Polyglycerol monofatty acid ester articles and methods of making same

Abstract

The invention provides a polyglycerol fatty acid monoester product with high purity. Also provided is a method for producing a polyglycerol fatty acid monoester with high purity. A polyglycerol monofatty acid ester product in which the number of carbon atoms in a fatty acid is 4-25, the peak intensity ratio represented by formula (X) is 0.20 or more, and the peak intensity ratio represented by formula (Y) is 0.46 or less. Formula (X) = P2 / P1; formula (Y) = P3 / P1: P1: the sum of peak intensities of a monoester, a monoester dehydrated product, a diester, a diester dehydrated product, a triester, and a triester dehydrated product of a polyglycerol fatty acid ester, and polyglycerol and a polyglycerol dehydrated product when mass spectrometry of a polyglycerol fatty acid ester product is performed using a time-of-flight mass spectrometer; p2: the peak intensity of the monoester of the polyglycerol fatty acid ester when the mass spectrometry of the polyglycerol fatty acid ester product is performed using a time-of-flight mass spectrometer; and P3: the sum of the peak intensities of the polyglycerol and the polyglycerol anhydrate when the mass spectrometry of the polyglycerol fatty acid monoester product is performed using a time-of-flight mass spectrometer.

Description

Technical Field

[0001] This disclosure relates to polyglycerol monofatty acid ester products and methods for manufacturing the same. Background Technology

[0002] Polyglycerol monofatty acid esters exhibit various properties through combinations of polyglycerol with fatty acids of different degrees of polymerization and chain lengths. As surfactants, they are widely used in food additives, cleaning agent compositions, and cosmetics (cosmetic compositions). Methods for manufacturing such polyglycerol fatty acid esters include esterification reactions of polyglycerol with fatty acids, transesterification reactions of polyglycerol with fatty acid esters, and addition polymerization reactions of glycidyl esters with fatty acids (Patent Documents 1-6).

[0003] Furthermore, Patent Document 7 describes a polyglycerol monolaurate obtained by simultaneously supplying lauric acid / glycidyl oleate / phosphoric acid to a reactor in a specific ratio and reacting the mixture. Moreover, Patent Document 8 describes an invention that involves adding chain-like diglycerol monooleate to a flask and simultaneously adding glycidyl oleate and phosphoric acid, thereby reacting the mixture to obtain a polyglycerol monooleate composition.

[0004] However, known polyglycerol monofatty acid esters to date contain a large number of byproducts other than the monoester (e.g., monoester dehydrates, diesters, diester dehydrates, trimers, and trimer dehydrates), so the purity of the monoester cannot be considered high. Therefore, when using polyglycerol monofatty acid esters as surfactants, there are problems such as the inability to efficiently reduce surface tension.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 8-109153

[0008] Patent Document 2: Japanese Patent Application Publication No. 9-117258

[0009] Patent Document 3: Japanese Patent Application Publication No. 9-216813

[0010] Patent Document 4: Japanese Patent Application Publication No. 9-272893

[0011] Patent Document 5: Japanese Patent Application Publication No. 2006-111539

[0012] Patent Document 6: International Publication No. 2004 / 048304

[0013] Patent Document 7: Japanese Patent Application Publication No. 2001-139679

[0014] Patent Document 8: Japanese Patent Application Publication No. 2017-071586 Summary of the Invention

[0015] The problem that the invention aims to solve

[0016] The polyglycerol monofatty acid ester product cited in Reference 7 is obtained by a method of continuously supplying and reacting fatty acids, an acidic catalyst, and glycidyl ether together, and therefore does not meet the range of peak intensity ratios shown in formulas (X) and (Y) of this disclosure described later. Furthermore, the polyglycerol monofatty acid ester product cited in Reference 8 is a product made from diglycerol monofatty acid esters rather than fatty acids, and therefore does not meet the range of peak intensity ratios shown in formulas (X) and (Y) of this disclosure described later.

[0017] Therefore, the object of this disclosure is to provide a polyglycerol monofatty acid ester product with high purity. Another object of this disclosure is to provide a method for manufacturing polyglycerol monofatty acid esters with high purity.

[0018] Solution for solving the problem

[0019] The inventors of this disclosure conducted in-depth research to solve the aforementioned problems, and as a result discovered polyglycerol monofatty acid ester products with high purity. The invention disclosed herein is based on these insights.

[0020] That is, this disclosure provides a polyglycerol monofatty acid ester product, wherein the number of carbon atoms in the fatty acid is 4 to 25, the peak intensity ratio shown in the following formula (X) is 0.20 or more, and the peak intensity ratio shown in the following formula (Y) is 0.46 or less.

[0021] Equation (X) = P2 / P1

[0022] Equation (Y) = P3 / P1

[0023] P1: The sum of peak intensities of monoesters, dehydrated monoesters, diesters, dehydrated diesters, trimesters and dehydrated trimesters, as well as polyglycerol and dehydrated polyglycerol, when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer.

[0024] P2: Peak intensity of the monoester of polyglycerol fatty acid ester during mass spectrometry analysis of polyglycerol monoester products using a time-of-flight mass spectrometer.

[0025] P3: The sum of peak intensities of polyglycerol and polyglycerol dehydrate when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer.

[0026] Preferably, the fatty acid in the above-mentioned polyglycerol monofatty acid ester product has 15 to 25 carbon atoms.

[0027] Preferably, the fatty acid in the above-mentioned polyglycerol monofatty acid ester product has 4 to 14 carbon atoms.

[0028] Preferably, the fatty acid in the above-mentioned polyglycerol monofatty acid ester product has 16 to 18 carbon atoms.

[0029] Preferably, the fatty acid in the above-mentioned polyglycerol monofatty acid ester product has 8 to 14 carbon atoms.

[0030] Preferably, the average degree of polymerization of glycerol in the above-mentioned polyglycerol monofatty acid ester products is 2 to 20.

[0031] Preferably, the fatty acids in the above-mentioned polyglycerol monofatty acid ester products are straight-chain fatty acids.

[0032] Preferably, the fatty acids in the above-mentioned polyglycerol monofatty acid ester products are unsaturated fatty acids.

[0033] Preferably, the fatty acids in the above-mentioned polyglycerol monofatty acid ester products are branched-chain fatty acids.

[0034] Preferably, the above-mentioned polyglycerol monofatty acid ester product is a product of the reaction of glycidyl ether and fatty acid.

[0035] This disclosure also provides a cosmetic composition comprising the above-mentioned polyglycerol monofatty acid ester product.

[0036] This disclosure also provides a method for manufacturing polyglycerol monofatty acid ester products, which includes an addition polymerization reaction step of glycidyl ether and fatty acid.

[0037] Preferably, in the above-mentioned method for manufacturing polyglycerol monofatty acid ester products, the addition polymerization reaction is carried out by continuously or intermittently supplying glycidyl ester to fatty acids.

[0038] Preferably, in the above-mentioned method for manufacturing polyglycerol monofatty acid ester products, the addition polymerization reaction is carried out by continuously or intermittently supplying glycidyl ester to fatty acids and continuously or intermittently supplying an acidic catalyst.

[0039] Preferably, the acidic catalyst is a phosphoric acid or an acidic phosphate ester.

[0040] Invention Effects

[0041] The polyglycerol monofatty acid ester products disclosed herein, having the above-described composition, contain polyglycerol monofatty acid esters in high purity. Furthermore, the manufacturing method of this disclosure can yield polyglycerol monofatty acid ester products of high purity. Attached Figure Description

[0042] Figure 1 This is a chromatogram of the HPLC analysis of polyglycerol monodecanoate from Example 1.

[0043] Figure 2 This is a graph showing the corrected molecular weight of polyglycerol monodecanoate from Example 1 and its corresponding peak intensities. The hollow bar graph represents the monoester. Detailed Implementation

[0044] [Polyglycerol monofatty acid ester products]

[0045] The polyglycerol monofatty acid ester product disclosed herein is characterized in that the fatty acid has 4 to 25 carbon atoms, the peak intensity ratio shown in the following formula (X) is 0.20 or more, and the peak intensity ratio shown in the following formula (Y) is 0.46 or less.

[0046] Equation (X) = P2 / P1

[0047] Equation (Y) = P3 / P1

[0048] P1: The sum of peak intensities of monoesters, dehydrated monoesters, diesters, dehydrated diesters, trimesters and dehydrated trimesters, as well as polyglycerol and dehydrated polyglycerol, when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer.

[0049] P2: Peak intensity of the monoester of polyglycerol fatty acid ester during mass spectrometry analysis of polyglycerol monoester products using a time-of-flight mass spectrometer.

[0050] P3: The sum of peak intensities of polyglycerol and polyglycerol dehydrate when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer.

[0051] The polyglycerol monofatty acid ester products disclosed herein contain at least polyglycerol monofatty acid esters. In addition to polyglycerol monofatty acid esters, they may also contain polyglycerol polyfatty acid esters such as polyglycerol difatty acid esters and polyglycerol trifatty acid esters. Furthermore, they may also contain polyglycerol, etc., which are raw materials for the aforementioned polyglycerol monofatty acid ester products. Moreover, they may also contain dehydrated forms of these substances, as described later.

[0052] The aforementioned polyglycerol monofatty acid esters are represented, for example, by the following formula (1).

[0053] RC (=O)-[C3H6O2) n -OH……(1)

[0054] In formula (1), R represents an aliphatic hydrocarbon group with 3 to 24 carbon atoms. Examples of such aliphatic hydrocarbon groups include alkyl, alkenyl, or alkyl groups having hydroxyl groups. The number of carbon atoms in the aliphatic hydrocarbon group is equivalent to the value obtained by subtracting 1 from the "number of carbon atoms in fatty acids" described later. n is the average degree of polymerization of glycerol, for example, 2 to 20.

[0055] The C3H6O2 in parentheses of the above formula (1) includes at least one structure selected from the group consisting of the following formulas (2), (3) and (4).

[0056] -O-CH2-CH(OH)-CH2-……(2)

[0057] -O-CH(CH2OH)-CH2-…(3)

[0058] -O-CH2-CH(CH2OH)-……(4)

[0059] In this specification, polyglycerol mono-fatty acid esters are sometimes simply referred to as "mono-esters." Polyglycerol di-fatty acid esters are substances synthesized by forming ester bonds between the two hydroxyl groups of polyglycerol and the carboxyl groups of fatty acids. Such polyglycerol mono-fatty acid esters are sometimes simply referred to as "di-esters." Polyglycerol tri-fatty acid esters are substances synthesized by forming ester bonds between the three hydroxyl groups of polyglycerol and the carboxyl groups of fatty acids. Such polyglycerol mono-fatty acid esters are sometimes simply referred to as "tri-esters." Furthermore, polyglycerol poly-fatty acid esters other than polyglycerol di-fatty acid esters and polyglycerol tri-fatty acid esters are sometimes referred to as "tetra-esters," "penta-esters," "hexa-esters," etc., in the same way as above. Additionally, these polyglycerol poly-fatty acid esters are sometimes referred to as "poly-esters."

[0060] In the manufacture of polyglycerol monofatty acid ester products disclosed herein, a portion of the polyglycerol is sometimes dehydrated. The substance obtained by dehydrating a portion of the polyglycerol in a polyglycerol monofatty acid ester is sometimes referred to as a polyglycerol monofatty acid ester dehydrated product or a monoester dehydrated product of a polyglycerol fatty acid ester; otherwise, it is sometimes simply referred to as a monoester dehydrated product. Similarly, polyglycerol polyfatty acid esters such as polyglycerol difatty acid esters and polyglycerol trifatty acid esters are also sometimes referred to as polyglycerol polyfatty acid ester dehydrated products or diester dehydrated products, polyglycerol trifatty acid ester dehydrated products or triester dehydrated products, etc. These dehydrated products sometimes have a cyclic structure.

[0061] The polyglycerol monofatty acid ester disclosed herein can be (1) a polyglycerol monofatty acid ester obtained by addition polymerization of glycidol and fatty acids, (2) a polyglycerol monofatty acid ester obtained by esterification of polyglycerol and fatty acids, or (3) a polyglycerol monofatty acid ester obtained by transesterification of polyglycerol and fatty acid esters. The polyglycerol monofatty acid ester obtained by the above reaction (1) can be referred to as a reactant of glycidol and fatty acids. The polyglycerol monofatty acid ester obtained by the above reaction (2) can be referred to as an esterified polyglycerol and fatty acid. The polyglycerol monofatty acid ester obtained by the above reaction (3) can be referred to as a transesterified polyglycerol and fatty acid ester. Among these, considering the increase in the proportion of monoesters in the polyglycerol monofatty acid ester product, the reactant of glycidol and fatty acids in (1) is preferred.

[0062] (Time-of-flight mass spectrometer (TOF-MS))

[0063] The time-of-flight mass spectrometer (TOF-MS) and its determination conditions in the polyglycerol monofatty acid ester products disclosed herein are not particularly limited, and determinations can be performed using, for example, the following apparatus and conditions.

[0064] ·Device: Xevo G2-XSQTof (Waters Co., Ltd.).

[0065] • Injection method: Injected via infusion (5 μL / min).

[0066] • Measurement mode: Neg.

[0067] • Conegas gas: 50L / h.

[0068] • Desolvation gas: 1000L / h.

[0069] • Source temperature (Source temp): 120℃.

[0070] • Desolvation temperature: 500℃.

[0071] • Capillary: 2.0kV.

[0072] • Sampling cone: 40.

[0073] • Source offset: 80.

[0074] • Sample concentration: 25 ppm (methanol).

[0075] MS range: 50~3000.

[0076] In this disclosure, the peak intensity ratio shown in equation (X) is calculated using P2 / P1. Furthermore, the peak intensity ratio shown in equation (Y) is calculated using P3 / P1.

[0077] The above P1 is the sum of the peak intensities of the monoester, monoester dehydrate, diester, diester dehydrate, trimester and trimester dehydrate, as well as polyglycerol and polyglycerol dehydrate, when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer.

[0078] The above P2 represents the peak intensity of the monoester of polyglycerol fatty acid esters during mass spectrometry analysis of polyglycerol monoester products using a time-of-flight mass spectrometer.

[0079] The above P3 represents the sum of the peak intensities of polyglycerol and polyglycerol dehydrate when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer.

[0080] The peak intensities of each component used in P1 to P3 above are obtained from the mass spectrometry analysis of polyglycerol monofatty acid ester products performed using the time-of-flight mass spectrometer described above.

[0081] When performing mass spectrometric analysis of polyglycerol monofatty acid ester products using the aforementioned time-of-flight mass spectrometer, peaks corresponding to the molecular weight of the monoester (i.e., polyglycerol monofatty acid ester) as a polyglycerol fatty acid ester can be observed, as well as peaks corresponding to the molecular weights of impurities such as monoester dehydrated products, diesters, diester dehydrated products, trimesters, and trimster dehydrated products. Furthermore, peaks corresponding to the molecular weights of impurities such as tetraesters, tetraester dehydrated products, pentesters, and pentester dehydrated products of polyglycerol polyfatty acid esters and their dehydrated products (other than those mentioned above) can be observed. Moreover, peaks corresponding to the molecular weights of impurities such as polyglycerol and polyglycerol dehydrated products, which are raw materials or byproducts of polyglycerol monofatty acid ester products, can also be observed.

[0082] Polyglycerol monofatty acid esters and impurities can be determined based on the molecular weight measured during mass spectrometry analysis of polyglycerol monofatty acid ester products using the aforementioned time-of-flight mass spectrometer.

[0083] The following is a summary of the calculation methods for equations (X), (Y), and P1 to P3. It should be noted that the specific methods are described in the embodiments.

[0084] (a) Mass spectrometry analysis of polyglycerol monofatty acid ester products was performed using a time-of-flight mass spectrometer to obtain the molecular weight and peak intensity of each component recorded in P1 to P3. The decimal part of each molecular weight value was rounded down to the nearest integer, and the corresponding peak intensity values ​​were summed. The purpose of rounding the molecular weight to the nearest integer is to correspond to the corrected molecular weight in (c) described later.

[0085] (b) Calculate the theoretical molecular weight of each component recorded in P1 to P3.

[0086] (c) Consider the following (i) to (iv) to correct the theoretical molecular weight in (b), and specify the corrected molecular weight.

[0087] (i) The molecular weight determined / detected by time-of-flight mass spectrometry comes from molecules obtained by deprotonation through ionization; (ii) For (i), for substances with large molecular weights, the molecular weight at the peak intensity sometimes deviates further from 1; (iii) Among the components recorded in P1 to P3, there are substances with the same molecular weight, so appropriate selection is required to calculate; (iv) Considering the esterification number and degree of polymerization of polyglycerol fatty acid esters, if the degree of dehydration becomes impossible, it needs to be excluded.

[0088] (d) The intensities obtained in (a) are matched with the corrected molecular weights of the components of the polyglycerol monofatty acid ester product calculated in (c), and they are summed up as the peak intensities of "monoester," "dehydrated monoester," "diplast," "dehydrated diester," "triester," "dehydrated triester," "polyglycerol," and "dehydrated polyglycerol" as described in P1 to P3. The peak intensities of the above components are calculated as follows.

[0089] • Monoester, diester, trimer, and polyglycerol are obtained by summing the peak intensities of glycerol with a degree of polymerization of 1 to 20.

[0090] • The dehydrated monoester, dehydrated diester, dehydrated trimer, and dehydrated polyglycerol were obtained by summing the peak intensities of glycerol with a degree of polymerization of 1 to 20 and a degree of dehydration of 1 to 3 (substances obtained by removing 1 to 3 water molecules), respectively.

[0091] (e) Using the peak intensities of each component of the polyglycerol monofatty acid ester product calculated in (d), calculate the above formulas (X) and (Y).

[0092] The above P1 is the sum of the peak intensities of the monoester, monoester dehydrate, diester, diester dehydrate, trimester and trimester dehydrate, as well as polyglycerol and polyglycerol dehydrate, when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer.

[0093] The P2 mentioned above represents the peak intensity of polyglycerol monofatty acid esters during mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer. Therefore, the peak intensity ratio shown in equation (X) = P2 / P1 can be considered an indicator of the content of polyglycerol monofatty acid esters (monoesters of polyglycerol fatty acids) in the polyglycerol monofatty acid ester product. That is, a larger value for equation (X) indicates higher purity of polyglycerol monofatty acid esters in the polyglycerol monofatty acid ester product.

[0094] The P3 mentioned above represents the sum of peak intensities of polyglycerol and polyglycerol dehydrates during mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer. Therefore, the peak intensity ratio shown in equation (Y) = P3 / P1 can be considered an indicator of the content of polyglycerol and polyglycerol dehydrates in the polyglycerol monofatty acid ester product. That is, a smaller value for equation (Y) indicates a lower content of polyglycerol and polyglycerol dehydrates in the polyglycerol monofatty acid ester product, implying a relatively higher content of monoesters of polyglycerol fatty acids (higher purity).

[0095] The polyglycerol monofatty acid ester product disclosed herein has high purity, thus enabling it to effectively reduce surface tension when used as a surfactant. Furthermore, it exhibits good cleansing power and liquid crystal (e.g., bicontinuous cubic) formation ability. Moreover, when used as a makeup remover, it provides a refreshing feeling on the skin after makeup dissolution, removal, and rinsing. This is believed to be due to the high purity, which results in the formation of orderly micelles.

[0096] The peak intensity ratio shown in formula (X) above is not particularly limited as long as it is 0.20 or higher, but is more preferably 0.21 or higher, more preferably 0.23 or higher, more preferably 0.24 or higher, more preferably 0.25 or higher, more preferably 0.26 or higher, more preferably 0.28 or higher, more preferably 0.3 or higher, more preferably 0.31 or higher, more preferably 0.33 or higher, more preferably 0.35 or higher, more preferably 0.37 or higher, more preferably 0.40 or higher, more preferably 0.44 or higher, more preferably 0.48 or higher, and more preferably 0.52 or higher. Furthermore, the peak intensity ratio shown in formula (X) above is not particularly limited, for example, it is 1 or less, preferably 0.9 or less, more preferably 0.8 or less, more preferably 0.75 or less, more preferably 0.7 or less, more preferably 0.65 or less, and more preferably 0.6 or less.

[0097] The peak intensity ratio shown in the above formula (Y) is not particularly limited as long as it is 0.46 or less, preferably 0.45 or less, more preferably 0.44 or less, more preferably 0.42 or less, more preferably 0.39 or less, more preferably 0.37 or less, more preferably 0.35 or less, more preferably 0.33 or less, more preferably 0.32 or less, and more preferably 0.30 or less. Furthermore, the peak intensity ratio shown in the above formula (Y) is not particularly limited, for example, it is 0.01 or more, preferably 0.05 or more, and more preferably 0.10 or more.

[0098] In the polyglycerol monofatty acid ester products disclosed herein, the average degree of polymerization of glycerol is not particularly limited, but is preferably 2 to 40. The average degree of polymerization of the aforementioned glycerol can be 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, or 9 or more. Furthermore, the average degree of polymerization of the aforementioned glycerol can be 35 or less, 30 or less, 25 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less. Additionally, the average degree of polymerization of the aforementioned glycerol can also be 3 to 20 or 4 to 10.

[0099] In polyglycerol monofatty acid ester products, there is no particular limitation on the method for determining the average degree of polymerization of glycerol. For example, in the case of a polyglycerol monofatty acid ester product obtained by the reaction described in (1) above, it can be determined by the number of moles of glycidyl glycerol that undergo addition polymerization with 1 mole of fatty acid. For example, the average degree of polymerization of glycerol is n, which means that the average degree of polymerization of glycerol in the polyglycerol monofatty acid ester product obtained by adding polymerization of n moles of glycidyl glycerol with 1 mole of fatty acid is n. Furthermore, for example, in the case of polyglycerol monofatty acid ester products obtained by the reactions described in (2) and (3) above, the average degree of polymerization of glycerol is the same as that of glycerol in the polyglycerol used. For example, in the case of a polyglycerol monofatty acid ester product obtained by esterification reaction of polyglycerol with an average degree of polymerization of glycerol of m and fatty acid, the average degree of polymerization of glycerol is m.

[0100] Another method for determining the average degree of polymerization of glycerol is the method using the hydroxyl value. The hydroxyl value refers to the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl groups when 1 g of sample is acetylated (refer to JIS K 0070-1992). The average degree of polymerization of polyglycerol monofatty acid ester products can be determined by calculating the amount of hydroxyl groups in the polyglycerol chain based on the hydroxyl value.

[0101] In the polyglycerol monofatty acid ester products disclosed herein, the hydroxyl value is not particularly limited, but is preferably 317 to 754 KOH / g. The hydroxyl value of the aforementioned polyglycerol monofatty acid ester products can be 317 KOH / g or higher, 389 KOH / g or higher, 413 KOH / g or higher, 475 KOH / g or higher, 483 KOH / g or higher, or 539 KOH / g or higher. Furthermore, the hydroxyl value of the aforementioned polyglycerol monofatty acid ester products can be 754 KOH / g or lower, 751 KOH / g or lower, 745 KOH / g or lower, 741 KOH / g or lower, 734 KOH / g or lower, 725 KOH / g or lower, 713 KOH / g or lower, 698 KOH / g or lower, or 677 KOH / g or lower.

[0102] In the polyglycerol monofatty acid ester products disclosed herein, the fatty acid used is not particularly limited, but fatty acids with 4 to 25 carbon atoms are preferred. The fatty acid can be a saturated fatty acid or an unsaturated fatty acid. Furthermore, it can be a straight-chain fatty acid or a branched-chain fatty acid (a fatty acid with side chains). Moreover, it can also be a substituted fatty acid formed by replacing a portion of the hydrogen atoms bonded to the carbon chain with hydroxyl groups. It should be noted that the fatty acid referred to here is the fatty acid that is a constituent component of the polyglycerol monofatty acid ester.

[0103] The number of carbon atoms in the aforementioned fatty acids is not particularly limited and can be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 15 or more, 16 or more, or 18 or more. Furthermore, the number of carbon atoms in the aforementioned fatty acids is not particularly limited and can be 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, or 8 or less. Additionally, the number of carbon atoms in the aforementioned fatty acids can be 4 to 14, 15 to 25, or 8 to 14 or 16 to 18.

[0104] The fatty acids mentioned above are not specifically limited, but examples include: hexanoic acid (C6, saturated fatty acid), caprylic acid (C8, saturated fatty acid), nonanoic acid (C9, saturated fatty acid), 2-ethylhexanoic acid (C8, branched-chain fatty acid), and decanoic acid (C9, saturated fatty acid). 10 saturated fatty acids), lauric acid (C 12 saturated fatty acids), isotriadecanoic acid (C 13 Branched-chain fatty acids), myristic acid (C 14 saturated fatty acids), pentadecanoic acid (C 15 saturated fatty acids), palmitic acid (C 16 saturated fatty acids), palmitoleic acid (C 16 Unsaturated fatty acids), stearic acid (C 18 saturated fatty acids), isostearic acid (C 18 Branched-chain fatty acids), oleic acid (C 18(unsaturated fatty acids), linoleic acid (C 18 Unsaturated fatty acids), ricinoleic acid (C 18 Unsaturated fatty acids), hydroxystearic acid (C 18 (replaced fatty acids), arachidic acid (C 20 saturated fatty acids), behenic acid (C 22 saturated fatty acids), erucic acid (C 22 Unsaturated fatty acids), nervonic acid (C 24 (unsaturated fatty acids, etc.)

[0105] When the number of carbon atoms in the above-mentioned fatty acid is 4 to 14 (especially 8 to 14), the peak intensity ratio shown in the above formula (X) is not particularly limited as long as it is 0.20 or more, more preferably 0.23 or more, more preferably 0.25 or more, more preferably 0.30 or more, more preferably 0.33 or more, more preferably 0.35 or more, and more preferably 0.40 or more.

[0106] When the number of carbon atoms in the aforementioned fatty acids is 4 to 14 (especially 8 to 14), the peak intensity ratio shown in formula (Y) is not particularly limited as long as it is 0.46 or less, preferably 0.45 or less, more preferably 0.42 or less, more preferably 0.39 or less, and even more preferably 0.37 or less. Furthermore, the peak intensity ratio shown in formula (Y) is not particularly limited, for example, it is 0.01 or more, preferably 0.05 or more, and even more preferably 0.10 or more.

[0107] When the number of carbon atoms in the above-mentioned fatty acids is 4 to 14 (especially 8 to 14), the average degree of polymerization of glycerol is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, even more preferably 4 to 10, and particularly preferably 6 to 10.

[0108] When the number of carbon atoms in the fatty acid is 15 to 25 (especially 16 to 18), the peak intensity ratio shown in the above formula (X) is not particularly limited as long as it is 0.20 or more, more preferably 0.23 or more, more preferably 0.24 or more, more preferably 0.25 or more, more preferably 0.28 or more, more preferably 0.30 or more, more preferably 0.31 or more, more preferably 0.33 or more, and more preferably 0.35 or more.

[0109] When the number of carbon atoms in the aforementioned fatty acids is 15 to 25 (particularly 16 to 18), the peak intensity ratio shown in formula (Y) is not particularly limited as long as it is 0.46 or less, preferably 0.44 or less, more preferably 0.37 or less, more preferably 0.32 or less, more preferably 0.30 or less, and more preferably 0.28 or less. Furthermore, the peak intensity ratio shown in formula (Y) is not particularly limited, for example, it is 0.01 or more, preferably 0.05 or more, and more preferably 0.10 or more.

[0110] When the number of carbon atoms in the above-mentioned fatty acids is 15 to 25 (especially 16 to 18), the average degree of polymerization of glycerol is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0111] In the case of straight-chain fatty acids with 15 to 25 carbon atoms (especially 16 to 18), the peak intensity ratio shown in formula (X) is not particularly limited as long as it is 0.20 or higher, more preferably 0.24 or higher, more preferably 0.28 or higher, and even more preferably 0.30 or higher. In this case, the average degree of polymerization of glycerol is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0112] In the case of straight-chain fatty acids with 15 to 25 carbon atoms (especially 16 to 18) as described above, the average degree of polymerization of glycerol is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0113] In the case of branched fatty acids with 15 to 25 carbon atoms (particularly 16 to 18), the peak intensity ratio shown in formula (X) is not particularly limited as long as it is 0.20 or higher, preferably 0.25 or higher, more preferably 0.30 or higher, and even more preferably 0.33 or higher. In this case, the average degree of polymerization of glycerol is not particularly limited, preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0114] In the case of branched fatty acids with 15 to 25 carbon atoms (especially 16 to 18), the peak intensity ratio shown in formula (Y) is not particularly limited as long as it is 0.46 or less, preferably 0.40 or less, more preferably 0.37 or less, and even more preferably 0.35 or less. Furthermore, the peak intensity ratio shown in formula (Y) is not particularly limited, for example, it is 0.01 or more, preferably 0.05 or more, and even more preferably 0.10 or more.

[0115] In the case of branched fatty acids with 15 to 25 carbon atoms (especially 16 to 18) as described above, the average degree of polymerization of glycerol is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0116] In the case of unsaturated fatty acids with 15 to 25 carbon atoms (especially 16 to 18), the peak intensity ratio shown in formula (X) is not particularly limited as long as it is 0.20 or higher, more preferably 0.23 or higher, more preferably 0.25 or higher, more preferably 0.30 or higher, and even more preferably 0.33 or higher. In this case, the average degree of polymerization of glycerol is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0117] In the case of unsaturated fatty acids with 15 to 25 carbon atoms (especially 16 to 18), the peak intensity ratio shown in formula (Y) is not particularly limited as long as it is 0.46 or less, preferably 0.44 or less, more preferably 0.32 or less, more preferably 0.30 or less, and even more preferably 0.28 or less. Furthermore, the peak intensity ratio shown in formula (Y) is not particularly limited, for example, it is 0.01 or more, preferably 0.05 or more, and even more preferably 0.10 or more.

[0118] In the case of unsaturated fatty acids with 15 to 25 carbon atoms (especially 16 to 18) as described above, the average degree of polymerization of glycerol is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0119] In the polyglycerol monofatty acid ester products disclosed herein, the area ratio of the peaks corresponding to the monoesters, dehydrated monoesters, polyesters and dehydrated polyesters, and polyglycerol and dehydrated polyglycerol fatty acid esters in the following HPLC (high performance liquid chromatography) analysis is not particularly limited, but is preferably 50% or more, more preferably 60% or more, further preferably 80% or more, and particularly preferably 90% or more.

[0120] In the polyglycerol monofatty acid ester products disclosed herein, the area fraction of the peaks corresponding to the monoesters, dehydrated monoesters, polyesters, and dehydrated polyesters of polyglycerol fatty acid esters in the following HPLC (high performance liquid chromatography) analysis is preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more. Furthermore, the area fraction of the peaks corresponding to polyglycerol and dehydrated polyglycerol is, for example, 1% or more, 5% or more, 10% or more, or 20% or more; more preferably 80% or less, more preferably 70% or less, and even more preferably 60% or less.

[0121] (HPLC analysis)

[0122] The HPLC analysis method for polyglycerol monofatty acid ester products disclosed herein is not particularly limited; for example, the following apparatus and conditions can be used for determination.

[0123] • Device: LC-2030C 3D (Shimadzu Corporation).

[0124] • Chromatographic column: Two Wakosil 5C18 Φ4.6mm×250mm (W) columns are connected in series.

[0125] • Detector: RID-20A (manufactured by Shimadzu Corporation).

[0126] Furnace temperature: 40℃.

[0127] • Sample: 10% methanol solution.

[0128] • Sample injection volume: 10 μl.

[0129] • Mobile phase flow rate: 0.75 ml / min.

[0130] It should be noted that the aforementioned "peaks corresponding to the monoesters, dehydrated monoesters, polyesters and dehydrated polyesters, and polyglycerol and dehydrated polyglycerol fatty acid esters" refer to, for example, peaks in the HPLC analysis method described above that have a peak apex between 6.0 and 20.0 minutes in the HPLC chromatogram. Therefore, the area ratio of the aforementioned peaks is the sum of the peak area ratios between 6.0 and 20.0 minutes in the HPLC chromatogram.

[0131] The aforementioned "peaks corresponding to the monoesters, dehydrated monoesters, polyesters, and dehydrated polyesters of polyglycerol fatty acid esters" refer to, for example, peaks in the HPLC analysis method described above that have a peak apex between 8.2 and 20.0 minutes in the HPLC chromatogram. Therefore, the area ratio of the aforementioned peaks is the sum of the peak area ratios between 8.2 and 20.0 minutes in the HPLC chromatogram.

[0132] The aforementioned "peaks corresponding to polyglycerol and polyglycerol dehydrated products" refer to, for example, peaks in the HPLC analysis method described above that have a peak apex between 6.0 and 8.2 minutes of retention time in the HPLC chromatogram. Therefore, the area ratio of the aforementioned peaks is the sum of the peak area ratios between 6.0 and 8.2 minutes of retention time in the HPLC chromatogram.

[0133] [Manufacturing method of polyglycerol monofatty acid ester products]

[0134] The polyglycerol monofatty acid ester product disclosed herein can be obtained by any of the following reactions: (1) an addition polymerization reaction of glycidyl ether with fatty acids; (2) an esterification reaction of polyglycerol with fatty acids; and (3) an transesterification reaction of polyglycerol with fatty acid esters. Among these, the polyglycerol monofatty acid ester product obtained by the reaction described above (1) is preferred from the perspective of increasing the proportion of monoesters. That is, the polyglycerol monofatty acid ester product disclosed herein is preferably a polyglycerol monofatty acid ester product obtained by a manufacturing method having an addition polymerization reaction step of fatty acids and glycidyl ether.

[0135] The reaction described in (1) above can be carried out in the presence or absence of a catalyst. From the viewpoint of increasing the proportion of monoesters, it is preferable to carry it out in the presence of a catalyst (especially an acidic catalyst). In particular, when the average degree of polymerization of glycerol in the desired polyglycerol monoester product exceeds 5, the reaction described in (1) above is preferably carried out in the presence of a catalyst. This is because a tendency has been observed that the proportion of monoesters in the resulting polyglycerol monoester product increases significantly. Conversely, when the average degree of polymerization of glycerol in the desired polyglycerol monoester product is 5 or less, the reaction described in (1) above is preferably carried out in the presence of a catalyst, but even when carried out in the absence of a catalyst, no significant difference in the proportion of monoesters has been observed.

[0136] The aforementioned acidic catalyst is not particularly limited, but organic acids commonly used in cosmetics are preferred as catalysts, such as ascorbic acid; carboxylic acids such as acetic acid, formic acid, citric acid, succinic acid, and adipic acid; and phosphoric acid-based acidic catalysts. Organic acids with high acid dissociation constants are preferred as the aforementioned acid catalysts. From the viewpoint of the purity of polyglycerol monofatty acid ester products, phosphoric acid-based acidic catalysts are preferred.

[0137] Phosphoric acid catalysts mentioned above can be categorized into phosphoric acid derivatives or esters of phosphoric acid, such as: phosphoric acid, phosphoric anhydride, polyphosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, etc.; and acidic phosphate esters such as methyl phosphate, ethyl phosphate, isopropyl phosphate, butyl phosphate, 2-ethylhexyl phosphate, etc. Among these, phosphoric acid is preferred.

[0138] It should be noted that the above-mentioned catalyst can be used alone, or two or more can be used in combination. The amount of catalyst is 0.001 to 10 parts by weight relative to 100 parts by weight of fatty acid, preferably 0.01 to 5 parts by weight. A catalyst amount within the above range is preferred from the perspective of increasing the proportion of monoesters.

[0139] In the case of manufacturing polyglycerol monofatty acid ester products by the reaction described in (1) above, the reaction can be carried out, for example, (1-1) by continuously or intermittently supplying glycidol to fatty acids and continuously or intermittently supplying an acidic catalyst, and (1-2) by continuously or intermittently supplying glycidol to a mixture of fatty acids and an acidic catalyst. Furthermore, as an option to carry out the reaction in the absence of a catalyst, (1-3) can also be carried out by continuously or intermittently supplying glycidol to fatty acids.

[0140] To elaborate on (1-1) above, it refers to adding fatty acids to the reaction vessel and carrying out an addition polymerization reaction by continuously or intermittently supplying glycidol and an acidic catalyst to the reaction vessel. That is, it means continuously or intermittently supplying glycidol and an acidic catalyst to the fatty acids simultaneously for at least a certain period of time. It should be noted that, for example, dropwise addition can be used as a supply method. To elaborate on (1-2) above, it refers to adding fatty acids and an acidic catalyst to the reaction vessel and mixing them as needed, and carrying out an addition polymerization reaction by continuously or intermittently supplying glycidol to the reaction vessel. It should be noted that, for example, dropwise addition can be used as a supply method. To elaborate on (1-3) above, it refers to adding fatty acids to the reaction vessel and carrying out an addition polymerization reaction by continuously or intermittently supplying glycidol to the reaction vessel. That is, continuously or intermittently supplying glycidol to the fatty acids simultaneously for at least a certain period of time.

[0141] In the reaction described in (1) above, in the reaction system (e.g., in the reaction vessel), not only polyglycerol monofatty acid esters are formed, but polyglycerol is also formed. However, by adding glycidyl ether dropwise continuously or intermittently, the concentration of glycidyl ether in the system can be suppressed to a low level. Therefore, there is a tendency for the formation of polyglycerol monofatty acid esters to be more dominant than the formation of polyglycerol.

[0142] An acidic catalyst can be used to carry out the addition reaction with glycidyl ester on the basis of mixing with fatty acids, or the reaction can be carried out while fatty acids are continuously or intermittently supplied with glycidyl ester as needed. From the viewpoint of improving the purity of the obtained polyglycerol monofatty acid ester product, it is preferable to carry out the reaction while continuously or intermittently supplying an acidic catalyst with fatty acids and glycidyl ester. That is, the reaction described in (1) above is preferably carried out by the operation described in (1-1) above. This is because the acidic catalyst not only promotes or advances the formation of polyglycerol monofatty acid ester, but also promotes or advances the formation of polyglycerol. As a result, when an acidic catalyst is continuously or intermittently supplied with fatty acids and glycidyl ester, the formation of polyglycerol monofatty acid ester is particularly dominant than the formation of polyglycerol. For the same reason, when an acidic catalyst is supplied to fatty acids and glycidyl ester at one time, there is a tendency for the formation of polyglycerol to be dominant than the formation of polyglycerol monofatty acid ester. Therefore, from this viewpoint, it can also be said that it is preferable to carry out the above reaction by the operation described in (1-1) above.

[0143] In the reaction described in (1) above, the reactants may be ripened as needed after the operations described in (1-1) to (1-3) above. The reaction temperature in the reaction described in (1) above is not particularly limited, but is preferably 50–180°C, more preferably 70–160°C, even more preferably 100–140°C, and particularly preferably 110–135°C. Within the above temperature range, there is a tendency for side reactions such as the decomposition of glycidol to be less likely to occur. Ideally, the above reaction is carried out under a nitrogen atmosphere, but pressure may also be applied as needed.

[0144] The reactions described in (2) and (3) above can be carried out, for example, in the presence or absence of a catalyst (base catalyst or acid catalyst), under normal or reduced pressure. The amount of polyglycerol and fatty acid or polyglycerol and fatty acid esters is not particularly limited and can be selected appropriately. The reaction temperature is not particularly limited, but is preferably 20–180°C, more preferably 30–160°C, and even more preferably 40–140°C.

[0145] The obtained polyglycerol monofatty acid esters can be purified as needed. Purification methods can be implemented using well-known techniques, without particular limitation. Examples of purification methods include: adsorption treatment using activated carbon, activated clay, etc.; treatment under reduced pressure using water vapor, nitrogen, etc., as carrier gases; washing with acids or alkalis; and molecular distillation. Furthermore, liquid-liquid partitioning, adsorbents, resins, molecular sieves, loose reverse osmosis membranes, ultrafiltration membranes, etc., can also be used to remove impurities.

[0146] [Cosmetic composition]

[0147] The cosmetic composition disclosed herein is characterized by comprising the aforementioned polyglycerol monofatty acid ester product. Furthermore, the cosmetic composition may be combined with other ingredients without impairing the inventive effects of this disclosure. Examples of such other ingredients include, for instance: polyols, sugars, polysaccharides, amino acids, various surfactants (excluding the aforementioned polyglycerol monofatty acid ester product), organic salts, inorganic salts, pH adjusters, chelating agents, antioxidants, bactericides, blood flow promoters, anti-inflammatory agents, ultraviolet absorbers, ultraviolet scattering agents, vitamins, pigments, and fragrances.

[0148] The content of polyglycerol monofatty acid esters in the above-mentioned cosmetic composition is not particularly limited, but is preferably 0.01 to 80% by weight, more preferably 0.1 to 50% by weight, even more preferably 0.1 to 30% by weight, and particularly preferably 0.5 to 20% by weight. With the content of polyglycerol monofatty acid esters within the above range, there is a tendency for sufficient ease of application and spreadability when the makeup is dissolved and mixed.

[0149] The following are examples of particularly preferred embodiments of the above-mentioned cosmetic composition.

[0150] A cosmetic composition comprising a polyglycerol monofatty acid ester product (A) and a polyglycerol monofatty acid ester product (B), wherein the polyglycerol monofatty acid ester product (A) has a fatty acid with 15 to 25 carbon atoms (preferably 16 to 18), a peak intensity ratio shown by formula (X) of 0.31 or higher (preferably 0.33 or higher, more preferably 0.35 or higher, even more preferably 0.4 or higher), and a peak intensity ratio shown by formula (Y) of 0.46 or lower (preferably 0.37 or lower, more preferably 0.35 or lower). The average degree of polymerization of glycerol is 2 to 4 (preferably 4), and in the polyglycerol monofatty acid ester product (B), the number of carbon atoms of the fatty acid is 15 to 25 (preferably 16 to 18), the peak intensity ratio shown in the following formula (X) is 0.23 or more (preferably 0.24 or more, more preferably 0.25 or more, even more preferably 0.26 or more), the peak intensity ratio shown in the following formula (Y) is 0.46 or less (preferably 0.44 or less), and the average degree of polymerization of glycerol is 5 to 12 (preferably 6 to 10, more preferably 6 or 10).

[0151] Equation (X) = P2 / P1

[0152] Equation (Y) = P3 / P1

[0153] P1: The sum of peak intensities of monoesters, monoester dehydrates, diesters, diester dehydrates, trimesters and trimester dehydrates, as well as polyglycerol and polyglycerol dehydrates, when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using the above-mentioned time-of-flight mass spectrometer.

[0154] P2: Peak intensity of the monoester of polyglycerol fatty acid ester when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using the above-mentioned time-of-flight mass spectrometer.

[0155] P3: The sum of peak intensities of polyglycerol and polyglycerol dehydrate when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer.

[0156] When the cosmetic composition of this disclosure adopts the above-described scheme, there is a tendency for a pleasant feeling of freshness on the skin after makeup dissolution, removal, and rinsing. This tendency becomes significant by combining the above-described polyglycerol monofatty acid ester product (A) with a lower HLB value with the above-described polyglycerol monofatty acid ester product (B) with a higher HLB value, setting the HLB value to 9 to 13 (particularly 11 to 12.5). It should be noted that the HLB value in this case is a weighted average of the HLB values ​​of the polyglycerol monofatty acid ester product (A) and the polyglycerol monofatty acid ester product (B). The HLB value of the above-described polyglycerol monofatty acid ester product (A) is not particularly limited, but is preferably 9 to 11, more preferably 9.5 to 10.8, and even more preferably 10 to 10.6. The HLB value of the above-described polyglycerol monofatty acid ester product (B) is not particularly limited, but is preferably 11 to 17, more preferably 11.2 to 15.5, and even more preferably 11.5 to 15. Therefore, regarding the proportions of the polyglycerol monofatty acid ester product (A) and the polyglycerol monofatty acid ester product (B) in the cosmetic composition of this disclosure, considering their respective HLB values, it is preferable to adjust the proportions so that the combined HLB value is 9 to 13 (particularly 11 to 12.5). Specifically, for example, the weight ratio of the polyglycerol monofatty acid ester product (A) to the polyglycerol monofatty acid ester product (B) is preferably 20 to 80:80 to 20, more preferably 30 to 70:70 to 30, and even more preferably 40 to 60:60 to 40.

[0157] It should be noted that the HLB (Hydrophile-Lypophile Balance) value represents the affinity of surfactants such as polyglycerol monofatty acid esters for water and oil. The organic value (OV) and inorganic value (IV) can be obtained through an organic concept diagram and calculated according to the following formula.

[0158] HLB = IV / OV × 10 = IOB (Inorganic-Organic Equilibrium) × 10

[0159] There are no particular limitations on the specific products or forms of the cosmetic compositions disclosed herein. Examples include: lotions, emulsions, skin creams, sunscreens, facial cleansers, cleansing lotions, makeup removers, shampoos, conditioners, conditioning agents, hair styling products, hair creams, hair oils, hair styling liquids, hair bleaching agents, perming liquids, lipsticks, lip glosses, eyeshadows, nail polishes, mascaras, and eyeshadows.

[0160] In addition to the cosmetic compositions described above, the polyglycerol monofatty acid ester products disclosed herein can also be used in food additives, cleaning agent compositions, and general industrial applications.

[0161] The various solutions disclosed in this specification can also be combined with any other features disclosed in this specification. The various configurations and combinations thereof in each embodiment are merely examples, and appropriate additions, omissions, substitutions, and other modifications can be made to the configuration without departing from the spirit of this disclosure. Furthermore, the inventions of this disclosure are not limited to the embodiments or the following examples, but only to the claims.

[0162] Example

[0163] The embodiments of this disclosure will now be described in more detail.

[0164] (Mass spectroscopic analysis using a time-of-flight mass spectrometer (TOF-MS))

[0165] In the examples and comparative examples, the polyglycerol monofatty acid ester products were subjected to mass spectrometry analysis using the following apparatus and conditions.

[0166] ·Device: Xevo G2-XSQTof (Waters Co., Ltd.).

[0167] • Injection method: Injected via infusion (5 μL / min).

[0168] • Measurement mode: Neg.

[0169] • Conegas gas: 50L / h.

[0170] • Desolvation gas: 1000L / h.

[0171] • Source temperature (Source temp): 120℃.

[0172] • Desolvation temperature: 500℃.

[0173] • Capillary: 2.0kV.

[0174] • Sampling cone: 40.

[0175] • Source offset: 80.

[0176] • Sample concentration: 25 ppm (methanol).

[0177] MS range: 50~3000.

[0178] (Determination of HLB value)

[0179] In the examples and comparative examples, the HLB (Hydrophile-Lypophile Balance) values ​​of polyglycerol monofatty acid ester products can be obtained by using an organic concept diagram to determine the organic value (OV) and inorganic value (IV) according to the following formula.

[0180] HLB = IV / OV × 10 = IOB (Inorganic-Organic Equilibrium) × 10

[0181] (HPLC analysis)

[0182] In the examples and comparative examples, the polyglycerol monofatty acid ester products were analyzed by HPLC using the following apparatus and conditions.

[0183] • Device: LC-2030C 3D (Shimadzu Corporation).

[0184] • Chromatographic column: Two Wakosil 5C18 Φ4.6mm×250mm (W) columns are connected in series.

[0185] • Detector: RID-20A (manufactured by Shimadzu Corporation).

[0186] Furnace temperature: 40℃.

[0187] • Sample: 10% methanol solution.

[0188] • Sample injection volume: 10 μl.

[0189] • Mobile phase flow rate: 0.75 ml / min.

[0190] (Example 1)

[0191] 0.81 mol (139.7 g) of decanoic acid was added to a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature regulator, and dropping cylinder, and the mixture was heated to 120°C. Then, while maintaining the reaction temperature at 120°C, 4.86 mol (360.4 g) of glycidyl ether was added dropwise over 10 hours, with 0.004 mol (0.4 g) of 42.5% phosphoric acid added dropwise during the glycidyl ether addition. The mixture was then aged at 120°C for 3 hours. Next, the temperature was raised to 130°C, and the reaction was continued until the concentration of ethylene oxide in the system was less than 0.1%. After cooling, the reactants were removed, yielding approximately 500 g of polyglycerol monodecanoate with an average degree of polymerization of 6.

[0192] HPLC analysis of the obtained polyglycerol monodecanoate showed that the area fraction of the peaks corresponding to the monoester, monoester dehydrated product, polyester and polyester dehydrated product, and polyglycerol and polyglycerol dehydrated product in the HPLC chromatogram between retention times of 6.0 and 20.0 min was 93.0%. Furthermore, the area fraction of the peaks corresponding to the monoester, monoester dehydrated product, polyester and polyester dehydrated product in the HPLC chromatogram between retention times of 8.2 and 20 min was 47.9%. Additionally, the area fraction of the peaks corresponding to polyglycerol and polyglycerol dehydrated product in the HPLC chromatogram between retention times of 6.0 and 8.2 min was 45.1%. Figure 1 The figure shows the HPLC analysis results. In the figure, the peaks corresponding to monoesters, monoester dehydrates, polyesters and polyester dehydrates are labeled as "PGL esters, etc.", and the peaks corresponding to polyglycerols and polyglycerol dehydrates are labeled as "PGL, etc."

[0193] Furthermore, the obtained polyglycerol monodecanoate was analyzed by mass spectrometry using the aforementioned time-of-flight mass spectrometer (TOF-MS). The peak intensity ratio (P2 / P1) was calculated according to formula (X), and the result was 0.325. The peak intensity ratio (P3 / P1) was calculated according to formula (Y), and the result was 0.287.

[0194] Equation (X) = P2 / P1

[0195] Equation (Y) = P3 / P1

[0196] P1: The sum of peak intensities of monoesters, dehydrated monoesters, diesters, dehydrated diesters, trimesters and dehydrated trimesters, as well as polyglycerol and dehydrated polyglycerol, when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer.

[0197] P2: Peak intensity of the monoester of polyglycerol fatty acid ester during mass spectrometry analysis of polyglycerol monoester products using a time-of-flight mass spectrometer.

[0198] P3: The sum of peak intensities of polyglycerol and polyglycerol dehydrate when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer.

[0199] Furthermore, the HLB value of the obtained polyglycerol monodecanoate is 15.4.

[0200] [Method for calculating peak intensity ratio]

[0201] The following sections (a) to (e) provide a detailed explanation of the calculation method for peak intensity ratio.

[0202] (a) The molecular weight and peak intensity of each component contained in the polyglycerol monofatty acid ester product are obtained by means of a time-of-flight mass spectrometer. The decimal part of each molecular weight value is rounded down to the nearest integer, and the corresponding peak intensities are summed to obtain the peak intensity of the rounded molecular weight. For example, if the measured values ​​are 31 for a molecular weight of 50.0012, 5 for a molecular weight of 50.0041, and 15 for a molecular weight of 50.0241, the sum of the peak intensities of molecular weights of 50 and above but less than 51 (31 + 5 + 15 + ...) is the peak intensity of the rounded molecular weight of 50. It should be noted that the molecular weight range is set to 50 to 2999. This molecular weight range is determined considering the number of carbon atoms of the fatty acids and the degree of polymerization of glycerol in the polyglycerol monofatty acid ester product of this disclosure. That is, the range is determined based on the idea that the product can contain polyglycerol fatty acid esters and that there are almost no polyglycerol fatty acid esters outside the above molecular weight range.

[0203] Hereinafter, (a) of Example 1 will be described.

[0204] The molecular weights and peak intensities of each component in the polyglycerol monodecanoate obtained in Example 1 were determined by time-of-flight mass spectrometry. The decimal places of each molecular weight value were rounded down to the nearest integer, and the corresponding peak intensities were summed to obtain the values ​​shown in Tables 1-6.

[0205] [Table 1]

[0206]

[0207] [Table 2]

[0208]

[0209] [Table 3]

[0210]

[0211] [Table 4]

[0212]

[0213] [Table 5]

[0214]

[0215] [Table 6]

[0216]

[0217] (b) Calculate the theoretical molecular weights of the monoester, dehydrated monoester, diester, dehydrated diester, trimer, and dehydrated trimer of polyglycerol fatty acid esters, as well as polyglycerol and dehydrated polyglycerol. It should be noted that the monoester, diester, trimer, and polyglycerol are theoretical molecular weights for a degree of polymerization of glycerol of 1–20. Furthermore, the dehydrated monoester, dehydrated diester, dehydrated trimer, and dehydrated polyglycerol are theoretical molecular weights for a degree of polymerization of glycerol of 1–20 and for a degree of dehydration of 1–3 (the substance obtained by removing 1–3 water molecules).

[0218] Hereinafter, (b) of Example 1 will be described.

[0219] In Example 1, the theoretical molecular weight of the monoester of polyglycerol monodecanoate is recorded in the "Monoester" field of Table 7. The theoretical molecular weight of the dehydrated monoester is recorded in the "Dehydrated Monoester (Dehydration = 1)", "Dehydrated Monoester (Dehydration = 2)", and "Dehydrated Monoester (Dehydration = 3)" fields of Table 7. Similarly, diesters and other constituent components are also recorded.

[0220] [Table 7]

[0221]

[0222] (c) In order to correspond with the molecular weights obtained in (a) from the time-of-flight mass spectrometer, the theoretical molecular weights in (b) are corrected by the following method and are referred to as the “corrected molecular weights”.

[0223] • Correction method

[0224] The components whose molecular weight was determined and detected by time-of-flight mass spectrometry were molecules obtained by ionization followed by deprotonation [MH]. -Therefore, the molecular weights obtained in (a) are basically obtained by subtracting 1 from the integerized molecular weight (which is the theoretical molecular weight in (b)). However, if the molecular weight increases, the molecular weight at the intensity peak may deviate from 1 due to errors in molecular weight calculation and integerization. Therefore, for substances with a theoretical molecular weight of 700 or higher in (b), the peak intensities corresponding to the three values ​​are compared: the integerized molecular weight (M1), the value obtained by subtracting 1 from M1 (M2), and the value obtained by subtracting 2 from M1 (M3). The molecular weight with the highest peak intensity is taken as the "corrected molecular weight". Furthermore, for substances with a theoretical molecular weight less than 700 in (b), the value obtained by subtracting 1 from the integerized molecular weight (which is the theoretical molecular weight in (b)) is taken as the "corrected molecular weight".

[0225] • Adjustments after correction

[0226] Regarding the corrected molecular weight obtained by the above method, depending on the degree of dehydration of the polyglycerol chain, the degree of polymerization of the polyglycerol chain, and the number of bonds (esterification number) between the polyglycerol chain and fatty acids, sometimes even different structures can have the same molecular weight. In molecular design, the content of polyglycerol fatty acid esters with more esterification numbers and higher degrees of dehydration is reduced. Therefore, in the following benchmarks, polyglycerol fatty acid esters with the same corrected molecular weight are not included in the peak intensity except for the molecule with the highest order.

[0227] • Priority principle

[0228] 1. Number of esterifications: less > more.

[0229] 2. Dehydration degree: Less > More.

[0230] 3. In the above criteria 1 and 2, when the superiority or inferiority of the compared objects differs, the superiority or inferiority shall be judged in the order of 1>2. For example, in the comparison of specific components (A) and (B), if 1. component (B) has fewer esterifications and 2. component (A) has less glycerol dehydration, then in the above criteria, 1>2, so component (B) with fewer esterifications shall be given priority.

[0231] Furthermore, considering the esterification number and degree of polymerization of polyglycerol fatty acid esters, polyglycerol fatty acid esters are not included in peak intensity when the degree of dehydration becomes impossible. For example, to remove one water molecule from a polyglycerol fatty acid ester (with a dehydration degree of 1), the polyglycerol fatty acid ester requires more than two hydroxyl groups. Therefore, polyglycerol fatty acid esters with only one hydroxyl group do not have a dehydration degree of 1 to 3.

[0232] Hereinafter, (c) of Example 1 will be described.

[0233] For each component of polyglycerol monodecanoate calculated in Table 7, for components in (b) with a theoretical molecular weight less than 700, the value obtained by subtracting 1 from the molecular weight rounded to an integer after discarding the theoretical molecular weight is used as the "corrected molecular weight". For example, the theoretical molecular weight of the monoester (degree of polymerization of glycerol = 4) is 468.58, and the corrected molecular weight becomes 467.

[0234] For substances with a theoretical molecular weight of 700 or higher in (b), the peak intensities corresponding to the following three values ​​are compared: the molecular weight (M1) obtained by rounding down the theoretical molecular weight of (b), the value obtained by subtracting 1 from M1 (M2), and the value obtained by subtracting 2 from M1 (M3). The molecular weight with the highest intensity is taken as the "corrected molecular weight". For example, the theoretical molecular weight of polyglycerol (degree of polymerization of glycerol = 11, degree of dehydration = 3) is 778.83, so the molecular weight (M1) becomes 778, the molecular weight (M2) becomes 777, and the molecular weight (M3) becomes 776. Furthermore, the peak intensity corresponding to the molecular weight (M1) is 6780, the peak intensity corresponding to the molecular weight (M2) is 8510, and the peak intensity corresponding to the molecular weight (M3) is 6740 (refer to Table 2). Therefore, the molecular weight (M2) with the highest peak intensity, 8510, is taken as the "corrected molecular weight".

[0235] Furthermore, for example, the theoretical molecular weight of the trimer (glycerol degree of polymerization = 4) is 777.8, so the molecular weight (M1) becomes 777, the molecular weight (M2) becomes 776, and the molecular weight (M3) becomes 775. The peak intensity corresponding to molecular weight (M1) is 8510, the peak intensity corresponding to molecular weight (M2) is 6740, and the peak intensity corresponding to molecular weight (M3) is 7840 (refer to Table 2). Therefore, the highest peak intensity of 8510, i.e., 777, equals molecular weight (M1), and can be considered the "corrected molecular weight." However, the polyglycerol (glycerol degree of polymerization = 11, dehydration degree = 3) has the same corrected molecular weight. Therefore, according to the aforementioned "priority order principle," polyglycerol (glycerol degree of polymerization = 11, dehydration degree = 3) becomes the corrected molecular weight "777," and the trimer (glycerol degree of polymerization = 4) is not included in the peak intensity calculation.

[0236] Furthermore, the monoester (degree of polymerization of glycerol = 1) has two hydroxyl groups, resulting in a dehydration degree of 1, which is therefore included in the peak intensity calculation. However, there are no dehydration degrees of 2 or 3, so they are not included in the peak intensity calculation. The diester (degree of polymerization of glycerol = 1) has only one hydroxyl group, therefore there are no dehydration degrees of 1–3, and they are not included in the peak intensity calculation. Considering the above, the corrected molecular weights of each component are summarized in Table 8. "-" indicates components not included in the peak intensity calculation.

[0237] [Table 8]

[0238]

[0239] (d) Make the intensity obtained in (a) correspond to the corrected molecular weight of each component of the polyglycerol monofatty acid ester product calculated in (c), and sum them up in such a way that they become the peak intensities of “monoester", “monoester dehydrated product”, “diester", “diester dehydrated product”, “triester", “triester dehydrated product”, “polyglycerol”, and “polyglycerol dehydrated product” as specified in P1 to P3.

[0240] Hereinafter, (d) in Example 1 will be described.

[0241] The results of matching the intensity obtained in (a) with the corrected molecular weights of each component of polyglycerol monodecanoate calculated in (b) are shown in Table 9. Based on Table 9, the peak intensities of “monoester,” “monoester dehydrated product,” “diester,” “diester dehydrated product,” “triester,” “triester dehydrated product,” “polyglycerol,” and “polyglycerol dehydrated product” as specified in P1 are explained.

[0242] Figure 2 This is a graph showing the corrected molecular weight of polyglycerol monodecanoate from Example 1 and its corresponding peak intensity percentage (%). The hollow bar graph represents the monoester.

[0243] [Table 9]

[0244]

[0245] The peak intensity of "monoester" is the sum of the values ​​of 1,324,420 for the monoesters in Table 9 with a degree of polymerization of glycerol ranging from 1 to 20.

[0246] The peak intensity of "diester" is the sum of the values ​​of glycerol in the diesters in Table 9 when the degree of polymerization is 1 to 20, which is 244,000.

[0247] The peak intensity of the "triester" is the sum of the values ​​of 122,900 for the glycerol in the trimer in Table 9 with a degree of polymerization of 1 to 20.

[0248] The peak intensity of "polyglycerol" is the sum of the values ​​of 1 to 20 for the polyglycerol in Table 9, which is 320-400.

[0249] The peak intensity of “monoester dehydrated product” is the sum of the values ​​of glycerol in the monoester dehydrated products in Table 9 when the degree of polymerization of glycerol is 1 to 20 and the degree of dehydration is 1 to 3, which is 555300 (=207830+188370+159100).

[0250] The peak intensity of “diester dehydrated product” is the sum of the values ​​of glycerol in the diester dehydrated products in Table 9 when the degree of polymerization of glycerol is 1 to 20 and the degree of dehydration is 1 to 3, which is 533110 (=201130+169410+162570).

[0251] The peak intensity of the “triester dehydrated product” is the sum of the values ​​of glycerol in the trimester dehydrated products in Table 9 when the degree of polymerization of glycerol is 1 to 20 and the degree of dehydration is 1 to 3, which is 128630 (=42650+43130+42850).

[0252] The peak intensity of “polyglycerol dehydrated product” is the sum of the values ​​of glycerol in the polyglycerol dehydrated products in Table 9 when the degree of polymerization of glycerol is 1 to 20 and the degree of dehydration is 1 to 3, which is 848470 (=445710+258400+144360).

[0253] (e) Using the peak intensities of each component of the polyglycerol monofatty acid ester product calculated in (d), calculate the above formulas (X) and (Y).

[0254] Hereinafter, (e) in Example 1 will be described.

[0255] Equation (X) = P2 / P1 = 1324420 / 4077230 = 0.325

[0256] Equation (Y) = P3 / P1 = (320400 + 848470) / 4077230 = 0.287

[0257] (Example 2)

[0258] 0.55 mol (94.3 g) of decanoic acid was added to a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature regulator, and dropping cylinder, and the mixture was heated to 120°C. Then, while maintaining the reaction temperature at 120°C, 5.48 mol (405.67 g) of glycidyl ether was added dropwise over 10 hours, with 0.004 mol (0.4 g) of 42.5% phosphoric acid added dropwise during the glycidyl ether addition. The mixture was then aged at 120°C for 3 hours. Next, the temperature was raised to 130°C, and the reaction was continued until the concentration of ethylene oxide in the system was less than 0.1%. After cooling, the reactants were removed, yielding approximately 500 g of polyglycerol monodecanoate with an average degree of polymerization of 10.

[0259] HPLC analysis of the obtained polyglycerol monodecanoate showed that the area of ​​the peaks corresponding to the monoester, monoester dehydrate, polyester and polyester dehydrate, and polyglycerol and polyglycerol dehydrate in the HPLC chromatogram between 6.0 and 20.0 minutes was 93.8%.

[0260] Furthermore, the obtained polyglycerol monodecanoate was subjected to mass spectrometry analysis in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X), with a result of 0.353. The peak intensity ratio (P3 / P1) was calculated according to the above formula (Y), with a result of 0.322.

[0261] Furthermore, the HLB value of the obtained polyglycerol monodecanoate is 16.8.

[0262] (Example 3)

[0263] 0.53 mol (106.4 g) of lauric acid was added to a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature regulator, and dropping cylinder, and the mixture was heated to 120°C. Then, while maintaining the reaction temperature at 120°C, 5.31 mol (393.6 g) of glycidyl ether was added dropwise over 10 hours. 0.004 mol (0.4 g) of 42.5% phosphoric acid was added dropwise during the addition of glycidyl ether. The mixture was then aged at 120°C for 3 hours. Next, the temperature was raised to 130°C, and the reaction was continued until the concentration of ethylene oxide in the system was less than 0.1%. After cooling, the reactants were removed, yielding approximately 500 g of polyglycerol monolaurate with an average degree of polymerization of 10.

[0264] The obtained polyglycerol monolaurate was analyzed by HPLC. The results showed that the area of ​​the peaks corresponding to the monoester, the dehydrated monoester, the polyester and the dehydrated polyester, and the polyglycerol and the dehydrated polyglycerol in the HPLC chromatogram was 98.9%.

[0265] Furthermore, the obtained polyglycerol monolaurate was subjected to mass spectrometry analysis in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X), with a result of 0.429. The peak intensity ratio (P3 / P1) was calculated according to the above formula (Y), with a result of 0.348.

[0266] Furthermore, the HLB value of the obtained polyglycerol monolaurate is 16.0.

[0267] (Example 4)

[0268] 0.74 mol (169.7 g) of myristic acid was added to a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature regulator, and dropping cylinder, and the mixture was heated to 120°C. Then, while maintaining the reaction temperature at 120°C, 4.46 mol (330.3 g) of glycidyl ether was added dropwise over 10 hours, with 0.004 mol (0.4 g) of 42.5% phosphoric acid added dropwise during the glycidyl ether addition. The mixture was then matured at 120°C for 3 hours. Next, the temperature was raised to 130°C, and the reaction was continued until the concentration of ethylene oxide in the system was less than 0.1%. After cooling, the reactants were removed, yielding approximately 500 g of polyglycerol monomyristic ester with an average degree of polymerization of 6.

[0269] HPLC analysis of the obtained polyglycerol monomyristate showed that the area of ​​the peaks corresponding to the monoester, monoester dehydrated product, polyester and polyester dehydrated product, and polyglycerol and polyglycerol dehydrated product in the HPLC chromatogram between 6.0 and 20.0 minutes was 96.2%.

[0270] Furthermore, the obtained polyglycerol monomyristate was subjected to mass spectrometry analysis in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X), with a result of 0.446. The peak intensity ratio (P3 / P1) was calculated according to the above formula (Y), with a result of 0.267.

[0271] Furthermore, the HLB value of the obtained polyglycerol monomyristate is 13.4.

[0272] (Example 5)

[0273] 0.52 mol (117.8 g) of myristic acid was added to a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature regulator, and dropping cylinder, and the mixture was heated to 120°C. Then, while maintaining the reaction temperature at 120°C, 5.16 mol (382.18 g) of glycidyl ether was added dropwise over 10 hours, with 0.004 mol (0.4 g) of 42.5% phosphoric acid added dropwise during the glycidyl ether addition. The mixture was then aged at 120°C for 3 hours. Next, the temperature was raised to 130°C, and the reaction was continued until the concentration of ethylene oxide in the system was less than 0.1%. After cooling, the reactants were removed, yielding approximately 500 g of polyglycerol monomyristic ester with an average degree of polymerization of 10.

[0274] HPLC analysis of the obtained polyglycerol monomyristate showed that the area of ​​the peaks corresponding to the monoester, monoester dehydrate, polyester and polyester dehydrate, and polyglycerol and polyglycerol dehydrate in the HPLC chromatogram between 6.0 and 20.0 minutes was 97.4%.

[0275] Furthermore, the obtained polyglycerol monomyristate was subjected to mass spectrometry analysis in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X), with a result of 0.391. The peak intensity ratio (P3 / P1) was calculated according to the above formula (Y), with a result of 0.314.

[0276] Furthermore, the HLB value of the obtained polyglycerol monomyristate is 15.2.

[0277] (Example 6)

[0278] 0.69 mol (195.1 g) of stearic acid was added to a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature regulator, and dropping cylinder, and the mixture was heated to 120°C. Then, while maintaining the reaction temperature at 120°C, 4.12 mol (304.9 g) of glycidyl ether was added dropwise over 10 hours, with 0.004 mol (0.4 g) of 42.5% phosphoric acid added dropwise during the glycidyl ether addition. The mixture was then matured at 120°C for 3 hours. Next, the temperature was raised to 130°C, and the reaction was continued until the concentration of ethylene oxide in the system was less than 0.1%. After cooling, the reactants were removed, yielding approximately 500 g of polyglycerol monostearate with an average degree of polymerization of 6.

[0279] The obtained polyglycerol monostearate was insoluble in the assay solvent (10% methanol solution) and could not be analyzed by HPLC. However, considering its manufacturing method and the tendency of polyglycerol monofatty acid ester products in other examples, it is presumed that the area fraction of the peaks corresponding to monoesters, monoester dehydrates, polyesters and polyester dehydrates, and polyglycerol and polyglycerol dehydrates in the HPLC chromatogram between retention times of 6.0 and 20.0 minutes is at least 80%.

[0280] Furthermore, the obtained polyglycerol monostearate was subjected to mass spectrometry analysis in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X), with a result of 0.256. The peak intensity ratio (P3 / P1) was calculated according to the above formula (Y), with a result of 0.457.

[0281] Furthermore, the HLB value of the obtained polyglycerol monostearate is 11.9.

[0282] (Example 7)

[0283] 0.49 mol (138.7 g) of stearic acid was added to a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature regulator, and dropping cylinder, and the mixture was heated to 120°C. Then, while maintaining the reaction temperature at 120°C, 4.88 mol (361.3 g) of glycidyl ether was added dropwise over 10 hours, with 0.004 mol (0.4 g) of 42.5% phosphoric acid added dropwise during the glycidyl ether addition. The mixture was then aged at 120°C for 3 hours. Next, the temperature was raised to 130°C, and the reaction was continued until the concentration of ethylene oxide in the system was less than 0.1%. After cooling, the reactants were removed, yielding approximately 500 g of polyglycerol monostearate with an average degree of polymerization of 10.

[0284] The obtained polyglycerol monostearate was insoluble in the assay solvent (10% methanol solution) and could not be analyzed by HPLC. However, considering its manufacturing method and the tendency of polyglycerol monofatty acid ester products in other examples, it is presumed that the area fraction of the peaks corresponding to monoesters, monoester dehydrates, polyesters and polyester dehydrates, and polyglycerol and polyglycerol dehydrates in the HPLC chromatogram between retention times of 6.0 and 20.0 minutes is at least 80%.

[0285] Furthermore, the obtained polyglycerol monostearate was subjected to mass spectrometry analysis in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X), with a result of 0.410. The peak intensity ratio (P3 / P1) was calculated according to the above formula (Y), with a result of 0.414.

[0286] Furthermore, the HLB value of the obtained polyglycerol monostearate is 14.0.

[0287] (Example 8)

[0288] 0.86 mol (244.0 g) of oleic acid was added to a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature controller, and dropping cylinder, and the mixture was heated to 120°C. Then, while maintaining the reaction temperature at 120°C, 3.46 mol (256.0 g) of glycidyl ether was added dropwise over 20 hours. The mixture was then matured at 120°C for 3 hours. Next, the temperature was raised to 130°C, and the reaction was continued until the concentration of ethylene oxide in the system was less than 0.1%. After cooling, the reactants were removed, yielding approximately 500 g of polyglycerol monooleate with an average degree of polymerization of 4.

[0289] The obtained polyglycerol monooleate was analyzed by HPLC. The results showed that the area of ​​the peaks corresponding to the monoester, the dehydrated monoester, the polyester and the dehydrated polyester, and the polyglycerol and the dehydrated polyglycerol in the HPLC chromatogram was 95.5%.

[0290] Furthermore, the obtained polyglycerol monooleate was subjected to mass spectrometry analysis in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X), with a result of 0.502. The peak intensity ratio (P3 / P1) was calculated according to the above formula (Y), with a result of 0.316.

[0291] Furthermore, the HLB value of the obtained polyglycerol monooleate is 10.4.

[0292] (Example 9)

[0293] 0.69 mol (194.3 g) of oleic acid was added to a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature regulator, and dropping cylinder, and the mixture was heated to 120°C. Then, while maintaining the reaction temperature at 120°C, 4.13 mol (305.7 g) of glycidyl ether was added dropwise over 10 hours, with 0.004 mol (0.4 g) of 42.5% phosphoric acid added dropwise during the glycidyl ether addition. The mixture was then matured at 120°C for 3 hours. Next, the temperature was raised to 130°C, and the reaction was continued until the concentration of ethylene oxide in the system was less than 0.1%. After cooling, the reactants were removed, yielding approximately 500 g of polyglycerol monooleate with an average degree of polymerization of 6.

[0294] The obtained polyglycerol monooleate was analyzed by HPLC. The results showed that the area of ​​the peaks corresponding to the monoester, the dehydrated monoester, the polyester and the dehydrated polyester, and the polyglycerol and the dehydrated polyglycerol in the HPLC chromatogram was 95.8%.

[0295] Furthermore, the obtained polyglycerol monooleate was subjected to mass spectrometry analysis in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X), with a result of 0.558. The peak intensity ratio (P3 / P1) was calculated according to the above formula (Y), with a result of 0.382.

[0296] Furthermore, the HLB value of the obtained polyglycerol monooleate is 12.0.

[0297] (Example 10)

[0298] 0.49 mol (138.0 g) of oleic acid was added to a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature regulator, and dropping cylinder, and the mixture was heated to 120°C. Then, while maintaining the reaction temperature at 120°C, 4.89 mol (362.0 g) of glycidyl ether was added dropwise over 10 hours, with 0.004 mol (0.4 g) of 42.5% phosphoric acid added dropwise during the glycidyl ether addition. The mixture was then matured at 120°C for 3 hours. Next, the temperature was raised to 130°C, and the reaction was continued until the concentration of ethylene oxide in the system was less than 0.1%. After cooling, the reactants were removed, yielding approximately 500 g of polyglycerol monooleate with an average degree of polymerization of 10.

[0299] HPLC analysis of the obtained polyglycerol monooleate showed that the area of ​​the peaks corresponding to the monoester, monoester dehydrated product, polyester and polyester dehydrated product, and polyglycerol and polyglycerol dehydrated product in the HPLC chromatogram between 6.0 and 20.0 minutes was 98.6%.

[0300] Furthermore, the obtained polyglycerol monooleate was subjected to mass spectrometry analysis in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X), with a result of 0.274. The peak intensity ratio (P3 / P1) was calculated according to the above formula (Y), with a result of 0.435.

[0301] Furthermore, the HLB value of the obtained polyglycerol monooleate is 14.0.

[0302] (Example 11)

[0303] 0.86 mol (244.9 g) of isostearic acid was added to a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature regulator, and dropping cylinder, and the mixture was heated to 120°C. Then, while maintaining the reaction temperature at 120°C, 3.44 mol (255.1 g) of glycidyl ether was added dropwise over 20 hours. The mixture was then matured at 120°C for 3 hours. Next, the temperature was raised to 130°C, and the reaction was continued until the concentration of ethylene oxide in the system was less than 0.1%. After cooling, the reactants were removed to obtain approximately 500 g of polyglycerol monoisostearate with an average degree of polymerization of 4.

[0304] The obtained polyglycerol monoisostearate was analyzed by HPLC. The results showed that the area of ​​the peaks corresponding to the monoester, the dehydrated monoester, the polyester and the dehydrated polyester, and the polyglycerol and the dehydrated polyglycerol in the HPLC chromatogram was 97.6%.

[0305] Furthermore, the obtained polyglycerol monoisostearate was subjected to mass spectrometry analysis in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X), with a result of 0.507. The peak intensity ratio (P3 / P1) was calculated according to the above formula (Y), with a result of 0.307.

[0306] Furthermore, the HLB value of the obtained polyglycerol monoisostearate is 10.5.

[0307] (Comparative Example 1)

[0308] HPLC analysis of SY Glyster MO-7S (polyglycerol monooleate with an average degree of polymerization of 10 glycerol, manufactured by Sakamoto Pharmaceutical Co., Ltd.) showed that the area of ​​peaks corresponding to the monoester, dehydrated monoester, polyester and dehydrated polyester, and polyglycerol and dehydrated polyglycerol in the HPLC chromatogram between retention times of 6.0 and 20.0 minutes was 95.5%. Furthermore, mass spectrometry analysis was performed in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X), resulting in a value of 0.167. Additionally, the peak intensity ratio (P3 / P1) was calculated according to the above formula (Y), resulting in a value of 0.447.

[0309] In addition, the HLB value in the SY Glyster MO-7S is 14.0.

[0310] (Comparative Example 2)

[0311] 0.5 mol (100.1 g) of lauric acid and 0.118 g of 42.5% phosphoric acid were added to a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature regulator, and dropping cylinder, and the mixture was heated to 140°C. Then, while maintaining the reaction temperature at 140°C, 5.0 mol (370.40 g) of glycidyl ether was added dropwise over 5 hours until the concentration of ethylene oxide in the system was less than 0.1%. After cooling, the reactants were removed, yielding approximately 470 g of polyglycerol monolaurate with an average degree of polymerization of 10.

[0312] The obtained polyglycerol monolaurate was analyzed by HPLC. The results showed that the area of ​​the peaks corresponding to the monoester, the dehydrated monoester, the polyester and the dehydrated polyester, and the polyglycerol and the dehydrated polyglycerol in the HPLC chromatogram was 98.4%.

[0313] Furthermore, the obtained polyglycerol monolaurate was subjected to mass spectrometry analysis in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X), with a result of 0.410. In addition, the peak intensity ratio (P3 / P1) was calculated according to the above formula (Y), with a result of 0.496.

[0314] Furthermore, the HLB value in polyglycerol monolaurate is preferably 16.0.

[0315] [evaluate]

[0316] Sample 1 (cosmetic composition) was prepared in a ratio of 10:10:80 (by weight) comprising polyglycerol monooleate with an average degree of polymerization of 4 obtained in Example 8, polyglycerol monooleate with an average degree of polymerization of 6 obtained in Example 9, and MORESCO-WHITE P-70 (liquid paraffin, manufactured by MORESCO Co., Ltd.) as an oiling agent. The HLB value of Sample 1 was 11.2.

[0317] Sample 2 (cosmetic composition) was prepared in a ratio of 10:10:80 (by weight) comprising polyglycerol monooleate with an average degree of polymerization of 4 obtained in Example 8, polyglycerol monooleate with an average degree of polymerization of 10 obtained in Example 10, and MORESCO-WHITE P-70 (liquid paraffin, manufactured by MORESCO Co., Ltd.) as an oiling agent. The HLB value of Sample 2 was 12.2.

[0318] Sample 3 (cosmetic composition) was prepared in a ratio of 10:10:80 (by weight) comprising polyglycerol monooleate with an average degree of polymerization of 4 obtained in Example 8, SY Glyster MO-7S (polyglycerol monooleate with an average degree of polymerization of 10, manufactured by Sakamoto Pharmaceutical Co., Ltd.), and MORESCO-WHITE P-70 (liquid paraffin, manufactured by MORESCO Co., Ltd.) as an oiling agent. The HLB value of Sample 3 was 12.2.

[0319] Lipstick (brand name: Lipstick Y, manufactured by Chifure Holdings Co., Ltd.) was applied to the arm of the test subject, and samples 1-3 were mixed on it, then rinsed with water. The evaluation of samples 1-3 was carried out as described below.

[0320] [Makeup Removal]

[0321] 〇: Remove lipstick cleanly.

[0322] ×: Lipstick not removed.

[0323] [The texture of the skin after cleansing]

[0324] 〇: Refreshing.

[0325] ×: Sticky.

[0326] The evaluation results showed that for Sample 1 and Sample 2, both the [makeup removal] and [skin texture after cleansing] results were "0". On the other hand, for Sample 3, both the [makeup removal] and [skin texture after cleansing] results were "×". Based on these evaluations, it can be seen that by incorporating the polyglycerol monofatty acid ester product of this disclosure into a cosmetic composition, the cosmetic effects of [makeup removal] and [skin texture after cleansing] can be achieved.

[0327] In summary, the following notes pertain to the composition and variations of this disclosure.

[0328] [1]

[0329] A polyglycerol monofatty acid ester product, wherein the fatty acid has 4 to 25 carbon atoms, the peak intensity ratio shown in the following formula (X) is 0.20 or higher, and the peak intensity ratio shown in the following formula (Y) is 0.46 or lower.

[0330] Equation (X) = P2 / P1

[0331] Equation (Y) = P3 / P1

[0332] P1: The sum of peak intensities of monoesters, dehydrated monoesters, diesters, dehydrated diesters, trimesters and dehydrated trimesters, as well as polyglycerol and dehydrated polyglycerol, when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer.

[0333] P2: Peak intensity of the monoester of polyglycerol fatty acid ester during mass spectrometry analysis of polyglycerol monoester products using a time-of-flight mass spectrometer.

[0334] P3: The sum of peak intensities of polyglycerol and polyglycerol dehydrate when performing mass spectrometry analysis of polyglycerol monofatty acid ester products using a time-of-flight mass spectrometer.

[0335] [2]

[0336] According to the polyglycerol monofatty acid ester product described in [1], the number of carbon atoms of the fatty acid is 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 15 or more, 16 or more or 18 or more; and / or 22 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less or 8 or less.

[0337] [3]

[0338] According to the polyglycerol monofatty acid ester product described in [1] or [2], wherein the number of carbon atoms of the fatty acid is 4 to 14, 15 to 25, 8 to 14 or 16 to 18.

[0339] [4]

[0340] The polyglycerol monofatty acid ester product according to any one of [1] to [3], wherein the peak intensity ratio shown by the formula (X) is 0.21 or more, 0.23 or more, 0.24 or more, 0.25 or more, 0.26 or more, 0.28 or more, 0.3 or more, 0.31 or more, 0.33 or more, 0.35 or more, 0.37 or more, 0.40 or more, 0.44 or more, 0.48 or more, or 0.52 or more; and / or 1 or less, 0.9 or less, 0.8 or less, 0.75 or less, 0.7 or less, 0.65 or less, or 0.6 or less.

[0341] [5]

[0342] The polyglycerol monofatty acid ester product according to any one of [1] to [4], wherein the peak intensity ratio shown by the formula (Y) is 0.45 or less, 0.44 or less, 0.42 or less, 0.39 or less, 0.37 or less, 0.35 or less, 0.33 or less, 0.32 or less, or 0.30 or less; and / or 0.01 or more, 0.05 or more, or 0.10 or more.

[0343] [6]

[0344] The polyglycerol monofatty acid ester product according to any one of [1] to [5], wherein the average degree of polymerization of glycerol is 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more or 9 or more; and / or 35 or less, 30 or less, 25 or less, 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less or 4 or less.

[0345] [7]

[0346] The polyglycerol monofatty acid ester product according to any one of [1] to [6], wherein the average degree of polymerization of glycerol is 2 to 40, 3 to 20 or 4 to 10.

[0347] [8]

[0348] The polyglycerol monofatty acid ester product according to any one of [1] to [7], wherein the fatty acid is a straight-chain fatty acid or a branched-chain fatty acid.

[0349] [9]

[0350] The polyglycerol monofatty acid ester product according to any one of [1] to [8], wherein the fatty acid is a saturated fatty acid or an unsaturated fatty acid.

[0351]

[10]

[0352] The polyglycerol monofatty acid ester product according to any one of [1] to [9], wherein the fatty acid is selected from hexanoic acid (C6, saturated fatty acid), caprylic acid (C8, saturated fatty acid), nonanoic acid (C9, saturated fatty acid), 2-ethylhexanoic acid (C8, branched-chain fatty acid), decanoic acid (C9, branched-chain fatty acid), and 2-ethylhexanoic acid (C8, branched-chain fatty acid). 10 saturated fatty acids), lauric acid (C 12 saturated fatty acids), isotriadecanoic acid (C 13 Branched-chain fatty acids), myristic acid (C 14 saturated fatty acids), pentadecanoic acid (C 15 saturated fatty acids), palmitic acid (C 16 saturated fatty acids), palmitoleic acid (C 16 Unsaturated fatty acids), stearic acid (C 18 saturated fatty acids), isostearic acid (C 18 Branched-chain fatty acids), oleic acid (C 18 (unsaturated fatty acids), linoleic acid (C 18 Unsaturated fatty acids), ricinoleic acid (C 18 Unsaturated fatty acids), hydroxystearic acid (C 18 (replaced fatty acids), arachidic acid (C 20 saturated fatty acids), behenic acid (C 22 saturated fatty acids), erucic acid (C 22 (unsaturated fatty acids) and nervonic acid (C 24 It consists of at least one of the group consisting of unsaturated fatty acids.

[0353]

[11]

[0354] The polyglycerol monofatty acid ester product according to any one of [1] to

[10] , wherein the area ratio of the peak corresponding to the monoester, monoester dehydrate, polyester and polyester dehydrate, and polyglycerol and polyglycerol dehydrate in HPLC (high performance liquid chromatography) analysis is 50% or more, 60% or more, 80% or more, or 90% or more.

[0355]

[12]

[0356] The polyglycerol monofatty acid ester product according to any one of [1] to

[11] , wherein the area of ​​the peak corresponding to the monoester, monoester dehydrate, polyester and polyester dehydrate of the polyglycerol fatty acid ester in HPLC (high performance liquid chromatography) analysis is 5% or more, 10% or more or 20% or more.

[0357]

[13]

[0358] The polyglycerol monofatty acid ester product according to any one of [1] to

[12] , wherein the area of ​​the peak corresponding to polyglycerol and polyglycerol dehydrate in HPLC analysis is less than 80%, less than 70%, or less than 60%.

[0359]

[14]

[0360] The polyglycerol monofatty acid ester product according to any one of [1] to

[13] is a reaction product of glycidyl ester and fatty acid, an esterified product of polyglycerol and fatty acid, or an ester exchanger of polyglycerol and fatty acid ester.

[0361]

[15]

[0362] A cosmetic composition comprising a polyglycerol monofatty acid ester product according to any one of [1] to

[14] .

[0363]

[16]

[0364] According to the cosmetic composition described in

[15] , the content of the polyglycerol monofatty acid ester product is 0.01 to 80% by weight, 0.1 to 50% by weight, 0.1 to 30% by weight, or 0.5 to 20% by weight.

[0365]

[17]

[0366] According to the cosmetic composition of

[15] or

[16] , wherein the HLB value of the polyglycerol monofatty acid ester contained in the cosmetic composition is 9 to 13 or 11 to 12.5.

[0367]

[18]

[0368] A method for manufacturing polyglycerol monofatty acid ester products, comprising: an addition polymerization reaction step of glycidyl ether and fatty acid.

[0369]

[19]

[0370] According to the method for manufacturing polyglycerol monofatty acid ester products described in

[18] , an addition polymerization reaction is carried out in the presence of an acidic catalyst.

[0371]

[20]

[0372] According to the method for manufacturing polyglycerol monofatty acid ester products as described in

[18] or

[19] , wherein the acidic catalyst is at least one selected from the group consisting of ascorbic acid, acetic acid, formic acid, citric acid, succinic acid, adipic acid and phosphoric acid catalysts.

[0373] [twenty one]

[0374] According to the manufacturing method of polyglycerol monofatty acid ester products described in

[20] , the phosphoric acid catalyst is a phosphoric acid or an acidic phosphate ester.

[0375] [twenty two]

[0376] The method for manufacturing polyglycerol monofatty acid ester products according to any one of

[18] to

[21] , wherein an addition polymerization reaction is carried out by continuously or intermittently supplying glycidyl esters to fatty acids.

[0377] [twenty three]

[0378] The method for manufacturing polyglycerol monofatty acid ester products according to any one of

[18] to

[21] , wherein an addition polymerization reaction is carried out by continuously or intermittently supplying glycidyl esters to fatty acids and continuously or intermittently supplying an acidic catalyst.

Claims

1. A polyglycerol mono fatty acid ester preparation, wherein, the number of carbon atoms of the fatty acid is 4 to 25, the peak intensity ratio represented by the following formula (X) is 0.20 or more, the peak intensity ratio represented by the following formula (Y) is 0.46 or less, Formula (X) = P2 / P1; Formula (Y) = P3 / P1, P1: the total of the peak intensities of the monoester, the monoester anhydride, the diester, the diester anhydride, the triester, the triester anhydride, the polyglycerol, and the polyglycerol anhydride of the polyglycerol mono fatty acid ester product when mass spectrometric analysis of the polyglycerol mono fatty acid ester product is performed using a time-of-flight mass spectrometer, P2: the peak intensity of the monoester of the polyglycerol mono fatty acid ester when mass spectrometric analysis of the polyglycerol mono fatty acid ester product is performed using a time-of-flight mass spectrometer, P3: the total of the peak intensities of the polyglycerol and the polyglycerol anhydride when mass spectrometric analysis of the polyglycerol mono fatty acid ester product is performed using a time-of-flight mass spectrometer.

2. The polyglycerol monofatty acid ester preparation according to claim 1, wherein, the number of carbon atoms of the fatty acid is 15 to 25.

3. The polyglycerol monofatty acid ester preparation according to claim 1, wherein, the number of carbon atoms of the fatty acid is 4 to 14.

4. The polyglycerol monofatty acid ester preparation according to claim 2, wherein, the number of carbon atoms of the fatty acid is 16 to 18.

5. The polyglycerol monofatty acid ester preparation according to claim 3, wherein, the number of carbon atoms of the fatty acid is 8 to 14.

6. The polyglycerol monofatty acid ester preparation according to claim 2 or 3, wherein, the average degree of polymerization of the glycerol is 2 to 20.

7. The polyglycerol monofatty acid ester preparation according to claim 2 or 3, wherein, the fatty acid is a straight-chain fatty acid.

8. The polyglycerol monofatty acid ester preparation according to claim 2 or 3, wherein, the fatty acid is an unsaturated fatty acid.

9. The polyglycerol monofatty acid ester preparation according to claim 2 or 3, wherein, the fatty acid is a branched-chain fatty acid.

10. The polyglycerol monofatty acid ester preparation according to claim 1, wherein, the polyglycerol mono fatty acid ester product is a reaction product of glycidol and a fatty acid.

11. A cosmetic composition comprising the polyglycerol mono fatty acid ester product according to claim 1.

12. A method for producing a polyglycerol mono fatty acid ester product, comprising: a step of addition polymerization reaction of glycidol and a fatty acid.

13. The method of manufacturing a polyglycerol monofatty acid ester preparation according to claim 12, wherein, The addition polymerization reaction is performed by continuously or intermittently supplying glycidol to the fatty acid.

14. The method for producing a polyglycerol mono fatty ester preparation according to claim 12, wherein, The addition polymerization reaction is performed by continuously or intermittently supplying glycidol to the fatty acid and continuously or intermittently supplying an acidic catalyst.

15. The method for producing a polyglycerol mono fatty acid ester preparation according to claim 13 or 14, wherein, The acidic catalyst is a phosphoric acid or an acidic phosphoric ester.

Images