Granular compositions comprising a co-crystal of malic acid and an alkali metal hydrogen malate

Abstract

The present invention relates to a particle composition having a volume weighted average diameter D 4,3 The particle composition is 20-180 μm and comprises at least 50% by weight of malic acid / salt particles, wherein the malic acid / salt particles comprise at least 70% by weight of a eutectic of malic acid and an alkali metal hydrogen malate. The particle composition is advantageously used in or on confectionery products.

Description

Technical Field

[0001] The present invention relates to a granular composition comprising malic acid / salt particles comprising at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate. The present invention also provides a method for preparing such a granular composition.

[0002] The particulate composition of the present invention can be advantageously applied in or on confectionery products, in particular in hard and soft panned coatings, compressed confectionery and chocolates. Background Art

[0003] Malic acid (2-hydroxysuccinic acid) is the predominant acid in many fruits, including apricots, blackberries, blueberries, cherries, grapes, mirabelles, peaches, pears, plums, and quinces, and is present in lower concentrations in other fruits such as citrus. It also adds tartness to green (unripe) apples. The flavor of malic acid in rhubarb is very clear and pure, and malic acid is the primary flavoring substance in this plant. Malic acid is used as a food additive in non-carbonated beverages, wine, candy, chewing gum, desserts, and baked goods.

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

[0005] Hard and soft tumbling are made in similar ways, but with different ingredients and at different speeds. Hard tumbling is a process in which a thin coating of a sugar or sugar alcohol solution is applied to each tumbling core, followed by evaporation of the water, causing the sugar or sugar alcohol to crystallize into a thin layer. The process is repeated until the desired thickness of hard coating is achieved. Any material that does not deform under its own weight and can tumble freely (without flat surfaces that could stick together) is a candidate for hard tumbling. Soft tumbling uses a syrup that does not crystallize, such as glucose. To aid drying, powdered sugar or granulated sugar is added during tumbling.

[0006] WO 2019 / 063623 describes a granular acidulant composition comprising 20-70 wt. % malic acid, 3-40 wt. % lactic acid and 0-40 wt. % of a food acid selected from citric acid, fumaric acid, adipic acid, tartaric acid and acetic acid, and combinations thereof, wherein the acidulant composition comprises:

[0007] 40-90 wt% M-granules comprising co-crystals of malic acid and a partially neutralized polycarboxylic acid selected from the group consisting of malic acid, citric acid, fumaric acid, adipic acid, tartaric acid, and combinations thereof, the M-granules containing at least 30 wt% malic acid and at least 30 wt% of the partially neutralized polycarboxylic acid;

[0008] 5-60 wt% L-granules comprising co-crystals of lactic acid and an at least partially neutralized carboxylic acid selected from the group consisting of lactic acid, malic acid, citric acid, fumaric acid, adipic acid, tartaric acid, and combinations thereof, the L-granules containing at least 30 wt% lactic acid and at least 30 wt% of the at least partially neutralized carboxylic acid; and

[0009] wherein the combination of the M-particles and the L-particles constitutes at least 50% by weight of the acidulant composition.

[0010] The examples of the aforementioned international patent application describe a powder blend comprising 80 wt. % PURAC Powder MA (42-50 wt. % sodium hydrogen malate and 50-58 wt. % malic acid), which is prepared in a fluidized bed dryer by spraying a partially neutralized aqueous solution of malic acid onto a bed of malic acid particles. PURAC Powder MA typically contains 40-50 wt. % of a eutectic of malic acid and sodium hydrogen malate.

[0011] WO 2020 / 260194 describes a granular composition comprising at least 1 wt% of malic acid / salt particles having a diameter of 50-1000 μm and comprising at least 70 wt% of a eutectic of malic acid and an alkali metal hydrogen malate.

[0012] Van Havere et al. (Crystal structure of bis(potassium hydrogen L-malate)·malic acid,2[K + (C4H5O5)-]·C4H6O5, Journal of Crystallogrhic and Spectroscopic Research (1985), 15(1), 45-52) describes the crystal structure of bis(potassium hydrogen L-malate)·malic acid.

[0013] Fleck et al. (Dielectric and Pyroelectric Properties of Lithium Hydrogen Dimalate, LiH3(C4H4O5)2. Z. Naturforsch. 41a, 1289-1296 (1986); received July 5, 1986) describe how to prepare LiH3(C4H4O5)2 from an aqueous solution containing stoichiometric amounts of LiOH and malic acid (1:2). Large single crystals (15 x 8 x 6 mm) can be grown by slowly evaporating H2O from an aqueous solution at 290 K. Summary of the Invention

[0014] The present inventors have developed a malic acid / salt powder which is suitable for use in and on confectionery products to impart an acidic flavour. The malic acid / salt powder comprises particles comprising at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate.

[0015] Therefore, a first aspect of the present invention relates to a particle composition having a volume weighted average diameter D 4,3 The invention relates to a eutectic of malic acid and an alkali metal hydrogen malate, wherein the eutectic is 20-180 μm and comprises at least 50% by weight of malic acid / salt particles, wherein the malic acid / salt particles comprise at least 70% by weight of a eutectic of malic acid and an alkali metal hydrogen malate. Examples of such eutectics include sodium hydrogen malate·malic acid (Na + (C4H5O5)-·C4H6O5), bis(potassium hydrogen L-malate)·malic acid, dipotassium tetrahydrogen trimalate (2[K + (C4H5O5) - ]·C4H6O5).

[0016] The granular composition of the present invention is advantageously applied to or on a confectionery product in a manner such that the malic acid / salt particles remain substantially intact. While the inventors do not wish to be bound by theory, it is believed that when the malic acid / salt particles come into contact with saliva, the eutectic of malic acid and alkali metal hydrogen malate immediately dissociates into malate. 2- or hydrogen malate-, Na + / K + and H + Thus, upon consumption of a confectionery product containing the malic acid / salt particles of the present invention, the smooth sour taste of the malic acid is immediately released.

[0017] The malic acid / salt powder of the present invention offers the advantage that it remains free-flowing even at high temperatures and high humidity and that the composition of the malic acid / salt particles does not vary with particle size. Thus, the malic acid / salt powder can be provided in the form of a fine powder by grinding the crude malic acid / salt powder to the desired particle size.

[0018] A second aspect of the present invention relates to a method for preparing powdered malic acid / salt powder, the method comprising:

[0019] Providing a crude malic acid / salt powder comprising at least 90% by weight malic acid / salt particles, wherein the malic acid / salt particles comprise at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate, wherein the crude malic acid / salt powder has a volume weighted average diameter D 4,3 is at least 100 μm; and

[0020] Reducing the particle size of the crude malic acid / salt powder to produce a powdered malic acid / salt powder having a volume weighted average diameter D 4,3 Than the volume weighted average diameter D of the crude malic acid / salt powder 4,3 At least 50% smaller.

[0021] A third aspect of the present invention relates to a confectionery product comprising at least one of the following:

[0022] A hard roll-on or soft roll-on coating containing 0.1-6% by weight of malic acid / salt granules;

[0023] A compressed confectionery containing at least 0.1-50% by weight of malic acid / salt particles; and

[0024] Chocolate containing at least 0.1-30% by weight of malic acid / salt particles;

[0025] The malic acid / salt particles contain at least 70% by weight of a eutectic of malic acid and an alkali metal hydrogen malate.

[0026] A fourth aspect of the present invention relates to a method for preparing a hard-rolled candy, the method comprising:

[0027] Provides a cohesive edible core;

[0028] applying at least one coating layer of a syrup comprising a crystallizable sweetener selected from the group consisting of crystallizable sugars, crystallizable sugar alcohols, and combinations thereof to the edible core; and

[0029] • Applying at least one coating layer comprising malic acid / salt particles containing at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate. DETAILED DESCRIPTION

[0030] In a first aspect, the present invention relates to a particle composition having a volume weighted average diameter D of 20-180 μm. 4,3 and comprises at least 50% by weight of malic acid / salt particles comprising at least 70% by weight of a eutectic of malic acid and an alkali metal hydrogen malate.

[0031] As used herein, the term "malate" refers to malic acid, malate salts, and combinations thereof.

[0032] As used herein, the term "co-crystal" refers to a crystalline single-phase material comprising two or more different molecular or ionic compounds in a stoichiometric ratio, which is neither a solvate nor a simple salt.

[0033] As used herein, the term "sugar" refers to sweet monosaccharides and disaccharides.

[0034] As used herein, the term "sugar alcohol" refers to a sweet tasting polyol that is not a sugar and contains 6 to 12 carbon atoms.

[0035] As used herein, the term "syrup" refers to a viscous liquid consisting primarily of a solution of sugars and / or sugar alcohols in water.

[0036] The term "crystallizable" as used herein with respect to a sugar or a sugar alcohol refers to the ability of the sugar or sugar alcohol to exist in a crystalline state at 20°C and normal temperature.

[0037] The term "crystalline" or "crystalline" refers to a material that is in a crystalline state at 20°C and atmospheric pressure.

[0038] The particle size distribution mentioned here can suitably be determined by laser diffraction (Malvern).

[0039] Confirmed to be sodium dihydrogen dimalate (Na + (C4H5O5) - The X-ray diffraction pattern of the eutectic of malic acid and sodium hydrogen malate in C4H6O5) is as follows Figure 1 shown.

[0040] The granular composition of the present invention is particularly suitable for application in or on confectionery products because of its stability, the instantaneous smooth sour taste provided by the malic acid / salt particles and because it can be provided in the form of a very fine powder (relevant for example for hard coating).

[0041] The volume weighted average diameter D of the particle composition 4,3 It is preferably 40-170 μm, and most preferably 80-160 μm.

[0042] Preferably, the volume weighted average diameter D of the malic acid / salt particles in the granular composition is 4,3 It is 20-180 μm, more preferably 40-170 μm, and most preferably 80-160 μm.

[0043] According to a preferred embodiment, the granular composition has the following particle size distribution:

[0044] ·D10 ≥1μm;

[0045] 40μm≤D 50 ≤200μm;

[0046] ·D 90 ≤320μm;

[0047] The diameter is smaller than D x The volume % of particles is equal to x volume % and wherein the diameter is greater than D x The volume % of particles is equal to (100-x) volume %. Even more preferably, the particle composition has the following particle size distribution:

[0048] ·D 10 ≥5μm;

[0049] 60μm≤D 50 ≤140μm;

[0050] ·D 90 ≤280μm.

[0051] The span of the particles in the granular composition (D 90 -D 10 ) / D 50 Preferably, the dispersion is not more than 3.5, and more preferably, the dispersion is not more than 3.0.

[0052] The malic acid / salt particles in the granular composition preferably contain at least 80 wt%, more preferably at least 90 wt% and most preferably at least 95 wt% of the eutectic of malic acid and alkali metal hydrogen malate.

[0053] In addition to the malic acid / salt granules, the granular composition of the present invention may comprise other granular components such as sugar, salt or acid powder.

[0054] In a preferred embodiment of the present invention, the malic acid / salt particles represent the bulk of the granular composition. Thus, the granular composition preferably comprises at least 70 wt%, more preferably at least 80 wt%, most preferably at least 90 wt% malic acid / salt particles.

[0055] The granular composition will typically contain no more than 5% water by weight, more preferably no more than 3% water by weight.

[0056] According to a particularly preferred embodiment, the eutectic of malic acid and an alkali metal hydrogen malate is a eutectic of malic acid and sodium hydrogen malate or a eutectic of malic acid and potassium hydrogen malate. Even more preferably, the eutectic is sodium dihydrogen malate (Na + (C4H5O5) - C4H6O5) or dipotassium tetrahydrogen trimalate (2[K +(C4H5O5) - ]·C4H6O5). Most preferably, the eutectic used according to the present invention is sodium dihydrogen dimalate (Na + (C4H5O5) - ·C4H6O5).

[0057] Yet another aspect of the present invention relates to a method for preparing powdered malic acid / salt powder, the method comprising:

[0058] Providing a crude malic acid / salt powder comprising at least 90% by weight malic acid / salt particles, wherein the malic acid / salt particles comprise at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate, wherein the crude malic acid / salt powder has a volume weighted average diameter D 4,3 is at least 100 μm;

[0059] Reducing the particle size of the crude malic acid / salt powder to produce a powdered malic acid / salt powder having a volume weighted average diameter D 4,3 Than the volume weighted average diameter D of the crude malic acid / salt powder 4,3 At least 50% smaller.

[0060] Preferably, the volume weighted average diameter D of the malic acid / salt particles in the crude malic acid / salt powder is 4,3 It is at least 200 μm, most preferably 250-600 μm.

[0061] The malic acid / salt particles of the crude malic acid / salt powder preferably contain at least 80 wt%, more preferably at least 90 wt% and most preferably at least 95 wt% eutectic of malic acid and alkali metal hydrogen malate.

[0062] The water content of the malic acid / salt particles in the crude malic acid / salt powder is preferably not more than 5% by weight, more preferably not more than 3% by weight.

[0063] According to a particularly preferred embodiment, the eutectic of malic acid and alkali metal hydrogen malate in the crude malic acid / salt powder is a eutectic of malic acid and sodium hydrogen malate or a eutectic of malic acid and potassium hydrogen malate. Even more preferably, the eutectic is sodium dihydrogen malate (Na + (C4H5O5) - C4H6O5) or dipotassium tetrahydrogen trimalate (2[K + (C4H5O5) - ]·C4H6O5). Most preferably, the eutectic used according to the present invention is sodium dihydrogen dimalate (Na + (C4H5O5) - ·C4H6O5).

[0064] Preferably, the volume weighted average diameter D of the powdered malic acid / salt produced by the method of the present invention is 4,3 The diameter is 20-180 μm, more preferably 40-170 μm, and most preferably 70-160 μm.

[0065] According to another preferred embodiment, the powdered malic acid / salt powder produced by the method has the following particle size distribution:

[0066] ·D 10 ≥1μm;

[0067] 40μm≤D 50 ≤200μm;

[0068] ·D 90 ≤300μm;

[0069] The diameter is smaller than D x The volume % of particles is equal to x volume % and wherein the diameter is greater than D x The volume % of particles is equal to (100-x) volume %.

[0070] In one embodiment of the process of the present invention, the crude malic acid / salt powder is prepared as follows:

[0071] providing seed particles comprising at least 80% by weight of a crystalline material selected from the group consisting of a crystalline organic acid, a crystalline organic acid salt, and combinations thereof;

[0072] providing a malic acid / brine solution containing sodium and malate in a molar ratio of 4:10 to 6:10, or potassium and malate in a molar ratio of 5.5:10 to 7.5:10;

[0073] Spraying the malic acid / saline solution onto the seed granules to prepare coated granules;

[0074] • Removal of water from the coated granules.

[0075] The crystalline material in the seed particles is preferably selected from the group consisting of crystalline organic acids, crystalline organic acid salts, and combinations thereof, wherein the organic acid is selected from the group consisting of malic acid, lactic acid, acetic acid, citric acid, fumaric acid, adipic acid, tartaric acid, and combinations thereof. More preferably, the crystalline material is selected from the group consisting of crystalline malic acid, crystalline malic acid salts, and combinations thereof. Even more preferably, the crystalline material is a eutectic of malic acid and sodium hydrogen malate (Na + (C4H5O5) - C4H6O5) or the eutectic of malic acid and potassium hydrogen malate (2[K + (C4H5O5) - ]·C4H6O5). Most preferably, the crystalline material is a eutectic of malic acid and sodium hydrogen malate (Na+ (C4H5O5) - ·C4H6O5).

[0076] The malic acid / salt water solution sprayed onto the particles preferably contains malic acid / salt in a concentration of at least 1 mol / L, more preferably at least 1.5 mol / L, most preferably 2-5 mol / L.

[0077] The malic acid / brine solution preferably has a dry matter content of 20-70 wt.-%, more preferably 25-65 wt.-% and most preferably 30-60 wt.-%.

[0078] The malic acid / brine solution is preferably prepared from malic acid by dissolving the malic acid in water and adding a neutralizing agent thereto. More preferably, a fully neutralized sodium malate solution is prepared by dissolving the malic acid in water and adding a neutralizing agent thereto, and mixing this with the aqueous solution of malic acid such that the desired ratio of sodium to malate or potassium to malate is achieved.

[0079] The amount of seed particles used in the process of the present invention is preferably 3-70 wt%, more preferably 5-60 wt%, even more preferably 9-50 wt% of the coated particles obtained after removal of water.

[0080] The malic acid / brine solution is preferably sprayed onto the fluidized bed of seed particles. The bed temperature of the fluidized bed is preferably in the range of 40-100°C, more preferably in the range of 42-90°C, even more preferably in the range of 44-80°C, and most preferably in the range of 45-70°C.

[0081] Besides water, malate and sodium or potassium cations, the malic acid / brine solution preferably contains no other components in a concentration greater than 0.1% by weight.

[0082] The malic acid / brine solution can be prepared by dissolving malic acid and sodium hydrogen malate or potassium hydrogen malate in water. Alternatively, the malic acid / brine solution can be prepared by dissolving malic acid and sodium hydroxide or potassium hydroxide in water. Another alternative method is to prepare the malic acid aqueous solution by dissolving malic acid and disodium malate or dipotassium malate.

[0083] According to a particularly preferred embodiment of the process, spraying the malic acid / saline solution and removing the water from the coated granules are carried out simultaneously.

[0084] In a preferred embodiment of the process, spraying and water removal are carried out in a fluidized bed dryer. In another preferred embodiment, spraying and water removal are carried out in a co-current spray dryer with fines recycled to the nozzle (to serve as seeds).

[0085] In an alternative embodiment of the present invention, the crude malic acid / salt powder is prepared as follows:

[0086] Providing malic acid particles comprising at least 80% by weight malic acid;

[0087] providing sodium hydrogen malate particles containing at least 80% by weight sodium hydrogen malate or potassium hydrogen malate particles containing at least 80% by weight potassium hydrogen malate;

[0088] Combine 100 parts by weight of malic acid granules with 100-138 parts by weight of sodium hydrogen malate granules or 200-300 parts by weight of potassium hydrogen malate, and 1-10 parts by weight of water;

[0089] The resulting combination is mechanically sheared.

[0090] Another aspect of the present invention relates to a confectionery product comprising at least one of the following:

[0091] Hard or soft roll-on coating of granules containing 0.1-6% by weight of malic acid / salt;

[0092] Compressed confectionery containing at least 0.1-50% by weight of malic acid / salt particles;

[0093] Chocolate containing at least 0.1-30% by weight of malic acid / salt particles;

[0094] The malic acid / salt particles contain at least 70% by weight of a eutectic of malic acid and an alkali metal hydrogen malate.

[0095] The weight of the confectionery product of the present invention is preferably in the range of 0.2-500 g, more preferably in the range of 0.4-400 g, most preferably in the range of 0.5-350 g.

[0096] The hard roll coating or soft roll coating of the confectionery product preferably contains 0.5-5.0 wt. %, more preferably 1.0-4.5 wt. % and most preferably 2.0-4.0 wt. % of the malic acid / salt particles.

[0097] The compressed confectionery of the confectionery product preferably contains 0.2-45 wt. %, more preferably 0.5-40 wt. % and most preferably 1.0-30 wt. % of the malic acid / salt particles.

[0098] The chocolate component of the confectionery product preferably contains 0.2-25 wt%, more preferably 0.5-20 wt% and most preferably 1.0-15 wt% of malic acid / salt particles.

[0099] Volume weighted mean diameter D of malic acid / salt particles contained in coated, compressed candies or chocolate 4,3More preferably, the volume weighted average diameter D of these malic acid / salt particles is 20-180 μm. 4,3 The maximum particle size is 50-170 μm, and the most preferred particle size is 80-160 μm.

[0100] According to a preferred embodiment, the malic acid / salt particles have the following particle size distribution:

[0101] ·D 10 ≥1μm;

[0102] 40μm≤D 50 ≤200μm;

[0103] ·D 90 ≤320μm;

[0104] The diameter is smaller than D x The volume % of particles is equal to x volume % and wherein the diameter is greater than D x The volume % of particles of is equal to (100-x) volume %. Even more preferably, the malic acid / salt particles have the following particle size distribution:

[0105] ·D 10 ≥5μm;

[0106] 60μm≤D 50 ≤140μm;

[0107] ·D 90 ≤280μm.

[0108] The malic acid / salt particles preferably contain at least 80 wt %, more preferably at least 90 wt % and most preferably at least 95 wt % eutectic of malic acid and alkali metal hydrogen malate.

[0109] According to a preferred embodiment, the eutectic of malic acid and alkali metal hydrogen malate is of the formula Na + (C4H5O5) - · Sodium dihydrogen dimalate represented by C4H6O5 or formula 2[K + (C4H5O5) - ]· Potassium tetrahydrogen trimalate represented by C4H6O5. Most preferably, the eutectic is of formula Na + (C4H5O5) - Sodium dihydrogen dimalate represented by C4H6O5.

[0110] The confectionery product of the present invention preferably comprises an edible core coated with a hard-rolled coating comprising at least 50% by weight of a crystalline sweetener selected from the group consisting of crystalline sugars, crystalline sugar alcohols, and combinations thereof, the hard-rolled coating further comprising at least 0.1% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate.

[0111] Preferably, the average thickness of the hard roll coating is 0.1-5 mm, more preferably 0.2-3 mm and most preferably 0.3-2.5 mm.

[0112] The hard roll-on coating of the present invention typically contains 10-300 coating layers, more preferably 20-100 coating layers and most preferably 30-60 coating layers.

[0113] Preferably, the roll-on coating contains at least 70 wt%, more preferably at least 80 wt% and most preferably at least 90 wt% crystalline sweetener.

[0114] The one or more sugars used as crystalline sugars in the hard roll-on 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.

[0115] The one or more sugar alcohols used as crystalline sugar alcohols are 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.

[0116] According to a particularly preferred embodiment, the crystalline sweetener is selected from sucrose, glucose, fructose and combinations thereof.

[0117] Another aspect of the present invention relates to a method for preparing a hard-rolled candy, the method comprising:

[0118] Provides a cohesive edible core;

[0119] applying at least one coating layer of a syrup comprising a crystallizable sweetener selected from the group consisting of crystallizable sugars, crystallizable sugar alcohols, and combinations thereof to the edible core; and

[0120] - Applying at least one further coating layer comprising malic acid / salt particles containing at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate.

[0121] The weight of the cohesive edible core is typically in the range 0.2-400g, more preferably 0.3-250g.

[0122] The syrup used preferably contains 60-80% by weight of crystallizable sweetener, more preferably 65-78% by weight of crystallizable sweetener.

[0123] The water content of the syrup is preferably in the range of 20-40 wt%, more preferably in the range of 22-35 wt%.

[0124] The sweetener and water together preferably constitute 80-100% by weight, more preferably 90-100% by weight of the syrup.

[0125] The crystallizable sugar is preferably selected from sucrose, glucose, fructose, galactose and combinations thereof.Most preferably, the crystallizable sugar is selected from sucrose, glucose, fructose and combinations thereof.

[0126] 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.

[0127] According to a particularly preferred embodiment, the crystallizable sweetener is selected from sucrose, glucose, fructose and combinations thereof.

[0128] According to a particularly preferred embodiment, the malic acid / salt particles used in the process for preparing hard-rolled confectionery are applied in the form of a granular composition as defined herein before.

[0129] The malic acid / salt particles generally have a water content of no more than 5% by weight, more preferably a water content of no more than 3% by weight.

[0130] In a preferred embodiment, the malic acid / salt particles contain at least 80 wt %, more preferably at least 90 wt %, and most preferably at least 95 wt % of the eutectic of malic acid and alkali metal hydrogen malate.

[0131] The eutectic of malic acid and alkali metal hydrogen malate in the malic acid / salt particles is preferably a eutectic of malic acid and sodium hydrogen malate or a eutectic of malic acid and potassium hydrogen malate. Even more preferably, the eutectic is sodium dihydrogen malate (Na + (C4H5O5)-·C4H6O5) or dipotassium tetrahydrogen trimalate (2[K + (C4H5O5) - ]·C4H6O5). Most preferably, the eutectic used according to the present invention is sodium dihydrogen dimalate (Na + (C4H5O5)-·C4H6O5).

[0132] The present invention is further illustrated by the following non-limiting examples.

[0133] Example

[0134] Example 1

[0135] Cocrystals containing sodium hydrogen malate and malic acid (Na + (C4H5O5)-·C4H6O5) powder, hereinafter referred to as crystalline MASHM.

[0136] First, MASHM seed crystals were prepared by crystallization from an aqueous solution containing equimolar amounts of sodium hydrogen malate and malic acid, followed by grinding to a mass-weighted mean diameter of approximately 200 μm. Three different seed crystal compositions were prepared. One seed crystal composition consisted of MASHM crystals (Composition 1). Two seed crystal compositions (Compositions 2 and 3) were prepared by mixing MASHM crystals with malic acid particles in the ratios shown in Table 1.

[0137] Separately, a spray aqueous solution containing 1304 mM C4H5NaO5 and 1304 mM C4H6O5 was prepared.

[0138] Table 1

[0139]

[0140] Next, seed crystals were loaded into the granulator to create a fluidized bed of seed crystals, which was heated to 55°C. When the desired bed temperature was reached, spraying of the aqueous solution began. The bed temperature was maintained at 55°C during spraying. The total amount of the 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.

[0141] After the spraying is completed, the powder is discharged from the granulator. The mass-weighted average diameter of the powder is about 300 μm.

[0142] Another powder was prepared by dry mixing MASHM powder and malic acid powder in a weight ratio of 85:15 (Powder 4).

[0143] The compositions of the four powders thus prepared and of a reference consisting of commercial malic acid powder (P The composition of Powder MA (malic acid granules coated with sodium hydrogen malate) is shown in Table 2.

[0144] Table 2

[0145]

[0146] The MASHM content of the samples was determined by DSC analysis. DSC analysis revealed endothermic and exothermic phase transitions when the samples were heated. The melting peaks of MASHM and malic acid are known. The area under the peak is related to the amount of material and is compared to the area under the melting peak of a pure MASHM sample (confirmed by X-ray analysis). The composition was then confirmed by mass balance or Na and K content analysis. This confirmed that powders 1, 2, 3, and 4 were completely crystallized into MASHM.

[0147] The hygroscopicity of these five powders was measured at 30°C and 75% relative humidity. The results are shown in Table 3.

[0148] Table 3

[0149] Water absorption after 14 days (wt%) Powder 1 0.0 Powder 2 6.8 Powder 3 11.5 Powder 4 10.6 Reference 14.1

[0150] The results for Powder 1 are consistent with the dynamic vapor sorption test results for this material, showing that there is hardly any change in the product quality after the sorption test at 0-90% humidity, which indicates that this material is non-hygroscopic.

[0151] Example 2

[0152] 51.36 g (0.383 mol) of DL-malic acid and 30.17 g of demineralized water were placed in a 100 ml jacketed glass container. The container was connected to a circulating thermostatic bath 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 allowed to cool to room temperature while stirring.

[0153] To obtain seed crystals, a small amount of the liquid was transferred to an open aluminum cup and concentrated by allowing the water to evaporate slowly at ambient temperature. After two weeks, all the water present evaporated and a crystalline product was formed.

[0154] A small piece of this crystalline material was used as a seed for the rest of the liquid (now in the glass bottle).After a weekend, a slightly cloudy solution containing small crystals had formed.

[0155] Analysis of the crystals revealed that they were composed of bis(DL-potassium hydrogenmalate)·malic acid.

[0156] Example 3

[0157] 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) were placed in a jacketed 100 ml glass container. The container was connected to a circulating thermostatic bath and heated to 40°C while stirring with a magnetic stirrer until the malic acid was completely dissolved. Next, the solution was slowly cooled. At 30°C, some of the slurry obtained in Example 1 was added as seed crystals. Further cooling to 21.5°C did not result in significant crystal formation. After one night, a viscous slurry containing needle-shaped / rod-shaped crystals had formed.

[0158] After stirring slowly for another 3 days, the slurry was filtered on 55 mm filter paper (200 mbar). The filtration time was about 5 minutes. No washing was performed.

[0159] The cake (8.38 g) was dried at room temperature and a pressure of less than 10 mbar for 2.5 hours. The dried product (7.49 g) was ground in a mortar and pestle.

[0160] Crystal analysis showed that they were composed of bis(DL-potassium hydrogenmalate)·malic acid.

[0161] Dynamic vapor sorption testing of the crystalline material showed that it was stable up to 70% humidity but began to absorb moisture at higher humidities.

[0162] Example 4

[0163] Crystalline MASHM was prepared on a plant scale using a batch fluidized bed granulator as described in Example 1. Next, the powder thus obtained was ground in a pen mill.

[0164] The pen mill has 480 pins with metal ribs. The mill itself is cooled with nitrogen. Crystalline MASHM powder is introduced into the mill and ground via a bag unloading station, a vacuum conveyor, and a conveying screw.

[0165] The mill settings used are shown in Table 4.

[0166] Table 4

[0167] Rotation speed 3,000rpm Nitrogen addition 30％ Yield 500kg / hour

[0168] The particle size distribution of the free-flowing ground powder is as follows:

[0169] 98% <150μm

[0170] 90% <100 μm

[0171] A total of 1140 kg of ground powder was prepared and packaged in 20 kg bags in boxes.

[0172] Example 5

[0173] Crystalline MASHM was prepared on a plant scale using a batch fluidized bed granulator as described in Example 1. Almost 100% by weight of the powder thus obtained had a particle size in the range of 180 to μm (determined by sieving). Next, the MASHM powder was ground in a Hosokawa UPZ 160 fine impact mill using a pin-on-disc milling apparatus.

[0174] The mill settings used are shown in Table 5.

[0175] Table 5

[0176] Rotation speed 3,000rpm frequency 100％ Yield 30kg / hour

[0177] The characteristics of the free-flowing ground powder thus obtained are shown in Table 6.

[0178] Table 6

[0179] Aerated density (g / mL) 0.787 Tap density (g / mL) 1.033 <![CDATA[D 10 (μm) 1 ]]> 13 <![CDATA[D 50 (μm)1]]> 86 <![CDATA[D 90 (μm) 1 ]]> 263 <![CDATA[D 3,2 (μm) 1 ]]> 19 <![CDATA[D 4,3 (μm) 1 ]]> 137 Dynamic vapor adsorption 20℃ / 90% relative humidity ≤2% moisture absorption Differential Scanning Calorimetry <![CDATA[T 熔融 :158 / 160℃]]>

[0180] 1 Malvern Mastersizer 3000 0.5 bar

[0181] The ground powder was also sieved through 3 size sieves to determine the particle size distribution. The results are shown in Table 7.

[0182] Table 7

[0183] weight% >710μm 0.06 180-710μm 10.44 106-180μm 26.37 <106μm 63.13

[0184] After storage for 1 week at 40°C / 75% relative humidity, the ground powder was found to still be free-flowing.

[0185] Example 6

[0186] The ground MASHM powder of Example 5 was used to prepare hard rolled chewing gum.

[0187] A closed rotating disk system with an inner diameter of 1200 mm was used. 35 kg of chewing gum cores (0.9 g) were placed in the tulip-shaped rotating disk. A pre-made engrossing syrup containing 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 was prepared. The engrossing syrup was placed in a buffer tank, from which it could be pumped through a nozzle into the rotating disk. The syrup was maintained at 75-80°C.

[0188] The gum cores were coated by applying 17 "coats", each comprising 1 to 5 coating layers. The process details are shown in Table 8.

[0189] Table 8

[0190]

[0191]

[0192] The chewing gum obtained in this manner was stored for five months. A panel of judges evaluated the chewing gum one week and five months after production. There was no noticeable change in the product's appearance during the five-month period. The acidity of the chewing gum after five months was found to be the same as it was one week after production.

[0193] Example 7

[0194] Based on the recipe shown in Table 9, candies were prepared using the ground MASHM powder of Example 5.

[0195] Table 9

[0196]

[0197] 1 Contains 7.5% gelatin by weight (mass-weighted mean diameter approximately 300 μm)

[0198] The candies were prepared by mixing the above ingredients and then compressing the resulting mixture into tablets in a FETTE tablet press.

[0199] The hygroscopicity of the tablets was measured at different temperatures and humidities. The results are shown in Table 10.

[0200] Table 10

[0201]

[0202]

Claims

1. A particle composition having a volume weighted average diameter D 4,3 The invention relates to a method for preparing a malic acid / salt particle having a particle size of 20 to 180 μm and comprising at least 50% by weight of malic acid / salt particles comprising at least 70% by weight of a eutectic of malic acid and an alkali metal hydrogen malate.

2. The granular composition according to claim 1, wherein the particles of the granular composition have the following particle size distribution: ·D 10 ≥1μm; 40μm≤D 50 ≤200 μm; and ·D 90 ≤320μm; The diameter is smaller than D x The volume % of particles is equal to x volume % and wherein the diameter is greater than D x The volume % of particles is equal to (100-x) volume %.

3. A granular composition according to claim 1 or 2, wherein the malic acid / salt particles comprise at least 80% by weight of the co-crystal.

4. The granular composition of claim 3, wherein the malic acid / salt particles comprise at least 90% by weight of the co-crystal.

5. The particle composition according to claim 1 or 2, wherein the eutectic is Na + (C4H5O5) - · Sodium dihydrogen dimalate or 2[K + (C4H5O5) - ]·Dipotassium tetrahydrogen trimalate represented by C4H6O5.

6. The particle composition of claim 5, wherein the eutectic is Na + (C4H5O5) - Sodium dihydrogen dimalate represented by C4H6O5.

7. A method for preparing powdered malic acid / salt powder, the method comprising: Providing a crude malic acid / salt powder comprising at least 90% by weight malic acid / salt particles, wherein the malic acid / salt particles comprise at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate, wherein the crude malic acid / salt powder has a volume weighted average diameter D 4,3 is at least 100 μm; reducing the particle size of the crude malic acid / salt powder to produce a powdered malic acid / salt powder, The volume weighted average diameter D of the powdered malic acid / salt powder 4,3 Than the volume weighted average diameter D of the crude malic acid / salt powder 4,3 At least 50% smaller, The malic acid / salt powder produced by the method has a volume weighted average diameter D 4,3 20-180μm.

8. The method of claim 7, wherein the crude malic acid / salt powder is prepared as follows: providing seed particles comprising at least 80% by weight of a crystalline material selected from the group consisting of a crystalline organic acid, a crystalline organic acid salt, and combinations thereof; providing a malic acid / brine solution comprising sodium and malate in a molar ratio of 4:10 to 6:10, or potassium and malate in a molar ratio of 5.5:10 to 7.5:10; Spraying the malic acid / saline aqueous solution onto the seed granules to prepare coated granules; • Removal of water from the coated granules.

9. A confectionery product comprising at least one of the following: A hard or soft roll-on coating containing 0.1-6 wt% malic acid / salt granules; Compressed confectionery comprising at least 0.1-50% by weight of malic acid / salt particles; Chocolate comprising at least 0.1-30% by weight of malic acid / salt particles; wherein the malic acid / salt particles comprise at least 70 wt% of a eutectic of malic acid and an alkali metal hydrogen malate, and the volume weighted average diameter D of the malic acid / salt particles is 4,3 20-180μm.

10. The confectionery product of claim 9, wherein the malic acid / salt particles comprise at least 80% by weight of the co-crystal.

11. The confectionery product of claim 9, wherein the malic acid / salt particles comprise at least 90% by weight of the co-crystal.

12. The confectionery product of claim 9 or 10, wherein the eutectic is Na + (C4H5O5) - · Sodium dihydrogen dimalate or 2[K + (C4H5O5) - ]·Dipotassium tetrahydrogen trimalate represented by C4H6O5.

13. The confectionery product of claim 12, wherein the eutectic is Na + (C4H5O5) - Sodium dihydrogen dimalate represented by C4H6O5.

14. The confectionery product of claim 9 or 10, wherein the confectionery product comprises an edible core coated with a hard-rolled coating, the hard-rolled coating comprising at least 30% by weight of a crystalline sweetener selected from the group consisting of crystalline sugars, crystalline sugar alcohols, and combinations thereof, the hard-rolled coating further comprising at least 0.1% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate.

15. A method for preparing a hard-rolled candy, the method comprising: Provides a cohesive edible core; applying at least one coating layer of a syrup onto the edible core, the syrup comprising a crystallizable sweetener selected from the group consisting of crystallizable sugars, crystallizable sugar alcohols, and combinations thereof; and applying at least one further coating layer comprising malic acid / salt particles comprising at least 70% by weight of a co-crystal of malic acid and an alkali metal hydrogen malate, The volume weighted average diameter D of the malic acid / salt particles is 4,3 20-180μm.

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