WO2021013855A1

WO2021013855A1 - Process for the preparation of crystalline particles

Info

Publication number: WO2021013855A1
Application number: PCT/EP2020/070597
Authority: WO
Inventors: Nicholas David Hedges; John Turner Mitchell
Original assignee: Unilever Ip Holdings B.V.; Conopco, Inc., D/B/A Unilever
Priority date: 2019-07-25
Filing date: 2020-07-21
Publication date: 2021-01-28

Abstract

A process for the preparation of crystalline particles comprising the steps of: providing one or more amorphous particles in a hydrophobic medium; and, heating and stirring the amorphous particles in a hydrophobic medium of step a. at a temperature greater than the Tg of the amorphous particles. Crystalline particles obtainable by the process. A composition comprising crystalline particles obtainable by the process, wherein the Casson Yield of the composition is less than 0.1 Pa measured by Method B. Use of the crystalline particles obtainable by the process or composition comprising crystalline particles obtainable by the process for confectionery products.

Description

Process for the Preparation of Crystalline Particles

Field of the invention A process for the preparation of crystalline particles comprising the steps of: providing one or more amorphous particles in a hydrophobic medium; and, heating and stirring the amorphous particles in a hydrophobic medium of step a. at a temperature greater than the Tg of the amorphous particles. Crystalline particles obtainable by the process, A composition comprising crystalline particles obtainable by the process, wherein the Casson Yield of the composition is less than 0.1 Pa measured by Method B. Use of the crystalline particles obtainable by the process or composition comprising crystalline particles obtainable by the process for confectionery products.

Background of the invention

Chocolates and couvertures typically comprise dispersions of small particles of sugar (10-25 microns), cocoa powder solids and emulsifier in a fat continuous phase (The Science of Ice Cream’; C. Clarke, RSC Paperbacks 2004, page 57). Such chocolates and couvertures may be used as frozen confection coating compositions.

Calories in such frozen confection coating compositions, also known as fat-based food product compositions, may be reduced through the reduction of sugar or fat present in the composition. However, reduction of the sugar or fat content of the frozen confection coating compositions affects the Casson viscosity and Casson yield stress of the composition, consequently directly affecting the quality and quantity of the composition applied to a frozen confection core.

The amount of fat present and the surface area of the particles per unit volume of a fat- based food product composition affect the viscosity of the composition (US 5,342,636). Reduction of the amount of fat, or substitution of the sugar with an alternative, would result in an increased viscosity of the fat-based food product composition (and consequently thicker coatings: The Science of Ice Cream’; C. Clarke, RSC Paperbacks 2004, pages 85-86 and US 5,342,636. Furthermore, US 5,342,636 discloses that calorie reduction through a sugar substitute is limited because greater than 50% of the additive present in the substitute results in an excess of additive not bound to the fibre, i.e. : fines are present in the particle size distribution of the sugar substitute.

There is a need to provide reduced calorie fat-based food product compositions wherein the amount of sugar, amount of fat or both amount of fat and sugar of the fat- based food composition are reduced without affecting the physical characteristics and therefore quality, in particular sensory qualities, of the food product. Additionally, there is a need for novel, reduced calorie fat-based food product compositions that are suitable for use in current manufacturing processes; i.e.: can withstand environments comprising water. Anhydrous manufacturing conditions for the preparation of food products are not required.

Summary of the invention A process for the preparation of crystalline particles comprising the steps of: providing one or more amorphous particles in a hydrophobic medium; and, heating and stirring the amorphous particles in a hydrophobic medium of step a. at a temperature greater than the Tg of the amorphous particles. Crystalline particles obtainable by the process, A composition comprising crystalline particles obtainable by the process, wherein the Casson Yield of the composition is less than 0.1 Pa measured by Method B. Use of the crystalline particles obtainable by the process or composition comprising crystalline particles obtainable by the process for confectionery products.

Detailed description of the invention

The present invention relates to a process for the preparation of crystalline particles comprising the steps of:

a. Providing amorphous particles and one or more emulsifiers in a hydrophobic medium;

b. Heating and stirring the amorphous particles in a hydrophobic medium of step a. at a temperature greater than the Tg of the amorphous particles. wherein the amorphous particles comprise sugar and surface active agent, wherein the ratio of sugar to surface active agent is from 2000:1 to 4:1. In a second embodiment the invention related to the process for the preparation of

crystalline particles comprising the steps of:

a. Providing amorphous particles in a hydrophobic medium;

b. Heating and stirring the amorphous particles in a hydrophobic medium of step a. at a temperature greater than the Tg of the amorphous particles. wherein the amorphous particles comprise sugar and surface active agent, wherein the ratio of sugar to surface active agent is from 2000:1 to 4:1.

In a third embodiment the present invention relates to a process for the preparation of crystalline coated bulking agent particles comprising the steps of:

c. Providing amorphous coated bulking agent particles and one or more emulsifiers in a hydrophobic medium;

d. Heating and stirring the amorphous coated bulking agent particles in a

hydrophobic medium of step a. at a temperature greater than the Tg of the amorphous particles. wherein the amorphous coated bulking agent particles comprise a bulking agent and a coating composition comprising sugar and surface active agent, wherein the ratio of sugar to surface active agent of the coating composition is from 2000:1 to 4:1. In a fourth embodiment the invention related to the process for the preparation of crystalline coated bulking agent particles comprising the steps of:

c. Providing amorphous coated bulking agent particles in a hydrophobic medium; d. Heating and stirring the amorphous coated bulking agent particles in a

hydrophobic medium of step a. at a temperature greater than the Tg of the amorphous particles. wherein the amorphous coated bulking agent particles comprise a bulking agent and a coating composition comprising sugar and surface active agent, wherein the ratio of sugar to surface active agent of the coating composition is from 2000: 1 to 4: 1. Coated bulking agent particle means a particle comprising a bulking agent and a coating composition. Coated bulking agent particle means a particle comprising a bulking agent core and a coating composition present on at least the outer surface of the bulking agent core.

The bulking agent core may be substantially or fully coated with the coating composition. Preferably the bulking agent is fully coated with the coating composition.

Amorphous particles means particles comprising a sugar and surface active agent composition wherein from 50 wt% to 100 wt% of the sugar of the composition is in the amorphous phase. Preferably, from 80 wt% to 100 wt% of the sugar is in the amorphous phase. More Preferably from 95 wt% to 100 wt% of the sugar is in the amorphous phase.

Amorphous coated bulking agent particles means a coated bulking agent particle comprising a bulking agent and coating composition wherein from 50 wt% to 100 wt% of the sugar of the coating composition is in the amorphous phase. Preferably, from 80 wt% to 100 wt% of the sugar of the coating composition is in the amorphous phase. More Preferably from 95 wt% to 100 wt% of the sugar of the coating composition is in the amorphous phase. Amorphous materials that are able to transfer from an amorphous phase to a crystalline phase have a glass transition temperature T(g).

Crystalline particles means particles comprising a sugar and surface active agent composition wherein from 50 wt% to 100 wt% of the sugar of the composition is in the crystalline phase. Preferably, from 80 wt% to 100 wt% of the sugar of the composition is in the crystalline phase. More Preferably from 95 wt% to 100 wt% of the sugar of the composition is in the crystalline phase.

Crystalline coated bulking agent particles means a coated bulking agent particle comprising a bulking agent and coating composition wherein from 50 wt% to 100 wt% of the sugar of the coating composition is in the crystalline phase. Preferably, from 80 wt% to 100 wt% of the sugar of the coating composition is in the crystalline phase. More Preferably from 95 wt% to 100 wt% of the sugar of the coating composition is in the crystalline phase. Crystalline phase means that the molecules of a composition are in a highly ordered state. Hydrophobic medium means an inert reaction medium that typically repels water.

Hydrophobic reaction mediums include fats, oils and organic solvents. Fats and oils are selected from the group consisting of: cocoa butter, medium chain length triglyceride (MCT), sunflower oil, olive oil, rapeseed oil, linseed oil, flax seed oil, coconut oil, corn oil, canola oil, cottonseed oil, olive oil, palm oil, peanut oil, canola oil, safflower oil, sesame oil, soybean oil, sunflower oil, nut oils, and citrus oils. Nut oils may be almond oil and hazelnut oil. Organic solvents include food grade solvents. Organic solvents are selected from the group consisting of: ethanol.

The hydrophobic medium is liquid above 35 °C. The hydrophobic medium is liquid at temperatures from 35 °C to 130 °C, from 40 °C to 120 °C.

Although the hydrophobic medium typically repels water, water may be present in the reaction medium. Amorphous and crystalline particles comprising a composition comprising sugar and surface active agent, wherein the ratio of sugar to surface active agent of the coating composition is from 2000:1 to 4:1, are not substantially soluble in the liquid hydrophobic reaction medium. Amorphous and crystalline particles comprising a composition comprising sugar and surface active agent, wherein the ratio of sugar to surface active agent of the coating composition is from 2000:1 to 4:1, are dispersed in the liquid hydrophobic reaction medium.

Emulsifiers are selected from the group consisting of lecithin and Polyglycerol polyricinoleate (PGPR). Lecithin may be soy lecithin. The frozen confection coating composition comprises from 0.1 wt% to 1.5 wt%; from 0.2 wt% to 1.2 wt%; from 0.3 wt% to 1.0 wt% of one or more emulsifiers. The frozen confection coating composition comprises from 0.1 wt% to 0.7 wt%; from 0.2 wt% to 0.6 wt%; from 0.3 wt% to 0.5 wt% of at least one emulsifier. Sugar is selected from the group consisting of sucrose, glucose, lactose, galactose, allulose, trehalose and mixtures thereof.

Sugar is present in an amount of from 80 wt% to 99.995 wt%; from 80 wt% to 99.99 wt%; from 88 wt% to 99.95 wt%; from 90 wt% to 99.95 wt%; from 92 wt% to 99.95 wt%; from 95 wt% to 99.90 wt%; from 98 wt% to 99.90 wt%; based on the total weight of the sugar and surface active agent present in the composition comprising sugar and surface active agent or total weight of coating composition of the coated bulking agent particle.

Surface active agent is selected from the group consisting of proteins, lecithins, and mixtures thereof. Protein means water soluble protein and is selected from the group consisting of: whey protein, sodium caseinate, potassium caseinate, calcium caseinate, soluble vegetable proteins, protein hydrolysates, albumins and mixtures thereof.

Soluble vegetable proteins may be for example: soy protein, pea protein and rice protein. Protein hydrolysates may be for example: hydrolyzed whey protein such as HYGEL from Kerry Foods Ltd; or hydrolyzed caseinates. Albumins may be for example: bovine serum and egg albumin.

Surface active agent is present in an amount from 0.005 wt% to 20 wt%; from 0.01 wt% to 20 wt%; from 0.05 wt% to 12 wt%; from 0.05 wt% to 10 wt%; from 0.05 wt% to 8 wt%; from 0.10 wt% to 5 wt%; from 0.10 wt% to 2 wt% based on the total weight of the sugar and surface active agent present in the composition comprising sugar and surface active agent or total weight of coating composition of the coated bulking agent particle.

The coating composition comprises sugar and surface active agent in the ratio of 2000:1 to 4:1 ; preferably from 100:1 to 16:1.

The bulking agent is insoluble cellulosic fibre derived from plant-based material such as coffee beans, dried tea leaves, cocoa, fruit, vegetable, nuts, seeds and is present in particulate form. Insoluble cellulosic fibre is selected from the group consisting of oat fibre; bran fibre; vegetable powders; tomato powder; beetroot powder; ground cinnamon; spent coffee grounds; milled tea particles; debittered cocoa; fruit powders and mixtures thereof. The bulking agent may also be an insoluble protein obtainable from, for example: wheat, zein, pea, rice, soya, fava, milk or lentil. The bulking agent is an insoluble protein selected from the group consisting of: wheat, zein, pea, rice, soya, fava lentil and mixtures thereof. The bulking agent may also be an insoluble mineral, for example: calcium carbonate or calcium phosphate. The bulking agent is an insoluble mineral selected from the group consisting of: calcium carbonate, calcium phosphate and mixtures thereof.

Preferably the bulking agent has been treated to remove flavour, aroma or both flavour and aroma. Preferably, the bulking agent has reduced flavour, reduced aroma or both reduced flavour and reduced aroma compared to an untreated bulking agent.

Preferably, the bulking agent is without aroma, without flavour or without both aroma and flavour. During treatment to reduce flavour, aroma or both flavour and aroma, the bulking agent is centrifuged to obtain a pellet that comprises the bulking agent and water. Consequently, the bulking agent has a reduced water binding capacity in comparison to the bulking agent in dry form prior to centrifugation. The water binding capacity of the bulking agent is preferably less than 4g per g of dry bulking agent.

The coated bulking agent comprises from 1 wt% to 70 wt% bulking agent and from 30 wt% to 99 wt% of a coating composition comprising sugar and surface active agent; from 2 wt% to 49 wt% bulking agent and from 51 wt% to 98 wt% of a coating composition comprising sugar and surface active agent; from 3 wt% to 44 wt% bulking agent and from 56 wt% to 97 wt% of a coating composition comprising sugar and surface active agent. The coated bulking agent particle comprises: from 10.00 wt% to 98.00 wt % sugar; from 0.05 wt% to 20.00 wt % surface active agent; and from 1.95 wt% to 70.00 wt % bulking agent.

The coated bulking agent particle comprising: from 20.00 wt% to 97.50 wt % sugar; from 0.05 wt% to 20.00 wt % surface active agent; and from 2.45 wt% to 60.00 wt % bulking agent. The coated bulking agent particle comprising: from 31.00 wt% to 97.00 wt % sugar; from 0.05 wt% to 20.00 wt % surface active agent; and from 3.00 wt% to 49.00 wt % bulking agent. The coated bulking agent particle comprising: from 35.00 wt% to 91.00 wt % sugar; from 0.05 wt% to 20.00 wt % surface active agent; and from 9.00 wt% to 45.00 wt % bulking agent.

The coated bulking agent particle comprising: from 35.00 wt% to 85.00 wt % sugar; from 0.05 wt% to 20.00 wt % surface active agent; and from 14.95 wt% to 45.00 wt % bulking agent.

The coated bulking agent particle comprising: from 51.00 wt% to 95.00 wt % sugar; from 0.05 wt% to 20.00 wt % surface active agent; and from 4.95 wt% to 48.95 wt % bulking agent.

In a further aspect of the invention the process comprises cooling the product of step b. to room temperature (25 °C).

Tg means the glass transition temperature of an amorphous material. Glass transition temperature means the temperature that an amorphous material changes from a rigid, glassy solid to a viscous liquid. When further thermal energy is applied to the viscous liquid (by increasing the temperature above the Tg), a crystalline solid may be formed.

The amorphous particles of step a. have a Tg of from 30 °C to 90 °C; from 35 °C to 85 °C; preferably from 40 °C to 80 °C, more preferably from 41 °C to 70 °C.

The duration of step b. is from 0.5 minutes to 1000 minutes, from 2 minutes to 900 minutes, preferably from 4 minutes to 180 minutes, more preferably from 5 minutes to 120 minutes; more preferably from 6 minutes to 90 minutes.

The temperature of step b. is from 40 °C to 120 °C, preferably from 50 °C to 110 °C, more preferably from 60 °C to 100 °C, more preferably from 75 °C to 90 °C, with the proviso that the temperature of the reaction is greater than the Tg of the amorphous particles and less than the melting point of the crystalline particles The difference in temperature values between the Tg of the amorphous particles and the reaction temperature is from 15 °C to 70 °C, preferably from 20 °C to 60 °C, preferably from 23 °C to 60 °C, preferably from 24 °C to 55 °C, more preferably from 25 °C to 55 °C, more preferably from 31 °C to 49 °C. more preferably from 24 °C to 40 °C more preferably from 24 °C to 35 °C

The particle size distribution of the crystalline particles of the product of step b. have a D(0.1) of from 5 mm to 80 mm, preferably from 10 mm to 70 mm, more preferably from 15 mm to 60 mm.

The particle size distribution of the crystalline particles of the product of step b. have a D(3,2) of from 10 mm to 80 mm, preferably from 15 mm to 70 mm, more preferably from 20 mm to 60 mm.

The particle size distribution of the crystalline particles of the product of step b. have a D(0.1) of from 5 mm to 80 mm, preferably from 10 mm to 70 mm, more preferably from 15 mm to 60 mm and a D(3,2) of from 10 mm to 80 mm, preferably from 15 mm to 70 mm, more preferably from 20 mm to 60 mm.

The particle size distribution of the crystalline particles of the product of step b. have a D(4,3) of from 30 mm to 220 mm, preferably from 35 mm to 210 mm.

In a further aspect, the invention relates to crystalline particles obtainable by the process of the invention. Furthermore, 90% of the crystalline particles of the product of step b. have an aspect ratio of from 1.2 to 1.0; preferably from 1.15 to 1.0, more preferably from 1.12 to 1.0. Aspect ratio may be provided in a ratio of the longest length of the particle to the shortest length, consequently, 90% of the crystalline particles of the product of step b. have an aspect ratio of from 0.8 to 1.0; preferably from 0.85 to 1.0, more preferably from 0.88 to 1.0.

The invention further relates to a fat-based confection composition comprising crystalline particles prepared by the process of the invention. The fat-based confection composition may be added to any fat-based food product in order for the crystalline particles to replace, wholly or in part, granulated sugar.

The fat-based food product must be substantially anhydrous. Substantially anhydrous means that the composition comprises from 0 wt% to 5 wt% water, preferably from 0 wt% to 3 wt% water and more preferably from 0 wt% to 1 wt% water. In an

embodiment the fat-based food product is a fat-based confection composition. A fat- based confection composition may also be known as an oil-based confection composition.

Exemplary fat-based confection compositions include: ambient chocolate, chocolate flavour coating; frozen confection coating compositions, fat-based sauces and inclusions. Preferably, the fat-based confection composition is a frozen confection coating composition. Frozen confection coating composition means a composition that, when in liquid form and applied to the surface of a frozen confection, solidifies on or shortly after contact with the frozen confection. Frozen confection coating composition means a fat-based edible material for use to form a coating layer on the surface of a frozen confection. Such coating compositions include chocolate or chocolate analogues (also known as couverture or compound chocolate). Exemplary coating composition formulations are provided in WO 2010/072481 A1 ;‘Ice Cream’ 5^th Ed., Marshall and Arbuckle, 1996, Chapman & Hall, New York. N.Y., page 300; and‘Ice Cream’ 7^th Ed., Goff and Hartel, 2013 Springer, New York, N. Y., pages 274-283.

The term‘chocolate’ means dark, chocolate, milk chocolate, white chocolate, flavoured chocolate. Compound chocolate is made from a combination of cocoa solids, non- cocoa butter vegetable fats and sweeteners.

In a further embodiment, the crystalline coated bulking agent particles obtainable by the process of the invention may be used independently or together with other dry ingredients as, for example, a dry sugar coating for bakery or sweet products.

The invention further relates to a composition obtainable by the process according to the invention, wherein the Casson Yield of the resultant composition of step b. is less than 0.1 Pa. measured according to Method B. The invention further relates to a composition obtainable by the process according to the invention, wherein the resultant composition of step b. comprises from 30 wt% to 60 wt% hydrophobic medium and the Casson Yield of the resultant composition of step b. is less than 0.1 Pa. measured according to Method B.

The invention further relates to a fat-based confection composition comprising from 48.5 to 70 wt % crystalline particles prepared according to the invention; from 0.0 wt% to 1.5 wt% of one or more emulsifiers; and, from 30 to 50 wt% fat, wherein the Casson Yield of the composition is less than 0.1 Pa. measured according to Method B.

The invention further relates to a frozen confection product comprising a frozen confection core and a coating composition, wherein the frozen confection coating composition is a fat-based composition prepared according to the process of the invention.

Figures:

Figure 1 : Example 6: Polarised light microscopy image of milled crystalline sugar: The milled crystalline sugar particles of Example 6 are more irregular than the crystalline coated bulking agent particles of Example 7. (Size measurement key is 40 microns).

Figure 2: Polarised light microscopy image of the amorphous coated bulking agent particles (starting material) of Example 7a. Amorphous particles are not illuminated by polarised light.

Figure 3: Polarised light microscopy Image of Crystalline coated bulking agent of Example 7. The crystalline coated bulking agent milled particles of Example 7 are more regular (more spherical) than the crystalline sugar particles of Example 6. (Size measurement key is 40 microns).

Figure 4: Example 1a: (Size measurement key is 40 microns).

Figure 5: Example 1 b: (Size measurement key is 40 microns).

Figure 6: Example 1c: (Size measurement key is 40 microns). Figure 7: Example 3a: (Size measurement key is 40 microns).

Figure 8: Example 3b: (Size measurement key is 40 microns).

Examples

General Measurement Methods:

Method A

Method for Measurement of D(4,3) and D(3,2):

Spray Dried Coated Bulking Agent Particles:

The coated bulking agent particles were dispersed in a medium chain triglyceride (MCT; DANISCO) and heated to 40°C. Aliquots of the dispersion were added to a medium chain triglyceride (MCT; DANISCO) as the dispersant. Samples of particles were added to the dispersant chamber until the required sample obscuration was achieved. An average of 3 replicates were analyzed [Mastersizer 2000; Malvern Pananlytica] to give the final particle size, calculated using the Mastersizer software. Values of D[4,3] and D[3,2] were included in the standard output. The particle size was calculated using Fraunhofer approximations according to the Mastersizer 2000 analysis software.

Method B

Method for Measurement of Casson Viscosity and Casson Yield:

Chocolate and oil rheology measurements were made on a Physica MCR501 at 40°C using a 17mm profiled cup and bob (cd 7-0-25/p6 and c-cc17/T200/SS/P).

The method was a step method:

Step 1 is a pre-shear to condition the composition comprising crystalline particles of Examples 4, 5, 6 or 7 at a shear rate of 5 s^-1

Step 2 is shear rate ramp from 2 to 50 s^-1 over 3 mins

Step 3 constant shear rate at 50 s^-1 for 1 min

Step 4 is shear rate ramp from 50 to 2 s^-1 over 3 mins

Only step 4 is analyzed to extract the Casson parameters. Data analyzed is from 50 s^-1 to 5 s^-1.

Square root of stress is plotted on the y-axis and square root of shear rate is plotted on the x-axis. The square of the slope of the line of best fit gives the Casson viscosity and the square of the intercept of the line of best fit with the y-axis gives the Casson yield. Method C

Method for Measurement of Glass transition:

Differential Scanning Calorimetry (DSC) (measurement of glass transition temperature (T_g), crystallisation temperature and crystallisation enthalpy).

Differential scanning calorimetric (DSC) measurements were performed using Perkin Elmer Diamond DSC. Samples were seal into stainless steel pans. Samples were scanned for 20°C to 200°C at 10 degrees per minute. Thermograms were analyzed using standard Perkin Elmer software for peak onset, peak temperature, peak area (DH) and glass transition temperature (T_g). Tg was quoted as the temperature at the mid-point of the specific heat capacity change.

General method of preparing amorphous particles:

Method D

Preparation of amorphous particles comprising sugar and whey protein concentrate: Sucrose (20 kg), whey protein concentrate (1.0 kg) were dissolved in water (20 kg) to form a solution. The resulting solution was heated and retained at 70 °C, and spray dried on a Buchi Mini B290 mini-spray dryer. The spray dryer conditions were as follows:

Flow rate= 25 I h^-1

Inlet temp= 190 °C

Outlet temp = 100°C

Method E

Preparation of amorphous particles comprising sugar, bulking agent and whey protein: Method E (Part 1)

Preparation of Bulking Agent (washed cocoa particles):

3kg of Cocoa particles [Barry Callebaut (alkalised: 10-12% fat)] were washed with 151 hot water (>70°C). The cocoa particles were then cooled to 45°C and centrifuged on an RC3C centrifuge [ThermoFisher Scientific] at 5000 rpm for 15 minutes at 4°C. The pellet was re-suspened in hot water and centrifugation process was repeated. The washing and centrifugation process were repeated until the cocoa particles were substantially free of aroma. The resultant pellet comprised cocoa [17 wt%, dry weight] and the remainder was water.

Method E (Part 2)

Sucrose (14 kg), whey protein concentrate (0.14 kg) and wet bulking agent [35 kg (dry weight 6 kg)] were slurried in water (41.23 I) to form a homogenous slurry. The slurry was heated and retained at 70 °C, and spray dried on a Buchi Mini B290 mini-spray dryer. The spray dryer conditions were as follows:

Flow rate= 25 I h^-1

Inlet temp= 190 °C

Outlet temp = 100°C

Table 1 : Composition of amorphous particles:

Method F

General Method for preparing crystalline particles from amorphous particles:

Amorphous particles (100 g) were heated and stirred in a reaction medium comprising a hydrophobic reaction medium (98 g), soy lecithin (Bolec,1.0 g) and PGPR (1.0 g) at the specified temperature and duration provided in Tables 2-4. Examples 1-3: Preparation of crystalline particles from amorphous particles comprising sugar and whey protein. The general method (Method D) was followed to obtain amorphous particles comprising 99 wt% sugar and 1.0 wt% whey protein. Method F was followed to prepare crystalline particles. The hydrophobic reaction medium was medium chain length triglyceride (MCT, DANISCO).

Table 2: Preparation of crystalline particles from amorphous particles comprising sugar and whey protein.

Examples 1 to 3 illustrate that heating a composition of amorphous particles in a hydrophobic medium at a temperature greater than the Tg of the amorphous particles results in larger particles and a reduction in the smaller particles of the starting reaction medium. This result indicates that the smaller particles of the starting material, i.e. : the particles with a particle size less than the D(0.1) value of the sample coalesce with larger particles, consequently forming larger particles, as can be seen by the increase in D(3,2) particle size.

Examples 1 to 3 also show that the degree of coalescence can be controlled by controlling the temperature and duration of the reaction. Examples 1 to 3 show that increasing the difference in temperature between the Tg of the amorphous particles and the temperature of the reaction, increases the rate of coalescence.

Examples A-D: The general method for preparing crystalline particles was followed (Method F). The amorphous particles were prepared by Method E and comprised sugar (62 wt%); whey protein (1 wt%); and washed cocoa powder (37 wt%). The hydrophobic reaction medium was cocoa butter (50 wt%) and the example was heated to at the temperature and for the duration provided in Table 2b. The reaction time is the time taken for the amorphous particles to crystallise.

Table 2b: Preparation of crystalline particles from amorphous particles comprising sugar, bulking agent and whey protein.

Examples A to D show that increasing the difference in temperature between the Tg of the amorphous particles and the temperature of the reaction increases the rate of crystallisation of the amorphous particles to crystalline particles. Amorphous particles that have a higher Tg require a similar difference between the Tg and reaction temperature. Examples 4-5:

The general method for preparing crystalline particles was followed (Method F). The amorphous particles (Tg = 41) were prepared by Method E and comprised 69.5 wt% sugar; 0.7 wt% whey protein; and 29.8 wt% washed cocoa powder. The hydrophobic reaction medium was cocoa butter and the example was heated to 90 °C for 60 minutes.

The same method as used for Example 4 was followed for Example 5 with the exception that the amorphous particles were crystalline particles of milled and sieved sucrose and the composition was heated to 40 °C rather than 90 °C.

Table 4: Comparison of Casson Yield and Viscosity of crystalline particles and crystalline particles of milled sugar.

Example 4 demonstrates that the composition comprising crystalline particles have a significantly lower Casson Yield than the milled crystalline sugar particles of Example 5. A significantly lower Casson Yield enables a reduction in pick-up weight compared to known milled crystalline sugar compositions and consequently, the level of emulsifier of the composition may be reduced. Examples 6-7: Comparison of Casson Yield and Casson Viscosity of milled sugar particles, amorphous particles and crystalline particles in chocolate.

Preparation of particles:

Milled Sugar particles:

Sugar (Brantag) was milled in a Waring Commercial Laboratory Blender. The milled sugar was then sieved using a Retsch VIBROTRONIC Type VE 1 sieving machine, using 53 and 40 micron sieves.

Amorphous Particles:

Amorphous particles were prepared according to the general experimental method for preparing amorphous particles (Method E). The amorphous particles were sieved following the same procedure for the milled sugar particles.

Crystalline Particles:

Amorphous particles and cocoa butter (weight ratio 1 :2), were stirred at 500 rpm and 90 °C for 70 mins. Cocoa butter was removed by centrifugation and the crystalline particles (precipitate) were sieved following the same procedure for the milled sugar particles.

Preparation of chocolate comprising milled sugar particles, amorphous particles or crystalline particles.

Preparation of a fat-based composition:

Cocoa butter, butter oil, and emulsifiers (lecithin and PGPR) were combined and heated to 40 °C to form a fat-based composition. The composition of the fat-based composition is provided in Table 5.

Table 5: Fat-Based Composition.

Preparation of unsweetened chocolate:

Cocoa powder (21.4 g) was ball milled with in the fat-based composition (Table 5,

36.39 g) for 120 minutes at 40 °C to obtain a homogenous fat phase comprising cocoa powder (unsweetened chocolate).

Preparation of chocolate comprising milled sugar particles, amorphous particles or crystalline particles (sweetened chocolate):

Milled crystalline sugar particles (21.2 g), amorphous (21.2 g) or crystalline particles (21.2 g) were added to unsweetened chocolate (20.1 g) and hand mixed for about 1 minute at from 42 to 45 °C to form a homogenous dispersion of solids. Examples 6 and 7 were stored in an oven at 42-45°C. Before each analysis, Examples 6 and 7 were microwaved at 150W (Samsung Snack mate CM 1039) (Stortz and Marangoni, 2013; Glicerina et al. 2015a) for about 10 seconds, then hand mixed again to ensure a homogenous microstructure with well-dispersed solids in oil.

The final composition of the chocolate comprising particles and sweetened chocolate is provided in Table 6. Table 6: Composition of Chocolate comprising particles.

Table 7: Comparison of Casson Yield and Casson Viscosity of milled sugar or crystalline particles in chocolate.

Example 6 illustrates the Casson Yield (0.225Pa) and Casson Viscosity (1.167 PaS) for milled sugar (sieved to 40-53 microns) in chocolate; i.e. : the Casson Yield and

Viscosity for chocolate comprising granulated, milled sugar of a particular particle size distribution (sieved to 40-53 microns). It can be seen that Example 7b has a

significantly reduced Casson Yield (0.014 Pa) in comparison to Example 6 (0.225 Pa).

It should be noted that the particle size of the crystalline particles of Example 7b are smaller than those of Example 6, and, following the principle that smaller particles have a larger surface area per unit volume, the viscosity of the composition of Example 7b should increase (US 5,342,636). The same principle applies to Casson Yield. However, it can be seen that the Casson Yield of Example 7b is significantly reduced compared to Example 6. The significant reduction is due to the crystalline particles of Example 7b having greater sphericity and less particle- particle interaction. Particles that have greater sphericity and less particle- particle interaction flow around each other in a hydrophobic medium more easily, in comparison to particles that are very irregular (Example 6).

The consequence of a significantly reduced Casson Yield is a significantly reduced pick-up weight when a frozen confection coating composition is applied to a frozen confection core of a frozen confection coating composition; for example: by dipping a frozen confection core into liquid frozen confection coating composition. A significantly reduced pick-up weight has the consequence that the amount of emulsifiers such as PGPR that are typically added to chocolate to reduce Casson Yield may be reduced, or their use may be avoided. Consequently, a frozen confection coating composition with a reduced number of ingredients becomes viable for coating frozen confection cores.

Sphericity Measurements of Milled Crystalline Sugar or Crystalline Coated Bulking

Agent Particles. Images of Examples 6 and 7b were binarized and analyzed using the Image J software (ImageJ 1.50i).

Table 8: Sphericity measurements for Milled Crystalline Sugar or Crystalline Coated

Bulking Agent Particles.

Example 7b demonstrates that crystalline particles have greater sphericity (are more spherical) than milled crystalline sugar particles. Particles that have greater sphericity and less particle-particle interaction flow around each other in a hydrophobic medium more easily, in comparison to particles that are very irregular (Example 6).

Consequently, the Casson yield of the particles of Example 7b is significantly lower than Example 6.

Claims

1. A process for the preparation of crystalline particles comprising the steps of: a. Providing one or more amorphous particles in a hydrophobic medium; b. Heating and stirring the amorphous particles in a hydrophobic medium of step a. at a temperature greater than the Tg of the amorphous particles,

wherein the amorphous particles comprise a composition comprising sugar and surface active agent, wherein the ratio of sugar to surface active agent in the composition is from 2000:1 to 4:1.

2. A process according to claim 1 , wherein the process comprises cooling the product of step b. to room temperature.

3. A process according to claim 1 or 2, wherein the hydrophobic medium of step a. comprises one or more emulsifiers.

4. A process according to claims 1 to 3, wherein the amorphous particles of step a. have a Tg of from 35 °C to 80 °C.

5. A process according to claims 1 to 4, wherein the duration of step b. is from 0.5 minutes to 1000 minutes.

6. A process according to claims 1 to 5, wherein the temperature of step b. is from 40 °C to 120 °C.

7. A process according to claims 1 to 6, wherein the difference in temperature between the Tg of the amorphous particles and the temperature of step b. is from 15 °C to 70 °C.

8. A process according to claims 1 to 7, wherein the crystalline particles of the product of step b. have a D(0.1) of from 5 to 80 micron and a D(3,2) of from 10 to 80 microns.

9. A process according to claims 1 to 8, wherein the amorphous particles comprise a coated bulking agent particle comprising from 1 wt% to 70 wt% bulking agent and from 30 wt% to 99 wt% of a coating composition comprising sugar and surface active agent.

10. A process according to claims 1 to 9, wherein 90% of the crystalline particles of the product of step b. have an aspect ratio of from 1.2 to 1.0.

11. Crystalline particles obtainable by the process of claims 1 to 10.

12. A fat-based confection composition comprising crystalline particles according to claim

11.

13. A fat-based confection composition according to claim 12 for use in a frozen confection coating composition.

14. A frozen confection product comprising a frozen confection core and a frozen confection coating composition, wherein the frozen confection coating composition is a fat-based confection composition according to claims 12 or 13.