JP3744015B2 - Polyglycerin fatty acid ester composition, emulsion thereof and method for producing the same - Google Patents
Polyglycerin fatty acid ester composition, emulsion thereof and method for producing the same Download PDFInfo
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- JP3744015B2 JP3744015B2 JP02071295A JP2071295A JP3744015B2 JP 3744015 B2 JP3744015 B2 JP 3744015B2 JP 02071295 A JP02071295 A JP 02071295A JP 2071295 A JP2071295 A JP 2071295A JP 3744015 B2 JP3744015 B2 JP 3744015B2
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims description 69
- 239000000194 fatty acid Substances 0.000 title claims description 69
- 229930195729 fatty acid Natural products 0.000 title claims description 69
- -1 fatty acid ester Chemical class 0.000 title claims description 38
- 239000000203 mixture Substances 0.000 title claims description 37
- 239000000839 emulsion Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000005886 esterification reaction Methods 0.000 claims description 24
- 229920000223 polyglycerol Polymers 0.000 claims description 22
- 230000032050 esterification Effects 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000344 soap Substances 0.000 description 13
- 238000004945 emulsification Methods 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 235000015071 dressings Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000003084 food emulsifier Nutrition 0.000 description 2
- 239000008268 mayonnaise Substances 0.000 description 2
- 235000010746 mayonnaise Nutrition 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015067 sauces Nutrition 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Colloid Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、ポリグリセリン脂肪酸エステル（以下、ＰＯＧＥと略すこともある。）組成物、該ポリグリセリン脂肪酸エステル組成物を含有する乳化物及び該ポリグリセリン脂肪酸エステルに関するものである。
【０００２】
【従来の技術】
ＰＯＧＥは食品添加物として認可された界面活性剤として知られており、主に食品用乳化剤として利用されている他、最近では医薬、化粧品、或いは工業用途にも幅広く利用されている。ＰＯＧＥは、ポリグリセリンの平均重合度や構成脂肪酸の鎖長、置換度をコントロールすることで、親水性から親油性まで広範囲の物性を有するものが得られる。中でもＨＬＢが１０以上のＰＯＧＥは、他の食品用乳化剤にない優れた耐酸性、耐塩性、耐熱性を有し、タレ、ドレッシング、マヨネーズ等に代表される酸性或いは高塩濃度下でのＯ／Ｗ型乳化に有効である。またＰＯＧＥを単独使用では耐酸性に問題のある他の乳化剤に併用することにより酸性でも安定な乳化物を得ることができる。
【０００３】
ＰＯＧＥの製造方法としては、ポリグリセリンと脂肪酸とをアルカリ触媒の存在下直接エステル化させる方法が一般的である。この反応においては、アルカリ触媒が脂肪酸と反応し、脂肪酸のアルカリ金属塩（石鹸）を生成するのでポリグリセリンと脂肪酸との相溶性を高めるが反応後精製しない限り製品であるＰＯＧＥ組成物中に石鹸が混入する。例えば市販されているＰＯＧＥ組成物中の石鹸含量は通常１〜４％程度である。石鹸は親水性の高いアニオン性界面活性剤であるので、ＨＬＢが上昇し、特にＯ／Ｗ乳化系では乳化安定に悪影響を与えることが多い。例えば、石鹸含有量の多いＰＯＧＥ組成物を使用して酸性高塩濃度下でＯ／Ｗ型乳化を行った場合、乳化物の安定性は不良となり、保存安定性は勿論、殺菌工程での耐熱性や流通時の耐振性においても問題があった。
一方石鹸含量の少ないＰＯＧＥを得るために、アルカリ触媒量を少なくすると、ポリグリセリンと脂肪酸との相溶性が不充分であり、生成するＰＯＧＥのエステル化率が不均一化となり、Ｏ／Ｗ型乳化や分散可溶化に優れた高ＨＬＢのＰＯＧＥ組成物を得ることは困難であった。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、酸性かつ高塩濃度下でも優れたＯ／Ｗ型乳化能を有し、遊離のポリグリセリン含量及び脂肪酸アルカリ金属塩含量の少ないポリグリセリン脂肪酸エステル組成物及び該ポリグリセリン脂肪酸エステル組成物を含有するＯ／Ｗ型乳化物を提供することにある。又、本発明の目的は、上記ポリグリセリン脂肪酸エステル組成物の製造方法を提供することにある。
【０００５】
【発明を解決するための手段】
本発明は、上述の問題を解決するためになされたものであり、その要旨は、ポリグリセリン脂肪酸エステルの平均エステル化率が２０〜３０モル％であり、遊離のポリグリセリンの含有量が３５重量％以下で、且つ脂肪酸アルカリ金属塩の含有量が０．２重量％以下であるポリグリセリン脂肪酸エステル組成物に存する。
以下、本発明につき、詳細に説明する。
【０００６】
本発明におけるポリグリセリン脂肪酸エステル組成物は、ポリグリセリンと脂肪酸とを反応させて得られるものである。
ポリグリセリンとしては、平均重合度が６〜１２、水酸基価９７２〜８６７のものが挙げられる。構成脂肪酸としては、炭素数１２〜２２の直鎖状または分岐状の飽和または不飽和脂肪酸から選ばれる。この様な脂肪酸の例としては、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、エルカ酸、エライジン酸、リシノール酸、イソステアリン酸等が挙げられる。これらの脂肪酸は目的に応じて１種類または２種類以上の組み合わせで用いることも出来る。
【０００７】
本発明における平均エステル化率は、遊離のポリグリセリンを除いたエステル化されたポリグリセリンの総水酸基に対する脂肪酸の結合数の百分率で定義される。ＰＯＧＥのエステル化率は２０〜３０モル％、好ましくは２２〜２７モル％である。平均エステル化率が３０モル％を超えるとＰＯＧＥ組成物の親水性が急激に低下するため、酸性高塩濃度下で良好なＯ／Ｗ型乳化、分散可溶化が困難となる。ＰＯＧＥ組成物中の遊離のポリグリセリン含有量は３５重量％以下である。遊離ポリグリセリンが多すぎると乳化剤としての機能が低下し好ましくない。
【０００８】
脂肪酸アルカリ金属塩（石鹸）の含有量は０．２重量％以下、好ましくは０．１重量％、更に好ましくは０．０５重量％以下である。石鹸含有量が多いと酸性高塩濃度下で安定なエマルションが得られにくい。本発明のポリグリセリン脂肪酸エステル組成物を水と油との混合物に含有させることにより、ｐＨが６〜２、塩濃度が１〜２０重量％においても安定性に優れた、油と水の重量比が１／９９〜５０／５０、好ましくは５／９５〜４５／５５程度のマヨネーズ、ドレッシング、タレ等のＯ／Ｗ型（水中油型）乳化物を得ることができる。
【０００９】
本発明のポリグリセリン脂肪酸エステル組成物は、ポリグリセリンと脂肪酸との直接エステル化反応において、原料に対して０．００１〜０．０２５重量％の極めて少量のアルカリ触媒を用い、しかも反応温度２００〜３００℃、好ましくは脂肪酸の転化率が少なくとも７０％に達する迄の反応温度を２００〜２４０℃とし、以降、反応温度を更に２０〜６０℃高めて反応させることによって製造することができる。
【００１０】
ポリグリセリンに対する脂肪酸の仕込モル比は１〜５、好ましくは１〜３である。仕込モル比が１より小さいと平均エステル化率２０％以下となり、またＰＯＧＥ中の遊離ポリグリセリンも多くなる。仕込モル比が５を超えるとＨＬＢが低下し、Ｏ／Ｗ型の乳化に適さなくなる。
本発明で用いるアルカリ触媒の量は、原料であるポリグリセリンと脂肪酸との総和に対して０．００１〜０．０２５重量％、好ましくは０．００２〜０．０２重量％である。アルカリ触媒の使用量が上記範囲より少ない場合、平均エステル化率が２０〜３０モル％のＰＯＧＥが得られにくい。アルカリ触媒としては、例えば炭酸カリ、炭酸ナトリウム、水酸化カリウム、水酸化ナトリウムなどが挙げられる。
【００１１】
本発明におけるポリグリセリンと脂肪酸とのエステル化反応では脂肪酸の転化率が少なくとも７０％、好ましくは８０％、更に好ましくは９５％に到達するまでの反応温度を２００〜２４０℃、好ましくは２２０〜２４０℃とし、その後、更に２０〜６０℃、好ましくは２０〜４０℃高い温度で反応を続行する。昇温後の反応温度としては２４０〜２６０℃が好ましい。反応時間は昇温時までが通常１〜５時間程度であり、昇温後の昇温反応は１〜８時間、好ましくは４〜６時間である。
【００１２】
本発明の方法におけるエステル化反応では原料脂肪酸が消費された時点が必らずしも反応終了ではなくてＰＯＧＥの平均エステル化率を所定の範囲に制御するため、脂肪酸の転化率が９９％以上に達した以降も上記の昇温反応を所定時間継続する。
この昇温反応の時間は原料ポリグリセリンと脂肪酸との仕込モル比に応じて、適宜選択され、例えば仕込モル比が１の場合は６時間、仕込モル比が５の場合は４時間程度が好ましい。
【００１３】
昇温反応の時間が短すぎると、ＰＯＧＥの平均エステル化率が所定の範囲となりにくく、また長すぎるとＰＯＧＥの色相、臭いが悪く熱分解による酸価上昇が生ずるため、好ましくない。
本発明では極めて少量のアルカリ触媒を用いてエステル化反応を実施するため、脂肪酸の転化率が少なくとも７０％の時点では、生成しているＰＯＧＥにはエステル化率の非常に高いものが含まれているが、脂肪酸の転化率が少なくとも７０％に達した以降に、反応生成物の温度を２０〜６０℃高めることにより、ＰＯＧＥのエステル化率の分布を均一化することができ、平均エステル化率が２０〜３０モル％のＰＯＧＥを得ることができる。
【００１４】
反応は通常、撹拌槽タイプの反応器にポリグリセリン、脂肪酸、触媒を仕込み、撹拌しながら所定温度に加熱して、生成水を反応系外へ留去しながら行う。なお、一連の反応中は反応器気相部に窒素等の不活性ガスを流通させておくのが好ましい。
【００１５】
【実施例】
以下、本発明を実施例により更に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。
ＰＯＧＥ中の遊離ポリグリセリン量、脂肪酸アルカリ金属塩含有量、平均エステル化率は以下の方法で測定した。
【００１６】
〔ＰＯＧＥ中の遊離ポリグリセリン含量〕
ＰＯＧＥを親水性有機溶媒に溶解した溶液を、逆相系吸着剤を充填したカラムに導入してＰＯＧＥを該吸着剤に吸着させ、遊離ポリグリセリンは通過させることによりＰＯＧＥを含まないポリグリセリン溶液を得、次いでこの溶液をゲルパーミエーションクロマトグラフィーにより分析して製品中の遊離ポリグリセリンを定量した。標準手法は以下の通りである。
【００１７】
〔ＰＯＧＥ中の脂肪酸アルカリ金属塩（石鹸）含有量〕
基準油脂分析試験法（日本油化学協定制定）に準じて以下の方法に従い測定した。
１）トールビーカーに反応生成物を約１０ｇ精秤し、ＴＨＦ／エタノール／水＝ＶＯＬ％溶液１００ｍｌに溶解させる。
２）自動滴定装置（三菱化学（株）社製ＧＴ−０５）により滴定する。まずＮ／１０塩酸エタノール性溶液を過剰に滴定し、次にＮ／１０水酸化ナトリウムエタノール性溶液で逆滴定し、滴定値−電位曲線の変曲点から当量点を求める。
【００１９】
３）両滴定値を基に下記の式から、試料中の総酸・総アルカリ量を計算し、総酸＞総アルカリから製品中のアルカリ金属が全て脂肪酸塩となっていることを確認する。
▲１▼ 総アルカリ量（ｍｏｌ／ｇ）＝滴定量（ｍｌ）×０．１×力価×１０００×試料（ｇ）
▲２▼ 総酸量（ｍｏｌ／ｇ）＝（第２滴定値−第１滴定値）（ｍｌ）×０．１×力価×１０００×試料（ｇ）
４）総アルカリ量から石鹸含有量を計算する。
石鹸含有量（ｗｔ％）＝総アルカリ量（ｍｏｌ／ｇ）×石鹸分子量×１００
【００２０】
〔ＰＯＧＥの平均エステル化率〕
ＰＯＧＥ組成物について、その水酸基価（ＯＨＶ（１））、ケン化価（ＳＶ）、及び酸価（ＡＶ）を、基準油脂分析試験法（日本油化学協定制定）に基づいて測定する。また該ＰＯＧＥ組成物を完全にケン化して遊離ポリグリセリンとしたものについて、その水酸基価（ＯＨＶ（２））を測定した。尚、ＰＯＧはＰＯＧＥ組成物中の遊離ポリグリセリン含量（重量％）を表わす。平均エステル化率は、エステル化された水酸基を含む試料中の全水酸基数から、遊離のポリグリセリンに由来する水酸基数を差し引いたもので、エステル化した水酸基を除する次式で算出される。
【００２１】
【数１】
〔Ｏ／Ｗ型乳化試験〕
ＰＯＧＥ組成物を使用したＯ／Ｗ型乳化物の乳化安定性の評価は以下の方法に従った。
〔処方〕
ポリグリセリン脂肪酸エステル １．０
ナタネ油 ３０．０
酢酸 ０．５
食塩 ２．０
キサンタンガム ０．１
水 バランス分 （全て重量％）
【００２３】
〔乳化方法〕
乳化剤を水全体の８０重量％に６０℃にて分散溶解させた後、酢酸、食塩、キサンタンガムを含む残りの水２０重量％と混合する。得られた水相部をＴＫホモジナイザー（特殊器化（株）製）により３０００ｒｐｍで撹拌しながら６０℃のナタネ油をゆっくりと添加、その後、回転数を１００００ｒｐｍとし、更に１０分間撹拌する。乳化後は氷水中にて急冷し、乳化物（エマルション）を得、下記要領で加熱試験、振とう試験を行った。
【００２４】
１）加熱試験
エマルションを６０℃にて３０分間加熱した後、２５℃で１週間静置保存した。
２）振とう試験
エマルションに横振とう（振幅３０ｃｍ、６０往復／１分間で８時間）を与えた後、２５℃にて１昼夜静置保存した。
〔評価〕
エマルションの安定性は下式で定義される離水率、及びオイルオフの発生を観察することで評価した。
【００２５】
【数２】
離水率は小さいほど乳化が安定なことを表す。
〔基準〕
◎：ほぼ均一なエマルション（離水率 ５％以下）
○：若干の離水がみられる（離水率５〜１０％）
×：離水量が多く、２相状態（離水率１０％以上）
××：オイルオフ、離水が顕著にみられ乳化破壊状態
【００２７】
〔実施例１〕
ポリグリセリン（平均重合度１０．９、平均分子量８２５、水酸基価８８８ｍｇＫＯＨ／ｇ）８３０．７ｇ（１モル）と脂肪酸（ステアリン酸／パルミチン酸＝７５／２５ｗｔ％、平均分子量２７７）６６９．３ｇ（２．４モル）を加熱ジャケット付き撹拌型反応器に仕込み、２４０℃に昇温した後、１０ｗｔ％水酸化ナトリウム水溶液０．３７５ｍｌ（対原料総量０．００２５重量％）加え、３時間エステル化反応を行った（酸価３．８ｍｇＫＯＨ／ｇ、脂肪酸転化率９５．８％）。更にこの反応混合物を２６０℃にて４時間反応させ、最終生成物とした。得られたＰＯＧＥ組成物中の残存ポリグリセリン量、石鹸量、及びエステル体の平均エステル化率を定量した。また前記処方のＯ／Ｗ型乳化物を調整し、保存安定性及びストレス耐性を評価した。結果は表−１に示した。
【００２８】
〔実施例２〕
１０ｗｔ％水酸化ナトリウム水溶液の添加量を１．８７５ｍｌとした以外は実施例１と同様の方法で行った。結果は表−１に示した。
〔実施例３〕
脂肪酸をオレイン酸（純度９０％以上）とし、ポリグリセリンとの仕込モル比を１．５ (ポリグリセリン９９１ｇ、脂肪酸５０９ｇ）とした以外は実施例１と同様の方法で行った。
【００２９】
〔比較例１〕
１０ｗｔ％水酸化ナトリウム水溶液の添加量を１８．７５ｍｌとし、反応混合物の昇温を行わずに実施例１と同様の反応を行った。結果は表−１に示した。
〔比較例２〕
反応混合物の昇温を行わずに７時間で反応を終了した以外、実施例１と同様の方法で行った。結果は表−１に示した。
【００３０】
〔比較例３〕
市販品のデカグリセリンモノステアレートとして阪本薬品（株）社製品（商標名ＳＹグリスターＭＳＷ−７５０）を用い、実施例１と同様の方法で評価したところ、表−１に示す結果であった。
〔比較例４〕
市販品のデカグリセリンモノステアレートとして日光ケミカルズ（株）社製品（商標名ＮＩＫＫＯＬ Ｄｅｃａｇｌｙｎ−１Ｓ）を用い、実施例１と同様の方法で評価したところ、表−１に示す結果であった。
【００３１】
【表１】
【発明の効果】
本発明のポリグリセリン脂肪酸エステル組成物は、酸性、高塩濃度下でも極めて安定性に優れた乳化剤として有用である。また、該ポリグリセリン脂肪酸エステル組成物を含有するＯ／Ｗ型乳化物は、酸性及び／又は高塩濃度下でも耐熱、耐振とう性を有し、非常に安定な乳化性を示す。また、本発明の製造方法によれば、酸性、高塩濃度下でも乳化安定性に優れたポリグリセリン脂肪酸エステル組成物を比較的簡単に工業的に有利な方法で製造することができる。[0001]
[Industrial application fields]
The present invention relates to a polyglycerin fatty acid ester (hereinafter sometimes abbreviated as POGE) composition, an emulsion containing the polyglycerin fatty acid ester composition, and the polyglycerin fatty acid ester.
[0002]
[Prior art]
POGE is known as a surfactant approved as a food additive, is mainly used as a food emulsifier, and has recently been widely used for pharmaceutical, cosmetics, and industrial applications. By controlling the average degree of polymerization of polyglycerol, the chain length of constituent fatty acids, and the degree of substitution, POGE has a wide range of properties from hydrophilic to lipophilic. Among them, POGE having an HLB of 10 or more has excellent acid resistance, salt resistance, heat resistance, which is not found in other food emulsifiers, and is O // under high salt concentration typified by sauce, dressing, mayonnaise, etc. Effective for W-type emulsification. In addition, when POGE is used alone, it can be used in combination with other emulsifiers having a problem with acid resistance, whereby an emulsion which is stable even in acidity can be obtained.
[0003]
As a method for producing POGE, a method in which polyglycerol and a fatty acid are directly esterified in the presence of an alkali catalyst is generally used. In this reaction, the alkali catalyst reacts with the fatty acid to produce an alkali metal salt (soap) of the fatty acid, so that the compatibility between the polyglycerin and the fatty acid is increased, but the soap is contained in the product POGE composition unless purified after the reaction. Is mixed. For example, the soap content in a commercially available POGE composition is usually about 1 to 4%. Since soap is an anionic surfactant having high hydrophilicity, the HLB increases, and particularly in an O / W emulsification system, the emulsion stability is often adversely affected. For example, when O / W type emulsification is carried out under acidic high salt concentration using a POGE composition with a high soap content, the stability of the emulsion becomes poor, and storage stability as well as heat resistance in the sterilization process There was also a problem in the properties and vibration resistance during distribution.
On the other hand, in order to obtain POGE with a low soap content, if the amount of alkali catalyst is reduced, the compatibility between polyglycerol and fatty acid is insufficient, the esterification rate of the produced POGE becomes non-uniform, and O / W type emulsification In addition, it has been difficult to obtain a high HLB POGE composition excellent in dispersion solubilization.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a polyglycerin fatty acid ester composition having an excellent O / W emulsifying ability even under acidic and high salt concentration, and having a low content of free polyglycerin and fatty acid alkali metal salt, and the polyglycerin fatty acid ester The object is to provide an O / W emulsion containing the composition. Another object of the present invention is to provide a method for producing the polyglycerin fatty acid ester composition.
[0005]
[Means for Solving the Invention]
The present invention has been made to solve the above-mentioned problems, and the gist thereof is that the average esterification rate of the polyglycerol fatty acid ester is 20 to 30 mol%, and the content of free polyglycerol is 35% by weight. % Polyglycerin fatty acid ester composition having a fatty acid alkali metal salt content of 0.2% by weight or less.
Hereinafter, the present invention will be described in detail.
[0006]
The polyglycerol fatty acid ester composition in the present invention is obtained by reacting polyglycerol and a fatty acid.
Examples of the polyglycerol include those having an average degree of polymerization of 6 to 12 and a hydroxyl value of 972 to 867. The constituent fatty acid is selected from linear or branched saturated or unsaturated fatty acids having 12 to 22 carbon atoms. Examples of such fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, erucic acid, elaidic acid, ricinoleic acid, isostearic acid and the like. These fatty acids can be used alone or in combination of two or more according to the purpose.
[0007]
The average esterification rate in the present invention is defined as a percentage of the number of fatty acid bonds to the total hydroxyl groups of the esterified polyglycerol excluding free polyglycerol. The esterification rate of POGE is 20 to 30 mol%, preferably 22 to 27 mol%. If the average esterification rate exceeds 30 mol%, the hydrophilicity of the POGE composition is drastically lowered, so that it is difficult to achieve good O / W emulsification and dispersion solubilization under acidic high salt concentration. The free polyglycerin content in the POGE composition is not more than 35% by weight. When there is too much free polyglycerol, the function as an emulsifier falls and it is unpreferable.
[0008]
The content of the fatty acid alkali metal salt (soap) is 0.2% by weight or less, preferably 0.1% by weight, more preferably 0.05% by weight or less. When the soap content is large, it is difficult to obtain a stable emulsion under acidic high salt concentration. By containing the polyglycerin fatty acid ester composition of the present invention in a mixture of water and oil, the weight ratio of oil to water is excellent even when the pH is 6 to 2 and the salt concentration is 1 to 20% by weight. Of 1/99 to 50/50, preferably about 5/95 to 45/55, may be obtained O / W type (oil-in-water type) emulsion such as mayonnaise, dressing, sauce.
[0009]
The polyglycerin fatty acid ester composition of the present invention uses an extremely small amount of 0.001 to 0.025% by weight of an alkali catalyst in a direct esterification reaction of polyglycerin and a fatty acid, and a reaction temperature of 200 to It can be produced by reacting at 300 ° C., preferably 200 to 240 ° C. until the conversion of fatty acid reaches at least 70%, and further increasing the reaction temperature by 20 to 60 ° C.
[0010]
The molar ratio of fatty acid to polyglycerin is 1 to 5, preferably 1 to 3. If the charged molar ratio is less than 1, the average esterification rate is 20% or less, and the free polyglycerol in POGE also increases. When the charged molar ratio exceeds 5, the HLB is lowered and is not suitable for O / W type emulsification.
The amount of the alkali catalyst used in the present invention is 0.001 to 0.025% by weight, preferably 0.002 to 0.02% by weight, based on the total of the polyglycerol and the fatty acid as raw materials. When the usage-amount of an alkali catalyst is less than the said range, it is difficult to obtain POGE with an average esterification rate of 20-30 mol%. Examples of the alkali catalyst include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide and the like.
[0011]
In the esterification reaction of polyglycerin and fatty acid in the present invention, the reaction temperature until the conversion rate of fatty acid reaches at least 70%, preferably 80%, more preferably 95% is 200 to 240 ° C., preferably 220 to 240. Then, the reaction is continued at a temperature 20 to 60 ° C., preferably 20 to 40 ° C. higher. The reaction temperature after the temperature rise is preferably 240 to 260 ° C. The reaction time is usually about 1 to 5 hours until the temperature rises, and the temperature rise reaction after the temperature rise is 1 to 8 hours, preferably 4 to 6 hours.
[0012]
In the esterification reaction in the method of the present invention, the time when the raw fatty acid is consumed is not necessarily the end of the reaction, and the average esterification rate of POGE is controlled within a predetermined range, so that the conversion rate of fatty acid is 99% or more. After reaching the above, the above temperature rising reaction is continued for a predetermined time.
The temperature raising reaction time is appropriately selected according to the charged molar ratio of the raw polyglycerin and the fatty acid. For example, when the charged molar ratio is 1, it is preferably 6 hours, and when the charged molar ratio is 5, approximately 4 hours is preferable. .
[0013]
If the temperature raising reaction time is too short, the average esterification rate of POGE is hardly within a predetermined range, and if it is too long, the hue and smell of POGE are poor and an acid value rises due to thermal decomposition, which is not preferable.
In the present invention, since the esterification reaction is carried out using a very small amount of an alkali catalyst, at the time when the conversion rate of the fatty acid is at least 70%, the produced POGE contains a very high esterification rate. However, after the conversion rate of the fatty acid reaches at least 70%, by increasing the temperature of the reaction product by 20 to 60 ° C., the distribution of the esterification rate of POGE can be made uniform, and the average esterification rate 20 to 30 mol% of POGE can be obtained.
[0014]
The reaction is usually carried out while charging polyglycerol, fatty acid and catalyst in a stirred tank type reactor, heating to a predetermined temperature while stirring, and distilling the produced water out of the reaction system. During a series of reactions, it is preferable to circulate an inert gas such as nitrogen in the gas phase part of the reactor.
[0015]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to a following example, unless the summary is exceeded.
The amount of free polyglycerin in POGE, the content of fatty acid alkali metal salt, and the average esterification rate were measured by the following methods.
[0016]
[Free polyglycerol content in POGE]
A solution in which POGE is dissolved in a hydrophilic organic solvent is introduced into a column packed with a reverse-phase adsorbent to adsorb POGE on the adsorbent, and free polyglycerin is allowed to pass therethrough so that a polyglycerin solution not containing POGE is obtained. The solution was then analyzed by gel permeation chromatography to quantify the free polyglycerol in the product. The standard method is as follows.
[0017]
[Fatty acid alkali metal salt (soap) content in PAGE]
Measurement was performed according to the following method in accordance with the standard method for analyzing fats and oils (established by Japan Oil Chemical Agreement).
1) About 10 g of the reaction product is precisely weighed in a tall beaker and dissolved in 100 ml of THF / ethanol / water = VOL% solution.
2) Titrate with an automatic titrator (GT-05 manufactured by Mitsubishi Chemical Corporation). First, an N / 10 hydrochloric acid ethanolic solution is titrated excessively, then back titrated with an N / 10 sodium hydroxide ethanolic solution, and the equivalence point is determined from the inflection point of the titration value-potential curve.
[0019]
3) Calculate the total acid / total alkali amount in the sample from the following formula based on both titration values, and confirm that all alkali metals in the product are fatty acid salts from total acid> total alkali.
(1) Total alkali amount (mol / g) = Titration (ml) × 0.1 × Titer × 1000 × Sample (g)
(2) Total acid amount (mol / g) = (second titration value−first titration value) (ml) × 0.1 × titer × 1000 × sample (g)
4) Calculate the soap content from the total alkali amount.
Soap content (wt%) = total alkali amount (mol / g) × soap molecular weight × 100
[0020]
[Average esterification rate of PAGE]
About a POGE composition, the hydroxyl value (OHV (1)), saponification value (SV), and acid value (AV) are measured based on the reference | standard oil-fat analysis test method (Japan Oil Chemical Agreement establishment). Further, the hydroxyl value (OHV (2)) of the saponified POGE composition was converted into a free polyglycerin. POG represents the free polyglycerin content (% by weight) in the POGE composition. The average esterification rate is obtained by subtracting the number of hydroxyl groups derived from free polyglycerin from the total number of hydroxyl groups in the sample containing the esterified hydroxyl group, and is calculated by the following formula that removes the esterified hydroxyl group.
[0021]
[Expression 1]
[O / W type emulsification test]
The evaluation of the emulsion stability of the O / W emulsion using the POGE composition was performed according to the following method.
[Prescription]
Polyglycerin fatty acid ester 1.0
Rapeseed oil 30.0
Acetic acid 0.5
Salt 2.0
Xanthan gum 0.1
Water balance (all weight%)
[0023]
[Emulsification method]
The emulsifier is dispersed and dissolved in 80% by weight of the whole water at 60 ° C., and then mixed with the remaining 20% by weight of water containing acetic acid, salt and xanthan gum. While stirring the obtained water phase part at 3000 rpm with a TK homogenizer (manufactured by Tokushu Kaika Co., Ltd.), rapeseed oil at 60 ° C. is slowly added. After emulsification, the mixture was quenched in ice water to obtain an emulsion (emulsion), and a heating test and a shaking test were performed as follows.
[0024]
1) Heat test The emulsion was heated at 60 ° C. for 30 minutes and then stored at 25 ° C. for 1 week.
2) Shaking Test The emulsion was given lateral shaking (amplitude 30 cm, 60 reciprocations / one minute for 8 hours), and then stored at 25 ° C. for one day and night.
[Evaluation]
The stability of the emulsion was evaluated by observing the water separation rate defined by the following equation and the occurrence of oil-off.
[0025]
[Expression 2]
The smaller the water separation rate, the more stable the emulsification.
[Standard]
A: Almost uniform emulsion (water separation rate of 5% or less)
○: Some water separation is observed (water separation rate 5 to 10%)
×: Large amount of water separation, two-phase state (water separation rate of 10% or more)
XX: Oil-off, water separation is noticeable and emulsion breakage
[Example 1]
Polyglycerin (average degree of polymerization 10.9, average molecular weight 825, hydroxyl value 888 mg KOH / g) 830.7 g (1 mol) and fatty acid (stearic acid / palmitic acid = 75/25 wt%, average molecular weight 277) 669.3 g (2 .4 mol) was charged into a stirring reactor equipped with a heating jacket, heated to 240 ° C., and 0.375 ml of a 10 wt% aqueous sodium hydroxide solution (based on a total amount of raw materials of 0.0025% by weight) was added. (Acid value 3.8 mgKOH / g, fatty acid conversion 95.8%). The reaction mixture was further reacted at 260 ° C. for 4 hours to obtain a final product. The amount of residual polyglycerol in the obtained POGE composition, the amount of soap, and the average esterification rate of the ester were determined. Moreover, the O / W type emulsion of the said prescription was adjusted and storage stability and stress tolerance were evaluated. The results are shown in Table 1.
[0028]
[Example 2]
The same procedure as in Example 1 was performed except that the addition amount of 10 wt% sodium hydroxide aqueous solution was 1.875 ml. The results are shown in Table 1.
Example 3
The same procedure as in Example 1 was carried out except that the fatty acid was oleic acid (purity 90% or more), and the molar ratio to polyglycerin was 1.5 (polyglycerin 991 g, fatty acid 509 g).
[0029]
[Comparative Example 1]
The addition amount of 10 wt% sodium hydroxide aqueous solution was 18.75 ml, and the same reaction as in Example 1 was performed without raising the temperature of the reaction mixture. The results are shown in Table 1.
[Comparative Example 2]
The reaction was performed in the same manner as in Example 1 except that the reaction was completed in 7 hours without raising the temperature of the reaction mixture. The results are shown in Table 1.
[0030]
[Comparative Example 3]
When a product (trade name: SY Glyster MSW-750) manufactured by Sakamoto Yakuhin Co., Ltd. was used as a commercially available decaglycerin monostearate, the results shown in Table 1 were obtained.
[Comparative Example 4]
When a product of Nikko Chemicals Co., Ltd. (trade name: NIKKOL Decaglyn-1S) was used as a commercially available decaglycerin monostearate, the results shown in Table 1 were obtained.
[0031]
[Table 1]
【The invention's effect】
The polyglycerin fatty acid ester composition of the present invention is useful as an emulsifier having excellent stability even under acidic and high salt concentrations. Further, the O / W emulsion containing the polyglycerin fatty acid ester composition has heat resistance and vibration resistance even under acidic and / or high salt concentration, and exhibits very stable emulsification properties. Moreover, according to the production method of the present invention, a polyglycerin fatty acid ester composition excellent in emulsion stability even under acidic and high salt concentrations can be produced in a relatively simple and industrially advantageous manner.
Claims (11)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309815C (en) | 2000-10-17 | 2007-04-11 | 三菱化学株式会社 | Polyglyceryl fatty acid esters for detergents and detergents containing them |
| JP4674961B2 (en) * | 2000-12-08 | 2011-04-20 | 三菱化学株式会社 | Oil-in-water emulsion |
| CN1794922A (en) * | 2003-06-26 | 2006-06-28 | 三菱化学株式会社 | Polyglycerol fatty acid ester and emulsified or solubilized composition containing it |
| JP6746212B2 (en) * | 2016-09-21 | 2020-08-26 | 日清オイリオグループ株式会社 | Method for producing oil and fat composition for heating cooking, method for suppressing deterioration of oil and fat for heating cooking by heating, oil and fat composition for heating cooking, and oil and fat composition containing high tocopherol |
-
1995
- 1995-02-08 JP JP02071295A patent/JP3744015B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014030374A (en) * | 2012-08-02 | 2014-02-20 | Taiyo Kagaku Co Ltd | Fat solidification inhibitor for milk-containing beverage |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08217724A (en) | 1996-08-27 |
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