JP6004397B2 - Method for producing sucrose fatty acid ester - Google Patents

Description

  The present invention relates to a method for producing a sucrose fatty acid ester mixture rich in sucrose difatty acid ester (degree of esterification 2) or sucrose trifatty acid ester (degree of esterification 3). The present invention relates to an efficient method for producing a mixture of sucrose fatty acid esters rich in the content of sucrose difatty acid ester or sucrose trifatty acid ester that is suitably used for cosmetics, pharmaceuticals, foods, etc., particularly for cake mixes.

The sucrose fatty acid ester is obtained by esterifying an arbitrary hydroxyl group with a fatty acid among the eight hydroxyl groups contained in the sucrose molecule. The degree of esterification of a sucrose fatty acid ester is determined by the number of esterified hydroxyl groups. For example, a sucrose fatty acid ester having a degree of esterification of 2 means that two hydroxyl groups are esterified. Since sucrose fatty acid esters have good safety and biodegradability, they have been conventionally used as surfactants, emulsifiers, food additives, cosmetic materials and the like.
Sucrose fatty acid esters are usually produced by reacting sucrose with fatty acids or fatty acid alkyl esters. For example, in Non-Patent Document 1, sucrose fatty acid ester is produced by reacting sucrose with fatty acid methyl. Patent Document 1 discloses that sucrose is reacted with fatty acid methyl, and sucrose is further reacted to have a sucrose mono-fatty acid ester content of 38% by mass or more, and both sucrose di-fatty acid ester and sucrose tri-fatty acid ester content. It is described that a low sucrose fatty acid ester mixture was obtained (see Tables 1 and 3).
On the other hand, in Patent Document 2, lauric acid and a lipase enzyme derived from Candida cylindracea are added to a solution in which sucrose is dissolved in water and reacted, so that the monoester is about 20%, the diester is about 45%, and the triester is about It is described that a 35% sucrose fatty acid ester mixture was obtained (Example 3). Also, Example 2 of Patent Document 3 describes that a sucrose fatty acid ester mixture having about 20% monoester, about 45% diester, and about 35% triester was obtained.
Since the characteristics of sucrose fatty acid esters vary depending on the degree of esterification, various methods for obtaining sucrose fatty acid ester mixtures rich in a specific degree of esterification have been proposed. For example, Patent Document 4 discloses 5 to 14% by weight of a monoester component having an esterification degree of 1, 55 to 65% by weight of a diester component having an esterification degree of 2, and 26 to 35 of an ester component having an esterification degree of 3 or more. Although a sucrose fatty acid ester consisting of% by weight is disclosed, such a sucrose fatty acid ester mixture is fractionated from a reaction product obtained by an ordinary synthesis method using a column or the like, and the fraction is appropriately selected. By combining and mixing, a plurality of commercially available sucrose fatty acid esters may be mixed and mixed, or a commercially available sucrose fatty acid ester may be fractionated using a column or the like, and the fractions may be combined in an appropriate combination. It is described that it can be obtained. Also, Patent Document 5 discloses a sucrose fatty acid ester mixture containing 55 to 65% by weight of a diester component having a degree of esterification of 2, which, as in Patent Document 4, is a component using a column or the like. It is described that it was obtained by painting.

JP 2006-169237 A Japanese Patent Application Laid-Open No. 7-115983 JP-A-9-71594 JP 2009-214079 A JP 2009-215262 A

"Sugar ester story", published by Daiichi Kogyo Seiyaku Co., Ltd., 1984, pages 35 and 40-41

  An object of the present invention is to provide an efficient method for producing a sucrose fatty acid ester mixture rich in the content of sucrose difatty acid ester or sucrose trifatty acid ester.

In the present invention, among the sucrose fatty acid ester mixture produced by a normal production method, the content of sucrose monofatty acid ester is large and above a specific value, while the content of sucrose difatty acid ester and sucrose trifatty acid ester is Sucrose fatty acid ester rich in sucrose difatty acid ester or sucrose trifatty acid ester content by selecting a small sucrose fatty acid ester mixture that is smaller than a specific value and subjecting it to an enzymatic reaction together with fatty acid or its lower alkyl ester This is based on the knowledge that a mixture can be efficiently produced and the above problems can be solved.
That is, in the present invention, the sucrose monofatty acid ester content is 38% by mass or more based on at least one compound selected from the group consisting of fatty acids and C1-C6 alkyl esters of fatty acids and all sucrose fatty acid ester components. The sucrose fatty acid ester mixture in which both the sucrose difatty acid ester and the sucrose trifatty acid ester content are 40% by mass or less are subjected to an enzymatic reaction, with respect to the total sucrose fatty acid ester component in the sucrose fatty acid ester mixture Provided is a method for producing a sucrose fatty acid ester mixture in which either the sucrose difatty acid ester content or the sucrose trifatty acid ester content is 47% by mass or more.

According to the present invention, a sucrose fatty acid ester mixture rich in the content of sucrose difatty acid ester or sucrose trifatty acid ester is efficiently obtained by simple means without using a complicated process such as fractionation using a column or the like. Therefore, the production method of the present invention is excellent as an industrial production method.
Furthermore, the sucrose fatty acid ester mixture rich in the content of the sucrose difatty acid ester produced by the production method of the present invention is easy to make a lamellar liquid crystal and is easy to stabilize O / W emulsification. Can function as an emulsifier.

A sucrose fatty acid ester mixture having a sucrose monofatty acid ester content of 38% by mass or more and a sucrose difatty acid ester content and a sucrose trifatty acid ester content of 40% by mass or less based on the total sucrose fatty acid ester component used in the present invention, It can be easily manufactured by the methods described in Patent Document 1 and Non-Patent Document 1. Ryoto Sugar Ester S-1670 (Mitsubishi Chemical Foods Co., Ltd.), Ryoto Sugar Ester S-770 (Mitsubishi Chemical Foods Co., Ltd.), DK Ester F-160 (Daiichi Kogyo Seiyaku Co., Ltd.), DK Ester It can also be obtained as a commercial product such as F-110 (Daiichi Kogyo Seiyaku Co., Ltd.).
Among these, the sucrose monofatty acid ester content is 40% by mass or more (more preferably 50% by mass or more, most preferably 55 to 85% by mass) with respect to the total sucrose fatty acid ester component, and sucrose difatty acid ester and sucrose trifatty acid. It is preferable to use a sucrose fatty acid ester mixture having an ester content of 37% by mass or less (more preferably 20% by mass or less, more preferably 45% by mass or less, particularly 10 to 30% by mass).

Here, aliphatic carboxylic acid is mentioned as a fatty acid which comprises sucrose fatty acid ester. As the aliphatic carboxylic acid, a linear saturated aliphatic carboxylic acid, a linear unsaturated aliphatic carboxylic acid, a branched chain of an aliphatic carboxylic acid having 2 to 22, preferably 8 to 22, and more preferably 14 to 22 carbon atoms is used. Chain saturated aliphatic carboxylic acids and mixtures thereof can be used. Examples include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, palmitooleic acid, oleic acid, elaidic acid, linoleic acid Linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, arachidonic acid, erucic acid, acetic acid, isobutyric acid and the like, but are not limited thereto.
Preferred are palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and erucic acid.
In the present invention, it is particularly preferable that the constituent fatty acid of the total sucrose fatty acid ester is a linear saturated aliphatic carboxylic acid having 14 to 22 carbon atoms and a linear unsaturated fatty acid having 14 to 22 carbon atoms. Most preferred are palmitic acid, stearic acid, behenic acid, oleic acid and the like.

As the fatty acid in at least one compound selected from the group consisting of a fatty acid used in the reaction and an alkyl ester having 1 to 6 carbon atoms of the fatty acid, the same fatty acid as that constituting the sucrose fatty acid ester is preferably used. However, a different fatty acid may be used.
As a C1-C6 alkylester of a fatty acid, a C1-C3 alkylester is preferable.
The ratio of at least one compound selected from the group consisting of raw sucrose fatty acid ester mixture to fatty acid and fatty acid and C1-C6 alkyl ester is preferably 1/10 to 10/1 by mass ratio, 1/5 to 5/1 is more preferable, and 1/2 to 2/1 is particularly preferable.

In this invention, the enzyme which can contribute to the enzyme reaction which increases content of the sucrose difatty acid ester or the sucrose trifatty acid ester with respect to all the sucrose fatty acid ester components in the raw material sucrose fatty acid ester mixture can be used. As such an enzyme, lipase is preferable. Examples thereof include lipoprotein lipase, monoacyl glycero lipase, diacyl glycero lipase, triacyl glycero lipase, galacto lipase, and phospho lipase. Of these, triacylglycerolipase is preferred.
Microorganisms that produce these lipases are not particularly limited to bacteria, yeasts, filamentous fungi, actinomycetes, and the like, but include Algenigenes sp., Pseudomonas sp., Arthrobacter. sp.), Staphylococcus sp., Torulopsis sp., Escherichia sp., Mycotorula sp., Propionibacterium, Propionibacterum. Bacteria (Chromobacterium sp.), Xanthomonas (L.), Lactobacillus (Lacto) Bacillus sp.), Clostridium sp., Candida sp., Geotrichum sp., Saccharomycopsis sp., Nocardia sp. ), Fuzarium sp., Aspergillus sp., Rhizomucor sp., Mucor sp., Thermomyces sp., Rhizopus p. Genus (Penicillium sp.), Phycomyces sp., Puccinia sp. , The genus Bacillus (Bacillus sp.), The genus Streptomyces (Streptmyces sp.) And the like.
In the present invention, among these, lipases derived from Alkaligenes, Pseudomonas, Candida, Aspergillus, Rhizomucor, Mucor, Thermomyces, Rhizopus, or Penicillium are preferred. Of these, lipases of the genus Thermomyces, Candida or Rhizopus are particularly preferred.

The lipase used in the present invention may or may not have positional specificity. When it has position specificity, it is preferably 1,3-specificity.
The lipase used in the present invention may be obtained by culturing and drying a lipase-containing aqueous liquid containing a lipase medium component or the like, but it does not contain these, that is, the lipase itself substantially. What is comprised from this is preferable. As the lipase that can be used in the present invention, a lipase-containing aqueous liquid or a powder containing lipase can be used. For example, a lipase-containing aqueous liquid produced by removing cells after culturing lipase, immobilized, or further powdered is more preferable.

  Immobilized lipase should be lipase immobilized on a carrier such as silica, celite, diatomaceous earth, pearlite, polyvinyl alcohol, anion exchange resin, phenol adsorption resin, hydrophobic carrier, cation exchange resin, chelate resin, etc. Can do. Such an immobilized lipase is not particularly limited. For example, the product Lipozyme TLIM of Novozymes Japan Ltd., derived from Thermomyces lanuginosus, derived from Candida antarctica (Candida antarctica) Novozymes Japan Co., Ltd. product Novozyme 435, Amano Enzyme Co., Ltd. product lipase DN “Amano” 50 derived from Rhizopus oryzae. The immobilized lipase can be used as it is, or one obtained by pulverizing the immobilized lipase can be used.

The powdered lipase is obtained by drying and pulverizing a lipase-containing aqueous liquid by a method such as spray drying, freeze drying, drying after solvent precipitation, and is not particularly limited. For example, Candida rugosa Products from Amano Enzyme, Inc .: Lipase AY “Amano” 50G, Rhizopus oryzae-derived lipase DF “Amano” 15 and the like can be used.
In the present invention, at least one compound selected from the group consisting of raw materials of sucrose fatty acid ester mixture and fatty acid and C1-C6 alkyl ester of fatty acid is dissolved in an organic solvent for dissolving them, and an enzyme, preferably The lipase should be added to the enzyme reaction. The reaction is preferably performed at an optimal enzyme temperature and a raw material dissolution temperature, for example, 30 to 100 ° C. for about 2 to 150 hours, more preferably at 40 to 80 ° C. for about 3 to 100 hours. Let The reaction is preferably performed, for example, with stirring under normal pressure.
At this time, the water content in the reaction system is preferably about 10 to 2000 ppm, preferably about 100 to 1500 ppm, more preferably about 200 to 1000 ppm. In particular, it is preferable to perform a dehydration operation in the reaction step so that the water content in the reaction system at the end of the reaction is about 200 to 1000 ppm.

  As the organic solvent used in the reaction, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), methyl ethyl ketone, isooctane, acetone, xylene, toluene, hexane, chloroform, chlorobenzene, or the like can be used. The solvent only needs to have an amount capable of dissolving the sucrose fatty acid ester mixed raw material to some extent, and DMSO, DMF, ketone-based, and alcohol-based solvents are preferable because they can also dissolve the sucrose fatty acid ester. Particularly preferred are tertiary alcohols having 4 to 10 carbon atoms, such as t-pentyl alcohol, from the viewpoint of suppressing enzyme deactivation. For example, 0.5 to 30 ml, preferably 1 to 20 ml, more preferably 2 to 5 ml may be added to 1 g of the sucrose fatty acid ester mixture raw material. As the lipase, the lipase described above and optionally an auxiliary agent can be used. For example, the lipase is preferably added in an amount of 0.01 to 20% by mass with respect to the sucrose fatty acid ester mixture raw material.

In the present invention, the sucrose fatty acid ester in which either the sucrose difatty acid ester content or the sucrose trifatty acid ester content is 47% by mass or more based on the total sucrose fatty acid ester component in the sucrose fatty acid ester mixture by subjecting to the enzyme reaction described above. Mixtures can be produced. In particular, the sucrose monofatty acid content is preferably 33% by mass or less, more preferably 28% by mass or less based on the total sucrose fatty acid ester component, and the sucrose difatty acid ester or sucrose trifatty acid ester is based on the total sucrose fatty acid ester component. A sucrose fatty acid ester mixture in which any of the contents is preferably 52% by mass or more, more preferably 55% by mass or more can be obtained. Further, preferably, the total content of sucrose difatty acid ester and sucrose trifatty acid ester is 65% by mass or more, more preferably 70% by mass or more based on the total sucrose fatty acid ester component. Also, a sucrose fatty acid ester mixture having a sucrose monofatty acid ester content of 5% by mass or less, a sucrose difatty acid ester content of 20-30% by mass, and a sucrose trifatty acid ester content of 55-70% by mass with respect to the total sucrose fatty acid ester component. Can be manufactured.
These sucrose fatty acid ester mixtures can be separated from the reaction system by means of filtration, extraction and removal after completion of the enzyme reaction. For example, it can be purified by the method of Patent Document 1. Moreover, in order to improve the handling property of a sucrose fatty acid ester mixture, fats and oils, water, alcohol, etc. can be mixed suitably as needed, and also in order to improve an emulsification characteristic and storage stability, other emulsifiers , Thickeners, antioxidants and the like can be mixed as appropriate.

Next, the present invention will be specifically described with reference to examples and comparative examples.
[Method for measuring ester composition of sucrose fatty acid ester]
Composition analysis of all sucrose fatty acid ester components contained in the sucrose fatty acid ester mixture was performed using high performance liquid chromatography. Specifically, a GPC column was used to measure the composition of sucrose fatty acid esters having an esterification degree of 1, 2, 3 and an esterification degree of 4 or more. Moreover, the ratio of the sucrose with respect to the sucrose fatty acid ester mixture was analyzed using the gas chromatography. The analysis conditions used are shown below.
GPC column analysis conditions Detector: Shodex differential refractometer RI-74
Column (two connected columns 1 and 2): (Column 1) PL-gel (manufactured by Polymer Laboratories) Particle size 5 μm Pore diameter 10 nm 300 mm × 7.5 mm, (Column 2) PL-gel (Polymer Laboratories) Manufactured) particle size 5μm pore size 50nm 300mm × 7.5mm
Column temperature: 30 ° C
Eluent: Special grade tetrahydrofuran (containing stabilizer)
Flow rate: 0.6 mL / min Injection volume: 10 μL
Analysis time: 43 minutes

Gas chromatography analysis conditions Detector FID 380 ° C
Column DB-1ht 5m × 320μm × 0.10μm
Column temperature 100 ° C. → 12.5 ° C./min→380° C. 5 min
Flow rate 7.1 mL / min He
Inlet 390 ° C Split ratio 50: 1
Injection volume 1μL

[Example 1]
As the lipase, Lipozyme TLIM (manufactured by Novozymes Japan Ltd .: derived from Thermomyces lanogeneus), which is an immobilized lipase, was used. As a raw material sucrose fatty acid ester mixture, Ryoto sugar ester S-1670 (HLB = 16, manufactured by Mitsubishi Chemical Foods, Ltd., less than 1% by mass of free sucrose, ester composition (based on the total sucrose fatty acid ester component): monoester 79 wt%, diester 19 wt%, triester 2 wt%). In addition, stearic acid (special grade stearic acid: manufactured by Junsei Chemical Co., Ltd.) was prepared as a fatty acid. 2 g of stearic acid and 1 g of sucrose fatty acid ester mixture were put into a sample bottle (20 g capacity), and 2 mL of t-pentyl alcohol (special grade t-pentyl alcohol: manufactured by Kanto Chemical Co., Ltd.) was added and dissolved at 80 ° C. ( Water content of the reaction system: about 1200 ppm at the start of the reaction, about 1600 ppm at the end of the reaction).
Here, 0.1 g of lipozyme TLIM was added, and the sample bottle was reacted with stirring with a stirrer while keeping the temperature at 80 ° C. When the sucrose fatty acid ester composition of the product after 22 hours of reaction was measured, it was found that the total sucrose fatty acid ester component was 32 wt% monoester, 54 wt% diester, 13 wt% triester, and 1 wt% over tetraester. It was.

[Example 2]
As the lipase, the product (sucrose fatty acid ester mixture) was prepared in the same manner as in Example 1 except that Novozyme 435 (manufactured by Novozymes Japan Ltd .: derived from Candida antarctica), which is an immobilized lipase, was used. Obtained (water content of the reaction system: about 1200 ppm at the start of the reaction, about 1800 ppm at the end of the reaction). When the sucrose fatty acid ester composition after 98 hours of reaction was measured, it was 24% by weight of monoester, 58% by weight of diester, 17% by weight of triester, and 1% by weight of tetraester or more based on the total sucrose fatty acid ester component.

[Example 3]
A product was obtained in the same manner as in Example 2 except that the molecular sieve was placed in a sample bottle and reacted while dehydrating (water content of the reaction system: about 1200 ppm at the start of the reaction, about 400 ppm at the end of the reaction). When the sucrose fatty acid ester composition after 46 hours of reaction was measured, it was 21% by weight of monoester, 65% by weight of diester, and 14% by weight of triester with respect to the total sucrose fatty acid ester component.

[Example 4]
A product was obtained in the same manner as in Example 3 except that lipase DN “Amano” 50 (manufactured by Amano Enzyme Inc .: derived from Rhizopus oryzae) was used as the lipase (moisture content of the reaction system: at the start of the reaction) About 1200 ppm, about 800 ppm at the end of the reaction). When the sucrose fatty acid ester composition after 46 hours of reaction was measured, it was found to be 2% by weight of monoester, 24% by weight of diester, 61% by weight of triester, and 13% by weight of tetraester or more based on the total sucrose fatty acid ester component.

[Example 5]
Ryoto sugar ester S-770 (HLB = 7, manufactured by Mitsubishi Chemical Foods Co., Ltd., ester composition: 41% by weight of monoester, 35% by weight of diester, 17% by weight of triester, 7 or more of tetraester as raw material sucrose fatty acid ester mixture The product was obtained in the same manner as in Example 1 except that (% by weight) was used (water content of the reaction system: about 1200 ppm at the start of the reaction, about 1400 ppm at the end of the reaction). When the sucrose fatty acid ester composition after 6 hours of reaction was measured, it was found to be 26% by weight of monoester, 49% by weight of diester, 21% by weight of triester, and 4% by weight of tetraester or more based on the total sucrose fatty acid ester component.

この結果から、本発明によれば、蔗糖脂肪酸エステル混合物中の蔗糖ジ脂肪酸エステル又は蔗糖トリ脂肪酸エステル含量のいずれかが４７質量％以上である蔗糖脂肪酸エステル混合物を、簡易にかつ効率的に製造できることがわかる。 [Comparative Example 1]
A product was obtained in the same manner as in Example 2 except that sucrose was used as a raw material (water content of the reaction system: about 800 ppm at the start of the reaction, about 900 ppm at the end of the reaction). When the ester composition after 94 hours of reaction was measured, it was 98% of unreacted sucrose, 1% by weight of diester, and 1% by weight of triester.
The results are summarized in Table 1.
Table 1

From this result, according to the present invention, it is possible to easily and efficiently produce a sucrose fatty acid ester mixture in which either the sucrose difatty acid ester or the sucrose trifatty acid ester content in the sucrose fatty acid ester mixture is 47% by mass or more. I understand.

Claims (5)

  At least one compound selected from the group consisting of fatty acids and fatty acid alkyl esters having 1 to 6 carbon atoms, and a sucrose monofatty acid ester content of 38% by mass or more based on the total sucrose fatty acid ester component, A sucrose difatty acid ester or a sucrose with respect to the total sucrose fatty acid ester component in the sucrose fatty acid ester mixture, wherein the sucrose fatty acid ester mixture having a sucrose trifatty acid ester content of 40% by mass or less is subjected to an enzymatic reaction A method for producing a sucrose fatty acid ester mixture in which any of the tri fatty acid ester contents is 47% by mass or more.   The production method according to claim 1, wherein lipase is used as the enzyme.   The production method according to claim 2, wherein a lipase derived from the genus Alkagenes, Pseudomonas, Candida, Aspergillus, Rhizomucor, Mucor, Thermomyces, Rhizopus or Penicillium is used as the lipase.   The manufacturing method of any one of Claims 1-3 which perform an enzyme reaction in the organic solvent which can melt | dissolve the reaction raw material.   The method according to claim 4, wherein the organic solvent is a tertiary alcohol having 4 to 10 carbon atoms.