JP2006346526A - Polyglycerol fatty acid ester and composition containing the same - Google Patents
Polyglycerol fatty acid ester and composition containing the same Download PDFInfo
- Publication number
- JP2006346526A JP2006346526A JP2005172428A JP2005172428A JP2006346526A JP 2006346526 A JP2006346526 A JP 2006346526A JP 2005172428 A JP2005172428 A JP 2005172428A JP 2005172428 A JP2005172428 A JP 2005172428A JP 2006346526 A JP2006346526 A JP 2006346526A
- Authority
- JP
- Japan
- Prior art keywords
- polyglycerol
- polyglycerin
- fatty acid
- acid
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000223 polyglycerol Polymers 0.000 title claims abstract description 93
- -1 fatty acid ester Chemical class 0.000 title claims abstract description 83
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 77
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 77
- 239000000194 fatty acid Substances 0.000 title claims abstract description 77
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 125
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 26
- 235000013305 food Nutrition 0.000 claims description 13
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- 150000002148 esters Chemical class 0.000 abstract description 23
- 239000004094 surface-active agent Substances 0.000 abstract description 16
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- 238000002360 preparation method Methods 0.000 description 59
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 29
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Abstract
Description
本発明は、乳化、可溶化などを目的とする食品用、化粧品用、医薬品用及び工業用の界面活性剤として利用できるポリグリセリン脂肪酸エステルを含有する組成物に関する。 The present invention relates to a composition containing a polyglycerin fatty acid ester that can be used as a surfactant for foods, cosmetics, pharmaceuticals and industrial purposes for emulsification, solubilization and the like.
乳化剤または可溶化剤として従来、種々の化合物、例えばポリオキシエチレンアルキルエ−テル、ポリオキシエチレン多価アルコール脂肪酸エステル、ポリオキシエチレンアルキルフェニルエーテル等の酸化エチレン系の非イオン界面活性剤、イオン性界面活性剤があり、食品分野では安全性が高いソルビタン脂肪酸エステル、ショ糖脂肪酸エステル、ポリグリセリン脂肪酸エステル、ポリグリセリン縮合リシノール酸エステル等の界面活性剤が知られている。その中でもポリグリセリン脂肪酸エステルは人体、環境への安全性と、多種類の組成を得るこことができるために汎用性が高いために最も有用な界面活性剤である。 Conventionally, various compounds such as polyoxyethylene alkyl ethers, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene alkylphenyl ethers and the like as emulsifiers or solubilizers, nonionic surfactants based on ethylene oxide, ionic properties Surfactants such as sorbitan fatty acid esters, sucrose fatty acid esters, polyglycerin fatty acid esters, polyglycerin condensed ricinoleic acid esters, which have surfactants and are highly safe in the food field, are known. Among them, polyglycerin fatty acid ester is the most useful surfactant because of its high versatility because it can be used for a variety of compositions and safety to the human body and the environment.
ポリグリセリン脂肪酸エステルに関して、ポリグリセリンの重合度およびHLBを規定したポリグリセリン脂肪酸エステルが従来から報告されている(特許文献1参照)が、1級水酸基の割合を規定したポリグリセリン脂肪酸エステルは報告されていない。 Regarding polyglycerin fatty acid esters, polyglycerin fatty acid esters that define the degree of polymerization of polyglycerol and HLB have been reported (see Patent Document 1), but polyglycerin fatty acid esters that define the proportion of primary hydroxyl groups have been reported. Not.
一方、ポリグリセリン脂肪酸エステルの原料として用いられるポリグリセリンは一般にはグリセリンを原料として水酸化ナトリウムなどの触媒の存在下で加熱下に脱水縮合し、必要に応じて蒸留、脱色、脱臭、イオン交換樹脂処理などにより精製して得られる。脱水縮合の終点は通常その水酸基価を測定した結果をもって決定される。 On the other hand, polyglycerin used as a raw material for polyglycerin fatty acid ester is generally dehydrated and condensed under heating in the presence of a catalyst such as sodium hydroxide using glycerin as a raw material, and distilled, decolored, deodorized, and ion exchange resin as necessary. Obtained by purification by treatment. The end point of the dehydration condensation is usually determined from the result of measuring the hydroxyl value.
このような工程で調製されたポリグリセリンは、構造の異なるグリセリンの脱水縮合化合物の混合物である。その原因としては、グリセリンには2個の1級水酸基と1個の2級水酸基を有するため、グリセリン同士が縮合するときにどの水酸基が反応に関与するかにより生成するポリグリセリンの分子構造が変わってくることがあげられる。ポリグリセリンの構造はポリグリセリン脂肪酸エステルの性能に大きな影響を及ぼす。現在市販されているポリグリセリン脂肪酸エステルは、使用目的に合わせて親水基の構造まで考慮して設計されておらず、そのためその性能を十分に発揮されていなかった。このポリグリセリンの分子構造を反映する情報は種々の方法で得ることができるが、上記のように混合物であるため、厳密な分子構造の決定は意味をもたない。しかし、合成方法や精製方法を組み合わせることにより混合物であってもある傾向をもつ分子種を増やすことは可能である。例えば1級水酸基と2級水酸基の比率もその一つであり、これは後述するように核磁気共鳴スペクトルを測定することで容易に確認することができる。 The polyglycerol prepared in such a process is a mixture of dehydrated condensation compounds of glycerol having different structures. The cause is that glycerin has two primary hydroxyl groups and one secondary hydroxyl group, so the molecular structure of the polyglycerin produced changes depending on which hydroxyl group is involved in the reaction when glycerin condenses. Can come. The structure of polyglycerol has a great influence on the performance of polyglycerol fatty acid ester. The polyglycerol fatty acid ester currently marketed is not designed in consideration of the structure of the hydrophilic group according to the purpose of use, and therefore its performance has not been sufficiently exhibited. Information reflecting the molecular structure of polyglycerin can be obtained by various methods, but since it is a mixture as described above, strict determination of the molecular structure is meaningless. However, it is possible to increase the number of molecular species having a tendency even in a mixture by combining synthesis methods and purification methods. For example, the ratio of primary hydroxyl groups to secondary hydroxyl groups is one of them, and this can be easily confirmed by measuring a nuclear magnetic resonance spectrum as described later.
現在、市場に流通しているポリグリセリンは1級水酸基の割合が50%未満であり、そのポリグリセリンと脂肪酸とのエステルでは高い乳化、可溶化力を発揮することができなかった。例えば、既存の食品用界面活性剤、ポリオキシエチレンソルビタンエステルなどの化粧品用および医薬品用界面活性剤を用いてビタミンEなどの脂溶性ビタミン、βカロチンなどの有用物質を飲料として製造する場合、透明可溶化することができず、保存安定性の良い製品を製造することができなかった。従って、十分な可溶化能力を得るためにエタノールなどの助剤を添加しなければならなかった。そのため、多量にその飲料を飲用すると酩酊状態になり、特に若年者の場合に社会問題になっている。更には、化粧品業界では親水性の乳化剤としてポリオキシエチレン誘導体が使用されているものの、皮膚刺激性など安全性に問題があり代替品が求められているが、従来のポリグリセリン脂肪酸エステルやショ糖脂肪酸エステルでは乳化、可溶化および乳化安定性の性能が不十分であり代替できないものである。 Currently, the polyglycerin on the market has a primary hydroxyl group ratio of less than 50%, and the ester of polyglycerin and a fatty acid could not exhibit high emulsification and solubilization power. For example, when manufacturing useful substances such as fat-soluble vitamins such as vitamin E and β-carotene as beverages using existing surfactants for foods, surfactants for cosmetics such as polyoxyethylene sorbitan ester and pharmaceuticals, transparent The product could not be solubilized and a product with good storage stability could not be produced. Therefore, auxiliary agents such as ethanol had to be added in order to obtain sufficient solubilizing ability. Therefore, if a large amount of the drink is drunk, it becomes a cocoon state, which is a social problem especially in the case of young people. Furthermore, although the polyoxyethylene derivative is used as a hydrophilic emulsifier in the cosmetics industry, there are problems with safety such as skin irritation, and there is a need for an alternative. However, conventional polyglycerin fatty acid esters and sucrose are required. Fatty acid esters have insufficient emulsification, solubilization and emulsion stability performance and cannot be replaced.
従って、本発明は、従来の界面活性剤では不可能であった可溶化物や安定な乳化物の製造を可能にするポリグリセリン脂肪酸エステルを含有する組成物を提供することを課題とする。 Accordingly, an object of the present invention is to provide a composition containing a polyglycerin fatty acid ester that makes it possible to produce a solubilized product and a stable emulsion that were impossible with conventional surfactants.
本発明者らは上記の点に鑑み、鋭意検討の結果本発明に至った。即ち、本発明は、水酸基価が1200以下であり、かつ全ての水酸基のうち1級水酸基が50%以上であるポリグリセリンと脂肪酸とがエステル化されたポリグリセリン脂肪酸エステルを含有する組成物に関する。 In view of the above points, the present inventors have intensively studied to arrive at the present invention. That is, the present invention relates to a composition containing a polyglycerol fatty acid ester in which a polyglycerol having a hydroxyl value of 1200 or less and a primary hydroxyl group of 50% or more of all hydroxyl groups and a fatty acid are esterified.
本発明により従来の界面活性剤では不可能であった可溶化物や安定な乳化物の製造が可能となる。 According to the present invention, it is possible to produce a solubilized product and a stable emulsion which are impossible with conventional surfactants.
以下、詳細に本発明を説明する。 Hereinafter, the present invention will be described in detail.
本発明のポリグリセリン脂肪酸エステルは、水酸基価が1200以下であり、かつ全ての水酸基のうち1級水酸基が50%以上であるポリグリセリンと、脂肪酸とがエステル化されていることに一つの大きな特徴を有する。 The polyglycerin fatty acid ester of the present invention has one major characteristic in that the fatty acid is esterified with a polyglycerin having a hydroxyl value of 1200 or less and a primary hydroxyl group of 50% or more of all hydroxyl groups. Have
かかる特徴を有することにより、本発明のポリグリセリン脂肪酸エステルは可溶化性能および乳化性能に優れた界面活性剤として使用することができる。 By having such characteristics, the polyglycerol fatty acid ester of the present invention can be used as a surfactant having excellent solubilization performance and emulsification performance.
本発明において界面活性剤とは、親油性物質と親水性物質を混合する際に安定化の目的で添加する物質で、強い界面活性能を持つ物質をいう。これらの物質はその分子内に親油性の官能基と親水性の官能基の両方を有するもので、水の表面張力を低下させるものである。 In the present invention, a surfactant is a substance added for the purpose of stabilization when mixing a lipophilic substance and a hydrophilic substance, and means a substance having a strong surface activity. These substances have both a lipophilic functional group and a hydrophilic functional group in the molecule, and reduce the surface tension of water.
本発明においてポリグリセリンとは、グリセリンを脱水縮合するなどして得られる分子内に水酸基とエーテル結合を有している物質をいう。 In the present invention, polyglycerin refers to a substance having a hydroxyl group and an ether bond in the molecule obtained by dehydration condensation of glycerin.
本発明に使用されるポリグリセリンは、ポリグリセリン中の全ての水酸基のうち1級水酸基が50%以上であるポリグリセリンであり、得られるポリグリセリン脂肪酸エステルの可溶化性能および乳化安定性をさらに向上する観点から、1級水酸基が好ましくは55%以上のポリグリセリン、より好ましくは60%以上のポリグリセリンである。さらに上限値は、特に規定するものではないが、その効果を最大限に発揮させるためには90%以下であることが望ましい。本願のポリグリセリンにおける全水酸基のうち1級水酸基の占める割合はポリグリの縮合度に応じて変化するため、また一般的に流通しているポリグリセリンの重合度の種類がテトラ、ペンタ、ヘキサ、デカであることを考慮してその上限値を例示するならば、テトラグリセリンでは70%以下、好ましくは65%以下、ペンタグリセリンでは75%以下、好ましくは70%以下、ヘキサグリセリンでは80%以下、好ましくは75%以下、デカグリセリンでは85%以下、好ましくは80%以下といった数値を示すことができる。さらに、ポリグリセリンの水酸基価は、1200以下であり、用途に応じてポリグリセリン脂肪酸エステルの親水性(HLB)を調整できる観点から、1100以下がより好ましく、1000以下がさらに好ましい。また、作業性および脂肪酸とのエステル化の容易性の観点から、水酸基価は770以上が好ましい。 The polyglycerol used in the present invention is a polyglycerol having a primary hydroxyl group of 50% or more of all hydroxyl groups in the polyglycerol, and further improves the solubilization performance and emulsion stability of the resulting polyglycerol fatty acid ester. Therefore, the primary hydroxyl group is preferably 55% or more of polyglycerin, more preferably 60% or more of polyglycerin. Further, the upper limit value is not particularly specified, but is desirably 90% or less in order to maximize the effect. The proportion of primary hydroxyl groups out of all hydroxyl groups in the polyglycerol of the present application changes depending on the degree of condensation of the polyglycerol, and the types of polymerization degree of polyglycerol that are generally distributed are tetra, penta, hexa, deca In view of the above, the upper limit value is exemplified by 70% or less, preferably 65% or less for tetraglycerin, 75% or less, preferably 70% or less for pentaglycerin, 80% or less for hexaglycerin, preferably Is 75% or less, decaglycerin is 85% or less, preferably 80% or less. Furthermore, the hydroxyl value of polyglycerol is 1200 or less, and 1100 or less is more preferable, and 1000 or less is more preferable from the viewpoint that the hydrophilicity (HLB) of the polyglycerol fatty acid ester can be adjusted according to the use. Further, from the viewpoint of workability and ease of esterification with a fatty acid, the hydroxyl value is preferably 770 or more.
全ての水酸基のうちの1級水酸基の割合は、炭素原子に対する核磁気共鳴スペクトル(NMR)を測定する方法を用いて測定される。また、水酸基価は当該分野で公知の方法により測定することができる。 The proportion of primary hydroxyl groups among all hydroxyl groups is measured using a method of measuring a nuclear magnetic resonance spectrum (NMR) for carbon atoms. The hydroxyl value can be measured by a method known in the art.
なお、炭素原子に対する核磁気共鳴スペクトル(NMR)は、以下のようにして測定することができる。ポリグリセリン500mgを重水2.8mlに溶解し、ろ過後ゲートつきデカップリングにより13C−NMR(125MHz)スペクトルを得る。ゲートデカップルド測定手法によりピーク強度は炭素数に比例する。1級水酸基と2級水酸基の存在を示す13C化学シフトはそれぞれメチレン炭素(CH2OH)が63ppm付近、メチン炭素(CHOH)が71ppm付近であり、2種それぞれのシグナル強度の分析により、1級水酸基と2級水酸基の存在比を算出する。但し、2級水酸基を示すメチン炭素(CHOH)は、1級水酸基を示すメチレン炭素に結合するメチン炭素にさらに隣接するメチレン炭素ピークと重なり、それ自体の積分値を得られないため、メチン炭素(CHOH)と隣り合うメチレン炭素(CH2)の74ppm付近のシグナル強度により積分値を算出する。 In addition, the nuclear magnetic resonance spectrum (NMR) with respect to a carbon atom can be measured as follows. Polyglycerin 500 mg is dissolved in 2.8 ml of heavy water, and after filtration, 13 C-NMR (125 MHz) spectrum is obtained by gated decoupling. The peak intensity is proportional to the carbon number by the gate decoupled measurement method. The 13 C chemical shifts indicating the presence of primary hydroxyl groups and secondary hydroxyl groups are about 63 ppm for methylene carbon (CH 2 OH) and about 71 ppm for methine carbon (CHOH), respectively. The abundance ratio of the primary hydroxyl group and the secondary hydroxyl group is calculated. However, the methine carbon (CHOH) indicating the secondary hydroxyl group overlaps with the methylene carbon peak further adjacent to the methine carbon bonded to the methylene carbon indicating the primary hydroxyl group, and the integral value of itself cannot be obtained. The integrated value is calculated from the signal intensity around 74 ppm of methylene carbon (CH 2 ) adjacent to (CHOH).
一般的なポリグリセリンは、まず、グリセリンをアルカリ触媒下に常圧または減圧下で加熱し、使用の目的によって窒素、水蒸気などの気体を通じて低沸点成分などを除去したり、イオン交換樹脂、イオン交換膜などによって使用した触媒などイオン成分を除去したり、活性炭など吸着剤を用いて色成分、臭成分を除去したり、水素添加などにより還元処理を行ったり、あるいはまた、分子蒸留、精留によって分画するなどにより精製して得られる。 General polyglycerin is first heated under normal pressure or reduced pressure under alkaline catalyst to remove low boiling point components through gases such as nitrogen and water vapor, ion exchange resin, ion exchange. Remove ionic components such as catalysts used by membranes, remove color and odor components using adsorbents such as activated carbon, perform reduction treatment by hydrogenation, etc., or also by molecular distillation and rectification It can be purified by fractionation.
あるいは、前記のようにグリセリンを原料としてポリグリセリンを製造した場合、脱水縮合に際して分子内縮合により6員環や8員環など好ましくない副生成物が多く発生するので、これら副生成物が発生しないようにグリシドール、エピクロルヒドリン、モノクロロヒドリンなどを原料として合成、精製して副生成物をほとんど含有しないポリグリセリンを調製することもできる。 Alternatively, when polyglycerin is produced using glycerin as a raw material as described above, many by-products such as 6-membered ring and 8-membered ring are generated due to intramolecular condensation during dehydration condensation, so that these by-products are not generated. Thus, polyglycerin containing almost no by-products can be prepared by synthesizing and purifying glycidol, epichlorohydrin, monochlorohydrin and the like as raw materials.
あるいはまた、ポリグリセリンと脂肪酸とを反応させる際に、一般に低分子量のポリグリセリンは高分子量のポリグリセリンに比べて脂肪酸との反応性が高いので広い分子量の分布をもつポリグリセリンを原料とした場合には均一なエステルを製造することができない。したがって、例えばグリセリンまたはその重合体の部分アルコラートとハロゲン化炭化水素またはオキシハロゲン化炭化水素を原料として脱ハロゲン化アルカリ金属塩反応によって、できるだけ狭い分子量分布を持つポリグリセリンを調製することもできる。 Alternatively, when polyglycerin and fatty acid are reacted, generally low molecular weight polyglycerin is more reactive with fatty acid than high molecular weight polyglycerin, so if polyglycerin with a wide molecular weight distribution is used as a raw material In this case, a uniform ester cannot be produced. Therefore, for example, polyglycerol having a molecular weight distribution as narrow as possible can be prepared by a dehalogenated alkali metal salt reaction using glycerin or a partial alcoholate thereof as a raw material and a halogenated hydrocarbon or oxyhalogenated hydrocarbon.
あるいは、ポリグリセリンとして太陽化学社製のグレートオイルDE−1、グレートオイルDE−2、グレートオイルTR−1などの市販のポリグリセリンを使用してもよい。 Alternatively, commercially available polyglycerin such as Great Oil DE-1, Great Oil DE-2, or Great Oil TR-1 manufactured by Taiyo Kagaku may be used as the polyglycerin.
本発明に使用される全ての水酸基のうち1級水酸基が50%以上であるポリグリセリンの調製方法は特に限定されるものではないが、例えば市販のポリグリセリンから分画精製により得ることができる。 Although the preparation method of polyglycerol whose primary hydroxyl group is 50% or more among all the hydroxyl groups used for this invention is not specifically limited, For example, it can obtain by fractional purification from commercially available polyglycerol.
上記のように調製したポリグリセリンまたは市販のポリグリセリンに、1級水酸基に選択的に結合反応する試薬、すなわち1級水酸基の保護基となる試薬を反応させる。そうするとポリグリセリン1分子中に1級水酸基の数が多いものほど保護基の数が多くなるので、結果としてそのポリグリセリンの極性が低下する。一方、2級水酸基を多く含むポリグリセリンには保護基が導入されにくいので、該ポリグリセリンはもとの高い極性を維持したままとなる。この極性の差を利用して両者を分別することが可能となる。分別した後のポリグリセリンは保護基の脱離処理を行い、1級水酸基を多く含むポリグリセリンを得ることができる。 The polyglycerin prepared as described above or a commercially available polyglycerin is reacted with a reagent that selectively binds to the primary hydroxyl group, that is, a reagent that serves as a protective group for the primary hydroxyl group. Then, since the number of protective groups increases as the number of primary hydroxyl groups in one molecule of polyglycerol increases, the polarity of the polyglycerol decreases as a result. On the other hand, since a protective group is difficult to be introduced into polyglycerin containing a lot of secondary hydroxyl groups, the polyglycerin maintains its original high polarity. It is possible to separate the two using this difference in polarity. The polyglycerin after the separation can be subjected to a protecting group elimination treatment to obtain polyglycerin containing a large amount of primary hydroxyl groups.
本発明に使用される1級水酸基に選択的に反応する試薬としては、例えば、クロロトリフェニルメチル、イソブテン、1−トリチルピリジニウムテトラフルオロボレートなどが挙げられる。1,2−ジオール以外に2級水酸基を有さないポリグリセリンについては、ポリグリセリンとアセトナイドを形成する化合物(例えば、メチルイソプロペニルエーテル、2,2−ジメトキシプロパン、2,2−ジエトキシプロパン、アセトンなど)を使用することもできる。なかでも、1級水酸基の導入および脱離のしやすさから、クロロトリフェニルメタンが好ましい。 Examples of the reagent that selectively reacts with the primary hydroxyl group used in the present invention include chlorotriphenylmethyl, isobutene, 1-tritylpyridinium tetrafluoroborate and the like. As for polyglycerin having no secondary hydroxyl group other than 1,2-diol, a compound that forms acetonide with polyglycerin (for example, methyl isopropenyl ether, 2,2-dimethoxypropane, 2,2-diethoxypropane, Acetone, etc.) can also be used. Of these, chlorotriphenylmethane is preferred because of the ease of introduction and elimination of primary hydroxyl groups.
ポリグリセリンと該試薬との反応比は、所望されるポリグリセリン中の1級水酸基の数にあわせて適宜調整されるが、確実に反応を進行させるため該試薬を過剰量使用することが好ましい。例えば、該試薬は、ポリグリセリン1モルに対して、好ましくは2〜10モル、より好ましくは3〜7モル使用される。 The reaction ratio of polyglycerin and the reagent is appropriately adjusted according to the desired number of primary hydroxyl groups in polyglycerin, but it is preferable to use an excessive amount of the reagent in order to surely proceed the reaction. For example, the reagent is preferably used in an amount of 2 to 10 mol, more preferably 3 to 7 mol, per 1 mol of polyglycerol.
ポリグリセリンと該試薬との反応は、反応性を向上させるため、有機溶剤中で行うことが好ましい。有機溶剤としては、ピリジン、ジメチルホルムアミドなどが挙げられる。有機溶剤の添加量は、ポリグリセリン100重量部に対して、好ましくは200〜1000重量部、より好ましくは300〜500重量部である。なお、試薬としてポリグリセリンとアセトナイドを形成する化合物を用いる場合、該化合物を大過剰量で用いることにより、溶剤を添加するのと同じ効果が期待できる。 The reaction between polyglycerin and the reagent is preferably performed in an organic solvent in order to improve the reactivity. Examples of the organic solvent include pyridine and dimethylformamide. The addition amount of the organic solvent is preferably 200 to 1000 parts by weight, more preferably 300 to 500 parts by weight with respect to 100 parts by weight of polyglycerol. In addition, when using the compound which forms polyglycerol and acetonide as a reagent, the same effect as adding a solvent can be expected by using the compound in a large excess amount.
ポリグリセリンと該試薬との反応は、反応の進行および保護の確実性の観点から、好ましくは5〜30℃、より好ましくは10〜25℃で行われる。 The reaction between polyglycerin and the reagent is preferably performed at 5 to 30 ° C, more preferably 10 to 25 ° C, from the viewpoint of the progress of the reaction and the certainty of protection.
反応終了後、通常の化学反応と同様に後処理を行えばよい。ピリジンなどの有機溶剤は減圧下蒸留により除去することができる。 After the reaction, post-treatment may be performed in the same manner as a normal chemical reaction. Organic solvents such as pyridine can be removed by distillation under reduced pressure.
得られた反応物から目的のポリグリセリンを分別する方法は、保護基が導入されたポリグリセリンの化学的および物理的差を利用して達成することができる。例えば、沸点の差を利用して蒸留、減圧蒸留、分子蒸留などの方法で目的のポリグリセリンを分別することができ、あるいは水または有機溶剤への溶解度の差を利用して目的のポリグリセリンを分画することもできる。例えば、反応物を水に分散させ、水と混和しない有機溶剤(例えば、クロロホルム、ジクロロメタン、石油エーテル、ヘキサン、ベンゼン、トルエン、エーテル、酢酸エチルなど)で抽出することにより目的のポリグリセリンを分画することができる。この分画方法を使用する場合、水の代わりに水含有エタノール、食塩水、硫酸ナトリウム溶液などの無機塩の溶液を使用することもできる。水と酢酸エチルを用いて目的のポリグリセリンを分画することが好ましい。 A method for fractionating the desired polyglycerol from the obtained reaction product can be achieved by utilizing the chemical and physical differences of the polyglycerol into which a protecting group has been introduced. For example, the target polyglycerol can be fractionated by a method such as distillation, vacuum distillation, molecular distillation using the difference in boiling points, or the target polyglycerol can be separated using the difference in solubility in water or an organic solvent. It can also be fractionated. For example, the target polyglycerin is fractionated by dispersing the reaction product in water and extracting it with an organic solvent immiscible with water (for example, chloroform, dichloromethane, petroleum ether, hexane, benzene, toluene, ether, ethyl acetate, etc.). can do. When this fractionation method is used, a solution of an inorganic salt such as water-containing ethanol, saline, or sodium sulfate solution can be used instead of water. It is preferable to fractionate the desired polyglycerol using water and ethyl acetate.
溶剤抽出した後に溶剤を除去することにより、極性の低いポリグリセリン誘導体、すなわち1分子中に保護基が多く導入されたポリグリセリンが得られる。この誘導体からの保護基の脱離は、一般の有機合成で行われている方法で行うことができる。例えば、メタノール中でp−トルエンスルホン酸を作用させる方法、酢酸水溶液中で加熱撹拌する方法などにより保護基の脱離が達成される。1例として、トリフェニルメチル基をポリグリセリンに導入した場合、得られた反応物に対して2〜3倍量の酢酸水溶液を加えて、55〜60℃で10時間撹拌することにより、保護基を脱離することができる。 By removing the solvent after solvent extraction, a low-polarity polyglycerin derivative, that is, polyglycerin in which many protective groups are introduced in one molecule is obtained. Removal of the protecting group from this derivative can be carried out by a method used in general organic synthesis. For example, removal of the protecting group can be achieved by a method of allowing p-toluenesulfonic acid to act in methanol, a method of heating and stirring in an acetic acid aqueous solution, or the like. As an example, when a triphenylmethyl group is introduced into polyglycerin, a protective group is obtained by adding 2 to 3 times the amount of acetic acid aqueous solution to the obtained reaction product and stirring at 55 to 60 ° C. for 10 hours. Can be released.
また、1級水酸基の割合が非常に高い単位構造物を調製し、1級水酸基の割合が少ないポリグリセリンと混合して本発明に使用するポリグリセリンを調製してもよい。湯浴にて混合すれば調製は容易である。1級水酸基の割合が少ないポリグリセリンとしては市販のポリグリセリンが有用であり、事前に、核磁気共鳴スペクトル(NMR)を測定する方法にて、1級水酸基の割合を測定しておけば、目的の組成を容易に得ることができる。 Alternatively, a unit structure having a very high ratio of primary hydroxyl groups may be prepared and mixed with polyglycerol having a low ratio of primary hydroxyl groups to prepare polyglycerol for use in the present invention. Preparation is easy if mixed in a hot water bath. A commercially available polyglycerin is useful as the polyglycerin having a small proportion of primary hydroxyl groups. If the proportion of primary hydroxyl groups is measured in advance by a method of measuring a nuclear magnetic resonance spectrum (NMR), the purpose is as follows. The composition can be easily obtained.
本発明に使用される全ての水酸基のうち1級水酸基が50%以上であるポリグリセリンは、上記の方法にて得ることができるが、この方法に特に限定されるものではない。 Polyglycerol having 50% or more of primary hydroxyl groups among all hydroxyl groups used in the present invention can be obtained by the above method, but is not particularly limited to this method.
水酸基価が1200以下のポリグリセリンを調製することは、ポリグリセリン反応工程を例えば以下のように調整することで可能である。例えば、グリセリン重合法を用いて調製する場合、重合反応時間の経過と共に水酸基価が低下するため、反応中のポリグリセリンの水酸基価低下過程を確認することで、水酸基価が1200以下のポリグリセリンを容易に得ることができる。 It is possible to prepare a polyglycerol having a hydroxyl value of 1200 or less by adjusting the polyglycerol reaction step as follows, for example. For example, when preparing using the glycerin polymerization method, the hydroxyl value decreases with the lapse of the polymerization reaction time. Therefore, by confirming the process of decreasing the hydroxyl value of the polyglycerol during the reaction, the polyglycerol having a hydroxyl value of 1200 or less can be obtained. Can be easily obtained.
本発明に使用される脂肪酸としては、天然の動植物より抽出した油脂を加水分解し、分離してあるいは分離せずに精製して得られるカルボン酸を官能基として含む物質であれば特に限定するものではない。あるいは石油などを原料にして化学的に合成して得られる脂肪酸であってもよい。あるいはまた、これら脂肪酸を水素添加などして還元したものや、水酸基を含む脂肪酸を縮重合して得られる縮合脂肪酸や、不飽和結合を有する脂肪酸を加熱重合して得られる重合脂肪酸であってもよい。これら脂肪酸の選択に当たっては所望の効果を勘案して適宜決めればよい。本発明に使用される脂肪酸の具体例としては、ベヘニン酸、ステアリン酸、ラウリン酸、ミリスチン酸、オレイン酸、イソステアリン酸、パルミチン酸、カプリン酸、カプリル酸、カプロン酸、縮合リシノール酸、縮合12−ヒドロキシステアリン酸、エルカ酸、パルミトオレイン酸、リノール酸、リノレン酸、オクチル酸、オクタン酸、リシノール酸、12−ヒドロキシステアリン酸などが挙げられるが、なかでも乳化・可溶化の観点から、ラウリン酸、ステアリン酸、イソステアリン酸、パルミチン酸、ミリスチン酸、オレイン酸、縮合リシノール酸が好ましい。 Fatty acids used in the present invention are particularly limited as long as they contain a carboxylic acid as a functional group obtained by hydrolyzing and extracting oils and fats extracted from natural animals and plants and purifying them with or without separation. is not. Alternatively, it may be a fatty acid obtained by chemically synthesizing petroleum or the like as a raw material. Alternatively, these fatty acids may be reduced by hydrogenation or the like, condensed fatty acids obtained by condensation polymerization of fatty acids containing hydroxyl groups, or polymerized fatty acids obtained by heat polymerization of fatty acids having unsaturated bonds. Good. The selection of these fatty acids may be appropriately determined in consideration of the desired effect. Specific examples of fatty acids used in the present invention include behenic acid, stearic acid, lauric acid, myristic acid, oleic acid, isostearic acid, palmitic acid, capric acid, caprylic acid, caproic acid, condensed ricinoleic acid, condensed 12- Examples include hydroxystearic acid, erucic acid, palmitooleic acid, linoleic acid, linolenic acid, octylic acid, octanoic acid, ricinoleic acid, and 12-hydroxystearic acid. Among them, from the viewpoint of emulsification and solubilization, lauric acid , Stearic acid, isostearic acid, palmitic acid, myristic acid, oleic acid, and condensed ricinoleic acid are preferred.
ポリグリセリンと脂肪酸とのエステル化は、当該分野で公知の方法に従って行われる。例えばアルカリ触媒下、酸触媒下、あるいは無触媒下にて、常圧あるいは減圧下エステル化することができる。また、ポリグリセリンと脂肪酸の混合量を変更することにより種々の性質をもつポリグリセリン脂肪酸エステルを調製することができる。例えば、親水性の界面活性剤に使用するためのポリグリセリン脂肪酸エステルを得る場合、ポリグリセリンの水酸基価と脂肪酸の分子量から計算により等モルになるように重量を計算してポリグリセリンと脂肪酸を仕込めばよく、親油性の界面活性剤に使用するためのポリグリセリン脂肪酸エステルを得る場合、脂肪酸のモル数を増加させればよい。得られたポリグリセリン脂肪酸エステルは使用される製品の使用上の要求によってさらに精製してもよい。精製の方法は公知のいかなる方法でもよく特に限定するものではない。たとえば、活性炭や活性白土などにて吸着処理したり、水蒸気、窒素などをキャリアーガスとして用いて減圧下脱臭処理を行ったり、あるいは酸やアルカリを用いて洗浄を行ったり、分子蒸留を行ったりして精製してもよい。 Esterification of polyglycerol and fatty acid is performed according to a method known in the art. For example, the esterification can be performed under normal pressure or reduced pressure in the presence of an alkali catalyst, an acid catalyst, or no catalyst. Moreover, the polyglycerol fatty acid ester which has various properties can be prepared by changing the mixing amount of polyglycerol and a fatty acid. For example, when obtaining a polyglycerin fatty acid ester for use in a hydrophilic surfactant, the polyglycerin and the fatty acid are charged by calculating the weight so as to be equimolar by calculation from the hydroxyl value of the polyglycerin and the molecular weight of the fatty acid. What is necessary is just to increase the number-of-moles of a fatty acid, when obtaining the polyglyceryl fatty acid ester for using for lipophilic surfactant. The resulting polyglycerol fatty acid ester may be further purified according to the usage requirements of the product used. The purification method may be any known method and is not particularly limited. For example, adsorption treatment with activated carbon or activated clay, deodorization treatment under reduced pressure using water vapor or nitrogen as a carrier gas, washing with acid or alkali, or molecular distillation. And may be purified.
さらに、本発明のポリグリセリン脂肪酸エステルは単独で用いられる他、目的に応じて他の物質を添加・混合した組成物としても利用できる。 Furthermore, the polyglycerin fatty acid ester of the present invention can be used alone or as a composition in which other substances are added and mixed depending on the purpose.
例えばポリグリセリン脂肪酸エステルの取り扱いを容易にするために、他の成分を添加することもできる。例えば、粘度を低下させるために、エタノール、プロピレングリコール、グリセリン、ポリグリセリン、水、液糖、油脂などを添加してもよい。あるいは、本発明のポリグリセリン脂肪酸エステルに乳糖、デキストリンなどの多糖類やカゼイネートなど蛋白質を添加して粉末化して使用してもよい。 For example, in order to facilitate handling of the polyglycerol fatty acid ester, other components can be added. For example, ethanol, propylene glycol, glycerin, polyglycerin, water, liquid sugar, fats and oils and the like may be added to reduce the viscosity. Alternatively, the polyglycerol fatty acid ester of the present invention may be used by adding a protein such as lactose, dextrin or other polysaccharides or caseinate to a powder.
本発明のポリグリセリン脂肪酸エステルはまた、乳化安定性を向上する観点から、他の界面活性剤と混合した乳化剤組成物として使用しても良い。混合される界面活性剤としては、グリセリン脂肪酸エステル、プロピレングリコール脂肪酸エステル、ショ糖脂肪酸エステル、ポリグリセリン脂肪酸エステル(ただし、本発明のポリグリセリン脂肪酸エステルを除く)などの非イオン界面活性剤、両性界面活性剤、アニオン界面活性剤、カチオン界面活性剤、レシチン、酵素分解レシチン、サポニンといった天然物由来の界面活性剤などが挙げられる。 The polyglycerol fatty acid ester of the present invention may also be used as an emulsifier composition mixed with other surfactants from the viewpoint of improving the emulsion stability. Examples of the surfactant to be mixed include nonionic surfactants such as glycerin fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, and polyglycerin fatty acid ester (excluding the polyglycerin fatty acid ester of the present invention), amphoteric interfaces. Examples thereof include surfactants derived from natural products such as activators, anionic surfactants, cationic surfactants, lecithin, enzymatically degraded lecithin, and saponin.
さらに、本発明のポリグリセリン脂肪酸エステルに油性物質を混合して、油性物質の乳化乃至可溶化組成物としてもよい。この場合の油性物質は特に限定するものではないが、例えば、ビタミンA、ビタミンD、ビタミンE、ビタミンKなどの脂溶性ビタミン、カロチン、カロチノイド系色素、アナトー色素、ターメリック色素などの油溶性色素、オレンジ油、レモン油、アンブレット種子油、オリス根油、カナンガ油、キャラウエイ油、キャロット種子油、グレープフルーツ油、ジンジャー油、ホップ油、ミルトン油、ローズ油、ローズマリー油などの天然香料、オイゲノール、カプリル酸エチル、ゲラニオール、メントール、シトラール、シトロネール、ボルネオールなどの合成香料、ウコン抽出物、ゴマ抽出物、トウガラシ抽出物、ニンニク抽出物、ワサビ抽出物などの香辛料抽出物、オリザノール、米ぬか油抽出物、トコフェロールなどの疎水性酸化防止剤、オレイン酸、リノール酸、リノレン酸、アラキドン酸、エイコサペンタエン酸、ドコサペンタエン酸、プロスタグランジンなどの脂肪酸またはそのエステル等の脂肪酸誘導体、オリーブ油、コーン油、ベニバナ油、魚油、サメ肝油、米ぬか油などの油脂の他、ミツロウ、ライスワックス、プロポリス、オクタコサノールなどの生理活性成分や有用成分を例示することができる。また、油性物質を別の観点から化学構造に着目して例示するならば、モノテルペン、セスキテルペン、ジテルペン、トリテルペンといったテルペノイド類、カロテノイド類、ステロイド類、フェニルプロパノイド類、ベンゾキノン、ナフトキノン、アントラキノンといったキノン類、γ−ピロン類、フラボン、フラボノール、フラバノン、ジヒドロフラボノール、イソフラボン、カルコン、オーロン、アントシアニン、ネオフラバノイドといったフラボノイド類、単環性α−ピロン類、クマリン類、イソクマリン類、フタリド類といったα−ピロン類、ジアリルヘプタノイド、スチルベン、クロロジルシン、ナフタレンといった芳香族化合物、ピロール誘導体、ピラゾール誘導体、イミダゾール誘導体、イソキサゾール誘導体、チアゾール誘導体、ピリジン誘導体、ピリミジン誘導体、ピラジン誘導体、インドール誘導体、ヒダントイン誘導体、プリン誘導体、プテリジン誘導体、ポルフィリン誘導体、カプサイシン類といった含窒素化合物、含硫化合物が挙げられる。これらの油性物質は単独で用いる他、目的に応じて2種以上の油性物質を混合して使用してもよい。 Furthermore, an oily substance may be mixed with the polyglycerin fatty acid ester of the present invention to obtain an emulsified or solubilized composition of the oily substance. The oily substance in this case is not particularly limited. For example, fat-soluble vitamins such as vitamin A, vitamin D, vitamin E, and vitamin K, oil-soluble dyes such as carotene, carotenoid pigments, anato pigments, turmeric pigments, Natural fragrances such as orange oil, lemon oil, amblet seed oil, Oris root oil, cananga oil, caraway oil, carrot seed oil, grapefruit oil, ginger oil, hop oil, Milton oil, rose oil, rosemary oil, eugenol , Synthetic flavors such as ethyl caprylate, geraniol, menthol, citral, citronell, borneol, spice extracts such as turmeric extract, sesame extract, pepper extract, garlic extract, wasabi extract, oryzanol, rice bran oil extract , Hydrophobic antioxidants such as tocopherols , Fatty acid derivatives such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, prostaglandin, etc., olive oil, corn oil, safflower oil, fish oil, shark liver oil, rice bran In addition to fats and oils such as oil, physiologically active components and useful components such as beeswax, rice wax, propolis, and octacosanol can be exemplified. Further, if the oily substance is exemplified by focusing on the chemical structure from another viewpoint, terpenoids such as monoterpenes, sesquiterpenes, diterpenes, and triterpenes, carotenoids, steroids, phenylpropanoids, benzoquinone, naphthoquinone, anthraquinone, etc. Quinones, γ-pyrones, flavones, flavonols, flavanones, dihydroflavonols, isoflavones, flavonoids such as chalcones, aurones, anthocyanins, neoflavanoids, monocyclic α-pyrones, coumarins, isocoumarins, phthalides -Aromatic compounds such as pyrones, diallylheptanoids, stilbene, chlorodilcine, naphthalene, pyrrole derivatives, pyrazole derivatives, imidazole derivatives, isoxazole derivatives, thiazole derivatives , Pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, indole derivatives, hydantoin derivatives, purine derivatives, pteridine derivatives, porphyrin derivatives, nitrogen-containing compounds such as capsaicin compounds, sulfur-containing compounds. These oily substances may be used alone, or two or more oily substances may be mixed and used according to the purpose.
この油性物質の乳化乃至可溶化組成物調製においては、本発明のポリグリセリン脂肪酸エステルと油溶性物質の他に、組成物の安定性向上や組成物を水に分散させたときの安定性向上を目的として、多価アルコールの配合が推奨される。この場合の多価アルコールとしては特に限定するものではないが、グリセリン、プロピレングリコール、ポリグリセリン、液糖といったものが例示でき、特に安全性や取り扱いやすさの点からグリセリンが好適に利用できる。また補助的に他の乳化剤や水、エタノールといった溶剤類の使用も可能である。この本発明のポリグリセリン脂肪酸エステルと油性物質および多価アルコールの配合割合は特に定めるものではなく、油性物質の物性や使用目的に応じて任意の割合で配合すればよい。乳化乃至可溶化組成物の安定性、取り扱いやすさ、水分散時の安定性から、推奨される配合割合を例示するならば、本発明のポリグリセリン脂肪酸エステル1〜40重量部、好ましくは5〜20重量部、油性物質2〜50重量部、好ましくは2〜30重量部、多価アルコール20〜90重量部、好ましくは50〜80重量部といった配合比率を挙げることができる。 In preparing an emulsified or solubilized composition of the oily substance, in addition to the polyglycerin fatty acid ester of the present invention and the oil-soluble substance, the stability of the composition is improved and the stability is improved when the composition is dispersed in water. For the purpose, blending of polyhydric alcohol is recommended. The polyhydric alcohol in this case is not particularly limited, and examples thereof include glycerin, propylene glycol, polyglycerin, and liquid sugar, and glycerin can be suitably used particularly from the viewpoint of safety and ease of handling. In addition, other emulsifiers, water, and solvents such as ethanol can be used. The blending ratio of the polyglycerin fatty acid ester of the present invention, the oily substance and the polyhydric alcohol is not particularly defined, and may be blended at an arbitrary ratio depending on the physical properties of the oily substance and the purpose of use. If the recommended blending ratio is exemplified from the stability of the emulsified or solubilized composition, ease of handling, and stability during water dispersion, the polyglycerol fatty acid ester of the present invention is 1 to 40 parts by weight, preferably 5 to 5 parts. Examples of the mixing ratio include 20 parts by weight, 2 to 50 parts by weight of an oily substance, preferably 2 to 30 parts by weight, and 20 to 90 parts by weight of a polyhydric alcohol, preferably 50 to 80 parts by weight.
本発明のポリグリセリン脂肪酸エステル組成物の使用方法は特に限定しないが、乳化、可溶化、分散、洗浄、起泡、消泡、浸透、抗菌等の目的で飲食品、化粧品、医薬品および工業用途で、特に飲食品ではこれらに加えてデンプン、タンパク質、油脂の改質にも利用できる。使用用途を具体的にあげると、飲食品分野では即席麺、レトルト食品、缶詰、電子レンジ食品、即席スープ・みそしる類、フリーズドライ食品等の即席食品類、清涼飲料、果汁飲料、野菜系飲料、豆乳飲料、コーヒー飲料、茶飲料、粉末飲料、濃縮飲料、栄養飲料、アルコール飲料等の飲料類、パン、パスタ、麺、ケーキミックス、から揚げ粉、パン粉等の小麦粉製品、キャラメル、キャンディー、チューイングガム、チョコレート、クッキー、ビスケット、ケーキ、パイ、スナック、クラッカー、和菓子、デザート菓子等の菓子類、ソース、トマト加工調味料、風味調味料、調理ミックス、たれ類、ドレッシング類、つゆ類、カレー・シチューの素類等の調味料、加工油脂、バター、マーガリン、マヨネーズ等の油脂類、乳飲料、ヨーグルト類、乳酸菌飲料、アイスクリーム類、クリーム類等の乳製品、冷凍食品、魚肉ハム・ソーセージ、水産練り製品等の水産加工品、畜肉ハム・ソーセージ等の畜産加工品、農産缶詰、ジャム・マーマレード類、漬け物、煮豆、シリアル等の農産加工品、栄養食品等、化粧品分野では石けん、クレンジング、シャンプー、リンス等の洗浄料、化粧水、乳液、クリーム、パック剤、ヘアトニック、ヘアクリーム等の基礎化粧料、口紅、アイシャドウ、セットローション、整髪料等の仕上げ化粧料、香水、ローション等の芳香剤、歯磨、含そう剤等の口中使用化粧品等、工業分野では樹脂に対する充填剤や顔料、塗料の分散、防曇、食品工業では機器の洗浄剤、加工助剤、野菜・果物の洗浄剤等があるがこれらに限定するものではない。 The method of using the polyglycerin fatty acid ester composition of the present invention is not particularly limited, but for the purposes of emulsification, solubilization, dispersion, washing, foaming, defoaming, penetration, antibacterial, etc., for foods and drinks, cosmetics, pharmaceuticals and industrial applications. Especially in foods and drinks, in addition to these, it can be used for modification of starch, protein and fats and oils. Specific uses include instant noodles, retort foods, canned foods, microwave foods, instant soups and miso soups, freeze-dried foods, soft drinks, fruit juice drinks, vegetable drinks , Soy milk drinks, coffee drinks, tea drinks, powdered drinks, concentrated drinks, nutrition drinks, alcoholic drinks and other beverages, bread, pasta, noodles, cake mix, fried flour, bread crumbs and other flour products, caramel, candy, chewing gum , Chocolate, cookies, biscuits, cakes, pies, snacks, crackers, Japanese confectionery, dessert confectionery, sauces, tomato processing seasonings, flavor seasonings, cooking mixes, sauces, dressings, soups, curry stew Seasonings such as nobles, processed fats and oils, butter, margarine, mayonnaise and other fats, milk drinks, yogurt Dairy products such as lactic acid bacteria beverages, ice creams, creams, frozen foods, processed fish products such as fish ham and sausage, fish paste products, livestock processed products such as livestock ham and sausage, canned agricultural products, jams and marmalades, Agricultural processed products such as pickles, boiled beans, cereals, nutritional foods, etc. In the cosmetics field, soaps, cleansings, shampoos, rinses, etc., basic cosmetics such as lotions, emulsions, creams, packs, hair tonics, hair creams, etc. Dispersion of fillers, pigments, and paints for resins in the industrial field such as lipsticks, eye shadows, set cosmetics such as set lotions and hair styling, fragrances such as perfumes and lotions, and cosmetics used in the mouth such as toothpaste and emollients. In the anti-fogging and food industries, there are equipment cleaning agents, processing aids, vegetable and fruit cleaning agents, but not limited thereto.
以下、実施例を挙げて本発明をさらに具体的に説明するが、本発明がかかる実施例のみに限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited only to this Example.
調製例1 ポリグリセリンの精製
温度計、ジムロートおよび攪拌装置を付けた3つ口フラスコに、太陽化学社製のポリグリセリン(グレートオイルDE−1、デカグリセリン;水酸基価890、1級水酸基の割合46.6%、2級水酸基の割合53.4%)200gおよびピリジン600mlを加えた。ここへ1級水酸基に選択的に反応する試薬であるクロロトリフェニルメチル370g(和光純薬社製)を加えて100℃で1時間攪拌後室温に戻し、24時間攪拌した。さらに反応液を減圧下でピリジンの大部分を除去した。得られた反応物に水800mlを加え、分液ロートに移して酢酸エチル400mlで3回抽出した。酢酸エチル層を合わせて濃縮し、得られた残渣156gおよび酢酸300gを温度計、ジムロートおよび攪拌装置を付けた3つ口フラスコに加えて8時間加熱還流し、トリメチルフェニル基を脱離させた。上記工程を繰り返し、精製したポリグリセリンを混合し、一定量のポリグリセリンを得た。得られたポリグリセリンの水酸基価は886、1級水酸基の割合は61.3%、2級水酸基の割合は38.7%であった。
Preparation Example 1 Purification of Polyglycerin A three-necked flask equipped with a thermometer, a Dimroth, and a stirrer was charged with polyglycerin (Great Oil DE-1, Decaglycerin; hydroxyl value 890, primary hydroxyl group ratio 46) manufactured by Taiyo Kagaku. .6%, secondary hydroxyl group ratio 53.4%) 200 g and pyridine 600 ml were added. To this, 370 g of chlorotriphenylmethyl (manufactured by Wako Pure Chemical Industries, Ltd.), which is a reagent that selectively reacts with the primary hydroxyl group, was added, stirred at 100 ° C. for 1 hour, returned to room temperature and stirred for 24 hours. Further, most of the pyridine was removed from the reaction solution under reduced pressure. 800 ml of water was added to the obtained reaction product, transferred to a separatory funnel, and extracted three times with 400 ml of ethyl acetate. The ethyl acetate layers were combined and concentrated. The obtained residue (156 g) and acetic acid (300 g) were added to a three-necked flask equipped with a thermometer, a Dimroth and a stirrer, and heated under reflux for 8 hours to desorb the trimethylphenyl group. The above process was repeated, and purified polyglycerol was mixed to obtain a certain amount of polyglycerol. The resulting polyglycerol had a hydroxyl value of 886, a primary hydroxyl group ratio of 61.3%, and a secondary hydroxyl group ratio of 38.7%.
水酸基価は、第7版食品添加物公定書「油脂類試験法」または基準油脂分析試験法に準じて算出した。 The hydroxyl value was calculated in accordance with the 7th edition Food Additives Official “Fats and Fats Test Method” or the standard fat and oil analysis test method.
1級水酸基と2級水酸基の割合は、核磁気共鳴装置におけるスペクトル分析にて決定した。すなわち核磁気共鳴装置(13C−NMR)(日本電子社製、JNM−A500)を使用して、上記の通り分画したポリグリセリンの1級水酸基と2級水酸基の割合を分析した。分画したポリグリセリン500mgを重水2.8mlに溶解し、ろ過後ゲートつきデカップリングにより13C−NMR(125MHz)スペクトルを得た。ゲートデカップルド測定手法によりピーク強度は炭素数に比例する。1級水酸基と2級水酸基の存在を示す13C化学シフトはそれぞれメチレン炭素(CH2OH)が63ppm付近、メチン炭素(CHOH)が71ppm付近であり、2種それぞれのシグナル強度の分析により、1級水酸基と2級水酸基の存在比を算出した。但し、2級水酸基を示すメチン炭素(CHOH)は、1級水酸基を示すメチレン炭素に結合するメチン炭素にさらに隣接するメチレン炭素ピークと重なり、それ自体の積分値を得られないため、メチン炭素(CHOH)と隣り合うメチレン炭素(CH2)の74ppm付近のシグナル強度により積分値を算出した。 The ratio between the primary hydroxyl group and the secondary hydroxyl group was determined by spectral analysis using a nuclear magnetic resonance apparatus. That is, using a nuclear magnetic resonance apparatus ( 13 C-NMR) (manufactured by JEOL Ltd., JNM-A500), the ratio of primary hydroxyl groups and secondary hydroxyl groups of polyglycerol fractionated as described above was analyzed. 500 mg of the fractionated polyglycerol was dissolved in 2.8 ml of heavy water, and after filtration, 13 C-NMR (125 MHz) spectrum was obtained by gated decoupling. The peak intensity is proportional to the carbon number by the gate decoupled measurement method. The 13 C chemical shifts indicating the presence of primary hydroxyl groups and secondary hydroxyl groups are about 63 ppm for methylene carbon (CH 2 OH) and about 71 ppm for methine carbon (CHOH), respectively. The abundance ratio of the primary hydroxyl group and the secondary hydroxyl group was calculated. However, the methine carbon (CHOH) indicating the secondary hydroxyl group overlaps with the methylene carbon peak further adjacent to the methine carbon bonded to the methylene carbon indicating the primary hydroxyl group, and the integral value of itself cannot be obtained. The integrated value was calculated from the signal intensity around 74 ppm of methylene carbon (CH 2 ) adjacent to (CHOH).
なお、以下の調製例2〜6における水酸基価の値および1級水酸基と2級水酸基の割合も同様に算出した。 In addition, the value of the hydroxyl value and the ratio of primary hydroxyl group and secondary hydroxyl group in the following Preparation Examples 2 to 6 were calculated in the same manner.
調製例2 ポリグリセリンの精製
調製例1と同様の方法で太陽化学社製のポリグリセリン(グレートオイルDE−2、デカグリセリン;)を精製した。得られたポリグリセリンの水酸基価は883、1級水酸基の割合は56.2%、2級水酸基の割合は43.8%であった。
Preparation Example 2 Purification of Polyglycerol Polyglycerin (Great Oil DE-2, decaglycerol;) manufactured by Taiyo Kagaku was purified in the same manner as Preparation Example 1. The resulting polyglycerol had a hydroxyl value of 883, a primary hydroxyl group ratio of 56.2%, and a secondary hydroxyl group ratio of 43.8%.
調製例3 ポリグリセリンの精製
調製例1と同様の方法で太陽化学社製のポリグリセリン(グレートオイルTR−1、トリグリセリン;水酸基価1160、1級水酸基の割合38.5%、2級水酸基の割合61.5%)を精製した。得られたポリグリセリンの水酸基価は1148、1級水酸基の割合は52.5%、2級水酸基の割合は47.5%であった。
Preparation Example 3 Purification of Polyglycerin Polyglycerin manufactured by Taiyo Kagaku Co., Ltd. (Great Oil TR-1, Triglycerin; hydroxyl value 1160, primary hydroxyl group ratio 38.5%, secondary hydroxyl group 61.5%). The resulting polyglycerol had a hydroxyl value of 1148, a primary hydroxyl group ratio of 52.5%, and a secondary hydroxyl group ratio of 47.5%.
調製例4 ポリグリセリンの精製
調製例1の水層部分を濃縮して得られた残渣450gおよび酢酸900gを温度計、ジムロートおよび攪拌装置を付けた3つ口フラスコに加えて8時間加熱還流し、トリメチルフェニル基を脱離させた。上記工程を繰り返し、精製したポリグリセリンを混合し、一定量のポリグリセリンを得た。得られたポリグリセリンの水酸基価は893、1級水酸基の割合は34.4%、2級水酸基の割合は65.6%であった。
Preparation Example 4 Purification of Polyglycerol 450 g of the residue obtained by concentrating the aqueous layer of Preparation Example 1 and 900 g of acetic acid were added to a three-necked flask equipped with a thermometer, a Dimroth and a stirrer, and heated to reflux for 8 hours. The trimethylphenyl group was eliminated. The above process was repeated, and purified polyglycerol was mixed to obtain a certain amount of polyglycerol. The resulting polyglycerol had a hydroxyl value of 893, a primary hydroxyl group ratio of 34.4%, and a secondary hydroxyl group ratio of 65.6%.
調製例5 ポリグリセリンの精製
調製例3の水層部分を濃縮して得られた残渣450gおよび酢酸900gを温度計、ジムロートおよび攪拌装置を付けた3つ口フラスコに加えて8時間加熱還流し、トリメチルフェニル基を脱離させた。上記工程を繰り返し、精製したポリグリセリンを混合し、一定量のポリグリセリンを得た。得られたポリグリセリンの水酸基価は1165、1級水酸基の割合は32.2%、2級水酸基の割合は67.8%あった。
Preparation Example 5 Purification of Polyglycerin 450 g of the residue obtained by concentrating the aqueous layer portion of Preparation Example 3 and 900 g of acetic acid were added to a three-necked flask equipped with a thermometer, a Dimroth and a stirrer, and heated to reflux for 8 hours. The trimethylphenyl group was eliminated. The above process was repeated, and purified polyglycerol was mixed to obtain a certain amount of polyglycerol. The resulting polyglycerol had a hydroxyl value of 1165, a primary hydroxyl group ratio of 32.2%, and a secondary hydroxyl group ratio of 67.8%.
調製例6 ポリグリセリンの精製
調製例1と同様の方法で太陽化学社製のポリグリセリン(グレートオイルDI−1、ジグリセリン;水酸基価1353、1級水酸基の割合48.1%、2級水酸基の割合51.9%)を精製した。得られたポリグリセリンの水酸基価は1350、1級水酸基の割合は53.5%、2級水酸基の割合は46.5%であった。
Preparation Example 6 Purification of Polyglycerin Polyglycerin manufactured by Taiyo Kagaku Co., Ltd. (Great Oil DI-1, diglycerin; hydroxyl value 1353, ratio of primary hydroxyl group 48.1%, secondary hydroxyl group (51.9%). The obtained polyglycerol had a hydroxyl value of 1350, a primary hydroxyl group ratio of 53.5%, and a secondary hydroxyl group ratio of 46.5%.
調製例7
調製例1で精製したポリグリセリン126gとステアリン酸54gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら250℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンステアリン酸エステルを得た。このエステルの酸価は0.3であった。酸価は、第7版食品添加物公定書「油脂類試験法」または基準油脂分析試験法に準じて算出した。
Preparation Example 7
126 g of polyglycerin purified in Preparation Example 1, 54 g of stearic acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 250 ° C. while removing generated water under a nitrogen stream. 2 mL of phosphoric acid was added to obtain a polyglycerol stearate ester. The acid value of this ester was 0.3. The acid value was calculated according to the 7th edition Food Additives Official “Fats and Fats Test Method” or the Standard Oil and Fat Analysis Test Method.
なお、以下の実施例および比較例における酸価も同様に算出した。 The acid values in the following examples and comparative examples were calculated in the same manner.
調製例8
調製例1で得られたポリグリセリン135.2gとラウリン酸44.5gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら240℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンラウリン酸エステルを得た。このエステルの酸価は0.5であった。
Preparation Example 8
135.2 g of polyglycerin obtained in Preparation Example 1, 44.5 g of lauric acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 240 ° C. while removing generated water under a nitrogen stream. After the reaction, 0.2 mL of phosphoric acid was added to obtain polyglycerol laurate. The acid value of this ester was 0.5.
調製例9
調製例2で得られたポリグリセリン126gとステアリン酸54gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら250℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンステアリン酸エステルを得た。このエステルの酸価は0.2であった。
Preparation Example 9
126 g of polyglycerin obtained in Preparation Example 2, 54 g of stearic acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 250 ° C. while removing generated water under a nitrogen stream. .2 mL of phosphoric acid was added to obtain a polyglycerol stearate ester. The acid value of this ester was 0.2.
調製例10
調製例2で得られたポリグリセリン135.2gとラウリン酸44.5gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら240℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンラウリン酸エステルを得た。このエステルの酸価は0.4であった。
Preparation Example 10
135.2 g of polyglycerin obtained in Preparation Example 2, 44.5 g of lauric acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 240 ° C. while removing generated water under a nitrogen stream. After the reaction, 0.2 mL of phosphoric acid was added to obtain polyglycerol laurate. The acid value of this ester was 0.4.
調製例11
調製例3で得られたポリグリセリン126gとステアリン酸54gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら250℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンステアリン酸エステルを得た。このエステルの酸価は0.3であった。
Preparation Example 11
126 g of polyglycerin obtained in Preparation Example 3, 54 g of stearic acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 250 ° C. while removing the produced water under a nitrogen stream. .2 mL of phosphoric acid was added to obtain a polyglycerol stearate ester. The acid value of this ester was 0.3.
調製例12
調製例3で得られたポリグリセリン135.2gとラウリン酸44.5gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら240℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンラウリン酸エステルを得た。このエステルの酸価は0.5であった。
Preparation Example 12
135.2 g of polyglycerin obtained in Preparation Example 3, 44.5 g of lauric acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 240 ° C. while removing generated water under a nitrogen stream. After the reaction, 0.2 mL of phosphoric acid was added to obtain polyglycerol laurate. The acid value of this ester was 0.5.
調製例13
調製例3で得られたポリグリセリン130gとミリスチン酸49.5gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら240℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンミリスチン酸エステルを得た。このエステルの酸価は0.5であった。
Preparation Example 13
130 g of polyglycerol obtained in Preparation Example 3, 49.5 g of myristic acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 240 ° C. while removing the generated water under a nitrogen stream. Thereafter, 0.2 mL of phosphoric acid was added to obtain polyglycerol myristic acid ester. The acid value of this ester was 0.5.
調製例14
調製例3で得られたポリグリセリン126gとオレイン酸54gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら240℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンオレイン酸エステルを得た。このエステルの酸価は0.4であった。
Preparation Example 14
126 g of polyglycerin obtained in Preparation Example 3, 54 g of oleic acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 240 ° C. while removing generated water under a nitrogen stream. .2 mL of phosphoric acid was added to obtain polyglycerin oleate. The acid value of this ester was 0.4.
調製例15
調製例4で得られたポリグリセリン126gとステアリン酸54gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら250℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンステアリン酸エステルを得た。このエステルの酸価は0.3であった。
Preparation Example 15
126 g of polyglycerin obtained in Preparation Example 4, 54 g of stearic acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 250 ° C. while removing generated water under a nitrogen stream. .2 mL of phosphoric acid was added to obtain a polyglycerol stearate ester. The acid value of this ester was 0.3.
調製例16
調製例4で得られたポリグリセリン135.2gとラウリン酸44.5gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら240℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンラウリン酸エステルを得た。このエステルの酸価は0.5であった。
Preparation Example 16
135.2 g of polyglycerol obtained in Preparation Example 4, 44.5 g of lauric acid, and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 240 ° C. while removing generated water under a nitrogen stream. After the reaction, 0.2 mL of phosphoric acid was added to obtain polyglycerol laurate. The acid value of this ester was 0.5.
調製例17
太陽化学社製のポリグリセリン(グレートオイルDE−1、デカグリセリン)126gとステアリン酸54gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら250℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンステアリン酸エステルを得た。このエステルの酸価は0.3であった。
Preparation Example 17
126 g of polyglycerin (Great Oil DE-1, decaglycerin) manufactured by Taiyo Kagaku Co., Ltd., 54 g of stearic acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask. Reaction was performed at 0 ° C., and 0.2 mL of phosphoric acid was added after the reaction to obtain a polyglycerol stearate ester. The acid value of this ester was 0.3.
なお、太陽化学社製のポリグリセリン(グレートオイルDE−1、デカグリセリン)の水酸基価は890、1級水酸基の割合は46.6%、2級水酸基の割合は53.4%であった。 The hydroxyl value of polyglycerin (Great Oil DE-1, Decaglycerin) manufactured by Taiyo Kagaku Co. was 890, the proportion of primary hydroxyl groups was 46.6%, and the proportion of secondary hydroxyl groups was 53.4%.
調製例18
太陽化学社製のポリグリセリン(グレートオイルDE−1、デカグリセリン)135.2gとラウリン酸44.5gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら240℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンラウリン酸エステルを得た。このエステルの酸価は0.5であった。
Preparation Example 18
Put 135.2 g of Taiyo Kagaku polyglycerin (Great Oil DE-1, Decaglycerin), 44.5 g of lauric acid, and 0.06 g of sodium hydroxide in a 300 mL four-necked flask. It reacted at 240 degreeC, removing, 0.2 mL of phosphoric acid was added after reaction, and polyglycerin lauric acid ester was obtained. The acid value of this ester was 0.5.
調製例19
調製例5で得られたポリグリセリン126gとステアリン酸54gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら250℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンステアリン酸エステルを得た。このエステルの酸価は0.3であった。
Preparation Example 19
126 g of polyglycerol obtained in Preparation Example 5, 54 g of stearic acid, and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 250 ° C. while removing generated water under a nitrogen stream. .2 mL of phosphoric acid was added to obtain a polyglycerol stearate ester. The acid value of this ester was 0.3.
調製例20
調製例5で得られたポリグリセリン135.2gとラウリン酸44.5gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら240℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンラウリン酸エステルを得た。このエステルの酸価は0.5であった。
Preparation Example 20
135.2 g of polyglycerin obtained in Preparation Example 5, 44.5 g of lauric acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 240 ° C. while removing generated water under a nitrogen stream. After the reaction, 0.2 mL of phosphoric acid was added to obtain polyglycerol laurate. The acid value of this ester was 0.5.
調製例21
調製例5で得られたポリグリセリン135gとミリスチン酸49.5gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら240℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンミリスチン酸エステルを得た。このエステルの酸価は0.5であった。
Preparation Example 21
135 g of polyglycerin obtained in Preparation Example 5, 49.5 g of myristic acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 240 ° C. while removing generated water under a nitrogen stream. Thereafter, 0.2 mL of phosphoric acid was added to obtain polyglycerol myristic acid ester. The acid value of this ester was 0.5.
調製例22
調製例5で得られたポリグリセリン126gとオレイン酸45gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら240℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンオレイン酸エステルを得た。このエステルの酸価は0.5であった。
Preparation Example 22
126 g of polyglycerin obtained in Preparation Example 5, 45 g of oleic acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 240 ° C. while removing generated water under a nitrogen stream. .2 mL of phosphoric acid was added to obtain polyglycerin oleate. The acid value of this ester was 0.5.
調製例23
太陽化学社製のポリグリセリン(グレートオイルTR−1、トリグリセリン)126gとステアリン酸54gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら250℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンステアリン酸エステルを得た。このエステルの酸価は0.3であった。
Preparation Example 23
126 g of polyglycerin (Great Oil TR-1, Triglycerin) manufactured by Taiyo Chemical Co., Ltd., 54 g of stearic acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask, and 250% of the produced water was removed under a nitrogen stream. Reaction was performed at 0 ° C., and 0.2 mL of phosphoric acid was added after the reaction to obtain a polyglycerol stearate ester. The acid value of this ester was 0.3.
なお、太陽化学社製のポリグリセリン(グレートオイルTR−1、トリグリセリン)の水酸基価は1160、1級水酸基の割合は38.5%、2級水酸基の割合は61.5%であった。 The hydroxyl value of polyglycerin (Great Oil TR-1, Triglycerin) manufactured by Taiyo Kagaku Co. was 1160, the proportion of primary hydroxyl groups was 38.5%, and the proportion of secondary hydroxyl groups was 61.5%.
調製例24
太陽化学社製のポリグリセリン(グレートオイルTR−1、トリグリセリン)135.2gとラウリン酸44.5gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら240℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンラウリン酸エステルを得た。このエステルの酸価は0.5であった。
Preparation Example 24
Put 135.2 g of Taiyo Kagaku polyglycerin (Great Oil TR-1, Triglycerin), 44.5 g of lauric acid and 0.06 g of sodium hydroxide into a 300 mL four-necked flask, and supply the product water under a nitrogen stream. It reacted at 240 degreeC, removing, 0.2 mL of phosphoric acid was added after reaction, and polyglycerin lauric acid ester was obtained. The acid value of this ester was 0.5.
調製例25
調製例6で得られたポリグリセリン126gとステアリン酸54gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら250℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンステアリン酸エステルを得た。このエステルの酸価は0.3であった。
Preparation Example 25
126 g of polyglycerol obtained in Preparation Example 6, 54 g of stearic acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 250 ° C. while removing generated water under a nitrogen stream. .2 mL of phosphoric acid was added to obtain a polyglycerol stearate ester. The acid value of this ester was 0.3.
調製例26
調製例6で得られたポリグリセリン135.2gとラウリン酸44.5gおよび水酸化ナトリウム0.06gを300mLの4つ口フラスコに入れ、窒素気流下で生成水を除去しながら240℃で反応し、反応後0.2mLのリン酸を加えてポリグリセリンラウリン酸エステルを得た。このエステルの酸価は0.4であった。
Preparation Example 26
135.2 g of polyglycerin obtained in Preparation Example 6, 44.5 g of lauric acid and 0.06 g of sodium hydroxide were placed in a 300 mL four-necked flask and reacted at 240 ° C. while removing generated water under a nitrogen stream. After the reaction, 0.2 mL of phosphoric acid was added to obtain polyglycerol laurate. The acid value of this ester was 0.4.
実施例1
表1の処方に基づき調製例7〜26で得られたポリグリセリン脂肪酸エステルを用いて乳化ドレッシングを調製した。水に酢酸、食塩および乳化剤を加え、60℃に加熱しホモミキサーで5000rpmで撹拌しながら別に60℃に加熱したコーン油を徐々に加えた後10000rpmで5分間乳化を行い、40℃で5日間保存した後、目視にて乳化安定性を測出した。
Example 1
An emulsified dressing was prepared using the polyglycerin fatty acid esters obtained in Preparation Examples 7 to 26 based on the formulation in Table 1. Acetic acid, salt and emulsifier are added to water, heated to 60 ° C., stirred at 5000 rpm with a homomixer, gradually added to corn oil heated to 60 ° C., and then emulsified at 10,000 rpm for 5 minutes, then at 40 ° C. for 5 days After storage, the emulsion stability was measured visually.
<乳化安定性>
◎:調製直後と差なし
○:油層分離(油分の約5%未満)
△:油層分離(油分の約5〜10%)
×:油層分離(油分の約10%を超える)
なお、◎および○を合格品とする。
<Emulsification stability>
◎: No difference from immediately after preparation ○: Oil layer separation (less than about 5% of oil content)
Δ: Oil layer separation (about 5 to 10% of oil content)
X: Oil layer separation (over about 10% of oil content)
◎ and ○ are acceptable products.
表2より、水酸基価が1200以下であり且つ1級水酸基の割合が50%以上のポリグリセリンを用いた乳化ドレッシングが優れた乳化安定性を有することは明らかである。 From Table 2, it is clear that an emulsification dressing using polyglycerin having a hydroxyl value of 1200 or less and a primary hydroxyl group ratio of 50% or more has excellent emulsion stability.
実施例2
表3の処方に基づき調製例7〜26で得られたポリグリセリン脂肪酸エステルを用いてココア飲料を調製し、さらに水をバインダーとして造粒機にて流動造粒した。その10gを40mlの水に静かに加え、4時間放置後、液を静かにデカンテーションによって除去し、液中に分散せずに底部に沈殿した造粒品の量を測定した。
Example 2
A cocoa beverage was prepared using the polyglycerin fatty acid esters obtained in Preparation Examples 7 to 26 based on the formulation in Table 3, and further fluidized and granulated with a granulator using water as a binder. 10 g of the mixture was gently added to 40 ml of water, and after standing for 4 hours, the liquid was gently removed by decantation, and the amount of the granulated product precipitated at the bottom without being dispersed in the liquid was measured.
<沈殿量>
◎:0g
○:0.5g以下
△:0.5〜1.0g
×:1.0g以上
なお、◎および○を合格品とする。
<Precipitation amount>
A: 0 g
○: 0.5 g or less Δ: 0.5 to 1.0 g
X: 1.0 g or more ◎ and ○ are acceptable products.
表4より、水酸基価が1200以下であり且つ1級水酸基の割合が50%以上のポリグリセリンを用いたココア粉末造粒が優れた水中分散性を有することは明らかである。 From Table 4, it is clear that cocoa powder granulation using polyglycerin having a hydroxyl value of 1200 or less and a primary hydroxyl group ratio of 50% or more has excellent dispersibility in water.
実施例3
表5の処方に基づき調製例7〜26で得られたポリグリセリン脂肪酸エステルを用いてクレンジングクリームを調製した。調製方法は、60℃において各乳化剤、グリセリン、1、3−ブチレングリコールおよび精製水を混合しながら流動パラフィンを滴下した。得られた組成物を60℃で10日間保存した。
Example 3
Cleansing creams were prepared using the polyglycerin fatty acid esters obtained in Preparation Examples 7 to 26 based on the formulation in Table 5. In the preparation method, liquid paraffin was dropped while mixing each emulsifier, glycerin, 1,3-butylene glycol and purified water at 60 ° C. The resulting composition was stored at 60 ° C. for 10 days.
<安定性>
◎:調製直後と差なし
○:油層分離(油分の約5%未満)
△:油層分離(油分の約5〜10%)
×:油層分離(油分の約10%を超える)
なお、◎および○を合格品とする。
<Stability>
◎: No difference from immediately after preparation ○: Oil layer separation (less than about 5% of oil content)
Δ: Oil layer separation (about 5 to 10% of oil content)
X: Oil layer separation (over about 10% of oil content)
◎ and ○ are acceptable products.
表6より、水酸基価が1200以下であり且つ1級水酸基の割合が50%以上のポリグリセリンを用いたクレンジングクリームが優れた安定性を有することは明らかである。 From Table 6, it is clear that cleansing creams using polyglycerin having a hydroxyl value of 1200 or less and a primary hydroxyl group ratio of 50% or more have excellent stability.
実施例4
表7の処方に基づき調製例7〜26で得られたポリグリセリン脂肪酸エステルを用いてMCT(中鎖脂肪酸モノグリセライド)の可溶化製剤を調製した。ポリグリセリン脂肪酸エステルを加温融解させ、グリセリンにポリグリセリン脂肪酸エステルを加え、80℃以上に加温した。ホモミキサーを用いて10000rpmで攪拌しながら均質混合し、MCTを徐々に加え10分間攪拌した。冷却し、品温60℃にて水を加え、均質混合して可溶化製剤を仕上げた。これら製剤の0.1%水溶液を調製して透明溶解性を確認した。
Example 4
A solubilized preparation of MCT (medium chain fatty acid monoglyceride) was prepared using the polyglycerin fatty acid ester obtained in Preparation Examples 7 to 26 based on the formulation of Table 7. The polyglycerol fatty acid ester was heated and melted, the polyglycerol fatty acid ester was added to glycerol, and the mixture was heated to 80 ° C. or higher. Using a homomixer, the mixture was homogeneously stirred at 10,000 rpm, MCT was gradually added, and the mixture was stirred for 10 minutes. After cooling, water was added at a product temperature of 60 ° C. and homogeneously mixed to finish the solubilized preparation. Transparent solubility was confirmed by preparing 0.1% aqueous solutions of these preparations.
<分散安定性>
◎:透明(透過率98%以上)
○:やや白濁を認める(透過率90%以上98%未満)
△:白濁を認める(透過率90%未満)
×:油の分離を認める
なお、◎および○を合格品とする。
<Dispersion stability>
A: Transparent (transmittance 98% or more)
○: Some cloudiness is observed (transmittance is 90% or more and less than 98%)
Δ: White turbidity observed (transmittance less than 90%)
X: Separation of oil is recognized. ◎ and ○ are acceptable products.
表8より、水酸基価が1200以下であり且つ1級水酸基の割合が50%以上のポリグリセリンを用いた可溶化製剤が優れた透明溶解性を有することは明らかである。 From Table 8, it is clear that a solubilized preparation using polyglycerin having a hydroxyl value of 1200 or less and a primary hydroxyl group ratio of 50% or more has excellent transparent solubility.
上記実施例で証明した様に本発明によれば、水酸基価が1200以下であり且つ1級水酸基の割合が50%以上のポリグリセリンと脂肪酸を原料にして得られるポリグリセリン脂肪酸エステルを含有する組成物は品質安定性を向上し、食品、医薬品、化粧品の分野で今まで不可能であった完全な可溶化物や安定な乳化物の製造が可能となることは明白である。 As proved in the above examples, according to the present invention, a composition containing a polyglycerin fatty acid ester obtained by using polyglycerin having a hydroxyl value of 1200 or less and a proportion of primary hydroxyl group of 50% or more and a fatty acid as raw materials. It is clear that the product improves the quality stability and enables the production of completely solubilized products and stable emulsions that have been impossible in the food, pharmaceutical and cosmetic fields.
本発明のポリグリセリン脂肪酸エステルは、可溶化、乳化などを必要とする食品、医薬品、化粧品の分野で有効に利用される。 The polyglycerol fatty acid ester of the present invention is effectively used in the fields of foods, pharmaceuticals, and cosmetics that require solubilization, emulsification and the like.
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JP2009213366A (en) * | 2008-03-07 | 2009-09-24 | Taiyo Kagaku Co Ltd | Oil and fat solidification-preventing agent for milk-containing drink |
US7629479B2 (en) | 2004-10-12 | 2009-12-08 | Taiyo Kagaku Co., Ltd. | Polyglycerol fatty acid ester and composition containing same |
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JP2022129583A (en) * | 2021-02-25 | 2022-09-06 | 阪本薬品工業株式会社 | Polyglyceryl fatty acid ester, feeling regulator and cosmetic |
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