Polyglycerol monofatty acid ester product and producing method thereof

Abstract

To provide a highly pure polyglycerol monofatty acid ester product and a producing method capable of obtaining a highly pure polyglycerol mono-fatty acid ester.SOLUTION: Products of polyglycerol monofatty acid esters, where the number of carbon atoms in the fatty acids is between 4 and 25, the peak intensity ratio represented by the formula (X) is 0.20 or higher, and the peak intensity ratio represented by the formula (Y) is 0.46 or lower. Formula (X)=P2 / P1 Formula (Y)=P3 / P1, where P1: the sum total of the peak intensities of the monoester, monoester dehydrated product, diester, diester dehydrated product, triester, and triester dehydrated product of polyglycerol fatty acid esters, when conducted mass spectrometry of polyglycerol mono fatty acid ester products using a flight time mass spectrometer P2: the peak intensity of polyglycerol fatty acid ester P3: the sum total of the peak intensities of polyglycerol and polyglycerol dehydrated product, when mass spectrometry of the polyglycerol mono fatty acid ester product is conducted using a time-of-flight mass spectrometer.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to polyglycerol mono-fatty acid ester products and methods for making same. [Background technology]

[0002] Polyglycerol monofatty acid esters exhibit various properties depending on the combination of the degree of polymerization of polyglycerol with fatty acids having different chain lengths, and have been used as surfactants in a wide range of applications, such as food additives, detergent compositions, and cosmetics (cosmetic compositions), etc. Methods for producing such polyglycerol fatty acid esters include the esterification reaction of polyglycerol with fatty acids, the transesterification reaction of polyglycerol with fatty acid esters, and the addition polymerization reaction of glycidol with fatty acids (Patent Documents 1 to 6).

[0003] Patent Document 7 describes a polyglycerol monolaurate obtained by reacting lauric acid, glycidol, and phosphoric acid while feeding them to a reactor in a specific ratio. Patent Document 8 describes an invention of a polyglycerol monooleate composition obtained by adding a chain diglycerol monooleate to a flask and reacting it while adding glycidol and phosphoric acid dropwise.

[0004] However, polyglycerol mono-fatty acid esters known so far contain a large amount of by-products other than the monoester (e.g., monoester dehydrates, diesters, diester dehydrates, triesters, and triesters dehydrates, etc.), and the purity of the monoesters is not high. Therefore, when the polyglycerol mono-fatty acid esters are used as surfactants, there are problems such as the inability to efficiently reduce the surface tension. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 8-109153 [Patent Document 2] Japanese Patent Application Publication No. 9-117258 [Patent Document 3] Japanese Patent Application Publication No. 9-216813 [Patent Document 4] Japanese Patent Application Publication No. 9-272893 [Patent Document 5] JP 2006-111539 A [Patent Document 6] International Publication No. 2004 / 048304 [Patent Document 7] JP 2001-139679 A [Patent Document 8] JP 2017-071586 A Summary of the Invention [Problem to be solved by the invention]

[0006] The polyglycerol mono-fatty acid ester product of Reference 7 is obtained by a method in which fatty acids, an acid catalyst, and glycidol are continuously supplied and reacted together, and therefore does not satisfy the range of peak intensity ratios represented by formulas (X) and (Y) in the present disclosure, which will be described later. In addition, the polyglycerol mono-fatty acid ester product of Reference 8 uses diglycerol mono-fatty acid ester, not fatty acids, as a raw material, and therefore does not satisfy the range of peak intensity ratios represented by formulas (X) and (Y) in the present disclosure, which will be described later.

[0007] Therefore, an object of the present disclosure is to provide a polyglycerol mono-fatty acid ester product with high purity. Another object of the present disclosure is to provide a production method by which a polyglycerol mono-fatty acid ester with high purity can be obtained. [Means for solving the problem]

[0008] As a result of intensive research aimed at solving the above problems, the inventors of the present disclosure have discovered a polyglycerol mono-fatty acid ester product having high purity. The present invention has been completed based on these findings.

[0009] That is, the present disclosure relates to a fatty acid having 4 to 25 carbon atoms, The peak intensity ratio represented by the following formula (X) is 0.20 or more, The present invention provides a polyglycerol mono-fatty acid ester product having a peak intensity ratio represented by the following formula (Y) of 0.46 or less. Formula (X)=P2 / P1 Formula (Y)=P3 / P1 P1: The sum of peak intensities of monoesters, monoester dehydrates, diesters, diester dehydrates, triesters, and triester dehydrates of polyglycerol fatty acid esters, as well as polyglycerol and polyglycerol dehydrates, when mass spectrometry of polyglycerol mono fatty acid ester products is performed using a time-of-flight mass spectrometer. P2: Peak intensity of monoester of polyglycerol fatty acid ester when mass spectrometry of polyglycerol mono fatty acid ester product was performed using a time-of-flight mass spectrometer P3: The sum of the peak intensities of polyglycerin and polyglycerin dehydrates when the polyglycerin mono fatty acid ester product was subjected to mass spectrometry using a time-of-flight mass spectrometer.

[0010] The polyglycerol mono-fatty acid ester product preferably contains a fatty acid having 15 to 25 carbon atoms.

[0011] It is also preferable that the polyglycerol mono-fatty acid ester product has a fatty acid having 4 to 14 carbon atoms.

[0012] The polyglycerol mono-fatty acid ester product preferably contains fatty acids having 16 to 18 carbon atoms.

[0013] The polyglycerol mono-fatty acid ester product preferably contains a fatty acid having 8 to 14 carbon atoms.

[0014] In the polyglycerol monofatty acid ester product, the average polymerization degree of glycerin is preferably 2-20.

[0015] In the polyglycerol mono-fatty acid ester product, the fatty acid is preferably a straight-chain fatty acid.

[0016] In the polyglycerol mono-fatty acid ester product, the fatty acid is preferably an unsaturated fatty acid.

[0017] In the polyglycerol mono-fatty acid ester product, the fatty acid is preferably a branched chain fatty acid.

[0018] The polyglycerol mono fatty acid ester product is preferably a reaction product of glycidol and a fatty acid.

[0019] The present disclosure also provides a cosmetic composition comprising the polyglycerol mono-fatty acid ester product.

[0020] The present disclosure also provides a method for producing a polyglycerol mono-fatty acid ester product, comprising the step of an addition polymerization reaction between glycidol and a fatty acid.

[0021] In the above-mentioned method for producing a polyglycerol mono-fatty acid ester product, it is preferable to carry out the addition polymerization reaction by continuously or intermittently supplying glycidol to a fatty acid.

[0022] In the above-mentioned method for producing a polyglycerol monofatty acid ester product, it is preferable to carry out the addition polymerization reaction by continuously or intermittently supplying glycidol to a fatty acid while continuously or intermittently supplying an acidic catalyst to the fatty acid.

[0023] The acid catalyst is preferably a phosphoric acid or an acidic phosphoric acid ester. Effect of the Invention

[0024] As described above, the polyglycerol mono-fatty acid ester product of the present disclosure contains a polyglycerol mono-fatty acid ester with high purity. Moreover, the production method of the present disclosure can provide a polyglycerol mono-fatty acid ester product with high purity. [Brief description of the drawings]

[0025] [Figure 1] 1 is a chart of HPLC analysis of polyglycerol monocapric acid ester of Example 1. [Diagram 2] 1 is a chart showing the corrected molecular weight and the corresponding peak intensity for the polyglycerol monocapric acid ester of Example 1. The hollow bars indicate the monoester form. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] [Polyglycerol mono fatty acid ester products] The polyglycerol monofatty acid ester product of the present disclosure is characterized in that the number of carbon atoms in the fatty acid is 4 to 25, the peak intensity ratio represented by the following formula (X) is 0.20 or more, and 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 sum of peak intensities of monoesters, monoester dehydrates, diesters, diester dehydrates, triesters, and triester dehydrates of polyglycerol fatty acid esters, as well as polyglycerol and polyglycerol dehydrates, when mass spectrometry of polyglycerol mono fatty acid ester products is performed using a time-of-flight mass spectrometer. P2: Peak intensity of monoester of polyglycerol fatty acid ester when mass spectrometry of polyglycerol mono fatty acid ester product was performed using a time-of-flight mass spectrometer P3: The sum of the peak intensities of polyglycerin and polyglycerin dehydrates when the polyglycerin mono fatty acid ester product was subjected to mass spectrometry using a time-of-flight mass spectrometer.

[0027] The polyglycerin mono-fatty acid ester product of the present disclosure contains at least a polyglycerin mono-fatty acid ester. In addition to the polyglycerin mono-fatty acid ester, the product may contain a polyglycerin poly-fatty acid ester such as a polyglycerin di-fatty acid ester and a polyglycerin tri-fatty acid ester. The product may also contain polyglycerin, which is a raw material for the polyglycerin mono-fatty acid ester product. The product may also contain dehydrates thereof, which will be described later.

[0028] The polyglycerol monofatty acid ester is represented, for example, by the following formula (1). RC(=O)-[C3H6O2] n -OH···(1)

[0029] In formula (1), R represents an aliphatic hydrocarbon group having 3 to 24 carbon atoms. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkyl group having a hydroxyl group. The number of carbon atoms in the aliphatic hydrocarbon group corresponds to the "carbon number of fatty acid" described below minus 1. n represents the average degree of polymerization of glycerin, and is, for example, 2 to 20.

[0030] The C3H6O2 in the parentheses of the above formula (1) includes at least one structure selected from the group consisting of the following formulas (2), (3), and (4). -O-CH2-CH(OH)-CH2-...(2) -O-CH(CH2OH)-CH2-...(3) -O-CH2-CH(CH2OH)-···(4)

[0031] In this specification, polyglycerol mono-fatty acid esters are sometimes simply referred to as "monoesters". Polyglycerol di-fatty acid esters are formed by bonding two hydroxyl groups of polyglycerol with carboxyl groups of fatty acids by forming ester bonds. Such polyglycerol mono-fatty acid esters are sometimes simply referred to as "diesters". Polyglycerol tri-fatty acid esters are formed by bonding three hydroxyl groups of polyglycerol with carboxyl groups of fatty acids by forming ester bonds. Such polyglycerol mono-fatty acid esters are sometimes simply referred to as "tri-esters". In addition, 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 manner as above. In addition, these polyglycerol poly-fatty acid esters are sometimes referred to as "polyesters".

[0032] In the polyglycerin mono fatty acid ester product of the present disclosure, polyglycerin may be partially dehydrated during the manufacturing process. In the polyglycerin mono fatty acid ester, a part of polyglycerin may be referred to as a polyglycerin mono fatty acid ester dehydrate, or a monoester dehydrate of polyglycerin fatty acid ester, or may be simply referred to as a monoester dehydrate. Similarly, polyglycerin poly fatty acid esters such as polyglycerin di fatty acid esters and polyglycerin tri fatty acid esters may be referred to as polyglycerin di fatty acid ester dehydrates or diester dehydrates, polyglycerin poly fatty acid ester dehydrates or polyester dehydrates such as polyglycerin tri fatty acid ester dehydrates or triester dehydrates. These dehydrates may have a cyclic structure.

[0033] The polyglycerol mono-fatty acid ester of the present disclosure may be (1) one obtained by a reaction of addition polymerization of glycidol to a fatty acid, (2) one obtained by an esterification reaction of polyglycerol and a fatty acid, or (3) one obtained by an ester exchange reaction of polyglycerol and a fatty acid ester. The polyglycerol mono-fatty acid ester obtained by the reaction (1) above can be rephrased as a reaction product of glycidol and a fatty acid. The polyglycerol mono-fatty acid ester obtained by the reaction (2) above can be rephrased as an esterified product of polyglycerol and a fatty acid. The polyglycerol mono-fatty acid ester obtained by the reaction (3) above can be rephrased as an ester exchange product of polyglycerol and a fatty acid ester. Among these, the reaction product of glycidol and a fatty acid of (1) above is preferred in that the proportion of monoesters in the polyglycerol mono-fatty acid ester product is high.

[0034] (Time-of-flight mass spectrometer (TOF-MS)) The time-of-flight mass spectrometer (TOF-MS) and its measurement conditions for the polyglycerol mono-fatty acid ester product of the present disclosure are not particularly limited. For example, the measurement can be performed using the following device and conditions. Equipment: Xevo G2‐XSQTof (Waters Corporation) Injection method: Infusion (5μL / min) Measurement mode: Neg Conegas: 50L / h Desolvation gas: 1000L / h Source temperature: 120℃ Desolvation temperature: 500℃ Capillary: 2.0kV Sampling cone:40 Source offset: 80 Sample concentration: 25ppm (methanol) MS range: 50~3000

[0035] In the present disclosure, the peak intensity ratio represented by formula (X) is calculated by P2 / P1, and the peak intensity ratio represented by formula (Y) is calculated by P3 / P1. The above P1 is the sum of the peak intensities of the monoester, monoester dehydrate, diester, diester dehydrate, triester, and triester dehydrate of polyglycerol fatty acid ester, as well as polyglycerol and polyglycerol dehydrate, when mass spectrometry of a polyglycerol mono fatty acid ester product is performed using a time-of-flight mass spectrometer. The above P2 is the peak intensity of the monoester of the polyglycerol fatty acid ester when mass spectrometry of the polyglycerol mono fatty acid ester product is performed using a time-of-flight mass spectrometer. The above P3 is the sum of the peak intensities of polyglycerol and polyglycerol dehydrates when mass spectrometry of a polyglycerol mono-fatty acid ester product is performed using a time-of-flight mass spectrometer.

[0036] The peak intensities of the components used in the above P1 to P3 are derived from the peak intensities obtained when mass spectrometry of the polyglycerol mono-fatty acid ester product is carried out using the above time-of-flight mass spectrometer.

[0037] When the mass analysis of a polyglycerol mono fatty acid ester product is carried out using the above-mentioned time-of-flight mass spectrometer, in addition to the peak corresponding to the molecular weight of the monoester (i.e., polyglycerol mono fatty acid ester) as the polyglycerol fatty acid ester, peaks corresponding to the molecular weight of the monoester dehydrate, diester dehydrate, diester dehydrate, triester dehydrate, and triester dehydrate may be observed as impurities. In addition, peaks corresponding to the molecular weight of the tetraester, tetraester dehydrate, pentaester, and pentaester dehydrate as the polyglycerol polyfatty acid ester and its dehydrate other than the above may be observed as impurities. Furthermore, peaks corresponding to the molecular weight of polyglycerol, polyglycerol dehydrate, and the like as the raw material or by-product of the polyglycerol mono fatty acid ester product may be observed as impurities.

[0038] The polyglycerol mono-fatty acid ester and impurities can be identified by the molecular weights measured when mass spectrometry of the polyglycerol mono-fatty acid ester product is performed using the time-of-flight mass spectrometer.

[0039] The following provides an overview of how to calculate the above formulas (X), (Y), and P1 to 3. The specific methods are described in the Examples. (a) Mass analysis of the polyglycerol mono-fatty acid ester product is carried out using a time-of-flight mass spectrometer, the molecular weights and peak intensities derived from each component listed on P1 to P3 are obtained, and the values ​​of each molecular weight are rounded down to integers, and the corresponding peak intensities are added together. The above-mentioned conversion of the molecular weights to integers is intended to correspond to the correction molecular weight in (c) described later. (b) Calculate the theoretical molecular weight of each of the components described in P1 to P3. (c) The theoretical molecular weight in (b) is corrected in consideration of the following (i) to (iv) to determine the corrected molecular weight. (i) The molecular weight measured and detected by a time-of-flight mass spectrometer is derived from molecules deprotonated by ionization; (ii) with regard to (i), for those with a large molecular weight, the molecular weight of the peak top of the intensity may be shifted by 1; (iii) since some of the components listed on pages 1 to 3 have the same molecular weight, it is necessary to appropriately select and select them for calculation; (iv) taking into consideration the number of esterifications of polyglycerol fatty acid esters and the degree of polymerization of glycerol, if the degree of dehydration is impossible, it is necessary to exclude it. (d) The intensities obtained in (a) are assigned to the corrected molecular weights of each component of the polyglycerol mono fatty acid ester product calculated in (c), and these are summed up to obtain the peak intensities of the "monoester", "monoester dehydrate", "diester", "diester dehydrate", "triester", "triester dehydrate", "polyglycerol", and "polyglycerol dehydrate" described on pages 1 to 3. The peak intensities of each of the above components are calculated as follows. The monoester, diester, triester, and polyglycerol are the sum of peak intensities when the degree of polymerization of glycerol is 1 to 20. The peak intensities of monoester dehydrates, diester dehydrates, triester dehydrates, and polyglycerol dehydrates are the sum of the peak intensities when the degree of polymerization of glycerol is 1 to 20 and when the degree of dehydration is 1 to 3 (1 to 3 water molecules removed), respectively. (e) The above formulas (X) and (Y) are calculated using the peak intensities of each component of the polyglycerol mono-fatty acid ester product calculated in (d).

[0040] The above P1 is the sum of the peak intensities of the monoester, monoester dehydrate, diester, diester dehydrate, triester, and triester dehydrate of polyglycerol fatty acid ester, as well as polyglycerol and polyglycerol dehydrate, when mass spectrometry of a polyglycerol mono fatty acid ester product is performed using a time-of-flight mass spectrometer. The above P2 is the peak intensity of polyglycerol mono-fatty acid ester when the mass analysis of the polyglycerol mono-fatty acid ester product is performed using a time-of-flight mass spectrometer. Therefore, the peak intensity ratio represented by the formula (X)=P2 / P1 can be said to be an index of the content of polyglycerol mono-fatty acid ester (monoester of polyglycerol fatty acid ester) contained in the polyglycerol mono-fatty acid ester product. In other words, a large value of the formula (X) means that the purity of the polyglycerol mono-fatty acid ester in the polyglycerol mono-fatty acid ester product is high. The above P3 is the sum of the peak intensities of polyglycerin and polyglycerin dehydrate when the mass analysis of the polyglycerin mono fatty acid ester product is performed using a time-of-flight mass spectrometer. Therefore, the peak intensity ratio represented by the formula (Y)=P3 / P1 can be said to be an index of the content of polyglycerin and polyglycerin dehydrate contained in the polyglycerin mono fatty acid ester product. In other words, a small value of the formula (Y) means that the content of polyglycerin and polyglycerin dehydrate in the polyglycerin mono fatty acid ester product is small, and means that the content of monoester of polyglycerin fatty acid ester is relatively large (high purity).

[0041] The polyglycerol mono fatty acid ester product of the present disclosure has a high purity, and therefore can efficiently reduce surface tension when used as a surfactant. It also has good cleaning power and ability to form liquid crystals (e.g., bicontinuous cubic liquid crystals). Furthermore, when used as a cleansing oil, it has good makeup compatibility, makeup removal, and a refreshing feeling on the skin after washing off the makeup. This effect is thought to be due to the formation of beautiful micelles due to the high purity.

[0042] The peak intensity ratio represented by the above formula (X) is not particularly limited as long as it is 0.20 or more, but is more preferably 0.21 or more, more preferably 0.23 or more, more preferably 0.24 or more, more preferably 0.25 or more, more preferably 0.26 or more, more preferably 0.28 or more, more preferably 0.3 or more, more preferably 0.31 or more, more preferably 0.33 or more, more preferably 0.35 or more, more preferably 0.37 or more, more preferably 0.40 or more, more preferably 0.44 or more, more preferably 0.48 or more, more preferably 0.52 or more. The peak intensity ratio represented by the above formula (X) is not particularly limited, but is, for example, 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, more preferably 0.6 or less.

[0043] The peak intensity ratio represented by the above formula (Y) is not particularly limited as long as it is 0.46 or less, but is 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, more preferably 0.30 or less. In addition, the peak intensity ratio represented by the above formula (Y) is not particularly limited, but is, for example, 0.01 or more, preferably 0.05 or more, more preferably 0.10 or more.

[0044] In the polyglycerol monofatty acid ester product of the present disclosure, the average polymerization degree of glycerin is not particularly limited, but is preferably 2 to 40. The average polymerization degree of the glycerin may be 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, or 9 or more. The average polymerization degree of the glycerin may 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. The average polymerization degree of the glycerin may also be 3 to 20, or 4 to 10.

[0045] In the polyglycerol mono-fatty acid ester product, the method of specifying the average polymerization degree of glycerin is not particularly limited, but for example, in the case of a polyglycerol mono-fatty acid ester product obtained by the reaction (1) above, it can be specified by the number of moles of glycidol to be addition-polymerized with respect to 1 mole of fatty acid. For example, the average polymerization degree of glycerin is n, and when n moles of glycidol are addition-polymerized with respect to 1 mole of fatty acid, the average polymerization degree of glycerin in the obtained polyglycerol mono-fatty acid ester product is n. In addition, for example, in the case of a polyglycerol mono-fatty acid ester product obtained by the reactions (2) and (3) above, it is the same as the average polymerization degree of glycerin in the polyglycerin used. For example, a polyglycerol mono-fatty acid ester product obtained by the esterification reaction of a polyglycerol having an average polymerization degree of glycerin of m with a fatty acid has an average polymerization degree of glycerin of m.

[0046] Another method for determining the average degree of polymerization of glycerin is the method using the hydroxyl value. The hydroxyl value refers to the amount of potassium hydroxide required in mg to neutralize the acetic acid bonded to the hydroxyl group when 1 g of a sample is acetylated (see JIS K 0070-1992). The amount of hydroxyl groups in the polyglycerin chain of the polyglycerin mono fatty acid ester product can be calculated from the hydroxyl value, and the average degree of polymerization can be determined.

[0047] In the polyglycerol mono-fatty acid ester product of the present disclosure, the hydroxyl value is not particularly limited, but is preferably 317 to 754 KOH / g. The hydroxyl value of the polyglycerol mono-fatty acid ester product may be 317 KOH / g or more, 389 KOH / g or more, 413 KOH / g or more, 475 KOH / g or more, 483 KOH / g or more, or 539 KOH / g or more. The hydroxyl value of the polyglycerol mono-fatty acid ester product may be 754 KOH / g or less, 751 KOH / g or less, 745 KOH / g or less, 741 KOH / g or less, 734 KOH / g or less, 725 KOH / g or less, 713 KOH / g or less, 698 KOH / g or less, or 677 KOH / g or less.

[0048] In the polyglycerol mono-fatty acid ester product of the present disclosure, the fatty acid is not particularly limited, but for example, a fatty acid having 4 to 25 carbon atoms is preferable. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid. In addition, it may be a straight-chain fatty acid or a branched-chain fatty acid (a fatty acid having a side chain). Furthermore, it may be a substituted fatty acid in which a part of the hydrogen bonded to the carbon chain is replaced with a hydroxyl group. The fatty acid here means a fatty acid as a constituent component of the polyglycerol mono-fatty acid ester.

[0049] The number of carbon atoms in the fatty acid is not particularly limited, but may 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. The number of carbon atoms in the fatty acid is not particularly limited, but may 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. The number of carbon atoms in the fatty acid may also be 4 to 14 or 15 to 25, or 8 to 14 or 16 to 18.

[0050] The fatty acid is not particularly limited, but examples thereof include caproic acid (C6, saturated fatty acid), caprylic acid (C8, saturated fatty acid), pelargonic acid (C9, saturated fatty acid), 2-ethylhexanoic acid (C8, branched chain fatty acid), capric acid (C 10 , saturated fatty acid), lauric acid (C 12 , saturated fatty acid), isotridecanoic acid (C 13 , branched chain fatty acid), myristic acid (C 14 , saturated fatty acid), pentadecylic acid (C 15 , saturated fatty acid), palmitic acid (C 16 , saturated fatty acid), palmitoleic acid (C 16 , unsaturated fatty acid), stearic acid (C 18 , saturated fatty acid), isostearic acid (C 18 , branched chain fatty acid), 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 , substituted fatty acids), arachidic acid (C 20 , saturated fatty acid), behenic acid (C 22 , saturated fatty acids), erucic acid (C 22 , unsaturated fatty acid), Nervonic acid (C 24 , unsaturated fatty acids), etc.

[0051] When the fatty acid has 4 to 14 carbon atoms (particularly 8 to 14), the peak intensity ratio represented by the formula (X) is not particularly limited as long as it is 0.20 or more, but is 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.

[0052] When the fatty acid has 4 to 14 carbon atoms (particularly 8 to 14), the peak intensity ratio represented by the formula (Y) is not particularly limited as long as it is 0.46 or less, but is preferably 0.45 or less, more preferably 0.42 or less, more preferably 0.39 or less, and more preferably 0.37 or less. In addition, the peak intensity ratio represented by the formula (Y) is not particularly limited, but is, for example, 0.01 or more, preferably 0.05 or more, and more preferably 0.10 or more.

[0053] When the fatty acid has 4 to 14 carbon atoms (particularly 8 to 14), the average degree of polymerization of glycerin 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.

[0054] When the fatty acid has a carbon number of 15 to 25 (particularly 16 to 18), the peak intensity ratio represented by the above formula (X) is not particularly limited as long as it is 0.20 or more, but is 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.

[0055] When the fatty acid has a carbon number of 15 to 25 (particularly 16 to 18), the peak intensity ratio represented by the formula (Y) is not particularly limited as long as it is 0.46 or less, but is 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. In addition, the peak intensity ratio represented by the formula (Y) is not particularly limited, but is, for example, 0.01 or more, preferably 0.05 or more, and more preferably 0.10 or more.

[0056] When the fatty acid has 15 to 25 carbon atoms (particularly 16 to 18 carbon atoms), the average degree of polymerization of glycerin is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and further preferably 4 to 10.

[0057] When the fatty acid is a straight-chain fatty acid having 15 to 25 carbon atoms (particularly 16 to 18 carbon atoms), the peak intensity ratio represented by the formula (X) is not particularly limited as long as it is 0.20 or more, but is more preferably 0.24 or more, more preferably 0.28 or more, and more preferably 0.30 or more. In this case, the average degree of polymerization of glycerin is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0058] When the fatty acid is a straight-chain fatty acid having 15 to 25 carbon atoms (particularly 16 to 18 carbon atoms), the average degree of polymerization of glycerin is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0059] When the fatty acid is a branched chain fatty acid having 15 to 25 carbon atoms (particularly 16 to 18 carbon atoms), the peak intensity ratio represented by the formula (X) is not particularly limited as long as it is 0.20 or more, but is preferably 0.25 or more, more preferably 0.30 or more, and more preferably 0.33 or more. In this case, the average degree of polymerization of glycerin is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0060] When the fatty acid is a branched chain fatty acid having 15 to 25 carbon atoms (particularly 16 to 18), the peak intensity ratio represented by the formula (Y) is not particularly limited as long as it is 0.46 or less, but is preferably 0.40 or less, more preferably 0.37 or less, and more preferably 0.35 or less. In addition, the peak intensity ratio represented by the formula (Y) is not particularly limited, but is, for example, 0.01 or more, preferably 0.05 or more, and more preferably 0.10 or more.

[0061] When the fatty acid is a branched chain fatty acid having 15 to 25 carbon atoms (particularly 16 to 18 carbon atoms), the average degree of polymerization of glycerin is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0062] When the fatty acid is an unsaturated fatty acid having a carbon number of 15 to 25 (particularly 16 to 18), the peak intensity ratio represented by the formula (X) is not particularly limited as long as it is 0.20 or more, but is more preferably 0.23 or more, more preferably 0.25 or more, more preferably 0.30 or more, and more preferably 0.33 or more. In this case, the average degree of polymerization of glycerin is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0063] When the fatty acid is an unsaturated fatty acid having a carbon number of 15 to 25 (particularly 16 to 18), the peak intensity ratio represented by the formula (Y) is not particularly limited as long as it is 0.46 or less, but is preferably 0.44 or less, more preferably 0.32 or less, more preferably 0.30 or less, and more preferably 0.28 or less. In addition, the peak intensity ratio represented by the formula (Y) is not particularly limited, but is, for example, 0.01 or more, preferably 0.05 or more, and more preferably 0.10 or more.

[0064] When the fatty acid is an unsaturated fatty acid having 15 to 25 carbon atoms (particularly 16 to 18 carbon atoms), the average degree of polymerization of glycerin is not particularly limited, but is preferably 2 to 40, more preferably 3 to 20, and even more preferably 4 to 10.

[0065] In the polyglycerol monofatty acid ester product of the present disclosure, the area ratio of the peaks corresponding to the monoester form, monoester dehydrate, polyester form, and polyester dehydrate of the polyglycerol fatty acid ester, as well as polyglycerol and polyglycerol dehydrate, in the following HPLC (high performance liquid chromatography) analysis is not particularly limited, but is, for example, preferably 50% or more, more preferably 60% or more, even more preferably 80% or more, and particularly preferably 90% or more.

[0066] In the polyglycerol mono fatty acid ester product of the present disclosure, the area ratio of the peaks corresponding to the monoester, monoester dehydrate, polyester, and polyester dehydrate of the polyglycerol fatty acid ester in the following HPLC (high performance liquid chromatography) analysis is, for example, preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more. The area ratio of the peaks corresponding to polyglycerol and polyglycerol dehydrate is, for example, 1% or more, 5% or more, 10% or more, or 20% or more, and, for example, preferably 80% or less, more preferably 70% or less, and even more preferably 60% or less.

[0067] (HPLC analysis) The HPLC analysis method for the polyglycerol mono-fatty acid ester product of the present disclosure is not particularly limited, but for example, the measurement can be performed using the following apparatus and conditions. Equipment: LC-2030C 3D (Shimadzu Corporation) Column: Wakosil 5C18 Φ4.6mm×250mm(W), 2 pieces, connected in series Detector: RID-20A (Shimadzu Corporation) Oven temperature: 40℃ Sample: 10% methanol solution Sample injection volume: 10μl ·Mobile phase flow rate: 0.75ml / min

[0068] The above-mentioned "peaks corresponding to monoesters, monoester dehydrates, polyesters, and polyester dehydrates of polyglycerol fatty acid esters, as well as polyglycerol and polyglycerol dehydrates" refer to, for example, peaks whose tops are present between retention times of 6.0 to 20.0 minutes in the HPLC chart in the above-mentioned HPLC analysis method. Therefore, the area ratio of the above peaks is the sum of the peak area ratios between retention times of 6.0 to 20.0 minutes in the HPLC chart. The above-mentioned "peaks corresponding to monoesters, monoester dehydrates, polyesters, and polyester dehydrates of polyglycerol fatty acid esters" refer to, for example, peaks whose tops are present between retention times of 8.2 to 20.0 minutes in the HPLC chart in the above-mentioned HPLC analysis method. Therefore, the area ratio of the above-mentioned peaks is the sum of the peak area ratios between retention times of 8.2 to 20.0 minutes in the HPLC chart. The above-mentioned "peaks corresponding to polyglycerol and polyglycerol dehydrates" refer to, for example, peaks whose tops are present between 6.0 and 8.2 minutes of retention time on the HPLC chart in the above-mentioned HPLC analysis method. Therefore, the area ratio of the above-mentioned peaks is the sum of the peak area ratios between 6.0 and 8.2 minutes of retention time on the HPLC chart.

[0069] [Manufacturing method of polyglycerol mono fatty acid ester products] The polyglycerol mono-fatty acid ester product of the present disclosure may be obtained by any of the following reactions: (1) addition polymerization of glycidol to fatty acid, (2) esterification of polyglycerol with fatty acid, and (3) transesterification of polyglycerol with fatty acid ester. Among these, the polyglycerol mono-fatty acid ester product obtained by reaction (1) is preferred in that it has a high proportion of monoester. In other words, the polyglycerol mono-fatty acid ester product of the present disclosure is preferably obtained by a production method including an addition polymerization reaction step of fatty acid and glycidol.

[0070] The above reaction (1) can be carried out in the presence or absence of a catalyst, but from the viewpoint of increasing the proportion of monoesters, it is preferable to carry out the reaction in the presence of a catalyst (particularly, an acid catalyst). In particular, when the average degree of polymerization of glycerin in the polyglycerol mono-fatty acid ester product to be obtained exceeds 5, the above reaction (1) is preferably carried out in the presence of a catalyst. This is because there is a strong tendency for the proportion of monoesters in the obtained polyglycerol mono-fatty acid ester product to be high. Conversely, when the average degree of polymerization of glycerin in the polyglycerol mono-fatty acid ester product to be obtained is 5 or less, the above reaction (1) is preferably carried out in the presence of a catalyst, but there is no significant difference in the proportion of monoesters even if it is carried out in the absence of a catalyst.

[0071] The acid catalyst is not particularly limited, but it is preferable to use an organic acid that is generally used in cosmetics as a catalyst, such as ascorbic acid, carboxylic acid such as acetic acid, formic acid, citric acid, succinic acid, adipic acid, and phosphoric acid-based acid catalyst. As the acid catalyst, an organic acid with a large acid dissociation constant is preferable. Among them, from the viewpoint of the purity of the polyglycerol mono fatty acid ester product, a phosphoric acid-based acid catalyst is preferable.

[0072] The phosphoric acid-based acid catalyst includes phosphoric acids or phosphoric acid esters, such as phosphoric acid, phosphoric anhydride, polyphosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and other phosphoric acids, and acidic phosphoric acid esters such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, and other acids. Among these, phosphoric acid is preferred.

[0073] The catalyst may be used alone or in combination of two or more. The amount of the catalyst is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of fatty acid. The amount of the catalyst within the above range is preferred in that the proportion of monoesters is increased.

[0074] When a polyglycerol mono-fatty acid ester product is produced by the above reaction (1), the reaction may be carried out, for example, by continuously or intermittently supplying glycidol to (1-1) fatty acid while continuously or intermittently supplying an acid catalyst, or by continuously or intermittently supplying glycidol to (1-2) a mixture of fatty acid and acid catalyst. In addition, as an embodiment in which the reaction is carried out in the absence of a catalyst, the reaction may be carried out by continuously or intermittently supplying glycidol to (1-3) fatty acid.

[0075] Specifically, the above (1-1) means that an addition polymerization reaction is carried out by putting a fatty acid into a reaction vessel, continuously or intermittently supplying glycidol to the reaction vessel, and also continuously or intermittently supplying an acid catalyst to the reaction vessel. In other words, it means that glycidol and the acid catalyst are continuously or intermittently supplied to the fatty acid at the same time for at least a certain time. An example of the supply method is dropwise addition. Specifically, the above (1-2) means that a fatty acid and an acid catalyst are put into a reaction vessel, mixed as necessary, and glycidol is continuously or intermittently supplied to the reaction vessel to carry out an addition polymerization reaction. An example of the supply method is dropwise addition. Specifically, the above (1-3) means that an addition polymerization reaction is carried out by putting a fatty acid into a reaction vessel, and continuously or intermittently supplying glycidol to the reaction vessel. In other words, it means that glycidol is continuously or intermittently supplied to the fatty acid at the same time for at least a certain time.

[0076] In the above reaction (1), not only the formation of polyglycerol mono-fatty acid ester but also the formation of polyglycerol may proceed in the reaction system (for example, in a reaction vessel). However, by adding glycidol dropwise continuously or intermittently, the glycidol concentration in the system can be kept low, and therefore the formation of polyglycerol mono-fatty acid ester tends to prevail over the formation of polyglycerol.

[0077] The acid catalyst may be mixed with the fatty acid and then subjected to the addition reaction with glycidol, or the reaction may be carried out while continuously or intermittently supplying the acid catalyst together with glycidol to the fatty acid as necessary. However, from the viewpoint of increasing the purity of the obtained polyglycerol mono-fatty acid ester product, it is preferable to carry out the reaction while continuously or intermittently supplying the acid catalyst together with glycidol to the fatty acid. That is, it is preferable to carry out the reaction of the above (1) by the operation described in the above (1-1). This is because the acid catalyst promotes or advances the formation of not only polyglycerol mono-fatty acid ester but also polyglycerol, and by continuously or intermittently supplying the acid catalyst together with glycidol to the fatty acid, the formation of polyglycerol mono-fatty acid ester becomes particularly dominant over the formation of polyglycerol. From the same perspective, when the acid catalyst to be supplied together with glycidol is supplied to the fatty acid in a lump, the formation of polyglycerol tends to be dominant over the formation of polyglycerol mono-fatty acid ester. Therefore, from this viewpoint, it can be said that it is preferable to carry out the reaction by the operation described in the above (1-1).

[0078] In the reaction (1) above, after the operations described in (1-1) to (1-3) above, the reaction product may be aged as necessary. The reaction temperature in the reaction (1) above is not particularly limited, but is preferably 50 to 180°C, more preferably 70 to 160°C, even more preferably 100 to 140°C, and particularly preferably 110 to 135°C. By keeping the reaction temperature within the above range, side reactions such as decomposition of glycidol tend not to occur. The reaction is desirably carried out under a nitrogen gas atmosphere, and may be pressurized as necessary.

[0079] The above reactions (2) and (3) can be carried out, for example, in the presence or absence of a catalyst (alkali catalyst or acid catalyst) under normal pressure or reduced pressure. The charged amounts of polyglycerin and fatty acid or polyglycerin and fatty acid ester are not particularly limited and can be appropriately selected and used. The reaction temperature is not particularly limited, but is preferably, for example, 20 to 180°C, more preferably 30 to 160°C, and even more preferably 40 to 140°C.

[0080] The obtained polyglycerol mono-fatty acid ester may be purified as necessary. The purification method can be carried out using a known method, and is not particularly limited. Examples of the purification method include adsorption treatment using activated carbon, activated clay, etc.; treatment under reduced pressure using steam, nitrogen, etc. as a carrier gas; washing using acid or alkali; and molecular distillation. In addition, impurities can be removed using liquid-liquid distribution, adsorbents, resins, molecular sieves, loose reverse osmosis membranes, ultrafiltration membranes, etc.

[0081] [Cosmetic composition] The cosmetic composition of the present disclosure is characterized by containing the polyglycerol mono-fatty acid ester product. The cosmetic composition may contain other ingredients within a range that does not impair the effects of the present disclosure. Examples of other ingredients include polyhydric alcohols, sugars, polysaccharides, amino acids, various surfactants (excluding the polyglycerol mono-fatty acid ester product), organic salts, inorganic salts, pH adjusters, chelating agents, antioxidants, bactericides, blood flow promoters, anti-inflammatory agents, ultraviolet absorbing agents, ultraviolet scattering agents, vitamins, colorants, and fragrances.

[0082] The content of the polyglycerol mono-fatty acid ester product in the cosmetic composition is not particularly limited, but is, for example, 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. When the content of the polyglycerol mono-fatty acid ester product is within the above range, there is a tendency for the cosmetic composition to be sufficiently compatible with makeup and to have sufficient spreadability when blended with makeup.

[0083] Particularly preferred embodiments of the cosmetic composition include the following. The fatty acid has 15 to 25 carbon atoms (preferably 16 to 18 carbon atoms), A peak intensity ratio represented by the following formula (X) is 0.31 or more (preferably 0.33 or more, more preferably 0.35 or more, and even more preferably 0.4 or more), A peak intensity ratio represented by the following formula (Y) is 0.46 or less (preferably 0.37 or less, more preferably 0.35 or less), and A polyglycerol mono-fatty acid ester product (A) having an average polymerization degree of glycerol of 2 to 4 (preferably 4); The fatty acid has 15 to 25 carbon atoms (preferably 16 to 18 carbon atoms), A peak intensity ratio represented by the following formula (X) is 0.23 or more (preferably 0.24 or more, more preferably 0.25 or more, and even more preferably 0.26 or more), The peak intensity ratio represented by the following formula (Y) is 0.46 or less (preferably 0.44 or less), and and a polyglycerol mono-fatty acid ester product (B) having an average degree of polymerization of glycerin of 5 to 12 (preferably 6 to 10, more preferably 6 or 10). Formula (X)=P2 / P1 Formula (Y)=P3 / P1 P1: The sum of peak intensities of the monoester, monoester dehydrate, diester, diester dehydrate, triester, and triester dehydrate of polyglycerol fatty acid ester, as well as polyglycerol and polyglycerol dehydrate, when the mass spectrometry of the polyglycerol mono fatty acid ester product is performed using the time-of-flight mass spectrometer. P2: Peak intensity of monoester of polyglycerol fatty acid ester when mass spectrometry of polyglycerol mono fatty acid ester product is performed using the above-mentioned time-of-flight mass spectrometer P3: The sum of the peak intensities of polyglycerin and polyglycerin dehydrates when the polyglycerin mono fatty acid ester product was subjected to mass spectrometry using a time-of-flight mass spectrometer.

[0084] When the cosmetic composition of the present disclosure has the above-mentioned embodiment, it tends to have good makeup compatibility, makeup removal, and a refreshing feeling on the skin after washing off the makeup. This tendency becomes more pronounced by combining the polyglycerol mono-fatty acid ester product (A) having a relatively low HLB value with the polyglycerol mono-fatty acid ester product (B) having a relatively high HLB value to set the HLB value to 9 to 13 (particularly 11 to 12.5). In this case, the HLB value is a weighted average of the HLB value of the polyglycerol mono-fatty acid ester product (A) and the HLB value of the polyglycerol mono-fatty acid ester product (B). The HLB value of the polyglycerol mono-fatty 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 polyglycerol mono-fatty 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, in the cosmetic composition of the present disclosure, the blending amounts of the polyglycerol mono-fatty acid ester product (A) and the polyglycerol mono-fatty acid ester product (B) are preferably adjusted so that the HLB value after combination is 9 to 13 (particularly 11 to 12.5) in consideration of their respective HLB values. As a specific blending amount, for example, the weight ratio of the polyglycerol mono-fatty acid ester product (A) to the polyglycerol mono-fatty 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.

[0085] The HLB (Hydrophile-Lypophile Balance) value indicates the affinity of surfactants such as polyglycerol mono-fatty acid esters to water and oil, and can be calculated from the following formula using the organic value (OV) and inorganic value (IV) determined from an organic conceptual diagram. HLB=IV / OV×10=IOB(Inorganic Organic Balance)×10

[0086] The specific product or form of the cosmetic composition of the present disclosure is not particularly limited, and examples thereof include cosmetic liquid, milky lotion, skin cream, sunscreen cream, cleansing milk, cleansing lotion, cleansing oil, shampoo, rinse, treatment, hair setting lotion, hair cream, hair oil, hair liquid, hair bleach, permanent wave liquid, lipstick, lip gloss, eye gloss, nail gloss, mascara, eye shadow, and the like.

[0087] Furthermore, the polyglycerol monofatty acid ester product of the present disclosure can be used for purposes other than the above-mentioned cosmetic composition, such as a food additive, a cleaning agent composition, and general industrial purposes.

[0088] Each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Each configuration in each embodiment and their combinations are merely examples, and addition, omission, substitution, and other modifications of the configuration are possible as appropriate within the scope of the present disclosure. In addition, each invention according to this disclosure is not limited by the embodiments or the following examples, but is limited only by the claims. EXAMPLES

[0089] Hereinafter, the embodiments of the present disclosure will be described in more detail based on examples.

[0090] (Mass spectrometry using a time-of-flight mass spectrometer (TOF-MS)) In the examples and comparative examples, the polyglycerol mono-fatty acid ester products were subjected to mass spectrometry using the following apparatus and conditions. Equipment: Xevo G2‐XSQTof (Waters Corporation) Injection method: Infusion (5μL / min) Measurement mode: Neg Conegas: 50L / h Desolvation gas: 1000L / h Source temperature: 120℃ Desolvation temperature: 500℃ Capillary: 2.0kV Sampling cone:40 Source offset: 80 Sample concentration: 25 ppm (methanol) MS range: 50~3000

[0091] (HLB value measurement) In the examples and comparative examples, the HLB (Hydrophile-Lypophile Balance) value of the polyglycerol mono fatty acid ester product can be calculated from the following formula using the organic value (OV) and inorganic value (IV) determined from the organic conceptual diagram. HLB=IV / OV×10=IOB(Inorganic Organic Balance)×10

[0092] (HPLC analysis) In the examples and comparative examples, the polyglycerol mono-fatty acid ester products were subjected to HPLC analysis using the following apparatus and conditions. Equipment: LC-2030C 3D (Shimadzu Corporation) Column: Wakosil 5C18 Φ4.6mm×250mm(W), 2 pieces, connected in series Detector: RID-20A (Shimadzu Corporation) Oven temperature: 40℃ Sample: 10% methanol solution Sample injection volume: 10μl ·Mobile phase flow rate: 0.75ml / min

[0093] Example 1 0.81 mol (139.7 g) of capric acid was added to a 1-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder, and heated to 120°C. Next, 4.86 mol (360.4 g) of glycidol was added dropwise over 10 hours while maintaining the reaction temperature at 120°C, and 0.004 mol (0.4 g) of 42.5% phosphoric acid was added dropwise during the dropping of glycidol. Next, the mixture was aged for 3 hours while maintaining the temperature at 120°C. Next, the temperature was raised to 130°C, and the reaction was continued until the oxirane concentration in the system was less than 0.1%. After cooling, the reaction product was taken out, and about 500 g of polyglycerol monocapric acid ester with an average degree of polymerization of glycerol of 6 was obtained.

[0094] The obtained polyglycerol monocaprate was analyzed by HPLC. The area ratio of the peaks corresponding to the monoester, monoester dehydrate, polyester, and polyester dehydrate, as well as polyglycerol and polyglycerol dehydrate, present between retention times of 6.0 and 20.0 minutes on the HPLC chart was 93.0%. The area ratio of the peaks corresponding to the monoester, monoester dehydrate, polyester, and polyester dehydrate, present between retention times of 8.2 and 20 minutes on the HPLC chart was 47.9%. The area ratio of the peaks corresponding to the polyglycerol and polyglycerol dehydrate, present between retention times of 6.0 and 8.2 minutes on the HPLC chart was 45.1%. The chart of the HPLC analysis is shown in FIG. 1. In the figure, the peaks corresponding to the monoester, monoester dehydrate, polyester, and polyester dehydrate are indicated as "PGL ester, etc.", and the peaks corresponding to the polyglycerol and polyglycerol dehydrate are indicated as "PGL, etc."

[0095] The polyglycerol monocaprate thus obtained was subjected to mass spectrometry using the above-mentioned time-of-flight mass spectrometer (TOF-MS). The peak intensity ratio (P2 / P1) was calculated according to the following formula (X) and was found to be 0.325. The peak intensity ratio (P3 / P1) was calculated according to the following formula (Y) and was found to be 0.287.

[0096] Formula (X)=P2 / P1 Formula (Y)=P3 / P1 P1: The sum of peak intensities of monoesters, monoester dehydrates, diesters, diester dehydrates, triesters, and triester dehydrates of polyglycerol fatty acid esters, as well as polyglycerol and polyglycerol dehydrates, when mass spectrometry of polyglycerol mono fatty acid ester products is performed using a time-of-flight mass spectrometer. P2: Peak intensity of monoester of polyglycerol fatty acid ester when mass spectrometry of polyglycerol mono fatty acid ester product was performed using a time-of-flight mass spectrometer P3: The sum of the peak intensities of polyglycerin and polyglycerin dehydrates when the polyglycerin mono fatty acid ester product was subjected to mass spectrometry using a time-of-flight mass spectrometer.

[0097] The HLB value of the obtained polyglycerol monocaprate was 15.4.

[0098] [Calculation method of peak intensity ratio] The method of calculating the peak intensity ratio will be described in detail below in sections (a) to (e). (a) The molecular weight and its peak intensity derived from each component contained in the polyglycerol mono fatty acid ester product were obtained by measurement using a time-of-flight mass spectrometer. The decimal points of the numerical values ​​of each molecular weight were discarded to convert them into integers, and the numerical values ​​of the corresponding peak intensities were added together to obtain the peak intensity of the integerized molecular weight. For example, if a measured value is obtained in which the peak intensity is 31 when the molecular weight is "50.0012", the peak intensity is 5 when the molecular weight is "50.0041", and the peak intensity is 15 when the molecular weight is "50.0241", the sum of the peak intensities of molecular weights 50 or more and less than 51 (31 + 5 + 15 + ···) is the peak intensity of the integerized molecular weight "50". The molecular weight range was set to 50 to 2999. This molecular weight range was determined in consideration of the carbon number of the fatty acid and the polymerization degree of glycerin in the polyglycerol mono fatty acid ester product of the present disclosure. In other words, it was determined based on the idea that there are almost no polyglycerol fatty acid esters that can be contained in the above product that fall outside the above molecular weight range.

[0099] The item (a) in the first embodiment will be described below. Measurements using a time-of-flight mass spectrometer were performed to obtain the molecular weight and peak intensity derived from each component contained in the polyglycerol monocaprate obtained in Example 1. The values ​​of each molecular weight were rounded down to whole numbers, and the corresponding peak intensities were added up, as shown in Tables 1 to 6.

[0100] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6]

[0101] (b) The theoretical molecular weights of the monoester, monoester dehydrate, diester, diester dehydrate, triester, and triester dehydrate of polyglycerol fatty acid ester, as well as polyglycerol and polyglycerol dehydrate are calculated. Note that the monoester, diester, triester, and polyglycerol are theoretical molecular weights when the glycerol polymerization degree is 1 to 20. Also, the monoester dehydrate, diester dehydrate, triester dehydrate, and polyglycerol dehydrate are theoretical molecular weights when the glycerol polymerization degree is 1 to 20 and when the dehydration degree is 1 to 3 (1 to 3 water molecules removed).

[0102] The item (b) in the first embodiment will be described below. In Example 1, the theoretical molecular weight of the monoester of polyglycerol monocapric acid ester is shown in the section "Monoester" in Table 7. The theoretical molecular weights of the dehydrated monoesters are shown in the sections "Monoester dehydrate (degree of dehydration = 1)", "Monoester dehydrate (degree of dehydration = 2)", and "Monoester dehydrate (degree of dehydration = 3)" in Table 7. The same applies to the diesters and other components.

[0103] [Table 7]

[0104] (c) In order to correspond to each molecular weight derived from the time-of-flight mass spectrometer obtained in (a), the theoretical molecular weight in (b) was corrected by the following method to obtain the "corrected molecular weight". Correction method The components whose molecular weights were measured and detected by a time-of-flight mass spectrometer were deprotonated molecules [MH] by ionization. -Therefore, the molecular weights obtained in (a) are basically calculated by subtracting 1 from the molecular weights obtained by rounding down the theoretical molecular weights in (b) and converting them to integers. However, when the molecular weight increases, the molecular weight of the peak top of the intensity may shift by 1 due to errors in molecular weight calculations and in converting measured molecular weights to integers. Therefore, for those with a theoretical molecular weight of 700 or more in (b), the peak intensities corresponding to the three points of the molecular weights obtained by rounding down the theoretical molecular weights in (b) and converting them to integers (M1), M1 minus 1 (M2), and M1 minus 2 (M3) were compared, and the molecular weight with the greatest peak intensity was determined as the "corrected molecular weight." For those with a theoretical molecular weight of less than 700 in (b), the molecular weight obtained by rounding down the theoretical molecular weights in (b) and converting them to integers minus 1 was determined as the "corrected molecular weight."

[0105] Post-correction adjustments The corrected molecular weight obtained by the above method may be the same even if the structures are different, 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) of the polyglycerol chain to the fatty acid. In terms of molecular design, the content of polyglycerol fatty acid esters with a high number of esterifications and a high degree of dehydration is low, so that for those with the same corrected molecular weight, the peak intensity is not calculated for molecules other than those with the highest rank in the following criteria.

[0106] Priority thinking 1. Esterification number: low > high 2. Dehydration level: low > high 3. In the above criteria 1 and 2, when the comparison targets differ in superiority or inferiority, superiority is judged in the order of 1 > 2. For example, in comparing specific components (A) and (B), if 1. component (B) has a lower number of esterifications, and 2. component (A) has a lower degree of dehydration of glycerin, then 1. component (B) with a lower number of esterifications takes precedence because 1 > 2 in the above criteria.

[0107] In addition, taking into consideration the number of esterifications of the polyglycerol fatty acid ester and the degree of polymerization of glycerol, if the degree of dehydration is impossible, it is not included in the peak intensity. For example, in order for one water molecule to be removed from a polyglycerol fatty acid ester (to give a degree of dehydration of 1), the polyglycerol fatty acid ester must have two or more hydroxyl groups. Therefore, there are no polyglycerol fatty acid esters with only one hydroxyl group that have a degree of dehydration of 1 to 3.

[0108] The item (c) in the first embodiment will be described below. For each component of polyglycerol monocaprate calculated in Table 7, if the theoretical molecular weight in (b) is less than 700, the theoretical molecular weight is rounded down to an integer and then subtracted by 1 to give the "corrected molecular weight." For example, the monoester (glycerol polymerization degree = 4) has a theoretical molecular weight of 468.58, but the corrected molecular weight is 467.

[0109] For those with theoretical molecular weights of 700 or more in (b), the peak intensities corresponding to the three points of the molecular weight (M1) obtained by rounding down the theoretical molecular weight in (b) to an integer, the molecular weight (M2) obtained by subtracting 1 from M1, and the molecular weight (M3) obtained by subtracting 2 from M1 were compared, and the molecular weight with the greatest intensity among them was determined as the "corrected molecular weight". For example, the theoretical molecular weight of polyglycerin (glycerin polymerization degree = 11, dehydration degree = 3) is 778.83, the molecular weight (M1) is 778, the molecular weight (M2) is 777, and the molecular weight (M3) is 776. 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 (see Table 2). Therefore, the peak intensity of 8510 with the greatest peak intensity, i.e., 777 = molecular weight (M2), is determined as the "corrected molecular weight".

[0110] For example, the theoretical molecular weight of a triester (glycerin polymerization degree = 4) is 777.8, the molecular weight (M1) is 777, the molecular weight (M2) is 776, and the molecular weight (M3) is 775. The peak intensity corresponding to the molecular weight (M1) is 8510, the peak intensity corresponding to the molecular weight (M2) is 6740, and the peak intensity corresponding to the molecular weight (M3) is 7840 (see Table 2). Therefore, the highest peak intensity of 8510, i.e., 777 = molecular weight (M1), can be the "corrected molecular weight". However, since the corrected molecular weight is the same as that of the above polyglycerin (glycerin polymerization degree = 11, dehydration degree = 3), in accordance with the above "priority concept", polyglycerin (glycerin polymerization degree = 11, dehydration degree = 3) will have a corrected molecular weight of "777", and the triester (glycerin polymerization degree = 4) will not be included in the peak intensity.

[0111] Furthermore, monoesters (degree of glycerin polymerization = 1) have two hydroxyl groups, and are included in the peak intensity when the degree of dehydration is 1 because they are present, but are not included in the peak intensity when the degree of dehydration is 2 or 3 because they are not present. Diesters (degree of glycerin polymerization = 1) have only one hydroxyl group, and do not exist when the degree of dehydration is 1 to 3, and are not included in the peak intensity. Taking the above into consideration, the corrected molecular weight of each component is summarized in Table 8. "-" denotes a component that is not included in the peak intensity.

[0112] [Table 8]

[0113] (d) The intensities obtained in (a) are made to correspond to the corrected molecular weights of each component of the polyglycerol mono fatty acid ester product calculated in (c), and these are summed up to obtain the peak intensities of the “monoester,” “monoester dehydrate,” “diester,” “diester dehydrate,” “triester,” “triester dehydrate,” “polyglycerin,” and “polyglycerin dehydrate” defined in P1 to 3.

[0114] The item (d) in the first embodiment will be described below. Table 9 shows the intensity obtained in (a) corresponding to the corrected molecular weight of each component of polyglycerol monocaprate calculated in (b). Based on Table 9, the peak intensities of "monoester", "monoester dehydrate", "diester", "diester dehydrate", "triester", "triester dehydrate", "polyglycerol", and "polyglycerol dehydrate" defined in P1 will be explained.

[0115] 2 is a chart showing the corrected molecular weight and the corresponding peak intensity ratio (%) for the polyglycerol monocapric acid ester of Example 1. The hollow bars indicate the monoester form.

[0116] [Table 9]

[0117] The peak intensity of the "monoester" is the sum of the monoesters in Table 9 in which the degree of polymerization of glycerin is 1 to 20, and is 1,324,420. The peak intensity of the "diester form" is the sum of the diester forms in Table 9 in which the degree of polymerization of glycerin is 1 to 20, and is 244,000. The peak intensity of the "triester" is the sum of the triester compounds in Table 9 in which the polymerization degree of glycerin is 1 to 20, and is 122,900. The peak intensity of "polyglycerin" is the sum of the polyglycerin in Table 9 in which the polymerization degree of glycerin is 1 to 20, and is 320,400.

[0118] The peak intensity of the "monoester dehydrate" is the sum of the monoester dehydrates in Table 9 in which the polymerization degree of glycerin is 1 to 20 and the dehydration degree is 1 to 3, and is 555,300 (=207,830+188,370+159,100). The peak intensity of the "dehydrated diester" is the sum of the peaks when the degree of polymerization of glycerin in the dehydrated diesters in Table 9 is 1 to 20 and the degree of dehydration is 1 to 3, and is 533110 (=201130+169410+162570). The peak intensity of the "dehydrated triester" is the sum of the peak intensity when the polymerization degree of glycerin in the dehydrated triester in Table 9 is 1 to 20 and the dehydration degree is 1 to 3, and is 128630 (=42650+43130+42850). The peak intensity of the "dehydrated polyglycerol" is the sum of the peak intensity when the polymerization degree of glycerin in the dehydrated polyglycerol in Table 9 is 1 to 20 and the dehydration degree is 1 to 3, and is 848470 (=445710+258400+144360).

[0119] (e) The above formulas (X) and (Y) are calculated using the peak intensities of each component of the polyglycerol mono-fatty acid ester product calculated in (d).

[0120] The item (e) in the first embodiment will be described below. Formula (X)=P2 / P1=1324420 / 4077230=0.325 Formula (Y)=P3 / P1=(320400+848470) / 4077230=0.287

[0121] Example 2 0.55 mol (94.3 g) of capric acid was added to a 1-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder, and heated to 120°C. Next, 5.48 mol (405.67 g) of glycidol was added dropwise over 10 hours while maintaining the reaction temperature at 120°C, and 0.004 mol (0.4 g) of 42.5% phosphoric acid was added dropwise during the dropping of glycidol. Next, the mixture was aged for 3 hours while maintaining the temperature at 120°C. Next, the temperature was raised to 130°C, and the reaction was continued until the oxirane concentration in the system was less than 0.1%. After cooling, the reaction product was taken out, and about 500 g of polyglycerol monocapric acid ester with an average degree of polymerization of glycerol of 10 was obtained.

[0122] The obtained polyglycerol monocaprate was subjected to HPLC analysis, and the area ratio of the peaks existing in the retention time range of 6.0 to 20.0 minutes on the HPLC chart corresponding to the monoester, the monoester dehydrate, the polyester, the polyester dehydrate, polyglycerol, and the polyglycerol dehydrate was 93.8%.

[0123] Furthermore, the obtained polyglycerol monocaprate was subjected to mass spectrometry in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) calculated according to the above formula (X) was 0.353, and the peak intensity ratio (P3 / P1) calculated according to the above formula (Y) was 0.322.

[0124] The HLB value of the obtained polyglycerol monocaprate was 16.8.

[0125] Example 3 0.53 mol (106.4 g) of lauric acid was placed in a 1-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder, and heated to 120°C. Next, 5.31 mol (393.6 g) of glycidol was added dropwise over 10 hours while maintaining the reaction temperature at 120°C. 0.004 mol (0.4 g) of 42.5% phosphoric acid was added dropwise during the drop of glycidol. Next, the mixture was aged for 3 hours while maintaining the temperature at 120°C. Next, the temperature was raised to 130°C, and the reaction was continued until the oxirane concentration in the system was less than 0.1%. After cooling, the reaction product was taken out, and about 500 g of polyglycerol monolaurate with an average degree of polymerization of glycerol of 10 was obtained.

[0126] The obtained polyglycerol monolaurate was subjected to HPLC analysis, and the area ratio of the peaks existing in the retention time range of 6.0 to 20.0 minutes on the HPLC chart corresponding to the monoester, the monoester dehydrate, the polyester, the polyester dehydrate, polyglycerol, and the polyglycerol dehydrate was 98.9%.

[0127] Furthermore, the obtained polyglycerol monolaurate was subjected to mass spectrometry in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) calculated according to the above formula (X) was 0.429, and the peak intensity ratio (P3 / P1) calculated according to the above formula (Y) was 0.348.

[0128] The HLB value of the obtained polyglycerol monolaurate was 16.0.

[0129] Example 4 0.74 mol (169.7 g) of myristic acid was added to a 1-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder, and heated to 120°C. Next, 4.46 mol (330.3 g) of glycidol was added dropwise over 10 hours while maintaining the reaction temperature at 120°C, and 0.004 mol (0.4 g) of 42.5% phosphoric acid was added dropwise during the dropping of glycidol. Next, the mixture was aged for 3 hours while maintaining the temperature at 120°C. Next, the temperature was raised to 130°C, and the reaction was continued until the oxirane concentration in the system was less than 0.1%. After cooling, the reaction product was taken out, and about 500 g of polyglycerol monomyristate ester with an average degree of polymerization of glycerol of 6 was obtained.

[0130] The obtained polyglycerol monomyristate ester was subjected to HPLC analysis, and the area ratio of the peaks existing in the retention time range of 6.0 to 20.0 minutes on the HPLC chart corresponding to the monoester, the monoester dehydrate, the polyester, the polyester dehydrate, polyglycerol, and the polyglycerol dehydrate was 96.2%.

[0131] Furthermore, the polyglycerol monomyristate obtained was subjected to mass spectrometry in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) calculated according to the above formula (X) was 0.446, and the peak intensity ratio (P3 / P1) calculated according to the above formula (Y) was 0.267.

[0132] The HLB value of the obtained polyglycerol monomyristate was 13.4.

[0133] Example 5 0.52 mol (117.8 g) of myristic acid was added to a 1-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder, and heated to 120°C. Next, 5.16 mol (382.18 g) of glycidol was added dropwise over 10 hours while maintaining the reaction temperature at 120°C, and 0.004 mol (0.4 g) of 42.5% phosphoric acid was added dropwise during the dropping of glycidol. Next, the mixture was aged for 3 hours while maintaining the temperature at 120°C. Next, the temperature was raised to 130°C, and the reaction was continued until the oxirane concentration in the system was less than 0.1%. After cooling, the reaction product was taken out, and about 500 g of polyglycerol monomyristate ester with an average degree of polymerization of glycerol of 10 was obtained.

[0134] The obtained polyglycerol monomyristate ester was subjected to HPLC analysis, and the area ratio of the peaks existing in the retention time range of 6.0 to 20.0 minutes on the HPLC chart corresponding to the monoester, the monoester dehydrate, the polyester, the polyester dehydrate, polyglycerol, and the polyglycerol dehydrate was 97.4%.

[0135] Furthermore, the polyglycerol monomyristate obtained was subjected to mass spectrometry in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) calculated according to the above formula (X) was 0.391. The peak intensity ratio (P3 / P1) calculated according to the above formula (Y) was 0.314.

[0136] The HLB value of the obtained polyglycerol monomyristate was 15.2.

[0137] Example 6 0.69 mol (195.1 g) of stearic acid was added to a 1-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder, and heated to 120°C. Next, 4.12 mol (304.9 g) of glycidol was added dropwise over 10 hours while maintaining the reaction temperature at 120°C, and 0.004 mol (0.4 g) of 42.5% phosphoric acid was added dropwise during the dropping of glycidol. Next, the mixture was aged for 3 hours while maintaining the temperature at 120°C. Next, the temperature was raised to 130°C, and the reaction was continued until the oxirane concentration in the system was less than 0.1%. After cooling, the reaction product was taken out, and about 500 g of polyglycerol monostearate with an average degree of polymerization of glycerol of 6 was obtained.

[0138] The obtained polyglycerol monostearate was not soluble in the measurement solvent (10% methanol solution) and therefore could not be analyzed by HPLC. However, considering the manufacturing method and the tendency of the polyglycerol monofatty acid ester products in other examples, the area ratio of the peaks present in the retention time range of 6.0 to 20.0 minutes on the HPLC chart corresponding to the monoester, monoester dehydrate, polyester, polyester dehydrate, polyglycerol, and polyglycerol dehydrate is presumed to be at least 80% or more.

[0139] Furthermore, the polyglycerol monostearate obtained was subjected to mass spectrometry in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) calculated according to the above formula (X) was 0.256, and the peak intensity ratio (P3 / P1) calculated according to the above formula (Y) was 0.457.

[0140] The HLB value of the obtained polyglycerol monostearate was 11.9.

[0141] Example 7 0.49 mol (138.7 g) of stearic acid was added to a 1-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder, and heated to 120°C. Next, 4.88 mol (361.3 g) of glycidol was added dropwise over 10 hours while maintaining the reaction temperature at 120°C, and 0.004 mol (0.4 g) of 42.5% phosphoric acid was added dropwise during the dropping of glycidol. Next, the mixture was aged for 3 hours while maintaining the temperature at 120°C. Next, the temperature was raised to 130°C, and the reaction was continued until the oxirane concentration in the system was less than 0.1%. After cooling, the reaction product was taken out, and about 500 g of polyglycerol monostearate with an average degree of polymerization of glycerol of 10 was obtained.

[0142] The obtained polyglycerol monostearate was not soluble in the measurement solvent (10% methanol solution) and therefore could not be analyzed by HPLC. However, considering the manufacturing method and the tendency of the polyglycerol monofatty acid ester products in other examples, the area ratio of the peaks present in the retention time range of 6.0 to 20.0 minutes on the HPLC chart corresponding to the monoester, monoester dehydrate, polyester, polyester dehydrate, polyglycerol, and polyglycerol dehydrate is presumed to be at least 80% or more.

[0143] Furthermore, the polyglycerol monostearate obtained was subjected to mass spectrometry in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) calculated according to the above formula (X) was 0.410, and the peak intensity ratio (P3 / P1) calculated according to the above formula (Y) was 0.414.

[0144] The HLB value of the obtained polyglycerol monostearate was 14.0.

[0145] Example 8 0.86 mol (244.0 g) of oleic acid was placed in a 1-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder, and heated to 120°C. Next, 3.46 mol (256.0 g) of glycidol was added dropwise over 20 hours while maintaining the reaction temperature at 120°C. Next, the mixture was aged for 3 hours while maintaining the temperature at 120°C. Next, the temperature was raised to 130°C, and the reaction was continued until the oxirane concentration in the system was less than 0.1%. After cooling, the reaction product was taken out, and about 500 g of polyglycerol monooleate ester with an average degree of polymerization of glycerol of 4 was obtained.

[0146] The obtained polyglycerol monooleate was subjected to HPLC analysis, and the area ratio of the peaks existing in the retention time range of 6.0 to 20.0 minutes on the HPLC chart corresponding to the monoester, the monoester dehydrate, the polyester, the polyester dehydrate, polyglycerol, and the polyglycerol dehydrate was 95.5%.

[0147] Furthermore, the obtained polyglycerol monooleate was subjected to mass spectrometry in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) calculated according to the above formula (X) was 0.502, and the peak intensity ratio (P3 / P1) calculated according to the above formula (Y) was 0.316.

[0148] The HLB value of the obtained polyglycerol monooleate was 10.4.

[0149] Example 9 0.69 mol (194.3 g) of oleic acid was placed in a 1-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder, and heated to 120 ° C. Then, 4.13 mol (305.7 g) of glycidol was dropped over 10 hours while maintaining the reaction temperature at 120 ° C., and 0.004 mol (0.4 g) of 42.5% phosphoric acid was dropped during the dropping of glycidol. Then, the mixture was aged for 3 hours while maintaining the temperature at 120 ° C. Then, the mixture was heated to 130 ° C., and the reaction was continued until the oxirane concentration in the system was less than 0.1%. After cooling, the reaction product was taken out, and about 500 g of polyglycerol monooleate with an average degree of polymerization of glycerol of 6 was obtained.

[0150] The obtained polyglycerol monooleate was subjected to HPLC analysis, and the area ratio of the peaks existing in the retention time range of 6.0 to 20.0 minutes on the HPLC chart corresponding to the monoester, the monoester dehydrate, the polyester, the polyester dehydrate, polyglycerol, and the polyglycerol dehydrate was 95.8%.

[0151] Furthermore, the obtained polyglycerol monooleate was subjected to mass spectrometry in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) calculated according to the above formula (X) was 0.558, and the peak intensity ratio (P3 / P1) calculated according to the above formula (Y) was 0.382.

[0152] The HLB value of the obtained polyglycerol monooleate was 12.0.

[0153] Example 10 0.49 mol (138.0 g) of oleic acid was added to a 1-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder, and heated to 120°C. Next, 4.89 mol (362.0 g) of glycidol was added dropwise over 10 hours while maintaining the reaction temperature at 120°C, and 0.004 mol (0.4 g) of 42.5% phosphoric acid was added dropwise during the dropping of glycidol. Next, the mixture was aged for 3 hours while maintaining the temperature at 120°C. Next, the temperature was raised to 130°C, and the reaction was continued until the oxirane concentration in the system was less than 0.1%. After cooling, the reaction product was taken out, and about 500 g of polyglycerol monooleate with an average degree of polymerization of glycerol of 10 was obtained.

[0154] The obtained polyglycerol monooleate was subjected to HPLC analysis, and the area ratio of the peaks existing in the retention time range of 6.0 to 20.0 minutes on the HPLC chart corresponding to the monoester, the monoester dehydrate, the polyester, the polyester dehydrate, polyglycerol, and the polyglycerol dehydrate was 98.6%.

[0155] Furthermore, the obtained polyglycerol monooleate was subjected to mass spectrometry in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) calculated according to the above formula (X) was 0.274, and the peak intensity ratio (P3 / P1) calculated according to the above formula (Y) was 0.435.

[0156] The HLB value of the obtained polyglycerol monooleate was 14.0.

[0157] Example 11 0.86 mol (244.9 g) of isostearic acid was added to a 1-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder, and heated to 120°C. Then, 3.44 mol (255.1 g) of glycidol was added dropwise over 20 hours while maintaining the reaction temperature at 120°C. Then, the mixture was aged for 3 hours while maintaining the temperature at 120°C. Then, the mixture was heated to 130°C and the reaction was continued until the oxirane concentration in the system was less than 0.1%. After cooling, the reaction product was taken out, and about 500 g of polyglycerol monoisostearate with an average degree of polymerization of glycerol of 4 was obtained.

[0158] The obtained polyglycerol monoisostearate was subjected to HPLC analysis, and the area ratio of the peaks existing in the retention time range of 6.0 to 20.0 minutes on the HPLC chart corresponding to the monoester, the monoester dehydrate, the polyester, the polyester dehydrate, polyglycerol, and the polyglycerol dehydrate was 97.6%.

[0159] Furthermore, the obtained polyglycerol monoisostearate was subjected to mass spectrometry in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) calculated according to the above formula (X) was 0.507, and the peak intensity ratio (P3 / P1) calculated according to the above formula (Y) was 0.307.

[0160] The HLB value of the obtained polyglycerol monoisostearate was 10.5.

[0161] Comparative Example 1 SY Glystar MO-7S (polyglycerol monooleate with an average degree of polymerization of glycerol of 10, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was subjected to HPLC analysis, and the area ratio of the peaks present in the retention time range of 6.0 to 20.0 minutes on the HPLC chart corresponding to the monoester, monoester dehydrate, polyester, polyester dehydrate, polyglycerol, and polyglycerol dehydrate was 95.5%. Mass spectrometry was also performed in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X) to be 0.167. The peak intensity ratio (P3 / P1) was calculated according to the above formula (Y) to be 0.447.

[0162] In addition, the HLB value of SY Glystar MO-7S was 14.0.

[0163] Comparative Example 2 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-neck flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder, and the mixture was heated to 140°C. Next, 5.0 mol (370.40) of glycidol was added dropwise over 5 hours while maintaining the reaction temperature at 140°C, and the reaction was continued until the oxirane concentration in the system was less than 0.1%. After cooling, the reaction product was taken out, and about 470 g of polyglycerol monolaurate with an average degree of polymerization of glycerol of 10 was obtained.

[0164] The obtained polyglycerol monolaurate was subjected to HPLC analysis, and the area ratio of the peaks existing in the retention time range of 6.0 to 20.0 minutes on the HPLC chart corresponding to the monoester, the monoester dehydrate, the polyester, the polyester dehydrate, polyglycerol, and the polyglycerol dehydrate was 98.4%.

[0165] Furthermore, the obtained polyglycerol monolaurate was subjected to mass spectrometry in the same manner as in Example 1, and the peak intensity ratio (P2 / P1) was calculated according to the above formula (X) to be 0.410, and the peak intensity ratio (P3 / P1) was calculated according to the above formula (Y) to be 0.496.

[0166] The HLB value of the polyglycerol monolaurate was 16.0.

[0167] [evaluation] Sample 1 (cosmetic composition) was prepared containing the polyglycerol monooleate obtained in Example 8, the polyglycerol monooleate obtained in Example 9, the polyglycerol monooleate obtained in Example 9, and MORESCO White P-70 (liquid paraffin, manufactured by MORESCO Corporation) as an oil agent in a ratio of 10:10:80 (weight ratio). The HLB value of Sample 1 was 11.2.

[0168] Sample 2 (cosmetic composition) was prepared containing the polyglycerol monooleate obtained in Example 8, in which the average degree of polymerization of glycerin was 4, the polyglycerol monooleate obtained in Example 10, in which the average degree of polymerization of glycerin was 10, and MORESCO White P-70 (liquid paraffin, manufactured by MORESCO Corporation) as an oil in a ratio of 10:10:80 (weight ratio). The HLB value of Sample 2 was 12.2.

[0169] Sample 3 (cosmetic composition) was prepared containing the polyglycerol monooleate obtained in Example 8 having an average degree of polymerization of 4, SY Glystar MO-7S (polyglycerol monooleate having an average degree of polymerization of glycerol of 10, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), and MORESCO White P-70 (liquid paraffin, manufactured by MORESCO Corporation) as an oil agent in a ratio of 10:10:80 (weight ratio). Sample 3 had an HLB value of 12.2.

[0170] The subject applied lipstick (product name: Lipstick Y, manufactured by Chifure Holdings Co., Ltd.) to the arm of the subject, and then rubbed each of Samples 1 to 3 on top of the lipstick, and then washed it off with water. Samples 1 to 3 were evaluated as follows. [Makeup removal] 〇: Lipstick comes off cleanly ×: Lipstick doesn't come off [Skin texture after washing] 〇: Refreshing ×: Sticky

[0171] As a result of the evaluation, Samples 1 and 2 were both rated as "good" for [makeup removal] and [skin texture after cleansing]. On the other hand, Sample 3 was rated as "bad" for [makeup removal] and [skin texture after cleansing]. These evaluations show that by incorporating the polyglycerol monofatty acid ester product of the present disclosure into a cosmetic composition, the desired effects of cosmetics, such as [makeup removal] and [skin texture after cleansing], can be achieved.

[0172] In summary, the configuration of the present disclosure and its variations are set forth below. [1] The fatty acid has 4 to 25 carbon atoms. The peak intensity ratio represented by the following formula (X) is 0.20 or more, A polyglycerol mono-fatty acid ester product having a peak intensity ratio represented by the following formula (Y) of 0.46 or less. Formula (X)=P2 / P1 Formula (Y)=P3 / P1 P1: The sum of peak intensities of monoesters, monoester dehydrates, diesters, diester dehydrates, triesters, and triester dehydrates of polyglycerol fatty acid esters, as well as polyglycerol and polyglycerol dehydrates, when mass spectrometry of polyglycerol mono fatty acid ester products is performed using a time-of-flight mass spectrometer. P2: Peak intensity of monoester of polyglycerol fatty acid ester when mass spectrometry of polyglycerol mono fatty acid ester product was performed using a time-of-flight mass spectrometer P3: The sum of the peak intensities of polyglycerin and polyglycerin dehydrates when the polyglycerin mono fatty acid ester product was subjected to mass spectrometry using a time-of-flight mass spectrometer. [2] The polyglycerol mono-fatty acid ester product according to [1], wherein the number of carbon atoms in 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. [3] The polyglycerol mono-fatty acid ester product according to [1] or [2], wherein the fatty acid has 4 to 14, 15 to 25, 8 to 14, or 16 to 18 carbon atoms. [4] The polyglycerol monofatty acid ester product according to any one of [1] to [3], wherein the peak intensity ratio represented 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. [5] The polyglycerol mono-fatty acid ester product according to any one of [1] to [4], wherein the peak intensity ratio represented 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. [6] The polyglycerol mono-fatty acid ester product according to any one of [1] to [5], wherein the average degree of polymerization of glycerin 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. [7] The polyglycerol mono-fatty acid ester product according to any one of [1] to [6], wherein an average degree of polymerization of glycerin is 2 to 40, 3 to 20, or 4 to 10. [8] The polyglycerol mono-fatty 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. [9] The polyglycerol mono-fatty 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.

[10] The fatty acids are caproic acid (C6, saturated fatty acid), caprylic acid (C8, saturated fatty acid), pelargonic acid (C9, saturated fatty acid), 2-ethylhexanoic acid (C8, branched chain fatty acid), capric acid (C 10 , saturated fatty acid), lauric acid (C 12 , saturated fatty acid), isotridecanoic acid (C 13 , branched chain fatty acid), myristic acid (C 14 , saturated fatty acid), pentadecylic acid (C 15 , saturated fatty acid), palmitic acid (C 16 , saturated fatty acid), palmitoleic acid (C 16 , unsaturated fatty acid), stearic acid (C 18 , saturated fatty acid), isostearic acid (C 18 , branched chain fatty acid), 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 , substituted fatty acids), arachidic acid (C 20 , saturated fatty acid), behenic acid (C 22 , saturated fatty acids), erucic acid (C 22 , unsaturated fatty acids), and nervonic acid (C 24 , and unsaturated fatty acids).

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

[10] , wherein the area ratio of peaks corresponding to monoesters, monoester dehydrates, polyesters, and polyester dehydrates of polyglycerol fatty acid esters, as well as polyglycerol and polyglycerol dehydrates, in HPLC (high performance liquid chromatography) analysis is 50% or more, 60% or more, 80% or more, or 90% or more.

[12] The polyglycerol mono-fatty acid ester product according to any one of [1] to

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

[13] The polyglycerol mono-fatty acid ester product according to any one of [1] to

[12] , wherein the area ratio of the peaks corresponding to polyglycerol and polyglycerol dehydrates in HPLC (high performance liquid chromatography) analysis is 80% or less, 70% or less, or 60% or less.

[14] The polyglycerol mono-fatty acid ester product according to any one of [1] to

[13] , which is a reaction product of glycidol and a fatty acid, an esterification product of polyglycerol and a fatty acid, or a transesterification product of polyglycerol and a fatty acid ester.

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

[14] .

[16] The cosmetic composition according to

[15] , wherein 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.

[17] The cosmetic composition according to

[15] or

[16] , wherein the polyglycerol monofatty acid ester product contained therein has an HLB value of 9 to 13 or 11 to 12.5.

[18] 1. A method for producing a polyglycerol mono-fatty acid ester product, comprising: A method for producing a polyglycerol mono-fatty acid ester product, comprising an addition polymerization reaction step of glycidol and a fatty acid.

[19] The method for producing a polyglycerol mono-fatty acid ester product according to

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

[20] The method for producing a polyglycerol mono-fatty acid ester product according to

[18] or

[19] , wherein the acid 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-based acid catalysts. [twenty one] The method for producing a polyglycerol mono-fatty acid ester product according to

[20] , wherein the phosphoric acid-based acidic catalyst is a phosphoric acid or an acidic phosphoric acid ester. [twenty two] The method for producing a polyglycerol mono-fatty acid ester product according to any one of

[18] to

[21] , wherein an addition polymerization reaction is carried out by continuously or intermittently supplying glycidol to a fatty acid. [twenty three] The method for producing a polyglycerol mono-fatty acid ester product according to any one of

[18] to

[21] , wherein an addition polymerization reaction is carried out by continuously or intermittently supplying glycidol to a fatty acid while continuously or intermittently supplying an acidic catalyst to the fatty acid.

Claims

1. The fatty acid has 4 to 25 carbon atoms, The peak intensity ratio represented by the following formula (X) is 0.20 or more, A polyglycerol mono-fatty acid ester product having a peak intensity ratio represented by the following formula (Y) of 0.46 or less. Formula (X)=P2 / P1 Formula (Y)=P3 / P1 P1: The sum of the peak intensities of the monoester, monoester dehydrate, diester, diester dehydrate, triester, and triester dehydrate of polyglycerol fatty acid ester, as well as polyglycerol and polyglycerol dehydrate, when mass spectrometry of a polyglycerol mono fatty acid ester product is performed using a time-of-flight mass spectrometer. P2: Peak intensity of monoester of polyglycerol fatty acid ester when mass spectrometry of polyglycerol mono fatty acid ester product is performed using a time-of-flight mass spectrometer P3: The sum of the peak intensities of polyglycerin and polyglycerin dehydrate when the polyglycerin mono fatty acid ester product is subjected to mass spectrometry using a time-of-flight mass spectrometer.

2. 2. The polyglycerol mono-fatty acid ester product according to claim 1, wherein the fatty acid has 15 to 25 carbon atoms.

3. 2. The polyglycerol mono-fatty acid ester product according to claim 1, wherein the fatty acid has 4 to 14 carbon atoms.

4. 3. The polyglycerol mono-fatty acid ester product according to claim 2, wherein the fatty acid has 16 to 18 carbon atoms.

5. 4. The polyglycerol mono-fatty acid ester product according to claim 3, wherein the fatty acid has 8 to 14 carbon atoms.

6. 4. The polyglycerol mono-fatty acid ester product according to claim 2 or 3, wherein the average degree of polymerization of glycerol is 2 to 20.

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

8. 4. The polyglycerol mono-fatty acid ester product according to claim 2 or 3, wherein the fatty acid is an unsaturated fatty acid.

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

10. 2. The polyglycerol mono-fatty acid ester product of claim 1 which 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 an addition polymerization reaction step of glycidol and a fatty acid.

13. 13. The method for producing a polyglycerol mono-fatty acid ester product according to claim 12, wherein the addition polymerization reaction is carried out by continuously or intermittently supplying glycidol to a fatty acid.

14. 13. The method for producing a polyglycerol mono-fatty acid ester product according to claim 12, wherein the addition polymerization reaction is carried out by continuously or intermittently supplying glycidol to a fatty acid while continuously or intermittently supplying an acidic catalyst to the fatty acid.

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

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