ｄｓｉｎθ＝ｎλ（ｎ＝１，２，３・・・）
この式を満たす位置に回折ピークが現れる。ここでｄは格子定数、θは回折（入射）角、λはＸ線の波長、ｎは自然数である。短面間隔に対応する回折ピークの２θ＝１６～２７°からは、結晶中の側面のパッキング（副格子）に関する情報が得られ、多形の同定を行なうことができる。特にトリアシルグリセロールの場合、２θ＝１９、２３、２４°（４．６Å付近、３．９Å付近、３．８Å付近）にβ型の特徴的ピークが、２１°（４．２Å）付近にα型の特徴的なピークが出現する。なお、Ｘ線回折測定は、例えば、２０℃に維持したＸ線回折装置（例えば、（株）リガク、試料水平型Ｘ線回折装置ＵＩｔｉｍａＩＶ）を用いて測定される。Ｘ線の光源としてはＣｕＫα線（１．５４Å）が最もよく利用される。Ｘ線回折の測定により得られる回折ピークの強度解析においては、油脂の非晶質部分がベースラインに及ぼす影響を除くための補正を行うのが適切である。例えば、Ｓｏｎｎｅｖｅｌｄ－Ｖｉｓｓｅｒ法などによる、バックグラウンド除去処理を行ってもよい。
The X-ray diffraction method for identifying the above-mentioned crystalline polymorphs of fats and oils is explained below. The diffraction conditions are given by the following Bragg equation.
2d sin θ = nλ (n = 1, 2, 3, ...)
A diffraction peak appears at a position that satisfies this formula. Here, d is the lattice constant, θ is the diffraction (incidence) angle, λ is the wavelength of the X-ray, and n is a natural number. From the diffraction peak corresponding to the short spacing at 2θ=16 to 27°, information on the packing of the side surfaces (sublattice) in the crystal can be obtained, and the polymorph can be identified. In particular, in the case of triacylglycerol, a characteristic peak of the β type appears at 2θ=19, 23, and 24° (near 4.6 Å, near 3.9 Å, near 3.8 Å), and a characteristic peak of the α type appears at around 21° (4.2 Å). In addition, the X-ray diffraction measurement is performed, for example, using an X-ray diffraction device (for example, Rigaku Corporation, horizontal sample type X-ray diffraction device UItimaIV) maintained at 20°C. CuKα rays (1.54 Å) are most commonly used as a light source of X-rays. In the intensity analysis of the diffraction peak obtained by the measurement of X-ray diffraction, it is appropriate to perform a correction to remove the effect of the amorphous part of the oil on the baseline. For example, background removal processing may be performed using the Sonneveld-Visser method.
上記粉末油脂組成物に含まれる油脂粉末は、好ましくは、３０μｍ以下の平均粒径を有する。当該油脂粉末の平均粒径は、好ましくは２０μｍ未満であり、より好ましくは２～１６μｍであり、さらに好ましく４～１３μｍである。なお、平均粒径（有効径）は、粒度分布測定装置（例えば、日機装株式会社製 Microtrac MT3300ExII）でレーザー回折散乱法（ISO133201、ISO9276-1）によって測定した値（ｄ５０）である。有効径とは、測定対象となる油脂粉末の実測回折パターンが、球形と仮定して得られる理論的回折パターンに適合する場合の、当該球形の粒径を意味する。このように、レーザー回折散乱法の場合、球形と仮定して得られる理論的回折パターンと、実測回折パターンを適合させて有効径を算出しているので、測定対象が板状形状であっても球状形状であっても同じ原理で測定できる。５０℃以上の融点と２鎖長β型結晶を有する油脂粉末の平均粒径（平均粒子径）が上記範囲内にあると、可塑性油脂組成物は良好な口どけを有する。 The oil powder contained in the powdered oil composition preferably has an average particle size of 30 μm or less. The average particle size of the oil powder is preferably less than 20 μm, more preferably 2 to 16 μm, and even more preferably 4 to 13 μm. The average particle size (effective diameter) is a value (d50) measured by a laser diffraction scattering method (ISO133201, ISO9276-1) using a particle size distribution measuring device (e.g., Microtrac MT3300ExII manufactured by Nikkiso Co., Ltd.). The effective diameter means the particle size of a sphere when the measured diffraction pattern of the oil powder to be measured matches the theoretical diffraction pattern obtained assuming a sphere. In this way, in the case of the laser diffraction scattering method, the effective diameter is calculated by matching the theoretical diffraction pattern obtained assuming a sphere with the measured diffraction pattern, so that the measurement can be performed using the same principle whether the measurement target is a plate-like shape or a spherical shape. When the average particle size (average particle size) of the oil powder having a melting point of 50°C or higher and double-chain length β-type crystals is within the above range, the plastic oil composition has good meltability in the mouth.
上記粉末油脂組成物は、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末の他に、乳化剤、香料、脱脂粉乳、全脂粉乳、ココアパウダー、砂糖、デキストリン、カゼインナトリウムなどのその他の成分を含んでいてもよい。これらその他の成分の量は、本発明の効果を損なわない限り任意の量とすることができる。例えば、粉末油脂組成物の全質量を１００質量％とした場合、その他の成分は、好ましくは０～７０質量％であり、より好ましくは０～５０質量％であり、さらに好ましくは０～３０質量％である。その他の成分は、その９０質量％以上が、好ましくは平均粒径１０００μｍ以下の紛体であり、より好ましくは平均粒径５００μｍ以下の紛体である。 The powdered oil composition may contain other ingredients such as emulsifiers, flavorings, skim milk powder, whole milk powder, cocoa powder, sugar, dextrin, and sodium caseinate in addition to the oil powder having a melting point of 50°C or higher and double-chain length β-type crystals. The amount of these other ingredients can be any amount as long as it does not impair the effects of the present invention. For example, when the total mass of the powdered oil composition is taken as 100 mass%, the other ingredients are preferably 0 to 70 mass%, more preferably 0 to 50 mass%, and even more preferably 0 to 30 mass%. 90 mass% or more of the other ingredients are preferably powders having an average particle size of 1000 μm or less, and more preferably powders having an average particle size of 500 μm or less.
上記粉末油脂組成物の好ましい態様の１つとしては、実質的に上記５０℃以上の融点と２鎖長β型結晶を有する油脂粉末からなる粉末油脂組成物が挙げられる。また、「実質的に」とは、粉末油脂組成物に含まれる油脂粉末以外の成分の含有量が、粉末油脂組成物を１００質量％とした場合、例えば、０～１５質量％であり、好ましくは０～１０質量％であり、より好ましくは０～５質量％であることを意味する。 One preferred embodiment of the powdered oil composition is a powdered oil composition substantially consisting of an oil powder having a melting point of 50°C or higher and double-chain length β-type crystals. Furthermore, "substantially" means that the content of components other than the oil powder contained in the powdered oil composition is, for example, 0 to 15% by mass, preferably 0 to 10% by mass, and more preferably 0 to 5% by mass, when the powdered oil composition is taken as 100% by mass.
上記粉末油脂組成物の好ましい態様の１つとしては、また、上記５０℃以上の融点と２鎖長β型結晶を有する油脂粉末の粒子が、板状の形状を呈する（板状形状である）。ここで、板状形状は、アスペクト比が、好ましくは１．２以上である。アスペクト比は、より好ましくは１．２～３．０であり、さらに好ましくは、１．３～２．５であり、ことさらに好ましくは１．４～２．０である。なお、ここでいうアスペクト比とは、粒子図形に対して、面積が最小となるように外接する長方形で囲み、その長方形の長辺の長さと短辺の長さの比と定義される。よって、粒子が球状形状の場合は、アスペクト比は１．１より小さくなる。従来技術である、極度硬化油等の常温で固体脂含量の高い油脂を溶解して直接噴霧する方法では、油脂粉末の粒子が表面張力によって、球状形状となり、アスペクト比はおおよそ１．１未満となる。そして、前記アスペクト比は、例えば、光学顕微鏡や走査型電子顕微鏡などによる直接観察により、任意に選択した粒子について、その長軸方向の長さおよび短軸方向の長さを計測することによって、計測した個数の平均値として求めることができる。 In one preferred embodiment of the powdered oil composition, the oil powder particles having a melting point of 50°C or higher and double-chain length β-type crystals have a plate-like shape (plate-like shape). Here, the plate-like shape has an aspect ratio of preferably 1.2 or more. The aspect ratio is more preferably 1.2 to 3.0, even more preferably 1.3 to 2.5, and even more preferably 1.4 to 2.0. The aspect ratio here is defined as the ratio of the long side length to the short side length of a rectangle circumscribing the particle figure so as to minimize the area. Therefore, when the particles are spherical, the aspect ratio is smaller than 1.1. In the conventional method of dissolving oils and fats with a high solid fat content at room temperature, such as extremely hardened oils, and directly spraying them, the oil powder particles become spherical due to surface tension, and the aspect ratio is approximately less than 1.1. The aspect ratio can be calculated by measuring the length in the long axis direction and the length in the short axis direction of arbitrarily selected particles through direct observation using, for example, an optical microscope or a scanning electron microscope, and then calculating the average value of the number of particles measured.
また、上記５０℃以上の融点と２鎖長β型結晶を有する油脂粉末の粒子形状は、その粒子のアスペクト比（２）を用いて表現することも可能である。本発明におけるアスペクト比（２）とは、粒子の長径を厚さで除した値〔＝長径／厚さ〕のことである。粒子が、完全な球形の場合には、アスペクト比（２）の値は１〔＝１／１〕であり、粒子の扁平度合いが増す（厚さが薄くなる）ほど、アスペクト比（２）の値は大きくなる。
粒子のアスペクト比（２）は、例えば、以下の（ａ）及び（ｂ）の方法で測定することができる。
（ａ）粒子の電子顕微鏡写真から、１個１個の粒子について長径、及び厚さを測定できる場合
電子顕微鏡写真に写った１個１個の粒子について、長径及び厚さ（縦及び横）を測定し、それぞれの粒子について、アスペクト比（２）を求め、その平均値を粒子のアスペクト比（２）とする。例えば、粒子が球形のような場合に、この測定方法を用いることができる。
（ｂ）粒子の電子顕微鏡写真から、１つ１つの粒子について長径、又は厚さを測定できない場合
例えば、粒子が扁平な形や板状形状の場合、電子顕微鏡写真に写った１個１個の粒子について、長径を測定することはできるが、厚さは写真では見えないことが多く、写真から直接測定することが難しい。このような場合、粒子をガラスビーズのような芯物質の表面に付着させて電子顕微鏡写真を撮り、芯物質表面に付着した粒子の付着面からの垂直方向の長さを、粒子の厚さとして測定し、この値を厚さとして用いる。
これを図１の模式図で説明すると、図１のＡは芯物質、Ｂはアスペクト比（２）を測定する粒子で、線分ａｂの長さ（芯物質表面に付着した粒子の付着面からの垂直方向の長さ）が、この粒子の厚さの値である。また、長径の値は、上述のレーザー回折散乱法に基づいて測定した平均粒径（ｄ５０）を用いる。このようにして測定した粒子の長径と厚さの値から、アスペクト比（２）〔＝長径／厚さ〕を求めることができる。
The particle shape of the fat or oil powder having a melting point of 50°C or more and double-chain length β-type crystals can also be expressed using the aspect ratio (2) of the particle. In the present invention, the aspect ratio (2) is the value obtained by dividing the major axis of the particle by the thickness [=major axis/thickness]. When the particle is a perfect sphere, the value of the aspect ratio (2) is 1 [=1/1], and the more flat the particle is (the thinner the thickness is), the larger the value of the aspect ratio (2).
The aspect ratio (2) of a particle can be measured, for example, by the following methods (a) and (b).
(a) When the major axis and thickness can be measured for each particle from an electron microscope photograph, the major axis and thickness (length and width) are measured for each particle shown in the electron microscope photograph, the aspect ratio (2) is calculated for each particle, and the average value is taken as the aspect ratio (2) of the particle. For example, this measurement method can be used when the particles are spherical.
(b) When the major axis or thickness of each particle cannot be measured from the electron microscope photograph of the particle For example, when the particle has a flat or plate-like shape, the major axis can be measured for each particle in the electron microscope photograph, but the thickness is often not visible in the photograph and is difficult to measure directly from the photograph. In such a case, the particle is attached to the surface of a core material such as glass beads, an electron microscope photograph is taken, and the length of the particle attached to the surface of the core material in the vertical direction from the attachment surface is measured as the thickness of the particle, and this value is used as the thickness.
This is explained using the schematic diagram in Figure 1, where A in Figure 1 is the core material, B is the particle for which the aspect ratio (2) is to be measured, and the length of the line segment ab (the length in the vertical direction from the surface of the particle attached to the core material surface) is the thickness value of this particle. The value of the major axis is the average particle size (d50) measured based on the above-mentioned laser diffraction scattering method. From the values of the major axis and thickness of the particle measured in this way, the aspect ratio (2) [= major axis/thickness] can be calculated.
本発明の油脂粉末の粒子のアスペクト比（２）は、好ましくは２．５以上であり、より好ましくは２．５～１００であり、さらに好ましくは３～５０であり、ことさらに好ましくは３～２０であり、最も好ましくは３～１５である。上記５０℃以上の融点と２鎖長β型結晶を有する油脂粉末のアスペクト比および／またはアスペクト比（２）が上記範囲内にあると、油脂粉末が油脂の結晶化促進に効果的に機能する。 The aspect ratio (2) of the particles of the fat powder of the present invention is preferably 2.5 or more, more preferably 2.5 to 100, even more preferably 3 to 50, even more preferably 3 to 20, and most preferably 3 to 15. When the aspect ratio and/or aspect ratio (2) of the fat powder having a melting point of 50°C or more and double-chain length β-type crystals is within the above range, the fat powder effectively functions to promote crystallization of fats and oils.
上記粉末油脂組成物の好ましい態様の１つとしては、また、ゆるめ嵩密度が０．０５～０．６ｇ／ｃｍ３である、粉末油脂組成物が挙げられる。粉末油脂組成物のゆるめ嵩密度は、例えば実質的に油脂粉末のみからなる場合、好ましくは０．１～０．５ｇ／ｃｍ3であり、より好ましくは０．１～０．４ｇ／ｃｍ3または０．１５～０．４ｇ／ｃｍ3であり、さらに好ましくは０．２～０．３ｇ／ｃｍ3である。ここで「ゆるめ嵩密度」とは、粉体を自然落下させた状態の充填密度である。ゆるめ嵩密度（ｇ／ｃｍ3）の測定は、例えば、内径１５ｍｍ×２５ｍＬのメスシリンダーに、当該メスシリンダーの上部開口端から２ｃｍ程度上方から粉末油脂組成物の適量を落下させて疎充填し、充填された質量（ｇ）の測定と容量（ｍＬ）の読み取りを行い、ｍＬ当たりの当該粉末油脂組成物の質量（ｇ）を算出することで求められる。また、ゆるめ嵩密度は、（株）蔵持科学器械製作所のカサ比重測定器を使用し、JIS K-6720（又はISO 1060-1及び2）に基づいて測定したカサ比重から算出することもできる。具体的には、試料１２０ｍＬを、受器（内径４０ｍｍ×高さ８５ｍｍの１００ｍＬ円柱形容器）の上部開口部から３８ｍｍの高さの位置から、該受器に落とす。受器から盛り上がった試料はすり落とし、受器の内容積（１００ｍＬ）分の試料の質量（Ａｇ）を秤量し、以下の式からゆるめ嵩密度を求めることができる。
ゆるめ嵩密度（ｇ／ｍＬ）＝Ａ（ｇ）／１００（ｍＬ）
測定は３回行ってその平均値を取ることが好ましい。
A preferred embodiment of the powdered oil composition is a powdered oil composition having a loose bulk density of 0.05 to 0.6 g/cm 3. The loose bulk density of the powdered oil composition is preferably 0.1 to 0.5 g/cm 3, more preferably 0.1 to 0.4 g/cm 3 or 0.15 to 0.4 g/cm 3 , and even more preferably 0.2 to 0.3 g/cm 3 , when the powdered oil composition is substantially composed of oil powder alone. Here, the "loose bulk density" is the packing density of the powder allowed to fall naturally. The loose bulk density (g/cm 3 ) can be measured, for example, by dropping an appropriate amount of the powdered oil composition into a measuring cylinder having an inner diameter of 15 mm and a volume of 25 mL from about 2 cm above the upper opening end of the measuring cylinder to loosely pack the mixture, measuring the packed mass (g) and reading the volume (mL), and calculating the mass (g) of the powdered oil composition per mL. The loose bulk density can also be calculated from the bulk density measured based on JIS K-6720 (or ISO 1060-1 and 2) using a bulk density measuring device manufactured by Kuramochi Scientific Instruments Manufacturing Co., Ltd. Specifically, 120 mL of sample is dropped into a receiver (a 100 mL cylindrical container with an inner diameter of 40 mm and a height of 85 mm) from a position 38 mm above the upper opening of the receiver. The sample that rises from the receiver is scraped off, and the mass (Ag) of the sample corresponding to the internal volume (100 mL) of the receiver is weighed, and the loose bulk density can be calculated from the following formula.
Loose bulk density (g/mL) = A (g) / 100 (mL)
It is preferable to carry out the measurement three times and take the average value.
また、ゆるめ嵩密度は、次の方法でも測定することができる。
ゆるめ嵩密度（ｇ／ｃｍ３）は、ホソカワミクロン（株）のパウダテスタ（ｍｏｄｅｌ ＰＴ－Ｘ）で測定することができる。
具体的には、パウダテスタに試料を仕込み、試料を仕込んだ上部シュートを振動させ、試料を自然落下により下部の測定用カップに落とす。測定用カップから盛り上がった試料はすり落とし、受器の内容積（１００ｃｍ３）分の試料の質量（Ａｇ）を秤量し、以下の式からゆるめ嵩密度を求める。
ゆるめ嵩密度（ｇ／ｃｍ３）＝Ａ（ｇ）／１００（ｃｍ３）
また、内径１５ｍｍ×２５ｍＬのメスシリンダーに、当該メスシリンダーの上部開口端から２ｃｍ程度上方から粉末油脂組成物の適量を落下させて疎充填し、充填された質量（ｇ）の測定と容量（ｍＬ）の読み取りを行い、１ｍＬ当たりの当該粉末油脂組成物の質量（ｇ）を算出することでも求めることができる。
The loose bulk density can also be measured by the following method.
The loose bulk density (g/cm 3 ) can be measured by a Powder Tester (model PT-X) manufactured by Hosokawa Micron Corporation.
Specifically, a sample is placed in a powder tester, the upper chute containing the sample is vibrated, and the sample falls naturally into a measuring cup at the bottom. The sample that rises from the measuring cup is scraped off, and the mass (Ag) of the sample in the inner volume of the receiver (100 cm3 ) is weighed, and the loose bulk density is calculated from the following formula:
Loose bulk density (g/cm 3 )=A (g)/100 (cm 3 )
Alternatively, the mass (g) of the powdered oil or fat composition per 1 mL of a measuring cylinder having an inner diameter of 15 mm and a volume of 25 mL can be calculated by dropping an appropriate amount of the powdered oil or fat composition into the measuring cylinder from about 2 cm above the upper opening end of the measuring cylinder, measuring the mass (g) of the powdered oil or fat composition filled, and reading the volume (mL).
＜粉末油脂組成物の製造方法＞
本発明の可塑性油脂組成物に含まれる粉末油脂組成物の製造方法において、５０℃以上の融点を有する油脂を、２鎖長β型結晶を有する粉末状の油脂結晶（油脂粉末あるいは油脂結晶粉末ともいう）とする方法は特に限定されず、凍結粉砕、押出造粒、噴霧冷却造粒など、従来公知の方法を適用してもよい。しかし、５０℃以上の融点を有する油脂を、粉末状の油脂結晶とする好ましい態様の１つとしては、５０℃以上の融点を有する油脂として、グリセリンの１位～３位に炭素数ｘの脂肪酸残基Ｘを有する１種以上のＸＸＸ型トリグリセリドを含み、前記炭素数ｘは１４～２２から選択される整数である、油脂を使用する態様が挙げられる。
<Method of producing powdered oil composition>
In the method for producing the powdered oil/fat composition contained in the plastic oil/fat composition of the present invention, the method for converting an oil/fat having a melting point of 50° C. or higher into powdered oil/fat crystals having double-chain length β-type crystals (also referred to as oil/fat powder or oil/fat crystal powder) is not particularly limited, and conventionally known methods such as freeze pulverization, extrusion granulation, spray cooling granulation, etc. may be applied. However, one preferred embodiment for converting an oil/fat having a melting point of 50° C. or higher into powdered oil/fat crystals is an embodiment in which an oil/fat having a melting point of 50° C. or higher contains one or more XXX triglycerides having a fatty acid residue X with a carbon number x at positions 1 to 3 of glycerin, and the carbon number x is an integer selected from 14 to 22.
上記５０℃以上の融点を有する油脂に含まれるＸＸＸ型トリグリセリドは、グリセリンの１位～３位に炭素数ｘの脂肪酸残基Ｘを有するトリグリセリドであり、各脂肪酸残基Ｘは互いに同一である。ここで、当該炭素数ｘは１４～２２から選択される整数であり、好ましくは１６～２２から選択される整数、より好ましくは１６～２０から選択される整数、さらに好ましくは１６～１８から選択される整数である。脂肪酸残基Ｘは、飽和あるいは不飽和の脂肪酸残基であってもよい。具体的な脂肪酸残基Ｘとしては、例えば、ミリスチン酸、パルミチン酸、ステアリン酸、アラキジン酸、およびベヘン酸などの残基が挙げられる。しかし、これに限定するものではない。脂肪酸残基Ｘは、より好ましくは、パルミチン酸、ステアリン酸、アラキジン酸およびベヘン酸であり、さらに好ましくは、パルミチン酸、ステアリン酸、およびアラキジン酸であり、ことさら好ましくは、パルミチン酸およびステアリン酸である。５０℃以上の融点を有する油脂に含まれる当該ＸＸＸ型トリグリセリドの含有量は、油脂の全質量を１００質量％とした場合、例えば、５０質量％以上、好ましくは６０質量％以上、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上を下限とし、例えば、１００質量％以下、好ましくは９９質量％以下、より好ましくは９５質量％以下を上限とする範囲である。ＸＸＸ型トリグリセリドは１種類または２種類以上を用いることができ、好ましくは１種類または２種類であり、より好ましくは１種類が用いられる。ＸＸＸ型トリグリセリドが２種類以上の場合は、その合計値がＸＸＸ型トリグリセリドの含有量となる。 The XXX-type triglyceride contained in the oils and fats having a melting point of 50°C or higher is a triglyceride having a fatty acid residue X with a carbon number of x at the 1st to 3rd positions of glycerin, and each fatty acid residue X is the same as each other. Here, the carbon number x is an integer selected from 14 to 22, preferably an integer selected from 16 to 22, more preferably an integer selected from 16 to 20, and even more preferably an integer selected from 16 to 18. The fatty acid residue X may be a saturated or unsaturated fatty acid residue. Specific fatty acid residues X include, for example, residues of myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. However, the fatty acid residue X is not limited to these. More preferably, the fatty acid residue X is palmitic acid, stearic acid, arachidic acid, and behenic acid, more preferably palmitic acid, stearic acid, and arachidic acid, and even more preferably palmitic acid and stearic acid. The content of the XXX triglyceride contained in fats and oils having a melting point of 50°C or higher is, when the total mass of the fats and oils is taken as 100 mass%, for example, in a range of 50 mass% or more, preferably 60 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more as the lower limit, and for example, 100 mass% or less, preferably 99 mass% or less, and more preferably 95 mass% or less as the upper limit. One or two or more types of XXX triglycerides can be used, preferably one or two types, and more preferably one type is used. When there are two or more types of XXX triglycerides, the total value represents the content of the XXX triglyceride.
上記５０℃以上の融点を有する油脂は、上記ＸＸＸ型トリグリセリド以外の、その他のトリグリセリドを含んでいてもよい。その他のトリグリセリドは、複数の種類のトリグリセリドであってもよく、合成油脂であっても天然油脂であってもよい。天然油脂としては、例えば、パーム油、ココアバター、ヒマワリ油、菜種油、大豆油、綿実油などが挙げられる。上記５０℃以上の融点を有する油脂を１００質量％とした場合、上記ＸＸＸ型トリグリセリド以外のその他のトリグリセリドは、１質量％以上、例えば、５～５０質量％程度含まれていても問題はない。その他のトリグリセリドの含有量は、例えば、好ましくは０～３０質量％、より好ましくは０～１８質量％、さらに好ましくは０～１５質量％、ことさらに好ましくは０～８質量％である。 The fats and oils having a melting point of 50°C or higher may contain other triglycerides other than the XXX triglycerides. The other triglycerides may be multiple types of triglycerides, and may be synthetic or natural. Examples of natural fats and oils include palm oil, cocoa butter, sunflower oil, rapeseed oil, soybean oil, and cottonseed oil. When the fats and oils having a melting point of 50°C or higher are taken as 100% by mass, there is no problem if the other triglycerides other than the XXX triglycerides are contained in an amount of 1% by mass or more, for example, about 5 to 50% by mass. The content of the other triglycerides is, for example, preferably 0 to 30% by mass, more preferably 0 to 18% by mass, even more preferably 0 to 15% by mass, and even more preferably 0 to 8% by mass.
上記５０℃以上の融点を有し、かつ、ＸＸＸ型トリグリセリドを有する油脂は、溶融状態とし、特定の冷却温度に保ち、冷却固化することにより、噴霧やミル等の粉砕機による機械粉砕などの特別の加工手段を採らなくても、粉末状の油脂結晶（油脂粉末）を得ることができる。より具体的には、（ａ）上記５０℃以上の融点を有し、かつ、ＸＸＸ型トリグリセリドを有する油脂を準備し、任意に工程（ｂ）として、工程（ａ）で得られた油脂を加熱し、前記油脂に含まれるトリグリセリドを融解して溶融状態の前記油脂を得、さらに（ｄ）前記溶融状態の油脂を冷却固化して、２鎖長β型結晶を含有し、その粒子形状が板状である粉末状の油脂結晶（油脂粉末）を得る。 The fats and oils having a melting point of 50°C or higher and containing XXX triglycerides can be melted, kept at a specific cooling temperature, and cooled and solidified to obtain powdered fat and oil crystals (fat powder) without using special processing methods such as spraying or mechanical crushing with a crusher such as a mill. More specifically, (a) prepare fats and oils having a melting point of 50°C or higher and containing XXX triglycerides, and optionally, in step (b), heat the fat and oil obtained in step (a) to melt the triglycerides contained in the fat and oil to obtain the fat and oil in a molten state, and further (d) cool and solidify the fat and oil in the molten state to obtain powdered fat and oil crystals (fat powder) containing double-chain-length β crystals and having a plate-like particle shape.
上記工程（ｄ）の冷却は、例えば、溶融状態の油脂を、当該油脂の融点より低い温度であって、かつ、次式：
冷却温度（℃） ＝ 炭素数ｘ × ６．６ － ６８
から求められる冷却温度以上の温度で行われる。このような温度範囲で冷却すれば、β型の細かい油脂結晶ができるので、油脂結晶粉末を容易に得ることができる。
The cooling in the step (d) may be carried out, for example, by cooling the molten oil or fat at a temperature lower than the melting point of the oil or fat and satisfying the following formula:
Cooling temperature (℃) = carbon number x x 6.6 - 68
By cooling within this temperature range, fine β-type fat crystals are formed, so that fat crystal powder can be easily obtained.
また、上記工程（ｂ）と（ｄ）の間に、工程（ｃ）として粉末生成を促進するための任意工程、例えば（ｃ１）シーディング工程、（ｃ２）テンパリング工程、および／または（ｃ３）予備冷却工程を含んでいてもよい。さらに上記工程（ｄ）で得られる油脂結晶粉末は、工程（ｄ）の冷却後に得られる固形物を粉砕して粉末状の油脂結晶を得る工程（ｅ）によって得られるものであってもよい。 In addition, between the above steps (b) and (d), an optional step (c) for accelerating powder production, such as (c1) a seeding step, (c2) a tempering step, and/or (c3) a pre-cooling step, may be included. Furthermore, the fat crystal powder obtained in the above step (d) may be obtained by a step (e) of pulverizing the solid obtained after the cooling in step (d) to obtain powdered fat crystals.
上記工程（ｅ）において、冷却後に得られる固形物は、ハンマーミル、カッターミルなど、公知の粉砕加工手段を適用して、３０μｍ以下の平均粒径を有する粉末状の油脂結晶（油脂結晶粉末あるいは油脂粉末）を生産することもできる。なお、上記工程において、５０℃以上の融点を有し、かつ、ＸＸＸ型トリグリセリドを有する油脂は、すでに述べた油脂以外の成分を０～１５質量％含む油脂組成物の状態で工程（ａ）～（ｅ）に供されてもよいし、β型油脂結晶粉末とした後、すでに述べた油脂以外のその他の成分と混合され、粉末油脂組成物としてもよい。 In the above step (e), the solid obtained after cooling can be pulverized using a known pulverizing means such as a hammer mill or cutter mill to produce powdered fat crystals (fat crystal powder or fat powder) having an average particle size of 30 μm or less. In the above steps, fats and oils having a melting point of 50° C. or higher and containing XXX triglycerides can be subjected to steps (a) to (e) in the form of a fat and oil composition containing 0 to 15% by mass of the other fats and oils as described above, or can be made into a β-fat crystal powder and then mixed with the other fats and oils as described above to produce a powdered fat and oil composition.
上記のようにして得られた、本発明の可塑性油脂組成物に好適に使用できる、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末であって、かつ、ＸＸＸ型トリグリセリドを有する油脂粉末は、好ましくは、アスペクト比が１．２以上あるいはアスペクト比（２）が２．５以上の板状形状であり、ゆるめ嵩密度が０．０５～０．６ｇ／ｃｍ３である。なお、当該油脂粉末を含有する粉末油脂組成物については、本出願人が先に出願したＰＣＴ／ＪＰ２０１６／０７８１２２（特願２０１５－１８７２７１）の明細書に詳述されるので、詳細は割愛する。前記出願の内容は、本明細書の中に取り込まれる。 The oil powder having a melting point of 50°C or higher and double-chain length β-type crystals and containing XXX triglycerides obtained as described above, which can be suitably used in the plastic oil composition of the present invention, is preferably in a plate shape with an aspect ratio of 1.2 or higher or an aspect ratio (2) of 2.5 or higher, and has a loose bulk density of 0.05 to 0.6 g/ cm3 . The powdered oil composition containing the oil powder is described in detail in the specification of PCT/JP2016/078122 (Patent Application No. 2015-187271) previously filed by the applicant, and therefore the details will be omitted. The contents of the above application are incorporated herein by reference.
＜可塑性油脂組成物＞
本発明の可塑性油脂組成物は、上記の、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を含む粉末油脂組成物を含有する。本発明の可塑性油脂組成物に含まれる油脂に占める、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末の含有量は、好ましくは０．５～３０質量％であり、より好ましくは１～２０質量％であり、さらに好ましくは２～１３質量％であり、ことさらに好ましくは３～８質量％である。本発明の可塑性油脂組成物に含まれる、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末の含有量が上記範囲内にあると、可塑性油脂組成物に含まれる油脂の結晶化促進に効果的に機能する。
<Plastic oil composition>
The plastic oil composition of the present invention contains the above-mentioned powdered oil composition containing an oil powder having a melting point of 50°C or higher and double-chain length β-type crystals. The content of the oil powder having a melting point of 50°C or higher and double-chain length β-type crystals in the oil contained in the plastic oil composition of the present invention is preferably 0.5 to 30 mass%, more preferably 1 to 20 mass%, even more preferably 2 to 13 mass%, and particularly preferably 3 to 8 mass%. When the content of the oil powder having a melting point of 50°C or higher and double-chain length β-type crystals contained in the plastic oil composition of the present invention is within the above range, it effectively functions to promote crystallization of the oil contained in the plastic oil composition.
本発明の可塑性油脂組成物は、水の含有量が３質量％以下である実質的に無水物であってもよいし、乳化物であってもよい。乳化物は、油中水型乳化物、水中油型乳化物、あるいは複合乳化物であってもよい。しかし、本発明の可塑性油脂組成物は、好ましくは無水物である。本発明の可塑性油脂組成物の具体例としては、例えば、マーガリン、ショートニングなどが挙げられる。 The plastic oil composition of the present invention may be substantially anhydrous, with a water content of 3% by mass or less, or may be an emulsion. The emulsion may be a water-in-oil emulsion, an oil-in-water emulsion, or a composite emulsion. However, the plastic oil composition of the present invention is preferably anhydrous. Specific examples of the plastic oil composition of the present invention include margarine, shortening, etc.
本発明の可塑性油脂組成物に含まれる油脂の含有量は、粉末油脂組成物に含まれる油脂を含め、具体的な可塑性油脂組成物の特質に応じて適宜設定されればよい。例えば、ショートニングの場合、油脂の含有量は、好ましくは８０～１００質量％であり、より好ましくは９０～１００質量％であり、さらに好ましくは９５～１００質量％である。マーガリン（油中水型乳化物）の場合、油脂の含有量は、好ましくは４０～９６質量％であり、より好ましくは６０～９２質量％であり、さらに好ましくは７０～８８質量％である。 The content of the fat or oil contained in the plastic fat composition of the present invention may be appropriately set according to the characteristics of the specific plastic fat or oil composition, including the fat or oil contained in the powdered fat or oil composition. For example, in the case of shortening, the fat or oil content is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass. In the case of margarine (water-in-oil emulsion), the fat or oil content is preferably 40 to 96% by mass, more preferably 60 to 92% by mass, and even more preferably 70 to 88% by mass.
本発明の可塑性油脂組成物に含まれる油脂は、ＨＯＨを２０～６０質量％含有する。以下、Ｈ、ＯおよびＨＯＨは、次を意味する。Ｈは、炭素数１６～２４の飽和脂肪酸であり、好ましくは炭素数１６～１８の飽和脂肪酸である。Ｈは、好ましくは直鎖である。Ｏは、オレイン酸である。ＨＯＨは、グリセロールの２位にオレイン酸（Ｏ）、１位および３位に炭素数１６～２４の飽和脂肪酸（Ｈ）がエステル結合した対称型のトリアシルグリセロールである。ＨＯＨを構成するＨは、鎖長が異なる脂肪酸であってもよい。本発明の可塑性油脂組成物に含まれる油脂は、ＨＯＨを、好ましくは２２～５４質量％、より好ましくは２４～５０質量％、ことさらに好ましくは２６～４６質量％含有する。 The fats and oils contained in the plastic fat composition of the present invention contain 20 to 60% by mass of HOH. Hereinafter, H, O, and HOH have the following meanings. H is a saturated fatty acid having 16 to 24 carbon atoms, and preferably a saturated fatty acid having 16 to 18 carbon atoms. H is preferably linear. O is oleic acid. HOH is a symmetric triacylglycerol in which oleic acid (O) is ester-bonded to the 2nd position of glycerol, and saturated fatty acids (H) having 16 to 24 carbon atoms are ester-bonded to the 1st and 3rd positions of glycerol. The H constituting HOH may be fatty acids with different chain lengths. The fats and oils contained in the plastic fat composition of the present invention contain HOH preferably in an amount of 22 to 54% by mass, more preferably 24 to 50% by mass, and even more preferably 26 to 46% by mass.
本発明の可塑性油脂組成物に含まれる油脂は、好ましくは、ＨＨＯおよびＯＨＯを含有する。以下、ＨＨＯおよびＯＨＯは、次を意味する。ＨＨＯは、ＯＨＨを含む非対称型トリアシルグリセロールを意味する。すなわち、ＨＨＯは、グリセロールの１位または３位にオレイン酸（Ｏ）、２位および３位、または、１位および２位に炭素数１６～２４の飽和脂肪酸（Ｈ）がエステル結合したトリアシルグリセロールである。ＨＨＯを構成するＨは、鎖長が異なる脂肪酸であってもよい。ＯＨＯは、グリセロールの１位および３位にオレイン酸（Ｏ）、２位に炭素数１６～２４の飽和脂肪酸（Ｈ）がエステル結合したトリアシルグリセロールである。 The oils and fats contained in the plastic oil composition of the present invention preferably contain HHO and OHO. Hereinafter, HHO and OHO have the following meanings. HHO means an asymmetric triacylglycerol containing OHH. That is, HHO is a triacylglycerol in which oleic acid (O) is ester-bonded to the 1st or 3rd position of glycerol, and saturated fatty acids (H) having 16 to 24 carbon atoms are ester-bonded to the 2nd and 3rd positions, or to the 1st and 2nd positions. The H constituting HHO may be fatty acids with different chain lengths. OHO is a triacylglycerol in which oleic acid (O) is ester-bonded to the 1st and 3rd positions of glycerol, and saturated fatty acids (H) having 16 to 24 carbon atoms are ester-bonded to the 2nd position.
本発明の可塑性油脂組成物に含まれる油脂は、好ましくは、上記の、ＨＯＨ、ＨＨＯおよびＯＨＯを、合計で、２２～６４質量％含有する。ＨＯＨ、ＨＨＯおよびＯＨＯの合計含有量（以下、ＨＯＨ＋ＨＨＯ＋ＯＨＯとも表す）は、より好ましくは２４～５８質量％であり、さらに好ましくは２６～５４質量％、ことさらに好ましくは２８～５０質量％である。また、本発明の可塑性油脂組成物に含まれる油脂は、好ましくは、ＨＨＯ含有量とＯＨＯ含有量の合計量（ＨＨＯ＋ＯＨＯ）に対する、ＨＯＨ含有量の質量比（ＨＯＨ／（ＨＨＯ＋ＯＨＯ））が２．０を超える。ＨＯＨ／（ＨＨＯ＋ＯＨＯ）は、より好ましくは２．０～１０００であり、さらに好ましくは３～１００であり、ことさらに好ましくは４～４０である。本発明の可塑性油脂組成物に含まれる油脂の、ＨＯＨ＋ＨＨＯ＋ＯＨＯおよび／またはＨＯＨ／（ＨＨＯ＋ＯＨＯ）が上記範囲内にあると、可塑性油脂組成物に含まれる油脂は、結晶化による組織の硬度を得やすい。 The fats and oils contained in the plastic fat composition of the present invention preferably contain 22 to 64 mass% of HOH, HHO, and OHO in total. The total content of HOH, HHO, and OHO (hereinafter also referred to as HOH+HHO+OHO) is more preferably 24 to 58 mass%, even more preferably 26 to 54 mass%, and even more preferably 28 to 50 mass%. Furthermore, the fats and oils contained in the plastic fat composition of the present invention preferably have a mass ratio (HOH/(HHO+OHO)) of the HOH content to the total amount of the HHO content and the OHO content (HHO+OHO) of more than 2.0. HOH/(HHO+OHO) is more preferably 2.0 to 1000, even more preferably 3 to 100, and even more preferably 4 to 40. When the HOH+HHO+OHO and/or HOH/(HHO+OHO) of the fats and oils contained in the plastic fat composition of the present invention are within the above ranges, the fats and oils contained in the plastic fat composition tend to have hardness in their structure due to crystallization.
本発明の可塑性油脂組成物に含まれる油脂は、好ましくはＨＵ２およびＵ３を含有する。ここで、Ｕ、ＨＵ２、およびＵ３は、次を意味する。Ｕは、炭素数が１６～２４の不飽和脂肪酸であり、好ましくは炭素数１６～１８の不飽和脂肪酸である。Ｕは、好ましくは直鎖である。ＨＵ２は、グリセロールに、１分子（１つ）のＨおよび２分子（２つ）のＵがエステル結合したトリアシルグリセロールである。Ｕ３は、グリセロールに、３分子（３つ）のＵがエステル結合した、トリアシルグリセロールである。ＨＵ２およびＵ３を構成するＵは、鎖長の異なる脂肪酸であってもよい。本発明の可塑性油脂組成物に含まれる油脂に占めるＨＵ２およびＵ３の合計含有量（以下、ＨＵ２＋Ｕ３とも表す）は、好ましくは２０～７９．５質量％であり、より好ましくは３０～７０質量％であり、さらに好ましくは３３～６５質量％であり、ことさらに好ましくは３５．５～６０質量％である。本発明の可塑性油脂組成物に含まれる油脂に占めるＨＵ２およびＵ３の合計含有量が上記範囲内にあると、生成した油脂結晶が均一に分散しやすい。 The fats and oils contained in the plastic fat composition of the present invention preferably contain HU2 and U3. Here, U, HU2, and U3 have the following meanings. U is an unsaturated fatty acid having 16 to 24 carbon atoms, preferably an unsaturated fatty acid having 16 to 18 carbon atoms. U is preferably linear. HU2 is a triacylglycerol in which one molecule (one) of H and two molecules (two) of U are ester-bonded to glycerol. U3 is a triacylglycerol in which three molecules (three) of U are ester-bonded to glycerol. The Us constituting HU2 and U3 may be fatty acids with different chain lengths. The total content of HU2 and U3 (hereinafter also referred to as HU2+U3) in the fats and oils contained in the plastic fat composition of the present invention is preferably 20 to 79.5% by mass, more preferably 30 to 70% by mass, even more preferably 33 to 65% by mass, and even more preferably 35.5 to 60% by mass. When the total content of HU2 and U3 in the fats and oils contained in the plastic fat composition of the present invention is within the above range, the generated fat and oil crystals tend to disperse uniformly.
なお、油脂に含まれる各トリアシルグリセロール含有量は、ガスクロマトグラフィー法（例えば、ＡＯＣＳ Ｃｅ５－８６準拠）により測定できる。トリアシルグリセロールの対称性は、例えば、Ｊ．Ｈｉｇｈ Ｒｅｓｏｌ．Ｃｈｒｏｍａｔｏｇｒ．，１８，１０５－１０７（１９９５）に準じて測定できる。油脂を構成する各脂肪酸の含有量は、ガスクロマトグラフィー法（例えば、ＡＯＣＳ Ｃｅ１ｆ－９６準拠）により測定できる。また、油脂のヨウ素価は、社団法人日本油化学会編、「基準油脂分析試験法」の「２．３．４．１－１９９６ ヨウ素価（ウィイス－シクロヘキサン法）」に準じて測定できる。 The content of each triacylglycerol contained in fats and oils can be measured by gas chromatography (for example, in accordance with AOCS Ce5-86). The symmetry of triacylglycerol can be measured, for example, in accordance with J. High Resol. Chromatogr., 18, 105-107 (1995). The content of each fatty acid constituting fats and oils can be measured by gas chromatography (for example, in accordance with AOCS Ce1f-96). The iodine value of fats and oils can be measured in accordance with "2.3.4.1-1996 Iodine Value (Wiess-Cyclohexane Method)" in "Standard Methods for the Analysis of Fats, Oils and Oils" compiled by the Japan Oil Chemists' Society.
本発明の可塑性油脂組成物に含まれる油脂の供給源としては、粉末油脂組成物に含まれる５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を除き、通常の食用油脂および／または含油食品素材に含まれる油脂が使用できる。食用油脂の具体例としては、大豆油、菜種油、綿実油、サフラワー油、ひまわり油、米油、コーン油、ゴマ油、オリーブ油、パーム油、シア脂、シア分別油、サル脂、サル分別油、イリッペ脂、ココアバター、ヤシ油、パーム核油、豚脂、牛脂、乳脂などや、これらの混合油、加工油脂（水素添加油、エステル交換油、分別油など）などが挙げられる。これらの食用油脂は、１種または２種以上を組み合わせて使用してもよい。 As the source of the fats and oils contained in the plastic fat composition of the present invention, except for the fats and oils powders contained in the powdered fat composition having a melting point of 50°C or higher and double-chain length β-type crystals, fats and oils contained in ordinary edible fats and oils and oil-containing food materials can be used. Specific examples of edible fats and oils include soybean oil, rapeseed oil, cottonseed oil, safflower oil, sunflower oil, rice oil, corn oil, sesame oil, olive oil, palm oil, shea fat, shea fractionated oil, monkey fat, monkey fractionated oil, illipe fat, cocoa butter, coconut oil, palm kernel oil, lard, beef tallow, milk fat, etc., as well as mixed oils and processed fats and oils (hydrogenated oil, interesterified oil, fractionated oil, etc.). These edible fats and oils may be used alone or in combination of two or more.
本発明の１態様によれば、本発明の可塑性油脂組成物に含まれる油脂は、粉末油脂組成物に含まれる５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を除き、好ましくは、パーム系油脂を含有する。ここでパーム系油脂は、パーム油由来の油脂である。パーム系油脂としては、例えば、パーム油、パーム油の分別油およびそれらの加工油（硬化、エステル交換および分別のうち１種以上の処理がなされたもの）が挙げられる。より具体的には、１段分別油であるパームオレイン、パームステアリン、パームオレインの２段分別油であるパームオレイン（パームスーパーオレイン）およびパームミッドフラクション、パームステアリンの２段分別油であるパームオレイン（ソフトパーム）およびパームステアリン（ハードステアリン）、などが例示できる。パーム系油脂は、１種あるいは２種以上を使用してもよい。本発明の可塑性油脂組成物に含まれる油脂から、粉末油脂組成物に含まれる５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を除いた油脂に占めるパーム系油脂の含有量は、好ましくは３０～９９．５質量％であり、より好ましくは５０～９７質量％であり、さらに好ましくは７０～９５質量％である。なお、エステル交換の原料油脂として、パーム系油脂が含まれる場合、原料油脂に占めるパーム系油脂含有量を、パーム系油脂の含有量として割り当てる。 According to one aspect of the present invention, the oil and fat contained in the plastic oil and fat composition of the present invention preferably contains palm-based oil and fat, except for the oil and fat powder having a melting point of 50°C or more and a double-chain length β-type crystal contained in the powdered oil and fat composition. Here, the palm-based oil and fat are oil and fat derived from palm oil. Examples of palm-based oil and fat include palm oil, fractionated palm oil, and processed oils thereof (which have been subjected to one or more of hardening, transesterification, and fractionation). More specifically, examples of the palm-based oil and fat include palm olein and palm stearin, which are first-stage fractionated oils, palm olein (palm super olein) and palm mid fraction, which are second-stage fractionated oils of palm olein, and palm olein (soft palm) and palm stearin (hard stearin), which are second-stage fractionated oils of palm stearin. One or more types of palm-based oil and fat may be used. The content of palm-based fats in the fats and oils contained in the plastic fat composition of the present invention, excluding the fat and oil powder having a melting point of 50°C or higher and double-chain length β-type crystals contained in the powdered fat and oil composition, is preferably 30 to 99.5% by mass, more preferably 50 to 97% by mass, and even more preferably 70 to 95% by mass. When palm-based fats and oils are contained as the raw fats and oils for interesterification, the palm-based fat content in the raw fats and oils is allocated as the palm-based fat content.
本発明の１態様によれば、本発明の可塑性油脂組成物に含まれる油脂は、ＨＯＨの含有量が２５質量％以上であるＨＯＨに富む油脂（以下、ＨＯＨ油脂ともいう）を含んでもよい。ＨＯＨ油脂のＨＯＨ含有量は、好ましくは３５質量％以上であり、より好ましくは４５質量％以上であり、さらに好ましくは５５質量％以上である。ＨＯＨ油脂に含まれるＨＯＨ含有量の上限は特に限定されない。しかし、ＨＯＨ油脂に含まれるＨＯＨ含有量の上限は、好ましくは９０質量％以下であり、より好ましくは８０質量％以下であり、さらに好ましくは７０質量％以下である。ＨＯＨ油脂のＨＯＨ含有量の下限と上限は、上記の数値を任意に組合せてもよい。 According to one aspect of the present invention, the oils and fats contained in the plastic oil composition of the present invention may include HOH-rich oils and fats (hereinafter also referred to as HOH oils and fats) having an HOH content of 25% by mass or more. The HOH content of the HOH oils and fats is preferably 35% by mass or more, more preferably 45% by mass or more, and even more preferably 55% by mass or more. The upper limit of the HOH content contained in the HOH oils and fats is not particularly limited. However, the upper limit of the HOH content contained in the HOH oils and fats is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. The lower limit and upper limit of the HOH content of the HOH oils and fats may be any combination of the above numerical values.
上記ＨＯＨ油脂として、より具体的には、ココアバター、シア脂、サル脂、イリッペ脂、コクム脂、アランブラッキア脂、モーラー脂、マンゴー核油、牛脂などの動植物油脂、あるいはこれらに混合、分別、エステル交換、水素添加などの１種以上の処理が適用されることにより得られる加工油脂が挙げられる。ＨＯＨ油脂は、また、すでに知られているように、パルミチン酸、ステアリン酸、あるいは、それらの低級アルコールエステルと、ハイオレイックヒマワリ油などの高オレイン酸油脂との間で、１，３位選択性リパーゼ製剤を用いて、エステル交換反応をさせた後、必要に応じて分別することにより得られる油脂を使用してもよい。ＨＯＨ油脂は、好ましくは、前記エステル交換分別油、シア脂（ステアリン）、サル脂（ステアリン）、ココアバターである。ＨＯＨ油脂は、１種または２種以上を使用してもよい。パーム系油脂である、パーム油、パーム中融点画分などは、ＨＯＨ油脂に該当する。しかし、パーム系油脂がＨＯＨ油脂に該当する場合、パーム系油脂としての取り扱いが優先される。ＨＯＨ油脂のヨウ素価は、好ましくは３０～６５であり、より好ましくは３５～６０であり、さらに好ましくは４０～５５である。 More specifically, the above-mentioned HOH fats and oils include animal and vegetable fats such as cocoa butter, shea fat, monkey fat, illipe fat, kokum fat, Alanbrachia fat, mollar fat, mango kernel oil, and beef tallow, or processed fats and oils obtained by applying one or more treatments such as mixing, fractionation, interesterification, and hydrogenation to these. As already known, the HOH fats and oils may be obtained by interesterifying palmitic acid, stearic acid, or lower alcohol esters thereof with high oleic acid fats and oils such as high oleic sunflower oil using a 1,3-position selective lipase preparation, and then fractionating as necessary. The HOH fats and oils are preferably the interesterified fractionated oils, shea fat (stearin), monkey fat (stearin), and cocoa butter. One or more types of HOH fats and oils may be used. Palm-based fats and oils such as palm oil and palm mid-melting point fractions fall under the HOH fats and oils. However, when palm-based oils and fats fall under the category of HOH oils and fats, they are preferentially handled as palm-based oils and fats. The iodine value of HOH oils and fats is preferably 30 to 65, more preferably 35 to 60, and even more preferably 40 to 55.
本発明の１態様によれば、本発明の可塑性油脂組成物に含まれる油脂は、ＨＵ２およびＵ３の含有量が高い油脂（以下、ＨＵ２＋Ｕ３油脂ともいう）を含んでもよい。ＨＵ２＋Ｕ３油脂に含まれるＨＵ２とＵ３との合計含有量は、好ましくは４０質量％以上、より好ましくは５５質量％以上である。また、ＨＵ２＋Ｕ３油脂の融点は、好ましくは３０℃以下であり、より好ましくは２０℃以下である。ＨＵ２＋Ｕ３油脂は、以下に例示する油脂を、１種または２種以上使用してもよい。 According to one aspect of the present invention, the fats and oils contained in the plastic fat composition of the present invention may contain fats and oils having a high content of HU2 and U3 (hereinafter also referred to as HU2+U3 fats and oils). The total content of HU2 and U3 contained in the HU2+U3 fats and oils is preferably 40% by mass or more, more preferably 55% by mass or more. The melting point of the HU2+U3 fats and oils is preferably 30°C or less, more preferably 20°C or less. The HU2+U3 fats and oils may use one or more of the fats and oils exemplified below.
上記ＨＵ２＋Ｕ３油脂の好ましい例としては、常温（２５℃）で液状である植物油脂が挙げられる。具体的には、大豆油、菜種油、コーン油、ひまわり油、紅花油、胡麻油、綿実油、米油、オリーブ油、落花生油、および亜麻仁油等、並びに、それら含有する複数混合油、が挙げられる。さらに、これら単独の油および複数混合油の水素添加油、エステル交換油、および分別油などの加工油も挙げられる。かかる液状植物油脂の中でも、５℃において液状であって、かつ、透明性を有する油脂がより好ましい。ＨＵ２＋Ｕ３油脂の好ましい例としては、また、非ラウリン系エステル交換油脂が挙げられる。非ラウリン系エステル交換油脂は、エステル交換油脂の構成脂肪酸の全量に占めるラウリン酸の含有量が１０質量％未満（好ましくは０～５質量％、より好ましくは０～２質量％）であり、エステル交換処理されたものであれば、エステル交換処理の前後で、分別、水素添加などの、その他の加工処理が単回、もしくは複数回繰り返されたものであってもよい。エステル交換の方法は、特に制限されない。通常のエステル交換法を適用できる。例えば、ナトリウムメトキシド等の触媒を使用した化学的エステル交換、およびリパーゼを触媒とした酵素的エステル交換、のどちらの方法も適用できる。ＨＵ２＋Ｕ３油脂は、１種または２種以上を使用してもよい。また、パーム系油脂である、パームスーパーオレインなどは、ＨＵ２＋Ｕ３油脂に該当する。しかし、パーム系油脂がＨＵ２＋Ｕ３油脂に該当する場合、パーム系油脂としての取り扱いが優先される。ＨＵ２＋Ｕ３油脂のヨウ素価は、好ましくは６０～１４０であり、より好ましくは６５～１２０である。 Preferred examples of the above HU2+U3 oils and fats include vegetable oils and fats that are liquid at room temperature (25°C). Specific examples include soybean oil, rapeseed oil, corn oil, sunflower oil, safflower oil, sesame oil, cottonseed oil, rice oil, olive oil, peanut oil, and linseed oil, as well as mixed oils containing these. In addition, processed oils such as hydrogenated oils, transesterified oils, and fractionated oils of these single oils and mixed oils are also included. Among such liquid vegetable oils and fats, oils that are liquid at 5°C and have transparency are more preferable. Preferred examples of HU2+U3 oils and fats also include non-lauric transesterified oils and fats. Non-lauric transesterified oils and fats have a lauric acid content of less than 10% by mass (preferably 0-5% by mass, more preferably 0-2% by mass) of the total amount of constituent fatty acids of the transesterified oil and fats, and may be subjected to other processing treatments such as fractionation and hydrogenation once or multiple times before or after the transesterification treatment. The method of transesterification is not particularly limited. A normal transesterification method can be applied. For example, either chemical transesterification using a catalyst such as sodium methoxide or enzymatic transesterification using lipase as a catalyst can be applied. One or more types of HU2+U3 oils and fats may be used. Palm superolein, which is a palm-based oil and fat, falls under HU2+U3 oil and fat. However, when palm-based oil and fat falls under HU2+U3 oil and fat, it is preferred to handle it as a palm-based oil and fat. The iodine value of HU2+U3 oil and fat is preferably 60 to 140, more preferably 65 to 120.
本発明の１態様によれば、本発明の可塑性油脂組成物に含まれる油脂から、粉末油脂組成物に含まれる５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を除いた油脂は、２０～８０質量％（好ましくは３０～７０質量％、より好ましくは３５～６５質量％）のＨＯＨ油脂と２０～８０（好ましくは３０～７０質量％、より好ましくは３５～６５質量％）質量％のＨＵ２＋Ｕ３油脂とを含有してもよい。ＨＵ２＋Ｕ３油脂は、非ラウリン系エステル交換油脂を含有してもよい。非ラウリン系エステル交換油脂は、１０～７０（好ましくは２０～６０質量％、より好ましくは３５～５５質量％）質量％の常温（２５℃）で液状である植物油脂の極度硬化油および／またはＨＯＨ油脂と３０～９０（好ましくは４０～９０質量％、より好ましくは４５～６５質量％）質量％の常温（２５℃）で液状である植物油脂とを原料油脂とするエステル交換油脂であってもよい。 According to one aspect of the present invention, the fats and oils contained in the plastic fat composition of the present invention, excluding the fat powder having a melting point of 50°C or higher and double-chain length β-type crystals contained in the powdered fat composition, may contain 20 to 80% by mass (preferably 30 to 70% by mass, more preferably 35 to 65% by mass) of HOH fats and 20 to 80% by mass (preferably 30 to 70% by mass, more preferably 35 to 65% by mass) of HU2+U3 fats and oils. The HU2+U3 fats and oils may contain non-lauric interesterified fats and oils. The non-lauric interesterified oil may be an interesterified oil made from 10 to 70% (preferably 20 to 60% by mass, more preferably 35 to 55% by mass) of extremely hardened vegetable oil and/or HOH oil that is liquid at room temperature (25°C) and 30 to 90% (preferably 40 to 90% by mass, more preferably 45 to 65% by mass) of vegetable oil that is liquid at room temperature (25°C).
本発明の１態様によれば、本発明の可塑性油脂組成物は、また、乳由来の油脂（バター、乳脂肪ならびにその分別油など）を含有してもよい。本発明の可塑性油脂組成物に含まれる油脂に占める乳由来の油脂の含有量は、好ましくは０～３０質量％であり、より好ましくは０～２０質量％であり、さらに好ましくは０～１５質量％である。 According to one aspect of the present invention, the plastic oil composition of the present invention may also contain milk-derived oils and fats (butter, milk fat, and fractionated oils thereof, etc.). The content of milk-derived oils and fats in the oils and fats contained in the plastic oil composition of the present invention is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and even more preferably 0 to 15% by mass.
本発明の可塑性油脂組成物は、健康上懸念されるトランス脂肪酸の含有量を低減できる。本発明の可塑性油脂組成物のトランス脂肪酸含有量は、好ましくは０～５質量％であり、より好ましくは０～３質量％であり、さらに好ましくは０～１質量％である。 The plastic oil composition of the present invention can reduce the content of trans fatty acids, which are of health concern. The trans fatty acid content of the plastic oil composition of the present invention is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass.
本発明の可塑性油脂組成物は、油脂以外のその他の成分として、通常、ショートニング、マーガリンなどの可塑性油脂組成物に配合される成分を配合できる。その他の成分としては、水、レシチン、グリセリン脂肪酸エステル、ショ糖脂肪酸エステルなどの乳化剤、ゼラチン、グアーガム、キサンタンガムなどの増粘安定剤、食塩、塩化カリウムなどの塩味剤、酢酸、乳酸、グルコン酸などの酸味料、糖類、糖アルコール類、ステビア、アスパルテームなどの甘味料、β－カロテン、カラメル、紅麹色素などの着色料、トコフェロール、茶抽出物（カテキンなど）、ルチンなどの酸化防止剤、小麦蛋白、大豆蛋白などの植物蛋白、アミラーゼ、ヘミセルラーゼなどの酵素、全脂粉乳、脱脂粉乳、乳清蛋白などの乳製品、卵および卵加工品、香料、調味料、ｐＨ調整剤、食品保存料、果実、果汁、コーヒー、ナッツペースト、香辛料、カカオマス、ココアパウダー、穀類、豆類、野菜類、肉類、魚介類など、の食品素材や食品添加物が挙げられる。 The plastic oil composition of the present invention can contain, as components other than the oils and fats, components that are typically contained in plastic oil compositions such as shortening and margarine. Other ingredients include food ingredients and food additives such as water, emulsifiers such as lecithin, glycerin fatty acid esters, and sucrose fatty acid esters, thickening stabilizers such as gelatin, guar gum, and xanthan gum, salt seasonings such as salt and potassium chloride, acidulants such as acetic acid, lactic acid, and gluconic acid, sugars, sugar alcohols, sweeteners such as stevia and aspartame, colorants such as β-carotene, caramel, and red yeast rice pigment, antioxidants such as tocopherol, tea extract (catechin, etc.), and rutin, plant proteins such as wheat protein and soy protein, enzymes such as amylase and hemicellulase, dairy products such as whole milk powder, skim milk powder, and whey protein, eggs and egg products, flavorings, seasonings, pH adjusters, food preservatives, fruits, fruit juices, coffee, nut pastes, spices, cacao mass, cocoa powder, grains, beans, vegetables, meat, and seafood.
＜可塑性油脂組成物の製造方法＞
本発明の可塑性油脂組成物の製造方法は、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を含む粉末油脂組成物を含み、可塑化された状態にできる方法であれば、特に限定されない。しかし、好ましい態様の１つとしては、可塑化（結晶化）前の油脂が融解状態にあるベースとなる油脂組成物（以下、ベース油脂組成物ともいう）に、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を含む粉末油脂組成物を、混合ないし添加し、冷却可塑化（結晶化）する方法が挙げられる。融解状態にあるベース油脂組成物の温度は、好ましくは、粉末油脂組成物に含まれる油脂粉末の融点－５℃以下であり、より好ましくは、粉末油脂組成物に含まれる油脂粉末の融点－１０℃以下である。例えば、粉末油脂組成物に含まれる油脂粉末の融点が５５℃である場合、融解状態にあるベース油脂組成物の温度は、好ましくは、５０℃以下である。５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を含む粉末油脂組成物とベース油脂組成物とを混合する割合は、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末とベース油脂組成物に含まれる油脂とを基準として、質量比で、好ましくは０．５：９９．５～３０：７０であり、より好ましくは１：９９～２０：８０であり、さらに好ましくは２：９８～１３：８７であり、ことさらに好ましくは３：９７～８：９２である。
<Method for producing plastic oil composition>
The method for producing the plastic oil composition of the present invention is not particularly limited as long as it is a method that can produce a powdered oil composition containing an oil powder having a melting point of 50°C or higher and double-chain-length β-type crystals in a plasticized state. However, one of the preferred embodiments includes a method of mixing or adding a powdered oil composition containing an oil powder having a melting point of 50°C or higher and double-chain-length β-type crystals to a base oil composition (hereinafter also referred to as a base oil composition) in which the oil is in a molten state before plasticization (crystallization), and plasticizing (crystallizing) by cooling. The temperature of the base oil composition in a molten state is preferably the melting point of the oil powder contained in the powdered oil composition minus 5°C or lower, and more preferably the melting point of the oil powder contained in the powdered oil composition minus 10°C or lower. For example, when the melting point of the oil powder contained in the powdered oil composition is 55°C, the temperature of the base oil composition in a molten state is preferably 50°C or lower. The mixing ratio of the powdered oil/fat composition containing the oil/fat powder having a melting point of 50°C or higher and double-chain length β-type crystals and the base oil/fat composition is preferably 0.5:99.5 to 30:70, more preferably 1:99 to 20:80, even more preferably 2:98 to 13:87, and particularly preferably 3:97 to 8:92, in mass ratio based on the oil/fat powder having a melting point of 50°C or higher and double-chain length β-type crystals and the oil/fat contained in the base oil/fat composition.
本発明の可塑性油脂組成物がショートニングの場合、上記ベース油脂組成物は、典型的には。油脂と必要に応じて乳化剤などを含む、融液状の油脂組成物である。また、マーガリンの場合、典型的には、油脂と必要に応じて乳化剤などを含む融液状の油脂組成物に、水と必要に応じて食品添加素材などを含む水溶液を乳化させた、乳化油脂組成物である。ベース油脂組成物は、適時殺菌処理されてもよい。可塑化（結晶化）前の融解状態にあるベースとなる油脂組成物に、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を含む粉末油脂組成物を、混合攪拌した後は、通常の可塑性油脂組成物の製造で行われる冷却可塑化を行ってもよい。冷却可塑化は、密閉型連続式チューブ冷却機、例えば、ボテーター、コンビネーター、パーフェクターなどの冷却可塑化装置を使用できる。冷却条件は、例えば－２０℃／分より強く（冷却速度を速く）設定されてもよい。しかし、本発明の可塑性油脂組成物は、より緩慢な冷却条件で冷却可塑化されてもよい。より緩慢な冷却条件は、例えば、－５℃／分以下－２０℃／分以上に設定されてもよいし、－５℃／分より弱く（冷却速度を遅く）設定されてもよい。すなわち、本願の可塑性油脂組成物は、上記の冷却可塑化装置を使用しない緩慢な冷却であっても微細な油脂結晶構造を取り得る。 When the plastic fat composition of the present invention is shortening, the base fat composition is typically a melt-like fat composition containing fats and oils and, if necessary, an emulsifier. In the case of margarine, the base fat composition is typically an emulsified fat composition obtained by emulsifying a melt-like fat composition containing fats and oils and, if necessary, an emulsifier with an aqueous solution containing water and, if necessary, a food additive material. The base fat composition may be sterilized as appropriate. After mixing and stirring a powdered fat composition containing a fat powder having a melting point of 50°C or higher and a double-chain length β-type crystal with a base fat composition in a melted state before plasticization (crystallization), cooling plasticization may be performed as is performed in the manufacture of ordinary plastic fat compositions. For cooling plasticization, a cooling plasticization device such as a closed continuous tube cooler, for example, a votator, a combinator, or a perfector, may be used. The cooling conditions may be set to be stronger (faster cooling rate) than, for example, -20°C/min. However, the plastic fat composition of the present invention may be cooled and plasticized under slower cooling conditions. The slower cooling conditions may be set, for example, to -5°C/min or less and -20°C/min or more, or may be set to a slower rate (slower cooling rate) than -5°C/min. In other words, the plasticized oil composition of the present application can have a fine oil crystal structure even when cooled slowly without using the cooling and plasticizing device described above.
本発明の可塑性油脂組成物は、冷却可塑化後、調温されてもよい。より具体的には、上記冷却可塑化された可塑性油脂組成物は、好ましくは１５～３５℃で、より好ましくは１８～３２℃で、さらに好ましくは２０～２８℃で、調温されてもよい。調温時間は、例えば、３時間以上、６時間以上、１２時間以上、２４時間以上、３６時間以上、４８時間以上の、任意の時間に設定されてもよい。調温時間の上限は特に設定されない。しかし、２４０時間以下、１６８時間以下、１２０時間以下、７２時間以下の、任意の時間に設定されてもよい。夏期においては、屋内に放置することで調温に代えてもよい。調温により、本発明の可塑性油脂組成物に含まれる微細な油脂結晶の構造が安定になる。 The plastic oil composition of the present invention may be subjected to temperature control after cooling and plasticization. More specifically, the plasticized oil composition may be controlled at a temperature of preferably 15 to 35°C, more preferably 18 to 32°C, and even more preferably 20 to 28°C. The temperature control time may be set to any time, for example, 3 hours or more, 6 hours or more, 12 hours or more, 24 hours or more, 36 hours or more, or 48 hours or more. There is no particular upper limit to the temperature control time. However, it may be set to any time, such as 240 hours or less, 168 hours or less, 120 hours or less, or 72 hours or less. In summer, the temperature control may be replaced by leaving the composition indoors. The structure of the fine oil crystals contained in the plastic oil composition of the present invention becomes stable by controlling the temperature.
＜可塑性油脂組成物の特長と用途＞
本発明の可塑性油脂組成物は、製菓製パンにおける作業性がよい。また、可塑性油脂組成物に含まれる油脂が微細な油脂結晶を有するので、保存時の物性の変化が少ない（良好な作業性が維持される）。本発明の可塑性油脂組成物は、例えば、菓子・パンなどのベーカリー生地への練り込み用や折り込み用、ベーカリー食品へのスプレッド用やコーティング用、ならびに、無水クリームやバタークリームなどのクリーム用など、として好適に使用できる。特に、ベーカリー生地への練り込み用として好適に使用できる。
<Characteristics and applications of plastic oil and fat compositions>
The plastic fat composition of the present invention has good workability in confectionery and bread making. In addition, since the fats and oils contained in the plastic fat composition have fine fat crystals, there is little change in physical properties during storage (good workability is maintained). The plastic fat composition of the present invention can be suitably used, for example, for kneading or folding into bakery dough such as confectionery and bread, for spreading or coating bakery foods, and for creams such as anhydrous cream and butter cream. In particular, it can be suitably used for kneading into bakery dough.
次に、例を挙げ、本発明をさらに詳しく説明する。しかし、本発明はこれらに何ら限定されない。また。以下において「％」は、特別な記載がない場合、質量％を示す。 The present invention will now be described in more detail with reference to examples. However, the present invention is in no way limited to these. In the following, "%" refers to mass % unless otherwise specified.
＜分析方法＞
・トランス脂肪酸
油脂のトランス脂肪酸含有量は、ＡＯＣＳ Ｃｅ１ｆ－９６に準じてガスクロマトグラフィー法で測定した。
・トリアシルグリセロール
油脂の各トリアシルグリセロール含有量は、ガスクロマトグラフィー法（ＡＯＣＳ Ｃｅ５－８６準拠）で測定した。トリアシルグリセロールの対称性は、銀イオンカラムクロマトグラフィー法（Ｊ．Ｈｉｇｈ Ｒｅｓｏｌ．Ｃｈｒｏｍａｔｏｇｒ．，１８，１０５－１０７（１９９５）準拠）で測定した。
・Ｘ線回折測定
Ｘ線回折装置ＵｌｔｉｍａＩＶ（株式会社リガク社製）を用いて、ＣｕＫα（λ＝１．５４２Å）を線源とし、Ｃｕ用フィルタ使用、出力１．６ｋＷ、操作角０．９６～３０．０°、測定速度２°／分の条件で測定した。この測定により、４．６Å付近のピークのみを有し、４．１～４．２Å付近のピークを有しない場合は、油脂成分のすべてがβ型油脂結晶であると判断した。
なお、上記Ｘ線回析測定の結果から、ピーク強度比＝［β型の特徴的ピークの強度（２θ＝１９°（４．６Å））／（α型（およびβ’型）の特徴的ピークの強度（２θ＝２１°（４．２Å））＋β型の特徴的ピークの強度（２θ＝１９°（４．６Å）））］をβ型油脂結晶の存在量を表す指標として測定した。ピーク強度比が０．８以上であると、油脂結晶は実質的にβ型であるといえる。
<Analysis method>
Trans fatty acids The trans fatty acid content of fats and oils was measured by gas chromatography in accordance with AOCS Ce1f-96.
Triacylglycerol The content of each triacylglycerol in the oils and fats was measured by gas chromatography (based on AOCS Ce5-86). The symmetry of triacylglycerol was measured by silver ion column chromatography (based on J. High Resol. Chromatogr., 18, 105-107 (1995)).
- X-ray diffraction measurement Using an Ultima IV X-ray diffractometer (manufactured by Rigaku Corporation), measurements were taken using CuKα (λ = 1.542 Å) as a radiation source, a Cu filter, an output of 1.6 kW, an operating angle of 0.96 to 30.0°, and a measurement speed of 2°/min. If the measurement showed only a peak near 4.6 Å and no peak near 4.1 to 4.2 Å, it was determined that all of the fat and oil components were β-type fat and oil crystals.
From the results of the X-ray diffraction measurement, the peak intensity ratio = [β-type characteristic peak intensity (2θ = 19° (4.6 Å)) / (α-type (and β'-type) characteristic peak intensity (2θ = 21° (4.2 Å)) + β-type characteristic peak intensity (2θ = 19° (4.6 Å)))] was measured as an index representing the amount of β-type fat crystals present. If the peak intensity ratio is 0.8 or more, it can be said that the fat crystals are substantially β-type.
・ゆるめ嵩密度
実施例などで得られた粉末油脂組成物のゆるめ嵩密度（ｇ／ｃｍ3）は、内径１５ｍｍ×２５ｍＬのメスシリンダーに、当該メスシリンダーの上部開口端の２ｃｍ程度上方から粉末油脂組成物を落下させて疎充填し、充填された質量（ｇ）の測定と容量（ｍＬ）の読み取りを行い、ｍＬ当たりの当該粉末油脂組成物の質量（ｇ）を算出することで求めた。
・アスペクト比
走査型電子顕微鏡S-3400N（株式会社日立ハイテクノロジーズ製）により直接観察し、画像解析式粒度分布測定ソフトウェア（株式会社マウンテック製 Ｍａｃ－Ｖｉｅｗ）を用いて、任意に選択した粒子について、その長軸方向の長さおよび短軸方向の長さを計測し、計測した個数の平均値として測定した。
・アスペクト比（２）
（Ａ）本発明の粉末油脂組成物Ａ（００５６段落）の粒子のアスペクト比（２）
本発明の粉末油脂組成物Ａは、板状形状であるため、顕微鏡写真から粒子の厚さを測定することが難しい。したがって、粒子の厚さは、粉末油脂組成物Ａをガラスビーズに付着させたときの顕微鏡写真から測定した。また、長径の値は、レーザー回折散乱法に基づいて測定した平均粒径（ｄ５０）を用いた。
具体的には、ガラスビーズ（アズワン株式会社製、型番ＢＺ－０１、寸法０．１０５～０．１２５ｍｍφ）に粉末油脂組成物Ａを添加、混合することで、ガラスビーズ表面に粉末油脂組成物Ａを付着させ、その様子を３Ｄリアルサーフェスビュー顕微鏡ＶＥ－８８００（株式会社キーエンス製）で撮影した。ガラスビーズ表面に付着した１個の粉末油脂組成物Ａの粒子の付着面から垂直方向の長さを、その粒子の厚さとして測定し、計２５個の粒子の厚さの平均値を取り、その値を粉末油脂組成物Ａの粒子の厚さの値とした。
図２は、粉末油脂組成物Ａの粒子の厚さの測定に使用した電子顕微鏡写真（１５００倍）の１つで、この写真では、写真中の直線で示した部分（２か所）の長さ（ガラスビーズ表面に付着した粒子の付着面からの垂直方向の長さ）を、粉末油脂組成物Ａの粒子の厚さとして測定した。
また、長径の値は、上述のレーザー回折散乱法に基づいて測定した平均粒径（ｄ５０）を用いた。
このようにして測定した粉末油脂組成物Ａの粒子の長径と厚さの値から、アスペクト比（２）〔＝長径／厚さ〕を求めた。
（ａ）粉末油脂組成物ａ（００５６段落）の粒子のアスペクト比（２）
粉末油脂組成物ａは、ほとんどが球形であり、粒子の電子顕微鏡写真から１個１個の粒子について直接、長径及び厚さを測定できる。そこで、３Ｄリアルサーフェスビュー顕微鏡ＶＥ－８８００（株式会社キーエンス製）で撮影した写真に写った１個１個の粒子について、長径及び厚さ（縦及び横）を測定した。それぞれの粒子について、アスペクト比（２）を求め、計２０個の粒子のアスペクト比（２）の平均値を、粒子のアスペクト比（２）とした。
・平均粒径（ｄ５０）
粒度分布測定装置（日機装株式会社製 Ｍｉｃｒｏｔｒａｃ ＭＴ３３００ＥｘII）でレーザー回折散乱法（ISO133201,ISO9276-1）に基づいて測定した。なお、測定した平均粒径は、粉体をある粒子径から２つに分けたとき、大きい側と小さい側が等量となる径（ｄ５０）の値である。
Loose bulk density The loose bulk density (g/ cm3 ) of the powdered oil composition obtained in the examples was determined by loosely filling a 25 mL measuring cylinder with an inner diameter of 15 mm by dropping the powdered oil composition from approximately 2 cm above the upper opening end of the cylinder, measuring the filled mass (g) and reading the volume (mL), and calculating the mass (g) of the powdered oil composition per mL.
Aspect ratio: Particles were directly observed using a scanning electron microscope S-3400N (Hitachi High-Technologies Corporation), and the lengths of the major and minor axes of arbitrarily selected particles were measured using image analysis particle size distribution measurement software (Mac-View, Mountec Corporation), and the aspect ratio was calculated as the average value of the number of particles measured.
・Aspect ratio (2)
(A) Aspect ratio of particles of the powdered oil composition A of the present invention (paragraph 0056) (2)
Since the powdered oil composition A of the present invention has a plate-like shape, it is difficult to measure the particle thickness from a micrograph. Therefore, the particle thickness was measured from a micrograph of the powdered oil composition A adhered to glass beads. The major axis value was the average particle diameter (d50) measured based on a laser diffraction scattering method.
Specifically, powdered oil composition A was added to glass beads (manufactured by AS ONE Corporation, model number BZ-01, dimensions 0.105 to 0.125 mmφ) and mixed to adhere powdered oil composition A to the surfaces of the glass beads, and the state was photographed with a 3D real surface view microscope VE-8800 (manufactured by Keyence Corporation). The length in the vertical direction from the adhesion surface of one particle of powdered oil composition A adhered to the surface of the glass beads was measured as the thickness of the particle, and the average thickness of a total of 25 particles was calculated, and this value was used as the thickness value of the particle of powdered oil composition A.
FIG. 2 shows one of the electron microscope photographs (1,500x) used to measure the particle thickness of Powdered Oil Composition A. In this photograph, the lengths of the straight lines (two points) in the photograph (the length in the perpendicular direction from the adhesion surface of the particles adhered to the glass bead surface) were measured as the particle thickness of Powdered Oil Composition A.
The value of the major axis was determined as the average particle size (d50) measured based on the above-mentioned laser diffraction scattering method.
From the values of the major axis and thickness of the particles of the powdered oil composition A thus measured, the aspect ratio (2) [=major axis/thickness] was calculated.
(a) Aspect ratio of particles of powdered oil composition a (paragraph 0056) (2)
Powdered oil and fat composition a is mostly spherical, and the major axis and thickness of each particle can be measured directly from the electron microscope photograph of the particle. Therefore, the major axis and thickness (vertical and horizontal) of each particle in the photograph taken with a 3D real surface view microscope VE-8800 (manufactured by Keyence Corporation) were measured. The aspect ratio (2) of each particle was calculated, and the average value of the aspect ratios (2) of a total of 20 particles was taken as the aspect ratio (2) of the particle.
Average particle size (d50)
The measurements were made using a particle size distribution analyzer (Microtrac MT3300ExII, manufactured by Nikkiso Co., Ltd.) based on the laser diffraction scattering method (ISO133201, ISO9276-1). The measured average particle size is the diameter (d50) at which the larger and smaller particles are equal when the powder is divided into two particles of a certain diameter.
＜粉末油脂組成物の調製＞
以下の粉末油脂組成物Ａおよびａを準備した。
（１）粉末油脂組成物Ａ
１位～３位にステアリン酸残基（炭素数１８）を有するトリグリセリド（ＸＸＸ型：７９．１質量％、菜種極度硬化油、融点６７．３℃、横関油脂工業株式会社製）２５ｇを８０℃にて０．５時間維持して完全に融解し、６０℃恒温槽にて１２時間冷却し、体積が増加した空隙を有する固形物を形成させ、結晶化を完了させた後、室温（２５℃）状態まで冷却した。得られた固形物を機械粉砕することで粉末状の油脂結晶（ゆるめ嵩密度：０．２ｇ/ｃｍ3、アスペクト比：１．６、アスペクト比（２）：４．６、平均粒径８．０μｍ、Ｘ線回折測定回析ピーク：２鎖長、特徴ピーク４．６Å、ピーク強度比：０．８９）を得た。この油脂粉末を粉末油脂組成物Ａとした。
（２）粉末油脂組成物ａ
パーム極度硬化油（融点５８℃）を原料として、スプレークーラーによる噴霧冷却で、粉末状の油脂結晶（ゆるめ嵩密度：０．５ｇ/ｃｍ3、アスペクト比：１．１、アスペクト比（２）：１．１、平均粒径１６２μｍ、Ｘ線回折測定回析ピーク：２鎖長、特徴ピーク４．２Å、ピーク強度比：０．０３）を得た。この油脂粉末を粉末油脂組成物ａとした。
<Preparation of Powdered Oil and Fat Composition>
The following powdered oil compositions A and a were prepared.
(1) Powdered oil composition A
25 g of triglyceride (XXX type: 79.1% by mass, hardened rapeseed oil, melting point 67.3°C, manufactured by Yokozeki Oil & Fat Co., Ltd.) having stearic acid residues (18 carbon atoms) at positions 1 to 3 was maintained at 80°C for 0.5 hours to completely melt, and cooled in a 60°C thermostatic bath for 12 hours to form a solid having voids with an increased volume, and after completing crystallization, it was cooled to room temperature (25°C). The obtained solid was mechanically pulverized to obtain powdered oil and fat crystals (loose bulk density: 0.2 g/cm 3 , aspect ratio: 1.6, aspect ratio (2): 4.6, average particle size 8.0 μm, X-ray diffraction measurement diffraction peak: 2 chain lengths, characteristic peak 4.6 Å, peak intensity ratio: 0.89). This oil and fat powder was designated as powdered oil and fat composition A.
(2) Powdered oil composition a
Using extremely hardened palm oil (melting point 58°C) as a raw material, powdered oil crystals (loose bulk density: 0.5 g/ cm3 , aspect ratio: 1.1, aspect ratio (2): 1.1, average particle size 162 µm, X-ray diffraction measurement diffraction peaks: 2 chain lengths, characteristic peak 4.2 Å, peak intensity ratio: 0.03) were obtained by spray cooling using a spray cooler. This oil powder was named powdered oil composition a.
＜食用油脂の準備＞
（１）パーム油（日清オイリオ株式会社製、ヨウ素価５２、ＨＯＨ含有量３１．７質量％）を使用した。ＰＭＯと略号表記する場合がある。
（２）ステアリン酸エチルエステルと、高オレイン酸ひまわり油との間で、１，３位選択性リパーゼ製剤を用いて、エステル交換反応をさせた後、蒸留および分別により、エステル交換分別油脂を得た。得られた油脂を常法に従って精製し、ＨＯＨ含有量が８５．６質量％である油脂を使用した。ＥＳＯＳと略号表記する場合がある。
（３）パームスーパーオレイン（日清オイリオグループ株式会社製、ヨウ素価６５、ＨＵ２＋Ｕ３含有量６５．０質量％）を使用した。ＰＬ６５と略号表記する場合がある。
（４）高オレイン酸ひまわり油（日清オイリオグループ株式会社製、ヨウ素価８８、ＨＵ２＋Ｕ３含有量９８．７質量％）を使用した。ＨＯＳＦＯと略号表記する場合がある。
（５）菜種極度硬化油（横関油脂工業株式会社製、ヨウ素価値１）を使用した。ＦＨＲＳＯと略語表記する場合がある。
<Preparation of edible oils and fats>
(1) Palm oil (manufactured by Nisshin Oillio Co., Ltd., iodine value 52, HOH content 31.7% by mass) was used. It may be abbreviated as PMO.
(2) Stearic acid ethyl ester and high oleic acid sunflower oil were subjected to an ester exchange reaction using a 1,3-position selective lipase preparation, and then an ester exchange fractionated oil was obtained by distillation and fractionation. The obtained oil was refined according to a conventional method, and an oil with an HOH content of 85.6% by mass was used. It may be abbreviated as ESOS.
(3) Palm Superolein (manufactured by Nisshin Oillio Group, Ltd., iodine value 65, HU2 + U3 content 65.0% by mass) was used. It may be abbreviated as PL65.
(4) High oleic acid sunflower oil (manufactured by Nisshin Oillio Group, Ltd., iodine value 88, HU2 + U3 content 98.7% by mass) was used. It may be abbreviated as HOSFO.
(5) Hardened rapeseed oil (manufactured by Yokoseki Oil Industries Co., Ltd., iodine value 1) was used. It may be abbreviated as FHRSO.
＜可塑性油脂組成物の調製＞
以下の製造手順１～４により、表１～２に示す配合に従って、例１～８の可塑性油脂組成物（ショートニング）を製造した。２０℃の環境下で１週間静置後の各ショートニングをガラス板上に採り、バターナイフで伸ばして、組織の状態を観察した。結果を表１、２に示した。
（製造手順）
１．表１～２のベース油脂組成物の配合に従って、ベース油脂組成物を混合し、８０℃で融解した。
２．１で融解したベース油脂組成物を４５℃に調温し、表１～２に従って、粉末油脂組成物を添加した。
３．２で粉末油脂組成物を添加後、ミキサーで撹拌し、粉末油脂組成物が十分に分散した分散体を得た。
４．３の分散体を２０℃の環境下に静置して、油脂結晶を析出させ、ショートニングを作製した。冷却速度は、－５℃／分よりも緩やかであった。
<Preparation of plastic oil composition>
Plastic fat compositions (shortenings) of Examples 1 to 8 were produced according to the formulations shown in Tables 1 and 2 by the following production procedures 1 to 4. After standing for one week in an environment of 20°C, each shortening was placed on a glass plate and spread with a butter knife to observe the state of the texture. The results are shown in Tables 1 and 2.
(Manufacturing Procedure)
1. The base oil and fat compositions were mixed according to the formulations of the base oil and fat compositions in Tables 1 and 2, and melted at 80°C.
2. The base oil composition melted in step 1 was adjusted to 45° C., and a powdered oil composition was added according to Tables 1 and 2.
3. After the powdered oil composition in 2 was added, the mixture was stirred with a mixer to obtain a dispersion in which the powdered oil composition was thoroughly dispersed.
The dispersion of 4.3 was allowed to stand in an environment of 20° C. to precipitate fat crystals, thereby producing shortening. The cooling rate was slower than −5° C./min.
（ロールパンの製造および評価）
以下の手順に従って、パン職人歴２３年の職人が、ロールパンを製造した。すなわち、強力粉７００ｇ、生イースト３０ｇ、全卵１５０ｇ、水２７０ｇをミキサーボウルに投入し、低速で２分間、中速で２分間、混捏して。捏上げ温度２５℃の中種を得た。得られた中種を２８℃で２時間発酵させた。発酵させた中種をミキサーボウルに投入し、さらに強力粉３００ｇ、上白糖１２０ｇ、食塩１７ｇ、脱脂粉乳４０ｇ、水１８０ｇを投入し、低速で２分間、中速で５分間、混捏した。ここで、練り込み用油脂として、例６および例８において得られた可塑性油脂組成物１５０ｇを投入し、さらに低速で２分間、中速で５分間、混捏して、捏上げ温度２８℃の生地を得た。フロアタイムを３０分取った後、４５ｇに分割し、次いでベンチタイムを３０分取った後、テーブルロール成型を行った。さらに、３８℃で相対湿度８５％のホイロに６０分間入れて最終発酵を行った。最終発酵後、全卵を上面に塗布し、上火２１０℃、下火２００℃のオーブンに入れた。オーブンで、９分３０秒焼成し、例３および例１２の可塑性油脂組成物をそれぞれ生地に練り込んだロールパンを得た。
例８の可塑性油脂組成物は、例６と比較して生地に練り込まれ易く、明らかに作業性が良好であった。また、例８の可塑性油脂組成物を使用して製造されたロールパンは、例６２の可塑性油脂組成物を使用して製造されたロールパンと比較して、内層のキメが細かく、ボリュームがあり、ソフトであった。
(Production and evaluation of rolls)
According to the following procedure, a baker with 23 years of experience produced roll bread. That is, 700g of strong flour, 30g of fresh yeast, 150g of whole eggs, and 270g of water were put into a mixer bowl, and kneaded at low speed for 2 minutes and at medium speed for 2 minutes. A sponge with a kneading temperature of 25°C was obtained. The sponge obtained was fermented at 28°C for 2 hours. The fermented sponge was put into a mixer bowl, and 300g of strong flour, 120g of white sugar, 17g of salt, 40g of skim milk powder, and 180g of water were further put in, and kneaded at low speed for 2 minutes and at medium speed for 5 minutes. Here, 150g of the plastic oil composition obtained in Example 6 and Example 8 was put in as the oil for kneading, and kneaded at low speed for 2 minutes and at medium speed for 5 minutes to obtain a dough with a kneading temperature of 28°C. After 30 minutes of floor time, the dough was divided into 45g portions, and then rested for 30 minutes before being molded into table rolls. The dough was then placed in a proofing chamber at 38°C and 85% relative humidity for 60 minutes for final fermentation. After the final fermentation, whole eggs were applied to the top surface and the dough was placed in an oven with an upper heat of 210°C and a lower heat of 200°C. The dough was baked in the oven for 9 minutes and 30 seconds to obtain rolls in which the plastic fat and oil compositions of Examples 3 and 12 were kneaded into the dough.
The plastic fat composition of Example 8 was easily kneaded into dough and had clearly better workability than the plastic fat composition of Example 6. In addition, the roll bread produced using the plastic fat composition of Example 8 had a finer texture of the inner layer, was more voluminous, and was softer than the roll bread produced using the plastic fat composition of Example 62.
Claims (8)
前記粉末油脂組成物が、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を含み、
前記可塑性油脂組成物に含まれる油脂に占める前記油脂粉末の割合が、２～１３質量％であり、
前記可塑性油脂組成物に含まれる油脂に占めるＨＯＨの含有量が２０～６０質量％であり、
前記可塑性油脂組成物に含まれる油脂の、ＨＨＯ含有量とＯＨＯ含有量の合計量（ＨＨＯ＋ＯＨＯ）に対する、ＨＯＨ含有量の質量比（ＨＯＨ／（ＨＨＯ＋ＯＨＯ））が２．０を超える、
前記可塑性油脂組成物。
ただし、Ｈ、Ｏ、ＨＯＨ、ＨＨＯおよびＯＨＯは、以下を意味する。
Ｈ：炭素数１６～２４の飽和脂肪酸
Ｏ：オレイン酸
ＨＯＨ：グリセロールの２位にオレイン酸（Ｏ）、１位および３位に炭素数１６～２４の飽和脂肪酸（Ｈ）がエステル結合したトリアシルグリセロール
ＨＨＯ：グリセロールの１位または３位にオレイン酸（Ｏ）、２位および３位、または、１位および２位に炭素数１６～２４の飽和脂肪酸（Ｈ）がエステル結合したトリアシルグリセロール
ＯＨＯ：グリセロールの１位および３位にオレイン酸（Ｏ）、２位に炭素数１６～２４の飽和脂肪酸（Ｈ）がエステル結合したトリアシルグリセロール A plastic oil-and-fat composition containing a powdered oil-and-fat composition (excluding an embodiment in which the oil-and-fat contained in the plastic oil-and-fat composition contains 3% by mass or more of a trisaturated fatty acid glyceride and 0.3 to 5% by mass of an animal or vegetable wax) ,
The powdered oil/fat composition contains an oil/fat powder having a melting point of 50° C. or higher and a double-chain length β-type crystal,
The ratio of the oil powder to the oil contained in the plastic oil composition is 2 to 13% by mass,
The content of HOH in the oil and fat contained in the plastic oil and fat composition is 20 to 60% by mass,
The mass ratio (HOH/(HHO+OHO)) of the HOH content to the total amount (HHO+OHO) of the HHO content and the OHO content of the oil or fat contained in the plastic oil or fat composition is more than 2.0;
The plastic oil composition.
Here, H, O, HOH, HHO and OHO have the following meanings:
H: saturated fatty acid having 16 to 24 carbon atomsO: oleic acidHOH: triacylglycerol in which oleic acid (O) is ester-bonded to the 2nd position of glycerol and saturated fatty acid (H) having 16 to 24 carbon atoms is ester-bonded to the 1st and 3rd positions of glycerolHHO: triacylglycerol in which oleic acid (O) is ester-bonded to the 1st or 3rd position of glycerol and saturated fatty acid (H) having 16 to 24 carbon atoms is ester-bonded to the 2nd and 3rd positions or the 1st and 2nd positionsOHO: triacylglycerol in which oleic acid (O) is ester-bonded to the 1st and 3rd positions of glycerol and saturated fatty acid (H) having 16 to 24 carbon atoms is ester-bonded to the 2nd position of glycerol
ただし、Ｕ、ＨＵ２およびＵ３は、以下を意味する。
Ｕ：炭素数１６～２４の不飽和脂肪酸
ＨＵ２：グリセロールに、１分子（１つ）のＨおよび２分子（２つ）のＵがエステル結合したトリアシルグリセロール
Ｕ３：グリセロールに、３分子（３つ）のＵがエステル結合したトリアシルグリセロール A plastic oil composition according to claim 1 or 2, wherein the total content of HU2 and U3 in the oil contained in the plastic oil composition is 20 to 79.5 mass%.
Here, U, HU2 and U3 have the following meanings:
U: unsaturated fatty acid with 16 to 24 carbon atoms HU2: triacylglycerol in which one molecule (1) of H and two molecules (2) of U are ester-bonded to glycerol U3: triacylglycerol in which three molecules (3) of U are ester-bonded to glycerol
５０℃未満の融液状態にある油脂組成物に、５０℃以上の融点と２鎖長β型結晶を有する油脂粉末を含む粉末油脂組成物を分散した後、冷却する、前記可塑性油脂組成物の製造方法。 A method for producing a plastic oil composition according to any one of claims 1 to 6,
The method for producing the plastic oil composition comprises dispersing a powdered oil composition containing an oil powder having a melting point of 50°C or higher and double-chain length β-type crystals in an oil composition in a molten state below 50°C, and then cooling the oil composition.
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| DE2555262B2 (en) * | 1975-12-09 | 1981-05-21 | Dynamit Nobel Ag, 5210 Troisdorf | Solidification accelerator |
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