Microbead, microbead crystal starch decomposition, method for manufacturing microbead crystal starch decomposition, cosmetic, method for manufacturing cosmetic, and method for improving heat resistance of crystal starch decomposition

Abstract

Provided is a technology capable of reducing environmental load and obtaining microbeads with high heat resistance. The present technology provides a crystalline starch decomposition product for microbeads, wherein (a) the content of glucose with a polymerization degree (DP) of 8 to 19 is 30% or more, (b) the content of glucose with a polymerization degree (DP) of 5 or less is 5% or less, (c) the content of molecules with a molecular weight of 5000 or more is 25% or less, (d) the content of glucose with a polymerization degree (DP) of 4 or more remaining in a β-amylase digestion test is 15% or less, and (e) the solubility at 50°C is 20% or less.

Description

Technical Field

[0001] This technology relates to crystalline starch decomposition products for microbeads, microbeads, a method for manufacturing crystalline starch decomposition products for microbeads, cosmetics, a method for manufacturing cosmetics, and a method for improving the heat resistance of crystalline starch decomposition products. Background Technology

[0002] Plastic microbeads are used for a variety of purposes in various fields. For example, in the cosmetics industry, plastic microbeads are used extensively for purposes such as lubricants, texture modifiers, and abrasives.

[0003] Plastic microbeads are lightweight and, after use, can flow into rivers through drainage ditches. Furthermore, due to their small size, they are sometimes unable to be removed by wastewater treatment facilities and end up directly in the ocean, becoming a major cause of marine pollution. In addition, plastic microbeads have the property of adsorbing chemical pollutants in the ocean; plankton and fish ingest them, raising concerns not only about environmental pollution but also about potential health risks.

[0004] Against this backdrop, the development of microbeads made from starch, which is safe for both the environment and human health, is underway. For example, Patent Document 1 discloses a technique for manufacturing cosmetic compositions using naturally derived raw materials. This technique involves having starch particles and a lubricant containing fatty acids that coats at least a portion of the surface of the starch particles. The mass of the lubricant is 0.3% to 20% by mass relative to the total mass of the starch particles and the lubricant. This allows for efficient manufacturing, and the cosmetic composition exhibits good spreadability on the skin and excellent resistance to spoilage.

[0005] Furthermore, Patent Document 2 discloses a technique for manufacturing a cosmetic composition that uses a powder or granular material that meets the following conditions to manufacture a cosmetic composition that takes into account the global environment: the starch content is 75% by mass or more; it contains 3% by mass to 45% by mass of a low-molecular-weight starch with an amylose content of 10% by mass or more, and the peak molecular weight of the aforementioned low-molecular-weight starch is 3 × 10⁻⁶. 3 Above 5×10 4 The following are emulsifiers, or emulsifiers containing one or more of the group consisting of monoglyceride fatty acid esters, polyglyceride fatty acid esters and sucrose fatty acid esters, wherein the content of the aforementioned emulsifier is 0.01% by mass or more and 4.8% by mass or less; the cold water swelling degree at 25°C is 5% by mass or more and 20% by mass; and the content of the undersize material of a 0.5 mm sieve is 60% by mass or more and 100% by mass or less.

[0006] Existing technical documents Patent documents Patent Document 1: International Publication No. 2019-131755 Patent Document 2: International Publication No. 2023-008416 Summary of the Invention

[0007] The problem that the invention aims to solve Microspheres are processed into various products depending on their intended use. During the processing of these products, heating is sometimes required, making high heat resistance of the microspheres desirable. Furthermore, high heat resistance is also highly desirable when storing the processed products or the microspheres themselves to prevent deterioration.

[0008] Therefore, the main objective of this technology is to provide a technique that can reduce environmental impact and obtain microbeads with high heat resistance.

[0009] Methods for solving problems To address the aforementioned objectives, the inventors of this application conducted in-depth research and discovered that by specifically treating the crystallized starch decomposition products, which are predominantly composed of linear components, they successfully obtained crystalline starch decomposition products with improved heat resistance, thus completing this technology. Furthermore, by effectively utilizing this technology, it is also possible to manufacture microbeads that are entirely of natural or plant origin and that do not use organic solvents during the manufacturing process.

[0010] That is, in this technology, a crystalline starch decomposition product for microbeads is first provided, wherein, (a) The content of glucose with a degree of polymerization (DP) of 8 to 19 is 30% or more. (b) The content of glucose with a degree of polymerization (DP) of less than 5% is less than 5%. (c) The content of molecules with a molecular weight of 5000 or higher is less than 25%. (d) The content of residual glucose with a degree of polymerization (DP) of 4 or higher in the β-amylase digestibility test is less than 15%. (e) Solubility at 50°C is less than 20%.

[0011] The microbeads involved in this technology have a cumulative volume of 50% of the crystalline starch decomposition product and a particle size of 5–70 μm.

[0012] In this technology, microbeads containing crystalline starch decomposition products are then provided. In the aforementioned crystalline starch decomposition products, (a) The content of glucose with a degree of polymerization (DP) of 8 to 19 is 30% or more. (b) The content of glucose with a degree of polymerization (DP) of less than 5% is less than 5%. (c) The content of molecules with a molecular weight of 5000 or higher is less than 25%. (d) The content of residual glucose with a degree of polymerization (DP) of 4 or higher in the β-amylase digestibility test is less than 15%. (e) Solubility at 50°C is less than 20%.

[0013] The cumulative volume of the microspheres involved in this technology is 50%, and the particle size can be 5–70 μm.

[0014] This technology also provides a method for manufacturing crystalline starch decomposition products for microbeads, which includes: The crystallization process of crystallizing starch decomposition products; and The process involves heating the crystalline starch decomposition product that has undergone the aforementioned crystallization process to a temperature of 75°C or higher in the presence of water and / or steam.

[0015] The starch decomposition products used in the manufacturing methods involved in this technology may have the following characteristics.

[0016] (f) The content of glucose with a degree of polymerization (DP) of 8-19 is 42% or more. (g) The content of glucose with a degree of polymerization (DP) of 20 or higher is less than 35%. (h) The content of residual glucose with a degree of polymerization (DP) of 4 or higher in the β-amylase digestibility test is less than 15%.

[0017] In addition, the manufacturing method involved in this technology can include an enzymatic reaction step to obtain the aforementioned starch decomposition product, wherein the aforementioned enzymatic reaction step includes acting a debranching enzyme on one or more selected from starch, starch extract, and starch liquefaction liquid.

[0018] In this technology, a cosmetic product is further provided, which contains crystalline starch decomposition product of microbeads as described in this technology, or microbeads as described in this technology.

[0019] In addition, this technology provides a method for manufacturing cosmetics, which includes a step of using microbeads with crystalline starch decomposition products obtained by the manufacturing method involved in this technology.

[0020] In addition to the above, this technology also provides a method for improving the heat resistance of crystalline starch decomposition products, which includes a heating step of heating the aforementioned crystalline starch decomposition products to above 75°C in the presence of water and / or water vapor. In the aforementioned crystalline starch decomposition products, (a) The content of glucose with a degree of polymerization (DP) of 8 to 19 is 30% or more. (b) The content of glucose with a degree of polymerization (DP) of less than 5% is less than 5%. (c) The content of molecules with a molecular weight of 5000 or higher is less than 25%. (d) The content of residual glucose with a degree of polymerization (DP) of 4 or higher in the β-amylase digestibility test is less than 15%.

[0021] Here, the technical terms used in this technique are explained. "Debranching enzyme" is a general term for enzymes that catalyze the hydrolysis of α-1,6-glycosidic bonds, which are branching points of starch. Examples include "isoamylase (glycogen 6-glucanohydrolase)," "pullulanase (pullulan 6-glucan hydrolase)," and "amylo-1,6-glucosidase / 4-α-glucanotransferase." It should be noted that these debranching enzymes can be used in combination depending on the purpose.

[0022] "Branching enzymes" are a collective term for enzymes that function to form α-1,6-glycosidic bonds by acting on linear glucans linked by α-1,4-glycosidic bonds. They are found in animals, bacteria, and can also be purified from plants such as potato, rice seeds, and corn seeds. Detailed Implementation

[0023] The preferred embodiments for implementing this technology are described below. It should be noted that the embodiments described below illustrate one example of a representative implementation of this technology and are not intended to narrowly interpret the scope of this technology.

[0024] 1. Microbeads made from crystalline starch decomposition products The microbeads used in this technology have the following characteristics (a) to (e).

[0025] (a) The content of glucose with a degree of polymerization (DP) of 8 to 19 is 30% or more. (b) The content of glucose with a degree of polymerization (DP) of less than 5% is less than 5%. (c) The content of molecules with a molecular weight of 5000 or higher is less than 25%. (d) The content of residual glucose with a degree of polymerization (DP) of 4 or higher in the β-amylase digestibility test is less than 15%. (e) Solubility at 50°C is less than 20%. The microsphere crystalline starch decomposition product involved in this technology has high heat resistance. In this technology, "high heat resistance" means that the quality of the microsphere crystalline starch decomposition product remains intact even under high temperature conditions, such as above 40°C, preferably above 50°C, whether in its original state or dispersed in water or other solvents. For example, it means that under high temperature conditions, such as above 40°C, preferably above 50°C, the microsphere crystalline starch decomposition product will not exhibit the following properties: partial or complete disintegration due to deliquescence, resulting in loss of shape; reduction or loss of lubricity, improved tactile properties, etc.; or a decrease in quality due to partial dissolution into water or solvents, resulting in a sticky feeling.

[0026] The following is a detailed description of the crystalline starch decomposition product used in this technology for microbeads.

[0027] <Crystallized starch decomposition products> The microspheres involved in this technology are obtained by the following method: using starches such as corn starch, rice starch, wheat starch, sago starch, etc. (aerial starches), potato starch, cassava starch, sweet potato starch, etc. (underground starches) derived from underground stems or roots, their glutinous varieties, high amylose starches, and processed starches obtained by physically or chemically processing these starches individually or in combination, etc., as raw materials, at least decomposing them to obtain starch decomposition products, and then crystallizing them. There are no particular limitations on the type of starch used as raw material; all types of starch can be used.

[0028] <Content with glucose degree of polymerization (DP) 8-19, glucose degree of polymerization (DP) below 5, and molecular weight above 5000> As a compositional characteristic of the crystalline starch decomposition product for microbeads involved in this technology, the content of glucose with a degree of polymerization (hereinafter referred to as "DP") of 8 to 19 is 30% or more, the content of DP5 or less is 5% or less, and the content of molecular weight of 5000 or more is 25% or less. The crystalline starch decomposition product for microbeads involved in this technology contains a large amount of high molecular weight oligosaccharides and low molecular weight dextrins (DP8 to 19), and its components are basically linear sugar molecules, which are easy to crystallize, thus achieving a stable crystallization effect. It should be noted that in this technology, the contents of DP8 to 19, DP5 or less, and molecular weight of 5000 or more of the starch decomposition product are values ​​determined by the method described in the examples described later.

[0029] Regarding the crystalline starch decomposition product used in this technology for microbeads, the effect of this technology can be achieved when the content of DP8-19 is 30% or more, preferably 35% or more, more preferably 45% or more, further preferably 50% or more, and even more preferably 53% or more, or 58% or more. The higher the content of DP8-19, the more essentially linear sugar molecules are formed, as will be described later, thus making them easier to crystallize and resulting in higher crystallization stability.

[0030] As long as the function and effect of this technology are not compromised, the upper limit of the content of DP8-19 of crystalline starch decomposition products in the microbeads used in this technology can be freely set. For example, it can be set to below 90%, below 85%, below 75%, etc.

[0031] Furthermore, regarding the crystalline starch decomposition product used in this technology, the effect of this technology can be achieved when the content of DP5 or less is 5% or less, preferably 4% or less, more preferably 3% or less, and even more preferably 2% or less. The lower the content of DP5 or less, the lower the solubility at 50°C, which can suppress the stickiness of the crystalline starch decomposition product and the microspheres using the crystalline starch decomposition product.

[0032] There is no lower limit to the content of microbeads with DP5 or less of crystalline starch decomposition products used in this technology; it can be 0%.

[0033] Regarding the molecular weight of the crystalline starch decomposition product used in the microbeads involved in this technology, the effect of this technology can be achieved when the content of 5000 or more is 25% or less, preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. The lower the content of 5000 or more molecular weight, the less likely the particle size of the crystalline starch decomposition product will become smaller, thus preventing the crystalline starch decomposition product and the microbeads using it from developing a rough or astringent feel.

[0034] There is no lower limit to the content of crystalline starch decomposition products with a molecular weight of 5000 or higher in the microbeads involved in this technology. For example, it can be set to 0% or higher, 1% or higher, 2% or higher, etc.

[0035] <Content of residual glucose polymerization degree (DP) 4 or higher in β-amylase digestibility test> The microbeads involved in this technology have a residual glucose degree of polymerization (DP) of 4 or higher in the β-amylase digestion test of crystalline starch decomposition products of less than 15%. It should be noted that the residual glucose degree of polymerization (DP) of 4 or higher in the β-amylase digestion test is a value determined by the method described in the examples below.

[0036] Regarding the crystalline starch decomposition product for microbeads involved in this technology, the effect of this technology is achieved when the content of residual glucose degree of polymerization (DP) 4 or higher in the β-amylase digestion test is 15% or less, preferably 13% or less, and more preferably 10% or less. The lower the content of residual glucose degree of polymerization (DP) 4 or higher in the β-amylase digestion test, the more linear sugar molecules that are easy to crystallize, thus improving the crystallization stability of the crystalline starch decomposition product for microbeads.

[0037] It should be noted that β-amylase is a known enzyme that breaks down glucose polymers into maltose units from their non-reducing ends. Decomposition ceases when branched bonds such as α-1,6 bonds are present. Therefore, the evaluation of crystalline starch decomposition products based on β-amylase digestion assays is an indicator of the degree to which they possess a continuous linear portion with α-1,4 bonds, from a structural point of view. In other words, the evaluation based on β-amylase digestion assays is an indicator of the overall linear sugar molecules in the crystalline starch decomposition product.

[0038] <Solubility at 50℃> The solubility of the microbeads made from crystalline starch decomposition products at 50°C is less than 20%. By controlling the solubility at 50°C to less than 20%, a sticky feeling can be suppressed. It should be noted that the solubility of the crystalline starch decomposition products at 50°C is a value measured by the method described in the examples described later.

[0039] The solubility of the crystalline starch decomposition product in the microbeads involved in this technology at 50°C is 20% or less to achieve the desired effect, preferably 18% or less, more preferably 15% or less, and even more preferably 10% or less. The lower the solubility at 50°C, the better the crystalline starch decomposition product and the stickiness of the microbeads using it can be suppressed.

[0040] <Particle Size Distribution> Provided that the function and effect of this technology are not compromised, the particle size distribution of the microbeads made from the decomposition of crystalline starch can be freely set according to the intended use. It should be noted that the particle size distribution is a value determined by the method described in the examples below.

[0041] Specifically, the lower limit for the particle size at which the cumulative volume becomes 10% is, for example, 2 μm or more, preferably 4 μm or more, and more preferably 7 μm or more. Furthermore, the upper limit for the particle size at which the cumulative volume becomes 10% is, for example, 25 μm or less, preferably 19 μm or less, and more preferably 15 μm or less.

[0042] The lower limit for the cumulative volume to be 50% of the particle size is, for example, 5 μm or more, preferably 10 μm or more, and more preferably 12 μm or more.

[0043] The upper limit for the cumulative volume to be 50% of the particle size is, for example, 70 μm or less, preferably 50 μm or less, more preferably 40 μm or less, further preferably 28 μm or less, and even more preferably 22 μm or less.

[0044] The lower limit for the particle size at which the cumulative volume becomes 90% is, for example, 10 μm or more, preferably 15 μm or more. Furthermore, the upper limit for the particle size at which the cumulative volume becomes 90% is, for example, 160 μm or less, preferably 100 μm or less, more preferably 60 μm or less, even more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 22 μm or less.

[0045] By controlling the cumulative volume of the microspheres containing crystalline starch decomposition product to a lower limit of 10%, a lower limit of 50%, and a lower limit of 90% of the particle size, a rough feel can be prevented from occurring with the crystalline starch decomposition product or with the microspheres containing it. Furthermore, by controlling the cumulative volume of the microspheres containing crystalline starch decomposition product to an upper limit of 10%, an upper limit of 50%, and an upper limit of 90% of the particle size, the extensibility of the microspheres containing the crystalline starch decomposition product or with the microspheres containing it can be improved, and a rough feel can be reduced.

[0046] 2. Method for manufacturing microspheres using crystalline starch decomposition products <Overview of Manufacturing Method> Regarding the crystalline starch decomposition product for microbeads involved in this technology, its physical properties are novel. There are no particular limitations on its manufacturing method, and it can be obtained by: using starch as a raw material, performing at least a decomposition process to obtain starch decomposition product, and then performing a crystallization process on the obtained starch decomposition product. Alternatively, the processes of decomposing starch to obtain starch decomposition product and crystallizing the obtained starch decomposition product can be performed simultaneously and in parallel. That is, crystalline starch decomposition product can also be manufactured by sequentially crystallizing the obtained starch decomposition product while simultaneously decomposing starch.

[0047] In the process of manufacturing starch decomposition products, starches and / or starch extracts are decomposed using, for example, acids, alkalis, or enzymes. This can also be used in chromatography, separation membranes, or in combination with separation techniques based on differences in physical properties such as solubility. Furthermore, in the process of crystallizing the starch decomposition products, to make the solution containing the starch decomposition products readily crystallize, the temperature is lowered or the concentration is increased, for example. Moreover, in the method for manufacturing crystalline starch decomposition products for microbeads according to this technology, since the solubility of the crystalline starch decomposition products at 50°C can be reduced, if a process of heating the crystalline starch decomposition products to 75°C or higher in the presence of water and / or water vapor is performed, the crystalline starch decomposition products for microbeads according to this technology can be easily obtained.

[0048] <Process for manufacturing starch decomposition products> A method for efficiently obtaining the starch decomposition product before crystallization of the microbeads related to this technology includes the following steps: using starch as a raw material, and decomposing it by at least allowing a debranching enzyme to function. When the debranching enzyme is activated, the starch is selected from one or more of the following states: starch dispersion, starch extract, starch gelatinization liquid, starch liquefaction liquid, and starch decomposition product solution. In this invention, starch liquefaction liquid refers to a liquid substance obtained by heating starch in the presence of an enzyme and / or acid.

[0049] Furthermore, as a more efficient method for obtaining the starch hydrolysate before crystallization of the microbeads related to this technology, a step of inducing the branching enzyme to act may be included. The state of the starch when the branching enzyme acts is the same as that when the debranching enzyme acts, as described above. There is no particular limitation on the timing of inducing the debranching enzyme and the branching enzyme to act; for example, they may act simultaneously; the step of inducing the branching enzyme to act may occur after the step of debranching; the step of inducing the branching enzyme to act may occur after the step of debranching; and other steps may be included in between. Preferably, a step of inducing the debranching enzyme and the branching enzyme to act simultaneously may be included, or a step of inducing the debranching enzyme to act may occur after the step of inducing the branching enzyme to act. The debranching enzyme is an enzyme involved in the decomposition of starch branches, and the branching enzyme is an enzyme used for the synthesis of starch branches. Therefore, the two are not usually used together. However, by combining two enzymes that exhibit completely opposite effects, the starch hydrolysate related to this technology can be reliably manufactured.

[0050] The aforementioned debranching enzymes are not specifically limited. For example, pullulanase (pullulan 6-glucan hydrolase) and amylo-1,6-glucosidase / 4-α-glucanotransferase can be cited. As a more suitable example, isoamylase (glycogen 6-glucanohydrolase) can be used.

[0051] Furthermore, there are no particular limitations on the aforementioned branching enzymes. For example, branching enzymes purified from animals, bacteria, or plants such as potatoes, rice seeds, and corn seeds, as well as commercially available enzyme preparations, can be used.

[0052] The starch decomposition product of the microbeads used in this technology, before crystallization, preferably has the following characteristics. This prevents precipitation in this process and also allows for the purification process of the starch decomposition product, described later.

[0053] (f) The content of glucose with a degree of polymerization (DP) of 8-19 is 42% or more. (g) The content of glucose with a degree of polymerization (DP) of 20 or higher is less than 35%. (h) The content of residual glucose with a degree of polymerization (DP) of 4 or higher in the β-amylase digestibility test is less than 15%. The content of glucose degree of polymerization (DP) 8-19 in the starch decomposition product before crystallization is preferably 42% or more, more preferably 45% or more, and even more preferably 47% or more. There is no particular upper limit to the content of glucose degree of polymerization (DP) 8-19 in the starch decomposition product before crystallization, for example, it can be set to 90% or less, 85% or less, 75% or less, 70% or less, etc.

[0054] The content of glucose polymerization degree (DP) of starch decomposition product before crystallization with a value of 20 or higher is preferably 35% or less, more preferably 32% or less, and even more preferably 30% or less. There is no particular limitation on the lower limit of glucose polymerization degree (DP) of starch decomposition product before crystallization with a value of 20 or higher, and it can be set to 10% or more, 15% or more, 18% or more, 20% or more, etc.

[0055] The content of glucose degree of polymerization (DP) 4 or higher remaining in the starch decomposition product before crystallization in the β-amylase digestibility test is preferably 15% or less, more preferably 13% or less, and even more preferably 12% or less. By controlling the content of glucose degree of polymerization (DP) 4 or higher remaining in the starch decomposition product before crystallization in the β-amylase digestibility test within this range, more linear sugar molecules that are easy to crystallize are produced, thus enabling more efficient crystallization processes as described later.

[0056] <The process of crystallizing starch decomposition products (crystallization process)> The crystallization step in the method for manufacturing crystalline starch decomposition products of microbeads involved in this technology is a step of crystallizing the starch decomposition products. The crystallization step can be performed after the aforementioned step of manufacturing the starch decomposition products, or it can be performed simultaneously with the aforementioned step of manufacturing the starch decomposition products.

[0057] The crystallization method in the crystallization process is not particularly limited. One or more known crystallization methods can be freely selected and used to make the solution containing starch decomposition products ready for crystallization. In this technique, for example, the starch decomposition products can be crystallized by maintaining the solution at a specified concentration above and / or below a specified temperature. It should be noted that the crystallization in this technique can be determined by confirming diffraction peaks in powder X-ray diffraction analysis.

[0058] The concentration of the starch decomposition product solution supplied in the crystallization process is not particularly limited, and can be freely set as long as it does not impair the effect of this technology. For example, by maintaining it at 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, the aforementioned starch decomposition product can be crystallized. Furthermore, the temperature of the starch decomposition product solution in this case is not particularly limited, and can be freely set as long as it does not impair the effect of this technology. For example, by maintaining it at 85°C or below, preferably 80°C or below, and more preferably 75°C or below, the aforementioned starch decomposition product can be crystallized. The concentration and / or temperature of the starch decomposition product solution can also be changed during the crystallization process. In addition, the holding time is not particularly limited, and can be set to 20 days or less, preferably 10 days or less, and more preferably 7 days or less.

[0059] <Process of heating the decomposed crystalline starch> The method for manufacturing crystalline starch decomposition products for microspheres involved in this technology may include a step of heating the crystalline starch decomposition products to 75°C or higher in the presence of water and / or water vapor. In this technology, the heat resistance of the crystalline starch decomposition products is successfully improved by heating them. The step of heating the crystalline starch decomposition products can be performed after the crystallization step or simultaneously with the crystallization step. As a method for heating the crystalline starch decomposition products, for example, a solution containing the crystalline starch decomposition products can be heated to 75°C or higher, or the crystalline starch decomposition products can be heated to 75°C or higher in the presence of water vapor. As a heating method under water vapor conditions, for example, water can be added and heating can be performed in a sealed state, or water vapor can be added and heating can be performed in a sealed state. It should be noted that in this case, as long as the state is sealed, pressure reduction or pressure application is possible.

[0060] The heating temperature for the crystalline starch decomposition product is 75°C or higher. When heating a solution containing the crystalline starch decomposition product, 78°C or higher is preferred, and 85°C or higher is more preferred. The upper limit of the temperature can be freely set as long as it does not impair the function or effect of this technology; it can be 100°C or lower, or 98°C or lower, or 95°C or lower. It should be noted that, in the solution containing the crystalline starch decomposition product, the crystalline starch decomposition product preferably accounts for 30% by mass or more relative to the overall solution. On the other hand, when heating the crystalline starch decomposition product under steam conditions, 100°C or higher is preferred, 110°C or higher is more preferred, and 115°C is even more preferred. The upper limit of the temperature can be freely set as long as it does not impair the function or effect of this technology; for example, 150°C or lower is preferred, 140°C or lower is more preferred, and 130°C or lower is more preferred. The heating temperature for the crystalline starch decomposition product can also be changed during the process.

[0061] The heating time for the crystalline starch decomposition product can be freely set according to the temperature of the crystalline starch decomposition product, provided that the function and effect of this technology are not compromised. The lower limit of the heating time is, for example, 5 minutes or more, preferably 10 minutes or more, and more preferably 20 minutes or more. The upper limit of the heating time is, for example, 48 hours or less, preferably 24 hours or less, and more preferably 15 hours or less.

[0062] <Other processes> In addition to the aforementioned steps, the method for manufacturing crystalline starch decomposition products for microbeads may also include steps such as purifying the starch decomposition products, separating the crystalline starch decomposition products, and drying the crystalline starch decomposition products.

[0063] In the method for manufacturing crystalline starch decomposition products for microbeads according to this technology, a purification step may be included after the step of manufacturing the starch decomposition product. There are no particular limitations on the method for purifying the starch decomposition product, and one or more known methods can be freely combined. Examples include purifying a solution containing starch decomposition products by filtration using filters or filter aids, adsorption using activated carbon or ion exchange resins, or concentration. This step removes impurities from raw starch, processing aids, etc., as well as impurities generated during the process. For example, in order to suppress skin irritation when using the microbeads according to this technology in cosmetics, the method for manufacturing crystalline starch decomposition products for microbeads according to this technology preferably includes a purification step for the starch decomposition product after the step of manufacturing the starch decomposition product. It should be noted that this step, performed at 30°C or higher, preferably 40°C or higher, can prevent precipitation.

[0064] In the method for manufacturing crystalline starch decomposition products using microbeads disclosed in this technology, a step of separating the crystalline starch decomposition products can be included after the crystallization step. Methods for separating the crystalline starch decomposition products include, for example, separation from the liquid by filtration, centrifugation, or separation from highly soluble components by washing with water. Alternatively, these components can be combined.

[0065] In the method for manufacturing crystalline starch decomposition products for microbeads disclosed in this technology, a step of drying the crystalline starch decomposition products may be included after the crystallization step. Examples of methods for drying the crystalline starch decomposition products include air drying, vacuum drying, spray drying, and freeze drying.

[0066] 2. Microbeads The microspheres involved in this technology can be used as microspheres in their original state, or they can be granulated with additives commonly used in microsphere manufacturing to produce microspheres. Furthermore, microspheres whose properties have been further altered through physical or chemical treatments can also be produced. In addition, multilayer microspheres can be produced by coating them with surface materials commonly used in microsphere manufacturing.

[0067] 3. Methods to improve the heat resistance of crystalline starch decomposition products The method for improving the heat resistance of crystalline starch decomposition products involved in this technology is a method of heating crystalline starch decomposition products having the aforementioned characteristics (a) to (d) to 75°C or higher in the presence of water and / or steam. The composition, physical properties, details of the heating process, and details of the heat-resistant crystalline starch decomposition products before the heating process are the same as those in the aforementioned method for manufacturing crystalline starch decomposition products for microspheres and the aforementioned method for manufacturing crystalline starch decomposition products for microspheres involved in this technology, and therefore are omitted here.

[0068] 4. Cosmetics The microbeads, crystalline starch decomposition products, and heat-resistant crystalline starch decomposition products involved in this technology can be appropriately applied to all cosmetics due to their high heat resistance. Furthermore, the microbeads, crystalline starch decomposition products, and heat-resistant crystalline starch decomposition products involved in this technology have relatively uniform particle shape and size and are biodegradable, thus allowing for appropriate application in various cosmetics.

[0069] There are no particular limitations on its application methods in cosmetics. For example, it can be used as a powder matrix and excipient in powder cosmetics and solid cosmetics, and as a lubricant and texture improver in liquid, emulsion, gel, and cream cosmetics.

[0070] The microbeads and crystalline starch decomposition products involved in this technology have high heat resistance, so they can be used appropriately even in cosmetics manufactured under high temperature conditions or cosmetics that may be stored under high temperature conditions.

[0071] Furthermore, it can prevent the degradation of the user experience of cosmetics used under high-temperature conditions. In addition, when the microbeads involved in this technology, using crystalline starch decomposition products, microbeads, or crystalline starch decomposition products with improved heat resistance, are applied to cosmetics such as makeup and sunscreens that are continuously applied to the skin for a certain period of time, it can prevent the degradation of the quality and user experience of the cosmetics caused by external temperature or body temperature. Specifically, it can prevent makeup from fading and leaving a sticky feeling.

[0072] 5. Manufacturing methods of cosmetics The cosmetic manufacturing method described in this technology includes a process of incorporating one or more of the following: microbeads, crystalline starch decomposition products, microbeads, and heat-resistant crystalline starch decomposition products. Regarding the incorporation process, as long as it does not impair the function or effect of this technology, it can be performed once or multiple times within the steps of a conventional cosmetic manufacturing method, depending on the type of cosmetic and the manufacturing method.

[0073] The microbeads and crystalline starch decomposition products involved in this technology have high heat resistance, so they can be used appropriately even in cosmetics manufactured under high temperature conditions or cosmetics that may be stored under high temperature conditions.

[0074] 6. Other uses of microbeads, crystalline starch decomposition products, and heat-resistant crystalline starch decomposition products. The microbeads and heat-resistant crystalline starch decomposition products involved in this technology can be appropriately applied to all applications due to their high heat resistance. Furthermore, the crystalline starch decomposition products involved in this technology have a linear molecular structure, with relatively uniform particle shape and size, and are biodegradable; therefore, these properties allow for suitable applications in various fields.

[0075] The applications of the microbeads and crystalline starch decomposition products with improved heat resistance involved in this technology include, for example: industrial products such as carriers, various films, fibers, capsules, adhesives, release agents, anti-adhesion agents, bulking agents, abrasives, and excipients; processed foods such as seasonings, soups, creams, various dairy products, ice cream and other cold desserts, various powdered foods (including beverages), preserved foods, frozen foods, breads, pastries, rice, noodles, aquatic porridge products, and meat products; and health functional foods (including specific health functional foods and functionally labeled foods). Foods and beverages including nutritional functional foods, so-called health foods (including beverages), liquid foods, infant foods, weight-loss foods, and foods for diabetes; powdered bases for powders and granules, excipients for tablets, suspending agents for liquid preparations, semi-solid preparations, ointments, etc., osmotic pressure regulators, coloring (white) pigments, and carbohydrate sources (calorie sources) for enteral nutrition; feed for livestock such as cattle, horses, and pigs, poultry such as chickens and quails, reptiles, birds or small mammals, and farmed fish and insects; culture media and fertilizers for microbial culture, etc.

[0076] Example The present technology will now be described in more detail based on embodiments. It should be noted that the embodiments described below illustrate one example of a representative embodiment of the present technology and are not intended to be interpreted narrowly as limiting the scope of the present technology.

[0077] (1) Test methods [Cleft enzyme] In this experimental example, as an example of a branching enzyme, the method of Eur.J.Biochem.59, p615-625 (1975) was followed, using purified potato-derived enzyme (hereinafter referred to as "potato-derived branching enzyme") and Branchzyme (Novozymes Co., Ltd., hereinafter referred to as "bacterial branching enzyme").

[0078] It should be noted that the activity of the branching enzyme was determined using the following method.

[0079] As the substrate solution, a solution of 0.1% by mass amylose (catalog number: A0512, Sigma-Aldrich) dissolved in 0.1 M acetate buffer (pH 5.2) was used. Add 50 μL of enzyme solution to 50 μL of substrate solution, react at 30°C for 30 minutes, and then add 2 mL of iodine-potassium iodide solution (a mixture of 0.39 mM iodine, 6 mM potassium iodide, and 3.8 mM hydrochloric acid) to stop the reaction. Prepare a blank solution by adding water instead of enzyme solution. Measure the absorbance at 660 nm 15 minutes after the reaction stops. One unit of branched enzyme activity is defined as the enzyme activity that causes a 1% decrease in absorbance at 660 nm per minute under the above conditions.

[0080] [Content of DP8-19, DP20 and above, and DP5 and below] The contents of DP8–19, DP20 and above, and DP5 and below were determined by high performance liquid chromatography (HPLC) under the conditions shown in Table 1 below, based on the detected peak area ratio.

[0081] [Table 1] [Content with a molecular weight of 5000 or higher] Analysis was performed using gel filtration chromatography under the conditions shown in Table 2 below.

[0082] As a molecular weight standard, a Shodex Standard GFC (water-based GPC) column with a Standard P-82 (manufactured by Showa Denko Corporation) was used. Based on a standard curve calculated from the correlation between the elution time and molecular weight of the molecular weight standard, the content of samples with a molecular weight of 5000 or higher was determined.

[0083] [Table 2] [The amount of residual glucose with a degree of polymerization (DP) of 4 or higher in the β-amylase digestion test] 10 μL of β-amylase (NagaseChemteX Co., Ltd.) was added to 10 mL of a 10% (w / w) solid component solution prepared by dissolving starch decomposition products, crystalline starch decomposition products, or crystalline sugars in 10 mM acetate buffer (pH 5.5) through boiling. The reaction was stopped by reacting at 55°C for 72 hours and then heating at 100°C for 10 minutes. The reaction solution was desalted using an ion exchange resin and analyzed by high-performance liquid chromatography (HPLC) under the conditions shown in Table 3 below. The content of DP4 and above was determined based on the detected peak area ratio.

[0084] [Table 3] [Particle size distribution] The particle size distribution of each crystalline starch decomposition product and crystalline sugar was determined using a laser diffraction particle size analyzer (HELOS & RODOS, Japan Laser Corporation) and Fraunhofer diffraction. The cumulative particle sizes representing the 10%, 50%, and 90% percentage points were determined based on the volumetric baseline distribution (frequency distribution) of each crystalline starch decomposition product. It should be noted that the analytical conditions were set to a dispersion pressure of 2 bar. Regarding the measurement range, R5 was used in the analysis of the crystalline starch decomposition product of Manufacturing Example 7 and the crystalline sugars of Manufacturing Examples 16 and 17, while R3 was used in the others.

[0085] [Solubility at 50℃] Add nine times the volume of water at 20°C to the crystalline starch decomposition product or crystalline sugar, stir thoroughly, and measure the Brix value of the supernatant using a refractometer (RX-5000α, ATAGO Co., Ltd.). Record the obtained value as "Brix value (saccharimetry value) at 20°C". Then, set a constant temperature water bath shaker to 50°C and oscillate at 250 rpm for 10 minutes, measuring the Brix value of the supernatant again using a refractometer. Record the obtained value as "Brix value after heating at 50°C". Then, heat the dispersion in a boiling water bath with thorough stirring for 20 minutes, and measure the Brix value of the completely dissolved liquid using a refractometer. Record the obtained value as "Brix value after heating in a boiling water bath". It should be noted that if the product is not completely dissolved even when heated in a boiling water bath, the "Brix value after heating in a boiling water bath" is set to 10%. The solubility at 50°C is the value calculated using the following formula. In addition, if it completely dissolves when added to water at 20°C, the solubility at 50°C is set to 100%.

[0086] Solubility at 50℃ = {(Brix value after heating at 50℃) - (Brix value at 20℃))} ÷ {(Brix value after heating in a boiling water bath) - (Brix value at 20℃)} (2) Manufacturing of microbeads from crystalline starch decomposition products and crystalline sugars [Manufacturing Example 1] In a 30% corn starch slurry adjusted to pH 5.8 with 10% calcium hydroxide, 0.2% α-amylase (KLEISTASE T10S, Amano Enzyme Co., Ltd.) was added relative to the solid content (g), and liquefaction was carried out using a jet cooker (temperature 110°C). The liquefied solution was kept at 95°C, and the DE (degradation) was measured over time. At the time point when DE9 was reached, the pH was adjusted to 4 with 10% hydrochloric acid, and the reaction was stopped by boiling. After adjusting the pH of the stopped sugar solution to 5.8, 800 units of bacterial branching enzyme relative to the solid content (g) were added, and the reaction was carried out at 65°C for 30 hours. Then, 1.0% debranching enzyme (GODO-FIA, Contract Alcohol Co., Ltd.) relative to the solid content (g) was added, and the reaction was carried out at 50°C for 30 hours. The starch decomposition solution was decolorized with activated carbon, purified by ion exchange, and concentrated to a solid content concentration of 50% by mass. The concentrate was pulverized using a spray dryer to obtain the starch decomposition products (before crystallization) with sugar composition shown in Table 4 below.

[0087] The obtained starch decomposition powder was dissolved in water at 80°C to achieve a solid component concentration of 50% by mass. While stirring, the temperature was lowered to 25°C and maintained at 25°C for 2 days, yielding a solution containing crystals (hereinafter referred to as the "crystal-containing solution"). The crystals were repeatedly washed with water and centrifuged until no more solid components dissolved. After separation, the solution was filtered using qualitative filter paper No. 2 (ADVANTEC Toyo Co., Ltd.) to obtain a dehydrated filter cake. The dehydrated filter cake was loosened and thinly spread on a flat, square tray and dried at room temperature for 3 days. It was then passed through a 40-mesh sieve to obtain the crystalline starch decomposition product with the sugar composition shown in Table 4 below. The obtained crystalline starch decomposition product was used as the crystalline starch decomposition product for manufacturing microbeads in Example 1.

[0088] [Manufacturing Examples 2-5] The crystal-containing solution obtained in Manufacturing Example 1 was heated under the conditions shown in Table 4 below, and then crystalline starch decomposition product was obtained by the same method as in Manufacturing Example 1. It should be noted that the sugar composition was the same as that of the crystalline starch decomposition product in Manufacturing Example 1. The obtained crystalline starch decomposition product was used as the crystalline starch decomposition product for microbeads in Manufacturing Examples 2 to 5.

[0089] [Manufacturing Example 6] After humidifying the crystalline starch decomposition product obtained in Manufacturing Example 1 by adding water to achieve a moisture content of 25% by mass, it was subjected to heat treatment at 120°C for 30 minutes using an autoclave (LSX-500, TOMY SEIKO Co., Ltd.). The heat-treated crystalline starch decomposition product was then thinly spread on a flat square tray and dried at room temperature for one day. Finally, it was passed through a 40-mesh sieve to obtain the crystalline starch decomposition product. It should be noted that the sugar composition was the same as that of the crystalline starch decomposition product in Manufacturing Example 1. The obtained crystalline starch decomposition product was used as the crystalline starch decomposition product for microbeads in Manufacturing Example 6.

[0090] [Manufacturing Example 7] The starch decomposition powder obtained in Manufacturing Example 1 was dissolved in water at 80°C to achieve a solid content concentration of 50% by mass. Without stirring, the temperature was lowered to 25°C and maintained at 25°C for 2 days to obtain a solution containing crystals. The resulting crystal-containing solution was heated at 80°C for 12 hours, and then crystalline starch decomposition was obtained using the same method as in Manufacturing Example 1. It should be noted that the sugar composition was the same as that of the crystalline starch decomposition in Manufacturing Example 1. The obtained crystalline starch decomposition was used as the crystalline starch decomposition for the microbeads in Manufacturing Example 7.

[0091] [Manufacturing Example 8] The starch decomposition product powder (before crystallization) obtained in Manufacturing Example 1 was dissolved in water at 80°C to achieve a solid component concentration of 50% by mass. While stirring, the temperature was lowered to 10°C, and then maintained at 10°C for 3 days with continued stirring to obtain a solution containing crystals. The crystals were repeatedly washed with water and centrifuged until no more solid components dissolved. After separation, the solution was filtered using qualitative filter paper No. 2 (ADVANTEC Toyo Co., Ltd.) to obtain a dehydrated filter cake. The dehydrated filter cake was loosely and thinly spread on a flat square tray and dried at room temperature for 3 days. It was then passed through a 40-mesh sieve to obtain crystalline starch decomposition product. It should be noted that the sugar composition was the same as that of the crystalline starch decomposition product in Manufacturing Example 1. The obtained crystalline starch decomposition product was used as the crystalline starch decomposition product for microbeads in Manufacturing Example 8.

[0092] [Manufacturing Example 9] After humidifying the crystalline starch decomposition product obtained in Manufacturing Example 8 by adding water to achieve a moisture content of 25% by mass, it was subjected to heat treatment at 120°C for 30 minutes using an autoclave (LSX-500, TOMY SEIKO Co., Ltd.). The heat-treated crystalline starch decomposition product was then thinly spread on a flat square tray and dried at room temperature for one day. Finally, it was passed through a 40-mesh sieve to obtain the crystalline starch decomposition product. It should be noted that the sugar composition was the same as that of the crystalline starch decomposition product in Manufacturing Example 1. The obtained crystalline starch decomposition product was used as the crystalline starch decomposition product for microbeads in Manufacturing Example 9.

[0093] [Manufacturing Example 10] In a 30% by mass corn starch slurry adjusted to pH 5.8 with 10% by mass calcium hydroxide, 0.2% by mass α-amylase (Liquozyme Supra, Novozymes Japan Co., Ltd.) was added, and liquefaction was carried out using a jet cooker (temperature 110°C). The liquefied solution was kept at 95°C, and the DE (degradation) was measured over time. At the time point of DE8, the pH was adjusted to 4 with 10% by mass hydrochloric acid, and the reaction was stopped by boiling. After adjusting the pH of the stopped sugar solution to 5.8, 500 units of branching enzyme from potato were added, and the reaction was carried out at 65°C for 40 hours. Then, 0.5% by mass debranching enzyme (GODO-FIA, Contract Alcohol Co., Ltd.) was added, and the reaction was carried out at 50°C for 48 hours. The starch decomposition solution was decolorized with activated carbon, purified by ion exchange, and concentrated to a solid content concentration of 40% by mass. The concentrate was pulverized using a spray dryer to obtain the starch decomposition products (before crystallization) with sugar composition shown in Table 4 below.

[0094] The obtained starch decomposition powder was dissolved in water at 80°C to achieve a solid component concentration of 50% by mass. While stirring, the temperature was lowered to 70°C and maintained at 70°C for 7 days, yielding a solution containing crystals. These crystals were repeatedly washed with water and centrifuged until no more solid components dissolved. After separation, the solution was filtered using qualitative filter paper No. 2 (ADVANTEC Toyo Co., Ltd.) to obtain a dehydrated filter cake. The dehydrated filter cake was loosened and thinly spread on a flat, square tray and dried at room temperature for 3 days. It was then passed through a 40-mesh sieve to obtain the crystalline starch decomposition product with the sugar composition shown in Table 4 below. The obtained crystalline starch decomposition product was used as the crystalline starch decomposition product for manufacturing microbeads in Example 10.

[0095] [Manufacturing Example 11] The crystal-containing solution obtained in Manufacturing Example 10 was heated at 80°C for 12 hours, and then crystalline starch decomposition product was obtained by the same method as in Manufacturing Example 10. It should be noted that the sugar composition was the same as that of the crystalline starch decomposition product in Manufacturing Example 10. The obtained crystalline starch decomposition product was used as the crystalline starch decomposition product for microbeads in Manufacturing Example 11.

[0096] [Manufacturing Example 12] 30% by mass cassava starch paste, adjusted to pH 2 with 10% by mass hydrochloric acid, was decomposed to DE8 at 130°C. After returning to normal pressure, it was neutralized with 10% by mass sodium hydroxide. The pH of the resulting sugar solution was adjusted to 5.8, and 600 units of bacterial branching enzyme relative to the unit solid component (g) were added, reacting at 65°C for 15 hours. Then, 1.0% by mass of debranching enzyme (isoamylase, Sigma-Aldrich Japan) relative to the unit solid component (g) was added, reacting at 45°C for 40 hours. The starch decomposition solution was decolorized with activated carbon, purified by ion exchange, and concentrated to a solid component concentration of 45% by mass. The concentrated solution was pulverized using a spray dryer to obtain the starch decomposition product (before crystallization) with the sugar composition shown in Table 4 below.

[0097] The obtained starch decomposition powder was dissolved in water at 80°C to achieve a solid component concentration of 50% by mass. While stirring, the temperature was lowered to 50°C and maintained at 50°C for 5 days, yielding a solution containing crystals. These crystals were repeatedly washed with water and centrifuged until no more solid components dissolved. After separation, the solution was filtered using qualitative filter paper No. 2 (ADVANTEC Toyo Co., Ltd.) to obtain a dehydrated filter cake. The dehydrated filter cake was loosened and thinly spread on a flat, square tray and dried at room temperature for 3 days. It was then passed through a 40-mesh sieve to obtain the crystalline starch decomposition product with the sugar composition shown in Table 4 below. The obtained crystalline starch decomposition product was used as the crystalline starch decomposition product for manufacturing microbeads in Example 12.

[0098] [Manufacturing Example 13] After humidifying the crystalline starch decomposition product obtained in Manufacturing Example 12 by adding water to achieve a moisture content of 25% by mass, it was subjected to heat treatment at 120°C for 30 minutes using an autoclave (LSX-500, TOMY SEIKO Co., Ltd.). The heat-treated crystalline starch decomposition product was then thinly spread on a flat square tray and dried at room temperature for one day. Finally, it was passed through a 40-mesh sieve to obtain the crystalline starch decomposition product. It should be noted that the sugar composition was the same as that of the crystalline starch decomposition product in Manufacturing Example 12. The obtained crystalline starch decomposition product was used as the crystalline starch decomposition product for microbeads in Manufacturing Example 13.

[0099] [Manufacturing Example 14] In a 30% by mass corn starch slurry adjusted to pH 5.8 with 10% sodium hydroxide, 0.2% by mass α-amylase (Liquozyme Supra, Novozymes Co., Ltd.) was added, and liquefaction was carried out using a jet cooker (temperature 110°C). The liquefied solution was kept at 95°C, and the DE (degradation) was measured over time. At the point where DE6 was reached, the pH was adjusted to 4.0 with 10% hydrochloric acid, and the reaction was stopped by boiling. After adjusting the pH of the stopped sugar solution to 5.8, 2.0% by mass debranching enzyme (GODO-FIA, Contract Alcohol Co., Ltd.) was added, and the reaction was carried out at 50°C for 48 hours. A large amount of precipitate was observed in the reaction. After the reaction was completed, the mixture was cooled at room temperature for 1 day while continuing to stir. The precipitate obtained during the reaction and cooling was repeatedly washed with water and centrifuged until no more solid components dissolved. After separation, it was filtered using qualitative filter paper No. 2 (ADVANTEC Toyo Co., Ltd.) to obtain a dehydrated filter cake. The dehydrated filter cake was loosely and thinly spread on a flat square tray and dried at room temperature for 3 days. It was then passed through a 40-mesh sieve to obtain the crystalline starch decomposition product with the sugar composition shown in Table 4 below. The obtained crystalline starch decomposition product was used as the crystalline starch decomposition product for manufacturing microbeads in Example 14.

[0100] [Manufacturing Example 15] After humidifying the crystalline starch decomposition product obtained in Manufacturing Example 14 by adding water to achieve a moisture content of 25% by mass, it was subjected to heat treatment at 120°C for 30 minutes using an autoclave (LSX-500, TOMY SEIKO Co., Ltd.). The heat-treated crystalline starch decomposition product was then thinly spread on a flat square tray and dried at room temperature for one day. Finally, it was passed through a 40-mesh sieve to obtain the crystalline starch decomposition product. It should be noted that the sugar composition was the same as that of the crystalline starch decomposition product in Manufacturing Example 14. The obtained crystalline starch decomposition product was used as the crystalline starch decomposition product for microbeads in Manufacturing Example 15.

[0101] [Manufacturing Example 16] Anhydrous crystalline glucose (Showa Sangyo Co., Ltd.) was added to water at 80°C until undissolved residue was produced. Further addition of anhydrous crystalline glucose was made to ensure thorough dispersion, followed by heating at 80°C for 12 hours. The crystals were then separated by centrifugation, washed with warm water at 80°C, and filtered using qualitative filter paper No. 2 (ADVANTEC Toyo Co., Ltd.) to obtain a dehydrated filter cake. The dehydrated filter cake was loosely and thinly spread on a flat, square tray and dried at room temperature for 3 days. It was then passed through a 40-mesh sieve to produce the crystalline starch decomposition product for manufacturing Example 16.

[0102] [Manufacturing Example 17] Instead of crystalline starch decomposition products, commercially available fine sugar was used as the sugar for crystallization. The microbeads of Manufacturing Example 17 were manufactured by heating the product at 120°C for 30 minutes using an autoclave (LSX-500, TOMY SEIKO Co., Ltd.).

[0103] (3) Physical property determination For the starch decomposition products (before crystallization), crystalline starch decomposition products, and crystalline sugars obtained during the aforementioned manufacturing process, the contents of DP8-19 and DP20 and above were determined according to the aforementioned method. For the crystalline starch decomposition products and crystalline sugars, the contents of DP5 and below and molecular weight 5000 and above were determined according to the aforementioned method. The residual rate in the β-amylase digestion test was also determined according to the aforementioned method. Furthermore, the particle size distribution of the crystalline starch decomposition products and crystalline sugars used in the manufactured microbeads, as well as their solubility at 50°C, were determined according to the aforementioned method. The test results are shown in Table 4 below.

[0104] [Table 4] (4) Powder evaluation As an evaluation of the powder of crystalline starch decomposition product or crystalline sugar used in the aforementioned manufactured microbeads, a sensory evaluation was conducted on the feel when applied to the skin, considering aspects such as spreadability, lack of roughness, lack of stickiness, lack of astringency, and moisturizing sensation. It should be noted that the sensory evaluation was conducted by 10 professional evaluators according to the evaluation criteria below, and the average score was calculated to determine the evaluation. The results are shown in Table 5 below.

[0105] [Extensibility] 5: Very easy to stretch, very good 4: Easy to extend, good 3: Slightly easy to stretch, slightly good 2: Slightly difficult to stretch, poor 1. Difficult to stretch, very poor quality. [No roughness] 5: Very smooth, very good 4: Smooth, good 3: Slightly smooth, slightly good 2: It feels rough, poor quality. 1: Very rough texture, extremely poor quality. [Non-sticky] 5: Very refreshing, very good 4: Refreshing, good 3: Slightly refreshing, slightly good 2: It feels sticky, which is bad. 1: It feels very sticky, which is extremely bad. [No roughness] 5. It adheres very well to the skin and feels excellent. 4. Adheres well to the skin. 3: It adheres slightly to the skin, which is slightly better. 2: It has a rough and astringent feel, which is poor. 1: The texture is very rough and abrasive, which is very poor. [Moisturizing sensation] 5: Very moisturizing, very good. 4: Moisturizing, good 3: Slightly moisturizing, slightly good 2: Feels dry, poor 1: Extremely dry, very poor. [Table 5] The results of all evaluations for the microbeads of Examples 1-9 were satisfactory: (a) the content of glucose degree of polymerization (DP) 8-19 was 30% or more; (b) the content of glucose degree of polymerization (DP) 5 or less was 5% or less; (c) the content of glucose with molecular weight 5000 or more was 25% or less; (d) the content of glucose degree of polymerization (DP) 4 or more remaining in the β-amylase digestibility test was 15% or less; and (e) the solubility at 50°C was 20% or less.

[0106] On the other hand, regarding the microbeads of Comparative Examples 1 and 2, which have a solubility of more than 20% at 50°C, the evaluation of low heat resistance and lack of stickiness is undesirable.

[0107] (5) Manufacturing of cosmetics Cosmetics were manufactured using the aforementioned microbeads and crystalline starch decomposition products.

[0108] [Powder Foundation] The powder foundation was manufactured according to the following formula. It should be noted that the powder foundation was manufactured using microbeads and crystalline starch decomposition products as shown in Table 6.

[0109] Microbeads: 10.0% by mass Sericite: 56.0% by mass Talc: 5.0% by mass Mica: 10.0% by mass Titanium oxide: 10.0% by mass Iron oxide red: 0.4% by mass Iron oxide yellow: 1.2% by mass Iron oxide black: 0.2% by mass Methylparaben: 0.2% by mass Polydimethylsiloxane: 2.0% by mass Squalane: 2.0% by mass Triglyceride (ethylhexanoate): 3.0% by mass The spreadability, non-stickiness, and moisturizing properties of the manufactured powder foundation were evaluated using the same method as in (4) powder evaluation. The results are shown in Table 6 below.

[0110] [Table 6] [Liquid foundation] The liquid foundation was manufactured according to the following formula. It should be noted that the liquid foundation was manufactured using microbeads and crystalline starch decomposition products as shown in Table 7.

[0111] Microbeads: 5.0% by mass Polyglycerol-10 pentastearate: 0.5% by mass Glyceryl stearate: 1.0% by mass Behenyl alcohol: 1.0% by mass Cetearyl alcohol: 1.0% by mass Cyclopentadimethylsiloxane: 8.0% by mass Polydimethylsiloxane: 10.0% by mass Titanium oxide: 5.0% by mass Iron oxide red: 0.4% by mass Iron oxide black: 0.2% by mass Iron oxide yellow: 1.0% by mass 1,3-Butanediol: 8.0% by mass Sodium chloride: 1.0% by mass EDTA-2Na: 0.1% by mass Phenoxyethanol: 0.3% by mass Water: 57.5% by mass The smoothness and moisturizing feel of the manufactured liquid foundation were evaluated using the same method as in (4) powder evaluation. The results are shown in Table 7 below.

[0112] [Table 7] [Eyeshadow] The eyeshadow was manufactured according to the following formula. It should be noted that the eyeshadow was manufactured using microbeads and crystalline starch decomposition products as shown in Table 8.

[0113] Microbeads: 5.0% by mass Sericite: 5.0% by mass Mica: 35.0% by mass Talc: 40.8% by mass Titanium dioxide: 5.0% by mass Jojoba oil C14-18 alcohol ethylhexanoate: 4.0% by mass Octyl dodecyl lanolinate: 0.5% by weight Ethylhexyl hydroxystearate: 2.0% by mass Sorbitan isostearate: 1.5% by weight Colorant: 1.0% by mass Methylparaben: 0.2% by mass The spreadability and moisturizing properties of the manufactured eyeshadow were evaluated using the same method as in (4) powder evaluation. The results are shown in Table 8 below.

[0114] [Table 8]

Claims

1. Microbeads are made from the decomposition product of crystalline starch, wherein, (a) The content of glucose with a degree of polymerization (DP) of 8 to 19 is 30% or more. (b) The content of glucose with a degree of polymerization (DP) of less than 5% is less than 5%. (c) The content of molecules with a molecular weight of 5000 or higher is less than 25%. (d) The content of residual glucose with a degree of polymerization (DP) of 4 or higher in the β-amylase digestibility test is less than 15%. (e) Solubility at 50°C is less than 20%.

2. The microbead use crystalline starch decomposed product according to claim 1, wherein, The cumulative volume of 50% of the particles has a diameter of 5–70 μm.

3. Microbeads, which contain crystalline starch decomposition products. In the crystalline starch decomposition product (a) The content of glucose with a degree of polymerization (DP) of 8 to 19 is 30% or more. (b) The content of glucose with a degree of polymerization (DP) of less than 5% is less than 5%. (c) The content of molecules with a molecular weight of 5000 or higher is less than 25%. (d) The content of residual glucose with a degree of polymerization (DP) of 4 or higher in the β-amylase digestibility test is less than 15%. (e) Solubility at 50°C is less than 20%.

4. The microbead of claim 3, wherein, The cumulative volume of the crystalline starch decomposition products is 50% of the particle size, which is 5-70 μm.

5. A method for manufacturing microbeads from crystalline starch decomposition products, comprising: The crystallization process of crystallizing starch decomposition products; and The crystalline starch decomposition product that has undergone the crystallization process is then heated to above 75°C in the presence of water and / or steam. The microbeads have the following characteristics (a) to (e): (a) The content of glucose with a degree of polymerization (DP) of 8 to 19 is 30% or more. (b) The content of glucose with a degree of polymerization (DP) of less than 5% is less than 5%. (c) The content of molecules with a molecular weight of 5000 or higher is less than 25%. (d) The content of residual glucose with a degree of polymerization (DP) of 4 or higher in the β-amylase digestibility test is less than 15%. (e) Solubility at 50°C is less than 20%.

6. The method for producing a microbead crystal starch decomposed product according to claim 5, wherein The starch decomposition product has the following characteristics: (f) The content of glucose with a degree of polymerization (DP) of 8-19 is 42% or more. (g) The content of glucose with a degree of polymerization (DP) of 20 or higher is less than 35%. (h) The content of residual glucose with a degree of polymerization (DP) of 4 or higher in the β-amylase digestibility test is less than 15%.

7. The method for manufacturing crystalline starch decomposition product for microbeads as described in claim 5, comprising an enzymatic reaction step to obtain the starch decomposition product, wherein the enzymatic reaction step comprises acting a debranching enzyme on one or more selected from starch, starch extract, and starch liquefaction liquid.

8. A cosmetic product containing crystalline starch decomposition product of microbeads as described in claim 1 or 2, or microbeads as described in claim 3 or 4.

9. A method for manufacturing cosmetics, comprising a step of combining microbeads with crystalline starch decomposition product obtained by the manufacturing method according to any one of claims 5 to 7.

10. A method for improving the heat resistance of crystalline starch decomposition products, comprising a heating step of heating the crystalline starch decomposition products to above 75°C in the presence of water and / or water vapor. In the crystalline starch decomposition product (a) The content of glucose with a degree of polymerization (DP) of 8 to 19 is 30% or more. (b) The content of glucose with a degree of polymerization (DP) of less than 5% is less than 5%. (c) The content of molecules with a molecular weight of 5000 or higher is less than 25%. (d) The content of residual glucose with a degree of polymerization (DP) of 4 or higher in the β-amylase digestibility test is less than 15%.

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