JP6459115B2 - Modified sucrose fatty acid ester mixture and method for producing the same - Google Patents

Description

  The present invention relates to a method for producing a modified sucrose fatty acid ester mixture and a modified sucrose fatty acid ester mixture obtained thereby. Specifically, the present invention is to hydrolyze a sucrose fatty acid ester mixture raw material in the presence of a specific lipase to produce a sucrose difatty acid ester in which a fatty acid is bonded to positions 4 and 6 of the sucrose. The present invention relates to a method for producing a modified sucrose fatty acid ester mixture, a modified sucrose fatty acid ester mixture obtained by the method, and a food containing the modified sucrose fatty acid ester mixture.

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. 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.
Here, the sucrose fatty acid ester has a degree of esterification of 1-8. The degree of esterification is determined by the number of esterified hydroxyl groups. For example, a sucrose fatty acid ester having a degree of esterification of 6 means that 6 hydroxyl groups are esterified. Among these, sucrose fatty acid esters having a degree of esterification of 2 and rich in diesters are required in the fields of cosmetics, pharmaceuticals, foods and the like. In particular, since the physical action such as emulsification may differ depending on the bonding position of fatty acid, the bonding position selectivity of diester is regarded as important.
However, in the method of obtaining a sucrose fatty acid ester by a chemical reaction, it was difficult to prepare a diester-containing sucrose fatty acid ester having a desired regioselectivity (Patent Document 1).

JP 2009-215262 A

An object of the present invention is to produce a sucrose difatty acid ester in which a fatty acid is selectively bonded to the 4th and 6th positions of the sucrose from a sucrose fatty acid ester mixture raw material.
The present invention also provides a modified sucrose fatty acid ester mixture comprising a sucrose difatty acid ester in which a fatty acid is selectively bonded to positions 4 and 6 of sucrose as described above, and the modified sucrose fatty acid. The object is to provide a food product comprising an ester mixture.

In order to achieve the above object, the present inventors include a large amount of a sucrose fatty acid ester having a low degree of esterification as a starting material and a small amount of a sucrose fatty acid ester having a high degree of esterification, for example, a sucrose fatty acid having a degree of esterification of 6-8. By selecting a specific sucrose fatty acid ester mixture raw material whose ester is about 40% by mass or less based on the total sucrose fatty acid ester, and hydrolyzing the raw material in the presence of a lipase that does not exhibit 1,3-specificity. The present inventors have found that a sucrose difatty acid ester in which a fatty acid is bonded to positions 4 and 6 of sucrose can be produced, and the present invention has been achieved. That is, the present invention can include the following aspects.
[1] A sucrose fatty acid ester having an esterification degree of 3 to 5 is 1% by mass or more based on the total sucrose fatty acid ester, and a sucrose fatty acid ester having an esterification degree of 6 to 8 is 0 to the total sucrose fatty acid ester. The sucrose fatty acid ester mixture raw material containing ˜40% by mass is hydrolyzed in the presence of lipase that does not exhibit 1,3-specificity, and contains a sucrose difatty acid ester in which a fatty acid is bonded to positions 4 and 6 of sucrose. A method for producing the modified sucrose fatty acid ester mixture, characterized by obtaining a modified sucrose fatty acid ester mixture.
[2] The total sucrose fatty acid ester contained in the modified sucrose fatty acid ester mixture has a mass of sucrose difatty acid ester in which fatty acids are bonded to positions 4 and 6 of the sucrose contained in the modified sucrose fatty acid ester mixture. The method according to [1] above, which is 20% by mass or more based on the mass of
[3] The mass of the sucrose fatty acid ester having a degree of esterification of 6 to 8 contained in the sucrose fatty acid ester mixture raw material is 10% by mass or less based on the mass of the total sucrose fatty acid ester contained in the sucrose fatty acid ester mixture raw material. The method according to [1] or [2] above.
[4] The method according to any one of [1] to [3], wherein the sucrose fatty acid ester mixture raw material has an HLB value of 4 to 15.
[5] The lipase is a lipase derived from Candida rugosa, a lipase derived from Rhizopus oryzae, and a lipase selected from the group consisting of 1 or more species derived from Thermomyces lanuginosus. The method according to any one of [1] to [4].
[6] The above [1] to [5], wherein the constituent fatty acid of the sucrose difatty acid ester in which a fatty acid is bonded to positions 4 and 6 of the sucrose is a linear saturated aliphatic carboxylic acid having 14 to 22 carbon atoms. The method of any one of these.
[7] The method according to any one of [1] to [6], wherein the hydrolysis is performed in a mixture of water and an organic hydrophobic solvent.
[8] A modified sucrose fatty acid ester mixture obtained by the method according to any one of [1] to [7] and comprising a sucrose difatty acid ester in which a fatty acid is bonded to positions 4 and 6 of sucrose The mass of the sucrose difatty acid ester in which a fatty acid is bonded to positions 4 and 6 of the sucrose is 20% by mass or more based on the mass of the total sucrose fatty acid ester contained in the modified sucrose fatty acid ester mixture. A modified sucrose fatty acid ester mixture.
[9] A food containing the modified sucrose fatty acid ester mixture according to [8].

More specifically, the present invention may include the following aspects.
[A] All sucrose fatty acid esters having a degree of esterification of 3-5 with respect to the total sucrose fatty acid ester, containing 1% by mass or more of the total sucrose fatty acid ester, and having a degree of esterification of 6-8 A sucrose fatty acid ester mixture raw material containing 0 to 40% by mass with respect to sucrose fatty acid ester includes lipase derived from Candida rugosa, lipase derived from Rhizopus oryzae, and Thermomyces langus Hydrolyzed at a temperature of 40-60 ° C. in the presence of a lipase that is selected from the group consisting of 1 and 3-specificity and has 14 to 22 carbon atoms at positions 4 and 6 of sucrose. Fatty acids selected from linear saturated aliphatic carboxylic acids bind A modified sucrose fatty acid ester mixture containing sucrose difatty acid ester, wherein a fatty acid is bonded to positions 4 and 6 of the sucrose contained in the modified sucrose fatty acid ester mixture The manufacturing method of the modified sucrose fatty acid ester mixture whose mass of ester is 20 mass% or more with respect to the mass of the total sucrose fatty acid ester contained in the said modified sucrose fatty acid ester mixture.
[B] A modified sucrose fatty acid ester mixture obtained by the method of [A] and containing a sucrose difatty acid ester in which a fatty acid is bonded to positions 4 and 6 of the sucrose, The modified sucrose fatty acid ester mixture, wherein the mass of the sucrose difatty acid ester having fatty acid bonded to the 6-position is 20% by mass or more based on the total sucrose fatty acid ester contained in the modified sucrose fatty acid ester mixture.
[C] A food containing the modified sucrose fatty acid ester mixture.

  According to the present invention, a sucrose fatty acid ester mixture raw material containing a large amount of a sucrose fatty acid ester having a low esterification degree as a starting material, that is, 1% by mass of a sucrose fatty acid ester having an esterification degree of 3 to 5 with respect to the total sucrose fatty acid ester The sucrose fatty acid ester mixture raw material containing 0 to 40% by mass of the sucrose fatty acid ester having a degree of esterification of 6 to 8 with respect to the total sucrose fatty acid ester is hydrolyzed in the presence of a specific lipase to obtain sucrose Thus, a modified sucrose fatty acid ester mixture containing a sucrose difatty acid ester in which fatty acids are bonded to positions 4 and 6 can be obtained. In the production of the sucrose difatty acid ester, fatty acids are bonded to positions 4 and 6 of the sucrose contained in the modified sucrose fatty acid ester mixture with respect to the mass of the total sucrose fatty acid ester contained in the modified sucrose fatty acid ester mixture. The ratio of the mass of sucrose difatty acid ester can be 20 mass% or more, for example, Preferably it is 23 mass% or more. The modified sucrose fatty acid ester mixture thus obtained can be preferably used as a good surfactant for emulsification use, an oil absorption inhibitor for foods, a fat and oil crystal modifier, and the like.

The mass% (ester concentration [mass%]) of the sucrose fatty acid ester of each esterification degree 1-8 with respect to the total sugar fatty acid ester in the modified sucrose fatty acid ester mixture obtained in Example 1 is shown. The mass% (ester concentration [mass%]) of the sucrose fatty acid ester of each esterification degree 1-8 with respect to the total sugar fatty acid ester in the modified sucrose fatty acid ester mixture obtained in Example 2 is shown.

<Method for producing modified sucrose fatty acid ester mixture>
One embodiment of the present invention includes a sucrose fatty acid ester having a degree of esterification of 3 to 5% by mass based on the total sucrose fatty acid ester, and a sucrose fatty acid ester having a degree of esterification of 6 to 8 Hydrolysis of a sucrose fatty acid ester mixture raw material containing 0 to 40% by mass with respect to the ester in the presence of a specific lipase to contain a sucrose difatty acid ester in which a fatty acid is bonded to positions 4 and 6 of the sucrose A method for producing a modified sucrose fatty acid ester mixture, characterized in that a sucrose fatty acid ester mixture is obtained. Hereinafter, the manufacturing method will be described in detail.
<Rose sugar fatty acid ester mixture raw material>
The sucrose fatty acid ester mixture raw material is a mixture containing a plurality of sucrose fatty acid esters having different degrees of esterification, which is used as a raw material in the method for producing the modified sucrose fatty acid ester mixture of the present invention. The sucrose fatty acid ester is an ester in which an arbitrary number of 1 to 8 fatty acids are bonded to 8 hydroxyl groups of sucrose. Depending on the number of bound fatty acids (ie constituent fatty acids), sucrose fatty acid esters exist from 1-substituted (monoester) to 8-substituted (octaester). The esterification degree of the sucrose fatty acid ester indicates the number of the constituent fatty acids, and the 1-substituted product is expressed as 1 degree of esterification and the 8-substituted product is expressed as 8 degree of esterification.

The sucrose fatty acid ester mixture raw material that can be used in the present invention is preferably a sucrose fatty acid ester mixture containing a large amount of sucrose fatty acid ester having a low degree of esterification. Specifically, in the sucrose fatty acid ester mixture raw material, the sucrose fatty acid ester having a degree of esterification of 1 to 2 is preferably 99% by mass or less, more preferably 30 to 98% by mass, based on the total sucrose fatty acid ester. More preferably, it is contained in an amount of 40 to 98% by mass, particularly preferably 50 to 90% by mass. Moreover, it is preferable that the ratio of the sucrose fatty acid ester of the degree of esterification 3-5 in the sucrose fatty acid ester mixture raw material is 1 mass% or more with respect to the total sucrose fatty acid ester in the sucrose fatty acid ester mixture raw material. It is appropriate to contain 2 to 70% by mass, more preferably 5 to 50% by mass, and most preferably 10 to 30% by mass. Furthermore, the ratio of the sucrose fatty acid ester having a degree of esterification of 6 to 8 in the sucrose fatty acid ester mixture raw material to the total sucrose fatty acid ester in the sucrose fatty acid ester mixture raw material is preferably 0 to 40% by mass. 1 to 40% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, particularly preferably 0 to 3% by mass. It is suitable to contain.
The ratio of sucrose fatty acid esters having a degree of esterification of 1 to 3 in the sucrose fatty acid ester mixture raw material is 70% by mass or more, preferably 80% by mass or more, based on the total sucrose fatty acid ester in the sucrose fatty acid ester mixture raw material. The ratio is preferably 90 or more, and the ratio is preferably 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less.
Further, the mass ratio of [sucrose fatty acid ester having a degree of esterification of 1] / [sucrose fatty acid ester having a degree of esterification of 2] in the raw material of the mixture of sucrose fatty acid esters is, for example, 1/2 to 5/1, preferably 1. / 1 to 4/1, more preferably 1.2 / 1 to 3.5 / 1.

（式（Ｉ）及び（ＩＩ）中、Ａ₁及びＡ₂は、それぞれ独立に１価の脂肪酸基（構成脂肪酸）である。） In the sucrose difatty acid ester originally contained in the sucrose fatty acid ester mixture raw material of the present invention, there is almost no sucrose difatty acid ester in which a fatty acid is bonded to positions 4 and 6 of sucrose. The amount of sucrose difatty acid ester in which fatty acids are bonded to the 4th and 6th positions of sucrose with respect to the total mass of sucrose difatty acid ester having a degree of esterification of 2 contained in the raw material for sucrose fatty acid ester mixture of the present invention is usually 10 It is not more than mass%, preferably not more than 5 mass%, more preferably 0 to 3 mass%. On the other hand, the sucrose difatty acid ester normally contained in the sucrose fatty acid ester mixture raw material is a sucrose difatty acid ester in which a fatty acid is bonded to the 6,6 ′ positions. The amount of sucrose difatty acid ester in which a fatty acid is bonded to the 6,6′-position of sucrose with respect to the total mass of sucrose difatty acid ester having a degree of esterification of 2 contained in the sucrose fatty acid ester mixture raw material of the present invention is usually It is 90 mass% or more, preferably 95 mass% or more, more preferably 97 to 100 mass%. Here, the structural formula (I) of the sucrose difatty acid ester in which a fatty acid is bonded to the 6,6′-position, and the sucrose disaccharide in which a fatty acid is bonded to the 4,6-position of the sucrose focused in the present invention The structural formula (II) of the fatty acid ester is shown below.

(In formulas (I) and (II), A ₁ and A ₂ are each independently a monovalent fatty acid group (constituent fatty acid).)

Examples of constituent fatty acids of the sucrose fatty acid ester (for example, fatty acids constituting the A ₁ and A ₂ groups of the above formulas (I) and (II)) include aliphatic carboxylic acids. 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, oleic acid, linoleic acid, linolenic acid, and erucic acid.
In the present invention, it is particularly preferable that the constituent fatty acid of the sucrose fatty acid ester is a linear aliphatic carboxylic acid having 14 to 22 carbon atoms. Most preferred are linear aliphatic carboxylic acids such as stearic acid, oleic acid, palmitic acid, erucic acid and behenic acid. In this case, the constituent fatty acid other than the straight chain aliphatic carboxylic acid having 14 to 22 carbon atoms can also be included, but the constituent fatty acid other than the straight chain aliphatic carboxylic acid having 14 to 22 carbon atoms is 50% by mass. Is preferably less than 0, more preferably 0 to 40% by mass, still more preferably 0 to 10% by mass, and most preferably 0 to 5% by mass.
Particularly preferred is a combination of palmitic acid and stearic acid. More preferably, the mass ratio of palmitic acid: stearic acid is 20-40: 80-60, more preferably 25: 35: 75-65, and even more preferably 30:70.
The type of constituent fatty acid may be the same or different depending on the type of sucrose fatty acid ester. When a plurality of fatty acid esters are contained in one sucrose fatty acid ester, each constituent fatty acid in the sucrose fatty acid ester is the same or different. May be. For example, the sucrose difatty acid esters of the above formulas (I) and (II) contained in the sucrose fatty acid ester mixture raw material may have the same fatty acid ester or different fatty acid esters. Further, the fatty acids constituting A ₁ and A ₂ of the sucrose difatty acid ester (II) in which fatty acids are bonded to the 4th and 6th positions of the sucrose to which the present invention is focused may be the same or different. However, it is preferable that the fatty acids constituting the total sucrose fatty acid ester are the same.

<HLB value>
HLB is an abbreviation for Hydrophile Lipophile Balance and serves as an index for knowing whether an emulsifier is hydrophilic or lipophilic, and takes a value of 0 to 20. It shows that lipophilicity is so strong that an HLB value is small. In the present invention, a Griffin calculation method is used. The calculation method of Griffin is:
Griffin formula: HLB = 20 × {(molecular weight of hydrophilic portion) / (total molecular weight)}
The method of calculating the value of HLB from the above. In the formula, the hydrophilic part means a part obtained by removing the hydrocarbon chain of the constituent fatty acid from the whole sucrose fatty acid ester molecule.
In the present invention, the HLB value of the sucrose fatty acid ester mixture raw material can take any value, but it is, for example, 3 or more, preferably 4-15.

<Lipase>
Lipases that can be used in the present invention are lipases that do not exhibit 1,3-specificity. A lipase that does not exhibit 1,3-specificity is a lipase that acts almost indistinguishably on the 1,2,3 positions of glycerol when used in the reaction of glycerol or acylglycerol. Examples of these lipases 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. Among them, Alcaligenes sp. Lipase derived from Candida rugosa, Candida rugosa, lipase derived from Thermomyces lanuginosus, Rhizopus deremer from Rhizopus and Rhizopus A lipase derived from Rhizopus oryzae is more preferred. Particularly preferred are lipases derived from Candida rugosa, lipases derived from Rhizopus oryzae, and lipases derived from Thermomyces lanuginosus.
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 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.

  As the lipase-containing aqueous liquid, the lipase culture solution from which the bacterial cells have been removed, the purified culture solution, the lipase powder obtained from these dissolved and dispersed again in water, and the commercially available lipase powder dissolved and dispersed again in water And commercially available liquid lipases. Further, those obtained by removing low molecular components such as salts in order to further increase the lipase activity are more preferable, and those obtained by removing low molecular components such as sugars in order to further improve the powder properties.

  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, and the immobilized lipase can be used as it is or a pulverized 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 A product of Amano Enzyme Co., Ltd .: Lipase AY “Amano” 30, a product of Meito Sangyo Co., Ltd .: “Lipase OF” and the like can be used.
As the lipase used in the present invention, a powder lipase is more preferable.

<Hydrolysis>
As a hydrolysis reaction of the sucrose fatty acid ester mixture raw material of the present invention using lipase, a commonly used hydrolysis reaction can be used. Specifically, for example, water and a solvent other than water are added to the raw material sucrose fatty acid ester mixture, and a predetermined amount of lipase is further added to carry out the hydrolysis reaction. Here, for example, 1 to 50 g, preferably 5 to 25 g, and more preferably 10 to 20 g of water is added to 1 g of the sucrose fatty acid ester mixture raw material. As the solvent, an organic solvent, particularly an organic hydrophobic solvent can be preferably used. Specifically, examples of the solvent include dimethyl sulfoxide (DMSO), dimethylformamide (DMF), organic hydrophilic solvents such as methyl ethyl ketone, acetone and alcohol (dissolved in water), and isooctane, xylene, toluene, hexane, chloroform, An organic hydrophobic solvent (insoluble in water) such as chlorobenzene can be used as one kind or a mixture of two or more kinds. The solvent should have an amount that can dissolve the sucrose fatty acid ester mixture raw material to some extent. In particular, an organic hydrophobic solvent insoluble in water, such as isooctane and chloroform, is preferable because the enzyme and the organic hydrophobic solvent can be easily removed. As a mixture of water and a solvent, a mixture of water and an organic solvent is preferable, a mixture of water and an organic hydrophobic solvent is more preferable, and a mixture of water and isooctane is particularly preferable. For example, 0.5 to 30 g, preferably 1 to 20 g, more preferably 3 to 10 g is added to 1 g of the sucrose fatty acid ester mixture raw material. Preferably, a mixture of water and a solvent other than water is used, and the mass ratio of the solvent other than water / water is, for example, 5/1 to 1/5, preferably 3/1 to 1/3, more preferably 2 /. 1-1 / 1.
As the lipase used for hydrolysis, the above-mentioned lipase and optionally an auxiliary agent can be used. For example, 1 to 30 mL, preferably 2 to 20 mL, more preferably 3 to 15 mL of lipase having an enzyme concentration of 10,000 U / mL is added to 1 g of sucrose fatty acid ester mixture raw material.

  The hydrolysis reaction is performed at room temperature (20 ° C.) to 80 ° C., preferably 30 to 70 ° C., more preferably 40 to 60 ° C. under normal pressure, for example, for 1 to 48 hours, preferably 6 to 36 hours. More preferably, it is performed for 12 to 24 hours with arbitrary stirring. Moreover, a hydrolysis reaction may also include the preliminary stirring process stirred without adding a lipase before the hydrolysis reaction process which adds the above-mentioned lipase and performs a hydrolysis reaction. The preliminary stirring step is continued, for example, for 5 to 60 minutes, preferably 10 to 50 minutes, more preferably 20 to 40 minutes. In the hydrolysis reaction step, for example, the predetermined amount of lipase may be added at once, but the predetermined amount of lipase is divided into 2 to 30 times, preferably 3 to 20 times, more preferably 5 to 15 times. May be thrown in. When the dose is divided, the single dose depends on the number of administrations, but is, for example, 0.1 to 20 mL, preferably 0.5 to 10 mL, more preferably 0.7 to 5 mL. In addition to immediately after completion of the preliminary stirring step, the lipase may be added every 1 to 3 hours, preferably every 1 to 2 hours after the first lipase is added.

<Modified sucrose fatty acid ester mixture>
By performing hydrolysis as described above, a modified sucrose fatty acid ester mixture substantially containing a sucrose difatty acid ester in which a fatty acid is bonded to the 4th and 6th positions of sucrose can be obtained. The mass of the sucrose difatty acid ester in which fatty acids are bonded to the 4th and 6th positions of the sucrose contained in the modified sucrose fatty acid ester mixture is based on the total mass of the sucrose fatty acid ester contained in the modified sucrose fatty acid ester mixture. For example, it is 10-99 mass%, Preferably it is 15-80 mass%, More preferably, it is 20-60 mass%, More preferably, it is 23-50 mass%. The amount of sucrose difatty acid ester in which fatty acids are bonded to the 4th and 6th positions of the sucrose contained in the modified sucrose fatty acid ester mixture is the same as that in the 4th and 6th positions of the sucrose fatty acid ester mixture. Is increased compared to the amount of sucrose difatty acid ester bound. For example, preferably, [mass ratio of sucrose difatty acid ester in which fatty acids are bonded at positions 4 and 6 of the sucrose to the total sucrose fatty acid ester contained in the modified sucrose fatty acid ester mixture] / [said sucrose fatty acid ester mixture The ratio of the mass ratio of sucrose difatty acid ester in which fatty acids are bonded to positions 4 and 6 of the sucrose to the total sucrose fatty acid ester contained in the raw material] is 120/100 or more, more preferably 130/100 or more, and still more preferably. 140/100 to 300/100. In addition, a fatty acid is bonded to positions 4 and 6 of the sucrose contained in the modified sucrose fatty acid ester mixture with respect to the total mass of the sucrose difatty acid ester having a degree of esterification of 2 contained in the modified sucrose fatty acid ester mixture of the present invention. The amount of sucrose difatty acid ester is, for example, 20 to 99% by mass, preferably 25 to 90% by mass, more preferably 30 to 80% by mass, and further preferably 45 to 70% by mass.

The ratio of the sucrose fatty acid ester having an esterification degree of 1 to 2 with respect to the total sucrose fatty acid ester in the modified sucrose fatty acid ester mixture is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, More preferably, the content is 70 to 90% by mass. The ratio of the sucrose fatty acid ester having a degree of esterification of 3 to 5 with respect to the total sucrose fatty acid ester in the modified sucrose fatty acid ester mixture is, for example, 1% by mass or more, preferably 0 to 50% by mass, more preferably 0 to 40% by mass. % Or more, more preferably 1 to 30% by mass. Moreover, the ratio of the sucrose fatty acid ester having an esterification degree of 1 to 3 with respect to the total sucrose fatty acid ester in the modified sucrose fatty acid ester mixture is, for example, 70% by mass or more, preferably 80% by mass or more, and more preferably 90 to 95%. It is suitable that it is mass%. Furthermore, the ratio of the sucrose fatty acid ester having an esterification degree of 6 to 8 with respect to the total sucrose fatty acid ester in the modified sucrose fatty acid ester mixture is, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 4% by mass. Hereinafter, it is more preferably 0 to 3% by mass. More specifically, the total sucrose fatty acid ester in the modified sucrose fatty acid ester mixture is a sucrose fatty acid ester having a degree of esterification of 1 to 60% by mass, preferably 20 to 50% by mass. The degree 2 sucrose fatty acid ester is 30 to 70% by mass, preferably 40 to 50% by mass, and the degree 3 esterification sucrose fatty acid ester is 1 to 40% by mass, preferably 5 to 5% by mass. A sucrose fatty acid ester having an esterification degree of 4 in a proportion of 30% by mass is a proportion of 0-10% by mass, preferably 1-7% by mass, and a sucrose fatty acid ester having an esterification degree of 5 or more is 10% by mass. It is preferable to contain each in the following proportions, preferably 5% by mass or less, more preferably 0 to 3% by mass.
Furthermore, in the modified sucrose fatty acid ester mixture, the mass ratio of [sucrose fatty acid ester having a degree of esterification of 1] / [sucrose fatty acid ester having a degree of esterification of 2] is, for example, 2/1 to 1/4, preferably 1.5 / 1 to 1/3, more preferably 1.2 / 1 to 1/2.

  The suitable ester composition of the modified sucrose fatty acid ester mixture of the present invention is 10 to 60% by mass, preferably 20%, of sucrose fatty acid ester having a degree of esterification of 1 with respect to the total sucrose fatty acid ester of the modified sucrose fatty acid ester mixture. ~ 50% by mass; sucrose fatty acid ester having a degree of esterification of 2 to 30 to 60% by mass, preferably 40 to 50% by mass; sucrose fatty acid ester having a degree of esterification of 3 to 5 to 30% by mass, preferably 5% 0 to 15% by mass, preferably 0 to 10% by mass of sucrose fatty acid ester having an esterification degree of 4 to 0 to 10% by mass, preferably 0 to 10% by mass, -5% by mass; sucrose fatty acid ester having a degree of esterification of 6 or more is 0-5% by mass, preferably 0-2% by mass (provided that the total mass% of each sucrose fatty acid ester is 1 It is adjusted to be 0% by mass).

<Use of modified sucrose fatty acid ester mixture>
The modified sucrose fatty acid ester mixture of the present invention can be used as an emulsifier, a crystal modifier, an antifoaming agent, a release agent and the like in applications such as foods, beverages, cosmetics and detergents. Especially for foods, the modified sucrose fatty acid ester mixture of the present invention can be used for emulsification, crystal adjustment, viscosity adjustment, and water retention applications.
In particular, examples of the food containing the modified sucrose fatty acid ester mixture of the present invention include chocolate, margarine, shortening, dressing, cream and the like.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, these do not restrict | limit this invention in any meaning.
[Evaluation method]
-Ester composition The composition analysis of the ester contained in the sucrose fatty acid ester mixture was performed using high performance liquid chromatography (HPLC). Specifically, a GPC column and an ODS column were used. The analysis conditions using each column are shown below.

GPC column analysis condition 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

ODS column analysis condition detector Shodex differential refractometer RI-74
Column: ZORBAX Eclipse Plus C18 (manufactured by Agilent Technologies) Particle size 3.5 μm 150 mm × 4.6 mm
Column temperature: 25 ° C
Eluent: Special grade tetrahydrofuran (containing stabilizer): Special grade methanol = 55: 45
Flow rate: 0.8 mL / min Injection volume: 10 μL
Analysis time: 16 minutes

  First, the composition of sucrose fatty acid esters having an esterification degree of 1, 2, 3 and an esterification degree of 4 or more was measured using a GPC column. Next, the composition ratio of sucrose fatty acid esters having esterification degrees of 4, 5, 6, 7 and 8 was measured using an ODS column. Each composition of esterification degree 1-8 was computed from the measurement result of the previous GPC column, and the composition ratio result of the ODS column.

-NMR measurement of the diester fraction contained in the modified sucrose fatty acid ester mixture In order to measure the diester fraction contained in the modified sucrose fatty acid ester mixture by NMR, first the diester fraction was analyzed using thin layer chromatography (TLC). I made a picture. TLC conditions are as follows.
Developing solvent: Solvent prepared in chloroform / methanol / acetic acid / water = 80/10/8/2 TLC: Normal phase TLC of silica gel 70 plate Wako (manufactured by Wako Pure Chemical Industries)
Further, the obtained diester fraction was dissolved in CD ₃ OD and analyzed by NMR of Varian GEMINI 2000 (manufactured by Agilent Technologies).

[Production method of modified sucrose fatty acid ester mixture]
[Example 1]
As the lipase, lipase AY “Amano” 30 (manufactured by Amano Enzyme Co., Ltd., hereinafter referred to as lipase AY: derived from Candida rugosa), which is a powder lipase that does not exhibit 1,3-specificity, was used. This lipase AY was dissolved in water to prepare a lipase solution having an enzyme concentration of 10,000 U / mL. As a sucrose fatty acid ester mixture raw material, DK ester F-50 (HLB = 6, constituent fatty acids were about 30% by weight palmitic acid, about 70% by weight stearic acid, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). 1 g of this DK ester F-50 sucrose fatty acid ester mixture raw material was added to an 80 g sample bottle, and 6 g of special grade isooctane and 12 g of water were added as a solvent. The sample bottle was immersed in a 50 ° C. warm bath and stirred with a stirrer for 30 minutes (preliminary stirring step). Thereafter, 1 mL of the previously prepared lipase solution was added to start the hydrolysis reaction (hydrolysis reaction step). 1 mL of lipase solution is added every 2 hours from the addition of the first lipase solution (a total of 11 additions of lipase, 11 mL in total), and the reaction is terminated 22 hours after the addition of the first lipase solution. A reaction product containing a fatty acid ester mixture was obtained. After completion of the reaction, the reaction product containing the modified sucrose fatty acid ester mixture was subjected to an evaporator and lyophilization to remove the reaction solvent, and a crude modified sucrose fatty acid ester mixture was isolated. Thereafter, the resultant was redissolved in a chloroform / methanol (volume ratio) = 1/1 solution, and lipase AY was removed from the modified sucrose fatty acid ester mixture by filtration. After filtration, the chloroform / methanol (volume ratio) = 1/1 solution was removed by lyophilization with an evaporator to obtain a purified modified sucrose fatty acid ester mixture.
[Example 2]
Implemented except that DK ester F-160 (HLB = 15, constituent fatty acids are about 30% by weight palmitic acid, about 70% by weight stearic acid, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is used as a raw material for sucrose fatty acid ester mixture A modified sucrose fatty acid ester mixture was obtained in the same manner as in Example 1.

  These modified sucrose fatty acid ester mixtures of Examples 1 and 2 were subjected to the HPLC analysis described above, and the type and content (% by mass) of the sucrose fatty acid ester contained were analyzed. The results of Examples 1 and 2 are shown in Table 1 below and FIG. 1 (Example 1) and FIG. 2 (Example 2).

＊表中、実施例の数値は、エステル化度１〜８の全蔗糖脂肪酸エステルの混合物の合計質量に対する質量％（エステル濃度）である。 Table 1

* In the table, the numerical values of the examples are mass% (ester concentration) with respect to the total mass of the mixture of all sucrose fatty acid esters having a degree of esterification of 1 to 8.

Furthermore, in the modified sucrose fatty acid ester mixture obtained in the examples (especially in the sucrose difatty acid ester having a degree of esterification of 2), a sucrose difatty acid ester in which a fatty acid is bonded to positions 4 and 6 of sucrose is contained. In order to confirm this, NMR measurement was performed.
Under the NMR measurement conditions as described above, the modified sucrose fatty acid ester mixture obtained in Example 1 was developed on TLC, and the diester fraction contained in the modified sucrose fatty acid ester mixture was collected. When the diester fraction of the obtained modified sucrose fatty acid ester was subjected to NMR measurement, the following results were obtained.

・ NMR measurement results
1H NMR δ (ppm, 400MHz, 313K, CD ₃ OD): 0.89 (6H, t, J = 6.9 Hz), 1.28 (50H, m), 1.64-1.59 (4H, m), 2.38-2.31 (4H, m ), 3.52 (1H, dd, J = 9.9, 3.8 Hz, C-2), 3.63-3.57 (2H, m, C-1 '), 3.81-3.72 (3H, m, C-5', C-6 '), 3.86 (1H, t, J = 9.5 Hz, C-3), 3.97 (1H, t, J = 7.9 Hz, C-4'), 4.11-4.08 (3H, m, C-6, C- 3 '), 4.27-4.20 (1H, m, C-5), 4.85 (1H, t, J = 9.8 Hz, C-4), 5.43 (1H, d, J = 3.8 Hz, C-1)
13C NMR δ (ppm, 400 MHz, 313K, CD ₃ OD): 63.7 (C-6), 63.8 (C-6 ′), 64.3 (C-1 ′), 69.8 (C-5), 71.9 (C-4 ), 72.5 (C-3), 73.2 (C-2), 75.9 (C-4 '), 79.3 (C-3'), 83.8 (C-5 '), 93.2 (C-1), 105.3 (C -2 '), 174.8, 174.1 (ester carbon)

Table 2

  From these, it was found that the modified sucrose fatty acid ester of Example 1 contained a 4,6-substituted diester-containing sucrose fatty acid ester. In Example 2, the same NMR measurement as in Example 1 was performed, and it was found that the modified sucrose fatty acid ester in Example 2 also contained a 4,6-substituted diester-containing sucrose fatty acid ester.

  Here, the amount of the sucrose difatty acid ester in which fatty acids are bonded to the 4th and 6th positions of the sucrose contained in the modified sucrose fatty acid ester mixture obtained in Examples 1 and 2 is the same as that of the modified sucrose fatty acid ester mixture. They were 26 mass% (Example 1) and 23 mass% (Example 2) with respect to the total sucrose fatty acid ester contained, respectively. Furthermore, the sucrose difatty acid which the fatty acid has couple | bonded with the 4th, 6th position of sucrose with respect to the total mass of the sucrose difatty acid ester of the esterification degree 2 contained in the modified sucrose fatty acid ester mixture obtained in Example 1 and 2 The amount of ester was 58 mass% (Example 1) and 50 mass% (Example 2), respectively.

＊表中、実施例の数値は、質量％（エステル濃度）である。 Table 3

* In the table, the numerical values of the examples are mass% (ester concentration).

  Thus, in both Examples 1 and 2, a specific sucrose fatty acid ester mixture raw material is hydrolyzed in the presence of a specific lipase, whereby a sucrose difatty acid ester in which a fatty acid is bonded to positions 4 and 6 of sucrose. The content ratio could be increased.

[Comparative Example 3]
Other than using lipase A “Amano” 6 (manufactured by Amano Enzyme, Inc .: Asperus niger) or RM-IM (Novozymes A / S: derived from lysozyme Mihei), which is a lipase exhibiting 1,3-specificity, as the lipase Was hydrolyzed in the same manner as in Example 1, but formation of a sucrose difatty acid ester in which a fatty acid was bonded at positions 4 and 6 could not be confirmed.

Claims (9)

The sucrose fatty acid ester having a degree of esterification of 3 to 5 is contained in an amount of 1% by mass or more based on the total sucrose fatty acid ester, and the sucrose fatty acid ester having a degree of esterification of 6 to 8 is 0 to 40 mass based on the total sucrose fatty acid ester. % Modified sucrose containing a sucrose difatty acid ester in which fatty acids are bonded to the 4th and 6th positions of sucrose by hydrolyzing a sucrose fatty acid ester mixture raw material containing 1% in the presence of a lipase not exhibiting 1,3-specificity A method for producing the modified sucrose fatty acid ester mixture, wherein the fatty acid ester mixture is obtained. The mass of the sucrose difatty acid ester in which fatty acids are bonded to the 4th and 6th positions of the sucrose contained in the modified sucrose fatty acid ester mixture is the mass of the total sucrose fatty acid ester contained in the modified sucrose fatty acid ester mixture. The method of Claim 1 which is 20 mass% or more with respect to. The mass of the sucrose fatty acid ester having an esterification degree of 6 to 8 contained in the sucrose fatty acid ester mixture raw material is 10% by mass or less based on the mass of the total sucrose fatty acid ester mixture contained in the sucrose fatty acid ester mixture raw material. Item 3. The method according to Item 1 or 2. The method according to any one of claims 1 to 3, wherein the sucrose fatty acid ester mixture raw material has an HLB value of 4 to 15. The lipase is a lipase derived from Candida rugosa, a lipase derived from Rhizopus oryzae, and one lipase derived from Thermomyces lanuginosus, wherein the lipase is selected from the group consisting of one or more lipases. The method of any one of -4. The constituent fatty acid of the sucrose difatty acid ester in which a fatty acid is bonded to the 4th and 6th positions of the sucrose is a linear saturated aliphatic carboxylic acid having 14 to 22 carbon atoms. the method of. The method according to claim 1, wherein the hydrolysis is performed in a mixture of water and an organic hydrophobic solvent. A modified sucrose fatty acid ester mixture containing a sucrose difatty acid ester in which fatty acids are bonded to the 4th and 6th positions of the sucrose, wherein the mass of the sucrose difatty acid ester having a fatty acid bonded to the 4th and 6th positions of the sucrose is The modified sucrose fatty acid ester mixture, which is 20% by mass or more based on the mass of the total sucrose fatty acid ester contained in the modified sucrose fatty acid ester mixture. A food comprising the modified sucrose fatty acid ester mixture according to claim 8.

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