WO2014185245A1 - Polyglycerol aliphatic dicarboxylic acid ester - Google Patents
Polyglycerol aliphatic dicarboxylic acid ester Download PDFInfo
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- WO2014185245A1 WO2014185245A1 PCT/JP2014/061535 JP2014061535W WO2014185245A1 WO 2014185245 A1 WO2014185245 A1 WO 2014185245A1 JP 2014061535 W JP2014061535 W JP 2014061535W WO 2014185245 A1 WO2014185245 A1 WO 2014185245A1
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- acid ester
- carboxylic acid
- glycerin
- dialiphatic
- dialiphatic carboxylic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/58—Esters of straight chain acids with eighteen carbon atoms in the acid moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/02—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with glycerol
Definitions
- the present invention relates to a novel polyglycerin dialiphatic carboxylic acid ester.
- the polyglycerin dialiphatic carboxylic acid ester is useful as a two-chain surfactant.
- a two-chain surfactant is a compound having a shape in which two molecules of a monomeric surfactant (one hydrophobic group and one hydrophilic group type surfactant) are bound by a short spacer, and two hydrophobic surfactants bound by a short spacer.
- the group does not repel and is closely adsorbed at the interface between the aqueous phase and the oil phase. Therefore, when comparing a monomeric surfactant with a half-chain two-chain surfactant, the number of hydrophobic groups is the same, but the two-chain surfactant has a significantly higher interface. It is known that it exhibits an activity ability and can reduce the amount of the surfactant used to less than half that of the prior art and is environmentally friendly.
- an object of the present invention is to provide a novel polyglycerin dialiphatic carboxylic acid ester as a two-chain surfactant capable of easily adjusting the HLB value.
- Another object of the present invention is to provide a method for producing a polyglycerol dialiphatic carboxylic acid ester that selectively produces the polyglycerin dialiphatic carboxylic acid ester.
- the present inventor has a short compound having two hydrophobic groups (alkyl group or alkenyl group) obtained by reacting 1 mol of glycerin dialiphatic carboxylic acid ester with 2 mol or more of glycidol.
- Polyglycerin obtained by adjusting the amount of glycidol to be reacted with glycerin dialiphatic carboxylic acid ester because it is bonded with a spacer and has a highly water-soluble polyglycerin moiety as a hydrophilic group, thus having excellent surface activity. It has been found that the HLB value of dialiphatic carboxylic acid esters can be controlled.
- the present invention has been completed based on these findings.
- R 1 and R 2 are the same or different and are a linear or branched alkyl group or alkenyl group which may have a hydroxyl group.
- N represents the number of glycerin units; (It is an integer greater than or equal)
- the polyglycerol dialiphatic carboxylic acid ester represented by these is provided.
- the present invention also provides the following formula (2): (Wherein R 1 and R 2 are the same or different and are a linear or branched alkyl group or alkenyl group optionally having a hydroxyl group) 1 mol of glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by formula (1) is reacted with n mol of glycidol (n is an integer of 2 or more). (Wherein R 1 and R 2 are the same as above. N represents the number of glycerin units and is an integer of 2 or more) The manufacturing method of the polyglycerol dialiphatic carboxylic acid ester which obtains the polyglycerol dialiphatic carboxylic acid ester represented by these is provided.
- a hydroxyl group bonded to a secondary carbon atom (a carbon atom bonded to two carbon atoms) is referred to as a “secondary hydroxyl group”, and a primary carbon atom (bonded to one carbon atom).
- the hydroxyl group bonded to the carbon atom) is called “primary hydroxyl group”.
- the polyglycerin dialiphatic carboxylic acid ester of the present invention Since the polyglycerin dialiphatic carboxylic acid ester of the present invention has the above configuration, it exhibits extremely excellent surface activity. Therefore, when the polyglycerin dialiphatic carboxylic acid ester of the present invention is used as a surfactant, a sufficient effect can be exhibited even in a smaller amount than conventional, and the environmental load can be reduced. Furthermore, the HLB value can be easily adjusted to a desired range. Therefore, the polyglycerin dialiphatic carboxylic acid ester of the present invention can be suitably used as an antifoaming agent, a W / O type emulsifier, an O / W type emulsifier, a wetting agent, a cleaning agent, a solubilizing agent and the like. Moreover, according to the manufacturing method of the polyglycerol dialiphatic carboxylic acid ester of this invention, the said polyglycerol dialiphatic carboxylic acid
- the polyglycerol dialiphatic carboxylic acid ester of the present invention is represented by the above formula (1).
- R 1 and R 2 are the same or different and each represents a linear or branched alkyl group or alkenyl group which may have a hydroxyl group.
- n represents the number of glycerin units and is an integer of 2 or more.
- C 3 H 6 O 2 in parentheses in the formula (1) has both structures represented by the following formulas (1-1) and (1-2).
- Examples of the linear or branched alkyl group in R 1 and R 2 include n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl (lauryl).
- Examples of the linear or branched alkyl group having a hydroxyl group in R 1 and R 2 include one or more hydroxyl groups in the C 6-22 linear or branched alkyl group. And C 6-22 linear or branched hydroxyalkyl groups.
- Examples of the linear or branched alkenyl group for R 1 and R 2 include n-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, n-undecenyl, n-dodecenyl, n -C 6-22 linear alkenyl groups such as tridecenyl, n-tetradecenyl, n-pentadecenyl, n-hexadecenyl, n-heptadecenyl, n-oleyl, n-nonadecenyl, n-eicosenyl, n-heneicosenyl, n-docosenyl Isohexenyl, s-hexenyl, t-hexenyl, isoheptenyl, s-heptenyl, t-hepten
- Examples of the linear or branched alkenyl group having a hydroxyl group in R 1 and R 2 include one or more hydroxyl groups in the C 6-22 linear or branched alkenyl group. C 6-22 linear or branched hydroxyalkenyl groups.
- a strong fence layer can be formed on the interface, whereby a lamellar liquid crystal phase can be formed.
- the HLB Hydrophile Balance
- the HLB value is preferably adjusted to about 8 to 15 (preferably 10 to 15), for example.
- N represents the number of glycerin units and is an integer of 2 or more.
- n is adjusted to, for example, about 2 to 25 (preferably 2 to 10, particularly preferably 2 to 8, most preferably 4 to 8). It is preferable in terms of high solubility in aqueous components and high affinity for oil components.
- n is 6 or more
- the secondary hydroxyl group of polyglycerol which is a hydrophilic group, forms a hydrogen bond with water, so the solubility in water is high and the Kraft point is low (for example, 10 ° C. or less, preferably Is 0-5 ° C). Therefore, excellent solubility and solubilizing power can be exhibited even at low temperatures.
- polyglycerin dialiphatic carboxylic acid ester of the present invention examples include triglycerin dioctanoic acid ester, triglycerin didecanoic acid ester, triglycerin didodecanoic acid ester, triglycerin dimyristic acid ester, and triglycerin dioleic acid ester.
- the polyglycerin dialiphatic carboxylic acid ester of the present invention exhibits extremely excellent surface activity due to the fact that two groups (R 1 , R 2 ) bonded by a short spacer are closely adsorbed to the interface without repulsion. be able to. Therefore, the amount used can be reduced to less than half of the conventional amount, the environmental load is small, and the irritation to the skin and the like can be suppressed to a very low level.
- polyglycerin dialiphatic carboxylic acid ester having an excellent hydrophilicity with n of 6 or more has a low Kraft point and can exhibit excellent solubility and solubilizing power even at low temperatures.
- the polyglycerin dialiphatic carboxylic acid ester of the present invention has the above properties, it is suitably used as, for example, an antifoaming agent, a W / O type emulsifier, an O / W type emulsifier, a wetting agent, a cleaning agent, a solubilizing agent, and the like. can do.
- n is an integer of 2 or more
- R 1 , R 2 and n are the same as described above.
- Examples of the glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by the formula (2) include an aliphatic carboxylic acid represented by the following formula (3) and a glycidyl fat represented by the following formula (4). It can be produced by reacting a group carboxylic acid ester.
- R 1 and R 2 are the same as described above.
- the glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by the formula (2) is a highly unsaturated aliphatic carboxylic acid or a lower alkyl ester thereof and glycerin in the presence of an immobilized partial glyceride lipase.
- a method of reacting while removing generated water from the reaction system Japanese Patent Application Laid-Open No. 2004-208539
- a method of reacting glycerin and an aliphatic carboxylic acid (esterification) a method of reacting glycerin and an aliphatic carboxylic acid ester It can also be produced by a transesterification method (Japanese Patent Publication No. 6-65311).
- the glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by the above formula (2) is usually represented by the following formula (2 ′)
- the glycerol dialiphatic carboxylic acid ester which has the primary hydroxyl group represented by these is also contained. Therefore, in the method for producing the polyglycerin dialiphatic carboxylic acid ester, the following formula (1 ′) Is produced as a by-product, and the by-product rate is desirably 40% or less (preferably 30% or less).
- R 1 , R 2 and n are the same as above.
- the above addition polymerization reaction of glycidol can be carried out in the presence or absence of a solvent.
- the solvent include amines (particularly tertiary amine) such as triethylamine, piperidine, N-methylpiperidine, pyridine, N-methylpyrrolidone, nitrogen-containing heterocyclic compounds, and the like. These can be used alone or in combination of two or more.
- the reaction atmosphere of the glycidol addition polymerization reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.
- the reaction temperature for the above addition polymerization reaction of glycidol is, for example, about 0 to 100 ° C., preferably 40 to 80 ° C.
- the reaction time is, for example, about 5 to 20 hours, preferably 8 to 14 hours.
- reaction product After completion of the addition polymerization reaction of glycidol, the reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, and extraction, or a separation means combining these.
- separation means such as filtration, concentration, distillation, and extraction, or a separation means combining these.
- a polyglycerin dialiphatic carboxylic acid ester of the present invention by adjusting the amount of glycidol reacted with the glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by the formula (2).
- a polyglycerin dialiphatic carboxylic acid ester having a desired HLB value can be easily and selectively produced.
- Example 1 (Production of poly (11) glycerol dioleic acid ester) Glycerol diolenic acid ester was synthesized according to the method described in JP-B-6-65311. 400 mL of N-methylpyrrolidone was added to 621.0 g of the obtained glycerol dioleate. Thereafter, glycidol (740.8 g) in an amount of 10 mol with respect to 1 mol of the glycerin dioleate was added dropwise over 10 hours while maintaining 70 ° C., and aged for 1 hour. Thereafter, the solvent was removed at 190 ° C.
- Tetraglycerin dioleic acid ester (HLB: 6.0) was obtained in the same manner as in Example 1 except that the amount of glycidol used was changed from 10 mol to 3 mol with respect to 1 mol of glycerin dioleic acid ester. .
- Example 3 (Production of pentaglycerin dioleic acid ester) Pentaglycerin dioleate (HLB: 6.8) was obtained in the same manner as in Example 1 except that the amount of glycidol used was changed from 10 mol to 4 mol with respect to 1 mol of glycerin dioleate. .
- Example 4 (Production of heptaglycerin dioleate) A heptaglycerol dioleate (HLB: 8.2) was obtained in the same manner as in Example 1 except that the amount of glycidol used was changed from 10 mol to 6 mol with respect to 1 mol of glycerol dioleate. .
- Evaluation Cleaning agents 1 to 4 were prepared by mixing 80 parts by weight of water with 20 parts by weight of each polyglycerin dialiphatic carboxylic acid ester obtained in the examples. Detergency and foaming power were evaluated.
- ⁇ Detergency test> Place a flat 20 cm 2 glass plate with artificial fouling on a dedicated table in 700 mL of a 0.2% aqueous solution of cleaning agent (liquid temperature: 30 ° C.) and rotate the stirring blade for 3 minutes at 250 rpm. I let you. After completion of the rotation, the glass plate was taken out and weighed after drying, the cleaning rate was calculated using the following formula, and the cleaning power was evaluated according to the following criteria.
- Cleaning rate ⁇ (weight before cleaning ⁇ weight after cleaning) / (weight before cleaning ⁇ weight of glass plate) ⁇ ⁇ 100 Evaluation criteria ⁇ : Cleaning rate of 95% or more ⁇ : Cleaning rate of 85% or more and less than 95% ⁇ : Cleaning rate of 50% or more and less than 85% ⁇ : Cleaning rate of less than 50%
- ⁇ Foaming power test> A 20-fold diluted aqueous solution of the cleaning agent was prepared, and 100 mL of this solution (liquid temperature: 30 ° C.) was injected into a 500 mL graduated cylinder. Next, a stirring blade was installed in the solution, and stirring was performed for 1 minute at 1000 rpm. Thereafter, the volume (mL) of the generated foam was measured and used as the amount of foaming. From the amount of foaming, foaming power was evaluated according to the following criteria.
- Foaming amount is 300 mL or more ⁇ : Foaming amount is 250 mL or more and less than 300 mL ⁇ : Foaming amount is 200 mL or more and less than 250 mL X: Foaming amount is less than 200 mL
- the polyglycerin dialiphatic carboxylic acid ester of the present invention has an excellent surface activity and can exhibit an excellent detergency and foaming power when used as a cleaning agent.
- the polyglycerin dialiphatic carboxylic acid ester of the present invention exhibits extremely excellent surface activity. Therefore, when the polyglycerin dialiphatic carboxylic acid ester of the present invention is used as a surfactant, a sufficient effect can be exhibited even in a small amount compared to the conventional case, and the environmental load can be reduced. Furthermore, the HLB value can be easily adjusted to a desired range. Therefore, the polyglycerin dialiphatic carboxylic acid ester of the present invention can be suitably used as an antifoaming agent, a W / O type emulsifier, an O / W type emulsifier, a wetting agent, a cleaning agent, a solubilizing agent and the like. Moreover, according to the manufacturing method of the polyglycerol dialiphatic carboxylic acid ester of this invention, the said polyglycerol dialiphatic carboxylic acid ester can be manufactured easily and selectively.
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Abstract
Provided are: a novel polyglycerol aliphatic dicarboxylic acid ester that serves as a double-chain surfactant of which the HLB value can be easily adjusted; and a production method for the novel polyglycerol aliphatic dicarboxylic acid ester. The polyglycerol aliphatic dicarboxylic acid ester is represented by formula (1). In the formula, R1 and R2 are the same or different and each represent a linear or branched alkyl group or alkenyl group that may have a hydroxyl group. N represents the number of glycerol units and is an integer of 2 or more.
Description
本発明は、新規なポリグリセリンジ脂肪族カルボン酸エステルに関する。前記ポリグリセリンジ脂肪族カルボン酸エステルは２鎖型界面活性剤として有用である。本願は、２０１３年５月１４日に日本に出願した、特願２０１３－１０２４４０号の優先権を主張し、その内容をここに援用する。
The present invention relates to a novel polyglycerin dialiphatic carboxylic acid ester. The polyglycerin dialiphatic carboxylic acid ester is useful as a two-chain surfactant. This application claims the priority of Japanese Patent Application No. 2013-102440 for which it applied to Japan on May 14, 2013, and uses the content here.
２鎖型界面活性剤は、２分子のモノメリック型界面活性剤（一疎水基一親水基型界面活性剤）が短いスペーサーで結合した形状を有する化合物であり、短いスペーサーで結合した２つの疎水基は反発すること無く、水相と油相の界面に密に吸着する。そのため、モノメリック型界面活性剤と、その半分のモル数の２鎖型界面活性剤を比較すると、疎水基の数は等しいにもかかわらず、２鎖型界面活性剤の方が優位に高い界面活性能を示し、界面活性剤の使用量を従来の半分以下にまで低減することができ環境に優しいことが知られている。
A two-chain surfactant is a compound having a shape in which two molecules of a monomeric surfactant (one hydrophobic group and one hydrophilic group type surfactant) are bound by a short spacer, and two hydrophobic surfactants bound by a short spacer. The group does not repel and is closely adsorbed at the interface between the aqueous phase and the oil phase. Therefore, when comparing a monomeric surfactant with a half-chain two-chain surfactant, the number of hydrophobic groups is the same, but the two-chain surfactant has a significantly higher interface. It is known that it exhibits an activity ability and can reduce the amount of the surfactant used to less than half that of the prior art and is environmentally friendly.
上記のように優れた性能を有する２鎖型界面活性剤は、オレイン酸から合成されるものや、天然物から抽出されるもの等が知られている。しかし、オレイン酸からの合成や、天然物からの抽出には複雑な工程を要する上、低収率である。そのため、非常に高価なことが問題であった。また、所望するＨＬＢ値を有する２鎖型界面活性剤を選択的に製造することは非常に困難であった（引用文献１～２等）。
As the two-chain surfactant having excellent performance as described above, those synthesized from oleic acid and those extracted from natural products are known. However, the synthesis from oleic acid and the extraction from natural products require a complicated process and have a low yield. Therefore, it was a problem that it was very expensive. Further, it has been very difficult to selectively produce a two-chain surfactant having a desired HLB value (Cited documents 1 and 2 etc.).
従って、本発明の目的は、ＨＬＢ値を容易に調整することができる２鎖型界面活性剤として新規なポリグリセリンジ脂肪族カルボン酸エステルを提供することにある。
本発明の他の目的は、前記ポリグリセリンジ脂肪族カルボン酸エステルを選択的に製造するポリグリセリンジ脂肪族カルボン酸エステルの製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a novel polyglycerin dialiphatic carboxylic acid ester as a two-chain surfactant capable of easily adjusting the HLB value.
Another object of the present invention is to provide a method for producing a polyglycerol dialiphatic carboxylic acid ester that selectively produces the polyglycerin dialiphatic carboxylic acid ester.
本発明の他の目的は、前記ポリグリセリンジ脂肪族カルボン酸エステルを選択的に製造するポリグリセリンジ脂肪族カルボン酸エステルの製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a novel polyglycerin dialiphatic carboxylic acid ester as a two-chain surfactant capable of easily adjusting the HLB value.
Another object of the present invention is to provide a method for producing a polyglycerol dialiphatic carboxylic acid ester that selectively produces the polyglycerin dialiphatic carboxylic acid ester.
本発明者は上記課題を解決するため鋭意検討した結果、グリセリンジ脂肪族カルボン酸エステル１モルにグリシドールを２モル以上反応させて得られる化合物は２つの疎水基（アルキル基又はアルケニル基）が短いスペーサーで結合し、更に水溶性の高いポリグリセリン部分を親水基として有するため、優れた界面活性能を有すること、グリセリンジ脂肪族カルボン酸エステルに反応させるグリシドール量を調整することにより得られるポリグリセリンジ脂肪族カルボン酸エステルのＨＬＢ値を制御することができることを見いだした。本発明はこれらの知見に基づいて完成させたものである。
As a result of intensive studies to solve the above problems, the present inventor has a short compound having two hydrophobic groups (alkyl group or alkenyl group) obtained by reacting 1 mol of glycerin dialiphatic carboxylic acid ester with 2 mol or more of glycidol. Polyglycerin obtained by adjusting the amount of glycidol to be reacted with glycerin dialiphatic carboxylic acid ester because it is bonded with a spacer and has a highly water-soluble polyglycerin moiety as a hydrophilic group, thus having excellent surface activity. It has been found that the HLB value of dialiphatic carboxylic acid esters can be controlled. The present invention has been completed based on these findings.
すなわち、本発明は、下記式（１）
（式中、Ｒ1、Ｒ2は同一又は異なって、ヒドロキシル基を有していてもよい直鎖状若しくは分岐鎖状のアルキル基又はアルケニル基である。ｎはグリセリン単位の数を示し、２以上の整数である）
で表されるポリグリセリンジ脂肪族カルボン酸エステルを提供する。 That is, the present invention provides the following formula (1):
(In the formula, R 1 and R 2 are the same or different and are a linear or branched alkyl group or alkenyl group which may have a hydroxyl group. N represents the number of glycerin units; (It is an integer greater than or equal)
The polyglycerol dialiphatic carboxylic acid ester represented by these is provided.
で表されるポリグリセリンジ脂肪族カルボン酸エステルを提供する。 That is, the present invention provides the following formula (1):
The polyglycerol dialiphatic carboxylic acid ester represented by these is provided.
本発明は、また、下記式（２）
（式中、Ｒ1、Ｒ2は同一又は異なって、ヒドロキシル基を有していてもよい直鎖状若しくは分岐鎖状のアルキル基又はアルケニル基である）
で表される２級ヒドロキシル基を有するグリセリンジ脂肪族カルボン酸エステル１モルに対して、グリシドールｎモル（ｎは２以上の整数である）を反応させて、下記式（１）
（式中、Ｒ1、Ｒ2は前記に同じ。ｎはグリセリン単位の数を示し、２以上の整数である）
で表されるポリグリセリンジ脂肪族カルボン酸エステルを得るポリグリセリンジ脂肪族カルボン酸エステルの製造方法を提供する。 The present invention also provides the following formula (2):
(Wherein R 1 and R 2 are the same or different and are a linear or branched alkyl group or alkenyl group optionally having a hydroxyl group)
1 mol of glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by formula (1) is reacted with n mol of glycidol (n is an integer of 2 or more).
(Wherein R 1 and R 2 are the same as above. N represents the number of glycerin units and is an integer of 2 or more)
The manufacturing method of the polyglycerol dialiphatic carboxylic acid ester which obtains the polyglycerol dialiphatic carboxylic acid ester represented by these is provided.
で表される２級ヒドロキシル基を有するグリセリンジ脂肪族カルボン酸エステル１モルに対して、グリシドールｎモル（ｎは２以上の整数である）を反応させて、下記式（１）
で表されるポリグリセリンジ脂肪族カルボン酸エステルを得るポリグリセリンジ脂肪族カルボン酸エステルの製造方法を提供する。 The present invention also provides the following formula (2):
1 mol of glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by formula (1) is reacted with n mol of glycidol (n is an integer of 2 or more).
The manufacturing method of the polyglycerol dialiphatic carboxylic acid ester which obtains the polyglycerol dialiphatic carboxylic acid ester represented by these is provided.
尚、本明細書において、第２級炭素原子（２個の炭素原子と結合する炭素原子）に結合するヒドロキシル基を「２級ヒドロキシル基」、第１級炭素原子（１個の炭素原子と結合する炭素原子）に結合するヒドロキシル基を「１級ヒドロキシル基」と称する。
In this specification, a hydroxyl group bonded to a secondary carbon atom (a carbon atom bonded to two carbon atoms) is referred to as a “secondary hydroxyl group”, and a primary carbon atom (bonded to one carbon atom). The hydroxyl group bonded to the carbon atom) is called “primary hydroxyl group”.
本発明のポリグリセリンジ脂肪族カルボン酸エステルは上記構成を有するため、極めて優れた界面活性能を示す。そのため、界面活性剤として本発明のポリグリセリンジ脂肪族カルボン酸エステルを使用すると、従来に比べて少ない量でも十分な効果を発揮することができ、環境負荷を低減することができる。更に、ＨＬＢ値を所望する範囲に容易に調整することができる。そのため、本発明のポリグリセリンジ脂肪族カルボン酸エステルは、消泡剤、Ｗ／Ｏ型乳化剤、Ｏ／Ｗ型乳化剤、湿潤剤、洗浄剤、可溶化剤等として好適に使用することができる。また、本発明のポリグリセリンジ脂肪族カルボン酸エステルの製造方法によれば、前記ポリグリセリンジ脂肪族カルボン酸エステルを容易且つ選択的に製造することができる。
Since the polyglycerin dialiphatic carboxylic acid ester of the present invention has the above configuration, it exhibits extremely excellent surface activity. Therefore, when the polyglycerin dialiphatic carboxylic acid ester of the present invention is used as a surfactant, a sufficient effect can be exhibited even in a smaller amount than conventional, and the environmental load can be reduced. Furthermore, the HLB value can be easily adjusted to a desired range. Therefore, the polyglycerin dialiphatic carboxylic acid ester of the present invention can be suitably used as an antifoaming agent, a W / O type emulsifier, an O / W type emulsifier, a wetting agent, a cleaning agent, a solubilizing agent and the like. Moreover, according to the manufacturing method of the polyglycerol dialiphatic carboxylic acid ester of this invention, the said polyglycerol dialiphatic carboxylic acid ester can be manufactured easily and selectively.
［ポリグリセリンジ脂肪族カルボン酸エステル］
本発明のポリグリセリンジ脂肪族カルボン酸エステルは、上記式（１）で表される。式（１）中、Ｒ1、Ｒ2は同一又は異なって、ヒドロキシル基を有していてもよい直鎖状若しくは分岐鎖状のアルキル基又はアルケニル基である。ｎはグリセリン単位の数を示し、２以上の整数である。 [Polyglycerin dialiphatic carboxylic acid ester]
The polyglycerol dialiphatic carboxylic acid ester of the present invention is represented by the above formula (1). In the formula (1), R 1 and R 2 are the same or different and each represents a linear or branched alkyl group or alkenyl group which may have a hydroxyl group. n represents the number of glycerin units and is an integer of 2 or more.
本発明のポリグリセリンジ脂肪族カルボン酸エステルは、上記式（１）で表される。式（１）中、Ｒ1、Ｒ2は同一又は異なって、ヒドロキシル基を有していてもよい直鎖状若しくは分岐鎖状のアルキル基又はアルケニル基である。ｎはグリセリン単位の数を示し、２以上の整数である。 [Polyglycerin dialiphatic carboxylic acid ester]
The polyglycerol dialiphatic carboxylic acid ester of the present invention is represented by the above formula (1). In the formula (1), R 1 and R 2 are the same or different and each represents a linear or branched alkyl group or alkenyl group which may have a hydroxyl group. n represents the number of glycerin units and is an integer of 2 or more.
式（１）の括弧内のＣ3Ｈ6Ｏ2は、下記式（1-1）及び（1-2）で示される両方の構造を有する。
－ＣＨ2－ＣＨＯＨ－ＣＨ2Ｏ－ （1-1）
－ＣＨ（ＣＨ2ＯＨ）ＣＨ2Ｏ－ （1-2） C 3 H 6 O 2 in parentheses in the formula (1) has both structures represented by the following formulas (1-1) and (1-2).
—CH 2 —CHOH—CH 2 O— (1-1)
—CH (CH 2 OH) CH 2 O— (1-2)
－ＣＨ2－ＣＨＯＨ－ＣＨ2Ｏ－ （1-1）
－ＣＨ（ＣＨ2ＯＨ）ＣＨ2Ｏ－ （1-2） C 3 H 6 O 2 in parentheses in the formula (1) has both structures represented by the following formulas (1-1) and (1-2).
—CH 2 —CHOH—CH 2 O— (1-1)
—CH (CH 2 OH) CH 2 O— (1-2)
Ｒ1、Ｒ2における直鎖状若しくは分岐鎖状のアルキル基としては、例えば、ｎ－ヘキシル、ｎ－ヘプチル、ｎ－オクチル、ｎ－ノニル、ｎ－デシル、ｎ－ウンデシル、ｎ－ドデシル（ラウリル）、ｎ－トリデシル、ｎ－テトラデシル（ミリスチル）、ｎ－ペンタデシル、ｎ－ヘキサデシル、ｎ－ヘプタデシル、ｎ－ステアリル、ｎ－ノナデシル、ｎ－エイコシル、ｎ－ヘンエイコシル、ｎ－ドコシル基等のＣ6-22直鎖状アルキル基；イソヘキシル、ｓ－ヘキシル、ｔ－ヘキシル、イソヘプチル、ｓ－ヘプチル、ｔ－ヘプチル、イソオクチル、ｓ－オクチル、ｔ－オクチル、イソノニル、ｓ－ノニル、ｔ－ノニル、イソデシル、ｓ－デシル、ｔ－デシル、イソウンデシル、ｓ－ウンデシル、ｔ－ウンデシル、イソドデシル、ｓ－ドデシル、ｔ－ドデシル、イソトリデシル、ｓ－トリデシル、ｔ－トリデシル、イソテトラデシル、ｓ－テトラデシル、ｔ－テトラデシル、イソペンタデシル、ｓ－ペンタデシル、ｔ－ペンタデシル、イソヘキサデシル、ｓ－ヘキサデシル、ｔ－ヘキサデシル、イソヘプタデシル、ｓ－ヘプタデシル、ｔ－ヘプタデシル、イソステアリル、イソノナデシル、ｓ－ノナデシル、ｔ－ノナデシル、イソエイコシル、ｓ－エイコシル、ｔ－エイコシル、イソヘンエイコシル、ｓ－ヘンエイコシル、ｔ－ヘンエイコシル、イソドコシル、ｓ－ドコシル、ｔ－ドコシル等のＣ6-22分岐鎖状アルキル基等を挙げることができる。
Examples of the linear or branched alkyl group in R 1 and R 2 include n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl (lauryl). ), n- tridecyl, n- tetradecyl (myristyl), n- pentadecyl, n- hexadecyl, n- heptadecyl, n- stearyl, n- nonadecyl, n- eicosyl, n- heneicosyl, such as n- docosyl group C 6- 22 linear alkyl groups; isohexyl, s-hexyl, t-hexyl, isoheptyl, s-heptyl, t-heptyl, isooctyl, s-octyl, t-octyl, isononyl, s-nonyl, t-nonyl, isodecyl, s -Decyl, t-decyl, isoundecyl, s-undecyl, t-undecyl, isododecyl, s-dodecyl, t- Dodecyl, isotridecyl, s-tridecyl, t-tridecyl, isotetradecyl, s-tetradecyl, t-tetradecyl, isopentadecyl, s-pentadecyl, t-pentadecyl, isohexadecyl, s-hexadecyl, t-hexadecyl, isoheptadecyl, s-heptadecyl, t-heptadecyl, isostearyl, isononadecyl, s-nonadecyl, t-nonadecyl, isoeicosyl, s-eicosyl, t-eicosyl, isogeneicosyl, s-heneicosyl, t-heneicosyl, isodocosyl, s-docosyl, C 6-22 branched chain alkyl groups such as t-docosyl and the like can be mentioned.
Ｒ1、Ｒ2におけるヒドロキシル基を有している直鎖状若しくは分岐鎖状のアルキル基としては、例えば、前記Ｃ6-22直鎖状若しくは分岐鎖状アルキル基に１以上のヒドロキシル基を有する、Ｃ6-22直鎖状若しくは分岐鎖状ヒドロキシアルキル基を挙げることができる。
Examples of the linear or branched alkyl group having a hydroxyl group in R 1 and R 2 include one or more hydroxyl groups in the C 6-22 linear or branched alkyl group. And C 6-22 linear or branched hydroxyalkyl groups.
Ｒ1、Ｒ2における直鎖状若しくは分岐鎖状のアルケニル基としては、例えば、ｎ－ヘキセニル、ｎ－ヘプテニル、ｎ－オクテニル、ｎ－ノネニル、ｎ－デセニル、ｎ－ウンデセニル、ｎ－ドデセニル、ｎ－トリデセニル、ｎ－テトラデセニル、ｎ－ペンタデセニル、ｎ－ヘキサデセニル、ｎ－ヘプタデセニル、ｎ－オレイル、ｎ－ノナデセニル、ｎ－エイコセニル、ｎ－ヘンエイコセニル、ｎ－ドコセニル基等のＣ6-22直鎖状アルケニル基；イソヘキセニル、ｓ－ヘキセニル、ｔ－ヘキセニル、イソヘプテニル、ｓ－ヘプテニル、ｔ－ヘプテニル、イソオクテニル、ｓ－オクテニル、ｔ－オクテニル、イソノネニル、ｓ－ノネニル、ｔ－ノネニル、イソデセニル、ｓ－デセニル、ｔ－デセニル、イソウンデセニル、ｓ－ウンデセニル、ｔ－ウンデセニル、イソドデセニル、ｓ－ドデセニル、ｔ－ドデセニル、イソトリデセニル、ｓ－トリデセニル、ｔ－トリデセニル、イソテトラデセニル、ｓ－テトラデセニル、ｔ－テトラデセニル、イソペンタデセニル、ｓ－ペンタデセニル、ｔ－ペンタデセニル、イソヘキサデセニル、ｓ－ヘキサデセニル、ｔ－ヘキサデセニル、イソヘプタデセニル、ｓ－ヘプタデセニル、ｔ－ヘプタデセニル、イソオレイル、イソノナデセニル、ｓ－ノナデセニル、ｔ－ノナデセニル、イソエイコセニル、ｓ－エイコセニル、ｔ－エイコセニル、イソヘンエイコセニル、ｓ－ヘンエイコセニル、ｔ－ヘンエイコセニル、イソドコセニル、ｓ－ドコセニル、ｔ－ドコセニル等のＣ6-22分岐鎖状アルケニル基等を挙げることができる。
Examples of the linear or branched alkenyl group for R 1 and R 2 include n-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, n-undecenyl, n-dodecenyl, n -C 6-22 linear alkenyl groups such as tridecenyl, n-tetradecenyl, n-pentadecenyl, n-hexadecenyl, n-heptadecenyl, n-oleyl, n-nonadecenyl, n-eicosenyl, n-heneicosenyl, n-docosenyl Isohexenyl, s-hexenyl, t-hexenyl, isoheptenyl, s-heptenyl, t-heptenyl, isooctenyl, s-octenyl, t-octenyl, isononenyl, s-nonenyl, t-nonenyl, isodecenyl, s-decenyl, t- Decenyl, isoundecenyl, s-undecenyl, tert-u Ndecenyl, isododecenyl, s-dodecenyl, t-dodecenyl, isotridecenyl, s-tridecenyl, t-tridecenyl, isotetradecenyl, s-tetradecenyl, t-tetradecenyl, isopentadecenyl, s-pentadecenyl, t-pentadecenyl, Isohexadecenyl, s-hexadecenyl, t-hexadecenyl, isoheptadecenyl, s-heptadecenyl, t-heptadecenyl, isooleyl, isononadecenyl, s-nonadecenyl, t-nonadecenyl, isoeicosenyl, s-eicosenyl, t-eicosenyl, Examples thereof include C 6-22 branched alkenyl groups such as isoheneicosenyl, s-heneicosenyl, t-heneicosenyl, isodocosenyl, s-docosenyl, and t-docosenyl.
Ｒ1、Ｒ2におけるヒドロキシル基を有している直鎖状若しくは分岐鎖状のアルケニル基としては、例えば、前記Ｃ6-22直鎖状若しくは分岐鎖状アルケニル基に１以上のヒドロキシル基を有する、Ｃ6-22直鎖状若しくは分岐鎖状ヒドロキシアルケニル基を挙げることができる。
Examples of the linear or branched alkenyl group having a hydroxyl group in R 1 and R 2 include one or more hydroxyl groups in the C 6-22 linear or branched alkenyl group. C 6-22 linear or branched hydroxyalkenyl groups.
本発明におけるＲ1、Ｒ2としては、なかでも、界面上に強固な柵層を形成することができ、それにより、ラメラ液晶相を形成することができる点で、炭素数８～２０（特に好ましくは炭素数８～１８、最も好ましくは１０～１８）の直鎖状若しくは分岐鎖状のアルキル基又はアルケニル基が好ましい。
As R 1 and R 2 in the present invention, among others, a strong fence layer can be formed on the interface, whereby a lamellar liquid crystal phase can be formed. A linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, most preferably 10 to 18 carbon atoms is preferred.
本発明のポリグリセリンジ脂肪族カルボン酸エステルは、グリセリン単位の数（ｎ）を調整することにより、ＨＬＢ（Hydrophile-Lipophile Balance；親水親油バランス）を６～１６の範囲で適宜調整することができる。本発明のポリグリセリンジ脂肪族カルボン酸エステルを洗浄剤として使用する場合はＨＬＢ値を例えば８～１５程度（好ましくは１０～１５）に調整することが好ましい。ＨＬＢ値は、例えば下記式により算出することができる（有機概念図法）。
ＨＬＢ値＝無機性／有機性×１０ In the polyglycerol dialiphatic carboxylic acid ester of the present invention, the HLB (Hydrophile-Lipophile Balance) can be appropriately adjusted in the range of 6 to 16 by adjusting the number (n) of glycerol units. it can. When the polyglycerin dialiphatic carboxylic acid ester of the present invention is used as a cleaning agent, the HLB value is preferably adjusted to about 8 to 15 (preferably 10 to 15), for example. The HLB value can be calculated by, for example, the following formula (organic conceptual projection).
HLB value = inorganic / organic × 10
ＨＬＢ値＝無機性／有機性×１０ In the polyglycerol dialiphatic carboxylic acid ester of the present invention, the HLB (Hydrophile-Lipophile Balance) can be appropriately adjusted in the range of 6 to 16 by adjusting the number (n) of glycerol units. it can. When the polyglycerin dialiphatic carboxylic acid ester of the present invention is used as a cleaning agent, the HLB value is preferably adjusted to about 8 to 15 (preferably 10 to 15), for example. The HLB value can be calculated by, for example, the following formula (organic conceptual projection).
HLB value = inorganic / organic × 10
ｎはグリセリン単位の数を示し、２以上の整数である。本発明のポリグリセリンジ脂肪族カルボン酸エステルを洗浄剤として使用する場合は、ｎを例えば２～２５程度（好ましくは２～１０、特に好ましくは２～８、最も好ましくは４～８）に調整することが水性成分への溶解性が高く、油性成分への親和性が高い点で好ましい。また、特にｎが６以上である場合は、親水基であるポリグリセリンの２級ヒドロキシル基が水と水素結合を形成するため水への溶解度が高く、クラフト点が低い（例えば１０℃以下、好ましくは０～５℃）。そのため、低温でも優れた溶解性、及び可溶化力を発揮することができる。
N represents the number of glycerin units and is an integer of 2 or more. When the polyglycerol dialiphatic carboxylic acid ester of the present invention is used as a cleaning agent, n is adjusted to, for example, about 2 to 25 (preferably 2 to 10, particularly preferably 2 to 8, most preferably 4 to 8). It is preferable in terms of high solubility in aqueous components and high affinity for oil components. In particular, when n is 6 or more, the secondary hydroxyl group of polyglycerol, which is a hydrophilic group, forms a hydrogen bond with water, so the solubility in water is high and the Kraft point is low (for example, 10 ° C. or less, preferably Is 0-5 ° C). Therefore, excellent solubility and solubilizing power can be exhibited even at low temperatures.
本発明のポリグリセリンジ脂肪族カルボン酸エステルとしては、例えば、トリグリセリンジオクタン酸エステル、トリグリセリンジデカン酸エステル、トリグリセリンジドデカン酸エステル、トリグリセリンジミリスチン酸エステル、トリグリセリンジオレイン酸エステル、トリグリセリンジステアリン酸エステル、トリグリセリンジイソステアリン酸エステル、テトラグリセリンジオクタン酸エステル、テトラグリセリンジデカン酸エステル、テトラグリセリンジドデカン酸エステル、テトラグリセリンジミリスチン酸エステル、テトラグリセリンジオレイン酸エステル、テトラグリセリンジステアリン酸エステル、テトラグリセリンジイソステアリン酸エステル、ペンタグリセリンジオクタン酸エステル、ペンタグリセリンジデカン酸エステル、ペンタグリセリンジドデカン酸エステル、ペンタグリセリンジミリスチン酸エステル、ペンタグリセリンジオレイン酸エステル、ペンタグリセリンジステアリン酸エステル、ペンタグリセリンジイソステアリン酸エステル、ヘキサグリセリンジオクタン酸エステル、ヘキサグリセリンジデカン酸エステル、ヘキサグリセリンジドデカン酸エステル、ヘキサグリセリンジミリスチン酸エステル、ヘキサグリセリンジオレイン酸エステル、ヘキサグリセリンジステアリン酸エステル、ヘキサグリセリンジイソステアリン酸エステル、ヘプタグリセリンジオクタン酸エステル、ヘプタグリセリンジデカン酸エステル、ヘプタグリセリンジドデカン酸エステル、ヘプタグリセリンジミリスチン酸エステル、ヘプタグリセリンジオレイン酸エステル、ヘプタグリセリンジステアリン酸エステル、ヘプタグリセリンジイソステアリン酸エステル、オクタグリセリンジオクタン酸エステル、オクタグリセリンジデカン酸エステル、オクタグリセリンジドデカン酸エステル、オクタグリセリンジミリスチン酸エステル、オクタグリセリンジオレイン酸エステル、オクタグリセリンジステアリン酸エステル、オクタグリセリンジイソステアリン酸エステル、ノナグリセリンジオクタン酸エステル、ノナグリセリンジデカン酸エステル、ノナグリセリンジドデカン酸エステル、ノナグリセリンジミリスチン酸エステル、ノナグリセリンジオレイン酸エステル、ノナグリセリンジステアリン酸エステル、ノナグリセリンジイソステアリン酸エステル、デカグリセリンジオクタン酸エステル、デカグリセリンジデカン酸エステル、デカグリセリンジドデカン酸エステル、デカグリセリンジミリスチン酸エステル、デカグリセリンジオレイン酸エステル、デカグリセリンジステアリン酸エステル、デカグリセリンジイソステアリン酸エステル、ポリ（１１）グリセリンジオクタン酸エステル、ポリ（１１）グリセリンジデカン酸エステル、ポリ（１１）グリセリンジドデカン酸エステル、ポリ（１１）グリセリンジミリスチン酸エステル、ポリ（１１）グリセリンジオレイン酸エステル、ポリ（１１）グリセリンジステアリン酸エステル、ポリ（１１）グリセリンジイソステアリン酸エステル等を挙げることができる。
Examples of the polyglycerin dialiphatic carboxylic acid ester of the present invention include triglycerin dioctanoic acid ester, triglycerin didecanoic acid ester, triglycerin didodecanoic acid ester, triglycerin dimyristic acid ester, and triglycerin dioleic acid ester. , Triglyceryl distearate, triglycerin diisostearate, tetraglycerin dioctanoate, tetraglycerin didecanoate, tetraglycerin dododecanoate, tetraglycerin dimyristate, tetraglycerin dioleate, tetraglycerin Distearic acid ester, tetraglycerin diisostearic acid ester, pentaglycerin dioctanoic acid ester, pentaglycerin didecanoic acid Steal, pentaglycerin didodecanoic acid ester, pentaglycerin dimyristic acid ester, pentaglycerin dioleic acid ester, pentaglyceryl distearic acid ester, pentaglycerin diisostearic acid ester, hexaglycerin dioctanoic acid ester, hexaglycerin didecanoic acid ester, hexa Glycerin didodecanoate, hexaglycerin dimyristate, hexaglycerin dioleate, hexaglyceryl distearate, hexaglycerin diisostearate, heptaglycerin dioctanoate, heptaglycerin didecanoate, heptaglycerin didodecane Acid ester, heptaglycerin dimyristic acid ester, heptaglycerin dioleic acid ester Ter, heptaglycerin distearate, heptaglycerin diisostearate, octaglycerin dioctanoate, octaglycerin didecanoate, octaglycerin didodecanoate, octaglycerin dimyristate, octaglycerin dioleate, octa Glycerin distearate, octaglycerin diisostearate, nonaglycerin dioctanoic acid ester, nonaglycerin didecanoic acid ester, nonaglycerin didomycinate, nonaglycerin dimyristic acid ester, nonaglycerin dioleic acid ester, nonaglycerin distearic acid Esters, nonaglycerin diisostearate, decaglycerin dioctanoate, decagu Lysine didecanoic acid ester, decaglycerin didodecanoic acid ester, decaglycerin dimyristic acid ester, decaglycerin dioleic acid ester, decaglycerin distearic acid ester, decaglycerin diisostearic acid ester, poly (11) glycerin dioctanoic acid ester, poly (11 ) Glycerin didecanoic acid ester, poly (11) glycerin didodecanoic acid ester, poly (11) glycerin dimyristic acid ester, poly (11) glycerin dioleic acid ester, poly (11) glycerin distearic acid ester, poly (11) Examples thereof include glycerin diisostearic acid ester.
本発明のポリグリセリンジ脂肪族カルボン酸エステルは、短いスペーサーで結合した２つの基（Ｒ1、Ｒ2）が反発すること無く界面に密に吸着することにより極めて優れた界面活性能を発揮することができる。そのため、使用量を従来の半分以下にまで低減することができ、環境負荷が少なく、また、皮膚等への刺激性も極めて低く抑制することができる。特に、ｎが６以上の親水性に優れたポリグリセリンジ脂肪族カルボン酸エステルは、クラフト点が低く、低温でも優れた溶解性、及び可溶化力を発揮できることができる。
The polyglycerin dialiphatic carboxylic acid ester of the present invention exhibits extremely excellent surface activity due to the fact that two groups (R 1 , R 2 ) bonded by a short spacer are closely adsorbed to the interface without repulsion. be able to. Therefore, the amount used can be reduced to less than half of the conventional amount, the environmental load is small, and the irritation to the skin and the like can be suppressed to a very low level. In particular, polyglycerin dialiphatic carboxylic acid ester having an excellent hydrophilicity with n of 6 or more has a low Kraft point and can exhibit excellent solubility and solubilizing power even at low temperatures.
本発明のポリグリセリンジ脂肪族カルボン酸エステルは上記特性を有するため、例えば、消泡剤、Ｗ／Ｏ型乳化剤、Ｏ／Ｗ型乳化剤、湿潤剤、洗浄剤、可溶化剤等として好適に使用することができる。
Since the polyglycerin dialiphatic carboxylic acid ester of the present invention has the above properties, it is suitably used as, for example, an antifoaming agent, a W / O type emulsifier, an O / W type emulsifier, a wetting agent, a cleaning agent, a solubilizing agent, and the like. can do.
［ポリグリセリンジ脂肪族カルボン酸エステルの製造方法］
下記式（１）で表されるポリグリセリンジ脂肪族カルボン酸エステルは、例えば、下記式（２）で表される２級ヒドロキシル基を有するグリセリンジ脂肪族カルボン酸エステル１モルに対して、グリシドールｎモル（ｎは２以上の整数である）を反応させること（＝グリシドールの付加重合反応）により製造することができる。尚、下記式中のＲ1、Ｒ2、ｎは前記に同じ。 [Production method of polyglycerin dialiphatic carboxylic acid ester]
The polyglycerin dialiphatic carboxylic acid ester represented by the following formula (1) is, for example, glycidol with respect to 1 mol of glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by the following formula (2). It can be produced by reacting n moles (n is an integer of 2 or more) (= addition polymerization reaction of glycidol). In the following formula, R 1 , R 2 and n are the same as described above.
下記式（１）で表されるポリグリセリンジ脂肪族カルボン酸エステルは、例えば、下記式（２）で表される２級ヒドロキシル基を有するグリセリンジ脂肪族カルボン酸エステル１モルに対して、グリシドールｎモル（ｎは２以上の整数である）を反応させること（＝グリシドールの付加重合反応）により製造することができる。尚、下記式中のＲ1、Ｒ2、ｎは前記に同じ。 [Production method of polyglycerin dialiphatic carboxylic acid ester]
The polyglycerin dialiphatic carboxylic acid ester represented by the following formula (1) is, for example, glycidol with respect to 1 mol of glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by the following formula (2). It can be produced by reacting n moles (n is an integer of 2 or more) (= addition polymerization reaction of glycidol). In the following formula, R 1 , R 2 and n are the same as described above.
式（２）で表される２級ヒドロキシル基を有するグリセリンジ脂肪族カルボン酸エステルは、例えば、下記式（３）で表される脂肪族カルボン酸と下記式（４）で表されるグリシジル脂肪族カルボン酸エステルを反応させることにより製造することができる。尚、下記式中のＲ1、Ｒ2は前記に同じ。
Examples of the glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by the formula (2) include an aliphatic carboxylic acid represented by the following formula (3) and a glycidyl fat represented by the following formula (4). It can be produced by reacting a group carboxylic acid ester. In the following formula, R 1 and R 2 are the same as described above.
その他、式（２）で表される２級ヒドロキシル基を有するグリセリンジ脂肪族カルボン酸エステルは、高度不飽和脂肪族カルボン酸又はその低級アルキルエステルとグリセリンとを、固定化部分グリセリドリパーゼの存在下に、生成水を反応系外に除去しながら反応させる方法（特開２００４－２０８５３９号公報）や、グリセリンと脂肪族カルボン酸を反応させる（エステル化する）方法、グリセリンと脂肪族カルボン酸エステルのエステル交換法（特公平６－６５３１１号公報）等によっても製造することができる。
In addition, the glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by the formula (2) is a highly unsaturated aliphatic carboxylic acid or a lower alkyl ester thereof and glycerin in the presence of an immobilized partial glyceride lipase. In addition, a method of reacting while removing generated water from the reaction system (Japanese Patent Application Laid-Open No. 2004-208539), a method of reacting glycerin and an aliphatic carboxylic acid (esterification), a method of reacting glycerin and an aliphatic carboxylic acid ester It can also be produced by a transesterification method (Japanese Patent Publication No. 6-65311).
尚、上記式（２）で表される２級ヒドロキシル基を有するグリセリンジ脂肪族カルボン酸エステルには、通常下記式（２'）
で表される１級ヒドロキシル基を有するグリセリンジ脂肪族カルボン酸エステルも含有される。そのため、上記ポリグリセリンジ脂肪族カルボン酸エステルの製造方法では、下記式（１'）
で表されるポリグリセリンジ脂肪族カルボン酸エステルが副生するが、その副生率は４０％以下（好ましくは３０％以下）が望ましい。式（１'）及び（２'）中、Ｒ1、Ｒ2、ｎは前記に同じ。
The glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by the above formula (2) is usually represented by the following formula (2 ′)
The glycerol dialiphatic carboxylic acid ester which has the primary hydroxyl group represented by these is also contained. Therefore, in the method for producing the polyglycerin dialiphatic carboxylic acid ester, the following formula (1 ′)
Is produced as a by-product, and the by-product rate is desirably 40% or less (preferably 30% or less). In formulas (1 ′) and (2 ′), R 1 , R 2 and n are the same as above.
上記グリシドールの付加重合反応は溶媒の存在下又は非存在下で行うことができる。前記溶媒としては、例えば、トリエチルアミン、ピペリジン、Ｎ－メチルピペリジン、ピリジン、Ｎ－メチルピロリドン等のアミン類（特に、第３級アミン）や含窒素複素環化合物等が挙げられる。これらは１種を単独で、又は２種以上を組み合わせて使用することができる。
The above addition polymerization reaction of glycidol can be carried out in the presence or absence of a solvent. Examples of the solvent include amines (particularly tertiary amine) such as triethylamine, piperidine, N-methylpiperidine, pyridine, N-methylpyrrolidone, nitrogen-containing heterocyclic compounds, and the like. These can be used alone or in combination of two or more.
上記グリシドールの付加重合反応の反応雰囲気は反応を阻害しない限り特に限定されず、例えば、空気雰囲気、窒素雰囲気、アルゴン雰囲気等の何れであってもよい。また、反応はバッチ式、セミバッチ式、連続式等の何れの方法で行うこともできる。
The reaction atmosphere of the glycidol addition polymerization reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.
上記グリシドールの付加重合反応の反応温度としては、例えば０～１００℃程度、好ましくは４０～８０℃である。反応時間は、例えば５～２０時間程度、好ましくは８～１４時間である。
The reaction temperature for the above addition polymerization reaction of glycidol is, for example, about 0 to 100 ° C., preferably 40 to 80 ° C. The reaction time is, for example, about 5 to 20 hours, preferably 8 to 14 hours.
グリシドールの付加重合反応終了後、反応生成物は、例えば、濾過、濃縮、蒸留、抽出等の分離手段や、これらを組み合わせた分離手段により分離精製できる。
After completion of the addition polymerization reaction of glycidol, the reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, and extraction, or a separation means combining these.
本発明のポリグリセリンジ脂肪族カルボン酸エステルの製造方法によれば、式（２）で表される２級ヒドロキシル基を有するグリセリンジ脂肪族カルボン酸エステルに反応させるグリシドールの量を調整することにより、所望のＨＬＢ値を有するポリグリセリンジ脂肪族カルボン酸エステルを容易且つ選択的に製造することができる。
According to the method for producing a polyglycerin dialiphatic carboxylic acid ester of the present invention, by adjusting the amount of glycidol reacted with the glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by the formula (2). A polyglycerin dialiphatic carboxylic acid ester having a desired HLB value can be easily and selectively produced.
以下、実施例により本発明をより具体的に説明するが、本発明はこれらの実施例により限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
実施例１（ポリ（１１）グリセリンジオレン酸エステルの製造）
グリセリンジオレン酸エステルは、特公平６－６５３１１号公報に記載の方法に従って合成した。
得られたグリセリンジオレイン酸エステル６２１．０ｇに対し、Ｎ－メチルピロリドン４００ｍＬを加えた。
その後、上記グリセリンジオレイン酸エステル１モルに対して１０モルとなる量のグリシドール（７４０．８ｇ）を、７０℃を維持しつつ、１０時間かけて滴下して１時間の熟成を行った。その後、１９０℃、１ｔｏｒｒにて溶媒を除去し、さらに２ｍｍＨｇで他の低沸成分を留去することによりポリ（１１）グリセリンジオレイン酸エステル（ＨＬＢ：１０．２）１２００ｇを得た。
1H-NMR (270MHz, DMSO-D6):δ0.76-0.85(m,6H), 1.08-1.35(m,40H), 1.41-1.56(m,4H), 1.86-1.95(m,8H), 2.14-2.25(m,4H), 3.22-3.84(m,55H), 4.34-4.81(m,11H), 5.25-5.35(m,4H) Example 1 (Production of poly (11) glycerol dioleic acid ester)
Glycerol diolenic acid ester was synthesized according to the method described in JP-B-6-65311.
400 mL of N-methylpyrrolidone was added to 621.0 g of the obtained glycerol dioleate.
Thereafter, glycidol (740.8 g) in an amount of 10 mol with respect to 1 mol of the glycerin dioleate was added dropwise over 10 hours while maintaining 70 ° C., and aged for 1 hour. Thereafter, the solvent was removed at 190 ° C. and 1 torr, and other low-boiling components were distilled off at 2 mmHg to obtain 1200 g of poly (11) glycerol dioleate (HLB: 10.2).
1 H-NMR (270 MHz, DMSO-D6): δ 0.76-0.85 (m, 6H), 1.08-1.35 (m, 40H), 1.41-1.56 (m, 4H), 1.86-1.95 (m, 8H), 2.14-2.25 (m, 4H), 3.22-3.84 (m, 55H), 4.34-4.81 (m, 11H), 5.25-5.35 (m, 4H)
グリセリンジオレン酸エステルは、特公平６－６５３１１号公報に記載の方法に従って合成した。
得られたグリセリンジオレイン酸エステル６２１．０ｇに対し、Ｎ－メチルピロリドン４００ｍＬを加えた。
その後、上記グリセリンジオレイン酸エステル１モルに対して１０モルとなる量のグリシドール（７４０．８ｇ）を、７０℃を維持しつつ、１０時間かけて滴下して１時間の熟成を行った。その後、１９０℃、１ｔｏｒｒにて溶媒を除去し、さらに２ｍｍＨｇで他の低沸成分を留去することによりポリ（１１）グリセリンジオレイン酸エステル（ＨＬＢ：１０．２）１２００ｇを得た。
1H-NMR (270MHz, DMSO-D6):δ0.76-0.85(m,6H), 1.08-1.35(m,40H), 1.41-1.56(m,4H), 1.86-1.95(m,8H), 2.14-2.25(m,4H), 3.22-3.84(m,55H), 4.34-4.81(m,11H), 5.25-5.35(m,4H) Example 1 (Production of poly (11) glycerol dioleic acid ester)
Glycerol diolenic acid ester was synthesized according to the method described in JP-B-6-65311.
400 mL of N-methylpyrrolidone was added to 621.0 g of the obtained glycerol dioleate.
Thereafter, glycidol (740.8 g) in an amount of 10 mol with respect to 1 mol of the glycerin dioleate was added dropwise over 10 hours while maintaining 70 ° C., and aged for 1 hour. Thereafter, the solvent was removed at 190 ° C. and 1 torr, and other low-boiling components were distilled off at 2 mmHg to obtain 1200 g of poly (11) glycerol dioleate (HLB: 10.2).
1 H-NMR (270 MHz, DMSO-D6): δ 0.76-0.85 (m, 6H), 1.08-1.35 (m, 40H), 1.41-1.56 (m, 4H), 1.86-1.95 (m, 8H), 2.14-2.25 (m, 4H), 3.22-3.84 (m, 55H), 4.34-4.81 (m, 11H), 5.25-5.35 (m, 4H)
実施例２（テトラグリセリンジオレイン酸エステルの製造）
グリシドールの使用量を、グリセリンジオレイン酸エステル１モルに対して１０モルから３モルに変更した以外は実施例１と同様にして、テトラグリセリンジオレイン酸エステル（ＨＬＢ：６．０）を得た。 Example 2 (Production of tetraglycerin dioleate)
Tetraglycerin dioleic acid ester (HLB: 6.0) was obtained in the same manner as in Example 1 except that the amount of glycidol used was changed from 10 mol to 3 mol with respect to 1 mol of glycerin dioleic acid ester. .
グリシドールの使用量を、グリセリンジオレイン酸エステル１モルに対して１０モルから３モルに変更した以外は実施例１と同様にして、テトラグリセリンジオレイン酸エステル（ＨＬＢ：６．０）を得た。 Example 2 (Production of tetraglycerin dioleate)
Tetraglycerin dioleic acid ester (HLB: 6.0) was obtained in the same manner as in Example 1 except that the amount of glycidol used was changed from 10 mol to 3 mol with respect to 1 mol of glycerin dioleic acid ester. .
実施例３（ペンタグリセリンジオレイン酸エステルの製造）
グリシドールの使用量を、グリセリンジオレイン酸エステル１モルに対して１０モルから４モルに変更した以外は実施例１と同様にして、ペンタグリセリンジオレイン酸エステル（ＨＬＢ：６．８）を得た。 Example 3 (Production of pentaglycerin dioleic acid ester)
Pentaglycerin dioleate (HLB: 6.8) was obtained in the same manner as in Example 1 except that the amount of glycidol used was changed from 10 mol to 4 mol with respect to 1 mol of glycerin dioleate. .
グリシドールの使用量を、グリセリンジオレイン酸エステル１モルに対して１０モルから４モルに変更した以外は実施例１と同様にして、ペンタグリセリンジオレイン酸エステル（ＨＬＢ：６．８）を得た。 Example 3 (Production of pentaglycerin dioleic acid ester)
Pentaglycerin dioleate (HLB: 6.8) was obtained in the same manner as in Example 1 except that the amount of glycidol used was changed from 10 mol to 4 mol with respect to 1 mol of glycerin dioleate. .
実施例４（ヘプタグリセリンジオレイン酸エステルの製造）
グリシドールの使用量を、グリセリンジオレイン酸エステル１モルに対して１０モルから６モルに変更した以外は実施例１と同様にして、ヘプタグリセリンジオレイン酸エステル（ＨＬＢ：８．２）を得た。 Example 4 (Production of heptaglycerin dioleate)
A heptaglycerol dioleate (HLB: 8.2) was obtained in the same manner as in Example 1 except that the amount of glycidol used was changed from 10 mol to 6 mol with respect to 1 mol of glycerol dioleate. .
グリシドールの使用量を、グリセリンジオレイン酸エステル１モルに対して１０モルから６モルに変更した以外は実施例１と同様にして、ヘプタグリセリンジオレイン酸エステル（ＨＬＢ：８．２）を得た。 Example 4 (Production of heptaglycerin dioleate)
A heptaglycerol dioleate (HLB: 8.2) was obtained in the same manner as in Example 1 except that the amount of glycidol used was changed from 10 mol to 6 mol with respect to 1 mol of glycerol dioleate. .
評価
実施例で得られた各ポリグリセリンジ脂肪族カルボン酸エステル２０重量部に対して水を８０重量部混合して洗浄剤１～４を調製し、得られた洗浄剤について、下記試験方法により洗浄力及び起泡力を評価した。 Evaluation Cleaning agents 1 to 4 were prepared by mixing 80 parts by weight of water with 20 parts by weight of each polyglycerin dialiphatic carboxylic acid ester obtained in the examples. Detergency and foaming power were evaluated.
実施例で得られた各ポリグリセリンジ脂肪族カルボン酸エステル２０重量部に対して水を８０重量部混合して洗浄剤１～４を調製し、得られた洗浄剤について、下記試験方法により洗浄力及び起泡力を評価した。 Evaluation Cleaning agents 1 to 4 were prepared by mixing 80 parts by weight of water with 20 parts by weight of each polyglycerin dialiphatic carboxylic acid ester obtained in the examples. Detergency and foaming power were evaluated.
＜洗浄力試験＞
洗浄剤の０．２％水溶液７００ｍＬ（液温：３０℃）に、人工汚巧を付着させた平面２０ｃｍ2のガラス板を専用台にセットして沈め、撹拌羽を回転数２５０ｒｐｍで３分間回転させた。
回転終了後、ガラス板を取り出し、乾燥させた後の重量を測定し、下記式を用いて洗浄率を算出し、下記基準で洗浄力を評価した。
洗浄率＝｛（洗浄前の重量－洗浄後の重量）／（洗浄前の重量－ガラス板重量）｝×１００
評価基準
◎：洗浄率９５％以上
○：洗浄率８５％以上、９５％未満
△：洗浄率５０％以上、８５％未満
×：洗浄率５０％未満 <Detergency test>
Place a flat 20 cm 2 glass plate with artificial fouling on a dedicated table in 700 mL of a 0.2% aqueous solution of cleaning agent (liquid temperature: 30 ° C.) and rotate the stirring blade for 3 minutes at 250 rpm. I let you.
After completion of the rotation, the glass plate was taken out and weighed after drying, the cleaning rate was calculated using the following formula, and the cleaning power was evaluated according to the following criteria.
Cleaning rate = {(weight before cleaning−weight after cleaning) / (weight before cleaning−weight of glass plate)} × 100
Evaluation criteria ◎: Cleaning rate of 95% or more ○: Cleaning rate of 85% or more and less than 95% △: Cleaning rate of 50% or more and less than 85% ×: Cleaning rate of less than 50%
洗浄剤の０．２％水溶液７００ｍＬ（液温：３０℃）に、人工汚巧を付着させた平面２０ｃｍ2のガラス板を専用台にセットして沈め、撹拌羽を回転数２５０ｒｐｍで３分間回転させた。
回転終了後、ガラス板を取り出し、乾燥させた後の重量を測定し、下記式を用いて洗浄率を算出し、下記基準で洗浄力を評価した。
洗浄率＝｛（洗浄前の重量－洗浄後の重量）／（洗浄前の重量－ガラス板重量）｝×１００
評価基準
◎：洗浄率９５％以上
○：洗浄率８５％以上、９５％未満
△：洗浄率５０％以上、８５％未満
×：洗浄率５０％未満 <Detergency test>
Place a flat 20 cm 2 glass plate with artificial fouling on a dedicated table in 700 mL of a 0.2% aqueous solution of cleaning agent (liquid temperature: 30 ° C.) and rotate the stirring blade for 3 minutes at 250 rpm. I let you.
After completion of the rotation, the glass plate was taken out and weighed after drying, the cleaning rate was calculated using the following formula, and the cleaning power was evaluated according to the following criteria.
Cleaning rate = {(weight before cleaning−weight after cleaning) / (weight before cleaning−weight of glass plate)} × 100
Evaluation criteria ◎: Cleaning rate of 95% or more ○: Cleaning rate of 85% or more and less than 95% △: Cleaning rate of 50% or more and less than 85% ×: Cleaning rate of less than 50%
＜起泡力試験＞
洗浄剤の２０倍希釈水溶液を調製し、この溶液１００ｍＬ（液温：３０℃）を５００ｍＬメスシリンダーに注入した。次いで、撹拌羽根を上記溶液中に設置し、１０００ｒｐｍの回転数で１分間撹拌した。その後、生じた泡の体積（ｍＬ）を測定し泡立ち量とした。前記泡立ち量から、下記基準により起泡力を評価した。
評価基準
◎：泡立ち量が３００ｍＬ以上
○：泡立ち量が２５０ｍＬ以上、３００ｍＬ未満
△：泡立ち量が２００ｍＬ以上、２５０ｍＬ未満
×：泡立ち量が２００ｍＬ未満 <Foaming power test>
A 20-fold diluted aqueous solution of the cleaning agent was prepared, and 100 mL of this solution (liquid temperature: 30 ° C.) was injected into a 500 mL graduated cylinder. Next, a stirring blade was installed in the solution, and stirring was performed for 1 minute at 1000 rpm. Thereafter, the volume (mL) of the generated foam was measured and used as the amount of foaming. From the amount of foaming, foaming power was evaluated according to the following criteria.
Evaluation criteria ◎: Foaming amount is 300 mL or more ○: Foaming amount is 250 mL or more and less than 300 mL △: Foaming amount is 200 mL or more and less than 250 mL X: Foaming amount is less than 200 mL
洗浄剤の２０倍希釈水溶液を調製し、この溶液１００ｍＬ（液温：３０℃）を５００ｍＬメスシリンダーに注入した。次いで、撹拌羽根を上記溶液中に設置し、１０００ｒｐｍの回転数で１分間撹拌した。その後、生じた泡の体積（ｍＬ）を測定し泡立ち量とした。前記泡立ち量から、下記基準により起泡力を評価した。
評価基準
◎：泡立ち量が３００ｍＬ以上
○：泡立ち量が２５０ｍＬ以上、３００ｍＬ未満
△：泡立ち量が２００ｍＬ以上、２５０ｍＬ未満
×：泡立ち量が２００ｍＬ未満 <Foaming power test>
A 20-fold diluted aqueous solution of the cleaning agent was prepared, and 100 mL of this solution (liquid temperature: 30 ° C.) was injected into a 500 mL graduated cylinder. Next, a stirring blade was installed in the solution, and stirring was performed for 1 minute at 1000 rpm. Thereafter, the volume (mL) of the generated foam was measured and used as the amount of foaming. From the amount of foaming, foaming power was evaluated according to the following criteria.
Evaluation criteria ◎: Foaming amount is 300 mL or more ○: Foaming amount is 250 mL or more and less than 300 mL △: Foaming amount is 200 mL or more and less than 250 mL X: Foaming amount is less than 200 mL
上記結果を下記表にまとめて示す。
The above results are summarized in the following table.
表１より、本発明のポリグリセリンジ脂肪族カルボン酸エステルは優れた界面活性能を有し、洗浄剤として使用した場合は優れた洗浄力及び起泡力を発揮できることが分かる。
From Table 1, it can be seen that the polyglycerin dialiphatic carboxylic acid ester of the present invention has an excellent surface activity and can exhibit an excellent detergency and foaming power when used as a cleaning agent.
本発明のポリグリセリンジ脂肪族カルボン酸エステルは、極めて優れた界面活性能を示す。そのため、界面活性剤として本発明のポリグリセリンジ脂肪族カルボン酸エステルを使用すると、従来に比べて少ない量でも十分な効果を発揮することができ、環境負荷を低減することができる。更に、ＨＬＢ値を所望する範囲に容易に調整することができる。そのため、本発明のポリグリセリンジ脂肪族カルボン酸エステルは、消泡剤、Ｗ／Ｏ型乳化剤、Ｏ／Ｗ型乳化剤、湿潤剤、洗浄剤、可溶化剤等として好適に使用することができる。また、本発明のポリグリセリンジ脂肪族カルボン酸エステルの製造方法によれば、前記ポリグリセリンジ脂肪族カルボン酸エステルを容易且つ選択的に製造することができる。
The polyglycerin dialiphatic carboxylic acid ester of the present invention exhibits extremely excellent surface activity. Therefore, when the polyglycerin dialiphatic carboxylic acid ester of the present invention is used as a surfactant, a sufficient effect can be exhibited even in a small amount compared to the conventional case, and the environmental load can be reduced. Furthermore, the HLB value can be easily adjusted to a desired range. Therefore, the polyglycerin dialiphatic carboxylic acid ester of the present invention can be suitably used as an antifoaming agent, a W / O type emulsifier, an O / W type emulsifier, a wetting agent, a cleaning agent, a solubilizing agent and the like. Moreover, according to the manufacturing method of the polyglycerol dialiphatic carboxylic acid ester of this invention, the said polyglycerol dialiphatic carboxylic acid ester can be manufactured easily and selectively.
Claims (2)
- 下記式（１）
で表されるポリグリセリンジ脂肪族カルボン酸エステル。 Following formula (1)
A polyglycerin dialiphatic carboxylic acid ester represented by: - 下記式（２）
で表される２級ヒドロキシル基を有するグリセリンジ脂肪族カルボン酸エステル１モルに対して、グリシドールｎモル（ｎは２以上の整数である）を反応させて、下記式（１）
で表されるポリグリセリンジ脂肪族カルボン酸エステルを得るポリグリセリンジ脂肪族カルボン酸エステルの製造方法。 Following formula (2)
1 mol of glycerin dialiphatic carboxylic acid ester having a secondary hydroxyl group represented by formula (1) is reacted with n mol of glycidol (n is an integer of 2 or more).
The manufacturing method of the polyglycerol dialiphatic carboxylic acid ester which obtains the polyglycerol dialiphatic carboxylic acid ester represented by these.
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Citations (4)
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| JPH03129716A (en) * | 1989-10-14 | 1991-06-03 | Nippon Chemicon Corp | Electrolyte for electrolytic capacitor |
| JPH10114707A (en) * | 1996-10-09 | 1998-05-06 | Th Goldschmidt Ag | Polyglycerol partial ester of saturated or unsaturated linear or branched-chain fatty acid and polyfunctional carboxylic acid, its production and w/o-type emulsifying agent and dispersion assistant composed thereof |
| JP2007210961A (en) * | 2006-02-10 | 2007-08-23 | Nippon Shokubai Co Ltd | Method for producing glycerol carboxylic acid diester |
| JP2013194209A (en) * | 2012-03-22 | 2013-09-30 | Daicel Corp | Detergent composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE791534A (en) * | 1971-11-18 | 1973-05-17 | Oreal | |
| JPH06271895A (en) * | 1993-03-18 | 1994-09-27 | Lion Corp | Liquid detergent composition |
| JP3301182B2 (en) * | 1993-11-24 | 2002-07-15 | 三菱化学株式会社 | Method for producing polyglycerin fatty acid ester |
| JPH09249615A (en) * | 1996-03-18 | 1997-09-22 | Daicel Chem Ind Ltd | Polygrycerol monofatty acid ester and its production |
| US8785508B2 (en) * | 2009-06-18 | 2014-07-22 | Kaneka Corporation | Pre-expanded polypropylene resin beads and process for producing same |
| JP2011168548A (en) * | 2010-02-19 | 2011-09-01 | Toyobo Co Ltd | Oil-in-water type emulsified cosmetic |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03129716A (en) * | 1989-10-14 | 1991-06-03 | Nippon Chemicon Corp | Electrolyte for electrolytic capacitor |
| JPH10114707A (en) * | 1996-10-09 | 1998-05-06 | Th Goldschmidt Ag | Polyglycerol partial ester of saturated or unsaturated linear or branched-chain fatty acid and polyfunctional carboxylic acid, its production and w/o-type emulsifying agent and dispersion assistant composed thereof |
| JP2007210961A (en) * | 2006-02-10 | 2007-08-23 | Nippon Shokubai Co Ltd | Method for producing glycerol carboxylic acid diester |
| JP2013194209A (en) * | 2012-03-22 | 2013-09-30 | Daicel Corp | Detergent composition |
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