JP2010047634A - Method for depositing fine crystals of fat and oil - Google Patents
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Abstract
Description
本発明は、油脂の微細結晶析出方法および微細結晶析出促進剤に関する。 The present invention relates to a fine crystal precipitation method and a fine crystal precipitation accelerator for fats and oils.
マーガリン,ショートニングやチョコレート類といった固形脂を含有する油脂加工食品においては、その製造過程で油脂結晶をいかに微細にできるかが、製品の硬さ、展延性、口融けといった物性や経時的な保存安定性の面で重要な鍵となる。微細な結晶を生成させるために、油脂種の組合せや部分的な硬化油が採用されてきたが、健康面で硬化時に発生するトランス脂肪酸が問題視され、部分硬化油の使用は減少傾向にある。 In processed fats and oils containing solid fats such as margarine, shortening and chocolates, how fine the fat crystals can be in the manufacturing process depends on physical properties such as product hardness, extensibility, and meltability, and stable storage over time. It is an important key in terms of sex. In order to produce fine crystals, combinations of fats and oils and partially hardened oils have been adopted. However, trans fatty acids generated during hardening are regarded as a problem for health reasons, and the use of partially hardened oil is decreasing. .
一方、パーム油は各種天然油脂の中でも単位面積あたりの収穫量が極めて高く、安価で供給が安定している為、油糧資源として極めて重要であり種々の原料として多用されている。マーガリン,ショートニングといった油脂加工食品の製造においても、パーム油はその中にトランス酸を含まない為、その利用がおおいに期待されるところである。しかし、パーム油に由来する油脂等を高配合した油脂加工食品は、粗大結晶が発生しやすいために組織が粗く、使用量が制限されている。 On the other hand, palm oil has a very high yield per unit area among various types of natural fats and oils, is inexpensive and has a stable supply, and is therefore extremely important as an oil resource and is frequently used as various raw materials. Even in the production of processed oils and fats such as margarine and shortening, palm oil does not contain trans acid, so its use is greatly expected. However, processed fats and oils that are highly blended with fats and oils derived from palm oil tend to generate coarse crystals, so that the structure is rough and the amount used is limited.
そこでパーム油を改質する方法として、例えば硬化,エステル交換の様に分子種を変化させる方法や、分別などの分子種組成を選択する方法など、種々の提案がなされている。硬化は、先述のようにトランス脂肪酸を副生するため忌避される傾向にあり、エステル交換では、生成する非対称型油脂の影響で全般的に結晶化スピードが遅くなり、分別は、粗大化する油脂をさらに濃縮する方向に進むことがあり、何よりこれら処理方法は、生産能力に対して大型の装置が必要であり、適切ではない。一方、乳化剤の添加による微細化も検討されているが、価格面や近年の健康意識の高まりから、必ずしも望まれる方法ではない。 Therefore, various proposals have been made as methods for modifying palm oil, such as a method of changing molecular species such as curing and transesterification, and a method of selecting a molecular species composition such as fractionation. Hardening tends to be avoided as a result of by-production of trans fatty acids as described above. In transesterification, the crystallization speed is generally slowed down due to the influence of the asymmetrical fats and oils that are produced, and the fats and oils that become coarser are separated. In particular, these treatment methods are not appropriate because they require a large apparatus for the production capacity. On the other hand, miniaturization by addition of an emulsifier has been studied, but it is not always a desirable method due to price increase and recent health awareness.
特許文献1には、パーム系の油脂またはそのエマルションを冷却器中で加圧/晶析し、微細結晶とする方法が開示されているが、冷却器を高圧仕様にするなど特別な装置を必要とし、必ずしも簡便な方法ではない。また、特許文献2には、超音波を用いて微細結晶とする方法が開示されているが、同様に簡便な方法ではない。 Patent Document 1 discloses a method of pressurizing / crystallizing a palm-based oil or its emulsion in a cooler to obtain fine crystals. However, a special device such as a high-pressure specification for the cooler is required. It is not always a simple method. Patent Document 2 discloses a method for forming fine crystals using ultrasonic waves, but it is not a simple method as well.
特許文献3には、ベヘン酸を構成脂肪酸として含むトリアシルグリセロールが、パーム油を微細結晶とする旨が記載されているが、効果が弱く、大量の添加が必要である。 Patent Document 3 describes that triacylglycerol containing behenic acid as a constituent fatty acid makes palm oil fine crystals, but its effect is weak and a large amount of addition is required.
本願は、固形脂、特にパーム油に由来する油脂等に対し、簡便な方法でその結晶を微細に析出させることを目的とした。 The purpose of the present application is to precipitate crystals finely by a simple method with respect to solid fat, particularly fat and oil derived from palm oil.
本発明者らは、上記目的を達成する為に、各種添加剤を検討した結果、特定の鎖長の遊離脂肪酸に、微量の添加でパーム油の結晶径を制御する効果があることを発見し、本発明を完成するに至った。
すなわち上記課題を解決する本発明は、
(1)ベヘン酸が融解または溶解した油脂を、冷却することを特徴とする、油脂の微細結晶の析出方法。
(2)ベヘン酸を油脂に対し0.01重量%以上加える、(1)に記載の微細結晶析出方法。
(3)油脂が、POPで表されるトリアシルグリセロールを10重量%以上含む、(1)に記載の微細結晶析出方法。
(4)ベヘン酸を有効成分とする、油脂の微細結晶析出促進剤。
(5)(4)に記載の微細結晶析出促進剤を含む、油脂。
(6)(5)に記載の油脂を用いた、油脂加工食品。
である。
As a result of studying various additives in order to achieve the above object, the present inventors have found that a free fatty acid having a specific chain length has an effect of controlling the crystal diameter of palm oil by adding a small amount. The present invention has been completed.
That is, the present invention for solving the above problems
(1) A method for precipitating fine crystals of fats and oils, wherein the fats and oils in which behenic acid is melted or dissolved are cooled.
(2) The fine crystal precipitation method according to (1), wherein behenic acid is added in an amount of 0.01% by weight or more based on fats and oils.
(3) The fine crystal precipitation method according to (1), wherein the fat / oil contains 10% by weight or more of triacylglycerol represented by POP.
(4) A fine crystal precipitation accelerator for fats and oils containing behenic acid as an active ingredient.
(5) Oils and fats containing the fine crystal precipitation accelerator according to (4).
(6) Oil processed food using the fat according to (5).
It is.
本発明により、固形脂特に粗大結晶化の激しい油脂、特にパーム油に由来する油脂等を含有する油脂類について、複雑な装置や乳化剤の添加を必要とせずに、簡便に微細な結晶を析出させることが可能となった。 According to the present invention, fine fats can be easily precipitated without requiring the addition of a complicated apparatus or an emulsifier for fats and oils containing solid fats, particularly fats and oils with coarse crystallization, especially fats and oils derived from palm oil. It became possible.
本発明で用いる対象の油脂(ベース油脂)としては、好ましくは融点10℃以上のものであり、例えばパーム油,パーム核油,ヤシ油,牛脂,豚脂,乳脂,サル脂,シア脂,ココアバター(カカオ脂)等の天然固体脂、及びそれらを原料として分別,硬化,エステル交換等の加工を施したものが挙げられる。また、大豆油,ナタネ油,ヒマワリ油,コーン油,綿実油,米糠油,サフラワー油,魚油等の液状油を原料とした硬化油,エステル交換油等も用いることができる。本発明ではこれらの油脂を1種又は2種以上用いることができる。中でも、粗大な結晶を生じやすい、パーム油やココアバターに由来する油脂等を主たる構成成分とした油脂に対して、本願の微細結晶析出促進効果は有効で好ましい。特にパーム油に由来する油脂に好ましく、具体的には、POP(1,3-ジパルミトイル-2-オレオイル-トリアシルグリセロール)を10重量%以上含む油脂が好ましく、15重量%以上含む油脂が最も好ましい。 The target fats and oils (base fats and oils) used in the present invention are preferably those having a melting point of 10 ° C. or higher. For example, palm oil, palm kernel oil, coconut oil, beef tallow, lard fat, milk fat, monkey fat, shea fat, coco Examples thereof include natural solid fats such as avatar (cocoa butter) and those subjected to processing such as fractionation, curing, and transesterification using these as raw materials. Further, it is also possible to use hardened oils, transesterified oils and the like using liquid oils such as soybean oil, rapeseed oil, sunflower oil, corn oil, cottonseed oil, rice bran oil, safflower oil, fish oil and the like. In the present invention, one or more of these fats and oils can be used. Among them, the effect of promoting the precipitation of fine crystals of the present application is effective and preferable for fats and oils mainly composed of palm oil or cocoa butter and the like that easily generate coarse crystals. Particularly preferred for fats and oils derived from palm oil. Specifically, fats and oils containing 10% by weight or more of POP (1,3-dipalmitoyl-2-oleoyl-triacylglycerol) are preferred, and fats and oils containing 15% by weight or more are preferred. Most preferred.
ベヘン酸とは、炭素数22個の直鎖状飽和脂肪酸である。ベヘン酸は例えばハイエルシン菜種油を加水分解して得られるエルシン酸を、極度水素添加することで得ることができる。このベヘン酸を遊離脂肪酸のまま油脂に添加することが、本願発明である油脂の微細結晶析出促進方法の特徴である。ベヘン酸より低分子の脂肪酸であるステアリン酸やパルミチン酸、不飽和脂肪酸であるオレイン酸では、本願の効果を得ることは出来ない。また炭素数24の直鎖状飽和脂肪酸であるリグノセリン酸等の高分子の脂肪酸は、融点が高く扱いにくい為に、本発明には適さない。 Behenic acid is a linear saturated fatty acid having 22 carbon atoms. Behenic acid can be obtained, for example, by extremely hydrogenating erucic acid obtained by hydrolyzing Hyersin rapeseed oil. The addition of this behenic acid as a free fatty acid to fats and oils is a feature of the method for promoting fine crystal precipitation of fats and oils according to the present invention. The effects of the present application cannot be obtained with stearic acid and palmitic acid, which are lower fatty acids than behenic acid, and oleic acid, which is an unsaturated fatty acid. Also, polymer fatty acids such as lignoceric acid, which is a linear saturated fatty acid having 24 carbon atoms, are not suitable for the present invention because of their high melting point and difficulty in handling.
上記対象油脂(ベース油脂)に対し、ベヘン酸を添加するが、油脂に対して0.01重量%以上の添加が好ましい。また更に好ましくは0.12重量%以下である。0.01重量%未満では、微細結晶析出促進効果が弱くなる。0.12重量%を超えると、油脂中に一部融解しない成分が露見されることがあり、また、日本農林規格による精製油やショートニングの酸価基準(0.2以下)を超えてしまう。尚、本願において融解とはある固体物質が融点以上の環境で液体に相転移した状態を、溶解とは物質が他の液体中に均一に分散している状態を指す。 Although behenic acid is added to the target oil (base oil), 0.01% by weight or more is preferably added to the oil. More preferably, it is 0.12% by weight or less. If it is less than 0.01% by weight, the effect of promoting fine crystal precipitation is weakened. If it exceeds 0.12% by weight, components that do not melt partially may be found in the oil and fat, and the acid value standard (0.2 or less) of refined oil and shortening according to Japanese Agricultural Standards may be exceeded. In the present application, melting refers to a state in which a solid substance has undergone phase transition to a liquid in an environment having a melting point or higher, and dissolution refers to a state in which the substance is uniformly dispersed in another liquid.
ベヘン酸が固体あるいは液体で添加されたベース油脂について、ベース油脂が融解し、且つベヘン酸が融解または溶解するまでベース油脂を加熱する。その後、ベース油脂に撹拌等を行ない、ベヘン酸を十分に混合させることにより、微細結晶析出能を持った油脂を得ることができる。 For base fats and oils to which behenic acid is added in solid or liquid form, the base fats and oils are heated until the base fats and oils are melted and the behenic acid is melted or dissolved. Thereafter, the base oil and fat are stirred and the behenic acid is sufficiently mixed, whereby an oil and fat having fine crystal precipitation ability can be obtained.
ベヘン酸が融解または溶解したこれら油脂は、次に冷却することで、微細な油脂結晶を析出させることができる。冷却はベースとなった油脂の融点以下であり、その温度や冷却方法は、生産する油脂や油脂加工食品により選択することができる。例えば、チョコレート用油脂の場合は10℃の雰囲気下で急速に冷却し、またマーガリンであれば、生産機器の冷却塔内の壁面で接触させながら10℃までの冷却を行ない、クリームであれば、水中油型エマルションとなった液を蒸気殺菌後に、12時間かけて5℃まで冷却するなど、種々の条件を例示することができる。 These fats and oils in which behenic acid is melted or dissolved can then be cooled to precipitate fine fat crystals. Cooling is below the melting point of the base oil and fat, and the temperature and cooling method can be selected depending on the oil and fat or processed food. For example, in the case of fats and oils for chocolate, cool rapidly in an atmosphere of 10 ° C, and in the case of margarine, cool down to 10 ° C while making contact with the wall surface in the cooling tower of the production equipment. Various conditions, such as cooling the liquid which became an oil-in-water emulsion to 5 degreeC over 12 hours after steam sterilization, can be illustrated.
上記の微細結晶析出能を持った油脂を用いて、種々の油脂加工食品を調製することができる。原料油脂がパーム油,カカオ脂又はその代用脂,ラード等の、長期保存中に粗大化し易い結晶を有するものであっても、本願発明により結晶が微細化され、またその後の粗大化が抑制がされる。例えばマーガリン,ショートニングを初め、ホイップクリーム,コーヒークリーム,チョコレート類等、種々の油脂加工食品に用いることができる。 Various types of processed oils and fats can be prepared using the oils and fats having the ability to precipitate fine crystals. Even if the raw material fats and oils have crystals that are easily coarsened during long-term storage, such as palm oil, cacao fat or its substitute fat, lard, etc., the crystals are refined by the present invention, and the subsequent coarsening is suppressed. Is done. For example, it can be used for various oils and fats processed foods such as margarine and shortening, whipped cream, coffee cream, chocolates and the like.
以下に本発明の実施例を記載する。 Examples of the present invention will be described below.
○実施例1(各種脂肪酸、モノ/ジ アシルグリセロールによる微細結晶析出能の評価・マーガリン配合油脂)
先ず、高融点油脂(菜種油35重量%、パーム核油40重量%、ハイエルシン菜種油25重量%を混合し、ナトリウムメチラートを触媒として非選択的エステル交換を行った後、水洗、脱水して、さらに極度硬化、精製を行った極度硬化エステル交換油で融点52℃のもの)7重量%,パーム油(POP含量29重量%)70重量%、菜種油23重量%よりなる、マーガリン配合のベース油脂を調製した(融点40℃)。これに、ベヘン酸,ステアリン酸(以上、キシダ化学製),モノベヘノイルグリセロール,ジベヘノイルグリセロール,トリベヘン(トリベヘノイルグリセロール)(以上、NU-CHEK PREP社製)を0.036重量%添加した添加区と、無添加区を設けた。これら試料液を80℃温水槽にて融解後、マグネティックスターラーにて十分撹拌した後、スライドグラス上に5μl採取し、カバーグラスをかけて室温に放置した。インキュベーターにて70℃,10分で融解後、27℃に温調された偏光顕微鏡のステージ上に静置して油脂結晶の成長を観察/評価を行った。結晶の評価は、5分後の結晶粒子径および視野(220μm×310μm)中の5分後の結晶数を測定することで行なった。
Example 1 (Evaluation of fine crystal precipitation ability by various fatty acids and mono / diacylglycerols / margarine-containing fats and oils)
First, high melting point fat (35% by weight of rapeseed oil, 40% by weight of palm kernel oil, 25% by weight of hay erucin rapeseed oil) Prepared base oil and fat with margarine, consisting of 7% by weight, 70% by weight palm oil (POP content 29% by weight) and 23% by weight rapeseed oil. (Melting point 40 ° C.). 0.036% by weight of behenic acid, stearic acid (above, manufactured by Kishida Chemical Co., Ltd.), monobehenoylglycerol, dibehenoylglycerol, tribeheno (tribehenoylglycerol) (above, manufactured by NU-CHEK PREP) was added thereto. An additive zone and an additive-free zone were provided. These sample solutions were melted in an 80 ° C. hot water bath and sufficiently stirred with a magnetic stirrer, and then 5 μl was collected on a slide glass and left at room temperature with a cover glass. After melting in an incubator at 70 ° C. for 10 minutes, it was placed on a polarizing microscope stage adjusted to 27 ° C., and the growth of fat crystals was observed / evaluated. Crystals were evaluated by measuring the crystal particle diameter after 5 minutes and the number of crystals after 5 minutes in the field of view (220 μm × 310 μm).
○表1.各種添加剤と油脂結晶粒子径(マーガリン配合油脂)
○ Table 1. Various additives and fat crystal particle size (margarine blended fat)
マーガリン配合油脂での結果を表1に示す。添加物の中では、ベヘン酸の結晶粒子径のみが有意に小さく、また5分後の結晶個数も多く、結晶を微細化する作用のある事が分かった。また、他のトリグリセロール類や脂肪酸類、ベヘン酸を構成脂肪酸とするモノアシルグリセロール,ジアシルグリセロールでも顕著な微細結晶析出効果は見られなかった。従って、アシルグリセロールの構成脂肪酸としてではなく、ベヘン酸として存在することで効果が得られる事が分かった。 The results with margarine blended fats and oils are shown in Table 1. Among the additives, only the crystal particle diameter of behenic acid was significantly small, and the number of crystals after 5 minutes was large, which proved to have an effect of refining the crystals. In addition, other triglycerols and fatty acids, and monoacylglycerol and diacylglycerol containing behenic acid as constituent fatty acids did not show a remarkable fine crystal precipitation effect. Therefore, it was found that the effect can be obtained by existing as behenic acid, not as a constituent fatty acid of acylglycerol.
○実施例2(ベヘン酸添加量による微細結晶析出能の影響)
ベースの油脂にベヘン酸を0.018重量%、0.036重量%、0.072重量%添加する以外は、実施例1と同様の操作を行った。
Example 2 (Influence of fine crystal precipitation ability depending on the amount of behenic acid added)
The same operation as in Example 1 was carried out except that behenic acid was added to the base fat and oil at 0.018 wt%, 0.036 wt% and 0.072 wt%.
○表2.ベヘン酸添加量と油脂結晶粒子径
○ Table 2. Addition amount of behenic acid and fat crystal particle size
ベヘン酸添加量による結晶粒径の結果を、表2に示す。添加量0.018重量%以上で効果が見られ、更に添加量を増やしても効果は変わらなかった。 Table 2 shows the results of crystal grain size according to the amount of behenic acid added. The effect was observed when the addition amount was 0.018% by weight or more, and the effect was not changed even when the addition amount was further increased.
○実施例3(各種脂肪酸によるココアバターでの微細結晶析出能の評価)
ベース油脂を脱臭脱色されたココアバター(チョコレート配合油脂)(POP含量14重量%・融点33℃)とした以外は、実施例1と同様の方法で結晶析出の観察を行った。尚、添加区は、ココアバターにベヘン酸,ステアリン酸を0.036重量%添加した。
○ Example 3 (Evaluation of fine crystal precipitation ability in cocoa butter with various fatty acids)
Crystal precipitation was observed in the same manner as in Example 1 except that the base fat was deodorized and decolored cocoa butter (chocolate blended fat) (POP content 14 wt%, melting point 33 ° C.). In addition, 0.036% by weight of behenic acid and stearic acid were added to cocoa butter.
○表3.各種添加剤と油脂結晶粒子径(チョコレート配合油脂)
○ Table 3. Various additives and fat crystal particle size (chocolate blended fat)
結果を表3に示す。ココアバターに於ても、各種脂肪酸の中でも、ベヘン酸添加区で特に結晶が小さく、遊離ベヘン酸には、ココアバターの結晶を微細化する効果があることが分かった。 The results are shown in Table 3. In cocoa butter, among various fatty acids, crystals were particularly small in the behenic acid-added section, and free behenic acid was found to have the effect of refining cocoa butter crystals.
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JP2018191592A (en) * | 2017-05-18 | 2018-12-06 | 理研ビタミン株式会社 | Curing inhibitor for palm oil and fat |
JP2021036828A (en) * | 2019-09-03 | 2021-03-11 | ミヨシ油脂株式会社 | Fat composition for instant precooked food and instant precooked food including the same |
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2014109313A1 (en) * | 2013-01-11 | 2014-07-17 | 日清オイリオグループ株式会社 | Method for producing oil or fat |
JP2014133850A (en) * | 2013-01-11 | 2014-07-24 | Nisshin Oillio Group Ltd | Method of producing fat |
CN104640963A (en) * | 2013-01-11 | 2015-05-20 | 日清奥利友集团株式会社 | Method for producing oil or fat |
CN104640963B (en) * | 2013-01-11 | 2016-12-07 | 日清奥利友集团株式会社 | The manufacture method of oils and fats |
JP2018191592A (en) * | 2017-05-18 | 2018-12-06 | 理研ビタミン株式会社 | Curing inhibitor for palm oil and fat |
JP7029231B2 (en) | 2017-05-18 | 2022-03-03 | 理研ビタミン株式会社 | Curing inhibitor for palm-based fats and oils |
JP2021036828A (en) * | 2019-09-03 | 2021-03-11 | ミヨシ油脂株式会社 | Fat composition for instant precooked food and instant precooked food including the same |
JP7424776B2 (en) | 2019-09-03 | 2024-01-30 | ミヨシ油脂株式会社 | Oil and fat composition for instant cooking food and instant cooking food containing the same |
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