This invention relates to a method for preparing a creamer, to a creamer that is well resistant to separation, and to the use of a particular constituent as anti-separation agent.

Creamers are fat-containing compositions which form an emulsion in a suitable amount of water. Creamers are used to make a food creamier. Creamers are also used to change the color of a food, in particular for imparting a white color, or to make the color lighter.

Creamers can be administered dry - usually in powder form - or as liquid. Creamers can be used as end product, for instance as coffee or tea creamer, or as semifinished product in the preparation of a food, for instance an instant soup or sauce.

A creamer generally contains a surface-active substance having an emulsifying action. Suitable for this purpose is, for instance, a protein such as caseinate. A disadvantage of a protein as surface -active substance in a creamer is the resistance of a protein-containing creamer to separation. In particular upon exposure to high temperatures, a low pH and/or a high content of polyvalent cations, in particular calcium ions, a creamer based on (milk) protein has a tendency to separate. A conventional solution to this problem is adding a stabilizing salt, such as a sodium or potassium salt of a phosphate or a citrate. Apart from the unde sir ability of such an additive in some markets in view of the image with consumers, the addition of a stabilizing salt does not lead to the desired result in some products, in particular an acid soup such as tomato soup. Also, the salt can have an adverse effect on the taste, for instance when used in coffee, in particular coffee concentrates in cans ("canned coffee").

One object of the invention is to provide a protein-containing creamer which is well-resistant to separation, also when it is used in a food having an acidic pH, and/or in a hot food and/or in a food having a high polyvalent cation content, in particular a high calcium content (i.e. with a high hardness).

A further object of the invention is to provide a method for preparing such a creamer.

It has now been found that a particular conjugate of a protein, and in particular a conjugate of a protein and a carbohydrate polymer, is eminently suitable to be used in a creamer having a good resistance to separation, also when the creamer is used in an acid food, and/or a hot food and/or a food having a high degree of hardness. In addition, the creamer according to this invention provides the functionality so characteristic of protein-containing creamers, whereby a good creaminess of the food is combined with both sufficient whitening power and a neutral taste, which is an advantage over creamers where use is made of an emulsifying substitute for proteins, such as, for instance, emulsifying starch.

The invention accordingly relates to a creamer comprising a fat and a protein-carbohydrate polymer conjugate as emulsifier, the carbohydrate polymer being built up from at least three monosaccharide units.

A "conjugate" is herein understood to mean a compound consisting of a protein and one or more reducing carbohydrates, the carbohydrates being bound to the protein via a covalent bond. This covalent bond will as a rule be formed between an ε-amino group of a lysine side chain of the protein and the aldehyde group of the carbohydrate. The formation of such a covalent bond is known as the first step in the Maillard reaction.

It has been found that a protein-carbohydrate conjugate in which the carbohydrate polymer is built up from at least three monosaccharide units is very suitable as anti- separation agent in a creamer.

In particular, it has been found that a creamer according to the invention also has a very good resistance to separation if the creamer is administered to a liquid having a degree of hardness of at least 15 °DH.

Incidentally, United States patent application US 2001/041211 discloses a powdered agglomerated creamer, which is especially soluble at low temperatures, and which can undergo freeze/thaw cycles, as well as a method for the manufacture of such a creamer and the use thereof in cooled drinks. The creamer preferably comprises a sweetener (carbohydrate), a water-soluble or water-dispersible protein and an edible oil having a melting point below 20 ⁰ C.

That document is completely silent on the use of a protein-carbohydrate conjugate. Examples 1 and 2 of the above-mentioned United States patent application use potassium phosphate and sodium citrate as anti-separation agent. European patent application EP-A-O 579 328 relates to powder-form creamers for beverages and soups, consisting of fat, carbohydrate and protein, the protein being chicken albumen. The creamer forms a foam on the surface. It is noted that the chicken protein provides a better and stabler foam than for instance casein or casemate. The chicken protein furthermore denatures already at room temperature, during foam formation. Further, especially a glycose syrup having a DE of 36 is utilized (see Examples I and IV). This document, too, is completely silent on the use of a protein- carbohydrate conjugate. On the other hand, potassium phosphate is used. United States patent specification US-A-5, 571,334 discloses a starch- based opacifying agent, a method of manufacture thereof and formulations, both food and non-food, containing such an opacifying agent. A use of this agent is in a creamer. The problem outlined is the insolubility of (in)organic opacifying agents, such as titanium dioxide. This problem is resolved by forming a complex of an (in)organic insoluble compound with starch.

Examples 10 and 11 of US-A-5,571,334 show a creamer comprising a protein, a fat, and a starch having a DE of 1-5. For this creamer an optimum stability of this complex is found at a DE of 5.0 (20 monosaccharide units).

The formation of a protein-carbohydrate conjugate is not described. In German "Gebrauchsrαuster" 203 17533, a particulate creamer is described which includes 10-90% specific triglycerides, as well as the use thereof in foods. The examples use phosphate and/or citrate salts.

DE 23 25 651 Al discloses a free-flowing, non-fat, cream -like creamer. Example 1 discloses a protein-carbohydrate mixture, present in a creamer, which contains no fat. There does not seem to be any conjugate formation involved, nor is the use of an anti-separation agent suggested.

The formation of the protein-carbohydrate conjugates that are essential according to the invention is not described in any of the above- discussed publications. Incidentally, it is noted that should maillarding occur in the preparation of the foods through the presence of proteins and reducing carbohydrates, the processing in the above prior art shows too short reaction times and/or too low temperatures, while if maillarding should occur a conjugate possibly formed proceeds to react further to form the well known brown Maillard pigments. A creamer according to the invention is very suitable for use in an acid food such as coffee (usually having a pH of about 4.8-5.4) or an acid soup, such as tomato soup (usually having a pH of about 4-4.5).

The invention furthermore relates to a creamer comprising a fat and a protein-carbohydrate conjugate, the carbohydrate being built up from at least three monosaccharide units, which creamer, also in the absence of a stabilizing salt, is resistant to separation if the creamer is present in a liquid having a pH in the range of about 3.5 to about 7.5 and/or having a temperature in the range of about 70-100 ⁰ C and/or having a hardness of about 15-30 ⁰ DH. Preferably, the creamer is resistant to separation at a temperature, pH and hardness in the specified ranges.

In an embodiment, at the above-mentioned pH and hardness, the creamer is even resistant to separation at a temperature of up to about 150 ⁰ C or more. This is especially of interest because as a consequence during preparation use can be made of an ultra-high temperature treatment (UHT), which usually takes place at a temperature of about 140-150 ⁰ C for one or a few seconds (e.g. about 1 to about 10 sec), for instance to extend the storage life of the creamer.

Also, an emulsion of the creamer is stable in a beverage, i.e., for at least 15 min after addition of the creamer to the beverage, whitening power is maintained and no fat separation is to be seen.

A creamer according to the invention is preferably in powder form.

In principle, the creamer according to the invention can, if desired, contain a stabilizing salt, for instance in a relatively low concentration, for instance less than 1 wt. % based on the creamer dry matter. Preferably, however, the creamer is at least substantially free of added phosphate and/or added citrate. More preferably, a creamer according to the invention is at least substantially free of any added stabilizing salt.

By "substantially free" is meant herein that there is at least less of the salt present than is necessary in a conventional creamer with an unconjugated mixture of carbohydrate and protein as emulsifier to provide a sufficient stability at high temperature in an acid environment of a high hardness.

In particular, "substantially free" is understood to mean a content of less than about 0.2 wt.% based on the creamer dry matter, more particularly a content of 0-0.1 wt.%.

By terms such as "approximately", "about" and the like, at least a deviation of at most 5%, in particular of at most 2%, is included.

Dry matter is herein understood to include all components except water.

Protein-carbohydrate conjugates are known, for that matter. WO 00/18249 describes a process whereby a whey protein is glycosylated by storing powdered whey protein in an environment whose moistness and temperature are controlled. What is contemplated is to reduce the further occurrence of Maillard continuation reactions. The use of such a glycosylated protein in creamer for enhancing stability of the creamer at a high temperature, low pH and/or high degree of hardness is not mentioned. The present inventors have found that the process described in WO00/18249 generally leads to a difficult-to-handle, sticky or caked powdered protein- carbohydrate conjugate. Further, it has been found that a protein-carbohydrate conjugate which is disclosed in WO 00/18249 is not well-resistant to separation in a creamer at high hardness and/or low pH and/or high temperature (See present Example 3).

It has now been found that a creamer having a good stability to separation, also at high hardness and/or low pH and/or high temperature, can be prepared in an efficient manner by arranging for the protein-carbohydrate conjugate to be formed as part of the manufacture of the creamer, by allowing the reaction to take place in the presence of at least a part of the fat and any possible other constituents of the creamer. Therefore, the invention furthermore relates to a method for manufacturing a creamer, comprising:

- preparing a, usually liquid, reaction mixture of a fat, water (as liquid), a protein and a reducing carbohydrate;

- allowing the protein and the carbohydrate to react in the reaction mixture, usually with stirring, thereby forming a protein-carbohydrate conjugate; and

- forming a fat in water emulsion.

In a particular embodiment, the creamer is prepared by

- mixing a protein and a carbohydrate to form a mixture divided on a molecular scale, in particular by dissolving both components in a solvent; then

- drying the protein-carbohydrate mixture, preferably by spray-drying; then

- distributing the dried protein-carbohydrate through a fat;

- setting the water content (in particular the water saturation degree a _w ) thereby forming the reaction mixture,

- allowing the protein and the carbohydrate to react in the reaction mixture, usually with stirring, thereby forming a protein-carbohydrate conjugate; and

- forming a fat in water emulsion.

The creamer can then be used as liquid creamer. Preferably, the creamer is dried, more preferably to a powder-form creamer. Such a powder- form creamer has been found in general not to be sticky and not to give rise to any caking during storage when it is stored under conventional conditions.

A method according to the invention not only provides a creamer having desirable properties with a view to storage and with a view to its use, but is also simple in design and can be easily carried out on an industrial scale.

A method according to the invention can be very suitably carried out with standard equipment for a creamer preparation line. Thermostatted and moisture-controlled storage rooms are not needed. The skilled person will be able to determine suitable reaction conditions with general knowledge of the art and the present description and claims. Preferably, the reaction conditions are chosen such that a protein-carbohydrate conjugate with a glycosylation degree (average number of carbohydrate groups per lysine residue x 100%) of at least 15% is formed, more preferably at least 20% as determined by means of the OPA

method. This method is described in Broersen et al., Biotechnology and Bioengineering, vol 86, No 1, April 5, 2004, pp. 78-87.

Preferably, the glycosylation degree is up to 100%. From practical considerations (time and cost of preparation), a glycosylation degree of 50% or less is particularly preferred.

As raw materials for a creamer in the framework of the invention, conventional materials can be chosen.

The protein is preferably selected from milk proteins and vegetable proteins, as well as combinations thereof. Very good results have been achieved with caseins and casemates. Particularly suitable vegetable proteins are proteins that can be used as milk protein substitutes, such as wheat protein or soy protein.

The method according to the invention can in principle be used for the preparation of any type of protein-carbohydrate conjugate, hence also for conjugates having mono- and/or disaccharides therein. For this purpose, in principle any reducing carbohydrate can be deployed. The reducing carbohydrate can comprise one or more monosaccharides, disaccharides and/or polysaccharides. 'Polysaccharides' is herein understood to mean in particular carbohydrates having at least three saccharide units. Also counted among the polysaccharides are oligosaccharides, i.e. polysaccharides built up from 3-10 saccharide units.

For the preparation of a creamer according to the invention, which comprises a protein-carbohydrate conjugate of which the carbohydrate is built up from at least three monosaccharide units, in general a carbohydrate is used which is built up from at least three monosaccharide units

(trisaccharides and higher). A protein-carbohydrate conjugate prepared with a carbohydrate containing three or more monosaccharide units per molecule has been found to have a better resistance to separation than a conjugate prepared with a monosaccharide or disaccharide (such as lactose), in

particular at a temperature of about 90-100 ⁰ C, and/or a high hardness and/or a low pH.

Preferably, at least the greater part of the polysaccharide molecules have a chain length of at least 6. From practical considerations, such as glycosylation rate considerations, preferably at least the greater part of the polysaccharide molecules have a chain length of less than 20.

Preferably, the content of carbohydrates (used for the formation of the conjugate) built up from at least three saccharide units is at least 95 wt.% based on the total carbohydrate content (used for the formation of the conjugate). More preferably, the content of carbohydrates having a chain length of 6-20 is at least 95 wt.% based on the total carbohydrate content.

Very suitable are oligosaccharides (in particular tri- to decasaccharides) and polysaccharides which are at least substantially built up from galactose, fructose, glucose, lactose units or a combination thereof. Very good results have been achieved with a creamer containing a conjugate which has been prepared from a protein, preferably a milk protein or vegetable protein, and a maltodextrin.

Preferably, the maltodextrin has a dextrose equivalent (DE) - as determined by the Lane Eynon method (AOAC Official Method 935.62) - of about 5 to about 15. More preferably, the maltodextrin contains less than 5 wt.% of mono- and disaccharides.

The term fat is herein understood to mean a fatty acid glyceride (understood to include a mixture of fatty acid glycerides), in particular a fatty acid triglyceride. 'Fats' is understood to include oils (fats which are liquid at room temperature). In a preferred embodiment, the creamer comprises a solid fat, i.e. a fat which is solid at room temperature (25 ⁰ C). The fat can be of vegetable or animal origin. Good results have been obtained with a hardened fat, such as hardened palm fat.

As water, demineralized water, mains water or spring water can be used.

In a method according to the invention, a reaction mixture is prepared from water, fat, protein and carbohydrate, in which the protein- carbohydrate conjugate is subsequently formed.

The amounts used can be set within wide limits, depending inter alia on the desired degree of glycosylation.

Preferably, the weight ratio of protein to carbohydrate is from about 1:2 to about 1:6, more preferably from about 1:3 to about 1:5, in particular 1:4.

The needed fat/oil for the manufacture of the creamer can be added wholly or partly to the reaction mixture.

The amount of water is preferably set at a content corresponding to an a _w value (water saturation degree) (for instance as determined using a Novasina a _w meter) in the range of from about 0.3 to about 0.8.

A relatively high a _W) e.g. of at least 0,5, preferably of more than 0.6, is preferred because of a high glycosylation rate. With a view to a proper stirrability and the prevention of continuation reactions which can lead to browning, the a _w is preferably at most 0.75.

Of particular advantage is a method in which the a _w is set at a value in the range of 0.63-0.75, in particular 0.65-0.70. In such a method, on the one hand the glycosylation rate is high and on the other hand stirrability is good and the extent of undesired continuation reactions is low. Very good results have been achieved by means of a method in which the a _w was about 0.69.

In an embodiment for the preparation of a caseinate-carbohydrate conjugate, water is preferably added to a content of at least 8 wt.% based on the weight of the protein plus carbohydrate (in particular at a protein to carbohydrate weight ratio of from 1:2 to 1:6, for instance about 1:4). More preferably, the water content is at least 11 wt.%. For obtaining a conjugate that contributes to a creamer with a very good stability, also in the absence of a stabilizing salt, the water content in the reaction mixture is preferably at most about 25 wt.%, more preferably at most about 20%, still more

preferably at most about 14 wt.%, based on the weight of the protein plus carbohydrate.

The formation of the conjugate preferably takes place at a temperature above the melting point of the fat, in particular at a temperature between about 30 ⁰ C and about 90 ⁰ C.

With a view to the reaction rate, the reaction temperature is preferably at least about 50 ⁰ C, more preferably at least 55 °C.

The reaction temperature is preferably at most about 85 ⁰ C. At such a temperature, few to no undesired Maillard continuation reactions occur. To prevent lumping during the reaction in a simple manner, the temperature is preferably at most about 70 ⁰ C, in particular at most about 60 ⁰ C. However, if a tendency to lumping arises, this can also be reduced or prevented at higher temperature, for instance by stirring more intensively.

Usually, the reaction mixture is allowed to react for at least about 1 hour, preferably for at least about 6 hours. Usually, it is sufficient to allow the reaction mixture to react for about 18 hours at a maximum (in particular at a temperature of at least 55 ⁰ C). Very good results have been achieved with a reaction time of less than about 10 hours, in particular at a temperature of at least 55 ⁰ C. Optionally, the progress of the reaction can be monitored, by measuring the extent of glycosylation continuously or intermittently. Very suitable for this purpose is the OPA method.

After the desired degree of conversion has been reached, the mixture of water, fat and protein-carbohydrate conjugate is usually processed further. It is not necessary to store the mixture (for a longer time) at a controlled air humidity.

If desired, extra water and/or extra fat and/or extra carbohydrate is added to the mixture to obtain the desired emulsion of fat in water. The ratios of water, fat and protein-carbohydrate conjugate and possibly carbohydrate in the emulsion can be as specified in the following table:

Typical range for main constituents of a liquid creamer

Also, if desired, the creamer can contain one or more additives that are suitable for use in a creamer. In addition to the protein-carbohydrate conjugate, the creamer can for instance contain a low-molecular emulsifier. Suitable low-molecular emulsifiers are generally known in the art. Examples are monoglycerides such as glycerol monostearate. Other suitable emulsifiers are for instance described in Emulsifiers, Eagan Press Handbook Series, C. E. Stauffer, 1999.

Preferably, the emulsion is pasteurized or sterilized. Because of the resistance to separation of the emulsion in the presence of the protein- carbohydrate conjugate, UHT is very suitable to inactivate or kill off microorganisms. If desired, the emulsion can be spray-dried, thereby yielding a powder- form creamer. As spray-drying technique, a conventional technique for creamers can be used, such as described, for instance, in "Spraydrying Handbook", fifth edition, 1991, Keith Masters, Editor: Longman Scientific and Technical, ISBN 0582062667.

Typical range for main constituents of a powdered creamer

A powdered creamer comprises in a preferred embodiment up to 25 wt. % protein-carbohydrate conjugate (based on the total weight). A creamer according to the invention can be used as such as an end product, for instance instead of milk in coffee or tea.

It is also possible to incorporate a creamer according to the invention in a food, for instance in an acid food, such as tomato soup.

The invention accordingly relates also to a food comprising a creamer according to the invention.

The food has, in one embodiment, at least an aqueous phase whose degree of hardness is at least 5 ⁰ DH, preferably 15-30 ⁰ DH. The pH is preferably 3.5 - 7.5. The pH is herein the value as determined when the food has been brought into a liquid form intended for consumption. The food is usually heat-stable, which means in particular that the food is resistant to separation, at least for a few seconds (e.g. 2-10), preferably for at least 15 min, at a temperature of about 70-150 ⁰ C, in particular of about 90 ⁰ C.

In an embodiment, the food is a liquid food, for instance a soup, a sauce or a beverage, such as an alcoholic beverage.

Compared with a conventional food, such as a food with a creamer based on non-conjugated protein, such a food has been found to be very stable, also at a high temperature, for instance of about 90 ⁰ C, and/or a low (acidic) pH and/or hard water. Particularly good results have been achieved with a creamer in an acid soup, such as tomato soup.

In an embodiment, the food is a concentrate, preferably a powdered concentrate. Preferred examples of such concentrates are sauce, soup, coffee (in particular for variants such as cappuccino, cafe au lait, and the like) and tea. In an embodiment, the food is an instant product.

The invention will now be elucidated in and by the following examples.

Example 1 (reference; no formation of protein-carbohydrate conjugate)

In 1100 liters of water of about 50 ⁰ C, 180 kg sodium casemate were dissolved. After this, 720 kg maltodextrin (Glucidex IT 8 from Roquette, DE of 12.5; about 2 % mono/disaccharides, about 98 % higher saccharides) were dissolved therein. The solution was pasteurized at 75 °C and then dried to a moisture content of 7.5 wt. %, based on the weight of the protein- carbohydrate conjugate.

14.7 kg of the dried caseinate/maltodextrin powder were dissolved, with stirring, in 40 kg water at a temperature of about 60 ⁰ C. To the solution were added 45.3 kg hardened palm fat. After homogenization and pasteurization, a part of the emulsion was spray-dried.

Of the emulsion and the spray-dried part, the stability was determined in water of a pH of 3.5 (after addition of powder: pH 4.2), a hardness of 30° DH and a temperature of 90 ⁰ C. Both were unstable. Directly after addition of the water, the protein began to separate.

Example 2

14.7 kg of the dried caseinate/maltodextrin powder as obtained in Example 1 were mixed with 45.3 kg fat. Next, 0.7 kg water was gradually admixed with vigorous stirring, so that the total water content was about 12 wt.% based on the weight of caseinate/maltodextrin powder.

The whole was stirred at 60 ° C for 9 hours, yielding a conjugate with a degree of glycosylation of about 25 %.

Next, 39.3 kg water were added. After homogenization and pasteurization, a part of the emulsion was spray-dried. Both the emulsion and the powder resulted in stable systems after addition to water of a pH of 3.5 (after addition of powder: pH 4.2), a hardness of 30° DH and a temperature of 90 ⁰ C. Within 15 minutes, there was no separation observable.

Example 3

In 5 kg warm water, 600 g Na-caseinate and 2400 g lactose were dissolved.

The whole was heated to 70 ⁰ C and spray-dried. The moisture content of the powder was 1.9 %. In 4.3 kg molten hardened palm fat, 1.4 kg was caseinate/lactose conjugate was distributed, with stirring. The whole was adjusted to 60 ⁰ C.

With vigorous stirring, 170 g water were slowly added and heating was done to 60 ⁰ C.

After 4, 6, 8 and 10 hours, a sample was taken. This sample was adjusted to 60% dry matter and then homogenized using ultraturrax.

16.5 grams of this emulsion were tested in 200 cc water of 100 ⁰ C at a pH of 4.2. After 1 and also 15 minute assessment, actually in the sample after 10 hours of glycosylation still heavy separation occurred.