Granular composition and method for producing same

Abstract

Provided is a granular composition having high fluidity and excellent handleability even while containing 3-hydroxybutyric acid.　A granular composition containing a 3-hydroxybutyric acid compound including 3-hydroxybutyric acid and whey protein is prepared. The content ratio of the whey protein is more than 300 parts by mass with respect to 100 parts by mass of the 3-hydroxybutyric acid compound. The 3-hydroxybutyric acid compound may be the 3-hydroxybutyric acid. The 3-hydroxybutyric acid may include R-3-hydroxybutyric acid. The 3-hydroxybutyric acid may be amorphous. In the granular composition, the total amount of the 3-hydroxybutyric acid compound and the whey protein may be 50 % by mass or more in the composition. The granular composition may be substantially free of oils and fats. The granular composition may be a composite particle containing the 3-hydroxybutyric acid compound and the whey protein. The granular composition may be a protein supplement.

Description

Granular composition and method for producing the same

[0001] The present invention relates to a granular composition containing whey protein and 3-hydroxybutyric acids, including 3-hydroxybutyric acid (hereinafter sometimes simply referred to as "3HB"), and a method for producing this granular composition.

[0002] 3HB and its salts are substances naturally present in the human body and are expected to be a revolutionary energy source that can replace carbohydrates. Furthermore, 3HB not only serves as an energy source, but has also been shown to be effective in improving cognitive function, enhancing long-term memory, and preventing Alzheimer's disease. 3HB is absorbed into the bloodstream and converted into energy through the ingestion and metabolism of medium-chain fatty acids (MCTs) found in coconut oil and other sources. This process not only allows for faster energy conversion than carbohydrates via the glycolytic pathway, but also inhibits the absorption of fats and sugars into cells by suppressing their absorption. Therefore, 3HB is expected to be used as an energy substance for athletes and in the fields of diet and health foods. An example of the use of 3HB in the field of diet and health foods is disclosed in JP 2021-185799 A (Patent Document 1), which discloses an oil and fat composition containing 3HB and / or its salt and oil and fat particles. However, the composition of Patent Document 1 requires oils and fats, which tend to be avoided in the field of diet and health foods.

[0003] On the other hand, in the acid form, 3HB is difficult to prepare as a powdery solid with high fluidity, and has handling problems. 3HB does not easily crystallize even when water is removed from an aqueous solution, and it easily dimerizes when water is removed, making it difficult to isolate as a solid. For this reason, 3HB is generally provided as a powder in the form of a neutral salt of sodium, calcium, magnesium, etc., rather than in the acid form.

[0004] However, consuming a large amount of neutralized salt of 3HB results in excessive salt intake, which is undesirable from a health perspective in the field of diet and health foods. Therefore, a method for providing 3HB in the acid form in a solid state has been sought.

[0005] Furthermore, 3HB has a very sour taste in its acid form, making it difficult to ingest in large amounts.

[0006] Japanese Patent Application Laid-Open No. 2021-185799

[0007] Therefore, an object of the present invention is to provide a granular composition that has high fluidity and is easy to handle even when it contains 3-hydroxybutyric acid, and a method for producing the same.

[0008] As a result of intensive research to solve the above-mentioned problems, the inventors discovered that by combining 3-hydroxybutyric acids, including at least 3-hydroxybutyric acid, with whey protein in a specific ratio, it is possible to provide a granular composition that has high fluidity and excellent handleability, even though it contains 3-hydroxybutyric acid, and thus completed the invention.

[0009] That is, the granular composition of the present invention contains 3-hydroxybutyric acids, including 3-hydroxybutyric acid, and whey protein, and the proportion of the whey protein exceeds 300 parts by mass per 100 parts by mass of the 3-hydroxybutyric acids. The 3-hydroxybutyric acids may be the 3-hydroxybutyric acid. The 3-hydroxybutyric acid may include R-3-hydroxybutyric acid. The 3-hydroxybutyric acid may be in amorphous form. In the granular composition, the total amount of the 3-hydroxybutyric acids and the whey protein may be 50% by mass or more in the composition. The granular composition may be substantially free of oils and fats. The granular composition may be composite particles containing the 3-hydroxybutyric acids and the whey protein. The granular composition may be a protein supplement. It is preferable that the granular composition does not contain oils and fats.

[0010] The present invention also includes a method for producing the granular composition, which comprises granulating a raw material containing 3-hydroxybutyric acids and whey protein. In the production method, the raw material may be granulated by a wet granulation method. In the production method, the raw material may be granulated by a spray-drying granulation method.

[0011] In this specification and claims, the term "3-hydroxybutyric acids (3HBs)" collectively refers to 3HB and 3HB polymers (particularly, 3HB oligomers) and contains at least 3HB. That is, 3HBs refer to 3HB that may contain 3HB polymers (particularly, oligomers).

[0012] In the present invention, 3-hydroxybutyric acids including 3-hydroxybutyric acid are combined with whey protein in a specific ratio, so that a granular composition having high fluidity and excellent handleability can be obtained even though it contains 3-hydroxybutyric acid.

[0013] In addition, supplements (nutritional supplements) for athletes used in muscle training, etc., often contain protein as the main ingredient, rather than fats and oils. Furthermore, protein-based supplements (protein supplements) are often taken in relatively large quantities in powder form. Therefore, protein supplements require high fluidity and storage stability, such as maintaining fluidity without stickiness and not caking (forming lumps) even after opening each time they are used. For this reason, it was common knowledge that those skilled in the art would hesitate to incorporate 3HB in its acid form into protein supplements that require high fluidity and storage stability. However, as a result of research conducted by the present inventors, it was surprising to find that a granular composition with high fluidity was obtained by combining the 3-hydroxybutyric acid derivatives and whey protein in a specific ratio.

[0014] Furthermore, the acidity of the granular composition is reduced by the buffering effect of whey protein, and oral ingestion is less unpleasant than with 3HB alone, making the granular composition useful as a protein supplement for diet and health foods.

[0015] FIG. 1 is a scanning electron microscope photograph of whey protein, a raw material used in the examples. FIG. 2 is a scanning electron microscope photograph of the composite particles obtained in Example 1. FIG. 3 is an XRD spectrum of the composite particles obtained in Example 1 and particles obtained by spray-drying whey protein alone. FIG. 4 is a scanning electron microscope photograph of the composite particles obtained in Example 2. FIG. 5 is a scanning electron microscope photograph of the composite particles obtained in Example 3. FIG. 6 is a scanning electron microscope photograph of soy protein, a raw material used in Reference Example 2. FIG. 7 is a titration curve obtained in Reference Example 3, where whey protein was added to an aqueous solution in which crystalline R-3HB had been dissolved. FIG. 8 is a scanning electron microscope photograph of the composite particles obtained in Example 4. FIG. 9 is a scanning electron microscope photograph of casein protein, a raw material used in Reference Example 4.

[0016] [3HBs] In the granular composition of the present invention, the 3-hydroxybutyric acids (3HBs) contain at least 3-hydroxybutyric acid (3HB).

[0017] 3HB may be an optical isomer (R- or S-isomer) or a racemate, but from the standpoint of biocompatibility, it is preferable that it contains at least the R-isomer (R-3-hydroxybutyric acid).

[0018] The proportion of the R-isomer in 3HB, particularly the optical purity (enantiomer or optical isomer excess), is, for example, 50% e.e. or more (e.g., 80% e.e. or more), preferably 90% e.e. or more (e.g., 95 to 100% e.e.), and more preferably 98 to 100% e.e. (e.g., 99 to 100% e.e., particularly substantially 100% e.e.). If the optical purity is too low, there is a risk of reduced biocompatibility.

[0019] Furthermore, 3HB may be used in combination with the R-isomer (R-3HB or (R)-3HB) and the S-isomer (S-3HB or (S)-3HB), but the mass proportion of the R-isomer in 3HB is preferably 10 mass% or more, more preferably 50 mass% or more, even more preferably 90 mass% or more, and most preferably 100 mass%.

[0020] 3HB (particularly R-3HB) may be in a crystalline form in the granular composition, but is preferably in an amorphous form. In the granular composition of the present invention, even though 3HB is in an amorphous form, by combining it with whey protein, particles with high fluidity can be obtained. In particular, by forming particles composited with whey protein, composite particles (granular composition) with high fluidity and excellent handleability can be obtained.

[0021] The 3HB used may be a commercially available product, or may be produced by fermentation using microorganisms from biomass raw materials (biological resources).

[0022] The 3HBs may further contain a 3HB oligomer. The average degree of polymerization of the 3HB oligomer may be 2 or more, for example, 2 to 100, preferably 2 to 10, further preferably 2 to 5, more preferably 2 to 4.5, and most preferably 2 to 4.

[0023] The 3HBs [or (poly)3HB] may be 3HB alone or a combination of 3HB and a polymer thereof (particularly an oligomer thereof).

[0024] The proportion of 3HB in the 3HBs (total amount of 3HB and its oligomers) may be 10% by mass or more, preferably 30% by mass or more, further preferably 50% by mass or more, even more preferably 80% by mass or more, and most preferably 90% by mass or more. The 3HBs may be substantially 3HB only, or may be 3HB only.

[0025] From the viewpoint of enhancing the biocompatibility of 3HB and improving its function as an energy source and its pharmacological or physiological functions, it is more preferable that the 3HBs contain R-3HB. The proportion of R-3HB in the 3HBs may be 10% by mass or more, preferably 30% by mass or more, even more preferably 50% by mass or more, more preferably 80% by mass or more, and most preferably 90% by mass or more. From the viewpoint of biocompatibility, the 3HBs may be substantially composed of R-3HB alone, or may consist solely of R-3HB.

[0026] [Whey Protein] The granular composition of the present invention further contains whey protein in addition to the 3HBs. In the present invention, by combining the 3HBs with whey protein, even if the 3HBs contain 3HB, it is possible to form particles with high fluidity. In addition, the buffering action of the whey protein can suppress the strong sourness caused by 3HB, even if the 3HBs contain 3HB in the acid form.

[0027] The whey protein is not particularly limited as long as it is a whey protein contained in milk whey. Whey protein may contain, for example, β-lactoglobulin, α-lactalbumin, immunoglobulin, proteose peptin, etc., and preferably contains β-lactoglobulin as the main component. The proportion of β-lactoglobulin in the whey protein may be 10% by mass or more, for example, 30 to 70% by mass, preferably 40 to 60% by mass.

[0028] From the viewpoints of biocompatibility and ease of handling, whey protein may be a partially hydrolyzed product, such as a water-soluble hydrolyzate obtained by partially hydrolyzing raw whey protein with a protease, acid, or the like.

[0029] The molecular weight of the whey protein may be 1,000 or more, for example, 1,000 to 100,000, preferably 3,000 to 50,000, further preferably 5,000 to 30,000, more preferably 10,000 to 25,000, and most preferably 15,000 to 20,000. If the molecular weight of the whey protein is too small, there is a risk that the fluidity and handleability may decrease.

[0030] In the present specification and claims, the molecular weight of whey protein can be measured based on polyacrylamide gel electrophoresis (SDS-PAGE).

[0031] The pH of the whey protein may be 3 or higher, for example, 3 to 10, preferably 3.5 to 9, further preferably 4 to 8, more preferably 5 to 7, and most preferably 5.5 to 6.5. If the pH of the whey protein is too low, it may be difficult to suppress the sourness of the granular composition.

[0032] In this specification and claims, pH can be measured by a conventional method, and the pH of whey protein can be measured, for example, by preparing a 10% by mass aqueous solution and using a commercially available pH meter.

[0033] The proportion of whey protein exceeds 300 parts by mass per 100 parts by mass of 3HBs. If the proportion of whey protein is too low, the fluidity and handleability of the granular composition will decrease. A suitable proportion of whey protein may be 310 parts by mass or more (e.g., 310 to 3000 parts by mass) per 100 parts by mass of 3HBs, for example, 320 to 2000 parts by mass, preferably 330 to 1000 parts by mass, more preferably 350 to 500 parts by mass, more preferably 350 to 450 parts by mass, and most preferably 380 to 420 parts by mass. If the proportion of whey protein is too high, a large amount may need to be ingested to exert the function of 3HB. As described below, when the granular composition is a composite particle containing whey protein and 3HBs, these proportions may be the proportions within each composite particle.

[0034] The total amount of the 3HBs and the whey protein in the composition may be 50% by mass or more, preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, and may be 100% by mass.

[0035] [3HB Salt] The granular composition of the present invention may further contain a 3HB salt. The salt form of 3HB, including preferred embodiments, is the same as the 3HB exemplified in the 3HB category.

[0036] Examples of salts include alkali metal salts such as sodium, potassium, and lithium; alkaline earth metal salts such as magnesium and calcium; and ammonium salts. These 3HB salts can be used alone or in combination. Among these, potassium salt of 3HB is preferred, and potassium salt of R-3HB is particularly preferred, in terms of preventing excessive salt intake.

[0037] The proportion of 3HB salt may be 100 parts by weight or less, preferably 50 parts by weight or less (e.g., 0.1 to 50 parts by weight), more preferably 30 parts by weight or less, even more preferably 10 parts by weight or less, and most preferably 1 part by weight or less, per 100 parts by weight of 3HBs. If the proportion of 3HB salt is too high, there is a risk of excessive salt intake when the granular composition is used as a protein supplement.

[0038] The granular composition of the present invention may not substantially contain 3HB salt, and preferably does not contain 3HB salt, in order to suppress salt intake. In particular, it is preferable that the granular composition of the present invention does not use 3HB salt as a raw material.

[0039] [Other Proteins] The granular composition of the present invention may further contain proteins other than whey protein (other proteins). Examples of other proteins include casein protein, soy protein, pea protein, wheat protein, egg protein, and rice protein. These other proteins can be used alone or in combination.

[0040] The proportion of the other protein may be 100 parts by mass or less, preferably 50 parts by mass or less (e.g., 0.1 to 50 parts by mass), further preferably 30 parts by mass or less, even more preferably 10 parts by mass or less, and most preferably 1 part by mass or less, relative to 100 parts by mass of whey protein. If the proportion of the other protein is too high, the fluidity and handleability of the granular composition may decrease.

[0041] The granular composition of the present invention preferably contains substantially no other proteins, and particularly preferably does not contain any other proteins, in order to improve the flowability and handling properties of the granular composition.

[0042] [Oils and fats] The granular composition of the present invention contains whey protein as a physiologically functional component, and therefore oils and fats are not essential components, but may further contain oils and fats.

[0043] The oils and fats are not particularly limited as long as they are edible oils and fats, and may be any of vegetable oils and fats, animal oils and fats, and processed oils and fats.

[0044] Examples of vegetable oils include soybean oil, cottonseed oil, linseed oil, castor oil, safflower oil, rice oil, germ rice oil, corn oil, sesame oil, sunflower oil, rice bran oil, rapeseed oil such as canola oil, peanut oil, palm kernel oil, olive oil, grapeseed oil (salad oil, refined oil), etc.; palm oils such as coconut oil and carotino oil, and vegetable oils (vegetable fats) such as cocoa butter.

[0045] Examples of animal fats and oils include butter, beef tallow, milk fat, lard, and fish oil.

[0046] Examples of processed fats and oils include margarine, shortening, and medium-chain triglycerides (MCT) such as stearic acid triglyceride.

[0047] These oils and fats may be fractionated oils, interesterified oils, or hydrogenated oils. These oils and fats may be used alone or in combination.

[0048] In protein supplements taken for diet and health supplements or muscle training purposes, the intake of fats and oils tends to be suppressed, so when the granular composition of the present invention is used as a protein supplement, it is preferable that the fat and oil content be low.

[0049] The proportion of fats and oils may be less than 100 parts by mass per 100 parts by mass of 3HBs, for example, less than 50 parts by mass, preferably less than 30 parts by mass, even more preferably less than 10 parts by mass, more preferably less than 1 part by mass, and most preferably less than 0.5 parts by mass.

[0050] In addition, the proportion of oils and fats in the granular composition may be less than 50% by mass, for example less than 30% by mass, preferably less than 10% by mass, even more preferably less than 5% by mass, more preferably less than 2% by mass, and most preferably less than 1% by mass.

[0051] The granular composition of the present invention may be substantially free of fats and oils, and preferably does not contain any fats and oils.

[0052] [Sugars] When the granular composition of the present invention is used as a protein supplement or the like, 3HB also functions as an energy source, so sugars are not an essential component, but the composition may further contain sugars.

[0053] Examples of sugars include pentoses such as arabinose and xylose; hexoses such as glucose, fructose, galactose, mannose, and sorbose, rare sugars such as psicose, and monosaccharides such as honey; disaccharides such as sucrose (e.g., white sugar, refined white sugar, powdered sugar, granulated sugar, cane sugar, brown sugar, and brown sugar), lactose, isomerized lactose, maltose, isomaltose, and trehalose; oligosaccharides (trisaccharides or higher) such as maltotriose, isomaltotriose, panose, and starch hydrolysates (dextrins); and sugar alcohols such as xylitol, erythritol, sorbitol, mannitol, reduced maltose syrup (maltitol), reduced starch syrup, reduced palatinose, and reduced lactose (lactitol).

[0054] These sugars can be used alone or in combination. Among these, monosaccharides such as glucose and fructose, and disaccharides such as sucrose and lactose are preferred, with lactose being particularly preferred.

[0055] Since the granular composition of the present invention contains 3HB as an energy source, other energy sources are not essential components even when used as a protein supplement. Therefore, from the viewpoint of fully exerting the physiological functions of 3HB, it is preferable to reduce the content of sugars in the granular composition and increase the content of 3HBs.

[0056] The proportion of sugars may be 100 parts by mass or less, preferably 50 parts by mass or less (e.g., 0.1 to 50 parts by mass), more preferably 30 parts by mass or less, even more preferably 10 parts by mass or less, and most preferably 1 part by mass or less, per 100 parts by mass of 3HBs. If the proportion of sugars is too high, the content of 3HBs in the granular composition may decrease.

[0057] The granular composition of the present invention may be substantially free of sugars, and preferably is free of sugars.

[0058] [Other Components] The granular composition of the present invention may further contain conventional additives used in the field of diet and health foods.

[0059] Examples of conventional additives include ketone esters (e.g., ketone esters of 3HB and 1,3-butanediol), vitamins (e.g., vitamin A, vitamin D, vitamin E, vitamin B １ , Vitamin B ２ , Vitamin B ６ , Vitamin C, Vitamin B １２ etc.), dietary fiber (e.g., wheat bran, corn bran, oat bran, corn fiber, soybean dietary fiber, beet fiber, crystalline cellulose, agar, chitosan, chitin, hemicellulose, lignin, glucan, etc.), non-sugar sweeteners (e.g., natural sweeteners such as stevia, licorice, and amacha; artificial sweeteners such as saccharin, saccharin sodium, aspartame, acesulfame potassium, sucralose, and neotame), flavorings (menthol, vanilla bean, orange, etc.) fruit juice, lemon lime, lemon peel, etc.), coloring agents (food dyes such as Food Yellow No. 5, Food Red No. 2, Food Blue No. 2; food lake dye; red iron oxide, etc.), seasonings, leavening agents or foaming agents (such as baking soda), thickening stabilizers or water-retaining emulsion stabilizers (such as thickening polysaccharides such as pectin and cellulose), pH adjusters (such as inorganic salts such as baking soda, trisodium phosphate, and potassium dihydrogen phosphate), fortifying powders, preservatives (such as antiseptics and antibacterial agents), antifoaming agents, emulsifiers, antioxidants, light stabilizers, brewing agents, etc. These additives can be used alone or in combination of two or more.

[0060] The proportion (total proportion) of conventional additives can be selected from the range of about 0.01 to 50 parts by mass per 100 parts by mass of 3HBs, and is, for example, 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 3 parts by mass.

[0061] [Characteristics of Granular Composition] The granular composition of the present invention is not particularly limited as long as it contains 3HBs and whey protein in the above-mentioned ratio and is granular, but preferably the 3HBs and whey protein are combined to form composite particles.That is, the granular composition of the present invention may be a particle containing 3HBs and whey protein, preferably a composite particle containing 3HBs and whey protein, and particularly preferably a composite particle having a structure in which 3HBs are uniformly dispersed in whey protein.

[0062] The shape of the granular composition (particularly the composite particles) may be, for example, spherical, ellipsoidal, polyhedral, plate-like, fibrous, irregular, etc. Among these shapes, spherical shapes such as approximately spherical are preferred.

[0063] The average particle size (effective diameter) of the composite particles is, for example, 0.1 to 1000 μm, preferably 0.5 to 500 μm, further preferably 1 to 100 μm, and even more preferably 2 to 50 μm. If the average particle size of the composite particles is too small, the handleability of the granular composition may decrease, whereas if it is too large, productivity may decrease.

[0064] In this specification and claims, the average particle size (effective diameter) is the central particle size (D ５０ (wherein β is the measured value of the particle size at 50% of the cumulative value in the particle size distribution), and can be measured by wet measurement using a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., device name: Microtrac MT3300ExII) in accordance with the laser diffraction scattering method (ISO133201 and ISO9276-1).

[0065] The pH of the granular composition may be 2.6 or higher, for example, 2.6 to 7, preferably 2.8 to 6, further preferably 3 to 5, more preferably 3.2 to 4.5, and most preferably 3.5 to 4. If the pH of the granular composition is too low, there is a risk that the acidity will be too strong.

[0066] [Method for producing granular composition] The granular composition of the present invention (particularly, composite particles) can be obtained by granulating raw materials (granulation raw materials) containing 3HBs and whey protein. The method for granulating the raw materials is not particularly limited, and conventional granulation methods can be used. The conventional granulation method may be a dry granulation method, but a wet granulation method is preferred. The wet granulation method may be any method that granulates the raw materials using a granulation solvent, and examples thereof include extrusion granulation, tumbling granulation, fluidized bed granulation, mixing / stirring granulation, spray-drying granulation, and vibration granulation. These wet granulation methods may also be used in combination.

[0067] Among these wet granulation methods, spray drying granulation (spray drying) is preferred from the viewpoint of productivity, etc. In the spray drying granulation method, the granulation liquid only needs to contain a granulation solvent, and is usually an aqueous dispersion or solution containing the raw material and the granulation solvent.

[0068] The granulation solvent is not particularly limited, but from the viewpoint of safety, water, aqueous solvents, etc. can be used. Examples of aqueous solvents include lower alcohols (e.g., C 100, C 200, C 300, C 400, C 500, C 600, C 700, C 800, C 900, C 1000, C 1100, C 1200, C 1300, C ２－４ Examples of the solvent include water, alkanols, and aliphatic ketones (e.g., acetone). These solvents can be used alone or in combination. Among these, water and / or ethanol are preferred in terms of oral application and ease of use.

[0069] The proportion of the granulation solvent is, for example, 100 to 1000 parts by mass, preferably 200 to 800 parts by mass, and more preferably 300 to 500 parts by mass, relative to 100 parts by mass of the total of the raw materials. If the proportion of the granulation solvent is too low, granulation may become difficult, whereas if it is too high, the particle size may become too small.

[0070] In spray drying, the inlet temperature is, for example, 100 to 200° C., preferably 120 to 180° C., and more preferably 130 to 160° C. The outlet temperature is, for example, 50 to 90° C., preferably 60 to 80° C., and more preferably 65 to 75° C. If the spray drying temperature is too low, granulation may become difficult, and if it is too high, the whey protein may be denatured.

[0071] The 3HBs used as raw materials may be liquid or solid. The 3HB used as raw material may be amorphous, but is preferably crystalline. In the production method of the present invention, even if the raw material 3HB is crystalline, the 3HB in the resulting granular composition is obtained in an amorphous state. Crystalline R-3HB has a high melting point of 49 to 50°C, making it easy to handle.

[0072] The whey protein used as a raw material may be in a particulate form. The shape of the particles is not particularly limited and may be, for example, amorphous, fibrous, ellipsoidal, spherical, flat, or granular, and is usually amorphous or granular.

[0073] The average particle size (effective diameter) of the whey protein as a raw material is, for example, 1 to 2000 μm, preferably 5 to 1000 μm, and more preferably 10 to 500 μm.

[0074] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The raw materials and evaluation methods used are as follows.

[0075] [Raw Materials] (3HB) Crystalline R-3HB: R-3HB obtained by concentrating an aqueous solution of R-3-hydroxybutyric acid produced according to the method described in Example 1 of JP 2019-176839 A by removing water using an evaporator set at 70°C, adding 30% by mass of ethyl acetate and R-3HB seed crystals relative to the weight of the concentrate, leaving the solution at 4°C overnight, filtering, and drying. Crystalline S-3HB: S-3HB obtained by concentrating an aqueous solution of S-3-hydroxybutyric acid produced according to the method described in Example 1 of JP 2019-176839 A using S-3-hydroxybutyric acid ethyl ester as a raw material, by removing water using an evaporator set at 70°C, adding 30% by mass of ethyl acetate and R-3HB seed crystals relative to the weight of the concentrate, leaving the solution at 4°C overnight, filtering, and drying.

[0076] (Protein) Whey protein: "Bulk Sports Isopro Natural" manufactured by Body Plus International Co., Ltd. Soy protein: "Bulk Sports Soypro" manufactured by Body Plus International Co., Ltd. Casein protein: "Bulk Sports Big Casein" manufactured by Body Plus International Co., Ltd.

[0077] [XRD] Measurement was performed using the following X-ray diffractometer (XRD).

[0078] Apparatus: SmartLab manufactured by Rigaku Corporation X-ray tube: CuKα Tube voltage: 40 kV Tube current: 30 mA Detector: D / tex ultra 250 Measurement angle: 5 to 85°.

[0079] Example 1 20 g of crystalline R-3HB and 80 g of whey protein were added to distilled water to prepare a granulation liquid with a total volume of 500 mL. This granulation liquid was spray-dried using a spray dryer ("B-290" manufactured by Nippon Buchi Co., Ltd.) under conditions of an inlet temperature of 140°C and an outlet temperature of 70°C to obtain composite particles. The obtained composite particles had flowability.

[0080] A scanning electron microscope photograph of the raw material whey protein is shown in Figure 1, and a scanning electron microscope photograph of the obtained composite particles is shown in Figure 2. Furthermore, the results of XRD measurement of the obtained composite particles and the results of XRD measurement of particles obtained by spray-drying whey protein alone under the same conditions as in Example 1 are shown in Figure 3. From the results in Figure 3, it was confirmed that the R-3HB in the composite particles was amorphous, since the spectrum of the composite particles and the spectrum of particles of whey protein alone matched.

[0081] Example 2 Composite particles were obtained in the same manner as in Example 1, except that the blending amount of whey protein was changed to 100 g. The obtained composite particles had flowability. A scanning electron microscope photograph of the obtained composite particles is shown in Figure 4.

[0082] Example 3 20 g of crystalline R-3HB was subjected to reduced pressure for 3 hours in an evaporator set at 80°C to polymerize the crystalline R-3HB. Composite particles were obtained in the same manner as in Example 1, except that polymerized R-3HB was used instead of R-3HB. The obtained composite particles had flowability. A scanning electron microscope photograph of the obtained composite particles is shown in Figure 5.

[0083] Reference Example 1 Composite particles were obtained in the same manner as in Example 1, except that the blending amount of whey protein was changed to 60 g. The obtained composite particles were a powder lacking flowability and containing many lumps.

[0084] Reference Example 2 Composite particles were obtained in the same manner as in Example 1, except that 80 g of soy protein was used instead of 80 g of whey protein. A scanning electron microscope photograph of the raw material soy protein is shown in Figure 6. The obtained composite particles lacked fluidity and were a powder with many lumps.

[0085] Reference Example 3 Distilled water was added to 10 g of crystalline R-3HB to prepare a solution with a total volume of 200 mL. Whey protein was added to this solution while measuring the pH, thereby obtaining a titration curve. The obtained titration curve is shown in Figure 7.

[0086] Example 4 Composite particles were obtained in the same manner as in Example 1, except that 10 g of crystalline R-3HB and 10 g of crystalline S-3HB were used instead of 20 g of crystalline R-3HB. The obtained composite particles had flowability. A scanning electron microscope photograph of the obtained composite particles is shown in Figure 8.

[0087] Example 5 Composite particles were obtained in the same manner as in Example 1, except that 10 g of crystalline R-3HB and 90 g of whey protein were used instead of 20 g of crystalline R-3HB and 80 g of whey protein. The obtained composite particles had flowability.

[0088] Reference Example 4 Composite particles were obtained in the same manner as in Example 1, except that 80 g of casein protein was used instead of 80 g of whey protein. A scanning electron microscope photograph of the raw material casein protein is shown in Figure 9. The obtained composite particles were a powder with no fluidity and many lumps.

[0089] Three experienced panelists evaluated the sourness of the composite particles obtained in Examples 1 to 5, and all three panelists evaluated that the sourness of all Examples was suppressed.

[0090] Furthermore, the composite particles obtained in Examples 1 to 5 maintained their fluidity even after being left at room temperature for one week, and also maintained their fluidity when heated to 50°C. Therefore, the composite particles obtained in Examples 1 to 5 also had excellent storage stability. Because the melting point of crystalline R-3HB is 49 to 50°C, the composite particles obtained in Examples 1 to 5 were stable even near the melting point and had excellent handleability.

[0091] The granular composition of the present invention can be used as a protein supplement in the fields of medicine and food, and is particularly suitable as a protein supplement used as an energy substance for athletes and as a diet / health supplement.

Claims

1. A granular composition comprising 3-hydroxybutyric acids including 3-hydroxybutyric acid and whey protein, wherein the ratio of the whey protein exceeds 300 parts by mass per 100 parts by mass of the 3-hydroxybutyric acids.

2. The granular composition according to claim 1, wherein the 3-hydroxybutyric acid derivative is 3-hydroxybutyric acid.

3. The granular composition according to claim 1 or 2, wherein the 3-hydroxybutyric acid comprises R-3-hydroxybutyric acid.

4. A granular composition according to any one of claims 1 to 3, wherein the 3-hydroxybutyric acid is in amorphous form.

5. A granular composition according to any one of claims 1 to 4, wherein the total amount of the 3-hydroxybutyric acids and the whey protein is 50 mass% or more in the composition.

6. The granular composition according to any one of claims 1 to 5, which is a composite particle containing the 3-hydroxybutyric acids and the whey protein.

7. A granular composition according to any one of claims 1 to 6 which is a protein supplement.

8. A granular composition according to any one of claims 1 to 7, which does not contain any oil or fat.

9. A method for producing a granular composition according to any one of claims 1 to 8, which comprises granulating a raw material containing 3-hydroxybutyric acids and whey protein.

10. The method of claim 9, wherein the raw materials are granulated by a wet granulation method.

11. The method according to claim 9 or 10, wherein the raw material is granulated by a spray drying granulation method.

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