EP1150580A1

EP1150580A1 - Calcium supplemented food products and novel calcium-containing ingredient

Info

Publication number: EP1150580A1
Application number: EP00901799A
Authority: EP
Inventors: Svetlana A. Ermolaeva; Evgeny Naum Vulfson
Original assignee: Nutrahealth Ltd (UK)
Current assignee: NUTRAHEALTH LTD. (UK)
Priority date: 1999-02-06
Filing date: 2000-02-07
Publication date: 2001-11-07
Also published as: AU2309600A; GB9902670D0; CA2362909A1; WO2000045650A1

Abstract

This invention relates to food products and drinks in general and particularly to an emulsified fat spread which are supplemented with calcium and a process for the preparation thereof. This invention also relates to a novel calcium-containing ingredient and a method for its preparation and its use in the above said products and processes. Combining a source of calcium ions and a source of anions in an aqueous solution of milk derived solids, proteins or other suitably functionalised food additives, and using the resulting suspension as an aqueous phase for the preparation of an emulsified fat spread.

Description

1 CALCIUM SUPPLEMENTED FOOD PRODUCTS AND NOVEL CALCIUM-

CONTAINING INGREDIENT

FIELD OF THE INVENTION This invention relates to food products and drinks (or beverages) in

general and particularly to an emulsified spreadable food product which are

supplemented with calcium and a process for the preparation thereof. This

invention also relates to a novel calcium-containing ingredient and a method for its preparation and its use in the above said product and process.

BACKGROUND OF THE INVENTION

Calcium is an essential element in the human diet. It is necessary for the regulation of numerous metabolic functions in the body such as muscle contraction, blood clotting and neural transmission and also for normal growth

and development of bones and teeth. In recent years calcium has received

much attention due to its role in the prevention of bone mass reduction (osteoporosis). In the USA alone, osteoporosis affects about 25 million

people and it is the major cause of bone fracture in elderly and post menopausal women. It is generally accepted that the occurrence of

osteoporosis is dependent on the attainment of optimal bone mass in the

early years of life and on the rate of its loss in later years. It is also generally

accepted that an adequate dietary intake of calcium is an important preventive factor and consequently the fortification or supplementation of food products with calcium has become a common practice in recent years. The 2 recommended daily intake of calcium varies from country to country. For example, the recommended daily uptake of calcium for adolescents/young

adults in Britain is 1000 mg for men and 800 mg for women and it is even

higher (1200-1500 mg) for the same categories of people in the USA. Many calcium sources are currently used for the fortification or

supplementation of food products. Some eg calcium carbonate, calcium phosphate and calcium citrate and other organic acid salts of calcium are

poorly water soluble at neutral and slightly acidic pH which are most common

in food formulations. These salts, if precipitated in the aqueous phase of a food or drink or when used in food or drink in insoluble form, create an

undesirable sensation of powderiness in the mouth, so-called "chalky" mouth feel. Other calcium sources eg calcium chloride, calcium acetate and a few

organic acid salts of calcium are soluble in water in substantial quantities.

However, at high concentrations they have poor organoleptic properties and also interact with other food components such as, for example, proteins leading to their precipitation and coagulation.

Among various calcium-fortified food formulations available to

consumers, drinks remain the most numerous. This is due to the relative

ease of formulating a drink composition of acceptable organoleptic quality which contains about 1% (w/w) of a water soluble calcium salt to provide a

substantial part of the recommended daily uptake of calcium in several

hundred cm³ of the liquid product. However, in many countries, notably in

Europe, calcium fortified drinks are not consumed by a large proportion of the population on a regular basis. Thus, there is a need in the trade to develop and introduce new products to enable more people to benefit from calcium-

supplemented foods. It is also desirable for these food products to be an

integral part of people's diet so that they can draw the maximum benefit from calcium fortification with minimum expense. Fat spreads are particularly

suitable vehicles for the incorporation of calcium as they are consumed by a

large number of people on a daily basis.

Fat spreads and margarine can be prepared with different fat contents

as legally specified, typically between 10% and 80% fat by weight, and the products can be labelled accordingly as, for example, low fat or very low fat

spreads. The latter are especially appealing to many health conscious

consumers. Generally, depending on the fat content and other ingredients

used, a fat spread is a water-in-oil or oil-in-water emulsion (or a combination of the two) which has a butter like consistency and taste and which is spreadable. The daily intake of butter and fat spreads varies from country to

country but a typical adult consumes about 25 gram of butter or butter like

product a day. Thus, to provide a substantial part of the recommended daily

intake of calcium, a fat spread should contain several gram of calcium source

per 100 gram of product, depending on the calcium content of the source.

Given that the water content of a typical spread is only about 30% and of a

typical low fat spread is about 60%, a highly concentrated solution or

suspension of the calcium source in water or in oil must be used to provide the consumer with the health benefits sought.

Recently Cante et al (EP 0 549 290) disclosed a calcium citrate- vegetable oil composition which is spreadable. According to the invention of Cante et al a new crystalline calcium citrate in the form of distinct platelets of

about 1 by 1.5 micron, can be obtained by combining a source of calcium ions

and citric acid in a mole ratio from 2.5:2 to 2.95:2 under carefully controlled conditions of pH and temperature. It is claimed (EP 0 549 290) that the thus

obtained crystalline calcium citrate, when admixed into vegetable oils, results in a significant increase in the viscosity of the oil and this admixture gives a

semi-solid fat product which is spreadable. However, the invention of Cante

et al can only be practised with the disclosed calcium citrate platelets of

defined size, shape and composition. Also, according to the invention of Cante et al the calcium citrate platelets must be incorporated into the oil to

obtain the desirable increase in viscosity ie to produce a spreadable product.

Also, according to the invention of Cante et al the product does not contain a

mixture of vegetable oil and hardened fat which is necessary to provide the butter-like sensation in the mouth on melting. Also, according to the invention of Cante et al the product is not an emulsified spread and it is manufactured

by a process which is different from those employed for the production of

conventional fat spreads. The present invention provides a novel fat spread

which is an emulsified product and has a butter like taste and can be prepared with a variety of calcium sources and where the above said calcium

sources are not platelets of defined composition, size and shape and where

the calcium source is incorporated into the aqueous phase of the fat spread. The present invention also provides a novel calcium-containing ingredient and a method for the preparation thereof and its use in food products and drinks. SUMMARY OF THE INVENTION

This invention relates to the discovery that by combining a source of calcium ions and a source of anions in an aqueous solution of milk derived

solids, proteins or other suitably functionalised food additives, and using the resulting suspension as an aqueous phase for the preparation of an

emulsified fat spread, a spread with good organoleptic properties and no

undesirable chalky sensation in the mouth is produced. According to this

invention the calcium source is incorporated into the aqueous phase of the fat

spread in a largely insoluble form prior to emulsification. This invention also

provides a process for the preparation of calcium-supplemented or fortified fat

spreads with acceptable organoleptic properties. This invention also provides a novel calcium-containing ingredient and a method for the preparation

thereof and its use in food products and drinks.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to the discovery that by combining a source of

calcium ions and a source of anions ie counte ons in an aqueous solution of milk derived solids (or other suitable food additives as defined below), and

using the resulting suspension as an aqueous phase for the preparation of an

emulsified fat spread, a spread with good organoleptic properties and no undesirable chalky sensation in the mouth is produced. This is a surprising

finding because it is well known in the art that the organoleptic properties of

emulsified fat spreads are very sensitive to the composition of the aqueous phase. Thus, when a fat spread is prepared with commercially available calcium salts such as, for example, calcium citrate, calcium phosphate and

calcium carbonate, at a loading of about 4 gram per 100 gram of spread, the

resulting product has poor organoleptic properties. The addition of milk

solids, for example sodium caseinate, whey or whey proteins does not significantly improve the organoleptic properties of the product which remains

chalky. It was found that the sensation of powderiness in the mouth can be

somewhat reduced but not eliminated completely by incubating the above

mentioned calcium salts in an aqueous solution of milk derived solids, preferably from about 2% to about 10% by weight. However, when the

individual constituents of the same calcium salts are combined and

precipitated in the aqueous solution of milk derived solids under the same

conditions, a good fat spread is obtained and no sensation of powderiness is detected by organoleptic assessment of the product. This is a very surprising finding because the chemical composition of the two above said preparations

is identical as they contain the same amounts of the calcium ions source, the

source of anions and milk derived solids.

It was found, for example, that a fat spread with good organoleptic

properties can be obtained by adding Ca(OH)₂ to an aqueous solution of whey powder, preferably of high protein content, or milk-derived proteins such

as caseins or their salts, in citric acid, preferably at a temperature between

about 50°C and about 95°C with stirring. The contact time can be as short as

15-45 minutes or substantially longer, if desired. It was further found that the initial source of calcium ions and counterions (anions) is not crucial for practising the present invention. Thus, suitable calcium containing ingredients and fat spreads with good organoleptic properties are obtained when using CaCI₂, CaCO₃ or CaO as a source of calcium ions and organic acids such as, for example, citric acid or malic acid or a mixture thereof in any

molar ratio or inorganic acid such as phosphoric acid as a source of anions

(counterions). Salts of organic and inorganic acids can also be successfully used. For example, CaCI₂ can be combined with Na₂CO₃ or NaH₂PO₄, or sodium citrate or sodium malate. Also, various milk derived solids such as,

for example, milk powder, casein, sodium caseinate, whey, whey protein,

butter milk and the like can all be successfully employed. The above said

calcium preparations are largely water insoluble. In the context of this

invention, the term "largely water insoluble" is understood to mean a calcium preparation or salt which, at the concentration used, remains substantially

insoluble in an aqueous solution of pH from about 3 to about 9 at

temperatures used for the storage and consumption of the product, typically

from about 4°C to about 30°C. Typically, in the food product, at least 90% of the calcium composite remains insoluble.

It was further found that the fat spreads according to the present

invention can be further fortified or supplemented with water soluble calcium

salts, both inorganic, such as, for example, CaCI₂ and organic such as, for example, metastable calcium citrate malate (US 4 722 375), without affecting

the organoleptic properties of the product. In the context of this invention, the term "water soluble salt" is understood to mean a salt which, at the

concentration used, is substantially soluble (and, preferably substantially completely soluble) in an aqueous solution of pH from about 3 to about 9 temperatures used for the storage and consumption of the product, typically

from about 4°C to about 30°C. The combination of water soluble and largely

water insoluble salts and sources can be used, if desired, to further increase

the overall calcium content of the spread. Both largely water insoluble and water soluble calcium salts and sources can be calcium salts of organic and

inorganic acids and these salts can be combined in any combination. For

example, water soluble calcium chloride or metastable calcium citrate malate or a mixture thereof can be employed either with inorganic calcium phosphate or organic calcium citrate containing composites according to this invention,

or a mixture thereof.

An extensive study and research has been conducted to elucidate the

effect of milk solids on the calcium source and explain the difference in the taste perception. Without wishing to be bound by or advance any theory, it is

believed that multifunctional components and particularly proteins which are

present in milk derived solids interact with nucleation sites or small crystals or

particles of calcium salts formed in aqueous solution and this interaction alters the normal course of crystallisation or precipitation. It is known for

example, that in Nature proteins are incorporated into a largely crystalline matrix of calcium carbonate in, for example, shells of molluscs by a process

which is not yet well understood and this incorporation results in the formation

of composite mineral-organic materials of complex structure. It is likely therefore that multifunctional compounds which are present in milk derived

solids eg proteins exert a significant influence on the morphology of the resulting calcium containing material by forming a protein/calcium source composite with a distinctly different structure and sensory properties. It is further asserted that proteins from other sources eg soya protein or other

plant-derived proteins, and other protein containing food solids and protein

derivatives such as, for example, their acid or enzymatic hydrolysates and

other food additives which bare one or more of the same functional groups ie carboxyl, hydroxyl, amino, amido, thiol or phenol groups, when added to an

aqueous solution prior to combining a calcium ion source with a source of

anions, should exert a similar influence on the morphology of calcium

composites and influence the organoleptic properties of the above said

calcium composites, when incorporated in emulsified fat spreads and other food and drink formulations. The additive is any suitable additive which is

acceptable in food and have the functionality as disclosed herein. Preferably,

the additive has at least two, more preferably at least three and still more preferably at least four of the functional groups described above. Typically,

the additive is one which has been or will be approved for food use. The additive may be a proteolytic fragment of a protein or a peptide derived from a

protein. Proteolytic fragments or peptides derived from a protein which are

long enough to retain some element of secondary structure are preferred.

For the avoidance of doubt, the additive is not an insolubilizing anion as herein defined. In other words, the term additive does not include simple

inorganic or organic anions such as phosphate, carbonate, sulphate,

pyrophosphate, citrate, malate, lactate, citrate malate, propionate, gluconate, succinate, or ascorbate or mixtures thereof.

Examination of the calcium citrate-whey protein composite by, for example, SEM microscopy revealed a material of entirely different structure to that of a chemically identical sample of calcium citrate (control sample) precipitated in the absence of whey powder and subsequently treated with

solution of whey powder under the same conditions. At lower magnification

the composite material appears smooth with virtually no particulate matter observed and at higher magnification, ribbons or filaments of well structured,

probably crystalline or partially crystalline matter are clearly seen. This is

entirely different from the structure of whey protein-treated calcium citrate

which is appears relatively coarse at lower magnification and which

essentially consists of calcium citrate crystals of typical size and shape. The structural differences in the two above said materials of the same chemical

composition can also be observed by other physico-chemical methods, for example, FT-IR. The FT-IR spectrum of the control sample shows the same

characteristic bands occurring at essentially the same frequencies as a

commercially obtained sample of calcium citrate (Sigma Chemical Co). In the

spectrum of the calcium citrate-whey protein composite some of the bands were shifted in frequency or were absent or were replaced by new bands.

Thus a calcium composite according to this invention consists of a

largely insoluble mixture of calcium, an insolubilizing anion and protein (or

other suitable additive) where typically the co-precipitation of both components has altered the physical state of one or more components. Such

physical changes may include the morphology, habit or crystal size or degree of crystallinity of the calcium and are apparent from the examination of the

materials by methods such as FT-IR spectroscopy and SEM. Calcium composites therefore differ from material of the same chemical composition which is obtained by, for example, coating crystals of the calcium salt with

protein after precipitation of the calcium salt in that the thus coated crystals

exhibit the same physical characteristics as the uncoated salt as apparent from FT-IR spectroscopy and other techniques. A sample of the calcium citrate-whey protein composite which had been spray dried also showed the

same characteristic frequency shifts and pattern of bands in the FT-IR as the

composite described above. Thus the composite was unaffected by the drying process. By "insolubilizing anion" we mean an anion which, when present with

a calcium ion, leads to a substantially aqueous-insoluble salt.

The invention also includes a calcium composite material which

comprises a calcium salt and an additive where the additive is as defined above.

The calcium composite of the present invention can be produced in a

separate process or, for example, as a part of the fat spread (or other food

and drink) manufacturing process ie directly in an aqueous solution which is

to be used as an aqueous phase of the fat spread. It is preferred to make the composite first and to add other additives such as, for example, water soluble

flavours, thickeners or NaCI at a later stage. In the case when a calcium

source is combined with salts of organic and inorganic acids, preferably

sodium salts, it may not be necessary to add additional NaCI to the aqueous phase composition. The calcium composite of the present invention can also be produced separately and dried or partially dried by any conventional drying method. In this case, the above said composite can be added to an aqueous phase of fat spreads or other food or drink as a solid or a paste either before

or after the addition of other additives, depending on the preference of those

making the spread or other food or drink. A homogenisation step may be

desirable to reduce the particle size of the composite preparation. Any

conventional homogenisation technique can be successfully employed.

The calcium composite of the present invention as obtained or in dry

form or as a paste can be used for the manufacture of a wide range of food

and drink products such as, for example, fermented and non-fermented dairy

products, alcoholic and non-alcoholic drinks, soups, sauces, dips, salad dressings, mayonnaise, non-fat spreads, confectionery, bread, cakes, biscuits and breakfast cereals, to obtain foods and drinks which are supplemented

with calcium. The use of calcium containing composites of the present

invention in foods and drinks constitute yet another aspect of this invention.

For example, a yoghurt or a yoghurt drink can be fortified or supplemented with the calcium composite of the present invention and the resulting products

have a texture, flavour and appearance which is similar to or substantially

indistinguishable from the corresponding product compositions prepared with

no composite added. Although the present invention is illustrated by the preparation of fat spreads, yoghurt and yoghurt drinks, those skilled in the art will instantly recognise that it can be successfully practised with many other

food and drink products and as a food supplement in, for example, the form of

tablets and capsules. It will be appreciated that the calcium salt composite may be produced in situ during the preparation or manufacture of the food product or beverage (or drink), or it can be added separately during the

manufacturing or preparation process. The terms drink and beverage are

used interchangeably in this specification.

The fat spreads according to this invention can be made with a

different fat content, preferably with a fat content below 40%. Conventional

vegetable oils such as, for example, sunflower oil, soybean oil, rape seed oil

and the like can all be used as obtained or after hardening or any other

chemical or physical treatment, as known and acceptable in the art. Animal fats, preferably butter fat, may also be used. Other ingredients can be

optionally added to the oil phase. Examples of the above said ingredients

include flavouring and colouring agents and vitamins, preferably those which

are conventionally used in the manufacture of fat spreads.

When producing low and very low fat spreads according to this invention it is preferred to use stabilisers. The stabilisers which can be used

to practice the present invention include gelatine, maltodextrins, starch and

modified starch, cellulose and its derivatives and pectins and their derivatives

and other polysaccharides of plant or seaweed origin. However, this is not an exhaustive list and those skilled in the art will instantly recognise that other

stabilisers as well as various mixtures thereof can also be successfully employed.

Conventional emulsifiers, preferably mono/di-glycerides (E471 ), lecithin (E322) and polyglycerol esters (E476), can be used to produce the fat spreads according to this invention, preferably using the process of this invention. The above said emulsifiers can be used on their own or as a mixture or any combination thereof or in conjunction with other suitable emulsifiers which are known in the art. The emulsifier can be added to the oil

phase or to a part of the oil phase or to the aqueous phase, preferably after

combining a source of calcium ions with a source of anions and milk derived

solids.

The spreads according to this invention can be prepared to contain

vitamins, such as vitamins A and D, which are conventionally incorporated

into fat spreads or are required to be added by legislation. In addition the

spreads and other food products and drinks according to this invention can be further supplemented with any other additives known to be beneficial to

human health. For example, plant sterols or their esters can be included, if

desired, to provide the additional benefit of lowering cholesterol or additional

vitamins and minerals, carotenoids (eg lycopenes, -tocopherol), antioxidants

(eg ascorbic acid, flavonoids and isoflavones), lutein and other phytochemicals, which are known be beneficial to human health, can all be used. In the context of this invention the term "beneficial to human health" is

understood to mean any physiologically active compound which is not a

nutrient and can be shown to prevent or reduce the risk or ameliorate the conditions or symptoms of a disease when taken regularly as a part of the

diet. The above said physiologically active compounds do not have to be co-

precipitated or co-crystallised with the calcium-containing composites of the

present invention and can be added separately to the food product or beverage (or drink) of the present invention at an appropriate manufacturing stage. For example, water soluble additives such as, for example, vitamins and other minerals can be incorporated into the aqueous phase prior to emulsification, preferably after combining a source of calcium ions with a source of anions in a solution containing milk derived solids according to the present invention.

It will be appreciated that the calcium composite of the present

invention is incorporated in the food and drink products at an appropriate

stage of the manufacturing process. For example, in the production of yoghurt, the composite can be added to milk prior to fermentation with lactic

acid bacteria or much later at the stage of breaking the coagulum, if a stirred yoghurt is desired.

The calcium composites of the invention may conveniently be used in

food supplements. Typically, the food supplements are tablets containing the composite and suitable binding agents which allow the composite to bind and

form a tablet. The tablet may also contain other ingredients such as colouring

or flavouring or other ingredients known in the art. Conveniently, the tablet

may also be coated, for example with a candy coating. The food

supplements may also be capsules, in which case the calcium composite is present within the capsule either alone or in combination with some other

agent such as a flavouring agent. The food supplement may also be a

suspension of the calcium composite in a food-acceptable liquid. For example, the calcium composition may be in aqueous suspension. The food supplements may conveniently contain other desirable components such as

vitamins, minerals, carotenoids and the like as herein disclosed.

The present invention is further illustrated by specific examples and figures which are provided herein exclusively for the purpose of illustration

and are not intended to be limiting. Any person sufficiently skilled in the art

will recognise that numerous alterations to conditions and protocols presented

herein can be introduced within the spirit and scope of the present invention.

FIGURE LEGENDS

Figure 1 is a Fourier transform infra red (FT-IR) spectrum of air dried

composite and control materials.

Figure 2 shows SEM (scanning electronic microscope)

photomicrographs of the air-dried composite and control materials, (a) and

(c) are the composite and (b) and (d) are the control sample, (a) and (b) are

at lower magnification and (c) and (d) are at higher magnification (see scale bars).

Figure 3 shows SEM photomicrographs of calcium phosphate (control; top); calcium phosphate/whey composite (middle); and calcium phosphate +

whey protein (control; bottom). Further details are given in Example 5 (the

left hand side are at lower magnification and the right hand side is at higher magnification; see scale bars).

Figure 4 shows SEM photomicrographs of calcium carbonate + whey

(control; left) and calcium carbonate/whey composition (right) at different

magnifications (see scale bars). See Example 6 for further details. EXAMPLES

Example 1.

Preparation of the calcium citrate composite: Whey protein

concentrate (Alacen, New Zealand Dairy Products; 56 g/L) was dissolved in an aqueous solution of citric acid monohydrate (210.16 g/L) and heated to

60°C. 77.88 gram of Ca(OH)₂ was added and the resulting mixture was

stirred for a further 45 minutes. A control sample of whey protein-coated calcium citrate was prepared in exactly the same way except whey protein

concentrate was added after combining the aqueous solution of citric acid

and Ca(OH)₂ and the sample containing calcium citrate precipitate and whey powder was incubated for 45 minutes at 60°C. The SEM photomicrographs are shown in Figure 1 and FT-IR spectra of the air-dried composite and control materials are shown in Figure 2.

Example 2.

Whey protein (56 g/L) was dissolved in an aqueous solution of citric

acid monohydrate (210.16 g/L) and heated up to 60°C. 77.88 gram of

Ca(OH)₂ was added and the resulting mixture was stirred for a further 45

minutes. NaCI (4.5%) was added, the pH adjusted to 5.8, and 30 parts of this suspension was emulsified with 70 parts of an oil mixture consisting of

sunflower oil (79%) and hydrogenated vegetable oil (21%). Emulsifiers E471 and E322 (0.5%), fat soluble butter flavours (0.035%) and colouring (0.04%) were included in the oil. Example 3.

A fat spread was prepared as described in Example 2 but the

suspension containing calcium citrate was first diluted 1 :1 with water, gelatine

(3%) and NaCI (2.5%) was added, and 62 parts of the resulting aqueous phase was emulsified with 38 parts of oil using E471 and E322 (1 %) as

emulsifiers.

Example 4.

A calcium citrate composite was prepared as described in Example 1 but a mixture of citric acid monohydrate (105.1 g/L) and malic acid (55.1 g/L)

at 1 :1 molar ratio was used. A fat spread was prepared as described in Example 3.

Example 5.

A calcium phosphate-whey protein composite was prepared as

described in Example 1 but using 104 g/L of NaH₂PO₄x2H₂O instead of citric

acid monohydrate (210.16 g/L). A solution of NaH₂PO₄ (265.3 g) was dissolved in water (2000 mL) and to this solution whey protein (140 g; 56g/L

final concentration) was added. The mixture was heated up to 60°C with

stirring, CaCI₂x6H₂O (558.9 g) was added slowly and the volume was made

up to 2500 mL with water. The stirring was continued for a further 45 min,

after which time the suspension was cooled down to room temperature with stirring. The resulting calcium phosphate/protein composite was washed with water to remove the excess of salt, gelatine (3%) and citric acid (1%) were added, the pH was adjusted to 5.8 and a fat spread was prepared as described in Example 3. SEM microphotographs of the calcium

phosphate/whey composition, calcium phosphate and calcium phosphate

crystals with whey protein added after the crystallisation was completed

(controls) are shown in Figure 3.

Example 6.

A calcium carbonate-whey protein composite was prepared as follows: a solution of NaHCO₃ (168 g) in water (800 mL) was prepared. This was heated gently to about 40°C to aid the dissolution of the salt. To this solution

protein-rich whey powder (56 g; 56 g/L final concentration) was added and

the mixture was heated up to 60°C with stirring. CaCI₂x6H₂O (223 g) was

then added slowly and a little water to give a final volume of 2500 ml. The

stirring continued for further 45 min and the suspension was cooled down to room temperature with stirring. The resulting calcium carbonate/whey

composite was washed with water to remove the excess of sodium chloride

and the pH was adjusted to 5.8 by adding solid citric acid. After appropriate

dilution and addition of gelatine, the composite was used for the preparation of fat spread as described in Example 3. SEM microphotographs of the

calcium carbonate/whey composite and calcium carbonate crystals with whey

added after the crystallisation was completed (calcium carbonate + whey control) are shown in Figure 4. Example 7.

A calcium citrate composite was prepared as described in Example 1 but sodium caseinate (60 g/L) was used instead of whey powder and the

solution of sodium caseinate in citric acid and Ca(OH)₂ were combined at

90°C rather than 60°C. A fat spread was prepared as described in Examples

2 and 3.

Example 8.

A fat spread was prepared as described in Example 3 but the amount

of NaCI in the aqueous phase was reduced to 0.85% and CaCI₂ was

dissolved in the aqueous phase to a final concentration of 8 g/L prior to emulsification.

Example 9.

A fat spread was prepared as described in Example 5 but the amount of NaCI was reduced to 1.0% and metastable water soluble calcium citrate

malate was dissolved in the aqueous phase to a final concentration of 6 g/L.

Example 10.

A fat spread was prepared as described in Example 1 and 3 but 0.06%

of a concentrated (α-tocopherol (E307) or lycopene) was added to the oil

phase and 0.5% ascorbic acid (E300) was added to the aqueous phase prior to emulsification. Example 11.

A calcium citrate-whey protein composite was prepared as described in

Example 1 but was recovered by filtration and partially dried to obtain a very

thick paste. A fat spread was prepared as described in Example 3 but the paste was added to the aqueous phase of the spread alongside other components and was pasteurised prior to emulsification.

Example 12.

Calcium salt-whey protein composites were prepared as described in Examples 1 (calcium citrate) and Example 5 (calcium phosphate) and were

recovered by spay-drying. The dried composites were added to the aqueous

phase of fat spreads at 7.2 gram (calcium citrate-whey protein composite)

and 5 gram (calcium phosphate-whey protein composite) per 100 gram of spread, together with other components and the resulting aqueous phase was used for the preparation of fat spreads as described in Examples 3 or 11 respectively.

Example 13.

A calcium citrate composite was prepared by spray-drying as

described in Example 12 and analysed by FT-IR. The spectrum obtained was

very similar to that obtained with the calcium citrate composite prepared as

described in Example 1 and showed the same characteristic frequency shifts and pattern of bands. Example 14.

A standard yoghurt base was prepared by adding 1.5% by weight of

high protein whey powder to pasteurised skimmed milk. 1.5 gram of the calcium citrate-whey composite prepared as described in Example 12 was

added per 100 gram of milk and the mixture was homogenised, heated to

80°C and held at this temperature for 30 minutes. The mixture was then cooled to 45°C and the yoghurt mix was inoculated with starter culture

containing 1 :1 Lactobacillus bulgaricus and Streptococcus thermophilis.(0.5-

0.8% w/v), distributed into containers and incubated at 43°C until pH 4.5 was

reached. Typically, the fermentation took about 5 hours. No significant difference between the time required to reach the desired pH was noted

between the yoghurts made with and without the calcium containing ingredient. The two yoghurts were virtually indistinguishable organoleptically

and on examination with the naked eye.

Example 15.

A yoghurt base was prepared as described in Example 14. The

yoghurt base was cooled down to 15°C, and 3% of water and food grade citric

acid was added to adjust the pH to about 4.0. 1.9% by weight of citric pectin

and 4.1 % by weight of orange essence was added and, after intensive stirring, the mixture was homogenised under pressure and heated to about

50°C and cooled down to 3-5°C to provide a drink. Example 16.

A milk shake was prepared with calcium-containing composite

obtained as described in Example 1 (5%) and non-fat dry milk (6%), whey

concentrate (5%), sugar (9%) fructose-dextrose syrup (12%), corn syrup (3%), whey (5%), butter (7.5%), flavouring (0.5%), and water (42%). The syrups and flavouring were added to water combined with the sterol crystals

and mixed under high shear with heating up to the pasteurising temperature.

Other components were added and, when the sugar dissolved, the mixture

was homogenised and cooled directly into a heat-exchanger until the temperature of the product reached about 35°C. The product was stored overnight and then whipped.

Example 17.

A fat spread, a yoghurt and a milk shake were prepared as described in Examples 1 , 14 and 16 respectively but Soya isoflavones were added to

give an isoflavone content of 100 mg per 100 g of fat spread; 20 mg per

serving of yoghurt (125 g) and 30 mg per serving of the milk shake (200 ml).

The addition was made at the stage of preparing the aqueous phase (fat spread) breaking the coagulum (yoghurt) and together with syrups and flavouring (milk shake).

Claims

1. A composite material which comprises (1 ) calcium, (2) insolubilising anion and (3) an additive, where the additive (a) has more than one functional groups selected from the group comprising carboxyl, hydroxyl, amino, amido,

thiol and phenol, and any combination thereof and (b) is acceptable for food

use.

2. A composite material as described in Claim 1 , where the additive is a protein or derived from a protein.

3. A composite material as claimed in Claim 1 or 2, where the additive is a milk derived solid.

4. A composite material as claimed in Claim 3, where the milk derived solid is selected from the group comprising casein, caseinate, whey protein, whey, milk powder, buttermilk and butterfat.

5. A composite material as claimed in any of the Claims 1 to 4, where the

insolubilising anion is the conjugate base of an inorganic acid.

6. A composite material as claimed in any of the Claims 1 to 5, where the

insolubilising anion is selected from the group comprising phosphate, carbonate, sulphate, pyrophosphate and mixtures thereof.

7. A composite material as claimed in any of the Claims 1 to 4, where the

insolubilising anion is the conjugate base of an organic acid.

8. A composite material as claimed in any of the Claims 1 to 4 and 7, where the insolubilising anion is selected from the group comprising citrate, malate, lactate, citrate malate, propionate, glycerophosphate, gluconate, succinate, ascorbate and mixtures thereof.

9. A method for the preparation of a calcium composite the method

comprising combining a source of calcium ions and a source of anions which

can produce largely water insoluble calcium in the presence of a third

ingredient (additive), which (a) has more than one functional groups selected from the group comprising carboxyl, hydroxyl, amino, amido, thiol and phenol, and any combination thereof and (b) is acceptable for food use.

10. A method as claimed in Claim 9, where the source of calcium ion is

selected from the group comprising calcium hydroxide, calcium oxide, calcium carbonate, calcium chloride.

11. A method as claimed in any of the Claims 9 and 10, where the source of anions is selected from the group comprising phosphoric, citric, malic,

succinic, carbonic acids and food acceptable salts thereof.

12. A method as claimed in any of the Claims 9 to 11 , where the third ingredient is a protein or derived from a protein.

13. A method as claimed in any of the Claims 9 to 11 , where the third ingredient is a milk derived solid.

14. A method as claimed in Claim 13, where the milk derived solid is

selected from the group comprising casein, caseinate, whey protein, whey, milk powder, buttermilk and butterfat.

15. A method as claimed in any of the Claims 9 to 14, where a calcium source, a source of anions and the third ingredient are combined in aqueous solution at a pH between 2 and 10.

16. A method as claimed in any of the Claims 9 to 15, where the calcium

source, the source of anions and the third ingredient are combined at a

temperature from 0°C to 95°C, with stirring.

17. A method as claimed in any of the Claims 8 to 16, where the calcium

composite is dried.

18. A calcium salt composite obtainable by the method of any one of

Claims 9 to 17.

19. A method of supplementing a food product or beverage with calcium the method comprising the step of including in the food product or beverage a calcium composite according to any one of Claims 1 to 8 or 18.

20. A method according to Claim 19 wherein the calcium composite is

formed in situ during the preparation of the food product or beverage.

21. A food product or beverage supplemented with calcium obtainable by the method of Claims 19 or 20.

22. A food product or beverage containing a calcium composite according

to any one of Claims 1 to 8 or 18.

23. The use of the composite as claimed in any of the Claims 1 to 8 or 18 in food products, drinks and food supplements.

24. The use of the composite prepared by the method as claimed in any of

the Claims 9 to 16 in food products, drinks and supplements.

25. The use of the composite as claimed in any of the Claims 23 and 24, where the food products are fat spreads.

26. The use of the composite as claimed in any of the Claims 23 and 24, where the food products are yoghurts.

27. The use of the composite as claimed in any of the Claims 23 and 24, where the drinks are yoghurt drinks.

28. A food product or beverage according to Claim 21 or 22 or obtained by

the method of Claims 19 or 20 which is additionally supplemented with

another physiologically active food additive which can be shown to be beneficial to human health.

29. A food product or beverage according to Claim 28 wherein the

additional food additive is selected from the group consisting of vitamins,

minerals, plant sterols, lycopenes, carotenoids, flavonoids, isoflavones, antioxidants, lutein and mixtures thereof.

30. A food product or beverage according to Claim 29 wherein the food additive is soya isoflavone added in excess of 10 mg per serving of the food product or beverage.

31. A food product according to Claim 21 or 22 or obtained by the methods of Claim 19 or 20 which is an emulsified fat spread.

32. An emulsified fat spread which is supplemented with calcium, where

the calcium source is included in the aqueous phase of the product

composition in a largely insoluble form obtainable by the method of Claim 19 or 20.

33. An emulsified fat spread which is supplemented with calcium, where the calcium source is included in the aqueous phase of the product composition in a largely insoluble form.

34. An emulsified fat spread which is supplemented with calcium, where the calcium source is included in the aqueous phase of the product composition in a largely insoluble form and where the aqueous phase of the

product composition contains milk derived solids.

35. An emulsified fat spread as claimed in any one of Claims 32 to 34,

where the calcium source comprises calcium and an insolubilising anion of an organic acid, and is present in a largely insoluble form.

36. An emulsified fat spread as claimed in any one of Claims 32 to 34,

where the calcium source comprises calcium and an insolubilising anion of an inorganic acid, and is present in a largely insoluble form.

37. An emulsified fat spread as claimed in any of the Claims 32 to 36, where the spread contains an additional water soluble calcium salt.

38. An emulsified fat spread as claimed in Claim 37, where the largely

water insoluble calcium source contains an insolubilising anion of an organic acid and the water soluble calcium salt is a salt of an organic acid.

39. An emulsified fat spread as claimed in Claim 37, where the largely

water insoluble calcium source contains insolubilising anion of an inorganic

acid and the water soluble calcium salt is a salt of an organic acid.

40. An emulsified fat spread as claimed in Claim 37, where the largely water insoluble calcium source contains an insolubilising anion of an organic

acid and the water soluble calcium salt is a calcium salt of an inorganic acid.

41. An emulsified fat spread as claimed in Claim 37, where the largely

water insoluble calcium source contains insolubilising anion of an inorganic acid and the water soluble calcium salt is a calcium salt of an inorganic acid.

42. An emulsified fat spread as claimed in any of the Claims 32 to 41 , where the insolubilising anion is selected from the group comprising citrate, malate, lactate, citrate malate, propionate, glycerophosphate, gluconate, succinate, ascorbate and mixtures thereof.

43. An emulsified fat spread as claimed in any of the Claims 32 to 41 , where the insolubilising anion of an inorganic acid is selected from the group

comprising carbonate, phosphate, pyrophosphate, sulphate, chloride, and

mixtures thereof.

44. An emulsified fat spread as claimed in any of the Claims 32 to 43, where milk derived solids are selected from the group consisting of casein,

caseinate, whey protein, whey, milk powder, buttermilk and butterfat.

45. An emulsified fat spread as claimed in any of the Claims 32 to 44, which is further supplemented with another physiologically active food additive which can be shown to be beneficial to human health in addition to those required by legislation.

46. An emulsified fat spread as claimed in Claim 45 where the further physiologically active food additive is selected from the group consisting of vitamins, minerals, plant sterols, lycopenes, carotenoids, flavonoids, isoflavones, antioxidants, lutein and mixtures thereof.

47. An emulsified fat spread as claimed in Claim 45 where the further food additive is soya isoflavone added in excess of 10 mg per serving.

48. An emulsified fat spread as claimed in any of the Claims 32 to 47, which contains less than 40% fat.

49. A process for the production of emulsified fat spreads as claimed in any of the Claims 32 to 48, which comprises of contacting (i) milk derived solids and (ii) a source of calcium ions and (iii) a source of insolubilising anions which can produce a largely water insoluble calcium salt, in the aqueous phase of the product composition prior to emulsification.

50. A process for the production of emulsified fat spreads as claimed in any of the Claims 32 to 48, where the combined milk derived solids, the calcium source and the source of insolubilising anions which can produce a

largely water insoluble calcium salt, are treated at a temperature and exposure time combination which is sufficient for pasteurisation.

51. An emulsified fat spread as claimed in any one of Claim 32 to 48 which contains the composite material as claimed in any one of Claims 1 to 8 and 18.

52. An emulsified fat spread as claimed in any one of Claims 32 to 48 which contains the composite material as claimed in any one of Claims 9 to 17.

53. A food supplement containing the composite material as claimed in any one of Claims 1 to 8 and 18.

54. A food supplement according to Claim 53 which is a tablet containing the composite material and a binding agent.

55. A food supplement according to Claim 53 which is a capsule

containing the composite material.

56. A food supplement according to Claim 53 which is a suspension of the composite material in a food acceptable liquid.