Particulate composition containing a cocrystal of malic acid and alkali metal hydrogen malate.

Abstract

The present invention provides a volume-weighted average diameter D 4,3 and comprising at least 50% by weight of malate particles, the malate particles comprising at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate, the particulate composition being advantageously deposited in or on a confectionery product.

Description

Detailed Description of the Invention

[0001] [Technical Field] The present invention relates to a malate granule containing at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate. child The present invention further provides a method for preparing such a particulate composition.

[0002] The particulate composition of the present invention can advantageously be attached to or on the surface of confectionery products, especially hard and soft panned coatings, tabletted candies and chocolates.

[0003] [Background of the Invention] Malic acid (2-hydroxybutanedioic acid) is the main acid in many fruits including apricots, blackberries, blueberries, cherries, grapes, mirabelles, peaches, pears, plums, quinces, and is present in other fruits such as citrus fruits at lower concentrations than in those fruits. Malic acid also contributes to the sour taste of green (unripe) apples. In rhubarb, where malic acid is the main flavorant, the taste of malic acid is very distinct and pure. Malic acid is used as a food additive in non-carbonated beverages, wines, confectionery, chewing gum, desserts, and baked goods.

[0004] Sugar panning, or simply panning, is a method of adding a candy "shell" to candies or nuts. Popular candies that utilize this process in manufacturing include dragées, M&M's, gobstoppers, rock candy, and jelly beans. Jelly beans use soft panning, and the other three are examples of hard panning.

[0005] Hard panning and soft panning are both produced in a similar manner, but different ingredients and rates are used. Hard panning is a process in which a thin film of sugar or sugar alcohol solution is applied to each tumbling core, and then the water is evaporated, causing the sugar or sugar alcohol to crystallize into a thin layer. This process is repeated until a hard coating of the desired thickness is obtained. Any material that does not deform under its own weight and can roll freely (without flat surfaces that can stick together) is a candidate for hard panning. Soft panning uses non-crystallizing syrups such as glucose. Powdered sugar or refined sugar is added during rolling to aid drying.

[0006] International Publication No. 2019 / 063623 describes a particulate acidulant composition comprising 20-70% by weight of malic acid, 3-40% by weight of lactic acid, and 0-40% by weight of an edible acid selected from citric acid, fumaric acid, adipic acid, tartaric acid, acetic acid, and combinations thereof, M grains containing cocrystals of malic acid and partially neutralized polycarboxylic acids selected from malic acid, citric acid, fumaric acid, adipic acid, tartaric acid, and combinations thereof. child M grains containing at least 30% by weight of malic acid and at least 30% by weight of partially neutralized polycarboxylic acid. child 40-90% by weight, and L-grains containing cocrystals of lactic acid and at least partially neutralized carboxylic acids selected from lactic acid, malic acid, citric acid, fumaric acid, adipic acid, tartaric acid, and combinations thereof. child The L-grains contain at least 30% by weight of lactic acid and at least 30% by weight of at least partially neutralized carboxylic acid. child 5~60% by weight Contains M granules child and L grain child The present invention describes an acidulant composition in which the combination of the above constitutes at least 50% by weight of the acidulant composition.

[0007] In the aforementioned example of an international patent application, malic acid granules are dried in a fluidized bed dryer. child The document describes a powder blend containing 80% by weight of Purac® Powder MA (42-50% by weight of sodium bimalate and 50-58% by weight of malic acid), which is prepared by spraying a partially neutralized aqueous malic acid solution onto a layer. Purac® Powder MA typically contains 40-50% by weight of a cocrystal of malic acid and sodium bimalate.

[0008] International Publication No. 2020 / 260194 describes malate granules. child A particulate composition comprising at least 1% by weight of the malate granules child The present invention describes a particulate composition having a diameter of 50 to 1,000 μm and containing at least 70% by weight of a cocrystal of malic acid and alkali metal hydrogen malate.

[0009] Van Havere et al. (Crystal structure of bis(potassium hydrogen L-malate) malic acid,2[K + (C4H5O5) - The crystal structure of bis(L-potassium hydrogen malate)·malic acid is described in ]·C4H6O5, Journal of Crystallographic and Spectroscopic Research (1985), 15(1), 45~52).

[0010] Fleck et al. (Dielectric and Pyroelectric Properties of Lithium Hydrogen Dimalate, LiH3(C4H4O5)2. Z. Naturforsch. 41a, 1289~1296 (1986), accepted July 5, 1986) describe how LiH3(C4H4O5)2 was prepared from an aqueous solution containing stoichiometric amounts of LiOH and malic acid (1:2). A large single crystal (15 × 8 × 6 mm) can be grown by slowly evaporating H2O from this aqueous solution at 290 K.

[0011] [Overview of the prefecture] The inventors have developed a malate powder that can preferably adhere to the inside and surface of confectionery products and impart a sour flavor. The malate powder is composed of granules containing at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate. child It is composed of granules.

[0012] Therefore, a first aspect of the present invention is a particulate composition having a volume-weighted average diameter D of 20 to 180 μm and containing at least 50% by weight of malate granules, wherein the malate granules contain at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate. Examples of such co-crystals include sodium hydrogen malate·malic acid (Na(C4H5O5)·C4H6O5), as well as bis(potassium hydrogen L-malate)·malic acid, and dipotassium hydrogen tri-malate (2[K(C4H5O5)]·C4H6O5). 4,3 having, and containing malate granules child at least 50% by weight, a particulate composition, wherein the malate granules child contain at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate, relates to a particulate composition. Examples of such co-crystals include sodium hydrogen malate·malic acid (Na + (C4H5O5) - ·C4H6O5), as well as bis(potassium hydrogen L-malate)·malic acid, and dipotassium hydrogen tri-malate (2[K + (C4H5O5) - ·C4H6O5).

[0013] The particulate composition of the present invention preferably adheres to the inside or surface of confectionery products such that the malate granules remain substantially intact. The inventors do not wish to be bound by theory, but it is believed that when the malate granules come into contact with saliva, the co-crystal of malic acid and an alkali metal hydrogen malate dissociates immediately into malic acid child or hydrogen malate, Na child / K 2- or malic acid, and H - / K + / K + and H + / K child containing confectionery products of the present invention, a smooth tart flavor of malic acid is immediately released.

[0014] The malate powder of the present invention maintains its fluidity even at high temperatures and high humidities, and the malate granules childIt has the advantage that its composition does not change with particle size. Therefore, malate powder can be provided in the form of a fine powder by crushing crude malate powder to a desired particle size.

[0015] A second aspect of the present invention is a method for preparing pulverized malate powder, Malate granules containing at least 70% by weight of a cocrystal of malic acid and alkali metal hydrogen malate. child The step is to prepare a crude malate powder containing at least 90% by weight of the following, wherein the crude malate powder has a volume-weighted average diameter D of at least 100 μm. 4,3 Steps having, The particle size of the crude malate powder is reduced, and the volume-weighted average particle size D is at least 50% smaller than the particle size of the crude malate powder. 4,3 The present invention relates to a method comprising the step of preparing a pulverized malate powder having [a specific characteristic].

[0016] A third aspect of the present invention is: Malate granules child Hard panning or soft panning coating containing 0.1 to 6% by weight of; Malate granules child Tablet-shaped candy containing at least 0.1 to 50% by weight of [the substance]; Malate granules child Chocolate containing at least 0.1 to 30% by weight of It includes at least one of the following: Malate granules child The present invention relates to a confectionery product containing at least 70% by weight of a cocrystal of malic acid and alkali metal hydrogen malate.

[0017] A fourth aspect of the present invention is a process for preparing hard-panned confectionery, The steps include preparing a cohesive edible core, The steps include applying at least one syrup coating layer to the edible core, wherein the syrup comprises a crystallizable sweetener selected from crystallizable sugars, crystallizable sugar alcohols, and combinations thereof, Malate granules containing at least 70% by weight of a cocrystal of malic acid and alkali metal hydrogen malate. child The steps include applying at least one other coating layer, and This includes processes related to the process. [Brief explanation of the drawing]

[0018] [Figure 1] Figure 1 shows the X-ray diffraction pattern of a cocrystal of malic acid and sodium hydrogen malate, identified as sodium trihydrogen dimalate (Na+(C4H5O5)-·C4H6O5).

[0019] [Detailed description of the invention] In a first embodiment, the present invention relates to a volume-weighted average diameter D of 20 to 180 μm. 4,3 It has malate granules child A particulate composition comprising at least 50% by weight of the malate granules child However, the present invention relates to a particulate composition containing at least 70% by weight of a cocrystal of malic acid and alkali metal hydrogen malate.

[0020] As used herein, the term “malate” refers to malic acid, salts of malic acid, and combinations thereof.

[0021] As used herein, the term "cocrystal" refers to a crystalline single-phase substance that is neither a solvate nor a monosalt, composed of two or more different molecules or ionic compounds in stoichiometric ratios.

[0022] As used herein, the term "sugar" refers to sweet monosaccharides and disaccharides.

[0023] As used herein, the term "sugar alcohol" refers to a sweet-tasting polyol containing 6 to 12 carbon atoms, rather than sugar itself.

[0024] As used herein, the term "syrup" refers to a thick, viscous liquid consisting primarily of aqueous solutions of sugars and / or sugar alcohols.

[0025] As used herein with respect to sugars or sugar alcohols, the term "crystallizable" refers to the ability of a sugar or sugar alcohol to exist in a crystalline state at 20°C and ambient temperature.

[0026] The terms "crystalline" or "crystallized" mean that a substance is in a crystalline state at 20°C and atmospheric pressure.

[0027] The particle size distribution referred to herein can preferably be determined by laser diffraction (Malvern).

[0028] Sodium trihydrogen dimalate (Na) + (C4H5O5) - Figure 1 shows the X-ray diffraction pattern of a cocrystal of malic acid and sodium bicarbonate, identified as C4H6O5. The particulate composition of the present invention has stability, malate particles child The immediate, smooth acidity it provides, and the fact that it can be supplied in the form of a very fine powder (e.g., very relevant to hard panning), make it particularly suitable for application to the inside or surface of confectionery products.

[0029] The particulate composition has a volume-weighted average diameter D of preferably 40 to 170 μm, most preferably 80 to 160 μm. 4,3 It holds.

[0030] Preferably, malate particles in the particulate composition. child The volume-weighted average diameter D is 20-180 μm, more preferably 40-170 μm, and most preferably 80-160 μm. 4,3 It holds.

[0031] According to a preferred embodiment, the particulate composition, D 10 ≥1μm; 40μm≦D 50 ≤200μm; D 90 ≤320μm (Here, D x Grains with a smaller diameter child The volume % of is equal to the volume % of x, D x grains with a larger diameter child The volume % of has a particle size distribution equal to (100-x) volume %. More preferably, the particulate composition is D 10 ≥5μm; 60μm≦D 50 ≤140μm; D 90 It has a particle size distribution of ≤280 μm.

[0032] Particles in particulate composition child Preferably, the span (D) does not exceed 3.5. 90 -D 10 ) / D 50 It has a span not exceeding 3.0.

[0033] Malate particles in particulate composition child The product preferably contains at least 80% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight of a cocrystal of malic acid and alkali metal hydrogen malate.

[0034] Malate granules child In addition, the particulate composition of the present invention may contain other particulate components such as sugar, salt, or acid powder.

[0035] A preferred embodiment of the present invention, malate granules child This corresponds to the majority of the particulate composition. Therefore, the particulate composition is malate granules. child Preferably containing at least 70% by weight, more preferably at least 80% by weight, and most preferably at least 90% by weight.

[0036] The water content of the particulate composition is usually not more than 5% by weight, and more preferably not more than 3% by weight.

[0037] In a particularly preferred embodiment, the cocrystal of malic acid and alkali metal hydrogen malate is a cocrystal of malic acid and sodium hydrogen malate, or a cocrystal of malic acid and potassium hydrogen malate. More preferably, the cocrystal is sodium trihydrogen dimalate (Na + (C4H5O5) - • C4H6O5) or dipotassium trimalate (2[K) + (C4H5O5) - ]·C4H6O5). Most preferably, the cocrystal used in accordance with the present invention is sodium trihydrogen dimalate (Na + (C4H5O5) - It is C4H6O5.

[0038] Yet another aspect of the present invention is a method for preparing a pulverized malate powder, Malate granules containing at least 70% by weight of a cocrystal of malic acid and alkali metal hydrogen malate. child The step is to prepare a crude malate powder containing at least 90% by weight of the following, wherein the crude malate powder has a volume-weighted average diameter D of at least 100 μm. 4,3 Steps having, The particle size of the crude malate powder is reduced, and the volume-weighted average particle size D is at least 50% smaller than the particle size of the crude malate powder. 4,3 The present invention relates to a method comprising the step of preparing a pulverized malate powder having [a specific characteristic].

[0039] Preferably, the malate granules are made from crude malate powder. child The volume-weighted average diameter D is at least 200 μm, most preferably 250 to 600 μm. 4,3 It holds.

[0040] Crude malate powder malate granules childThe product preferably contains at least 80% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight of a cocrystal of malic acid and alkali metal hydrogen malate.

[0041] Crude malate powder malate granules child The moisture content is preferably not more than 5% by weight, and more preferably not more than 3% by weight.

[0042] In a particularly preferred embodiment, the cocrystal of malic acid and alkali metal hydrogen malate in the crude malate powder is a cocrystal of malic acid and sodium hydrogen malate, or a cocrystal of malic acid and potassium hydrogen malate. More preferably, the cocrystal is sodium trihydrogen dimalate (Na + (C4H5O5) - • C4H6O5) or dipotassium trimalate (2[K) + (C4H5O5) - ]·C4H6O5). Most preferably, the cocrystal used in accordance with the present invention is sodium trihydrogen dimalate (Na + (C4H5O5) - It is C4H6O5.

[0043] Preferably, this method yields a volume-weighted average diameter D of 20-180 μm, more preferably 40-170 μm, and most preferably 70-160 μm. 4,3 A pulverized malate powder containing the following properties is obtained.

[0044] According to another preferred embodiment, this method allows, D 10 ≥1μm; 40μm≦D 50 ≤200μm; D 90 ≤320μm (Here, D x Grains with a smaller diameter child The volume % of is equal to the volume % of x, D x grains with a larger diameter childA pulverized malate powder is obtained having a particle size distribution (where the volume % is equal to (100-x) volume %).

[0045] In one embodiment of this method, crude malate powder is Seed crystal grains containing at least 80% by weight of a crystalline substance selected from crystalline organic acids, crystalline organic acid salts, and combinations thereof. child Steps to prepare, The steps include: preparing an aqueous malate solution containing sodium and malate ions in a molar ratio of 4:10 to 6:10, or potassium and malate ions in a molar ratio of 5.5:10 to 7.5:10; Malate aqueous solution as seed crystal grains child Spray onto coated granules child The steps to produce and Coated grains child It is prepared by the step of removing moisture from it.

[0046] seed grain child The crystalline substance is preferably selected from crystalline organic acids, crystalline organic acid salts, and combinations thereof, and the organic acid is selected from malic acid, lactic acid, acetic acid, citric acid, fumaric acid, adipic acid, tartaric acid, and combinations thereof. More preferably, the crystalline substance is selected from crystalline malic acid, crystalline salts of malic acid, and combinations thereof. Most preferably, the crystalline substance is a cocrystal (Na) of malic acid and sodium bicarbonate. + (C4H5O5) - ·C4H6O5), or a cocrystal of malic acid and potassium bitumen (2[K + (C4H5O5) - ]·C4H6O5). Most preferably, the crystalline substance is malic acid and sodium bicarbonate (Na + (C4H5O5) - It is a cocrystal with C4H6O5.

[0047] grain childThe aqueous malate solution sprayed preferably contains malate at a concentration of at least 1 mol / L, more preferably at least 1.5 mol / L, and most preferably 2 to 5 mol / L.

[0048] The malate aqueous solution preferably has a dry matter content of 20-70% by weight, more preferably 25-65% by weight, and most preferably 30-60% by weight.

[0049] Malate aqueous solutions are preferably prepared from malic acid by dissolving malic acid in water and adding a neutralizing agent. More preferably, a completely neutralized sodium malate solution is prepared by dissolving malic acid in water and adding a neutralizing agent, the neutralizing agent being mixed with the malic acid aqueous solution to obtain a desired ratio of sodium to malate ions, or potassium to malate ions.

[0050] seed grain child Preferably, coated particles obtained after removing moisture. child It is used in this method in an amount equivalent to 3 to 70% by weight, more preferably 5 to 60% by weight, and even more preferably 9 to 50% by weight.

[0051] Malate aqueous solution preferably contains seed crystal grains child It is sprayed into a fluidized bed. The temperature of this fluidized bed is preferably in the range of 40 to 100°C, more preferably in the range of 42 to 90°C, even more preferably in the range of 44 to 80°C, and most preferably in the range of 45 to 70°C.

[0052] In addition to water, malate ions, and sodium or potassium cations, the aqueous malate solution preferably contains no other components at a concentration exceeding 0.1% by weight.

[0053] Malate aqueous solutions can be prepared by dissolving malic acid in water with either sodium bituminate or potassium bituminate. Alternatively, a malate aqueous solution can be prepared by dissolving malic acid in water with either sodium hydroxide or potassium hydroxide. Another alternative is to prepare a malate aqueous solution by dissolving malic acid in water with either disodium malate or dipotassium malate.

[0054] According to a particularly preferred embodiment of the method, a spray of an aqueous malate solution and coated particles child The removal of moisture from the material is carried out simultaneously.

[0055] In a preferred embodiment of this method, spraying and moisture removal are carried out in a fluidized bed dryer. In another preferred embodiment, spraying and moisture removal are carried out in a parallel flow spray dryer in which the fine powder is recirculated to the spray nozzle (to function as seed crystals).

[0056] In an alternative embodiment of the present invention, the crude malate powder is Malic acid granules containing at least 80% by weight of malic acid child Steps to prepare, Sodium bimalate granules containing at least 80% by weight of sodium bimalate child , or potassium bitomalate granules containing at least 80% by weight of potassium bitomalate. child Steps to prepare, 100 parts by weight of malic acid granules child 100-138 parts by weight of sodium bimalate granules child The steps include: or combining either 200-300 parts by weight of potassium bitamate with 1-10 parts by weight of water; The steps include subjecting the resulting combination to mechanical shear and It is prepared by [method].

[0057] Further aspects of the present invention include: Malate granules childHard panning or soft panning coating containing 0.1 to 6% by weight of; Malate granules child Tablet-shaped candy containing at least 0.1 to 50% by weight of [the substance]; Malate granules child Chocolate containing at least 0.1 to 30% by weight of, Malate granules child The present invention relates to a confectionery product containing at least 70% by weight of a cocrystal of malic acid and alkali metal hydrogen malate.

[0058] The confectionery product of the present invention preferably has a weight in the range of 0.2 to 500 g, more preferably 0.4 to 400 g, and most preferably 0.5 to 350 g.

[0059] Hard panning or soft panning coatings for confectionery products use malate granules. child It preferably contains 0.5 to 5.0% by weight, more preferably 1.0 to 4.5% by weight, and most preferably 2.0 to 4.0% by weight.

[0060] Tablet-shaped candies in confectionery products contain malate granules. child It preferably contains 0.2 to 45% by weight, more preferably 0.5 to 40% by weight, and most preferably 1.0 to 30% by weight.

[0061] The chocolate component in confectionery products is malate granules. child It preferably contains 0.2 to 25% by weight, more preferably 0.5 to 20% by weight, and most preferably 1.0 to 15% by weight.

[0062] Malate granules contained in coatings, tablet candies, or chocolates child Preferably, the volume-weighted average diameter D is 20 to 180 μm. 4,3 It has. More preferably these malate granules child The volume-weighted average diameter D is 50-170 μm, most preferably 80-160 μm. 4,3 It holds.

[0063] According to a preferred embodiment, malate granules child teeth, D 10 ≥1μm; 40μm≦D 50 ≤200μm; D 90 ≤320μm (Here, D x Grains with a smaller diameter child The volume % of is equal to the volume % of x, D x grains with a larger diameter child The volume % has a particle size distribution equal to (100-x) volume %. More preferably, malate particles child teeth, D 10 ≥5μm; 60μm≦D 50 ≤140μm; D 90 It has a particle size distribution of ≤280 μm.

[0064] Malate granules child The product preferably contains at least 80% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight of a cocrystal of malic acid and alkali metal hydrogen malate.

[0065] According to a preferred embodiment, the cocrystal of malic acid and alkali metal hydrogen malate is of the formula Na + (C4H5O5) - • Sodium trihydrogen dimalate represented by C4H6O5 or formula 2[K] + (C4H5O5) - It is dipotassium trimalate represented by ]·C4H6O5. Most preferably, the cocrystal is of the formula Na + (C4H5O5) - It is sodium trihydrogen dimalate, represented as C4H6O5.

[0066] The confectionery product of the present invention preferably comprises an edible core coated with a hard panning coating, the hard panning coating containing at least 50% by weight of a crystalline sweetener selected from crystalline sugars, crystalline sugar alcohols and combinations thereof, and the hard panning coating further containing at least 0.1% by weight of a cocrystal of malic acid and alkali metal hydrogen malate.

[0067] Preferably, the hard panning coating has an average thickness of 0.1 to 5 mm, more preferably 0.2 to 3 mm, and most preferably 0.3 to 2.5 mm.

[0068] The hard panning coating of the present invention typically contains 10 to 300 coating layers, more preferably 20 to 100 coating layers, and most preferably 30 to 60 coating layers.

[0069] Preferably, the panning coating contains at least 70% by weight, more preferably at least 80% by weight, and most preferably at least 90% by weight of a crystallized sweetener.

[0070] The one or more sugars to be attached as crystalline sugars in the hard panning coating are preferably selected from sucrose, glucose, fructose, galactose, and combinations thereof. Most preferably, the sugars are selected from sucrose, glucose, fructose, and combinations thereof.

[0071] The one or more sugar alcohols to be attached as crystallized sugar alcohols are preferably selected from sorbitol, maltitol, xylitol, isomalt, lactitol, mannitol, and combinations thereof. Most preferably, the sugar alcohols are selected from xylitol, mannitol, isomalt, and combinations thereof.

[0072] In a particularly preferred embodiment, the crystallized sweetener is selected from sucrose, glucose, fructose, and combinations thereof.

[0073] Another aspect of the present invention is a process for preparing hard-panned confectionery, The steps include preparing a cohesive edible core, The steps include applying at least one syrup coating layer to the edible core, wherein the syrup comprises a crystallizable sweetener selected from crystallizable sugars, crystallizable sugar alcohols, and combinations thereof, Malate granules containing at least 70% by weight of a cocrystal of malic acid and alkali metal hydrogen malate. child The process includes the step of applying at least one other coating layer, which includes the above.

[0074] The cohesive edible core typically has a weight in the range of 0.2 to 400 g, more preferably 0.3 to 250 g.

[0075] The syrup used preferably contains 60-80% by weight of crystalline sweetener, more preferably 65-78% by weight of crystalline sweetener.

[0076] The water content of the syrup is preferably in the range of 20 to 40% by weight, more preferably 22 to 35% by weight.

[0077] The sweetener and water together preferably constitute 80-100% by weight, more preferably 90-100% by weight, of the syrup.

[0078] The crystallizable sugars are preferably selected from sucrose, glucose, fructose, galactose, and combinations thereof. Most preferably, the crystallizable sugars are selected from sucrose, glucose, fructose, and combinations thereof.

[0079] The crystallizable sugar alcohol is preferably selected from sorbitol, maltitol, xylitol, isomalt, lactitol, mannitol, and combinations thereof. Most preferably, the sugar alcohol is selected from xylitol, mannitol, isomalt, and combinations thereof.

[0080] In a particularly preferred embodiment, the crystallizable sweetener is selected from sucrose, glucose, fructose, and combinations thereof.

[0081] In a particularly preferred embodiment, malate granules are used in the process of preparing hard-panned confectionery. child It adheres in the form of the particulate composition defined above.

[0082] Malate granules child The moisture content is usually not more than 5% by weight, and more preferably not more than 3% by weight.

[0083] In a preferred embodiment, malate granules child It contains at least 80% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight of a cocrystal of malic acid and alkali metal hydrogen malate.

[0084] Malate granules child The cocrystal of malic acid and alkali metal hydrogen malate is preferably a cocrystal of malic acid and sodium hydrogen malate, or a cocrystal of malic acid and potassium hydrogen malate. More preferably, the cocrystal is sodium trihydrogen dimalate (Na + (C4H5O5) - • C4H6O5) or dipotassium trimalate (2[K) + (C4H5O5) - ]·C4H6O5). Most preferably, the cocrystal used in accordance with the present invention is sodium trihydrogen dimalate (Na + (C4H5O5) - It is C4H6O5.

[0085] The present invention is further illustrated by the following non-limiting embodiments.

[0086] [Examples] Example 1 Cocrystal of sodium bicarbonate and malic acid (Na + (C4H5O5) - The powder containing C4H6O5 (hereinafter referred to as crystalline MASHM) was prepared using a laboratory-scale batch-type fluidized bed granulator.

[0087] First, MASHM seed crystals were prepared by crystallizing an aqueous solution containing equimolar amounts of sodium bitamate and malic acid, and then grinding it to a mass-weighted average diameter of approximately 200 μm. Three different seed crystal compositions were prepared. One seed crystal composition consisted of MASHM crystals (Composition 1). MASHM crystals were then processed into malic acid granules. child Two seed crystal compositions (compositions 2 and 3) were prepared by mixing them in the ratios shown in Table 1.

[0088] Furthermore, a spray aqueous solution containing 1,304 mM C4H5NaO5 and 1,304 mM C4H6O5 was prepared.

[0089] [Table 1]

[0090] Next, seed crystals were packed into a granulator to create a fluidized bed of seed crystals, which was then heated to 55°C. When the desired bed temperature was reached, spraying of the sprayed aqueous solution was started. During spraying, the bed temperature was maintained at 55°C. The total amount of sprayed aqueous solution sprayed onto the seed crystal bed was 3.18 mL / g for seed crystal composition 1 and 4.46 mL / g for seed crystal compositions 2 and 3.

[0091] After the spraying was completed, the powder was released from the granulator. The mass-weighted average diameter of the powder was approximately 300 μm.

[0092] Another powder was prepared by dry blending MASHM powder and malic acid powder in a weight ratio of 85:15 (Powder 4).

[0093] The four powders prepared in this manner, and commercially available malic acid powder (Purelac® Powder MA - malic acid granules coated with sodium bicarbonate) child Table 2 shows the control composition consisting of ).

[0094] [Table 2]

[0095] The MASHM content of the samples was determined by DSC analysis. DSC analysis shows endothermic and exothermic phase transitions during heating of the samples. Melting peaks for MASHM and malic acid are known. The area under the peak correlates with the amount of substance and is compared with the area under the melting peak of a pure MASHM sample (confirmed by X-ray analysis). The composition is then confirmed by mass balance or Na and K content analysis. In this way, it was confirmed that powders 1, 2, 3, and 4 had completely crystallized into MASHM.

[0096] The hygroscopic properties of these five powders were measured at 30°C and 75% relative humidity. The results are shown in Table 3.

[0097] [Table 3]

[0098] The results for powder 1 are consistent with the results of the dynamic vapor adsorption test of the substance, showing that there was almost no change in the mass of the product after adsorption at humidity levels of 0-90%, indicating that the substance is non-hygroscopic.

[0099] Example 2 A 100 ml jacketed glass container was filled with 51.36 g (0.383 mol) of DL-malic acid and 30.17 g of demineralized water. The container was connected to a circulating thermostat and heated to 55°C while stirring with a magnetic stirrer until the malic acid crystals were completely dissolved. Next, 50% potassium hydroxide (9.37 g, 0.083 mol) was added. The temperature was raised to 67°C to obtain a clear yellow solution. The solution was cooled to room temperature while stirring.

[0100] To obtain seed crystals, a small amount of liquid was transferred to an open aluminum cup and concentrated at ambient temperature by the slow evaporation of water. After two weeks, all the water present had evaporated, and a crystalline product had formed.

[0101] A small piece of this crystalline material was used as a seed crystal in the remaining liquid (currently in the glass bottle). After a weekend, a slightly cloudy solution containing small crystals had formed.

[0102] Crystal analysis revealed that these crystals consist of bis(DL-potassium bituminate) malic acid.

[0103] Example 3 A 100 ml jacketed glass container was filled with 51.26 g (0.382 mol) of DL-malic acid, 15.50 g of demineralized water, and 9.39 g of 50% potassium hydroxide (0.084 mol). The container was connected to a circulating thermostat and heated to 40°C while stirring with a magnetic stirrer to completely dissolve the malic acid. The solution was then slowly cooled. At 30°C, some crystalline slurry obtained from Example 1 was added as seed crystals. Further cooling to 21.5°C did not result in significant crystal formation. After overnight, a viscous slurry containing needle-shaped / rod-shaped crystals was formed.

[0104] After gently stirring for another three days, the slurry was filtered through a 55mm paper filter (200mbar). The filtration time was approximately 5 minutes. No washing was performed.

[0105] The crystal cake (8.38 g) was dried at room temperature under a pressure of less than 10 mbar for 2.5 hours. The dried product (7.49 g) was ground using a mortar and pestle.

[0106] Crystal analysis revealed that these crystals consist of bis(DL-potassium bituminate) malic acid.

[0107] Dynamic vapor adsorption tests of this crystalline substance revealed that it remains stable up to 70% humidity, but begins to absorb moisture at higher humidity levels.

[0108] Example 4 As described in Example 1, crystalline MASHM was produced on a plant scale using a batch-type fluidized bed granulator. The resulting powder was then crushed using a pen mill.

[0109] The pen mill had 480 metal-ribbed pins. The mill itself was cooled with nitrogen. Crystalline MASHM powder was introduced into the mill via a bag discharge station, vacuum transport, and transport screw, and then crushed.

[0110] The mill settings used are shown in Table 4.

[0111] [Table 4]

[0112] The particle size distribution of the fluid crushed powder was as follows: 98% < 150 μm 90% < 100 μm A total of 1140 kg of crushed powder was produced and packed into 20 kg bags inside the box.

[0113] Example 5 As described in Example 1, crystalline MASHM was produced on a plant scale using a batch-type fluidized bed granulator. Approximately 100% by weight of the powder thus obtained had a particle size in the range of 180 μm (determined by sieving). Next, this MASHM powder was crushed using a pin disc grinding unit in a Hosokawa Fine Impact Mill UPZ160.

[0114] Table 5 shows the mill settings used.

[0115] [Table 5]

[0116] The properties of the fluid crushed powder obtained in this way are shown in Table 6.

[0117] [Table 6]

[0118] Furthermore, the crushed powder was passed through three different sized sieves to determine its particle size distribution. The results are shown in Table 7.

[0119] [Table 7]

[0120] Even after being stored for one week at 40°C / 75% relative humidity, the crushed powder was confirmed to remain fluid.

[0121] Example 6 Hard-panned chewing gum was prepared using the crushed MASHM powder from Example 5.

[0122] An enclosed rotating pan system with an inner diameter of 1200 mm was used. 35 kg of chewing gum centers (0.9 g) were placed inside the tulip-shaped rotating pan. The commercially available engrossing syrup contained 68% by weight of a combination of mannitol and xylitol, 28% by weight of water, 3% by weight of gum arabic, and 1% by weight of titanium dioxide. The engrossing syrup was placed in a buffer tank, and the syrup could be fed from the tank to the rotating pan through a nozzle. The syrup was maintained at 75-80°C.

[0123] The chewing gum center was coated by applying 17 "coatings" (each coating containing 1 to 5 coating layers). The process details are shown in Table 8.

[0124] [Table 8]

[0125] The chewing gum obtained in this way was stored for 5 months. The chewing gum was evaluated by a panel one week and five months after preparation. There were no significant changes in the appearance of the product during this 5-month period. After 5 months, the chewing gum was found to have the same level of acidity as it did one week after preparation.

[0126] Example 7 Using the crushed MASHM powder from Example 5, candy was prepared based on the recipe shown in Table 9.

[0127] [Table 9]

[0128] The candy was prepared by mixing the above ingredients and then pressing the resulting mixture into tablets using a FETTE tablet press.

[0129] The hygroscopic properties of the tablets were determined at different temperatures and humidity levels. The results are shown in Table 10.

[0130] [Table 10]

Claims

1. Volume-weighted average diameter D of 20–180 μm ４，３ A particulate composition comprising at least 50% by weight of malate particles, wherein the malate particles comprise at least 70% by weight of a cocrystal of malic acid and alkali metal hydrogen malate.

2. The particulate composition is D １０ ≧1μm; 40μm≦D ５０ ≦200μm; D ９０ ≦320μm (Here, D ｘ The volume percentage of particles with a smaller diameter is equal to x volume percentage, D ｘ The particulate composition according to claim 1, wherein the particle size distribution has a volume percentage of (100 - x) of particles having a larger diameter.

3. The particulate composition according to claim 1 or 2, wherein the malate particles contain at least 80% by weight of the cocrystal.

4. The particulate composition according to claim 1 or 2, wherein the malate particles contain at least 90% by weight of the cocrystal.

5. wherein the cocrystal is sodium hydrogen malate represented by the formula Na ＋ (C ４ H ５ O ５ ) － ・C ４ H ６ O ５ or dipotassium hydrogen malate represented by the formula 2[K ＋ (C ４ H ５ O ５ ) － ・C ４ H ６ O ５ ; the particulate composition according to any one of claims 1 to 4.

6. The aforementioned cocrystal is Na ＋ (C ４ H ５ O ５ ) － ・C ４ H ６ O ５ The particulate composition according to claim 5, wherein the particulate composition is sodium trihydrogen dimalate represented by the formula:

7. A method for preparing pulverized malate powder, The step is to prepare a crude malate powder containing at least 90% by weight of malate particles, the crude malate powder having a volume-weighted average diameter D of at least 100 μm. ４，３ Steps having, The particle size of the crude malate powder is reduced to a volume-weighted average particle size D that is at least 50% smaller than the particle size of the crude malate powder. ４，３ A method comprising the step of preparing a pulverized malate powder having [a certain characteristic].

8. Volume-weighted average diameter D of 20–180 μm ４，３ The method according to claim 7, which provides a pulverized malate powder having the following properties.

9. The crude malate powder mentioned above A step of preparing seed crystal particles containing at least 80% by weight of a crystalline substance selected from crystalline organic acids, crystalline organic salts, and combinations thereof, The steps include: preparing an aqueous malate solution containing sodium and malate ions in a molar ratio of 4:10 to 6:10, or potassium and malate ions in a molar ratio of 5.5:10 to 7.5:10; The steps include spraying the aforementioned malate aqueous solution onto the seed crystal particles to produce coated particles, The method according to claim 7 or 8, which is prepared by the step of removing moisture from the coated particles.

10. Hard panning or soft panning coatings containing 0.1 to 6% by weight of malate particles; Tablet-shaped candy containing at least 0.1 to 50% by weight of malate particles; Chocolate containing at least 0.1 to 30% by weight of malate particles, comprising at least one of these, A confectionery product wherein the malate particles contain at least 70% by weight of a cocrystal of malic acid and alkali metal hydrogen malate.

11. The malate particles have a volume-weighted average diameter D of 20 to 180 μm. ４，３ A confectionery product according to claim 10, having the following characteristics.

12. The confectionery product according to claim 10 or 11, wherein the malate particles contain at least 80% by weight of the cocrystal.

13. The confectionery product according to claim 12, wherein the malate particles contain at least 90% by weight of the cocrystal.

14. The aforementioned cocrystal is Na ＋ (C ４ H ５ O ５ ) － ・C ４ H ６ O ５ Sodium dimalate or 2[K] represented by the formula ＋ (C ４ H ５ O ５ ) － ]・C ４ H ６ O ５ The confectionery product according to any one of claims 10 to 13, wherein the potassium trimalate is represented by the formula:

15. The aforementioned cocrystal is Na ＋ (C ４ H ５ O ５ ) － ・C ４ H ６ O ５ The confectionery product according to claim 14, wherein the sodium dimalate is represented by the formula:

16. The confectionery product according to any one of claims 10 to 15, wherein the confectionery product comprises an edible core coated with a hard panning coating, the hard panning coating contains at least 30% by weight of a crystalline sweetener selected from crystalline sugars, crystalline sugar alcohols and combinations thereof, and the hard panning coating further contains at least 0.1% by weight of a cocrystal of malic acid and alkali metal hydrogen malate.

17. A process for preparing hard-panned pastries, The steps include preparing a cohesive edible core, The step of applying at least one syrup coating layer to the edible core, wherein the syrup comprises a crystallizable sweetener selected from crystallizable sugars, crystallizable sugar alcohols, and combinations thereof. A process comprising the step of applying at least one other coating layer containing malate particles having a cocrystal of malic acid and alkali metal hydrogen malate in an amount of at least 70% by weight.

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