Crystalline starch decomposition product for microbeads, microbeads, method for producing crystalline starch decomposition product for microbeads, cosmetic, method for producing cosmetic, and method for improving heat resistance of crystalline starch decomposition product

Abstract

To provide a feature for obtaining microbeads capable of reducing an environmental load and having high heat resistance.　The present invention provides a crystalline starch decomposition product for microbeads, wherein: (a) the content of degree of polymerization (DP) of glucose of 8-19 is 30% or more; (b) the content of degree of polymerization (DP) of glucose of 5 or less is 5% or less; (c) the content of molecular weight of 5,000 or more is 25% or less; (d) the content of degree of polymerization (DP) of glucose of 4 or more remaining in the β-amylase digestibility test is 15% or less; and (e) the solubility at 50°C is 20% or less.

Description

Crystalline starch hydrolyzate for microbeads, microbeads, method for producing crystalline starch hydrolyzate for microbeads, cosmetics, method for producing cosmetics, and method for improving heat resistance of crystalline starch hydrolyzate

[0001] The present technology relates to crystalline starch hydrolyzates for microbeads, microbeads, a method for producing crystalline starch hydrolyzates for microbeads, cosmetics, a method for producing cosmetics, and a method for improving the heat resistance of crystalline starch hydrolyzates.

[0002] Plastic microbeads are used in a variety of fields for a variety of purposes. For example, in the field of cosmetics, many plastic microbeads are used as slip agents, feel improvers, scrubbing agents, etc.

[0003] Microplastic beads have a low specific gravity, and after use, they are washed down drains into rivers. Furthermore, because the particles are so small, they cannot be removed by wastewater treatment facilities and can flow directly into the sea via rivers, becoming a major cause of marine pollution. Furthermore, microplastic beads have the ability to adsorb chemical pollutants in the ocean, and when plankton and fish ingest them, they not only pollute the environment but also raise concerns about their impact on the human body.

[0004] Against this background, development of microbeads made from starch, which is safe for both the environment and the human body, is underway. For example, Patent Document 1 discloses a technology for producing a cosmetic composition made from naturally derived materials that can be produced efficiently, has good spreadability on the skin, and is highly resistant to decay, by including starch particles and a lubricant that coats at least a portion of the surface of the starch particles and contains a fatty acid, and by setting the mass of the lubricant to 0.3% by mass to 20% by mass relative to the total mass of the starch particles and the lubricant.

[0005] In addition, Patent Document 2 discloses a starch-based starch product containing 3% to 45% by mass of a degraded starch having a starch content of 75% by mass or more and an amylose content of 10% by mass or more, and wherein the degraded starch has a peak molecular weight of 3×10 ３ 5x10 or more ４The present invention discloses a technology for producing an environmentally friendly cosmetic composition by using a powdery or granular material that contains one or more emulsifiers selected from the group consisting of monoglycerin fatty acid esters, polyglycerin fatty acid esters, and sucrose fatty acid esters, and that satisfies the following requirements: the content of the 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 to 20, and the content of the particles that fall under a 0.5 mm mesh sieve is 60% by mass or more and 100% by mass or less.

[0006] International Publication No. 2019-131755 International Publication No. 2023-008416

[0007] Microbeads are processed into various products depending on the intended use. Heat may be applied when processing them into products for each use, so microbeads with high heat resistance are desired. Furthermore, there is a high demand for microbeads with high heat resistance from the perspective of preventing deterioration when storing processed products or the microbeads themselves.

[0008] Therefore, the main object of this technology is to provide a technology for obtaining microbeads that are highly heat-resistant and that can reduce the environmental load.

[0009] As a result of intensive research to achieve the above object, the inventors of the present application have succeeded in obtaining a crystalline starch hydrolyzate with improved heat resistance by subjecting a crystallized product of starch hydrolyzate containing a large amount of linear components to a specific treatment, thereby completing the present technology. Utilizing this technology, it is also possible to produce microbeads that are entirely natural or plant-derived, and microbeads that do not use organic solvents in the manufacturing process.

[0010] That is, the present technology first provides a crystalline starch hydrolyzate for microbeads having: (a) a content of glucose with a degree of polymerization (DP) of 8 to 19 of 30% or more; (b) a content of glucose with a degree of polymerization (DP) of 5 or less of 5% or less; (c) a content of molecular weight of 5000 or more of 25% or less; (d) a content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestibility test of 15% or less; and (e) a solubility at 50°C of 20% or less. The crystalline starch hydrolyzate for microbeads according to the present technology may have a particle size at 50% cumulative volume of 5 to 70 μm.

[0011] The present technology next provides microbeads containing a crystalline starch hydrolysate having: (a) a content of glucose with a degree of polymerization (DP) of 8 to 19 of 30% or more; (b) a content of glucose with a degree of polymerization (DP) of 5 or less of 5% or less; (c) a content of molecular weight of 5000 or more of 25% or less; (d) a content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestibility test of 15% or less; and (e) a solubility at 50° C. of 20% or less. The microbeads according to the present technology may have a particle size at 50% of the cumulative volume of 5 to 70 μm.

[0012] The present technology also provides a method for producing a crystalline starch hydrolyzate for microbeads, comprising: a crystallization step of crystallizing a starch hydrolyzate; and a heating step of heating the crystalline starch hydrolyzate that has undergone the crystallization step to 75°C or higher in the presence of water and / or water vapor. The starch hydrolyzate used in the production method of the present technology may have the following characteristics: (f) a content of glucose with a degree of polymerization (DP) of 8 to 19 of 42% or more; (g) a content of glucose with a degree of polymerization (DP) of 20 or more of 35% or less; and (h) a content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestibility test of 15% or less. The production method of the present technology may also include an enzymatic reaction step of obtaining the starch hydrolyzate, which includes treating one or more selected from starch, a starch extract, and a starch liquefied solution with a debranching enzyme.

[0013] The present technology further provides a cosmetic containing the crystalline starch hydrolyzate for microbeads according to the present technology or the microbeads according to the present technology. The present technology also provides a method for producing a cosmetic, including a step of blending the crystalline starch hydrolyzate for microbeads obtained by the production method according to the present technology.

[0014] The present technology also provides a method for improving the heat resistance of a crystalline starch hydrolysate, the method comprising a heating step of heating a crystalline starch hydrolysate to 75°C or higher in the presence of water and / or water vapor, the crystalline starch hydrolysate having: (a) a content of glucose with a degree of polymerization (DP) of 8 to 19 of 30% or more; (b) a content of glucose with a degree of polymerization (DP) of 5 or less of 5% or less; (c) a content of glucose with a molecular weight of 5000 or more of 25% or less; and (d) a content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestibility test of 15% or less.

[0015] Here, the technical terms used in this technology will be explained. "Debranching enzyme" is a general term for enzymes that catalyze the hydrolysis of the α-1,6-glucosidic bond, which is the branching point of starch. For example, "isoamylase (glycogen 6-glucanohydrolase)," "pullulanase (pullulan 6-glucan hydrolase)," and "amylo-1,6-glucosidase / 4-α-glucanotransferase" are known. These debranching enzymes may be used in combination depending on the purpose.

[0016] "Branching enzyme" is a general term for enzymes that act on linear glucans linked by α-1,4-glucosidic bonds to create α-1,6-glucosidic bonds. They exist in animals and bacteria, but can also be purified from plants such as potatoes, rice seeds, and corn seeds.

[0017] Preferred embodiments for carrying out the present technology will be described below. Note that the embodiments described below are examples of typical embodiments of the present technology, and the scope of the present technology should not be construed as being narrow.

[0018] 1. Crystalline starch hydrolyzate for microbeads The crystalline starch hydrolyzate for microbeads according to the present technology has the following characteristics (a) to (e): (a) a content of glucose with a degree of polymerization (DP) of 8 to 19 of 30% or more; (b) a content of glucose with a degree of polymerization (DP) of 5 or less of 5% or less; (c) a content of molecular weight of 5000 or more of 25% or less; (d) a content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestibility test of 15% or less; and (e) a solubility at 50°C of 20% or less.

[0019] The crystalline starch hydrolysate for microbeads according to the present technology has high heat resistance. In the present technology, "high heat resistance" refers to the property of maintaining the quality of the crystalline starch hydrolysate for microbeads under high-temperature conditions, for example, 40°C or higher, preferably 50°C or higher, either directly or when dispersed in water or other solvents. For example, under high-temperature conditions, for example, 40°C or higher, preferably 50°C or higher, the crystalline starch hydrolysate for microbeads does not partially or completely collapse due to deliquescence or the like, causing it to lose its shape, or to have its slipperiness or feel-improving properties reduced or lost, or to have its quality reduced by partial dissolution in water or a solvent, causing stickiness or other degradation. The crystalline starch hydrolysate for microbeads according to the present technology will be described in detail below.

[0020] <Crystalline Starch Hydrolysate> The crystalline starch hydrolysate for microbeads according to the present technology is obtained by at least hydrolyzing starches as raw materials, such as starches (aerial starches) such as corn starch, rice starch, wheat starch, sago starch, etc., starches derived from rhizomes or roots (underground starches) such as potato starch, tapioca starch, sweet potato starch, etc., waxy and high-amylose starches, and processed starches obtained by subjecting such starches to physical or chemical processing, either singly or in combination, to obtain starch hydrolysates, and then crystallizing the starch hydrolysates. The starch used as the raw material is not particularly limited, and any starch can be used.

[0021] <Content of glucose with a degree of polymerization (DP) of 8 to 19, a degree of polymerization (DP) of 5 or less, and a molecular weight of 5,000 or more> The compositional characteristics of the crystalline starch hydrolyzate for microbeads according to the present technology include a content of glucose with a degree of polymerization (hereinafter referred to as "DP") of 8 to 19 of 30% or more, a content of glucose with a DP of 5 or less of 5% or less, and a content of glucose with a molecular weight of 5,000 or more of 25% or less. The crystalline starch hydrolyzate for microbeads according to the present technology contains a large amount of high molecular weight oligosaccharide components and low molecular weight dextrin components (DP 8 to 19), and most of these components are linear sugar molecules that are easily crystallized, thereby achieving a crystal stabilization effect. Note that the contents of DP 8 to 19, DP 5 or less, and molecular weight 5,000 or more in the starch hydrolyzate according to the present technology are values ​​measured by the method described in the Examples below.

[0022] The crystalline starch hydrolyzate for microbeads used in the present technology can exhibit the functions and effects of the present technology if the content of DP8 to 19 is 30% or more, but is preferably 35% or more, more preferably 45% or more, even more preferably 50% or more, and even more preferably 53% or more, and 58% or more. The higher the content of DP8 to 19, the easier it is to crystallize and the greater the crystal stabilization effect, since most of the components are linear sugar molecules, as described below.

[0023] The upper limit of the content of DP8 to DP19 in the crystalline starch hydrolysate for microbeads used in the present technology can be freely set as long as it does not impair the action and effect of the present technology, for example, it can be set to 90% or less, 85% or less, 75% or less, etc.

[0024] Furthermore, the crystalline starch hydrolyzate for microbeads used in the present technology can exhibit the functions and effects of the present technology so long as the content of DP5 or less is 5% or less, but is 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, and the stickiness of the crystalline starch hydrolyzate and microbeads using the crystalline starch hydrolyzate can be reduced.

[0025] There is no lower limit to the content of DP5 or less of the crystalline starch hydrolyzate for microbeads used in the present technology, and it may be 0%.

[0026] The crystalline starch hydrolyzate for microbeads according to the present technology can exhibit the functions and effects of the present technology so long as the content of molecular weights of 5000 or more is 25% or less, but is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. The smaller the content of molecular weights of 5000 or more, the less likely the particle size of the crystalline starch hydrolyzate to become small, and the occurrence of creaking in the crystalline starch hydrolyzate and in microbeads using the crystalline starch hydrolyzate can be prevented.

[0027] There is no lower limit for the content of the crystalline starch hydrolyzate for microbeads having a molecular weight of 5,000 or more according to the present technology, and it can be set to, for example, 0% or more, 1% or more, 2% or more, etc.

[0028] <Content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestibility test> The content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestion test of the crystalline starch hydrolyzate for microbeads according to the present technology is 15% or less. The content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestion test is a value measured by the method described in the examples below.

[0029] The crystalline starch hydrolyzate for microbeads according to the present technology can exhibit the functions and effects of the present technology as long as the content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestion test is 15% or less, preferably 13% or less, and more preferably 10% or less. The lower the content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestion test, the more linear sugar molecules that are likely to crystallize, and therefore the crystal stability of the crystalline starch hydrolyzate for microbeads can be improved.

[0030] β-amylase is an enzyme that degrades glucose polymers in maltose units from the non-reducing end, and it is known that degradation stops when branched bonds such as α-1,6 bonds are present. Therefore, evaluation of crystalline starch hydrolysates by a β-amylase digestion test serves as an index showing the degree to which they have linear portions with continuous α-1,4 bonds from a structural perspective. In other words, evaluation by a β-amylase digestion test serves as an index of the linear sugar molecules of the entire crystalline starch hydrolysate.

[0031] <Solubility at 50°C> The solubility at 50°C of the crystalline starch hydrolysate for microbeads according to the present technology is 20% or less. By controlling the solubility at 50°C to 20% or less, stickiness can be suppressed. The solubility at 50°C of the crystalline starch hydrolysate is a value measured by the method described in the examples below.

[0032] The solubility of the crystalline starch hydrolyzate for microbeads according to the present technology at 50°C is 20% or less so that the action and effect of the present technology can be exhibited, but is preferably 18% or less, more preferably 15% or less, and even more preferably 10% or less. The lower the solubility at 50°C is controlled, the more the stickiness of the crystalline starch hydrolyzate and the microbeads using the crystalline starch hydrolyzate can be reduced.

[0033] <Particle size distribution> The particle size distribution of the crystalline starch hydrolyzate for microbeads according to the present technology can be freely set depending on the intended use, as long as it does not impair the action and effect of the present technology. The particle size distribution is a value measured by the method described in the examples below.

[0034] Specifically, the lower limit of 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, and the upper limit of 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.

[0035] The lower limit of the particle size at which the cumulative volume becomes 50% is, for example, 5 μm or more, preferably 10 μm or more, and more preferably 12 μm or more.

[0036] The upper limit of the particle size at which the cumulative volume becomes 50% is, for example, 70 μm or less, preferably 50 μm or less, more preferably 40 μm or less, even more preferably 28 μm or less, and still more preferably 22 μm or less.

[0037] The lower limit of the particle size at which the cumulative volume becomes 90% is, for example, 10 μm or more, preferably 15 μm or more, and the upper limit of 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, still more preferably 30 μm or less, and particularly preferably 22 μm or less.

[0038] By controlling the lower limit of the particle size at which the cumulative volume of the crystalline starch hydrolyzate for microbeads becomes 10%, the lower limit of the particle size at which the cumulative volume becomes 50%, and the lower limit of the particle size at which the cumulative volume becomes 90% within these ranges, it is possible to prevent the crystalline starch hydrolyzate and microbeads using the crystalline starch hydrolyzate from squeaking.Furthermore, by controlling the upper limit of the particle size at which the cumulative volume of the crystalline starch hydrolyzate for microbeads becomes 10%, the upper limit of the particle size at which the cumulative volume becomes 50%, and the upper limit of the particle size at which the cumulative volume becomes 90% within these ranges, it is possible to improve the spreadability of the crystalline starch hydrolyzate for microbeads and microbeads using the crystalline starch hydrolyzate and to reduce roughness.

[0039] 2. Method for Producing Crystalline Starch Hydrolysate for Microbeads <Outline of the Production Method> The crystalline starch hydrolysate for microbeads according to the present technology has novel physical properties, and its production method is not particularly limited. It can be obtained by using starches as raw materials, performing at least a decomposition step to obtain a starch hydrolysate, and then performing a crystallization step of the obtained starch hydrolysate. The step of decomposing starches to obtain a starch hydrolysate and the step of crystallizing the obtained starch hydrolysate can also be performed simultaneously in parallel. In other words, the crystalline starch hydrolysate can be produced by sequentially crystallizing the obtained starch hydrolysate while decomposing the starches.

[0040] In the process for producing a starch hydrolysate, for example, starches and / or starch extracts are decomposed with an acid, a base, or an enzyme. This may be accomplished by subjecting the starch hydrolysate to chromatography or a separation membrane, or by combining separation techniques based on differences in physical properties such as solubility. Furthermore, in the process for crystallizing the starch hydrolysate, the temperature may be lowered or the concentration may be increased so that the solution containing the starch hydrolysate is in a state in which crystals are more likely to precipitate. Furthermore, in the method for producing a crystalline starch hydrolysate for microbeads according to the present technology, the solubility of the crystalline starch hydrolysate at 50°C can be reduced, and therefore, the crystalline starch hydrolysate for microbeads according to the present technology can be easily obtained by heating the crystalline starch hydrolysate to 75°C or higher in the presence of water and / or water vapor.

[0041] <Step of Producing Starch Hydrolysate> A method for efficiently obtaining pre-crystallization starch hydrolysate for crystalline starch hydrolysate for microbeads according to the present technology includes a step of using starches as raw materials and hydrolyzing them with at least a debranching enzyme. When the debranching enzyme is applied, the starch is in one or more states selected from a starch dispersion, a starch extract, a starch gelatinized solution, a starch liquefied solution, and a starch hydrolysate solution. The starch liquefied solution in the present invention is a liquid obtained by heating starch in the presence of an enzyme and / or an acid.

[0042] Furthermore, a method for more efficiently obtaining pre-crystallization starch hydrolysate of the crystalline starch hydrolysate for microbeads according to the present technology may include a step of acting with a branching enzyme. The state of starch when acting with a branching enzyme is the same as when acting with a debranching enzyme described above. The timing of acting the debranching enzyme and the branching enzyme is not particularly limited; for example, they may be acted simultaneously, or a step of acting with a branching enzyme may be performed after a step of decomposition by the debranching enzyme, or a step of decomposition by the debranching enzyme may be performed after a step of acting with the branching enzyme, or other steps may be included in between. Preferably, the method includes a step of acting with a debranching enzyme and the branching enzyme simultaneously, or a step of acting with a debranching enzyme after a step of acting with the branching enzyme. The debranching enzyme is an enzyme involved in the decomposition of branched chains in starch, and the branching enzyme is an enzyme used in the synthesis of branched chains in starch. Therefore, the two are not usually used together. However, by using these enzymes, which have completely opposite actions, in combination, the starch hydrolysate according to the present technology can be reliably produced.

[0043] The debranching enzyme is not particularly limited, and examples thereof include pullulanase (pullulan 6-glucan hydrolase) and amylo-1,6-glucosidase / 4-α glucanotransferase, and a more preferred example is isoamylase (glycogen 6-glucanohydrolase).

[0044] The branching enzyme is not particularly limited, and examples thereof include enzymes purified from animals or bacteria, enzymes purified from plants such as potato, rice seeds, and corn seeds, and commercially available enzyme preparations.

[0045] The starch hydrolysate before crystallization of the crystalline starch hydrolysate for microbeads according to the present technology preferably has the following characteristics. This makes it possible to prevent precipitation during this process and also allows for the step of purifying the starch hydrolysate described below. (f) The content of glucose with a degree of polymerization (DP) of 8 to 19 is 42% or more. (g) The content of glucose with a degree of polymerization (DP) of 20 or more is 35% or less. (h) The content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestibility test is 15% or less.

[0046] The content of glucose with a degree of polymerization (DP) of 8 to 19 in the starch hydrolysate before crystallization is preferably 42% or more, more preferably 45% or more, and even more preferably 47% or more. The upper limit of the content of glucose with a degree of polymerization (DP) of 8 to 19 in the starch hydrolysate before crystallization is not particularly limited, and can be set to, for example, 90% or less, 85% or less, 75% or less, 70% or less, etc.

[0047] The content of glucose having a degree of polymerization (DP) of 20 or more in the starch hydrolysate before crystallization is preferably 35% or less, more preferably 32% or less, and even more preferably 30% or less. The lower limit of the glucose having a degree of polymerization (DP) of 20 or more in the starch hydrolysate before crystallization is not particularly limited, and can be set to, for example, 10% or more, 15% or more, 18% or more, 20% or more, etc.

[0048] The content of glucose with a degree of polymerization (DP) of 4 or more remaining in the starch hydrolyzate before crystallization in a 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 with a degree of polymerization (DP) of 4 or more remaining in the starch hydrolyzate before crystallization in a β-amylase digestibility test within this range, the number of linear sugar molecules that are easily crystallized increases, and the crystallization step described below can be carried out more efficiently.

[0049] <Step of crystallizing starch hydrolysate (crystallization step)> The crystallization step in the method for producing crystalline starch hydrolysate for microbeads according to the present disclosure is a step of crystallizing the starch hydrolysate. The crystallization step can be carried out after the step of producing the starch hydrolysate, or can be carried out simultaneously with the step of producing the starch hydrolysate.

[0050] The crystallization method in the crystallization step is not particularly limited, and one or more known crystallization methods can be freely selected and used so that the solution containing the starch hydrolysate can be in a state in which crystals can be precipitated. In the present technology, for example, the starch hydrolysate can be crystallized by maintaining the solution at a predetermined concentration or higher and / or by lowering the temperature to a predetermined value or lower. Note that crystallization in the present technology can be determined by confirming diffraction peaks in powder X-ray diffraction analysis.

[0051] The concentration of the starch hydrolysate solution subjected to the crystallization step is not particularly limited and can be freely set as long as the effects of the present technology are not impaired. For example, the starch hydrolysate can be crystallized by maintaining the concentration 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. Furthermore, the temperature of the starch hydrolysate solution in this case is also not particularly limited and can be freely set as long as the effects of the present technology are not impaired. For example, the starch hydrolysate can be crystallized by maintaining the temperature at 85°C or less, preferably 80°C or less, and more preferably 75°C or less. It is also possible to change the concentration and / or temperature of the starch hydrolysate solution during the crystallization step. Furthermore, the retention time is also not particularly limited and can be set to, for example, 20 days or less, preferably 10 days or less, and more preferably 7 days or less.

[0052] <Step of Heating Crystalline Starch Hydrolysate> The method for producing a crystalline starch hydrolysate for microbeads according to the present technology can include a step of heating the crystalline starch hydrolysate to 75°C or higher in the presence of water and / or water vapor. The present technology has succeeded in improving the heat resistance of the crystallized starch hydrolysate by heating the crystallized starch hydrolysate. The step of heating the crystalline starch hydrolysate can be carried out after the crystallization step or simultaneously with the crystallization step. Methods for heating the crystalline starch hydrolysate include, for example, heating a solution containing the crystalline starch hydrolysate to 75°C or higher, or heating the crystalline starch hydrolysate in the presence of water vapor. Examples of methods for heating under water vapor conditions include heating in a sealed state with the addition of water, or heating in a sealed state with the addition of water vapor. In this case, the sealed state is sufficient, and either reduced pressure or increased pressure may be used.

[0053] The temperature to which the crystalline starch hydrolysate is heated may be 75°C or higher. When a solution containing the crystalline starch hydrolysate is heated, it is preferably 78°C or higher, more preferably 85°C or higher. The upper limit of the temperature can be freely set as long as it does not impair the functions and effects of the present technology, but may be 100°C or lower, 98°C or lower, or 95°C or lower. It is preferable that the solution containing the crystalline starch hydrolysate contains 30% by mass or more of the crystalline starch hydrolysate relative to the entire solution. On the other hand, when the crystalline starch hydrolysate is heated under steam conditions, it is preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 115°C. The upper limit of the temperature can be freely set as long as it does not impair the functions and effects of the present technology, but is, for example, 150°C or lower, preferably 140°C or lower, and more preferably 130°C or lower. The temperature to which the crystalline starch hydrolysate is heated can also be changed during the process.

[0054] The heating time for the crystalline starch hydrolysate can also be freely set depending on the temperature of the crystalline starch hydrolysate, etc., as long as it does not impair the action and effect of the present technology. 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.

[0055] <Other Steps> In addition to the steps described above, the method for producing crystalline starch hydrolysate for microbeads according to the present technology may also include, for example, a step of purifying the starch hydrolysate, a step of separating the crystalline starch hydrolysate, a step of drying the crystalline starch hydrolysate, etc.

[0056] The method for producing crystalline starch hydrolysates for microbeads according to the present technology may include a step of purifying the starch hydrolysates after the step of producing the starch hydrolysates. The method for purifying the starch hydrolysates is not particularly limited, and one or more known methods can be freely combined and used. Examples include filtration of a solution containing the starch hydrolysates using a filter or filter aid, adsorption using activated carbon or ion exchange resin, or concentration. This step can remove impurities derived from raw starch, processing aids, etc., as well as impurities generated during the process. For example, in order to reduce irritation to skin that comes into contact with the microbeads according to the present technology when used in cosmetics, etc., the method for producing crystalline starch hydrolysates for microbeads according to the present technology preferably includes a step of purifying the starch hydrolysates after the step of producing the starch hydrolysates. Note that this step can be performed at 30°C or higher, preferably 40°C or higher, to prevent precipitation.

[0057] The method for producing crystalline starch hydrolysate for microbeads according to the present disclosure may include a step of separating the crystalline starch hydrolysate after the crystallization step. The method for separating the crystalline starch hydrolysate may include, for example, separation from the liquid by filtration or centrifugation, or separation from highly soluble components by washing with water, etc. These methods may also be combined.

[0058] The method for producing a crystalline starch hydrolyzate for microbeads according to the present disclosure may include a step of drying the crystalline starch hydrolyzate after the crystallization step. Methods for drying the crystalline starch hydrolyzate include, for example, blow drying, vacuum drying, spray drying, and freeze drying.

[0059] The crystalline starch hydrolyzate for microbeads according to the present technology can be used as microbeads as it is, but it can also be made into microbeads by compounding with additives and the like used in the production of general microbeads and granulating them, or by subjecting them to physical or chemical treatment to further change the physical properties of the microbeads. Furthermore, these can be coated with surface materials and the like used for general microbeads to make multilayered microbeads.

[0060] 3. Method for Improving Heat Resistance of Crystalline Starch Hydrolysate The method for improving heat resistance of a crystalline starch hydrolysate according to the present technology is a method comprising a step of heating a crystalline starch hydrolysate having the characteristics (a) to (d) above to 75°C or higher in the presence of water and / or water vapor. The composition and physical properties of the crystalline starch hydrolysate before the heating step, details of the heating step, and details of the crystalline starch hydrolysate with improved heat resistance are the same as those of the crystalline starch hydrolysate for microbeads according to the present technology and the heating step in the method for producing crystalline starch hydrolysate for microbeads according to the present technology, as described above, and therefore will not be described here.

[0061] 4. Cosmetics The crystalline starch hydrolyzate for microbeads, microbeads, and crystalline starch hydrolyzate with improved heat resistance according to the present technology can be suitably applied to all kinds of cosmetics by taking advantage of their high heat resistance, etc. Furthermore, the crystalline starch hydrolyzate for microbeads, microbeads, and crystalline starch hydrolyzate with improved heat resistance according to the present technology have relatively uniform particle shapes and sizes and are biodegradable, and therefore these properties can be taken advantage of to suitably apply them to a variety of cosmetics.

[0062] The method of application to cosmetics is not particularly limited, but it can be used, for example, as a powdered base material or excipient for powder cosmetics, solid cosmetics, etc., or as a slip agent or texture improver for liquid, milky, gel, creamy, or other cosmetics.

[0063] The crystalline starch hydrolyzate for microbeads, microbeads, and crystalline starch hydrolyzate with improved heat resistance according to the present technology have high heat resistance and can therefore be suitably used in cosmetics that are manufactured under high-temperature conditions or that may be stored under high-temperature conditions.

[0064] It is also possible to prevent deterioration in the feel of cosmetics used under high-temperature conditions. Furthermore, when the crystalline starch hydrolysate for microbeads, microbeads, or crystalline starch hydrolysate with improved heat resistance according to the present technology is used in cosmetics that are to be applied to the skin for a certain period of time, such as makeup cosmetics or sunscreen cosmetics, it is possible to prevent deterioration in the quality and feel of the cosmetics due to ambient temperature or body temperature. Specifically, it is possible to prevent makeup from coming off, stickiness, etc.

[0065] 5. Manufacturing Method of Cosmetics The manufacturing method of cosmetics according to the present technology includes a step of blending one or more selected from the crystalline starch hydrolyzate for microbeads according to the present technology, microbeads, and crystalline starch hydrolyzate with improved heat resistance. The blending step can be carried out once or multiple times in each step of a general manufacturing method of cosmetics, depending on the type of cosmetic and the manufacturing method, as long as it does not impair the action and effect of the present technology.

[0066] The crystalline starch hydrolyzate for microbeads, microbeads, and crystalline starch hydrolyzate with improved heat resistance according to the present technology have high heat resistance and can therefore be suitably used in cosmetics that are manufactured under high-temperature conditions or that may be stored under high-temperature conditions.

[0067] 6. Other Applications of Crystalline Starch Hydrolysate for Microbeads, Microbeads, and Crystalline Starch Hydrolysate with Improved Heat Resistance The crystalline starch hydrolysate for microbeads, microbeads, and crystalline starch hydrolysate with improved heat resistance according to the present technology can be used for a variety of applications by taking advantage of their high heat resistance, etc. Furthermore, the crystalline starch hydrolysate according to the present technology has a linear molecular structure, its particles are relatively uniform in shape and size, and is biodegradable, and these properties can be utilized to apply it to a variety of applications.

[0068] The crystalline starch hydrolysate for microbeads, microbeads, and crystalline starch hydrolysate with improved heat resistance according to the present technology can be used in applications such as industrial products such as carriers, various films, fibers, capsules, adhesives, release agents, anti-adhesion agents, bulking agents, abrasives, and excipients; seasonings, soups, creams, various dairy products, frozen desserts such as ice cream, various powdered foods (including beverages), preserved foods, frozen foods, breads, confectioneries, cooked rice, noodles, water-based paste products, processed foods such as meat products, and health-promoting foods (foods with specified health functions, foods with functional claims, nutritional supplements, etc.); foods and beverages such as functional foods, so-called health foods (including beverages), liquid foods, infant and toddler foods, diet foods, and diabetes foods; pharmaceuticals such as powdered base materials for powders and granules, excipients for tablets, etc., suspending agents for liquid preparations, semi-solid preparations, ointment preparations, etc., osmotic pressure adjusters, coloring (whitening) agents, carbohydrate sources (calorie sources) for enteral nutrients, etc.; feeds for livestock mammals such as cows, horses, and pigs, poultry such as chickens and quails, pets such as reptiles, birds, and small mammals, farmed fish, insects, etc.; media and fertilizers for microbial culture, etc.

[0069] The present technology will be described in more detail below based on examples. Note that the examples described below are examples of typical examples of the present technology, and the scope of the present technology should not be construed as being narrow.

[0070] (1) Test Method [Branching Enzyme] In this experimental example, as an example of a branching enzyme, a purified potato-derived enzyme (hereinafter referred to as "potato-derived branching enzyme") and Branchzyme (Novozymes Inc., hereinafter referred to as "bacterial branching enzyme") were used in accordance with the method of Eur. J. Biochem. 59, p615-625 (1975).

[0071] The activity of the branching enzyme was measured using the following method. The substrate solution used was an amylose solution prepared by dissolving 0.1% amylose (catalog number: A0512, Sigma-Aldrich) in 0.1 M acetate buffer (pH 5.2). 50 μL of enzyme solution was added to 50 μL of substrate solution, and the mixture was allowed to react at 30°C for 30 minutes. The reaction was then terminated by adding 2 mL of iodine-potassium iodide solution (0.39 mM iodine, 6 mM potassium iodide, 3.8 mM hydrochloric acid mixture). A blank solution was prepared by adding water instead of the enzyme solution. The absorbance at 660 nm was measured 15 minutes after the reaction was terminated. One unit of enzyme activity of the branching enzyme was defined as the amount of enzyme activity that reduces the absorbance at 660 nm by 1% per minute when tested under the above conditions.

[0072] [Contents of DP8 to 19, DP20 or more, and DP5 or less] Analysis was performed by high performance liquid chromatography (HPLC) under the conditions shown in Table 1 below, and the contents of DP8 to 19, DP20 or more, and DP5 or less were measured based on the detected peak area ratios.

[0073]

[0074] [Content of Molecular Weight of 5000 or More] Analysis was carried out by gel filtration chromatography under the conditions shown in Table 2. Shodex Standard GFC (Aqueous GPC) Column Standard P-82 (manufactured by Showa Denko K.K.) was used as the molecular weight standard, and the content of molecular weight of 5000 or more in the sample was measured based on a calibration curve calculated from the correlation between the elution time and molecular weight of the molecular weight standard.

[0075]

[0076] [Content of glucose with a degree of polymerization (DP) of 4 or more remaining in β-amylase digestion test] A starch hydrolysate, a crystalline starch hydrolysate, or a crystalline sugar was dissolved in 10 mM acetate buffer (pH 5.5) by boiling to prepare a 10% by mass solids solution, to which 10 μL of β-amylase (Nagase ChemteX Corporation) was added, and the reaction was carried out at 55° C. for 72 hours, followed by heat treatment at 100° C. for 10 minutes to terminate the reaction. 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, and the content of glucose with a degree of polymerization (DP) of 4 or more was measured based on the detected peak area ratio.

[0077]

[0078] [Particle size distribution] The particle size distribution of each crystalline starch hydrolyzate and crystalline sugar was measured by Fraunhofer diffraction using a laser diffraction particle size distribution analyzer (HELOS & RODOS, Japan Laser Co., Ltd.). From the volume-based distribution (frequency distribution) of each crystalline starch hydrolyzate, the particle sizes at 10%, 50%, and 90% cumulative were determined. The analysis conditions were a dispersion pressure of 2 bar, and the measurement range was R5 for the analysis of the crystalline starch hydrolyzate of Production Example 7 and the crystalline sugars of Production Examples 16 and 17, and R3 for the others.

[0079] [Solubility at 50°C] A 9-fold amount of water at 20°C was added to the crystalline starch hydrolysate or crystalline sugar and stirred thoroughly, and the Brix value of the supernatant was measured using a refractometer (RX-5000α, Atago Co., Ltd.). The obtained value was designated as the "Brix value at 20°C." Thereafter, a thermostatic water bath shaker was set to bring the dispersion to 50°C, and the dispersion was shaken reciprocally at 250 rpm for 10 minutes. The Brix value of the supernatant was again measured using the refractometer. The obtained value was designated as the "Brix value after heating at 50°C." Furthermore, the dispersion was heated in a boiling bath for 20 minutes with thorough stirring, and the Brix value of the completely dissolved solution was measured using the refractometer. The obtained value was designated as the "Brix value after heating in a boiling bath." If the dispersion was not completely dissolved even after heating in a boiling bath, the "Brix value after heating in a boiling bath" was designated as 10%. The solubility at 50°C was calculated using the following formula: If a substance completely dissolves in water at 20°C, the solubility at 50°C is taken as 100%. Solubility at 50°C = {(Brix value after heating at 50°C) - (Brix value at 20°C))} ÷ {(Brix value after heating in a boiling bath) - (Brix value at 20°C)}

[0080] (2) Production of Crystalline Starch Hydrolysate and Crystalline Sugar for Microbeads [Production Example 1] α-amylase (Clystase T10S, Amano Enzyme Inc.) was added at 0.2% by weight per g of solids to a 30% by weight cornstarch slurry adjusted to pH 5.8 with 10% by weight calcium hydroxide, and the mixture was liquefied in a jet cooker (temperature 110°C). The liquefied liquid was kept at 95°C, and the DE was measured continuously. When the DE reached 9, the pH was adjusted to 4 with 10% by weight hydrochloric acid, and the reaction was terminated by boiling. After adjusting the pH of the quenched sugar solution to 5.8, 800 units of bacterial branching enzyme per g of solids were added, and the mixture was allowed to react at 65°C for 30 hours. Subsequently, a debranching enzyme (GODO-FIA, Godo Shusei Co., Ltd.) was added at 1.0% by weight per g of solids, and the mixture was allowed to react at 50°C for 30 hours. The starch hydrolysate solution was decolorized with activated carbon, ion-purified, and concentrated to a solids concentration of 50% by mass. The concentrated solution was powdered using a spray dryer to obtain starch hydrolysates (before crystallization) having the sugar compositions shown in Table 4 below.

[0081] The resulting starch hydrolysate powder was dissolved in water at 80°C to a solids concentration of 50% by mass, and the temperature was lowered to 25°C while stirring with a mixer. The mixture was then kept at 25°C for 2 days with continued stirring to obtain a solution containing crystalline particles (hereinafter referred to as "crystalline particle-containing solution"). The crystalline particles were separated by repeated washing with water and centrifugation until no more solids were dissolved, and then subjected to suction filtration using qualitative filter paper No. 2 (Advantec Toyo Co., Ltd.) to obtain a dehydrated cake. The dehydrated cake was loosened and spread thinly on a tray, kept at room temperature for 3 days to dry, and then passed through a 40-mesh sieve to obtain a crystalline starch hydrolysate with the sugar composition shown in Table 4 below. The resulting crystalline starch hydrolysate was used as the crystalline starch hydrolysate for microbeads in Production Example 1.

[0082] [Production Examples 2 to 5] The crystalline particle-containing solution obtained in Production Example 1 was heat-treated under the conditions shown in Table 4 below, and then crystalline starch hydrolysates were obtained in the same manner as in Production Example 1. The sugar composition was the same as that of the crystalline starch hydrolysate of Production Example 1. The obtained crystalline starch hydrolysates were used as crystalline starch hydrolysates for microbeads in Production Examples 2 to 5.

[0083] [Production Example 6] Water was added to the crystalline starch hydrolysate obtained in Production Example 1 to adjust the moisture content to 25% by mass, and then the mixture was heat-treated at 120°C for 30 minutes using an autoclave (LSX-500, Tomy Seiko Co., Ltd.). The heat-treated crystalline starch hydrolysate was spread thinly on a tray, kept at room temperature for 1 day to dry, and then passed through a 40-mesh sieve to obtain a crystalline starch hydrolysate. The sugar composition was the same as that of the crystalline starch hydrolysate of Production Example 1. The obtained crystalline starch hydrolysate was used as the crystalline starch hydrolysate for microbeads in Production Example 6.

[0084] [Production Example 7] The starch hydrolysate powder obtained in Production Example 1 was dissolved in water at 80°C with a solids concentration of 50% by mass, and the temperature was lowered to 25°C without stirring. After that, the solution was kept at 25°C for 2 days to obtain a solution containing crystalline particles. The obtained solution containing crystalline particles was heat-treated at 80°C for 12 hours, and then a crystalline starch hydrolysate was obtained in the same manner as in Production Example 1. The sugar composition was the same as that of the crystalline starch hydrolysate of Production Example 1. The obtained crystalline starch hydrolysate was used as the crystalline starch hydrolysate for microbeads in Production Example 7.

[0085] [Production Example 8] The starch hydrolysate powder (before crystallization) obtained in Production Example 1 was dissolved in water at 80°C to a solids concentration of 50% by mass. The temperature was lowered to 10°C while stirring with a mixer, and then the solution was kept at 10°C for 3 days while continuing to stir, yielding a solution containing crystalline particles. The crystalline particles were separated by repeated washing with water and centrifugation until no more solids were dissolved, and then subjected to suction filtration using qualitative filter paper No. 2 (Advantec Toyo Co., Ltd.) to obtain a dehydrated cake. The dehydrated cake was loosened and spread thinly on a tray, kept at room temperature for 3 days to dry, and then passed through a 40-mesh sieve to obtain a crystalline starch hydrolysate. The sugar composition was the same as that of the crystalline starch hydrolysate of Production Example 1. The resulting crystalline starch hydrolysate was used as the crystalline starch hydrolysate for microbeads in Production Example 8.

[0086] [Production Example 9] Water was added to the crystalline starch hydrolysate obtained in Production Example 8 to adjust the moisture content to 25% by mass, and the mixture was then heat-treated at 120°C for 30 minutes using an autoclave (LSX-500, Tomy Seiko Co., Ltd.). The heat-treated crystalline starch hydrolysate was spread thinly on a tray, kept at room temperature for 1 day to dry, and then passed through a 40-mesh sieve to obtain a crystalline starch hydrolysate. The sugar composition was the same as that of the crystalline starch hydrolysate of Production Example 1. The obtained crystalline starch hydrolysate was used as the crystalline starch hydrolysate for microbeads in Production Example 9.

[0087] [Production Example 10] α-amylase (Licozyme Supra, Novozymes Japan Co., Ltd.) was added at 0.2% by mass per solids (g) to a 30% by mass waxy corn starch slurry adjusted to pH 5.8 with 10% by mass calcium hydroxide, and liquefied in a jet cooker (temperature 110 ° C). This liquefied liquid was kept at 95 ° C, and the DE was measured continuously. When the DE reached 8, 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 reaction-stopped sugar solution to 5.8, 500 units of potato-derived branching enzyme per solids (g) was added, and the reaction was allowed to proceed at 65 ° C for 40 hours. Thereafter, a debranching enzyme (GODO-FIA, Godo Shusei Co., Ltd.) was added at 0.5% by mass per solids (g), and the reaction was allowed to proceed at 50 ° C for 48 hours. The starch hydrolysate solution was decolorized with activated carbon, ion-purified, and concentrated to a solids concentration of 40% by mass. The concentrated solution was powdered using a spray dryer to obtain starch hydrolysates (before crystallization) having the sugar compositions shown in Table 4 below.

[0088] The resulting starch hydrolysate powder was dissolved in 80°C water to a solids concentration of 50% by mass, and the temperature was lowered to 70°C while stirring with a mixer. The mixture was then kept at 70°C for 7 days with continued stirring to obtain a solution containing crystalline particles. The crystalline particles were separated by repeated washing with water and centrifugation until no more solids were dissolved, and then subjected to suction filtration using qualitative filter paper No. 2 (Advantec Toyo Co., Ltd.) to obtain a dehydrated cake. The dehydrated cake was loosened and spread thinly on a tray, kept at room temperature for 3 days to dry, and then passed through a 40-mesh sieve to obtain a crystalline starch hydrolysate with the sugar composition shown in Table 4 below. The resulting crystalline starch hydrolysate was designated as the crystalline starch hydrolysate for microbeads in Production Example 10.

[0089] [Production Example 11] The crystalline particle-containing solution obtained in Production Example 10 was heat-treated at 80°C for 12 hours, and then a crystalline starch hydrolysate was obtained in the same manner as in Production Example 10. The sugar composition was the same as that of the crystalline starch hydrolysate of Production Example 10. The obtained crystalline starch hydrolysate was used as the crystalline starch hydrolysate for microbeads of Production Example 11.

[0090] [Production Example 12] A 30% by weight tapioca starch slurry adjusted to pH 2 with 10% by weight hydrochloric acid was hydrolyzed to DE 8 at a temperature of 130°C. After returning to normal pressure, the mixture was neutralized with 10% by weight sodium hydroxide. The pH of the resulting sugar solution was adjusted to 5.8, and a bacterial branching enzyme was added at 600 units per gram of solids. The mixture was then reacted at 65°C for 15 hours. A debranching enzyme (isoamylase, Sigma-Aldrich Japan LLC) was then added at 1.0% by weight per gram of solids, and the mixture was reacted at 45°C for 40 hours. The starch hydrolyzate solution was decolorized with activated carbon, ion-purified, and concentrated to a solids concentration of 45% by weight. The concentrate was powdered using a spray dryer to obtain a starch hydrolyzate (before crystallization) with the sugar composition shown in Table 4 below.

[0091] The resulting starch hydrolysate powder was dissolved in 80°C water to a solids concentration of 50% by mass, and the temperature was lowered to 50°C while stirring with a mixer. The mixture was then kept at 50°C for 5 days while continuing to stir, yielding a solution containing crystalline particles. The crystalline particles were separated by repeated washing with water and centrifugation until no more solids were dissolved, and then subjected to suction filtration using qualitative filter paper No. 2 (Advantec Toyo Co., Ltd.) to obtain a dehydrated cake. The dehydrated cake was loosened and spread thinly on a tray, dried at room temperature for 3 days, and then passed through a 40-mesh sieve to obtain a crystalline starch hydrolysate with the sugar composition shown in Table 4 below. The resulting crystalline starch hydrolysate was designated as the crystalline starch hydrolysate for microbeads in Production Example 12.

[0092] [Production Example 13] Water was added to the crystalline starch hydrolysate obtained in Production Example 12 to adjust the moisture content to 25% by mass, and then the mixture was heat-treated at 120°C for 30 minutes using an autoclave (LSX-500, Tomy Seiko Co., Ltd.). The heat-treated crystalline starch hydrolysate was spread thinly on a tray, kept at room temperature for 1 day to dry, and then passed through a 40-mesh sieve to obtain a crystalline starch hydrolysate. The sugar composition was the same as that of the crystalline starch hydrolysate of Production Example 12. The obtained crystalline starch hydrolysate was used as the crystalline starch hydrolysate for microbeads of Production Example 13.

[0093] [Production Example 14] α-amylase (Licozyme Supra, manufactured by Novozymes) was added at 0.2% by mass per g of solids to a 30% waxy corn starch slurry adjusted to pH 5.8 with 10% sodium hydroxide, and the mixture was liquefied in a jet cooker (temperature: 110°C). The liquefied liquid was kept at 95°C, and the DE was measured continuously. When the DE reached 6, the pH was adjusted to 4.0 with 10% hydrochloric acid, and the reaction was terminated by boiling. The pH of the syrup after the reaction was terminated was adjusted to 5.8, and then a debranching enzyme (GODO-FIA, manufactured by Godo Shusei Co., Ltd.) was added at 2.0% by mass per g of solids, and the mixture was allowed to react at 50°C for 48 hours. A large amount of precipitation was observed during the reaction, and after completion of the reaction, the mixture was allowed to cool at room temperature for 1 day with continued stirring. The precipitate obtained during the reaction and upon cooling was separated by repeated washing with water and centrifugation until no more solids were dissolved, and then suction filtered using qualitative filter paper No. 2 (Advantec Toyo Co., Ltd.) to obtain a dehydrated cake. The dehydrated cake was loosened and spread thinly on a tray, dried at room temperature for 3 days, and then passed through a 40-mesh sieve to obtain a crystalline starch hydrolysate having the sugar composition shown in Table 4 below. The obtained crystalline starch hydrolysate was used as the crystalline starch hydrolysate for microbeads in Production Example 14.

[0094] [Production Example 15] Water was added to the crystalline starch hydrolysate obtained in Production Example 14 to adjust the moisture content to 25% by mass, and then the mixture was heat-treated at 120°C for 30 minutes using an autoclave (LSX-500, Tomy Seiko Co., Ltd.). The heat-treated crystalline starch hydrolysate was spread thinly on a tray, kept at room temperature for 1 day to dry, and then passed through a 40-mesh sieve to obtain a crystalline starch hydrolysate. The sugar composition was the same as that of the crystalline starch hydrolysate of Production Example 14. The obtained crystalline starch hydrolysate was used as the crystalline starch hydrolysate for microbeads of Production Example 15.

[0095] [Production Example 16] Anhydrous crystalline glucose (Showa Sangyo Co., Ltd.) was added to water at 80°C until some of the glucose remained undissolved. Further anhydrous crystalline glucose was added and thoroughly dispersed, followed by heat treatment at 80°C for 12 hours. The crystalline particles were then separated by centrifugation, washed with warm water at 80°C, and subjected to suction filtration using qualitative filter paper No. 2 (Advantec Toyo Co., Ltd.) to obtain a dehydrated cake. The dehydrated cake was loosened and spread thinly on a tray, kept at room temperature for 3 days to dry, and then passed through a 40-mesh sieve to produce the crystalline starch hydrolyzate for microbeads of Production Example 16.

[0096] [Production Example 17] Commercially available granulated sugar was used as a crystallized sugar instead of a crystalline starch hydrolyzate, and the resulting mixture was heated at 120°C for 30 minutes using an autoclave (LSX-500, Tomy Seiko Co., Ltd.) to produce crystalline sugar for microbeads in Production Example 17.

[0097] (3) Measurement of physical properties The starch hydrolysates (before crystallization), crystalline starch hydrolysates, and crystalline sugars obtained during the above-mentioned production examples were measured for the content of DP 8 to 19, DP 20 or more, and for crystalline starch hydrolysates and crystalline sugars with DP 5 or less and molecular weights of 5,000 or more, and the residual rate in a β-amylase digestion test, using the methods described above. In addition, the particle size distribution and solubility at 50°C of the produced crystalline starch hydrolysates and crystalline sugars for microbeads were measured using the methods described above. The measurement results are shown in Table 4 below.

[0098]

[0099] (4) Powder Evaluation The powders of the crystalline starch hydrolysate or crystalline sugar for microbeads prepared above were evaluated by sensory evaluation of the feel when applied to the skin in terms of ease of spreadability, lack of roughness, lack of stickiness, lack of squeaky feeling, and moist feeling. The sensory evaluation was carried out by a panel of 10 experts according to the following evaluation criteria, and the average score was calculated to determine the evaluation. The results are shown in Table 5 below.

[0100] [Ease of spread] 5: Very easy to spread, very good 4: Easy to spread, good 3: Somewhat easy to spread, some good 2: Somewhat difficult to spread, poor 1: Very difficult to spread, poor

[0101] [Roughness] 5: Very smooth, very good 4: Smooth, good 3: Slightly smooth, somewhat good 2: Rough, poor 1: Very rough, very poor

[0102] [Non-stickiness] 5: Very smooth, very good 4: Smooth, good 3: Slightly smooth, somewhat good 2: Sticky, poor 1: Very sticky, very poor

[0103] [No squeaking] 5: Very well-fitted to the skin, very good 4: Well-fitted to the skin, good 3: Somewhat well-fitted to the skin, somewhat good 2: Squeaky, poor 1: Very squeaky, very poor

[0104] [Moisturizing feeling] 5: Very moist, very good 4: Moist, good 3: Slightly moist, somewhat good 2: Dry, poor 1: Very dry, very poor

[0105]

[0106] The crystalline starch hydrolysates for microbeads of Examples 1 to 9, which have (a) a content of glucose with a degree of polymerization (DP) of 8 to 19 of 30% or more, (b) a content of glucose with a degree of polymerization (DP) of 5 or less of 5% or less, (c) a content of molecular weight of 5000 or more of 25% or less, (d) a content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestibility test of 15% or less, and (e) a solubility at 50°C of 20% or less, achieved satisfactory results in all evaluations.

[0107] On the other hand, the crystalline starch hydrolysates for microbeads of Comparative Examples 1 and 2, which were prepared using Production Examples 1 and 2, each of which had a solubility at 50°C of more than 20%, had low heat resistance and were poorly rated for non-stickiness.

[0108] (5) Production of Cosmetics Cosmetics were produced using the crystalline starch hydrolyzate for microbeads produced above.

[0109] [Powder Foundation] A powder foundation was produced according to the following formulation. The powder foundation was produced using the crystalline starch hydrolysate for microbeads shown in Table 6. 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 Red iron oxide: 0.4% by mass Yellow iron oxide: 1.2% by mass Black iron oxide: 0.2% by mass Methylparaben: 0.2% by mass Dimethicone: 2.0% by mass Squalane: 2.0% by mass Triethylhexanoin: 3.0% by mass

[0110] The powder foundations thus produced were evaluated for ease of spread, non-stickiness, and moist feeling in the same manner as in (4) Powder Evaluation. The results are shown in Table 6 below.

[0111]

[0112] [Liquid Foundation] A liquid foundation was produced according to the following formulation. The liquid foundation was produced using the crystalline starch hydrolysate for microbeads shown in Table 7. Microbeads: 5.0% by mass, Polyglyceryl 10 pentastearate: 0.5% by mass, Glyceryl stearate: 1.0% by mass, Behenyl alcohol: 1.0% by mass, Cetearyl alcohol: 1.0% by mass, Cyclopentasiloxane: 8.0% by mass, Dimethicone: 10.0% by mass, Titanium oxide: 5.0% by mass, Red iron oxide: 0.4% by mass, Black iron oxide: 0.2% by mass, Yellow iron oxide: 1.0% by mass, 1,3-Butylene glycol: 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

[0113] The produced liquid foundations were evaluated for smoothness and moist feeling in the same manner as in (4) Powder Evaluation. The results are shown in Table 7 below.

[0114]

[0115] [Eye Shadow] Eye shadow was produced according to the following formulation. The eye shadow was produced using the crystalline starch hydrolysate for microbeads shown in Table 8. 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 alkyl ethylhexanoate (C14-18): 4.0% by mass Lanolin fatty acid octyldodecyl: 0.5% by mass Ethylhexyl hydroxystearate: 2.0% by mass Sorbitan isostearate: 1.5% by mass Colorant: 1.0% by mass Methylparaben: 0.2% by mass

[0116] The prepared eye shadows were evaluated for spreadability and moist feeling in the same manner as in (4) Powder Evaluation. The results are shown in Table 8 below.

[0117]

Claims

1. A crystalline starch hydrolyzate for microbeads having: (a) a glucose degree of polymerization (DP) of 8 to 19 of 30% or more; (b) a glucose degree of polymerization (DP) of 5 or less of 5% or less; (c) a molecular weight of 5000 or more of 25% or less; (d) a glucose degree of polymerization (DP) of 4 or more remaining in a β-amylase digestibility test of 15% or less; and (e) a solubility at 50°C of 20% or less.

2. The crystalline starch hydrolyzate for microbeads according to claim 1, wherein the particle size at 50% of the cumulative volume is 5 to 70 μm.

3. Microbeads containing crystalline starch hydrolysate having: (a) a glucose degree of polymerization (DP) of 8 to 19 of 30% or more; (b) a glucose degree of polymerization (DP) of 5 or less of 5% or less; (c) a molecular weight of 5000 or more of 25% or less; (d) a glucose degree of polymerization (DP) of 4 or more remaining in a β-amylase digestibility test of 15% or less; and (e) a solubility at 50°C of 20% or less.

4. The microbeads according to claim 3, wherein the particle size at which the cumulative volume of the crystalline starch hydrolyzate is 5 to 70 μm is 5 to 70 μm.

5. A method for producing crystalline starch hydrolyzate for microbeads, comprising: a crystallization step of crystallizing a starch hydrolyzate; and a heating step of heating the crystalline starch hydrolyzate that has undergone the crystallization step to 75°C or higher in the presence of water and / or water vapor, the method having the following characteristics (a) to (e): (a) a content of glucose with a degree of polymerization (DP) of 8 to 19 of 30% or more; (b) a content of glucose with a degree of polymerization (DP) of 5 or less of 5% or less; (c) a content of molecular weight of 5000 or more of 25% or less; (d) a content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestibility test of 15% or less; and (e) a solubility at 50°C of 20% or less.

6. The method for producing crystalline starch hydrolyzate for microbeads according to claim 5, wherein the starch hydrolyzate has the following characteristics: (f) a content of glucose with a degree of polymerization (DP) of 8 to 19 of 42% or more, (g) a content of glucose with a degree of polymerization (DP) of 20 or more of 35% or less, and (h) a content of glucose with a degree of polymerization (DP) of 4 or more remaining in a β-amylase digestibility test of 15% or less.

7. A method for producing a crystalline starch hydrolysate for microbeads according to claim 5, comprising an enzymatic reaction step of obtaining the starch hydrolysate, which comprises reacting a debranching enzyme with one or more selected from starch, a starch extract and a starch liquefied solution.

8. A cosmetic comprising the crystalline starch hydrolysate for microbeads according to claim 1 or 2, or the microbeads according to claim 3 or 4.

9. A method for producing a cosmetic, comprising a step of blending a crystalline starch hydrolyzate for microbeads obtained by the method according to any one of claims 5 to 7.

10. A method for improving the heat resistance of a crystalline starch hydrolysate, the method comprising a heating step of heating a crystalline starch hydrolysate to 75°C or higher in the presence of water and / or water vapor, the hydrolysate having (a) a glucose content of 8 to 19 degrees of polymerization (DP) of 30% or more, (b) a glucose content of 5 or less degrees of polymerization (DP) of 5, (c) a glucose content of 5000 or more molecular weight of 25% or less, and (d) a glucose content of 4 or more degrees of polymerization remaining in a β-amylase digestibility test of 15% or less.

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